Alexandra Elena PLESU (BONET RUIZ) PHD Thesis PDF

UNIVERSITY “POLITEHNICA” of BUCHAREST
Faculty of Applied Chemistry and Material Sciences

Department of Chemical Engineering
MODELLING AND SIMULATION OF CONTINUOUS CATALYTIC

DISTILLATION PROCESSES
A Thesis submitted to the

University POLITEHNICA of Bucharest
and
University of Barcelona
in joint collaboration
for ACADEMIC TITLE OF DOCTOR
by
Alexandra Elena BONET RUIZ
SPECIALITY: CHEMICAL ENGINEERING
under the supervision of
Professor Grigore BOZGA

Professor Joan LLORENS LLACUNA
Professor José COSTA LÓPEZ
July 2012
LIST OF PAPERS
PLESU A.E., BONET J., PLESU V., BOZGA G., GALAN M.I., 2008, Residue Curves Map
Analysis for tert-Amyl Metyl Ether Synthesis by Reactive Distillation in Kinetically Controlled
Conditions with Energy –Saving Evaluation, Energy, 33, 1572-1589
BONET-RUIZ, A.-E., BONET-RUIZ, J., PLEŞU, V., BOZGA, G., LLORENS LLACUNA, J.,
COSTA LOPEZ, J., 2009, New contributions to modelling and simulation of TAME synthesis by
catalytic distillation, Chemical Engineering Transactions, 18, 959-964
BONET-RUIZ A.E., BONET J., PLESU V., BOZGA G., 2010, Environmental performance
assessment for reactive distillation processes, Resources Conservation and Recycling, 54 (5),
315-325
BONET-RUIZ, J., BONET-RUIZ, A.-E., RADU, V.-C., LLACUNA, J.L., LOPEZ, J.C., 2010,
A simplified cost function for distillation systems evaluation, Chemical Engineering
Transactions, 21, 1405-1410
BONET-RUIZ, A.-E., BONET, J., BOZGA, G., LLACUNA, J.L., PLEŞU, V., 2010, Number
of transfer units information on residue curve maps, Chemical Engineering Transactions 21,
1417-1422.
CIORNEI, C.I., BUMBAC, G., PLESU, A.E., MOTELICA, A., IVANESCU, I., TOMA, A.,
2006, Catalytic Distillation Process Modelling and Simulation for the TAEE Synthesis on
Amberlyst 35, 33th International Conference of Slovak Society of Chemical Engineering, 22 – 26
May 2006, Tatranské Matliare, Slovakia, Proceedings - Slovak Society of Chemical Engineering,
ISBN 80-227-2409-2, paper no. Le-Fr-2 251.
BUMBAC, G., MOTELICA, A., PLESU, A.E., BOZGA, G., TOMA, A., 2006, Kinetic studies
on the etherification of isobutene to fuel ether ETBE, 17th International Congress of Chemical
and Process Engineering CHISA 2006 - 9th Conference PRES2006, 27 – 31 August 2006,
Prague, Czech Republic, Proceedings - Czech Society of Chemical Engineering
BUMBAC, G., CIORNEI, C.I., PLESU, A.E., SIMION, C., TOMA, A., 2007, Kinetic Studies
on the Etherification of C5-Alkenes To Fuel Ether TAME, 34th International Conference of
Slovak Society of Chemical Engineering, 21 – 25 May 2007, Tatranské Matliare, Slovakia,
Proceedings - Slovak Society of Chemical Engineering, Po-Th-5, 039p, ISBN 978-80-227-2640-
5
BUMBAC, G., PLESU, A.E., PLESU, V., 2007, Reactive Distillation Process Analysis in
Divided Wall Column, Proceedings of ESCAPE17, May 2007, Computer Aided Chemical
Engineering, vol. 24, pg. 443-448, V. Plesu and P.S. Agachi (Editors), Elsevier.
BUMBAC, G., PLESU, V., CIORNEI, C.I., PLESU, A.E., 2007, Modelling and simulation the
process in a reactive dividing wall column for gasoline additive TAME synthesis in the oil
refinery 10th Conference on Process Integration, Modelling and Optimisation for Energy Saving
and Pollution Reduction-PRES'07, vol 1, J. Klemeš Editor, 24-27 June 2007, Ischia Island Gulf
of Naples, Italy, Chem.Eng.Trans, vol 12, ISBN 88-901915-4-6, pp79-84, 2007.
PLESU, A.E., BONET, J., CIORNEI, C.I., PLESU, V., BOZGA, G., GALAN, M.I., 2008,
Energy-Saving Issues in Reactive Distillation Schemes, Energy for Sustainable Future
EMINENT 2 Workshop, 2008, University of Pannonia, Veszprem, Hungary, 5-8 May 2008,
ISBN 978-963-9696-38-9, pp257-266.
BONET, J, GALAN, M.I., COSTA, J., MEYER, X.M., MEYER, M., PLESU, A.E.,
Representation of Residue Curve Maps with Pinch Zones, 2008, 18th European Symposium on
Computer Aided Process Engineering - ESCAPE18, 1-4 June 2008, Computer-Aided Chemical
Engineering, 18, Lyon, France.
PLESU, V., BOZGA, G., PLESU, A.E., CIORNEI, C.I., BOLOGA, V., Experimental Devices
and Modelling Tools for Sustainable Processes Development, 2008, 11th Conference on Process
Integration, Modelling and Optimisation for Energy Saving and Pollution Reduction-
PRES2008, J. Klemeš Editor, 24-28 August 2008, Prague, vol 4, ISBN 978-80-02-02051-6,
paper J.4.1, pp1124.
PLESU, V., BOZGA, G., PLESU, A.E., CIORNEI, C.I., BOLOGA, V., 2008, Modelling and
Simulation Tools for Sustainable Processing and Production, 11th Conference on Process
Integration, Modelling and Optimisation for Energy Saving and Pollution Reduction-
PRES2008, J. Klemeš Editor, 24-28 August 2008, Prague, vol 4, ISBN 978-80-02-02051-6,
paper P.5.101, pp1459
PLESU, A.E., BONET, J., PLESU, V., BOZGA, G., GALAN, M.I., 2008, TAME Sustainable
Production – Infinite/Infinite Analysis for Synthesis by Reactive Distillation in Chemical non-
Equilibrium Conditions, 11th Conference on Process Integration, Modelling and Optimisation for
Energy Saving and Pollution Reduction- PRES2008, J. Klemeš Editor, 24-28 August 2008,
Prague, vol 4, ISBN 978-80-02-02051-6, paper P.5.102, pp1460
PLESU, V., BILDEA, C.S., IANCU, P., BUMBAC, G., DANCIU, T.D., BONET-RUIZ, J.,
BONET-RUIZ A.E., NEGHINA, I.L., 2009, A Systematic Approach To Graduation Project In
Chemical Engineering, Proceedings Romanian International Conference on Chemistry and
Chemical Engineering, RICCCE XVI, 9 – 12 September 2009, Sinaia – Romania, paper S4. K-
02.
BONET-RUIZ A.E., BOZGA G., LLORENS LLACUNA J., COSTA LOPEZ J., 2012, The
kinetics of TAME synthesis on solid acid catalysts, U.P.B. Sci. Bul., Series B - Chemistry and
Materials Science, ISSN 1454-2331, sent to journal.
CONTENTS
CHAPTER 1 Introduction............................................................................... ………………..1
CHAPTER 2 Survey regarding the catalytic distillation technique and synthesis methods of
ethers used as fuel additives. Catalysts, kinetics and thermodynamics…………………………...6
2.1. The principle of reactive distillation and its technical importance ..................................... 6
2.2. The importance of tertiary aliphatic ethers C5-C7. Legislation aspects and main
representatives............................................................................................................................... 11
2.2.1. Sources of tertiary olephins .............................................................................................. 17
2.2.2. Synthesis methods for C5-C7 aliphatic tertiary ethers series............................................. 18
2.2.3. Industrially applied technologies for fuel ethers synthesis and technical-economical .... 21
2.2.4. TAME ............................................................................................................................... 23
2.3. Termodynamics of liquid phase alcohol adition to C5 tertiary olefins ............................. 29
2.4. Kinetic models for TAME synthesis reactions ................................................................. 34
2.4.1. Literature survey ............................................................................................................... 34
2.4.2. Solid catalysts for synthesis of ethers by alcohol addition to tertiary olefins................... 54
2.4.2.1. Ion exchange resins....................................................................................................... 56
2.4.2.2. Inorganic solid acid catalysts ........................................................................................ 60
2.5. Industrial TAME production technologies ....................................................................... 62
2.6. Mathematical models used in the calculation of reactive distillation processes............... 65
2.6.1. Simplified (total equilibrium) models............................................................................... 66
2.6.2. Equilibrium models........................................................................................................... 67
2.6.3. Non – equilibrium models ................................................................................................ 69
Conclusions................................................................................................................................... 74
Chapter 3.The kinetics of TAME synthesis on solid acid catalysts…………………………...…76
3.1. Experimental study of isoamylenes etherification with methanol.................................... 76
3.1.1. Materials and method........................................................................................................ 76
3.1.2. Set-up description ............................................................................................................. 78
3.1.3. Sample analysis................................................................................................................. 82
3.1.4. Operating Procedure ......................................................................................................... 85
3.1.4.1. Set-up start-up............................................................................................................... 85
3.1.4.2. Experimental procedure ................................................................................................ 87
3.1.5. Experimental results.......................................................................................................... 88
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3.1.5.1. Influence of reaction temperature ................................................................................. 88
3.1.5.2. Influence of catalyst grain size ................................................................................. 89
3.1.5.3. Effect of isoamylenes concentration ......................................................................... 91
3.2. Modelling reaction kinetics for TAME synthesis ............................................................. 92
3.2.1. Comparison of experimental results with values calculated based on kinetic models
published in literature ................................................................................................................... 93
3.2.2. Parameters estimation for the kinetic model proposed ................................................. 97
Conclusions................................................................................................................................. 101
CHAPTER 4 Experimental study of vapour liquid equilibrium data ......................................... 104
4.1. Experimental device............................................................................................................. 103
4.1.1. Description of the dynamic vapour liquid equilibrium (VLE) apparatus ......................... 103
4.1.2. Operation and experimental procedure............................................................................. 109
4.1.3. Considerations related to the experimental error .............................................................. 112
4.2. Materials .............................................................................................................................. 112
4.3. Gas chromatograph analysis ................................................................................................ 113
4.4. Experimental results of the binary vapour liquid equilibrium ............................................. 114
4.4.1. 2-methyl-2-butene/Methanol ............................................................................................ 114
4.4.2. 2-methyl-2-butene / TAME .............................................................................................. 119
4.4.3. 2-methyl-1-butene / TAME .............................................................................................. 123
4.4.4. Isopentane / methanol ....................................................................................................... 127
4.4.5. Summary of the performances of different thermodynamic model.................................. 131
Conclusions ………………………………………………………………………………….135
CHAPTER 5 Feasibility and simulation of TAME synthesis-separation process……………...138
5.1. Market demand and basic economic feasibility................................................................... 138
5.2. Basic physical feasibility ................................................................................................ 138
5.2.1. Introduction to Residue Curve Maps: Theory and Practice........................................ 138
5.2.2. Mathematical model for the (reactive) residue curves................................................ 143
5.2.2.1. Residual Curves and Number of Transfer Units (NTU)......................................... 147
5.2.2.2. Singular Points ........................................................................................................ 153
5.2.3. Implementation of the reactive residue curve maps calculation ................................. 155
5.2.3.1. Data Input................................................................................................................ 155
5.2.3.2. Exploration of the map topology ............................................................................ 156
5.2.3.3. Residue curve calculation ....................................................................................... 157
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5.2.3.3. Residue curve calculation ....................................................................................... 157
5.2.3.4. Number of Transfer Units calculation .................................................................... 157
5.2.3.5. Implementation of the residue curve map model to the TAME case ..................... 158
5.2.4. Reactive residue curve maps calculated for TAME ....................................................... 160
5.2.5. Number of transfer units in the residue curve maps calculated for TAME .................... 165
5.2.6. Comparison of the reactive residue curves with the reactive distillation column profile at
infinite reflux for the TAME synthesis....................................................................................... 172
5.2.7. Analysis of the system .................................................................................................... 176
5.2.7.1. Simplification of the rigorous mathematical model....................................................... 176
5.2.7.2. The infinite/infinite analysis and the reactive residue curve maps ................................ 179
5.2.7.3. Application of the infinite/infinite analysis to non-chemical equilibrium systems ....... 181
5.2.7.4. Results of the infinite/infinite analysis to kinetically controlled reactive distillation for
TAME synthesis.......................................................................................................................... 185
5.2.7.5.Results of the infinite/infinite analysis to kinetically controlled hybrid reactive distillation
for TAME synthesis.................................................................................................................... 200
5.3. Technical assessment ...................................................................................................... 210
5.3.1. Rigorous simulation of reactive distillation column alternatives TAME synthesis ....... 210
5.3.2. Rigorous simulation taking into account the presence of isopentane inert..................... 219
5.4. Economical assessment................................................................................................... 221
5.4.1. Basic economic feasibility .............................................................................................. 221
5.4.2. Economical comparison of the reactive distillation alternatives .................................... 222
5.4.3. Techno-economic model with CO2 capture feasibility................................................... 226
5.5. Environmental performance assessment......................................................................... 227
5.5.1. Environmental Performance Index (EPI) ranking .......................................................... 228
Conclusions ………………………………………………………………………………….231
CHAPTER 6. Conclusions……………………………………………………………………..233
References……………………………………………………………………………………. 236
Appendix 1……………………………………………………………………………………. 256
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LIST OF FIGURES
Figure 2. 1 Typical scheme for a conventional process of (a) reaction and separation and (b)
reactive distillation.......................................................................................................................... 9
Figure 2. 2 Main tertiary ethers used at industrial scale ............................................................... 13
Figure 2. 3 Generation of tertiary alcohols by hydration of olephins........................................... 20
Figure 2. 4. Amounts of product used in various fields............................................................... 26
Figure 2. 5 The amount of TAME consumed in different EU countries ...................................... 27
Figure 2. 6 Main reactions for obtaining TAME .......................................................................... 28
Figure 2. 7 Secondary reaction – dimerization of isoamylenes .................................................. 28
Figure 2. 8 Secondary reaction – etherification (dehydration) of methanol ................................. 28
Figure 2. 9 Reactions for TAME synthesis................................................................................... 33
Figure 2. 10 The reaction network in the formation and splitting of TAME................................ 35
Figure 2. 11 Chemical structure of ion exchange resins............................................................... 57
Figure 2. 12 Mechanism of alcohols addition to olefins, in alcohol excess ................................. 59
Figure 2. 13 Mechanism of alcohols addition to olefins, without alcohol excess ........................ 59
Figure 2. 14 NexTAME process ................................................................................................... 63
Figure 2. 15 Philips etherification procedure with high conversion............................................. 64
Figure 2. 16 General structure of the plant for TAME synthesis by CDEtherol technology ....... 65
Figure 2. 17 Physical model of the reactive distillation column................................................... 66
Figure 2. 18 Simplified scheme of an equilibrium tray ................................................................ 67
Figure 2. 19. Schematic representation of non-equilibrium tray .................................................. 70
Figure 2. 20 Mass transfer in homogeneous reactive distillation ................................................. 71
Figure 2. 21 Transport processes in reactive distillation in the presence of non-porous catalysts72
Figure 3. 1 Autoclave-type reactor of the etherification plant...................................................... 79

Figure 3. 2. Batch plant scheme for kinetic studies ...................................................................... 81
Figure 3. 3 Time evolution of TAME concentration at different temperatures............................ 89
Figure 3. 4. Experimental results at 80oC for various granule sizes ............................................. 90
Figure 3. 5. Experimental results at 90oC for various granule sizes ............................................. 90
Figure 3. 6. Effect of isoamylenes concentration in the C5 fraction at 80oC. .............................. 92
Figure 3. 7. Parity diagram experimental conversion – calculated conversion ............................ 97
using kinetic model proposed by Rihko et al (1995, 1997) .......................................................... 97
Figure 3. 8. Variation in time of the experimental and calculated conversions............................ 98
Figure 3. 9. Energy of reactions scheme for the TAME synthesis ............................................... 99
iv
Figure 3. 10. Parity diagram experimental conversion – calculated conversion ........................ 100
Figure 4.1. Dynamic VLE apparatus used in the experimental work......................................... 103
Figure 4. 2. VLE apparatus scheme ............................................................................................ 104
Figure 4. 3. VLE apparatus control panel ................................................................................... 106
Figure 4.4. VLE 2-methyl-2-butene (1) / methanol (2), x-y diagram (P=1013 mbar) ............... 114
Figure 4.5. VLE 2-methyl-2-butene (1) / methanol (2), Txy diagram (P=1013 mbar) .............. 114
Figure 4.6. VLE 2-methyl-2-butene (1) / methanol (2), x-y diagram from data available in the
literature (P=1013 mbar)............................................................................................................. 115
Figure 4.7. VLE 2-methyl-2-butene (1) / methanol (2), Txy diagram from data available in the
Figure 4.8 VLE 2-methyl-2-butene (1) / methanol (2), .............................................................. 116
a) experimental activity coefficients, b) Herington consistency test (P=1013 mbar)................. 116
Figure 4.9 VLE 2-methyl-2-butene (1) / methanol (2), correlation of the experimental data to
several thermodynamic models (P=1013 mbar) ......................................................................... 117
Figure 4.10 VLE 2-methyl-2-butene (1) / methanol (2), predictions compared with the
experimental data (P=1013 mbar)............................................................................................... 118
Figure 4.11 VLE 2-methyl-2-butene (1) / methanol (2), comparison of Aspen database with the
Figure 4.12. VLE 2-methyl-2-butene (1) / TAME (2), x-y diagram (P=1013 mbar) ................. 119
Figure 4.13 VLE 2-methyl-2-butene (1) / TAME (2), Txy diagram (P=1013 mbar)................. 119
Figure 4.14. VLE 2-methyl-2-butene (1) / TAME (2), x-y diagram from data available in
Figure 4.15. VLE 2-methyl-2-butene (1) / TAME (2), Txy diagram from data available in the
Figure 4.16 VLE 2-methyl-2-butene (1) / TAME (2), correlation to a volatility coefficient for
ideal mixtures (P=1013 mbar) .................................................................................................... 122
Figure 4.17. VLE 2-methyl-2-butene (1) / TAME (2), a) experimental activity coefficients, b)
Herington consistency test (P=1013 mbar)................................................................................. 122
Figure 4.18 VLE 2-methyl-2-butene (1) / TAME (2), correlation of the experimental data to
Figure 4.19 VLE 2-methyl-2-butene (1) / TAME (2), predictions compared with the
Figure 4.20. VLE 2-methyl-1-butene (1) / TAME (2), x-y diagram (P=1013 mbar) ................. 124
Figure 4.21 VLE 2-methyl-1-butene (1) / TAME (2), Txy diagram (P=1013 mbar)................. 124
v
Figure 4.23 VLE 2-methyl-1-butene (1) / TAME (2), Txy diagram from data available in the
ideal mixtures (P=1013 mbar) .................................................................................................... 126
Figure 4. 25 VLE 2-methyl-1-butene (1) / TAME (2), a) experimental activity coefficients, b)
Figure 4. 26 VLE 2-methyl-1-butene (1) / TAME (2), correlation of the experimental data to
Figure 4.27 VLE 2-methyl-1-butene (1) / TAME (2), predictions compared with the
Figure 4.28 VLE isopentane (1) / methanol (2), x-y diagram (P=1013 mbar) ........................... 127
Figure 4.29 VLE isopentane (1) / methanol (2), Txy diagram (P=1013 mbar) .......................... 128
Figure 4.30 VLE isopentane (1) / methanol (2), x-y diagram from data available in the literature
(P=1013 mbar) ............................................................................................................................ 128
Figure 4.31 VLE isopentane (1) / methanol (2), Txy diagram from data available in the literature
(P=1013 mbar) ............................................................................................................................ 129
Figure 4.32 VLE isopentane (1) / methanol (2), a) experimental activity coefficients, b)
Figure 4.33. VLE isopentane (1) / methanol (2), correlation of the experimental data to several
thermodynamic models (P=1013 mbar) ..................................................................................... 130
Figure 4.34. VLE isopentane (1) / methanol (2), predictions compared with the experimental data
(P=1013 mbar) ............................................................................................................................ 130
Figure 4.35 VLE isopentane (1) / methanol (2), comparison of Aspen database with the
Figure 4. 36 Thermodynamic model correlation for each binary system. Root mean square error
for the temperatures. ................................................................................................................... 132
Figure 4. 37 Average temperature deviation.. ………………………………………………….133
Figure 5.1 Systematic procedure of the methodology proposed and used. ................................ 137
Figure 5.2 Rayleigh distillation scheme...................................................................................... 139
Figure 5.3 Residue curve map example. (TAME synthesis at Da=1, P=1 bar; .......................... 140
from Moreira Duarte, 2006)........................................................................................................ 140
Figure 5.4 Screen snapshot of the implemented user interface for initial concentration............ 159
Figure 5. 5 Reactive residue curve map at p = 4 bar and Da equal to 10-4 ................................. 160
Figure 5.6 Reactive residue curve map at p = 4 bar and Da equal to 10-3 .................................. 161
vi
Figure 5.1 Systematic procedure of the methodology proposed and used. ................................ 137
Figure 5.2 Rayleigh distillation scheme...................................................................................... 139
Figure 5.3 Residue curve map example. (TAME synthesis at Da=1, P=1 bar; .......................... 140
from Moreira Duarte, 2006)........................................................................................................ 140
Figure 5.4 Screen snapshot of the implemented user interface for initial concentration............ 159
Figure 5. 5 Reactive residue curve map at p = 4 bar and Da equal to 10-4 ................................. 160
Figure 5.10 Reactive residue curve map at p = 6 bar and Da equal to 10-3 ................................ 163
Figure 5.13. Number of transfer units in the residue curve map at .......................................... 167
p = 4 bar and Da equal to 10-4 .................................................................................................... 167
Figure 5.14 Number of transfer units in the reactive residue curve map at.............................. 167
p = 4 bar and Da equal to 10-3 ..................................................................................................... 167
Figure 5. 15 Number of transfer units in the reactive residue curve map at p = 4 bar and Da
equal to 10-2................................................................................................................................. 168
Figure 5.16 Number of transfer units in the reactive residue curve map at p = 4 bar and Da
equal to 10-1................................................................................................................................. 168
Figure 5.17 Number of transfer units in the reactive residue curve map at p = 6 bar and Da equal
to 10-4 .......................................................................................................................................... 169
equal to 10-3................................................................................................................................. 169
Figure 5. 19 Number of transfer units in the reactive residue curve map at p = 6 bar and Da
equal to 10-2................................................................................................................................. 170
equal to 10-1................................................................................................................................. 170
equal to 0..................................................................................................................................... 171
equal to 0 ………………………………………………………………………………….172
vii
Figure 5.23 Reactive residue curve map (discontinue line) and infinite reflux column profiles
(continuous line) for the TAME reactive distillation at 1 bar and a value of H/V of 0.0001 sec173
(continuous line) for the TAME reactive distillation at 1 bar and a value of H/V of 0.001 sec 174
(continuous line) for the TAME reactive distillation at 1 bar and a value of H/V of 0.01 sec... 174
(continuous line) for the TAME reactive distillation at 1 bar and a value of H/V of 0.1 sec..... 175
(continuous line) for the TAME reactive distillation at 1 bar and a value of H/V of 1 sec........ 175
(continuous line) for the TAME reactive distillation at 1 bar and a value of H/V of 100 sec.... 176
Figure 5.29 Three possible ∞/∞ column profiles....................................................................... 178
Figure 5.30. Possible feed locations ........................................................................................... 181
Figure 5.31 The illustration of the reactive lever rule in composition space.............................. 183
Figure 5.32 Mass balance for simple binary distillation............................................................. 185
Figure 5.33 Bifurcation diagram of distillate compositions for the TAME synthesis at Da=0, P=1
bar and real-feed composition at the corresponding chemical equilibrium at 1 bar. .................. 187
Figure 5.34 Bifurcation diagram of distillate compositions for the TAME synthesis at Da=
0.0001, P=1 bar and real-feed composition at the corresponding chemical equilibrium ........... 189
Figure 5.35 Bifurcation diagram of distillate compositions for the TAME synthesis at Da=0.001,
P=1 bar and real-feed composition at the corresponding chemical equilibrium at 1 bar. .......... 192
Figure 5.36 Bifurcation diagram of distillate compositions for the TAME synthesis at Da=1, P=1
bar and real-feed composition at the corresponding chemical equilibrium at 1 bar. .................. 193
Figure 5.37 Bifurcation diagram of distillate compositions for the TAME synthesis at Da=0,
P=10 bar and real-feed composition at the corresponding chemical equilibrium at 10 bar. ...... 194
0.0001, P=10 bar, real-feed composition at the corresponding chemical equilibrium. ............. 195
0.001,P=10 bar and real-feed composition at the corresponding chemical equilibrium ........... 196
Figure 5 40 Bifurcation diagram of distillate compositions for the TAME synthesis at Da=0, P=1
bar and real-feed composition at the corresponding chemical equilibrium at 10 bar. ............... 197
0.0001,P=1 bar and real-feed composition at the corresponding chemical equilibrium……. 198
viii
0.001, P=1 bar and real-feed composition at the corresponding chemical equilibrium ............. 199
P=1 bar and real-feed composition at the corresponding chemical equilibrium at 10 bar. ........ 200
Figure 5.44 Bifurcation diagram of distillate compositions for the TAME synthesis in hybrid
distillation column, at Da=0.0001, P=10 bar and real-feed composition. .................................. 202
distillation column, at Da=0.001, P=10 bar and real-feed composition ..................................... 204
distillation column, at Da=1, P=10 bar and real-feed composition ............................................ 205
distillation column, at Da=1, P=1 bar and real-feed composition .............................................. 206
Figure 5.48 Hybrid reactive distillation column overcoming chemical equilibrium................. 208
Figure 5.49 Traditional system of reactor and distillation column at 1 bar using an excess of
isoamylene on the reactor feed. .................................................................................................. 209
Figure 5 50 Traditional system of reactor and distillation column at 10 bar using an excess of
isoamylene in the reactor feed. ................................................................................................... 209
Figure 5.51 Hybrid reactive distillation column at 10 bar using an excess of isoamylene in the
column feed................................................................................................................................. 210
Figure 5.52 Influence of the reaction extent on the performance of various configurations...... 210
Figure 5.53 Traditional system of reactor and distillation column (a); entire reactive distillation
column (b); hybrid reactive distillation column (c). ................................................................... 213
Figure 5.54 Hybrid reactive distillation column compositions profile ....................................... 216
Figure 5.55 Hybrid reactive distillation column temperature profile ......................................... 216
Figure 5.56 Distribution of the reaction extent in the hybrid reactive distillation column......... 217
Figure 5.57 Internal hybrid reactive distillation column flow rates............................................ 217
Figure 5. 58 Correlation between reboiler duty and vapour flow rate........................................ 219
Figure 5.59 Influence of distillate flow rate and reflux on reboiler duty.................................... 219
Figure 5. 60. Flowsheet scheme for RDWC ............................................................................... 221
Figure 5. 61. Liquid phase composition profiles in the RDWC ................................................. 222
Figure 5. 62 Operational and investment costs for ideal mixtures K=1.8 and n=0.54. .............. 226
Figure 5. 63 Operational and investment costs crossing point for ideal mixtures...................... 226
Figure 5. 64 Operational and investment costs crossing point for ideal mixtures...................... 227
ix
LIST OF TABLES
Table 2. 1. Allowed concentration limits for reformulated gasoline compounds......................... 14

Table 2. 2 Allowed concentration limits for ethers used in gasoline............................................ 14
Table 2. 3. Worldwide tertiary ethers production in year 2000 .................................................... 15
Table 2. 4 Tertiary ethers and gasoline properties........................................................................ 16
Table 2. 5. Typical composition of C4 fraction from pyrolysis units............................................ 17
Table 2. 6 Typical composition of C4 fraction from catalytic cracking units............................... 17
Table 2. 7 Typical composition of C5 fraction from catalytic cracking units............................... 17
Table 2. 8 Main characteristics of industrial processes for the synthesis of tertiary ethers……. 21
Table 2. 9 TAME composition produced in European Union ...................................................... 23
Table 2. 10 Physicochemical properties of tert-amyl methyl ether .............................................. 24
Table 2. 11 Companies producing TAME with capacities of over 1000 t/year ........................... 25
Table 2. 12 Amounts (produced+imported), industrial branches and areas of use for TAME..... 26
Table 2. 13 The amount of TAME consumed in different EU countries in 2002 ........................ 26
Table 2. 14 Thermodynamical data for the participants in the reaction ....................................... 31
Table 2. 15 Equilibrium constants involved in the TAME’s synthesis ........................................ 34
Table 2. 16 Kinetic parameters for the reactions involved in the synthesis of TAME................. 36
Table 2 17 Kinetic constants involved in TAME’s synthesis....................................................... 40
Table 2. 18 Rate expressions for TAME synthesis process.......................................................... 43
Table 2 19 Characteristics of Amberlyst and Purolite – type catalysts ...................................... 57
Table 2. 20 Characteristic variables of the equilibrium model ..................................................... 69
Table 2. 21 Equations of the equilibrium model........................................................................... 69
Table 2. 22 Variables of the non-equilibrium model.................................................................... 73
Table 2. 23 Equations of the non-equilibrium model………………………………………. 73
Table 3. 1 Experimental plan ........................................................................................................ 77
Table 3. 2. Parameters of the model used for calculating the theoretical values .......................... 95
Table 3. 3. Estimated parameters of the kinetic model ………………………………….100
Table 4.1. Raw materials for VLE experiments ......................................................................... 112
Table 4. 2. Estimated thermodynamic models parameters. ........................................................ 133
Table 4. 3 Maximum error temperature prediction for the estimated parameters. ………….134
Table 5.1. Case studies used in the infinite-infinite analysis for traditional system reactor +
distillation column at stoichiometric feed................................................................................... 185
x
Table 5.2 Flow rates of the selected alternatives obtained by simulation. ................................. 214
Table 5.3 Comparison of the distillation columns and reactors for the several systems. ........... 215
Table 5. 4 Overall cost comparison of the several alternatives .................................................. 227
Table 5. 5 Results for the TAME synthesis (for 2.656 TAME Mt/h)......................................... 228
Table 5. 6 Normalised impact scores for different categories of potential environmental......... 230
Table 5. 7 Individual total PEI for each TAME process alternative (PEI/kg product)*............. 231
Table 5. 8 Factors for EPI determination of TAME process ...................................................... 232
xi
xii
CHAPTER 1
Introduction
An increasing environmental concern has promoted the use of some new products in detrimental
of some others less environmental friendly. Tert amyl methyl ether (TAME) is additive for clean
gasoline. TAME is the tertiary aliphatic ether most used nowadays in Europe as fuel additive and
therefore the present work is focused on it. The goal of this work is to contribute to the
understanding of chemical synthesis process, providing new experimental data and an original
approach taking into account the technical, economical and environmental aspects in process
design.
Chapter 2 presents the state of the art and the motivation of the present work. Several alternatives
for octane improvement of gasoline are presented from an historical perspective, until the
nowadays solution: tertiary aliphatic ethers C5-C7. The reasons for which these compounds
improve the octane number and what processes take place inside the engine are described. The
choice of various compounds as octane enhancers for gasoline throughout history is motivated
by their environmental impact and the legislation response to these evidences. A review of
several alternatives available is provided and they are discussed according to the legislative
framework. Information about their use and quantities mixed in the gasoline, properties inferred
to the gasoline, production capacities, factories and biodegradability routes in the environment
are discussed.
The reaction schemes used for tertiary aliphatic ethers synthesis are presented. The raw materials
usually employed are alcohols and the olefins contained in some light fractions from the oil
processing processes (as fluid catalytic cracking –FCC- or steam cracking). Several sources of
olefins are identified and the typical composition of these fractions is quantified. The reaction
conditions suitable for these reactions to take place and several catalysts useful for this purpose
are presented. The relative reactivity among several olefins is compared. The secondary
reactions possible to be present in the system are identified and explained in detail; the
recommended reaction conditions to avoid them are stated. TAME is produced by reaction of
methanol (MeOH) with two reactive C5 olefins, contained in C5 fraction separated in different
processes: 2-methyl-1-butene (2M1B) and 2-methyl-2-butene (2M2B). The reactions at
equilibrium are modelled and the values for the equilibrium constants are provided. Some of the
available thermodynamic models for estimation of physical-chemical properties are discussed in
Chapter 2 including the parameters used in prediction models.
1
A critical comparison of the available industrial processes for TAME production shows that
reactive distillation is a process integration/intensification technique providing very good
performance. Each process alternative is described in detail. The production capacities for
several sites around the world are tabulated indicating the licensor of the process.
The thermodynamic and chemical data as well as physical properties for this particular
component are provided. The main impurities present in industrially obtained TAME are
quantified depending on the source. The emissions of TAME to the environment from several
sources are quantified and tabulated, and effects evaluated. The evolution of TAME production
processes in Europe, main companies involved, production capacity, consumption in each
European country, and main uses are reviewed.
There are several classes of catalysts for synthesis of ethers used as ecological fuel additives as
already pointed out previously. They are classified and evaluated according to their main
properties. The ion exchange resins are discussed in more detail, as they are most applied in
industry and for this reason they are used later in this work. The reaction mechanism is discussed
showing that both 2M1B and 2M2B pass by the same intermediate carbocation tert-amyl before
obtaining final product, TAME. The catalyst review is closed by a section about inorganic solid
acid catalyst with emphasis on zeolites.
As pointed out previously, reactive distillation (RD) is a promising option for TAME synthesis.
In Chapter 2, reactive distillation is reviewed and potential advantages are underlined. The
historical framework in the use of reactive distillation is presented. Structural details on the
placement of the catalyst inside the RD column are shown. Several mathematical models useful
to describe the process are detailed.
Chapter 3 is dedicated to the thermodynamic and kinetic study for TAME synthesis process
scheme. A detailed literature review of kinetic models is provided along with the main
conclusions of main studies. An experimental kinetic study is performed using as raw materials
MeOH and isoamylenes enriched C5 fraction from FCC gasoline cut, as used in industry with
Amberlyst 35 ion exchange resin catalyst. A pressurized reactor connected to a gas
chromatograph with a FID detector is used. For an optimum tracking of operating parameters,
the set-up is endowed with a computer interface. This allows the transmission of temperature and
pressure values, determined by sensors in direct contact with work environment, to a computer
on which the momentary parameters are registered and presented in table or in graph format. To
increase the accuracy of sampling and analysis, the set-up is provided with a sealed system,
which connects the sampling device to the chromatograph where analysis of the reaction mixture
is performed at pre-established intervals. The influence of several parameters on the synthesis
process is studied: reactor temperature, catalyst size (to evaluate internal diffusion limitation),
2
and isoamylenes concentration. The activity coefficients are calculated using UNIFAC
thermodynamic model and the results are correlated to thermodynamic/kinetic models of Rihko
et al (1995, 1997). The model parameters are regressed in MATLAB and a parity diagram is
used to visualize the correlation of the results, obtaining a good quality of correlation.
Chapter 4 is devoted to experimental work and modelling of thermodynamic data, related to
vapour liquid equilibrium (VLE) for binary systems less studied in literature : MeOH / 2M2B,
2M2B / TAME, 2M1B / TAME and Isopentane / MeOH. At the beginning of the chapter, the
dynamic ebulliometer LABODEST 602 is described, providing details about the specific
operation procedure used in research. Samples analysis is performed by gas chromatography
with adapted procedure. For each of the binary mixtures studied, based on experimental data
obtained, xy and Txy diagrams are built, and compared to results published in literature. In
modelling work, experimental data is used to fit own parameters for several thermodynamic
activity models (Wilson, Van Laar, NRTL, UNIQUAC), based on computer tool implemented in
ASPEN Plus software. Then activity coefficient diagram and logarithm of activity coefficients
ratio are used to evaluate thermodynamic consistency. xy and Txy diagrams are used further to
compare : own experimental results with predictions of models (UNIFAC, UNIFAC Dortmund,
and COSMO which is an ab initio method) implemented in ASPEN Plus, along with prediction
of Wilson, Van Laar, NRTL, UNIQUAC having own fitted parameters. The root mean square
error for saturation temperatures and average temperature deviation are used to compare the
correlation of different thermodynamic models. Ideal gas phase behaviour fit correlation best.
From this chapter can be concluded that the experimental data and model parameters obtained in
this work is predict VLE for studied systems in agreement with the literature. Most of the
thermodynamic models considered provide good correlations.
In Chapter 5 a methodology to evaluate the feasibility of TAME synthesis process is proposed,
starting with fast calculations and evolving towards rigorous ones, taking into account
economical and environmental aspects, from early stages of process design. The residue curve
maps are used in the early stage to check the system behaviour and feasibility of component
separation. At the beginning of the chapter, the residue curve maps are introduced, identifying
the main topological aspects. The mathematical model to calculate the residue curves with
special features is formulated and implemented in MATLAB. Then model behaviour is
discussed. The Number of Transfer Units (NTU) is used to complement the residue curves for
checking the feasibility of separation process based on distillation. The suitability of the residue
curves for systems with reaction is discussed. Using the concept of NTUs and the mass balances
for a packed reactive distillation column operating at infinite reflux flow rate, a new expression
is obtained and compared to the results of the reactive residue curves for TAME synthesis
3
system. Above implemented software application objectives are: first, exploring the map
topology; second, the computation of the desired residue curves and third, computation of NTUs.
The residue curve maps plotted for different operation pressures of industrial interest, and for
different Damkhöler (Da) numbers are shown. They are plotted again with a smaller number of
residue curves but representing the difficulty of separation in the background by the NTUs.
Another series of maps discuss the differences between the residue curves and the curves
obtained at infinite reflux flow rate.
The infinite/infinite analysis, as a tool for process early analysis, is extended in the present work
to reactive systems, taking into account the reaction kinetics and the results obtained for the
TAME synthesis system. The infinite/infinite analysis is also applied to classical process (reactor
and separation column) as well as to a hybrid reactive distillation column. The originality of the
approach is that in all above cases, reaction kinetics is taken into account.
The results of the analysis are useful for rigorous simulation. Several alternatives are compared
according to the simulation results. A simulation taking into account the presence of isopentane
inert is provided, because this is the case industrial significance (isopentane is dominant in C5
fraction).
For comparing design alternatives, a simplified cost model is proposed and the results are
compared based on a techno-economical model available in literature. The originality of the cost
function proposed is that the goal is not to obtain a cost value, but a number proportional to the
cost. The main interest is not to calculate cost, but to optimize the process parameters.
Finally, environmental performance of TAME synthesis process is evaluated, based on potential
environmental impact (PEI), emissions, resource, and energy conservation factors. PEI is
obtained using waste reduction (WAR) algorithm as evaluation tool. For industrial processes
treating the same input (reactants) streams to provide the same product, the system boundaries
become fixed and their environmental impact depends only on the process itself. All the data
required for the environmental impact evaluation are obtained previously. From this chapter can
be concluded that the residue curve maps are a very useful tool for the analysis of the system and
that these first insights can be very useful for later rigorous simulations.
One of the main points stressed in this thesis is that the environmental and economical aspects
should be taken into account, from the early stages of any study.
The vapour liquid equilibrium experimental studies presented in this work are performed at the
Department of Chemical Engineering, Faculty of Chemistry of the University of Barcelona and
the kinetic experimental studies are performed in the Department of Chemical Engineering,
4
Faculty of Applied Chemistry and Materials Science of the University POLITEHNICA of
Bucharest.
Theoretical and experimental research developed for this doctoral program were partially funded
by the research grant TD GR 18/29.05.2007 offered by The National University Research
Council of Romania, by PN II IDEI project no. 1545 MASBIOGLI funded by Romanian National
Authority of Scientific Research, and by research fellowship to University of Barcelona partially
funded by ERASMUS program. During the stage in University of Barcelona infrastructure
created by the project CTQ 2009 – 11465 SEPBIO was intensively used.
5
CHAPTER 2
Survey regarding the catalytic distillation technique and synthesis

methods of ethers used as fuel additives. Catalysts, kinetics and
thermodynamics
2.1. The principle of reactive distillation and its technical importance
Chemical processes industry is permanently subjected to fast changes, which are not exclusively
related to society demands for new products of higher quality and safer which don’t affect the
environment, but also to the dynamics of business environment (Herder, 1999 a,b). The success
depends as well on the way we face the demands regarding process design and control in a short
time interval.
In chemical industry, chemical transformations and separation – products purification processes
are usually performed sequentially. Moreover, many of the technologies of commercial interest
are based on reversible reactions, subject to thermodynamic constraints, which limit the
maximum degree of transformation towards the valuable product. In this way, the untransformed
reactants must be recovered by an efficient separation system and recycled. As the dregree of
transformation is lower, the investment and operation costs due to the two additional operations
mentioned before are higher. Economic needs as well as ecological demands are major driving
forces in improving chemical processes and plants. To meet these goals, processes have to be
intensified to get products of higher quality, to increase yield by reducing or even avoiding by-
products and to minimise energy consumption. Therefore, advanced strategies emerged for
process control and real-time optimization. A special attention must be given to the synthesis of
new unit operations which integrate different functions and units in order to enhance efficiency
at process and plant level (Grossman and Westerberg, 2000; Stankiewicz and Moulijn, 2002).
These systems are conventionally named hybrid units and are characterized by reduced costs and
high process complexity. Catalytic distillation is an example of such operation.
A conventional scheme includes chemical reactor, separator and recycle streams. Chemical
reactors have different topologies (continuous stirred tank reactor (CSTR), tubular reactor, etc)
operating in continuous, discontinuous or batch continuous modes. Operating conditions are on
wide areas (catalytic, adiabatic, single/multiple phase etc). Separation systems are based on
different principles (vapour-liquid equilibria – distillation, gas-liquid equilibria –
adsorbtion/desorption, liquid – liquid equilibria – extraction, etc.). However, most widely used is
distillation. Recycle system is important for improving conversion / yield in reaction system, to
6
limit formation of by-products, to save energy by process integration as well as to improve
controllability.
Combining reaction – separation – recycle system in one apparatus are conventionally names
hybrid units. As examples are reactive distillation, reactive extraction, reactive absorption, etc.
Economic and environmental considerations have encouraged industry to focus on technologies
based on process “intensification”. Reactive distillation is an excellent example of process
intensification. It can provide an economically and environmentally attractive alternative to
conventional multiunit flowsheets in some systems (Luyben and Yu, 2008).
The first patents for this kind of processing appeared in the 1920s, but small progress in this
domain was performed until 1980 (Malone and Doherty, 2000; Agreda and Partin, 1984) when
reactive distillation attracted more attention, being considered a good alternative to replace the
traditional sequence chemical reaction – distillation. After this date, investigation in this domain
got intensified and diversified, the distillation procedures with solid catalysed chemical reactions
(catalytic distillation) having a major extent among other processes.
Integration is performed either with the purpose to improve separation through chemical
transformation (I), or to improve the performance of the latter with the help of sepation (II). A
representative example for the first case (I) is the process of CO2 capture from synthesis gas, in
ammonia technology. For the second case (II), according to LeChatelier principle, avoidance of
the thermodynamic limitations is performed by shifting the chemical equilibrium towards the
interesting products, eliminating a product from the reaction environment. Therefore, the degree
of reactants transformation into valuable products is improved and a relaxation of constraints
occurs for the system of separation and recycle. There are many representative examples for this
case, the most known being the synthesis of methyl acetate(MeAc) by Eastman Chemical Co.
procedure and the synthesis of MTBE.
The first industrial applications of reactive separation processes are registered in the 1920s
(Backhaus, 1921a,b,c), being applications of esterification with its versions transesterification
and hydrolisys. The success of catalytic distillation in the 1980 was mainly due to the success of
MTBE as gasoline additive replacing the ones based on lead (DeGarmo et al, 1992 and Schrans
et al, 1996). Together with the methyl acetate synthesis process by homogeneous reactive
distillation, catalytic distillation became a practical example of the advantages provided by
reactive separation techniques. For the MTBE case, the economy performed in the operating and
investment costs is due to a compact process schemes made of a single unit (catalytic distillation
column) which avoids the formation of three possible azeotropes. In the methyl acetate case, the
economy performed is determined by elimination of 28 equipments needed for purification and
azeotropes avoidance which are formed between reactants and between reactants and products
7
(Agreda et al, 1990). In a classical process scheme, the investment cost associated to this big
number of equipments is added to the operating cost and to the cost of additional solvents used.
Lately, there has been a growing interest in the field, by performing experimental research of
reactive distillation applications. For example, Doherty and Malone (2001) report more than 60
reactive distillation systems studied. Stankiewicz (2003) mentions the following important
industrial processes as potential candidates to adopt the reactive distillation technology: ethers
decomposition to high purity olephins, dimerization, aromatic and aliphatic hydrocarbons
alkylation, hydroisomerization, hydrolysis, ethers dehydration to alcohols, oxidative dehydration,
carbonylation. In the field of fine chemical products technologies, Omota et al (2001, 2003)
propose an innovative process of catalytic distillation for the esterification reaction of fatty acids.
The feasibility of this process is firstly suggested by the thermodynamic analysis combined with
modelling and computer simulation (Omota et al., 2003). The design methodology proposed is
successfully applied to a representative esterification reaction in kinetic regime. Liu et al (2012)
propose a new approach that substitutes the original two-step olefinic alkylation of thiophenic
sulfur (OATS) technology with a reactive distillation (RD) column was proposed to remove
sulfur compounds from fluid catalytic cracking (FCC) gasoline.
Reactive distillation represents the synergetic effect of combining the distillation process with
chemical transformation into a single multifunctional unit. The reactive zone inside the column
is identified by the presence of catalyst (liquid or solid). The feed is done usually at its
extremities, function of the compounds volatility. The products are continuosly removed at the
top or bottom part, while the reactants are maintained inside the column. In this way, the
importance of purification or recycle system is diminished or even eliminated, which provides
economy at energy and capital level and a high conversions.
The direct advantages of reactive distillation can be exemplified considering the chemical
reaction:
A B C  D
with the side reactions
AC  E
2C  F
The process can take place inside a conventional reactor (Figure 2.1a), the objective being the
production of C from A and B. Together with C, D is also produced, and side-reactions also take
place which lead to a reactor effluent made of a mixture of all these compounds. A and B must
be separated and recycled, C (the most volatile) must be separated and D (the heaviest), E and F
must be treated as by-products. This leads to the need of more rectification columns to be used.
Figure 2.1b illustrates the scheme of a typical reactive distillation process. The chemical
8
transformation takes places in the reactive zone, the stripping and rectifying zones being used for
product conditioning and by-products separation. Product C is rapidly removed from the reaction
volume producing in this way the shifting of chemical equilibrium towards products, increasing
the total conversion. Diminishing the concentration of product C in reaction volume determines
the reduction of side-reactions rate, so that less by-products are produced and the necessary
separations and purifications in the classical scheme can be elimated in this way.
Rectification area
Reactive area
Stripping area
Figure 2. 1 Typical scheme for a conventional process of (a) reaction and separation and (b)
reactive distillation
The main advantages of reactive distillation are highlighted as following:
 capital economy by separation system simplification or elimination
 energy saving needed for fluid recycle by improving the reactants conversion up to 100%
 selectivity improvement: removing one of the products from the reaction environment or
maintaining reduced concentrations of one of the reactants leads to the reduction of side-
reaction rates and to the reduction of by-products formation
 reduction of catalyst quantity needed for the same conversion degree
 azeotropes avoidance: when the reactor effluent is a mixture of chemical species forming
azeotropes. The process conditions permit avoiding them.
 Thermal integration: the reaction heat of an exothermal chemical transformation can be
used for vapour formation and reduction of reboiler thermal duty
 Avoidance of local hotspots in the catalyst layer through liquid partial vaporization.
However, reactive distillation presents also several disadvantages:
 The reactants and products must have compatible volatilities in order to maintain high
reactants concentrations in liquid phase and low products concentration in the reaction
zone
9
 Optimal conditions of temperature and pressure for separation must correspond to the
ones necessary for the chemical transformation
 Processing big quantities of raw materials determines issues related to liquid distribution
inside reactive distillation column packings.
This last issue determined intensive research for the design of column internals. Efficient
contacting of the reactive phase with the catalyst is necessary to avoid radial gradients, local
hotspots, maximize conversion and reduce the catalyst quantity necessary for a certain
conversion value. The catalyst particles used to diminish intra-particle diffusion effects have
dimensions in the interval 1 – 3 mm and < 1 mm in liquid phase. The elimination of possible
entrainment imposes their retention inside packings of various shapes:
 Porous grains impregnated with catalyst (Buchholz et al, 1995)
 Different metallic shapes: spheres, tablets, a.s.o. (Smith, 1984)
 Metallic structures disposed in forms of horizontal channels filled with catalyst (van
Hasselt, 1999)
 Horizontally disposed tubes containing the catalyst (Buchholz et al, 1995)
 Fabric packages which contain catalyst (Johnson et al, 1994) retained inside pockets
made of two fibre glass strips
 Catalyst particles disposed between metallic fibre strips in sandwhich shape (Stringaro,
1995). These structures are patented by Sulzer Co. (KATAPAK-S) and by Koch-Glitsch
(KATAMAX) and consist of two rectangular strips made of metallic fibres sealed at the
edges forming pockets of 1 – 5 cm wide. More such strips are connected in order to form
a packing cube which is mounted inside reactive distillation columns.
Inside tray columns, the catalyst is placed in vertical shapes disposed along the direction of
liquid flowing. These are completely immersed in liquid to assure an optimum contacting
between the reactive phase and the solid phase. An alternative is to place the catalyst in the tray
distributor or at its exit.
Even if most of the scientific studies deal with continous reactive distillation, many practical
applications are found also in the field of discontinous processes. The industries of fine
chemicals or specialities synthesis, such as the pharmaceutical industry, use discontinous
reactive distillation to favour the product formation of an equilibrium reaction or to avoid
secondary reactions. This technology is more versatile and appropriate compared to the
continous process to produce small quantities of valuable substances, and the flexibility of
operation offers more freedom to adapt to consumers demand on a more and more unpredictable
market. The high commercial value of finite products diminish the negative impact of energy
costs, which are higher than in the case of continous processes (Furlonge et al, 1999), on
10
economical performances. In this context, discontinous reactive distillation can be a viable
alternative to classical processes of reaction – separation (Sørensen et al, 1996). Three possible
configurations of discontinous reactive distillation columns are mentioned in literature (Guo et
al, 2003):
 Discontinous reactive rectifying column: the reactive mixture is fed to the bottom, where
reaction takes place, while products are collected at the top part, having low volatilities.
 Discontinous reactive stripping column: the reactants with low volatilities are introduced
in the condenser.
 Side-vessel column: contains a rectifying section and a stripping section, being used
when the reactants have intermediate volatilities compared to the products which are
collected both at the top an dat the bottom of the column.
In the present thesis, reactive distillation is applied to the synthesis of gasoline additives, such as
the TAME synthesis. This introductory chapter states the problem and evidences the usefulness
of reactive distillation for this purpose.
2.2. The importance of tertiary aliphatic ethers C5-C7. Legislation aspects

and main representatives
The car fuels used in engines with internal combustion originate from distillate fractions
obtained at crude-oil processing and possess usually an octane number under the interval of
values required (87–93). The tetra-ethyl-lead was firstly used in United States of America, while
in Europe, it was firstly used the alcohol as a gasoline additive. The advantage of leadded
gasoline, which provides a higher caloric capacity, made it worldwide used. One of the great
advantages of tetraethyl-lead was that it can be used in very small concentrations, while other
antiknocking agents needed to be used in higher concentrations, leading many times to the
decrease of gasoline caloric power.
The alcohol used as gasoline additive was causing the retention of humidity inside the
fuel, which leads to an effect of corrosion and rusting of fuel transport lines towards the engine.
While tetraethyl-lead is very soluble in gasoline, ethanol has a low solubility which decreases as
the humidity increases. Therefore, in time, drops or water areas can be formed inside the fuel
tank and this process creates the risk of fuel freezing. The great values of fuel humidity can also
favorise issues related to biological contamination with various bacteria which grow at the
interface water-gasoline. The antibacterian properties of tetraethyl-lead prevent the formation
and growth of such bacteria and fuel degradation. Therefore, this became an important
11
compound used worldwide a long time period as additive to increase the gasoline octane number.
It has been produced commercially since 1923 until 1986, a period during which approximately
7 million tones have been manufactured. However, the octane number enhancement by using
tetra-ethyl-lead as fuel additive induces great pollution problems, the toxic effect of Pb aerosols
in exhaust gases being well known.
In the most western countries, this additive was banned at the end of 20th century due to
issues related to air and soil pollution and the lead accumulative neurotoxicity. Starting from
2007, Pb-free gasoline was available worldwide, except countries like Yemen, Afganistan and
North Coreea which still use great quantities of Pb-based gasoline. However, tetra-ethyl-lead
remained the additive to be used in jet fuels (octanic number = 100) in piston-type engines and
until recently in fuels used for sportive car races.
Many cars manufactured before banning tetra-ethyl-lead needed modifications to be
able to function with Pb-free gasoline. These modifications can be divided in 2 categories:
‐ engines needed physical compatibility with Pb-free gasoline: the exhaust system was
modified (valve systems)
‐ modifications made to compensate the relative decrease of Pb-free gasoline octanic
number: decrease of pressure inside engines by thinning of piston cylinder head or
building piston engines which can reduce the compression rate.
The replacement of tetra-ethyl-lead started to be effective along with the introduction of
environmental protection restrictions in USA by “Clean Air Act Amendments” (CAAA) in 1990.
CAAA forbids the tetra-ethyl-lead usage and establishes the limits to maximum 1% benzene and
maximum 25% aromatic hydrocarbons in gasoline with high octane number. To cover the octane
deficit appeared by tetra-ethyl-lead banning, the only solution accepted at refineries level was the
usage of tertiary aliphatic compounds C5-C7, among which the most spread is methyl-tert-butyl-
ether (MTBE). This asymmetric ether presents superior characteristics in comparison with the
alcohols. It provides a high octane number and a series of other advantages such as reduction of
carbon monoxide content in exhaust gases, improved engine start-up in cold conditions,
chemical stability for the duration of storage, reduced toxicity (Krahenbuhl and Gmehling,
1994). However, the MTBE capacity, even in small concentrations, to modify in a not desired
way the taste and smell of water lead to new politics of MTBE usage as fuel additive. The need
to find new alternatives to replace MTBE emerged at this point and other oxygenate compounds
began to be studied: ethyl-tert-butyl-ether (ETBE), tert-amyl-methyl-ether (TAME), tert-amyl-
ethyl-ether (TAEE). The aliphatic tertiary ethers with practical use contain in their molecule two
alkyl groups, one tertiary (tert-butyl or tert-amyl) and the other primary (methyl, ethyl, and rarely
isopropyl). Figure 2.2 exhibits the most representative members of this class.
12
Superior ethers containing more than six carbon atoms have been synthesised and tested
as fuel additives as well, but their application is more restricted. Among these, the most known
are: 2-methyl-2-pentyl ethyl ether (THxEE1), 2,3-dimethyl-2-butyl ethyl ether (THxEE2), 3-
methyl-3-pentyl ethyl ether (THxEE3), 3-methyl-3-hexyl ethyl ether (THpEE), 3-methyl-3-hexyl
ethyl ether (THpME) and 3-methyl-3-pentyl methyl ether (THxME). Note also that di-isopropyl
ether is not a tertiary ether but possesses additive properties close to the tertiary ones.
Due to the ecological restrictions imposed in the last years, the tertiary aliphatic ethers
from C5-C7 series and the superior ethers have gained a great importance. These compounds
contain a tertiary radical containing 4 – 5 carbons, derived from a tertiary C4 – C5 olefine.
Nowadays, they are used as octane components for ecological gasoline preparation, successfully
replacing tetra-ethyl-lead.
C H3 C H3
CH 3 O C C H3 C H 3 CH 2 O C C H3
C H3 C H3
m e til te rt-b u til e te r ( M

Methyl-tert-butyl-ether TB E )
(MTBE) e til te rt-b u til e te r ( (ETBE)
Ethyl-tert-butyl-ether E TBE )
CH3 C H3
C H3 O C C H2 CH3 CH 3 CH 2 O C C H2 C H3
CH3 C H3
te rt-a m il m e til e te r ( (TAME)

T AM E ) te rt-a m il e til e te r ( T A E E )
tert-amyl-methyl-ether tert-amyl-ethyl-ether (TAEE)
Figure 2. 2 Main tertiary ethers used at industrial scale

The antiknocking properties of tertiary ethers are due to their capacity to form free
radicals, which are more stable than other alkyl radicals when colliding with other species in the
system. The most reactive group is the methylene in vicinal position of oxygen atom. These
radicals possess a greater stability due to the sp3 orbital semi-occupied with electrons that can
receive electrons from the neighbouring oxygen atom, obtaining in this way the characteristic of
a completely occupied orbital.
Due to the high concentrations of ether in fuels and to the high temperatures, other free
radicals may be obtained in the interactions between ether molecules with unstable radicals.
Gasoline combustion occurs by a free radical mechanism. During the compression of
the fuel mixture in the engine, the temperature increases and favours cracking reactions of the
alkanes presents in this mixture. Consequently, primary, secondary and tertiary radicals are
formed. Due to their higher reactivity, primary and secondary radicals are decomposing fast (by
β-splitting) generating explosions before the total compression of the fuel mixture. A way to
inhibit these early unwanted explosions is the transformation of the unstable radicals resulted
13
from alkanes during the compression into stable hydrocarbons. In this way, unstable radicals R 
and ether molecules are consumed resulting R-H hydrocarbons, α-ether alkyl radicals and tert-
amyl radicals, more stable than the primary alkyl ethers. The early explosion is avoided and the
fuel mixture can be compressed until the final point.
A high ethers content in gasoline leads to the increase of octane number and to the
decrease of toxic combustion products concentration (carbon monoxide, nitrogen oxides, carbon
oxides, unburnt hydrocarbons, polycyclic hydrocarbons, etc). Due to the low freezing point and
to the water solubility, the ethers decrease the freezing point of gasoline. Consequently, they can
be used at low temperature conditions. The fuels containing ethers are compatible to all types of
existing engines and feeding systems (injection, carburization) without any modification.
(Ullmann's Encyclopedia of Industrial Chemistry)
The European regulations (Council regulation 85/536/EEC from 5 September 1985) and
North-American regulations (EPA, Clear Air Act Sun Refining, 1988, 1995) imposed restrictions
both in the gasoline’s oxygen content and in aromatic hydrocarbons content. The minimum and
maximum limits for gasoline compounds, according to the above-mentioned regulations are
presented Table 2.1 (Oktar et al., 1999).
Table 2. 1. Allowed concentration limits for reformulated gasoline compounds

Compound Minimum content Maximum content
Oxygen (as ether) 2 wt % 2.7 wt %
Benzene - 1 % (volumetric)
Total aromatic
- 25 % (volumetric)
hydrocarbons
Heavy metals Total lack
Table 2.2 presents the maximum and minimum quantities of ether allowed in
reformulated gasoline according to the legislation mentioned above.
Table 2. 2 Allowed concentration limits for ethers used in gasoline

Minimum content Maximum content
Ether allowed in gasoline, allowed in gasoline,
[wt %] [wt %]
MTBE 11.000 14.850
ETBE 12.750 17.213
TAME 12.750 17.213
TAEE 14.500 19.575
14
The calculations are made based on the hypothesis that the entire oxygen content of an
ecological (reformulated) gasoline is provided by the added ether. The maximum ether
concentration in gasoline is imposed to maintain within allowed limits the quantity of toxic
compounds resulted at ether combustion (formaldehyde, acetaldehyde and their corresponding
acids). The minimum quantity of ether is imposed for complete hydrocarbons combustion (the
lowest possible quantities of carbon monoxide, nitrogen oxides, carbon, unburnt hydrocarbons,
polycyclic hydrocarbons etc in exhaust gases).
The immediate effect of tetra-ethyl-lead banning as fuel additive was the increase of
ethers consumption. To satisfy this demand, high production capacities have been implemented,
the majority of plants being able to produce hundreds of thousands of tons per year. Table 2.3
presents the worldwide production capacities in year 2000 for the main ethers. More than 95% of
ethers worldwide production is used as gasoline additive (Pääkkönen, 2003).
Table 2. 3. Worldwide tertiary ethers production in year 2000 (Pääkkönen, 2003)

Ether Worldwide production capacity (m3/year)
MTBE 33.370.000
ETBE 6.500.000
TAME 3.597.000
In December 2000, in Europe, there were 37 plants for the production of tertiary ethers
(MTBE, ETBE, TAME). The production capacities of the plants were betweem 15,000 and
600,000 t/year, the total ether production in Europe being estimated to 3,991,000 t/year.
The most used ether from the beginning of the mass production until nowadays is
methyl-tert-butyl-ether, followed by ethyl-tert-butyl-ether. The major disadvantage of these
ethers is their relatively high volatility. The vapours arrived in atmosphere are degraded slowly
and they are returned by rain in soil, in ground and surface waters, where they persist due to their
low biodegradability. In USA, important quantities of methyl-tert-butyl-ether accumulated in
ground waters, creating major problems of purification, for drinking water. Ethyl-tert-butyl-ether
has also been used in Europe, creating problems of environment contamination. However, the
phenomenon has lower amplitude due to its lower volatility and due to the lower fuel
consumption than in USA. The inconveniences associated to the usage of these ethers in gasoline
raised the problem of using other ethers, with lower vapour pressure but with similar octane
properties. Table 2.4 presents the main properties of tertiary ethers and of the gasoline that
contain them (Krahenbuhl and Gmehling , 1994; Pääkkönen, 2003).
15
It can be observed that tert-amyl-ethyl-ether presents an octane number closer to the
large scale used ethers, but its vapour pressure is considerably lower and it is produced from a
renewable raw material (ethanol).
The disadvantage of these ethers is their low degradation rate, despite their fairly low
toxicity. The natural degradation can be done chemically (in the atmosphere) or biochemically
(in soil and waters). Biochemically, the ether can be degraded until aldehydes (formaldehyde,
acetaldehyde) and tertiary alcohols (tert-butylic, tert-amylic) by using a certain type of bacterial
cultures such as those obtained from the soils polluted with gasoline (Becker, 2004), Kharoune et
al., 2001). In the atmosphere, their degradation proceeds until formic acid and tertiary alcohols
(Kasprzyk-Hordern et al., 2004). In both cases, the first step is the oxidation of methylene group
neighbour to the etheric oxygen atom, which possesses a greater reactivity than the rest of the
aliphatic groups in the molecule. The resulted alcoxy radical has two β splitting possibilities: in
the first, (a) a hydrogen atom is eliminated, and in the second, (b) a methyl group is eliminated.
The reaction proceeds mainly following the (b) alternative, fact proven in lab using oxidising
agents stronger than air (e.g. NO2). The main product in this case is the tert-amyl formiate
(Becker, 2004).
Table 2. 4 Tertiary ethers and gasoline properties
Compound
CH3OH C2H5OH MTBE ETBE TAME TAEE
Property
Pure component vapour
- 2.3 7.8 4 2.5 1.2
pressure at 37.8°C [psi]
Vapour pressure at 25°C of
gasoline with octane content* 59.46 18.0 8.0 4 2 2
[psi]
Octane number** of gasoline
120 115 110 112 105 109
with octane content *
Boiling point [K] 338 351 328 345 358 379
Oxygen content (wt %) 50 34.7 18.2 15.7 15.7 13.8
Water solubility at 25°C Totally Totally
48000 26000 20000 4000
[mg/L] miscible miscible
Relative atmospheric photo-
1 3.4 2.6 8.1 7.9 8.9
degradation***
*
gasoline with massic oxygen content of 2.7% or higher; 1 psi = 6.895·103 Pa
**
octane number as average of research octane number (RON) and motor octane number (MON). Research octane number
represents the fuel octane number measured in experimental engine under low severity engine operation. Motor octane number represents the fuel
octane number measured in experimental engine with more severe operation that might be incurred at high speed or high load.
***
refers to the ether reaction with oxygen in α position.
16
2.2.1. Sources of tertiary olephins
Fuel ethers are obtained by the addition of inferior alcohols to tertiary olephins C4 – C6, among
which only the tertiary ones are enough reactive for alcohol addition.
The olephins currently used in the industrial production of tertiary ethers are components of
fractions emerging from hydrocarbons cracking units. The isobutene is derived mainly from the
C4 fraction of thermal cracking units (pyrolysis) and from the C4 fractions of catalytic cracking
units respectively. The reactive isomers of C5 and C6 olefines, mainly 2-methyl-1-butene and 2-
methyl-2-butene, appear in the catalytic cracking fractions, respectively in the C5 fraction of
pyrolysis units. The typical compositions of these fractions are presented in Tables 2.5 – 2.7.
Table 2. 5. Typical composition of C4 fraction from pyrolysis units

Compound Concentration ( wt %)
i- butane 25
n-butane 25
isobutene 18  32
1-butene 14  22
2-butene 5  15
butadiene 35  50
Table 2. 6 Typical composition of C4 fraction from catalytic cracking units

i- butane 35  45
n-butane 7  12
isobutene 10  20
1-butene 9  12
2-butene 20 30
butadiene 0.5  1.5
Table 2. 7 Typical composition of C5 fraction from catalytic cracking units

Σ C4 2.51
3-methyl-1-butene 1.68
Isopentane 44.74
1-Pentene 3.56
17
2-methyl-1-butene 7.02
n-pentane 3.81
Isoprene 0.21
Trans-2-pentene 6.87
Cis-2-pentene 3.66
2-methyl-2-butene + trans-piperilene 8.68+0.12
2,2-dimethyl-butan + cis-piperilene 0.13+0.04
Cyclopentene 1.04
( 4-methyl + 3-methyl ) 1-pentene 0.38
Cyclopentane 0.34
2,3-dimethyl-butane + MTBE 1.38
2,3-dimethyl-1-butene 0.14
2-methyl-pentane 4.36
3-methyl-pentane 2.19
2-methyl-1-pentene 0.51+0.22
n-hexane 0.46
2-methyl-2-pentene 0.57
3-methyl-trans-2-pentene 0.26
3-methyl-cis-2-pentene 0.37
Σolephins C6 unidentified 1.76
Methyl-cyclopentane 1.31
Benzene 0.51
Methyl-cyclopentene 0.35
Σ (isoheptanes+ heptenes ) 0.82
TOTAL 100.00
2.2.2. Synthesis methods for C5-C7 aliphatic tertiary ethers series
The synthesis of fuel ethers is usually perfomed under pressure in liquid phase on a
strongly acidic macroporous ion exchange resin as catalyst. The conventional ion exchange
resins are sulfonated copolymers of divinylbenzene (DVB) with styrene. A tertiary ether is made
by the reaction between an alcohol and an alkene with a double bond involving at least a tertiary
carbon atom:
18
The synthesis of ethers is governed by thermodynamic equilibrium, which can be
pushed towards the formation of ethers at low temperatures, while the reaction rate is favoured
by high temperatures. Therefore, the reactor design makes a compromise between
thermodynamic and kinetic considerations. Sufficiently low temperatures can also reduce the
occurence of side reactions and favour the increase of catalyst life.
A ratio alcohol/olefin greater than 1 leads to the increase of conversion and elimination
of alkenes oligomerization, but in the same time it leads to the increase of cost for recovery and
recycle of unreacted alcohol. High alcohol concentrations favour the formation of dialkyl-ethers
by alcohol dehydration; therefore the optimum ratio alcohol/ether is around the stoichiometric
one. In the commercial applications based on the principle of reactive distillation, most
conversion is reached in the pre-reactor, which usually is an adiabatic fixed bed reactor. The best
compromise between kinetic and thermodynamic constraints is reached by achieving high
temperatures in the feed zones, which permits greater reaction rates and low temperatures in the
evacuation zones in order to get an approach to equilibrium at high conversions.
Reactive distillation combining chemical reaction and distillation in one single unit
operation can be used only in the second stage where the thermal effects are negligible. As
already mentioned, the only industrial method for the synthesis of C5-C7 aliphatic tertiary ethers
is the addition reaction of primary alcohol to tertiary alkenes in acid catalysis. Only the tertiary
olefines are basic enough to add alcohol molecules (Rihko et al., 1994; Linnekoski and Krause,
1997, Linnekoski and Krause, 1999).
As the number of carbon atoms increases, the number of tertiary olefines increases as well.
Among the butenes, isobutene is the only one able to react with alcohols.
In the amylenes series, only 2-methyl-1-butene and 2- methyl-2-butene are reactive, while in the
C6 and C7 series there are 8 and respectively 13 reactive isomers. The affinity of tertiary olephins
towards alcohols depends on the number of carbon atoms in the molecule and on the position of
the double bond in the molecule structure. Thus, the two amylenes are much less reactive than
isobutene, while 2-methyl-1-butene presents a higher reactivity than 2-methyl-2-butene. The
higher reactivity of the marginal alkenes is due to the easier access of the proton to the
unsaturated carbon atom. In the presence of acid catalysts, both the olephins and the alcohols
19
may participate independently to side reactions favoured by water presence, high reaction
temperatures, important alcohol excess or isoamylene excess. The main secondary reactions are:
Generation of tertiary alcohols by hydration of olephins :
CH3
H3C C CH CH3 + H2O H3C CH2 C OH
CH3 CH3
2-methyl - 2-butene (2M2B)
2-metil-2-butena (2M2B) alcool
-amylictert-amilic
Tert -amyl alcohol (TAA) (TA
CH3
H2C C CH2 CH3 + H2O H3C CH2 C OH
CH3 CH3
2-methyl - 1-butene (2M1B)
2-metil-1-butena (2M1B) alcool
Tert-amylictert-amilic
Tert-amyl alcohol (TAA) (TAA
Figure 2. 3 Generation of tertiary alcohols by hydration of olephins

Formation of symmetrical ethers due to intermolecular water elimination between two
molecules of alcohol:
C2H5 OH + C2H5 OH C2H5 O C2H5 + H 2O
Olephins dimerization may be practically avoided by using a high excess of alcohol and
maintaining a strict control of reaction temperature.
C5H10 + C5H10 C10H20
Several position isomers of C10H20 olefin are obtained, such as 3,3,5-trimethyl heptene
and 2,3,4,4-tetramethyl hexene are obtained. Their formation implies the addition of the tert-
amyl carbocation to the two isoamylenes, followed by the elimination of a proton. These
dimmers are formed in very small quantities (the order of tens of ppm) in conditions of industrial
reactions (temperatures between 60 – 80 oC, pressures of 7 – 8 atm). Polymerization reactions of
isoamylenes are possible if high temperatures are used. The formed polymers can block the
active centres of the catalyst, deactivating it (Boonthumtirawuti et al., 1993).
Olephins isomerisation: more important in the range of C5 and C6 olephins. For
instance, in the case of isoamylenes reactive isomers, the chemical equilibrium in the
isomerisation reaction is displaced towards the formation of 2-methyl-2-butene, which is more
thermodynamically stable due to the greater level of double bond substitution. The increased
stability of 2-methyl-2-butene implies a lower reactivity, which decreases the process rate. The
isomerisation reaction is represented by the equation:
20
Theoretically, the tertiary ethers may be obtained from C4-C6 alcohols as well:
Tert-amyl alcohol (TAA) Ethanol Tert-amyl ethyl ether (TAEE)
However, tert-amyl alcohol is available only in small quantities (a few percents in grain
oil, the heavy residue obtained at the distillation of ethylic alcohol of fermentation). Therefore,
the method remains important only from scientific point of view.
2.2.3. Industrially applied technologies for fuel ethers synthesis and technical-
economical data
Industrial technologies for tertiary ethers synthesis
There are a great number of technologies industrially applied for the synthesis of
tertiary ethers. The licences to produce oxygenated compounds used as gasoline additives are
mostly held by North-American companies such as CDTech, UOP and Phillips Petroleum Co
and by European companies such as Neste (Finland), Huls A.G (Germany), Snamprogetti SpA
(Italy) and Axens (France). The link between them is the existence of at least one reactor, usually
a fixed bed reactor and a distillation or reactive distillation column, according to the process. In
the cases in which the reactive distillation technology is applied, the reactants are firstly
transformed up to a concentration close to the equilibrium one, in one or more pre-reactors
(Ferreira et al., 2007). Table 2.8 briefly presents some of the existing technologies.
Table 2. 8 Main characteristics of some industrial processes for the synthesis of tertiary ethers
(Ferreira et al., 2007)
Procedure Application Description Company
Fixed bed trifunctional catalyst reactor

MTBE, TAME,
CDEtherol followed by a reactive distillation column; CDTech
ETBE
acidic ion exchange resin catalyst
Fixed bed adiabatic reactor (liquid is
MTBE, TAME,
CDMTBE heated at boiling point), followed by a CDTech
ETBE, TAEE
reactive distillation column
21
Fixed bed reactor followed by reactive
Hüls AG, UOP
MTBE, TAME, distillation column; acidic ion exchange
Ethermax and Koch
ETBE, TAEE resin (reactor catalyst) and KATAMAX
Engineering
packing in the reactive zone of the column
Two fixed bed adiabatic reactors, placed in

MTBE, TAME, Hüls AG and
Hüls series, followed by a distillation column;
ETBE, UOP
acidic ion exchange resin catalyst
MTBE, TAME, Extended layer adiabatic reactor, followed

ETBE and/or by a fixed bed reactor (optional) and the
Catacol Axens (IFP)
other heavy reactive distillation column (Catacol);
ethers acidic ion exchange resin catalyst.
Two fixed bed reactors, followed by

Phillips MTBE, TAME, Phillips
distillation column; acidic ion exchange
Etherification ETBE, TAEE Petroleum Co
resin catalyst
MTBE, TAME, Isothermal tubular reactor followed by
Snamprogetti
Snamprogetti ETBE, C6 and C7 adiabatic “drum” reactor and distillation
SpA
ethers column(s)
Fixed bed reactors, in series, followed by
TAME, THxME,
distillation columns with side streams,
NExTAME THpME/TAEE, Neste
recycles from reactors; acidic ion exchange
THxEE, THpEE
resins
MTBE, ETBE, Fixed bed reactors, followed by two
TAME, TAEE, distillation columns, in series, with side
NExETHERS Neste
THxME,THpME, streams recycle from reactors; acidic ion
THxEE, THpEE exchange resins
MTBE, TAME Fixed bed reactor at boiling point or CDTech and
CDTech/
or other heavy tubular reactor followed by reactive Snamprogetti
Snamprogetti
ethers distillation column Spa
The separation of methanol from the reaction products can be done in two ways:
 by distillation, which consists of methanol recovery based on the last distillation column
(in a first column, TAME is separated at the bottom and the azeotrope C5 fraction with
MeOH at the top, while in the second column the C5 fraction is separated at the bottom
and an azeotropic mixture MeOH with C5 fraction at the top).
 by extraction of methanol with water, which is later separated in a distillation column
(the extraction represents the first stage of products separation, eliminating in this way
the possible formation of azeotropes; TAME separation from C5 fraction is performed in
a distillation column providing TAME at the bottom and C5 fraction at the top).
The similarity between MTBE and TAME synthesis makes possible the easy interchange
between the two processes, some of the plants designed for MTBE synthesis being also used to
TAME synthesis without many changes. There are cases in which TAME and MTBE are
produced together from a mixture of C4 and C5 fraction together with the necessary methanol on
a proper catalyst layer.
22
2.2.4. TAME
International Union for Pure and Applied Chemistry (IUPAC) name: 2-methoxy-2-methylbutane
Molecular mass: 102.18 g/mol
Used names: tert-amyl-methyl-ether; 1,1-dimethylpropyl-ether; tert-pentyl-methyl-ether.
European regulations
Tert-amyl-methyl-ether (TAME) is a stable compound. Random polymerization like peroxide

formation will not take place in normal conditions of temperature. The purity of TAME
produced in European Union is placed above 96% (mass percent) if it is purified. However,
TAME is not normally purified to reach high concentration but it is produced and used in a blend
of 10 – 30% with hydrocarbons.
Table 2. 9 TAME composition produced in European Union

CAS No. Substance Value Reference
(refinery stream
Purities 994-05-6 tert-amyl methyl ether >96%
purity <30%)
Impurities 110-82-7 Cyclohexane ≤4% IUCLID
7732-18-5 Water <0,5% IUCLID
- C7 ethers <1% IUCLID
75-85-4 2-methyl 2-butanol 1,23%
- C5-C6 hydrocarbons 0.5%
67-56-1 Methanol 0.33%
1634-04-4 methyl tert-butyl ether 0.30% Erdölchemie ,
75-65-0 tert-butanol 0.17% 2000
- butyl tert-butyl ether 0.06%

637-92-3 ethyl tert-butyl ether 0.02%
563-46-3 2-methyl 1-butene
513-35-9 2-methyl 1-butene
71-43-2 Benzene IUCLID
Additives Without additives - - -
IUCLID - International Uniform Chemical Information Database (existing substances).
(Erdölchemie, 2000)
The evaluation of risk level involves the evaluation of TAME emissions (leakages) in the
environment and its usage at industrial scale which includes gasoline storage, transport and
distribution, usage by consumer when acquiring fuel gasoline, and its usage as intermediate to
produce other chemical compounds. These emissions have been estimated using the industrial
specifics and the information provided, but the base methods used to make these estimations
(TGD – Technical Guidance Document) are used for life cycle analysis and environmental areas.
23
TAME emissions in atmosphere are great if the evaluation is made in terms of volumes emitted.
More than 7000 tons (approximately 2.5% from total volume) are released in the atmosphere
every year due to evaporation and fuel emissions together with exhaust gases.
TAME emissions in the environment must be limited, especially in aquatic environment and in
ground water by considering seriously the measures to reduce risks due to:
‐ environmental exposure by intermittent TAME emissions into surface water from
storage, transport and distribution tanks towards gasoline terminals with direct discharge.
The measures taken to reduce risks must include also the possible residues.
‐ the general underground water quality, due to the possibility of affecting drinking water
by modification of taste and smell when continue exposal to leakages occurs from storage
tanks and transport pipes.
Human health is not directly affected by the use of TAME, but it can be indirectly affected by
exposure to indirect sources of TAME, like drinking water. There are no risks related to
irritations, mutations or body sensibilities, data regarding possible carcinogenic actions are
missing due to insufficient data.
Physico – chemical properties
TAME is a colourless, clear and volatile liquid at 20 °C and 1 atm with reduced viscosity. It is
soluble in most organic solvents and in water. TAME is a flammable compound which violently
reacts with substances like oxidizing agents, acids and strong bases. Physico-chemical properties
are presented in the table below:
Table 2. 10 Physicochemical properties of tert-amyl methyl ether

Property Value Ref.
Physical state in standard
Liquid
conditions
CHEMSAFE , 1994;
Melting point - 80 oC Weast 1989;
Huttunen et al., 1997a
Boiling point 86 oC Weast 1989;
CHEMSAFE , 1994;
Density 0.77 g/cm3 at 20 oC Weast 1989;
0.0888 atm at 20 oC
Vapor pressure Stephenson, 1992;
0.1184 atm at 25 oC Kivi et al, 1997
Stephenson, 1992;
Solubility in water 11 g/L at 25 oC Kivi et al, 1997;
Caprino and Tonga, 1998
Distribution coefficient
1.55 at 25 oC Stephenson, 1992;
n-octanol / water Kivi et al, 1997
24
(logarithmic value)
Conversion factors 1 ppm = 4.24 mg/m3
Flash point - 11 oC CHEMSAFE , 1994;

Self-ignition point 415 oC CHEMSAFE , 1994;
Ignition Very inflammable CHEMSAFE , 1994;
Weast, 1989
Inferior limit of explosion 1.0% (volumetric
percentages in air) – 42 g/m3;
Explosive properties Huttunen et al., 1997a
Superior limit of explosion 7.1% (volumetric
percentages in air) –300 g/ m3;
Does not have oxidizing prperties due to

Oxidizing properties
structural reasons
Viscosity 0.50 mm2/s at 40 oC Stephenson, 1992;

Kivi et al, 1997
Production capacities at European level
TAME started to be used as an important compound in production of commercial gasoline at the

beginning of the 1990s. The production of TAME at industrial scale started in USA in 1991, and
later (1992 – 1994) in Great Britain and Germany (the obtained TAME was used in chemical
industry).
The production of TAME in European Union depassed 175,000 t/year in 2000. The producing
companies with a capacity greater than 1000 t/year are located in the following ares, according to
the table below:
Table 2. 11 Companies producing TAME with capacities of over 1000 t/year

Company Location
AGIP Gela, Italy
BP Chemicals
Cologne, Germany
(ERDÖLCHEMIE)
FORTUM OIL OY Porvoo, Finland
SARAS SpA Sardinia, Italy
TOTALFINAELF
Killingholme, United Kingdom
(LIDSEY OIL)
25
TAME uses
The table below indicates the TAME valorificationin European Union at the level of
year 2002. The main usage of TAME is as fuel additive, being the second most used oxygenate
additive after MTBE. Another use of TAME is represented by its usage as an intermediate in the
synthesis of methyl-butene of high purity.
Table 2. 12 Amounts (produced+imported), industrial branches and areas of use for TAME
Percentage of the total
Industry Use Used quantity, t
quantity used
Mineral oils and Fuels Industry Additive for fuels 277000 97
Chemical industry, chemical substances
Intermediate 10000 3
used in synthesis
Total 287000 100
Additive
for fuels
Intermediate
Figure 2. 4. Amounts of product used in various fields

TAME is blended with gasoline as an unique additive or together with other oxygenate
additives (MTBE, ETBE or ethanol) and other compounds with properties of enhancing octane
number to reach desired properties for gasoline. Normally, gasoline can contain between 1 and
10 wt% TAME.
Table 2. 13 The amount of TAME consumed in different EU countries in 2002

Medium TAME concentration
Country from UE Consumption of TAME în 2002 (tons)
(wt%) în gasoline
Greece 2400 3.7%
Finland 55000 4-11%
France 500 3.7%
26
Italy 70500 0.9-3.7%
Holland 1200 3.7%
Spain 7200 3.7%
United Kingdom 45100 3%
Greece Finland France Italy Holland Spain United

Kingdom
Figure 2. 5 The amount of TAME consumed in different EU countries

Table 2.15 and Figure 2.54 contain information related to the quantity of TAME consumed in
different European Union countries in 2002 as well as average concentrations of TAME in
gasoline.
TAME synthesis processes
Due to the increased interest for using tertiary ethers as additives, the research intensified to
study thermodynamic and kinetic aspects of the chemical reactions involved in their synthesis.
Most of the models published so far to characterize the process for tertiary ethers synthesis were
focused only on the main reaction. However, the study of side-products formation is very
important due to the specifications provided by refineries for gasoline and for intermediates. The
etherification reactions (Figure 2.6) are exothermal and there is the possibility of formation of
high temperature areas due to uneven cooling of the reactor, which leads to undesired reactions.
The most frequent side reactions that can occur are isoamylenes dimerisation (Figure 2.7),
alcohols dehydration with formation of dialkylethers and water (Figure 2.8) and isoamylenes
hydration with formation of tertiary alcohols.
The reactions mentioned above take places only in the presence of an acid catalyst. The catalysts
that can be successfully used for the etherification of isoamylenes are solid acids (usually ion-
27
exchange resins) can be found as granules or as fibres. Among these, the most common ones are:
Amberlyst16, Amberlyst35, XE586 (granules) provided by Rohm&Haas company, Smopex-101
(fibres) provided by Smoptech Ltd. In the studies performed by Pääkkönen (2003), among the
catalysts mentioned above, Amberlyst35 presented the best catalytic activity, being followed by
Amberlyst16, the fibre-based catalyst not presenting spectacular results
2-methyl
-1-butene
2-methyl-1-butene Methanol
Methanol
(2M1B)
(2M1B) Tert
-amyl methyl
Tert-amyl esther
ether
methyl (TAME)
ether (TAME)
(TAME)
2-methyl-2-butene
2-methyl-2-butene Methanol
Tert-amyl
Tert-amyl methyl ether
esther
ether(TAME)
(TAME)
(TAME)
(2M2B)
(2M2B)
2-methyl
-1-butene
2-methyl-1-butene 2-methyl
-2-butene
2-methyl-2-butene
(2M1B)
(2M1B)
(2M2B)
(2M2B)
Figure 2. 6 Main reactions for obtaining TAME
2-methyl-2-butene 2-methyl-2-butene
Diiso-amylene
Di-isoamylene
(2M2B) (2M2B)
Figure 2. 7 Secondary reaction – dimerization of isoamylenes
Methanol
Methanol Methanol
Methanol Dimethyl
Dimethyl ether
ether
Figure 2. 8 Secondary reaction – etherification (dehydration) of methanol

.
28
2.3. Termodynamics of liquid phase alcohol adition to C5 tertiary olefins
Modelling of thermodynamic equilibrium
Mathematical modelling of tertiary ethers process synthesis in liquid phase includes a number of
elements characterizing the process thermodynamics: data related to liquid – vapour and
chemical equilibrium, thermal effects of physico-chemical transformations, data related to
deviations from ideal behaviour of the components in the two phases. This kind of information
needed to characterize the process thermodynamics are widely available from literature, but
sometimes with doubts related to accuracy, which leads to the necessity of experimental
checking.
The description of thermodynamics and chemical properties of the integrated reaction
and separation processes is very process-specific. Regardless of the model chosen (equilibrium
model or non-equilibrium model) to describe the reaction-separation, this will be based on a
thermodynamic model, which will provide consistent information related to the equilibrium
state. These models are available in literature for a variety of systems and are developed based
on state equations or expressions for excess free enthalpy GE.
The necessary conditions to simultaneously reach chemical and phase equilibrium are
expressed by the general equations (II.1) and (II.2):
Phase equilibrium:
i j  i j 1 (II. 1)
Chemical equilibrium:
N

i 1
i
r, j
i j  0 , i=1,2…nc (II. 2)
where:
i j represents the chemical potential of component i in phase j,
 ir , j represents the stoechiometric coefficient of component i in reaction r, in phase j.

The thermodynamic models characterizing the non-ideal behaviour of the compounds
involved in liquid phase etherification processes result from adapting the general equation to the
application type. The most used ones are as follows:
- for vapors phase components :
 pxiji j 
ij  iideal gas  T , p o   RT ln o

 p  (II. 3)
29
- for compounds in liquid phase (according to Raoult law):
i j  ipure liquid T , p 0   RT ln  xij  i j  (II. 4)
and for non-condensable compounds in liquid phase (according to Henry law):

p
   T, p
i
j *
i 
s
solvent ,xj 
i    i dp RT ln  xij i j*  (II. 5)
s
psolvent
where p0 is the reference pressure (0.1013 MPa), i j represents the fugacity coefficient and  i j the
activity coefficient. In the last expression, the reference chemical potential, i*, is a function of
the phase j composition, in case of infinite dilution of compound i, expressed as xij  . The vapour
s
pressure of the mixture at temperature T is psolvent .
Reaction enthalpy
Following the Hess law, reaction enthalpy is the stoichiometric sum of formation enthalpy of the
reaction participants. As the values for formation enthalpies i H 0 are usually found in literature
for gaseous phase, the reaction enthalpy in gaseous phase can be calculated:
N
 R H g0  i  f H i0,g (II. 6)
i 1
In the study published by Rihko et al., 1994, it is shown that the reaction enthalpy in
gaseous phase for the MTBE synthesis does not vary with temperature until the limit of 383 K
(110 oC). In the hypothesis that the reaction enthalpy in gaseous phase (  R H g0 ) for TAME
synthesis is also constant in the studied temperature zone, the reaction enthalpy in liquid phase
can be easily calculated as follows:
N
 R H g0 (T )   R H l0 T    vi V H i0 (T ) (II. 7)
i 1
where V Hi0 (T ) represents the vaporization heat of MeOH, 2M1B, 2M2B and TAME at
operating temperature.
Table 2.14 presents the thermodynamic data necessary to calculate the vaporization heat for each
component according to the above equation (Mao et al, 2008).
The effect of temperature on reaction enthalpy and equilibrium constants is described using
Kirchhoff and Van’t Hoff type equations:
 H l 
  C pl  al  blT  clT  ...
2
 (II. 8)
 T  p
30
 ln K l  R H l0
 (II. 9)
T RT 2
where, Δal, Δbl and Δcl are the coefficients of the polynomial which describes the temperature
dependence of Cp.
Table 2. 14 Thermodynamical data for the participants in the reaction

Unit of
Physical size MeOH 2M1B 2M2B TAME Ref
measurement
M g/mol 32.04 70.14 70.14 102.17
Tf K 337.7 304.3 311.7 259.3
Tc K 512.6 465.0 470.0 531.2
pc MPa 8.09 3.45 3.45 3.25
Vc cm3/mol 118.0 304.8 306.9 376.0 (Zhang and
s
P MPa 0.0170 0.0815 0.0622 0.0101 Datta, 1995)
fH 0
298, g kJ/mol -201.30 -36.34 -42.58 -298.7
 f G298,
0
g kJ/mol 162.6 65.34 59.70 -104.00
v H 0 kJ/mol 37.52 26 27.0 35.3
cp (liq) kJ/(mol·K) 0.0816 0.1569 0.1523 0.2192

a x 102 10.76 14.951 15.4 7.83
2
(Rihko et al,
a
b x 10 -38.06 -24.763 -29.335 44.92
cp 1994)
c x 102 9.79 9.1849 9.794
d x 102
a
The equation of temperature dependence for c p  a  bT  cT 2  dT 3
Integrating the above relations, the polynomial equations obtained permit the estimation of
temperature dependence for reaction enthalpies and equilibrium constants:
bl 2 cl 3
 R H l ,T  I l , H  alT  T  T  ... (II. 10)
2 3
I lH al b c
ln K l  I lK   ln T  l T  l T 2  ... (II. 11)
RT R 2R 6R
where IiH and IiK represent the integration constants whose values can be found solving the above
equatins using Gibbs-Helmholtz with known H iT0 0 and GiT0 0 (Mao et al, 2008):
GlT0
ln K l   (II. 12)
RT
Computation of reaction enthalpies (  R H 0 ) at 298 K using the data in the table above for
each compound in the TAME synthesis reactions lead to:
‐ 2 M 1B  MeOH  TAME  R H 10  32.8 kJ / mol
31
‐ 2M 2 B  MeOH  TAME  R H 20  25.6 kJ / mol
The experimental data for the two reactions obtained at 298 K indicate values for the two
reactions: -33.6 kJ/mol for TAME synthesis from 2M1B and -26.8 kJ/mol for TAME synthesis
from 2M2B (Renon et.al, 1968), results which confirm the precision of computation method.
From the values of reaction enthalpies above, it can be also obtained the enthalpy for
isomerisation reaction.
Equilibrium constant
Free standard reaction free Gibbs energy  RG0 which is necessary to calculate the equilibrium
constant Ka, can be computed using an analogous equation as (II.6) performing the sum of
standard free energies of formation for each participant to the liquid phase reaction:
N
 R G 0   vi  f G 0 (II. 13)
i 1
The values for  f Gi0 in gaseous phase are found in literature so that the free energy of
reaction in gaseous phase can be calculated according to equation II.14:
 s ps 
 RG *
298   RG 0
298, g  RT ln   0  (II. 14)
 p 
where ps represents the saturation pressure at standard temperature, p0 represents the standard
pressure (0.1013 MPa) and φ represents the fugacity coefficient.
The equilibrium constant relative to the activity is defined according to the reaction
below:
   RG* 
K a  exp  (II. 15)
 RT 
and can be calculated function of molar fractions according to:
N N N
K a   aivi    ivi  xivi  K  K x (II. 16)
i 1 i 1 i 1
where γ represents the activity coefficient.

The reactions taking place at TAME synthesis (isoamylenes etherification with methanol) is
presented as following.
The determination of the three equilibrium constants implies the study of etherification
reactions of isoamylenes with methanol, the third constant resulting from the equation below:
K a1  K a 2  K a 3 (II. 17)
32
Figure 2. 9 Reactions for TAME synthesis
The equilibrium constants for reaction of MeOH and 2M1B and of MeOH with 2M2B to
synthesise TAME are defined as a function of activities, as in equation (II.17).
As Ka3 can be calculated using constants Ka1 and Ka2, only these constants have been
compared to their values obtained theoretically. The theoretical form of equilibrium constant for
reaction “i” can be written function of temperature, having the following expression:
H 0 a 1 1
ln K ai (T )    ln T  bT  cT 2  I (II. 18)
RT R 2R 6R
where the reference factors have been published by Syed et al.,2000. These values have been
introduced in the equation (II.18) to obtain the equations for equilibrium constants characteristic
to each reaction (Abrams şi Prausnitz, 1975):
1.190  103
ln K a1   25.801ln(T )  7.599  10 2 T  4.377  10 5 T 2  1.299  102 (II. 19)
T
2.916  102
ln K a 2   24.9421ln(T )  7.356  10 2 T  4.192  10 5 T 2  1.255  102 (II. 20)
T
Table 2.19 presents equilibrium constant expressions defined according to the equation:
ln K i  A  B  T 1  C  ln T  D  T  E  T 2  F  T 3 (II. 21)
Modelling complex processes as the synthesis of tertiary ethers by catalytic distillation requires
the availability of phase equilibrium data on the entire operating domain to be used in binary
parameters determination. Availability of information for multicomponent mixtures is necessary
as well to study the consistency of the thermodynamic model used. When this data is missing,
they can be estimated using group contribution methods (see Appendix I), but their quality is
sometimes difficult to evaluate.
All the models associated to unit operations need properties computation for generation of
results. The properties frequently required are the fugacity for thermodynamic equilibrium
(equilibrium computation), as well as the enthalpy. Fugacities and enthalpies are often sufficient
33
information to calculate mass and heat balances. However, other thermodynamic properties and
transport properties are computed for all the process streams.
Table 2. 15 Equilibrium constants involved in the TAME’s synthesis

A B C D E F Ref
ln (Ka1) -39.065 5018.61 4.6866 0.00773 -2.635 x 10-5 1.547 x 10-8
(Al-Arfaj,
ln (Ka2) -34.798 3918.02 3.9168 0.01293 -3.121 x 10-5 1.805 x 10-8 Luyben,
ln (Ka3) -4.159 1100.69 0.7698 -0.00521 4.86 x 10-6 -2.580 x 10-9 2004)
ln (Ka1) 129.9 1190 -28.801 0.07599 -4.377 x 10-5

ln (Ka2) 125.5 291.6 -24.942 0.07356 -4.192 x 10-5 (Rihko et
al., 1997)
ln (Ka3) 4.4 898.4 -0.859 0.00243 -1.85 x 10-6
ln (Ka1) -8.3881 4041.2
(Paakkonen
ln (Ka2) -8.2473 3225.3 et al.,
ln (Ka3) -0.1880 833.3 1998)
ln (Ka1) -10.301 4747.278 (Abrams

ln (Ka2) -9.091 3527.151 and
Prausnitz,
ln (Ka3) -1.201 1217.060 1975)
2.4. Kinetic models for TAME synthesis reactions
2.4.1. Literature survey
Precise and detailed kinetic models permit the reactors to be designed in an optimal way,
e.g. from the point of view of operating conditions chosen so that the yield of desired product is
maximized and by-products minimized. Kinetic models based on reasonable mechanistic
knowledge or assumptions are generally preferred over empirical ones, because the scale-up
from laboratory to industrial process is on safer ground when a mechanistic model is available
(Kiviranta-Pääkkönen and Krause, 2003).
Because the etherification reactions are reversible, in order to diminish or even remove the
chemical equilibrium limitation they are carried out either in presence of excess of alcohol or by
removing the products continuously in a reactive-distillation column.
As mentioned previously, TAME is synthesized in an acid-catalysed reversible reaction
of isoamylenes (2-methyl-1-butene, 2M1B, 2-methyl-2-butene, 2M2B) with methanol (MeOH).
In the formation and splitting (the backward reaction of ether to isoamylenes and alcohol) of
TAME, there are three reversible reactions proceeding simultaneously (Figure 2.10), two
etherification reactions and one of reciprocal transformation of the two isoamylene tertiary
isomers.
34
CH3 r3 CH3
CH2 C CH2 CH3 CH3 C CH CH3
r6
2M 1B 2M 2B
r1 r2
CH3OH + CH3OH CH3OH
r4 CH3 r5
CH3 C CH2 CH3
CH3 TAME
Figure 2. 10 The reaction network in the formation and splitting of TAME

Generally, the process models based on the property conservation principles suppose
characterization of chemical transformation by sufficiently accurate kinetic models. The kinetic
models based on knowlegde of chemical reactions mechanism having a higher degree of
generality and higher accuracy are preffered at the expense of empirical models. The mechanistic
models cover a wider interval for the variation of operating conditions specific for etherification
processes that can reach conversions able to be maximized through configurations involving
side-reactor or reactive distillation. In these conditions, the ratio methanol/isoamylene can be
very different from its stoichiometric value.
The published kinetic models describing the tertiary olefins etherification on solid catalysts are
based on several hypothesis related to surface reaction mechanism:
A) Pseudo-homogeneous mechanism – neglecting the influence of reactant adsorption and using
the so called “power law” rate expressions
B) Eley-Rideal mechanism – reaction between adsorbed methanol (MeOH-X) and isoamylenes
from liquid phase
C) Langmuir – Hinshelwood mechanism – reaction between adsorbed molecules.
Kinetic equations are described relative to the compounds activities due to non-ideality of liquid
phase (mixture of polar and non-polar substances). The inert chemical species (hydrocarbons),
present in the reaction mixture, are not chemically adsorbed on the catalyst surface.
A) Power – law rate expressions
This type of mechanism assumes the presence of reaction only in liquid phase, without
adsorbtion of reaction participants on the catalyst. The concentration of species are represented
as molar fractions.
35
vR1  k1 xM x1B  k1 xT (II. 22)
vR 2  k2 xM x2 B  k2 xT (II. 23)
vR 3  k3 x1B  k3 x2 B (II. 24)
 Ei0   Ei'0 
k
,where i  k i
0
 exp    , k i  k i
'0
 exp  
 R T   R T .
A kinetic model of this type for TAME synthesis was proposed by Oktar et al (1999). Table 2.16
presents the kinetic parameters of the three reactions taking place in liquid phase for this model.
Table 2. 16 Kinetic parameters for the reactions involved in the synthesis of TAME
k0i Ei k’0i E’i

Reaction -1 -1 -1 -1
(kmol s kg ) (kJ/kmol) (kmol s kg ) (kJ/kmol)
1 1.3263 x 108 76.103737 x 103 2.3535 x 1011 110.540899 x 103

2 1.3718 x 1011 98.2302176 x 103 1.5414 x 1014 124.993965 x 103
3 2.7187 x 1010 96.5226384 x 103 4.2933 x 1010 104.196053 x 103
B) Kinetic model based on Eley – Rideal mechanism
Eley – Rideal (ER) type mechanism considers that only alcohol and TAME are adsorbed on the
surface of catalyst, the isoamylenes in liquid phase react with the adsorbed MeOH on the catalyst
resulting adsorbed TAME. The rate controlling step is considered the surface reaction.
The reaction presented above can be described according to the following mechanism:
MeOH  S a  MeOHSa ; (fast) K M 

 MeOHSa 
aM  S a 

k1
MeOHS a  2M 1B   TAMESa (slow)
 k1
TAMES a  TAME  S a ; (fast) KT 

TAMESa 
aT  S a 
where KM and KT represent the adsorbtion equilibrium constants of MeOH and TAME on
active centres of catalyst.
 Sa  - fraction of free active centres, [MeOHSa], [TAMESa] – fraction of active sites
blocked by MeOH and TAME adsorption.
The expression of reaction rate:
36
vR1  k1a1B  MeOHSa   k 1 TAMESa  (II. 25)
From the relations defining the adsorbtion constants results:
 MeOHSa   K M aM  Sa 
TAMESa   KT aT  Sa 
After replacing in the reaction rate expression:
vR1   Sa  ( k1K M a1B aM  k 1KT aT ) (II. 26)
The sum active centers fractions on the surface of the catalyst must be equal to 1:
 Sa    MeOHSa   TAMESa   1  Sa   K M aM  Sa   KT aT  Sa   1
The relations above can be rewritten in the following form of expression of free active
centres:
1
 Sa   (II. 27)
1  K M aM  KT aT
From (II.26) and (II.27), the following expression results:
k1K M a1B aM  k 1KT aT
v R1  (II. 28)
Rearranging the terms in (II.28), the expression of reaction rate for 2M1B etherification
with MeOH can be written as follows:
1
k1K M (a1B aM  aT )
K a1 (II. 29)
vR1 
k1K M
with K a1 
k 1KT
The etherification of 2M2B occurs by an identical scheme, so one obtains similarly the rate
expression:
1
k2 K M (a2 B aM  aT )
Ka 2 (II. 30)
vR 2 
The isomerisation reaction was found to occur more rapidly as compared with
etherification. Therefore, the kinetic hindrance by the adsorption steps is usually neglected, the
rate expression being used in the simpler form:
k 3 (II. 31)
vR 3  k3 ( a1B  a2 B )
k3
37
C) Kinetic models based on Langmuir – Hinshelwood mechanism
The mechanism based on Langmuir – Hinshelwood (LH) model implies the competitive
adsorbtion of all the reaction participants – methanol, isoamylenes and TAME, the surface reactions are
usually considered rate limiting stages while the adsorption steps are considered instantaneous.
In accord with the LH mechanism, the surface phenomena are described according to the
following mechanism:
2 M 1B  Sa  2M 1BSa ; (fast) K1B 

 2M 1BSa 
a1B  Sa 
MeOH  S a  MeOHS a ; (fast) K M 

TAMESa 
aM  S a 

k2
2 M 1BS a  MeOHS a   TAMES a  Sa (slow)
k2
TAMESa  TAME  Sa ; (fast) KT 

 MeOHSa 
aT  Sa 
In these expressions, the notations have the same significance as previously (paragraph B) K1B,
KM and KT represent the adsorbtion equilibrium constants of 2M1B, MeOH and TAME on the
active centres of catalyst.
The reaction rate expression is identical with the of controlling step:
vR1  k1  2 M 1BSa  MeOHSa   k 1 TAMESa  Sa  (II. 32)
, where  2 M 1BSa   K1B a1B  Sa 
 MeOHSa   K M aM  Sa 
TAMESa   KT aT  Sa 
Replacing in the reaction rate expression, the following expression is obtained:
vR1   Sa  (k1K1B KM a1BaM  k1KT aT )

2
(II. 33)
The sum of active centres fractions is equal to 1:

 Sa    MeOHSa   2 M 1BSa   2 M 2 BSa   TAMESa   1
 Sa   K M aM  Sa   K1B a1B  Sa   K2 B a2 B  Sa   KT aT  Sa   1
Rearranging the above equations, the fraction of free active centres is obtained:
1
 Sa   (II. 34)
1  K M aM  K1B a1B  K 2 B a2 B  KT aT
From equations (II.33) and (II.34) it results:
38
1
k1K1B K M (a1B aM  aT )
K a1 (II. 35)
vR1 
(1  K M aM  K1B a1B  K2 B a2 B  KT aT )2
k1K1B K M
with K a1 
k 1 K T
Repeating the same steps for the etherification of 2M2B, one obtains the expression:
1
k 2 K 2 B K M ( a2 B a M 
aT )
Ka 2 (II. 36)
vR 2 
(1  K M aM  K1B a1B  K2 B a2 B  KT aT )2
k2 K 2 B K M
with, K a 2 
k 2 K T
The isomerisation of 2M1B can be described according to a similar mechanism:
 2 M 1BS a ; ( fast ) K1B  

2 M 1BS a 

k3
2 M 1B  Sa 
k3 a1B  S a 
2 M 1BSa  2M 2 BSa (slow)
2 M 2 BS a  2 M 2 B  S a ; (fast) K2B 
 2M 2 BSa 
a2 B  S a 
The expression of the reaction rate is considered equal to that of surface reaction:
vR 3  k3  2 M 1BSa   k3  2 M 2 BSa  (II. 37)
where  2 M 1BSa   K1B a1B  Sa 
 2 M 2 BSa   K2 B a2 B  Sa 
Replacing in the expression of reaction rate, is obtained:
vR 3   Sa  ( k3 K1B a1B  k3 K 2 B a2 B ) (II. 38)
The sum of active centres fractions

on the catalyst surface must be equal to 1:
 Sa    MeOHSa   2 M 1BSa   2 M 2 BSa   TAMESa   1
 Sa   K M aM  Sa   K1B a1B  Sa   K2 B a2 B  Sa   KT aT  Sa   1
From the last equation results:
1 (II. 39)
 Sa  
1  K M aM  K1B a1B  K 2 B a2 B  KT aT
From equations (II.38) and (II.39), it results:
39
1
k3 K1B (a1B  a2 B )
Ka 3 (II. 40)
vR 3 
1  K M aM  K1B a1B  K2 B a2 B  KT aT
k3 K1B
with Ka 3 
k 3 K 2 B
The temperature dependence of rate constants is given by Arrhenius expression:

 Ei0 
k
where i  k i
0
 exp  
 R T 
and the adsorption equilibrium constants by van’t Hoff:

 H a , j 
K j  K j ,0  exp   
 RT 
where j = 1, …, N and parameter values appearing in rate constants involved in TAME synthesis
kinetic model are obtained in accord with LH mechanism and were published by Duarte (2006).
Table 2 17 Kinetic constants involved in TAME’s synthesis

k0i Ei0
Reaction Ref
(mol s-1 kg-1) (kJ/kmol)
1 3.287 x 1010 76800
2 3.9682 x 1013 99700 (Duarte, 2006)
3 7.4767 x 1010 81700
The adsorbtion equilibrium constants are expressed usually according to the equation:
 Aj  (II. 41)
K j  exp   B j 
 T 
Since the conditions in liquid phase for etherification reactions are highly non-ideal
(Colombo et al., 1983; Rihko et al., 1994), activities are usually used. The etherification
reactions occur with relatively high reaction rates when acidic ion-exchange resins are used as
catalyst and the process can be accomplished at relatively low temperatures (< 343 K). The
reaction is carried out under pressure (> 6 bar) in order to ensure liquid-phase operation. To limit
secondary reactions as olefins oligomerization, excess of alcohol is used.
Some results upon TAME synthesis reaction system catalysed by ion-exchange resins
reported in last decades are presented in subsequent paragraphs.
The isoamylene reactivity toward the methanol addition was first investigated by
Ancillotti et al. (1977). These authors underlined that 2M2B and 2M1B react both with methanol
and between them. The initial rate of double bond isomerization is faster than methanol addition,
so the two isoamylenes are in equilibrium before TAME synthesis equilibrium is achieved.
40
Moreover, the etherification rate for the two isomers proved to be different, 2M1B being
approximately 10 times more reactive than 2M2B. Ancillotti et al. (1977) assumed an ionic two
steps mechanism: for TAME synthesis, olefin protonation to a carbenium ion and nucleophilic
addition of the carbenium ion to methanol; since the two isoamylenes form the same carbenium
ion by protonation, it was inferred that the olefin protonation step had to be the rate-controlling
one.
Isoamylenes etherification using cationic resins (Vionit CS-34) as catalyst was published
by Muja et al. (1986). The authors of this study proved as well a higher reactivity of 2-methyl-1-
butene (2M1B) in the etherification reaction and the preferential formation of 2-methyl-2-butene
(2M2B) in the isomerisation reaction (due to the higher thermodynamic stability of 2M2B
compared to 2M1B). The reactivity difference between 2M1B and 2M2B is explained by the
greater steric hindrance which appears at H+ addition to 2M2B. Another experimental
observation of these authors is the independence of initial reaction rates of TAME formation on
methanol concentration (reaction order with respect to MeOH is zero). Kinetic model was
expressed in terms of concentrations.
Pavlova et al. (1986) proposed a kinetic model taking into consideration the activities of
the chemical species involved in the reaction and following a Langmuir-Hinshelwood (LH)
mechanism approach.
There are numerous papers on the kinetics of this reaction system. Ancilloti et al (1977)
studied this reaction scheme, proposing kinetic model dependent on alcohol/olefine molar ratio.
Acoording to their statement, for stoichiometric methanol : olefine ratio > 1, predominates ionic
mechanism (quasi-homogeneous). Inside the kinetic model, the rate determining step is supposed
the protonation of olefine by solvated proton. For alcohol/olefin ratio below unity, the
mechanism is concerted (quasi-heterogeneous), including undissociated sulfonic groups
participation. Ancilotti et al. (1977) found that TAME formation reaction rate was 2.1 greater
than isomerisation of 2M1B for a ratio MeOH : 2M1B = 1:1, at 343 K
Randriamahefa and Gallo (1988) describe a quasi-homogeneous model for TAME
synthesis and TAME splitting by LHHW mechanism. They formulated a kinetic model based on
the mechanism of Ancillotti et al. (1977) for electrophilic addition with a carbocationic
intermediate, where the rate-determining step was the protonation of alkene. The experimental
studies were carried out on cationic resins (Amberlyst 15, Dowex 50W, Dowex M31, Lewatit
SPC 118, Nafion 117). The reaction order with respect to MeOH is considered zero in this study
as well, taking into consideration the alcohol excess in resin granules. Methanol molecules are
strongly adsorbed on the catalyst, consequently there is a higher adsorption constant.
Consequently, methanol completely covers the active centres, forming a layer on catalyst
41
surface. The alkene molecules migrate through the excess of methanol towards the resin active
centres. Therefore, the methanol concentration is not felt. The rate expressions are formulated
function of molar concentrations, the authors neglecting the deviation from ideal behaviour of
mixture compounds. As underlined by other authors, this simplification may introduce important
errors.
Numerous thermodynamic and kinetic studies of TAME synthesis system were reported
in the years ’90s: Hwang and Wu (1994), Rihko et al. (1994), Piccoli and Lovisi (1995), Rihko
and Krause (1995), Oost and Hoffmann (1996), Rihko et al. (1997), Su and Chang (2000). The
most important rate expressions proposed are presented in Table 2.18. In the kinetic investigation
of TAME synthesis published by Rihko and Krause (1995), the effect of process variables
(pressure, temperature and reagent concentration) on the forward and reverse reactions were
evaluated. Three kinetic models power-law, Eley-Rideal (ER) and LHHW were proposed, based
on the experimental results. The best fitting was obtained with ER mechanism, where ether and
alcohol adsorb on the catalyst active site and the rate-determining step is the surface reaction.
In the concentration-based model proposed by Hwang and Wu (1994), the authors
lumped the two isoamylene isomers into a single pseudo-component, giving one rate parameter
and one equilibrium constant for both etherification reactions. Hwang and Wu (1994) took into
account the nonideality of the liquid phase by applying the UNIFAC method for the calculation
of the component activities under equilibrium conditions. In this way, they obtained the value of
the activity-based equilibrium constant, which was combined with the concentrations of
components in the rate equation. The rate expression was based on a pseudo-homogeneous
mechanism (power-law). Piccoli and Lovisi (1995) reported research results on thermodynamics
and kinetics for a scheme of transformation of each isoamylene in TAME, via a carbocation
intermediate, without considering mutual isomerisation of isoamylenes. In the experiments, C5
cut from naptha steam cracker and Amberlyst15 ion exchange resin (0.7 mm) are used. The
experiments are performed in 1L capacity steel autoclave with strong stirring to avoid influence
of external mass transfer. Care was taken, however, to avoid catalyst particle degradation by
agitation. Samples were taken manually from autoclave. Rate of reaction was based on
isoamylene concentration. Main experimental conditions considered: temperature (323 K, 333 K,
343 K and 353K), pressure (1013 kPa), molar ratio MeOH: IA 1.0, 1.3 and 3.0. They studied the
two isoamylenes separately, giving two rate constants and two equilibrium constants. However,
they gave no results or conclusions regarding the isomerisation reaction. The kinetic model was
based on the ionic mechanism, in which methanol forms a solvated layer around the catalyst site
through which the isoamylenes should migrate to adsorb on the site already occupied by
methanol.
42
Table 2. 18 Rate expressions for TAME synthesis process
Authors Chemical reaction Rate expression Rate constants expressions Observations

(1) (2) (3) (4) (5)
1. Piccoli 2M 1B  MeOH  TAME  CT  xj – molar fractions
and Lovisi ( B1) (M ) (T )
r1  k1 C B1   At 323 K: Cj – molar concentration
(1995) 2M 2 B  MeOH  TAME  K x1  xM   M  k1  8.5  103 s -1; K x ,1  119 of compund j
( B 2)
  K x,1 , K x, 2 - equilibrium
CT k2  0.72  103 s -1; K x , 2  10.7
r2  k2 CB 2   constants
 K x 2  xM   M 
At 343 K:
Authors determine  M  xM0.6 k1  5.2  104 s -1; K x ,1  53.4
Activation energies of the two reactions: k2  5.4  103 s -1; K x , 2  5.3
kcal kcal
E1  20.2 ; E 2  22.1
mol mol
2. Rihko k1
rR ,T  r2  r4 ; rR , M  r2  r4 ; Parameters values at 354 K: Liquid phase activities aj
and Krause 2 M 1B  MeOH  TAME k2 are calculated using
(1995)
k2
rR , B1  r2  r5 ; rR , B 2  r4  r5 ;  0.2437 UNIQUAC method.
k4
k3
2M 2 B  MeOH  TAME KT  K1aM aB1  K
k 4  T  0.1615
mol
k2 aT 1  
K M 
k4
aT KM g h
k5
r2  
2M 1B  2M 2 B mol KT
Num k5  3.1767 ;  0.1283
k6 g  h KM
K  Ka a 
Catalyst: Amberlyst 16 k4 T aT 1  2 M B 2 
KM  aT  Activation energies and pre-exponential
r4  factors:
The experiments consist of liquid Num
kJ kJ
phase TAME transformation into  aB 2  E2  100 ; E4  91.5
K mol mol
MeOH and isoamylenes (the Num  T aT  aM ; r5  k5 aB1 1   ;
reverse of synthesis reaction). KM  K 3aB1  E5  39.1
kJ
mol
rR , j  formation rates for species j;
mol
4041.2 k 2,0  1.7054  1014
K1  exp(8.3881  ) ; g h
T mol
3225.3 k 4,0  1.3282  1014
K 2  exp(8.2473  ) ; g h
T
43
833.3
K 3  exp(0.188  ) ;
T
3. Rihko et k1
 a 1  Values at 343 K: Liquid phase activities aj
al. (1997) 2M 1B  MeOH  TAME k1aM aB1 1  T   KT are calculated using
( B1) (M ) k2 (T )
 0,1283 ;
k3 r1   aM aB1 K1  ; KM UNIQUAC method. The
2M 2 B  MeOH  TAME Num kinetic model represents an
mol improvement of the one
( B 2) k4 k1  0.286
k5  a 1  gh published by Rihko and
k3aM aB 2 1  T  
2M 1B  2 M 2 B
( B1) k6 ( B 2)  aM aB 2 K 2  k3  0.125
mol Krause (1995)
r2  ; gh
Num
Catalyst Amberlyst 16 mol
 a 1  k5  0.107
k5 aB1 1  B 2   gh
 aB1 K 3 
r3  ;
Activation energies:
Num
kJ
KT E1  72.6
Num  aT  aM mol
KM
kJ
rR ,T  r1  r2 ; rR , M  r1  r2 E3  94.1
mol
rR , B1  r1  r3 ; rR , B 2  r2  r3 kJ
E5  81.6
mol
r1 , r2 , r3 - equivalent rates of the three reactions;
rR , j - formation rate of species j;
K1 , K 2 , K 3 - the same expressions as for the model at
point 2
4. Oost and k1
 E1, 2  1 1  The mixture 2M1B and
Hoffman 2M 1B  MeOH  TAME k1,2  k1, 2,0  exp     2M2B is considered at
( B1) (M ) k 1 (T ) a  1 1  aT   R  T 333 
(1996) k2 r1, 2  k1, 2  IA     2 
chemical equilibrium.
kJ
2M 2 B  MeOH  TAME  aM  K a ,1 K a , 2  aM  E1, 2  89.5
The rate expression
( B 2) k 2 mol represents the global rate
 4273.5  for the transformation of
k3
K a ,1  1.057  10 4  exp  k1,2,0  2576
m mol
2M 1B  2 M 2 B  T  isoamylenes mixture (IA).
( B1) k 3 ( B 2) echiv  s
 3374.4  Liquid phase activities aj
K a ,2  1.629  10  4  exp  are calculated using
Catalyst Lewatit SPC 118  T  UNIQUAC method.
5. Hwang k1
k13  1.9  1012 exp 94000 RT 
and Wu IA
( 2 M 1B  2 M 2 B )
 MeOH  TAME
(M ) k 1 (T ) rT  k13 CIACM  CT K12  K12  exp 7.84  2454 T 
(1994)
44
6. Su and kB1 Parameters values at 343K:
Chang 2M 1B  MeOH  TAME  1 aT   1 aT  Activation energies kJ and pre-
(2000)
( B1) (M ) kB 2 (T ) k B1aM a1B  1    k B 3 a M a2 B  1   mol
 K 1 a M a1 B   K 2 a M a2 B 
kB 3 RT  exponential factors mol :
2 M 2 B  MeOH  TAME Num
g h
( B 2) kB 4
kB 5
 1 aT  EkB1  72.6 ; EkB 3  94.1
2M 1B  2M 2 B  k B1aM a1B  1   EkB 5  86.1 k B1  0.286 ; k B 3  0.125 ;
( B1) kB 6 ( B 2)
R1B   K 1 aM a1 B   k a  1  1 a2 B 
B 5 1B  
Num  K 3 a1B  k B 5  0.107
 1 aT 
 k B 3 a M a2 B  1  
 K 2 a M a2 B   1 a2 B 
R2 B   k B 5 a1B  1  
Num  K 3 a1B 
KT 4041.2
Num  aT  aM ; K1  exp(8.3881  ) ;
KM T
3225.3
K 2  exp(8.2473  ) ;
T
833.3
K 3  exp(0.188  ) ;
T
KT
 0.1405  0.00061 T  334 
KM
45
The reaction would then occur by transfer of a H+ ion to the double bond of the iso-alkene,
forming an intermediate carbocation. This surface reaction was assumed to be the rate-
controlling step. They calculated the activities of components at equilibrium using the UNIFAC
method and further calculated the equilibrium constants expressed as molar fractions, which is
seen in the form of the rate equation.
Oost and Hoffmann (1996) used adsorption mechanism for reaction on active sites of
resin gel phase. They considered that rate-controlling step was chemical reactions of adsorbed
molecules. Their kinetic equations are expressed in terms of component activities. They lumped
the isoamylenes into a single pseudo-component as they concluded that the isomerisation
reaction is very fast compared to the etherification reaction. They gave one combined rate
parameter determining the etherification rate, and values of the equilibrium constants obtained
from calculations using thermodynamic data. However, the prediction of the equilibrium
constant from thermodynamic data proved not to be very accurate. Therefore, Thiel and
Hoffmann (1996) found a value of -114.65 kJ/mol for Gibbs free energy of TAME in liquid
state, deduced from experimentally determined values of the equilibrium constants published by
Rihko et al. (1994), should be used instead of the value of -109.55 kJ/mol obtained from
thermodynamic data, as proposed by Oost and Hoffmann (1996).
Ignatius et al (1995) revealed that in industrial conditions, this process is controlled
thermodynamically so neglecting this aspect limits the validity of Oost and Hoffmann model.
Rihko and Krause (1995) studied the kinetics of TAME reactions splitting, proposing
three mechanisms: power-law, Eley-Rideal and LHHW, concluding that experimental data was
best represented by Eley-Rideal mechanism with ether and alcohol adsorbing on active sites of
the catalyst and the surface reaction was rate-determining step.
In a second study of Rihko et al. (1997), the kinetics of reaction scheme of TAME
synthesis was investigated in batch reactors with Amberlyst16 catalyst. Different reaction
conditions were investigated: effect of temperature (333 – 353 K), methanol : isoamylene ratio,
initial rates of isomerisation 2M1B to 2M2B as well as etherification of 2M1B in the absence of
2M2B in the feed. The justification to investigate wide ranges of experimental conditions comes
from the request of industrial application for novel configurations as side reactors or reactive
distillation. This study is in agreement with investigation of Ignatius et al (1995).
It was found that the initial rate of etherification was 2.3 – 2.7 times bigger than the
initial rate of isomerisation. Kinetic models were developed considering the process mechanism
based on alcohol and ether adsorbed on the catalyst surface and isoamylenes reacted directly
from bulk liquid. Component activities were used in the expressions of kinetic models, based on
UNIQUAC method for activity coefficients. Activation energies reported by the authors are 81.6
46
kJ/mol for isomerisation reaction, 72.6 kJ/mol for etherification of 2M1B and 94.1 kJ/mol for
etherification of 2M2B. These results agree with early findings of Ancilotti et al (1977) but
disagree with Oost (1995). The last reported that isomerisation reaction was quicker than TAME
formation reaction. Maybe the difference is due to the conditions of reaction: Oost studied the
isomerisation reaction without methanol.
Based on experimental studies (Rihko et al., 1994), enthalpy of reaction was determined
for etherification of 2M1B ( H R  33.6  5.1 kJ/mol) and for etherification of 2M2B
( H R  26.5  2.3 kJ/mol). They are in good agreement with values determined from
thermodynamic data. On the other hand, it was underlined the important influence of the
enthalpy of reaction for TAME formation on the calculated reaction equilibrium constant, i.e. for
+1% error in H R , the value of equilibrium constant jumps from 10.5 to 36.3 at 323 K.
The range of validity of previously published models was evaluated by Päivi Pääkkönen
(2003) and Kiviranta-Pääkkönen et al (1998) by simulating their experimental conditions and by
comparing the adequacy of the models in predicting the experimental changes in composition as
a function of contact time, and composition at chemical equilibrium. According to these authors,
models based on component activities describe the etherification kinetics and reaction
equilibrium better within a wider range of conditions than models based on component
concentrations. The reason they offer is that the parameters of the two concentration-based
models were obtained from experiments where methanol was initially in excess. The activity-
based model of Oost and Hoffmann (1996) predicted the experimental changes under a wide
range of conditions after revisions to the originally presented values of the equilibrium and
isomerisation rate constants had been made. Pääkkönen (2003) found that under conditions of
methanol excess, the Oost and Hoffmann (1996) model predicts higher reaction rates than
experimentally obtained. The reason for this could be the diffusion limitations in their
experiments. The kinetic experiments of Päivi Pääkkönen (2003) and Kiviranta-Pääkkönen et al
(1998) were carried out with unsieved catalyst (mean size 0.7 mm), whereas the value of the
combined rate parameter for Oost and Hoffmann (1996) was obtained from experiments carried
out with particle sizes between 0.200 - 0.315 mm.
Su and Chang (2000) modified and used the rate equations derived by Rihko et al.(1995;
1997) to perform the simulation of a tubular reactor for the TAME synthesis over Amberlyst 15
(mean diameter 0.75 mm) as catalyst. The process they analysed occurs in two adiabatic catalyst
beds in series to enhance isoamylene conversion. A cooler between the catalyst beds was used to
lower the feed temperature of the second bed. Since the etherification reaction is exothermic and
equilibrium limited, decreasing the effluent temperature allows further conversion of isoamylene
47
in the second reactor. They found that the simulated reactor outlet temperatures agreed very well
with the operating data and that the predicted temperature profile was reasonably consistent.
Moreover, the calculated isoamylene conversions of 63.5% (after the first bed) and 71.7% (after
the second bed) were very close (within 3% deviation) to those of the performance test.
Various kinetic models proposed for the synthesis of TAME were tested against
experimental batch reactor data by Kiviranta- Pääkkönen et al (1998). The experiments were
carried out with methanol/isoamylenes molar ratios varying from 0.2 to 2.0 at temperatures
between 333 and 353 K. The range of validity of the various models was evaluated by simulating
the experimental conditions and by comparing the adequacy of the models to predict the
experimental changes of composition as a function of the catalyst contact time and composition
at reaction equilibrium. Again, activity-based models were found to predict the experimental
results better within a wider range of conditions than the concentration-based models.
Doğu et al (2001) performed experiments for the adsorption of ethanol, methanol, and
isobutylene and the vapor-phase reactions (methanol-isobutylene and ethanol-isobutylene
mixtures) in a flow reaction chamber (environmental chamber) of the diffuse reflectance FTIR
(DRIFT) cell. These experiments were carried out with Amberlyst 15. DRIFT spectra obtained
with alcohols (ethanol and methanol) and isobutylene on acidic ion-exchange resin catalysts
indicate that both alcohols and isobutylene adsorb on the -SO3H sites of the catalyst during
etherification reactions. Adsorbed alcohol molecules are bridged by hydrogen bonds to each
other and also to the -SO3H sites of the catalyst. It was concluded that the ether molecules
(MTBE and ETBE) are formed on the catalyst surface in the adsorbed state. All of these results
support a Langmuir-Hinshelwood-type reaction mechanism involving adsorbed alcohol and
isobutylene molecules in the synthesis of MTBE and ETBE on acidic ion-exchange resin
catalysts.
Later, Doğu et al (2003) studied the diffusion resistances and the contribution of surface
diffusion in TAME and TAEE production using Amberlyst-15 as catalyst. They concluded that
effective diffusion coefficients evaluated from batch adsorption experiments of methanol,
ethanol and 2M2B show that surface diffusion had significant contribution to the total
diffusion flux into the macroreticular resin catalyst Amberlyst-15.
Detailed kinetic studies for etherification reactions involved in TAME synthesis were
also reported by Boz (2004). In a first phase of this study, different acidic resin catalysts were
prepared by heat treatment of Amberlyst-15 catalysts at 220°C for different durations of time and
also by synthesis of sulfonated styrene divinylbenzene cross-linked resins in different conditions.
The data obtained from DRIFTS experiments carried out with alcohols, isobutylene, isoamylenes
and TAME, in a temperature range of 333-353 K, supported a Langmuir-Hinshelwood type
48
reaction mechanism involving adsorbed isoolefins molecules, forming a bridged structure
between –SO3H sites of the catalyst, and adsorbed alcohol molecules. The study included also
the evaluation of effective diffusivities and adsorption equilibrium constants of methanol,
ethanol and 2M2B, in Amberlyst-15. A batch Reflux-Recycle-Reactor (RRR) was proposed,
modelled and constructed to achieve high yields and selectivities in the equilibrium limited
reactions and a kinetic model was proposed.
Pääkkönen and Krause (2003a) measured the reaction rates to TAME with the ion-
exchange resin bead catalysts (A16, A35 and XE586) and a fibrous catalyst (SMOPEX-101) as a
function of temperature (323–353 K) with stoichiometric amount of reagents fed to a continuous
stirred tank reactor. The amount of divinyl-benzene (DVB) varies from 12 – 20% weight
determining the degree of crosslinking and rigidity of the structure. The catalyst beads are
bidisperse in some microagglomerations and macroagglomerations. Aditionally, there is gel
phase as well. Polar solvents determine beads swelling more when less DVB is in copolymer.
Catalyst is active due to sulfonic groups fixed on polymeric structure by sulfonation. Amberlyst
15 has ~ 4.8 mmol/g compared to Amberlyst35 hypersulfonated to 5.2 mmol/g. When the
reaction rates were assessed against the weight or acid capacities of the catalysts, the decreasing
activity order was A35>A16>SMOPEX-101>XE586. When the rates were calculated versus the
square of the acid capacity, the activities of the catalysts were similar. This indicated a dual-site
mechanism. The rates of TAME formation and the isomerisation of isoamylenes as a function of
temperature (333–353 K) and the feed MeOH/isoamylene molar ratio (0.5–2.0), as well as the
decomposition of TAME, were then measured in a batch reactor with the ion-exchange fibre
(SMOPEX-101) as catalyst. Kinetic modelling results favoured a single-site mechanism for the
isomerisation and a dual-site mechanism for the etherification. The activation energy was
determined to be 116.7 kJ/mol for the isomerisation of 2M1B to 2M2B, 92.7 kJ/mol for the
etherification of 2M1B to TAME and 93.0 kJ/mol for the etherification of 2M2B to TAME.
Parra et al (1998) studied the influence of different parameters on the ion exchange resin
or catalytic activity (acid capacity, BET surface area and pore diameter) for more catalysts types.
The conclusion was that actually acid capacity has greater influence compared to other variables.
Pääkkönen and Krause (2003b) studied the effects of temperature (323–353 K) and the
molar ratio of the reagents methanol/isoamylenes (0.3–3.0) on the formation rates of TAME with
different Amberlyst 16 (A16) particle sizes in a continuous stirred tank reactor. The effect of
catalyst swelling was studied with several mixtures of reagents (MeOH and IA) and product
(TAME) on Amberlyst 16. The particle size influenced the steady state reaction rates most
notably at higher temperatures and with substoichiometric feed of the reagents
(methanol/isoamylenes), i.e. when the reaction rate is faster. The estimated effectiveness factors
49
(0.5–1.0) decreased with increasing particle size and increasing temperature. At
nonstoichiometric feed ratios of the reagents the value of the estimated effectiveness factor
decreased more when methanol was fed in excess. Recalculations of the earlier results of TAME-
synthesis demonstrated that when dividing the rate constants obtained from the batch reactor
experiments by the effectiveness factors, the R-squared values of the regression analysis against
temperature increased (improved fit for Arrhenius-type dependency) and the activation energies
increased by about 9 kJ/mol.
Oktar et al. (1999) published results upon adsorption in this reaction system, providing
data on their measurements related to different mechanisms. There are three proposed
mechanisms (Rihko et al., 1997), as previously mentioned: power-law, Eley-Rideal (adsorption
of alcohol and ether), Langmuir Hinshelwood (adsorption of all components). Some kinetic
models inside each mechanism are possible to be derived. Linnekoski et al. (1999) presented a
kinetic model derived from Eley-Rideal mechanism.
More studies were accomplished in the last decades, considering two heterogeneous
mechanisms: Eley-Rideal (alcohol and ether adsorb on active sites) and Langmuir –
Hinshelwood (olefins, alcohol and ether adsorb on active sites). Initial reaction rates for
amylenes isomerisation and etherification with methanol at different temperatures and initial
ratio alcohol/2M1B affects as well the reaction scheme in different ways depending on
temperature. Rate determining step is ether protonation of olefin or the reaction between
protonated olefin and alcohol:
CH3 CH3
+ H+
CH2 C CH2 CH3 CH3 C CH2 CH3
H+ +
+ CH3OH
CH3
CH3 C CH2 CH3

+O H
CH3
Estimated parameters are mean pre-exponential factors and activation energies. Reaction
rate model with parameters for dependency on temperature is Arrhenius type. Estimation of
these parameters can be strongly affected by correlation between parameters. K values, when
obtained in a certain temperature interval, can be affected by data scattering. If logarithmic
dependency is considered:
Ea
ln k  ln A0  (II. 42)
RT
50
 E 
The origin intercept ln A0 can be compensated by errors in   a  , the slope issuing
 R
uncertainty for both parameters. In principle, k-values can be well fitted but model parameters
(pre-exponential factor A and activation energy Ea) can be uncertain. Parameter estimation is
improved by experiment orthogonalisation. This is achieved shifting the abscissa for temperature
with average temperature T   T  Tmean . This, it is obtained:
1 1
z  (II. 43)
T Tmean
and
 Ea 
k  kmean exp   zEa  , where kmean  A0 exp    (II. 44)
 Tmean  R 
Modified Eley-Rideal model is more accurate when alcohol/olefin ratio is low. LHHW
does not predict etherification rates with accuracy at low ratios. Adsorption of acohol and olefins
is not competitive. Apparent activation energies are comparable to other reported data.
The activity coefficients were calculated from Wilson model, based on experimental data.
More, using this data, earlier experimental data was reanalysed, reformulating experimental
reaction equilibrium constants and G298  109.6 kJ/mol is calculated for TAME in gaseous
phase at 298 K.
The equilibrium constants:
K1  exp  8.74435  4142.069 T 
K 2  exp  8.24371  3219.118 T  (II. 45)
K3  K1 K 2
were reported in Paakkonen and Krause (2003). Wilson model was selected because is
particularly fitted to alcohol/hydrocarbon mixtures. In the paper of Rihko et al (1994), reaction
equilibrium was studied experimentally and modelled in terms of activities. Activity coefficients
were determined with UNIQUAC model. It was noticed the dependency on methanol mole
fraction (equilibrium constants are higher when mole fraction of methanol < 0.02).
Another reaction mechanism is Lewis-Bronstedt (Tejero et al., 1987) type that considers
there are two kinds of acidic sites: the Bronstedt proton (H+) and the Lewis (:O: inside SO3H
groups). As a consequence, an etherification mechanism was proposed involving the formation
of an intermediate complex having the structure:
51
O
O S
O
CH3
H O O S
CH2CH3
H C H O
C O
H CH3
H H
O
S O
The kinetics and thermodynamic equilibrium of TAME liquid-phase synthesis from the
reactions between methanol and the isoamylenes 2-methyl-1-butene (2M1B) and 2-methyl-2-
butene (2M2B) were studied in a batch reactor in the temperature range 324-362 K at 10 bar
using Amberlyst 15Wet as catalyst by Ferreira and Loureiro (2004). A kinetic model based on a
Langmuir-Hinshelwood-type mechanism was developed assuming methanol as the most
abundant surface species. To ensure model applicability for a large range of species activities,
the fraction of vacant sites was not neglected. The reaction rates were written in terms of
activities, and the liquid phase activity coefficients were calculated by the modified UNIFAC
method of Dortmund. The number of active sites involved in TAME synthesis was also
investigated by using a partially deactivated catalyst. The results showed that the etherification
reaction rates are proportional to the square of the concentration of active sites of the catalyst,
i.e., there are two active sites involved in each etherification reaction, which indicates that a two-
site Langmuir-Hinshelwood mechanism is the most adequate for the description of the TAME
catalytic synthesis in the liquid phase.
Liu et al (2008) studied the reaction kinetics of the synthesis of TAME by tertiary
amylene, using C5 fractions separated from catalytic cracking (FCC) gasoline. The modified
UNIFAC method was used to calculate the component activity of reacting system. The kinetics
of etherification process of TAME synthesis was studied by using R-E mechanism and the L-H
mechanism. The results showed that the R-E mechanism model was more appropriate and the
proposed kinetic model was able to predict the equilibrium conversion and etherification rate
accurately.
Intrinsic kinetics for synthesis of TAME from pyrolysis C5 fraction and methanol on a
sulfonic ion exchange resin catalyst (QRE), in conditions free of both internal and external
diffusions, was studied in a continuous tubular reactor by Liu, Yu and Weng (2008). Activities
of components were calculated by Wilson model. Reaction rate constants of three kinetic
52
models, namely homogeneous, Rideal-Eley and Langmuir-Hinshelwood (LH) were estimated by
nonlinear least square method. Their results indicated that homogeneous model is not suitable
for the etherification. Under conditions of reaction temperature of 60 - 70oC and mole ratio of
methanol to isoamylene superior to 0.5, the average relative error of TAME activity predicted by
LH model to experimental data is less than 7%. The activation energies are determined to be
92.17 kJ/mol for isomerization of 2-methyl-1-butene to 2-methyl-2-butene, 100.19 kJ/mol for
etherification of 2-methyl-1-butene to TAME, and 102.48 kJ/mol for etherification of 2-methyl-
2-butene.
Mao et al (2008) studied the etherification of methanol with 2-methyl-1-butene and 2-
methyl-2-butene catalyzed by the macroporous cation ion-exchange resin (D005II) in a batch
reactor. The thermodynamic properties and kinetic data were obtained under different initial
molar ratio of methanol and isoamylenes (0.5–2) in the temperature range between 323 and
353K with pressure (1MPa) constant. Because of the nonideal behaviour of the reaction mixture,
activities were adopted to calculate equilibrium constants and the activity coefficients were
estimated by Wilson method. Three methods were adopted for developing reaction rate
equations, containing homogeneous reaction mechanism, Langmuir–Hinshelwood (LH) type
mechanism and Eley–Rideal (ER) type mechanism. The rate equations based on the LH type
mechanism was found to get better fit with the experimental data. The results showed that the
experimental data for thermodynamics agreed well with the theoretical predictions, and the
activation energies were 88.1 and 102.1 kJ/mol for the etherification of 2M1B and 2M2B,
respectively.
The reaction system and mechanism of etherification of C5 cut with methanol were
analyzed theoretically by Lixin et al (2008). Experiments were carried out in a tubular reactor at
temperatures of 50oC–80oC in the presence of a strong cation-exchange resin, QRE. At lower
temperature, the reaction rates were controlled by kinetic factors, but at temperature above 60oC,
both reactions were affected by thermodynamic equilibrium. The appropriate operating
conditions were: 60oC–65oC, molar ratio of methanol to isoamylenes 1.0–1.2, and liquid hourly
space velocity (LHSV) 1.0–1.5 h-1.
These kinetic and thermodynamic models are applied in numerous simulation studies.
Subawalla and Fair (1999) discussed design guidelines for solid catalyzed reactive distillation
systems. Iterative procedures and methods to estimate reactive column catalyst mass, reactive
zone height, theoretical stages, reflux ratio, packed height, and column diameter were presented.
The kinetic model and the design proposed for TAME synthesis was further implemented by
Luyben and Yu (2008) for the study of simulation and control of TAME process as a typical
example of a reactive distillation system.
53
The simulation of TAME synthesis process was also recently studied by Pulido et al
(2011). The study was performed in order to compare the performance of reactive distillation
column and a heat integrated reactive distillation column.
Bumbac et al (2007) studied the TAME synthesis kinetics and provided a methodology of
modelling and simulation that can be applicable to solve reactive-separation problems. They
studied the possibility to operate reactive distillation process in a dividing wall column apparatus
(RDWC) for TAME synthesis, using ion exchange resin Amberlyst 35. Rigorous simulation was
performed with ASPEN HYSYS. The case study illustrated the methodology allowing to obtain
acceptable solutions for TAME synthesis in industrial conditions, using RDWC. A similar
methodology was also applied to the synthesis of TAEE (tert-amyl-ethyl-ether) (Bumbac et al.,
2007), providing an attractive solution from industrial point of view.
The production of TAME was also studied by Moreira Duarte (2006). Although
experiments were not carried out for TAME synthesis, a model for the simulation of reactive
distillation columns was developed. The use of this model for TAME synthesis proved to be
reliable and showed that if the isoamylene feed is pure, full conversion and purity are possible. It
also showed that good modelling tools are becoming indispensable in designing, building and
operating reactive distillation columns, since small variations of the operating conditions can
have significant effects on the distribution of products and column performance.
For conceptual design of the industrial process, or for a safe operation of a complex
multifunctional apparatus as a reactive distillation column, it is necessary to analyse the process
behaviour based on a reliable mathematical model. In this context, experimental kinetic study
and kinetic modelling are necessary as a primary step in process modelling and scale-up.
2.4.2. Solid catalysts for synthesis of ethers by alcohol addition to tertiary

olefins
The choice of a catalyst significantly influences chemical reactions and thus the performance of
integrated reaction and separation processes. Different homogeneous and heterogeneous
chemical catalysts as well as enzymatic catalysts are currently used in organic synthesis. All of
them have advantages and disadvantages, which determine their field of useful application. For
instance, homogeneous catalysis is applied in carbonylation and hydroformylation processes
(Cornils and Herrmann, 1996)) whereas biocatalysts have successfully been used in several
reactions under mild reaction conditions with high chemo-, regio- and enantioselectivity (Drautz
and Waldman, 1995); Schuchardt et al., 1998; Bornscheuer, 2002).
Homogeneous catalysts usually provide faster overall reaction rates, while in the case of
54
heterogeneous catalysts, the kinetics may be slowed down by the mass transfer. Heterogeneous
catalysts have the advantage of an easy recovery in slurry catalytic distillation processes
(Barreira et al., 2003), can be immobilized inside the process units and are readily amenable to
continous processing. They have been applied in a wide range of processes, therefore detailed
experience and understanding for this class of catalysts is available.
A wide range of acidic solid catalysts is available on the market: acidic ion exchanger resins,
zeolites, silica-occluded heteropoly acids, nafion-silica composites and others. In principle, all of
them can be applied to manifold acid-catalyzed processes, e.g. etherifications, esterifications,
transesterifications, esther hydrolysis, alkylations, etc. The integration of a chemical reaction and
the separation via distillation into one single unit operation leads to certain requirements for a
heterogeneous catalyst (Kenig et al., 2004):
 High catalytic activity
The activity of a heterogeneous catalyst affects the reaction rate and, therefore, determines the
required liquid hold-up inside a CD unit to achieve a given conversion rate (the reaction taking
place in the liquid phase). Liquid hold-up must be large enough to cover all active sites of the
catalyst. However, from an economical point of view there is an upper limit to the liquid volume
fraction that can be reserved inside a column and under certain circumstances, a side reactor or
pre-reactor in addition to a catalytic distillation is preferable (Baur and Krishna, 2004). The
catalysts that have already been used in integrated reaction and separation processes comprise
the ion exchanger resins and zeolites.
 No or very slow catalyst deactivation
Independent of the chosen method of immobilization, the replacement of a
heterogeneous catalyst in a CD column is rather complex, time-consuming and, consequently,
costly. Therefore, it is necessary that the catalyst has a possibly small deactivation rate. The
acceptable loss of activity strongly depends on the process and product specifications, the initial
reaction rate of the fresh catalyst, the economical background of the overall process and mass
transfer factors, e.g. the type of internals used.
 Operating temperature within the range of the boiling point temperatures of the
reactants and products
Since the boiling point temperatures of the pure reaction product and inert components
and those of their resulting azeotropes determine the temperature range inside a catalytic
distillation column, the chosen catalyst should be working properly under these conditions
(Schembecker and Tlatlik, 2003). For example, some catalysts like zeolites have an optimal
operating temperature between 180 oC – 200 oC, and others like ion exchange resins degrade
above the temperature interval 60 – 125 oC, depending on the catalytic active group used. Thus,
55
the number of suitable catalysts for a certain reaction system is relatively narrow. In some cases,
pressurizing the CD column can help to adjust the temperature range, but this also affects the
investment and operating costs of the unit.
 Mechanical stability
Since the catalyst inside a CD column is usually immobilized, using various containers
made for example from wire gauze sheets, the mechanical stress on the catalyst particles is by far
lower than in other reactors, e.g. in a fluidized bed reactor. Nevertheless, a certain mechanical
stability is necessary to keep the catalyst inside these containments.
Despite some drawbacks, heterogeneous catalysis shows some advatanges over the
homogeneous one (Kenig et al., 2004):
 possibility of catalyst recovery and recycling
 reduced amount of waste streams
 less corrosion in pipings and vessels
 influencing of selectivity (including shape selectivity)
 safer handling of catalysts compared to organic or inorganic acids and bases used
for homogeneous catalysis.
2.4.2.1. Ion exchange resins
The only catalysts currently used industrially in the process of alcohols addition to olefins are the
sulfonated macromolecular resins, employed as ion exchangers. These catalysts are stable at
relatively low temperatures (30 – 125 oC) at which, due to the high acidity provided by sulfonic
groups, the addition reaction presents high enough rates. The zeolites, inorganic acid catalysts
less used in various industrial processes, are active only at higher temperatures. However, the
addition reactions of alcohols to olefins are highly exothermic; therefore, high temperatures do
not favour the achievement of high olefines conversions by classic procedures (shift to left,
towards the formation of the alcohol and alkene, favoured by the increase of temperature).
Furthermore, at high temperatures, olefins polymerisation reactions become important, the
formed polymers are blocking the catalyst active sites, deactivating it in time. In industrial
operating conditions characteristic to the current technologies based on ion exchange resins
(pressure of few atmospheres and temperatures of 30 – 80 oC), practical data show that these side
reactions are not significant, especially if a small excess of alcohol is used (Kirk-Othmer, 2001).
From structural point of view, these macroreticulated cationites present a rigid macroporous
structure, similar to the one of conventional adsorbents such as alumina, silicagel or active
carbon. The presence of large internal surface and continuous pores permits the liquid or gaseous
56
reactant molecules to access easily the hydrogen ions of sulphonic group inside resin particles.
Therefore, these solid macroreticulated structures, strongly sulfonated represent excellent
catalysts for a great number of reactions catalysed by Brőnsted acids (etherifications, alkylations,
esterifications, condensations, hydration, addition, a.s.o.) (Suciu and Tunescu, 1999). The
synthesis of such catalysts implies the existance of a polymer (co-polymer) matrix with porous
structure, followed by its sulphonation. The most used polymeric matrix is the copolymer styrene
– divinylbenzene, obtained by polymerizing a mixture of styrene and divinylbenzene of
controlled composition. (Figure 2.10).
Table 2.19 presents the features of some catalysts in this cathegory, more frequently used in
industrial applications (Linnekoski et al., 1998; Boz et al., 2004).
stiren
styrene divinilbenzen
divinyl-benzene
H2SO4 SO 3 H SO3H SO3H SO3H

SO3
SO3 H SO3H SO3H
Figure 2. 11 Chemical structure of ion exchange resins

Other etherification catalysts represented by macroporous resins styrene-divinylbenzene
sulfonated are Lewatit® K2621, Lewatit® K2624, Lewatit® K2631, Lewatit® K2634 (Bayer),
Dowex® 50/Nalcite® HCR (Dow Chemical Company) and XE586. The resins produced by
Bayer Company are often commercialized impregnated with small quantities of noble metals,
especially palladium (as Pd2+). The Pd content does not cross 3%, in most of the cases
approximately 1 g Pd is added for each litre of resin. The Pd impregnation necessity comes from
the presence of dienes in the olefins fractions from pyrolysis and cracking.
The dienes can oligomerise, Pd having the role to partially hydrate them. Such catalysts are
mostly used in modern production plants of fuel ethers using reactive distillation (catalytic
distillation). The catalysts which don’t contain noble metals are used in plants in which the
dienes mixture is partially hydrated before being introduced in the plant.
57
Table 2 19 Characteristics of Amberlyst and Purolite – type catalysts (Linnekoski et al.,1998;
Boz et al., 2004)
Catalyst
Amberlyst Amberlyst Amberjet Purolite Purolite
15 35 1500H CT-175 CT-275
Property
Rohm and Rohm and Rohm and
Producer company Purolite Purolite
Hass Hass Hass
Macro- Macro- Macro- Macro- Macro-
Type
porous porous porous porous porous
Grain BET
42 45-50 - 29 31
specific method
surface ISEC
2
157 166 - 193 181
(m /g) method
Specific volume (cm3/g) 0.336 0.28 - 0.48 0.29
Acidity (mol H+/kg) 4.7 5.2 5.2 4.98 5.2
Mean pores diameter, Ǻ 343 329 - 662 601
Porosity, mL/g (measured
by porosymeter with 0.35 0.41 - 0.5 0.45-0.55
mercury)
Divinylbenzene content (%) 20 20 - - -
Moisture Retention (%) - - - 50-57 51-59
Maximum operating
120 150 - 145 145
temperature, °C
A catalyst created on polyethylene matrix is Smopex101, produced by Smoptech company. This

is prepared by grafting polyethylene fibres with styrene, followed by sulfonation with
chlorosulfonic acid. It is delivered as fibres; however it is practically used as powder. This
catalyst proved to have favourable properties in the synthesis of fuel ethers with greater volume
(e.g. 2-methoxy-2,4,4-trimethyl-pentane) more than in the synthesis of C5 – C7 fuel ethers.
The presence of alcohol excess in internal macropores of cationite leads to swelling of its
internal structure. The gonflation forces of the tridimensional network are able to break the
network of hydrogen bonds, dissociating and solvating the protons. From kinetic point of view,
macroreticulated resins act as any acidic catalyst. Therefore, the protons of acidic groups in
cationite are fixed first on the alcohol molecules and then transferred to the olefins (Linnekoski
et al., 1997, 1999; Rohrbach and Rosenbaum, 2004). Figure 2.11 illustrates the reactions scheme
describing the mechanism.
58
- +
SO 3H + C2H5 OH SO 3 + C2H5 OH2
slow
+ lent +
H2C C CH2 CH3 + C2H5 OH2 H3C C CH2 CH3 + C2 H5 OH
CH3 CH3
2-metil-1-butena (2M1B) carbocation
tert-amyl tert-amil
carbocation
2-methyl-1-butene (2M1B)
2-methyl-1-butene (2M1B)
slow
lent +
+
H3C C CH CH3 + C2H5 OH2 H3 C C CH2 CH3 + C2H5 OH
CH3 CH3
2-metil-2-butena (2M2B)
2-methyl-2-butene (2M2B) carbocation
tert-amyl tert-amil
carbocation
CH3
+ +
H3C C CH2 CH3 + C2H5 OH C2H5 O C CH2 CH3
CH3 H CH3
carbocation tert-amil
tert-amyl carbocation
fast
rapid CH3
+
C2H5 O C CH2 CH3 + H
CH3
Figure 2. 12 Mechanism of alcohols addition to olefins, in alcohol excess
At stoichiometric or substoichiometric alcohol/olefin ratio, the olefins can directly take

the proton from the sulfonic groups, these being a more acid species than the solvated proton.
The addition of primary alcohols to tertiary olefins with higher basicity takes place by an acid-
base ionic mechanism – electrofile addition (Figure 2.12). In this process, the alcohol holds the
function of reaction protic solvent, dissociating protons from the cationite internal macroporous
network. Its concentration is important to stop the olefine dimerization, leading to a higher
selectivity of the process.
H2C C CH2 CH3 H3C C CH CH3
CH3 CH3
+
H +
H
lent
slow lent
slow
CH3
+ fast
rapid
H3C C CH2CH3 +C2H5 OH C2H5 O C CH2 CH3 +
+
H
CH3 CH3
Figure 2. 13 Mechanism of alcohols addition to olefins, without alcohol excess

Studies related to the etherification of 2-methyl-1-butene and 2-methyl-2-butene with ethanol on
various catalysts led to the conclusion that alkene dimerization starts after reaching the chemical
equilibrium. In the case when ethanol is used, the conversions are slightly smaller. This aspect
59
can be explained by the resin swelling and by etherification equilibrium. The least polar is the
alcohol used, the weaker is the resin tendency to swell. Therefore, when ethanol is used, there
are less free active centers in the catalyst pores, most of them being occupied by the alcohol.
When the alcohol content in the catalyst is low, izoamylenes have easier access to the active
centers, therefore 2-methyl-1-butene izomerizes easily into 2-methyl-2-butene, more stable but
less reactive in the etherification reaction. The lowest reaction rates were obtained on resins of
Amberjet type, which are not macroporous. The highest conversions are obtained on acid
catalysts Amberlyst – 35 and Purolite CT – 125, which posess high porosities.
The olefine basicity holds an important role in process selectivity. Tertiary olefins are more basic
compared to the linear ones due to the alkyl radicals that substitute de double bond. Thus, the
carbocations formed are more stable due to electrons rejecting effect of neighbouring alkyl
groups that diminishes the electrons deficit at the carbon atom with positive charge. This reason
makes linear alkenes inactive in the reaction with alcohols.
2.4.2.2. Inorganic solid acid catalysts
Zeolites, acid catalysts used in various industrial technologies (especially hydrocarbons

alkylations), are active at the alcohols addition to olefins, at relatively high temperatures. This
obliges to take measures for limiting the temperature effect on the progress of etherification
reactions (reversible and exothermal) and on olefins oligomerization side reactions. Compared to
the ion exchange resins, zeolites present the advantage of a higher stability at high temperatures
and of regenerability, permitting a longer operation life. The concerns about the alternative use
of zeolite catalysts in the synthesis of aliphatic ethers appeared especially due to the
disadvantages of industrially used ion exchange resins. The resins are not stable at temperatures
higher than 125 oC and their usage leads to the appearance of acid subtances in the reaction
media, strongly corrosive for the plant.
Currently, there is a lot of research work oriented towards the development of zeolitic structures
with catalytic activity in alcohols addition reactions to olefins, comparative to the one of ion
exchange resins. According to the results published in literature, the inorganic catalysts based on
zirconium sulfate, H-β and flourated H-β zeolites present performances close to the ones of
Amberlyst-35 in etherification reactions of i-butene with methanol (Horvath et al., 2000; Aboul-
Fotouh et al., 2004; Wang and Guin, 2003). Therefore, the zeolitic materials in these cathegories
correspond to the demands of gasolines etherification process.
As mentioned before, olefins etherification and izomerization takes place on the active centers of
the catalyst. The surface area can also influence the catalytic activity. Amberlyst 15 presents a
smaller specific surface area, but presents a stronger acidity with a capacity of 4.4 meq H+/g.
60
Montmorillonite presents a higher ion exchange capacity, as well as a higher acidity and surface
area than bentonite. SiO2 presents the highest surface area and moderate acidity. Due to the weak
acid properties of Al2O3, zirconium sulfate catalyst on this support does not present activity for
izomerization and etherification.
Heteropolyacids (HPA) are strong Bronsted acids with important applications in acid catalysis
and in oxidation reactions. Many processes in organic synthesis catalysed by Bronsted acids
(H2SO4, HCl) or by Lewis acids (AlCl3, FeCl3) present higher efficiency in milder conditions
and in the presence of HPA or polyoxometalates. These compounds are insoluble in non-polar
solvents and highly soluble in polar solvents. They can replace classical catalysts such as H2SO4
and HF, their application being limited due to very small specific surface (< 10 m2/g). Therefore,
HPA dispersion onto a support with a greater specific surface is taken into consideration.
Various materials, with neutral or acid characteristics, can be used as supports: silica, alumina,
active carbon, ion-exchange resins, clays and zeolites. In case of using zeolitic molecular sieves
(Y zeolites) and mesoporous materials as supports, the application domain for heteropolyacids
can be expanded. Thus, a catalyst more selective than the classic Amberlyst-type one for MTBE
or ETBE synthesis was obtained by incorporating trifluor methanesulfonic acid (triffic acid,
TFA) in the structure of H-Y zeolite.
Zeolitic catalysts are active in acid-catalysed reactions. Their acidity strength, number of active
centers and structure can be controlled in their fabrication process. Shape selectivity increases
the global selectivity of the chemical process, reducing the formation of by-products. For the
industrial processes of fuel ethers synthesis, the zeolites present less activity compared to the
ion-exchange resins. However, the control of their activity and shape selectivity by etherification
reactions leads to significant research results.
The conventional processes to obtain inferior aliphatic ethers use acid catalysts of ion-exchange
resins type, e.g. Amberlyst 15, the reactions taking place in liquid phase. The resins provide high
catalytic activity but are unstable at high temperatures; by overheating, they generate sulphonic
acid and sulphuric acid. The reactions equilibrium is more favourable at low temperatures, but
the reaction rate decreases considerably.
Among the zeolites studied as catalysts for etherification reactions can be mentioned the ones
with average porosity of type ZSM-4, ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-50
and the β-zeolite. Due to their lower acidity compared to the ion-exchange resins, the zeolites
must be used at high reaction temperatures to obtain the desired conversion. Zeolites are more
thermally stable than the ion-exchange resins, are less sensitive at the ratio methanol/alkene, do
not provide acid effluents and regenerate easily and fast.
A special class of zeolites are the mesoporous or macroporous materials, of MCM41 or MCM22
61
type. The increase of catalysts acidity is favoured by the H shape, such as in the case of the
HMCM22 catalyst. The mesoporous materials of MCM-41 and Al-MCM-41 type present a
system of open channels, similar to nanotubes, with diameters of 2.0 – 10.0 nm, as a result of the
modifications in synthesis networks and operating conditions used to obtain the structures of
amorphous silica and alumina-silica gels, respectively. The diameter of mesopores can vary, as
well as the acidity can be modified by the Si/Al ratio. Due to these variations, the nanomaterials
obtained present different specific areas in the interval 400 – 1200 m2/g and with very different
acidities and acid centers strength distribution. These catalysts present high thermal stability,
large specific area and a system of mesopores that avoid hinderence by diffusion and the ones
due to shape selectivity. The modification of these materials with cations during their synthesis,
by ion exchange or impregnation, enlarges the research field and opens the perspectives towards
new materials, with special catalytic properties and towards nanomaterials with magnetic
properties or matrixes for synthesis of polymer compositions.
The strict dimensions of zeolites pores determine their specific selectivity, “shape selectivity”.
On the acid centers, with strengths and densities that can be controlled during synthesis or by
modifications after synthesis, characteristic reactions can be promoted, e.g. cracking reactions,
isomerisations, alkylations – transalkylations, aromatizations, etherifications, acylations and
hydrations – dehydrations.
The modification of zeolites with transitional metals in the crystalline network, during synthesis,
in cationic positions or by ion exchange and the introduction of oxidation-reduction centers
enlarge the catalysis domain in which these materials can be used. The corresponding results are
superior to classical catalysts and can be the basis for new technologies – clean technologies with
no negative impact on environment.
As a drawback, catalysts based on micro and macropores present the disadvantage of steric
hinderance for reactants with large molecular volume and of molecular traffic hinderence within
their porous networks. This leads to fast deactivation, by coking. However, the results obtained
using micro and macroporous zeolitic materials bring important scientific contributions.
Extended research can lead to new catalysts, with superior properties in important chemical
processes.
2.5. Industrial TAME production technologies
The figures below present the schemes of three processes for TAME synthesis in which the
reaction zone and the separation zone are distinct, avoiding in this way issues related to reactive
distillation.
62
NexTAME process
In the NexTAME process, the general structure of the plant, given in Figure 2.14, includes two
pre-reactors, the temperatures in pre-reactors decrease successively, maximizing in this way the
global conversion which is around 65% for C5 alkenes, 35%for C6 alkenes and 25% for C7
alkenes. The main feature of this process is a system including a distillation column with side
reactor. The feed to this reactor is assured by the flowrate extracted from the side-stream located
above the feed to the rectification column, which is brought to optimum reaction temperature by
a heat-exchanger. Methanol cannot leave the column neither by the top nor by the bottom,
therefore it concentrates in the side cycle together with the alkenes. In this way, there is no need
for an addition section for methanol recovery.
Light
Light
petroleum
petroleum
Etherified
light
Rectification Lateral petroleum
Pre-reactors
column reactor
Figure 2. 14 NexTAME process
Philips process
The Philips process (Figure 2.15) uses a similar approach as the NexTAME process. In this
process, beside the pre-reactor, a catalyst bed is placed in the reflux cycle of the rectification
column, therefore the ratio alcohol/alkene is maintained at an optimum value on the entire
surface of the catalyst layer. This configuration also permits operation at an optimum
temperature for the catalyst without affecting the rectification operation. However, this
procedure needs a methanol recovery zone.
CDEtherol Process
The CDEtherol process (Figure 2.16) is based on reactive distillation technology, developed and
implemented by CD Tech enterprise. The majority of the plants, which produce tertiary ether,
built after 1990, are using this technology. The advantage towards the classical technologies is
related to the usage of a reactive distillation column that permits to reach conversions greater
63
than 95%. Moreover, the energy consumption for the separation phase is practically reduced to
zero for the case of reactive distillation.
Alcohol
Alcohol recovery
Refined
Ether
Alkenes Rectification
column
Figure 2. 15 Philips etherification procedure with high conversion
This process is based on a 3-stages reaction. In the first stage, the process takes place in a
catalytic reactor, with a patented trifunctional catalyst, followed by a fixed bed catalyst operated
at the boiling point of the fed mixture, the final conversion being achieved in a catalytic
distillation column in the presence of a patented catalyst.
In the first reactor, three processes take place on the same catalyst bed: selective hydrogenation
of alkadienes, isomerization of 3-methyl-1-butene to 2-methyl-2-butene and the etherification of
isoamylenes. The selective hydrogenation reduces also the precursors for the gum, which left
untreated, induces smell and unwanted color to the final product, in the same time reducing the
catalyst lifetime. The temperature in the reactor is controlled by recycling of cold reactants in the
reactor feed.
The reactor operated at boiling point is designed so that the maximum operating temperature can
be adjusted by modifying the reactor pressure. The temperature of the reactive liquid mixture
can’t depass the boiling temperature, therefore there is a strict control of the maximum
temperature to be reached in the reactor.
The distillation column combines the chemical reactor with the mixture separation. This permits
a high conversion of isoamylenes achieved easily and with reduced cost, depassing the
thermodynamic equilibrium of fixed bed reactors. Another advantage of catalytic distillation is
the higher reaction rates that can be reached due to the temperature increase, without affecting
the equilibrium conversion. An advanced control of the process maximizes the catalyst lifetime
and activity in order to continuously produce TAME.
64
Reactor
operated at
Fe eding and Trifunctional the boiling Catalytic Methanol Methanol
washing reactor point of the distillation extraction recover y
liquid
Methanol mixtur e Recir culated m ethanol
Refined C5
Hydrogen Methanol
and C5
fraction
Water
water
C5
fraction
Water and
contaminants TAME
Figure 2. 16 General structure of the plant for TAME synthesis by CDEtherol technology
2.6. Mathematical models used in the calculation of reactive distillation

processes
The development and implementation of realistic process models represents a key stage in
feasibility evaluation of a proposed reactive distillation process. The simplest models are the
“equilibrium models”, which consider reaching the thermodynamic equilibrium. However, the
real processes are most of the times limited to transport and property transfer phenomena so that
chemical and physical transformations take place away from equilibrium. The efficiency
concept, which defines the degree a system approaches equilibrium, is a first step in real
processes modelling. The geometry of column internals, the thermodynamic parameters as well
as the nature and composition of the chemical system influence the values of efficiencies. In
multicomponent systems, their estimation is difficult since these are different for each
compound. The concept of equivalent height of a theoretical tray (HETP), which represents the
packing height necessary for a separation equivalent to the one produced by an equilibrium tray,
is used for mass transfer modelling in packing columns. As in the case of efficiency, this concept
has a physical significance only for binary systems.
The non-equilibrium models take into consideration the kinetics of interphase mass and
hear transfer as well as chemical reaction kinetics. The mass and energy balance equations are
particularized for each phase and the interphase mass and energy transfers are characterized by
specific relations. Less detailed models neglect the pressure variation along the column, while
65
the detailed ones consider pressure drop as function of arrangement of column internals (tray or
packing geometry) and hydrodynamic conditions.
In what concerns the description of chemical transformations a simpler category of models
consider instaneously reaching of the chemical equilibrium state, while a more accurate category
is based on chemical kinetics to characterize the evolution of system composition.
2.6.1. Simplified (total equilibrium) models
A first mathematical model (Figure 2.17) of a reactive distillation column was presented by
Davies et al (1979). The column is divided into theoretical vapour – liquid contact units for
which instantaneous achievement of thermodynamic equilibrium is considered. The liquid
leaving the unit is transferred to an ideal chemical reactor operating at chemical equilibrium.
Liquid Vapors
Vapor-liquid
contact
Liquid
Chemical
reaction
Liquid Vapors
Liquid
Figure 2. 17 Physical model of the reactive distillation column proposed by Davies et al (1979)
The liquid reactor effluent is then fed to the next unit in order to repeat the previously described
steps. The model is similar to the conventional equilibrium models for distillation, including
possible effects that the chemical transformation may have on the phase equilibrium.
Barbosa et al (1988a,b,c,d) proposed a model that considers these interactions. However, the
hypothesis of instantaneous establishment of chemical equilibrium state leads to unsatisfactory
results with restricted applications, especially in the case of feasibility and conceptual design
studies. Usually, the liquid and vapour compositions are closer to physical liquid-vapour
equilibrium than to the chemical equilibrium. The reduced performances of the models
considering instaneous chemical equilibrium imposed the elimination of this hypothesis and
characterization of chemical transformation kinetic through reaction rates expressions. From this
66
point forward, the term “equilibrium” or “non-equilibrium” refers to phase equilibrium and not
chemical equilibrium.
2.6.2. Equilibrium models
Equilibrium models maintain the mass and heat balance and phase equilibrium equations of the
previous models but also include equations describing the chemical transformations through
chemical kinetics. The contribution of reaction of material balance is considered by the inclusion
of an additional term (Nelson, 1971; Chang et al, 1988; Ciric et al, 1994).
Figure 2.18 presents the simplified scheme of an equilibrium tray. The vapours coming from the
inferior tray and the liquid from superior tray are contacted on the current tray eventually with
the fluids fed or recycled from other areas of the column. The vapours and liquid leaving the tray
are considered in phase equilibrium. A separation column is modelled as a sequence of such
trays.
Extracted
vapors
Liquid Vapors
Che mic al
reaction
Extracted
liquid
Figure 2. 18 Simplified scheme of an equilibrium tray

The equations describing this model are found in literature under abbreviation MESH (M –
material (material balance), E – equilibrium (phase equilibrium), S – summation (normalization
of molar fractions), H – heat (energy balance)).
The balance equations are:
 Total balance
dM j NR NC
 V j 1  L j 1  FjV  FjL  1  sVj  V j  1  s Lj  L j   vi ,r Rr , j j (II. 46)
dt r 1 i 1
 Partial balance
dM j xi , j
   
NR
, j  F j xi , j  1  s j V j yi , j  1  s j L j xi , j   vi ,r Rr , j  j (II. 47)
 V j 1 yi , j 1  L j 1 xi , j 1  F jV xiFL L FV V L
dt r 1
In the above equations, M represents the liquid holdup (vapours one can be neglected at usual
67
pressures), i , r is the stoichiometric coefficient of compound i in reaction r, Rr , j is the rate of
reaction r on tray j,  j is the reaction volume or the catalyst mass, and sj is the ratio between
extracted vapour or liquid flowrate and the flowrate transferred inside the column.
The thermodynamic equilibrium equations for ideal behaviour of phases in equilibrium are
expressed as:
yi , j  K i , j xi , j (II. 48)
where Ki,j represents the equilibrium constant of compound i on tray j.

The normalization equations of molar fractions are written as:
NC NC
x
i 1
i, j  1 or y
i 1
i, j 1 (II. 49)
Some MESH models published in literature contain a term corresponding to reaction heat in the
heat balance equations. However, if the calculation of phase enthalpies is performed using
formation enthalpies of compounds, the reaction heat will be included without the need of an
additional term.
In steady state, the derivatives with respect to time of the model equations become zero.
Some other models may contain equations for pressure drop, control etc. Most of the studies
published in literature are concentrated on development of resolution methods for model
equations in steady state regime. The evolution of algorithms used with this purpose was
influence by: availability of computation power, development of mathematical techniques,
complexity of physical properties (equilibrium constants and enthalpies) and the shape of model
equations. Upon the analysis of algorithms and issues related to their convergence, Friday and
Smith (1964) suggested the simultaneous resolution of all the MESH model equations. However,
the authors did not implement such a technique. The most known studies in this domain are the
ones of Goldstein and Standfield (1970) and Naphtali and Sandholm (1971). The latter provide
various detailed of a case in which Newton-Raphson methods was used. The contribution of
Whitehouse (1964) implemented a resolution method based on Newton-Raphson methods that
allowed the specification of purities, temperature, products flowrates and energy flowrates.
In literature there are two ways of grouping equations and variables: according to
compound or according to trays. Group according to trays is prefered in the case of problems
with more trays than compounds (most of the distillation, absorbtion and extraction processes),
while group according to compounds is recommended to problems with more compounds than
trays.
Even if the MESH type models are relatively simple and provide satisfactory results, in
some cases, the reactive distillation processes do not take place at thermodynamic equilibrium.
68
The resistance to mass transfer between liquid and vapour phases can be representated by the
introduction of tray efficiency. Murphree efficiency is the most used in the simulation of
equilibrium trays and is defined as:
yi , j  yi , j 1
EiV, j  (II. 50)
yi*, j  yi , j 1
where yi,j represents the molar fraction of compound i in vapour phase on tray j and yi,j* is the
equilibrium composition. As the sum of molar fractions is equal to 1, only NC – 1 Murphree
efficiencies are independent. The resistance to mass transfer in packing columns is modelled
using HETP, but the evolution of these values, in case of multicomponent mixtures, is strongly
connected to the the efficiencies values.
The number of specific variables is 2NC+4 (Table 2.20) and the equations of the model
are presented in Table 2.21.
Table 2. 20 Characteristic variables of the equilibrium model

Type of variable Symbol Number of variables
Liquid and vapors flow L and V 2
Compositions of the phases xi and yi 2NC
Temperature T 1
Pressure p 1
Total 2NC+4
Table 2. 21 Equations of the equilibrium model

Type of equation Number of equations
Total mass conservation 1
Component’s mass conservation NC
Energy conservation 1
Thermodynamic equilibrium NC
Molar fractions summing 1
Pressure drop 1
Total 2NC+4
2.6.3. Non – equilibrium models
The development of a non-equilibrium model for reactive distillation is not as direct as in the
case of equilibrium models, since it contained an additional term in the mass balance equations
69
which considers chemical transformation. The first trials to characterize mass transfer in the
reactive distillation processes were presented by Sawitowski et al (1979) based on simplified
description of multicomponent diffusion.
A first rigurous non-equilibrium model of the distillation operation was presented by
Krishnamurthy and Taylor (1985). This model consists of a set of mass and energy balance
equations for vapour and liquid phase together with equations to evaluate the kinetics of mass
and heat transfer. The hypothesis of liquid – vapour equilibrium is considered only at interface.
A schematic representation is presented in Figure 2.19.
Liquid Vapors
C hemical
re action
Figure 2. 19. Schematic representation of non-equilibrium tray

The mass balance equations in liquid phase (equation II. 51) and in vapour phase (II.52) are
independently written:
L j xi , j  L j 1 xi , j 1  F jL xiFL
, j  N i, j  0
L
(II. 51)
V j yi , j  V j 1 yi , j 1  F jV yiFV
, j  N i, j  0
V
(II. 52)
where Ni,j is the compound flowrate transferred at the liquid – vapour interface and represents the
product between compound molar flux and transfer area. The continuity equations of transferred
fluxes are written as:
N iL, j  N iV, j (II. 53)

The total material balance is determined by summation of partial balance equations (II.54
and II.55):
NC
L j  L j 1  F jL   N iL, j  0 (II. 54)
i 1
NC
V j  V j 1  F jV   N iV, j  0 (II. 55)
i 1
The heat balance for the two phases is expressed as:
70
L j H Lj  L j 1 H Lj1  F jL H FL
j  E j  Qj  0
L L
(II. 56)
V j H Vj  V j 1 H Vj1  F jV H FV
j  E Vj  QVj  0 (II. 57)
Ej represents the energy flowrate transferred, for which is written the equation of
interface continuity:
E Lj  E Vj (II. 58)
A hypothesis of the non-equilibrium model is the instantaneous establishment of
thermodynamic equilibrium only at the interface:
yiI, j  K i , j xiI, j (II. 59)

Ki,j is the equilibrium constant of compound i tray j and is calculated based on the temperature
and compositions corresponding to the interface. Another equation to be considered is the
pressure drop:
p j  p j 1  p j 1  0 (II. 60)
where Δpj-1 represents the pressure drop between tray j and j-1 and is calculated according to the
fluids flowrate, physical properties and column internals geometry.
The system of equations is supplemented with relations to calculate material and energy
flowrates transferred at the interface, by Maxwell – Stefan theory.
As the MESH type models, the non-equilibrium tray model needs the calculation of
thermodynamic properties: enthalpies, fugacity and activity coefficients. The evaluation of
driving forces for mass and energy transfer involves the calculation of physical properties such
as superficial tension, diffusion coefficients, viscosity, thermal conductivity, specific heat,
density and interfacial area. Numerical methods used to solve the model are Newton – Raphson
or continuity methods (homotopy continuation).
Liquid Vapors
Mass of liquid
film film
Chemical Chemical
Reaction Reaction
Figure 2. 20 Mass transfer in homogeneous reactive distillation

The non-equilibrium models for reactive distillation operations are not easy to build as in the
71
case of equilibrium models for which a consumption term is added to the mass balance. The
phase in which the chemical transformations take place differenciates the processes in:
homogeneous – for which the reaction (with or without catalyst) takes place only in liquid phase
- and heterogeneous – the solid phase is present to catalyse the transformation.
The homogeneous systems involve the following stages (Figure 2.20): mass transfer through
vapour film, mass transfer through liquid film with chemical reaction and chemical reaction in
liquid mass. The heterogeneous processes are characterized by the presence of a catalyst in solid
phase. This can be: porous (Raschig rings of ion exchange resins – Amberlyst) or non-porous
(various metal plated solid forms). The stages taken in the presence of non-porous catalysts
(Figure 2.21) are:
 Transport of reactants from vapour phase to liquid phase
 Transport of reactants from liquid mass to catalyst surface
 Surface reaction
 Transport of reaction products from catalyst to liquid mass
 Transport of reaction products from liquid phase to vapour phase
The first and the last stages are modelled using Maxwell – Stefan theory. The surface reaction
represents the limit condition for the mass transfer process between liquid and solid. In some
cases, some of these stages can become rate limiting step allowing some simplifications.
Liquid Liquid Vapors
Mass of liquid
film film film
C a ta l ys t
Chemical
reaction
Figure 2. 21 Transport processes in reactive distillation in the presence of non-porous catalysts

However, most of the time, the catalyst is porous so that there are more transport processes than
in the previous case. The stages in this case are:
 Transport of reactants from vapour phase to liquid phase
 Transport of reactants from liquid phase to catalyst surface
 Diffusion together with chemical reaction in the pores of the catalyst grains
 Transport of reaction products from the catalyst surface to the mass liquid
72
 Transport of products from liquid phase to vapour phase.
The variables of the non-equilibrium tray are grouped in Table 2.22 and the characteristic
equations in Table 2.23.
Table 2. 22 Variables of the non-equilibrium model

Type of variable Symbol Number of
variables
Liquid and vapors flow L and V 2
Composition in the mass of phases xi and yi 2NC
Temperature in the mass of phases TL and TV 2
Mass fluxes transferred to the interface Ni NC
Interface composition of phases xil and yil 2NC
Interface temperature Tl 1
Pressure p 1
Total 5NC+6
Table 2. 23 Equations of the non-equilibrium model

Type of equation Number of equations
Total mass conservation 2
Component’s mass conservation 2NC
Energy conservation 2
Mass transfer 2NC-2
Energy transfer 1
Thermodynamic equilibrium NC
Molar fractions summing 2
Pressure drop 1
Total 5NC+6
The model of a reactive distillation column, besides the equations mentioned above, also
contains equations customizing the process. In this way, the column configuration must be
specified (the type and number of trays or the type and height of packing, condenser and reboiler
type, number and position of feed streams, energy flowrates used, reflux ratio, pressure) together
with a model to calculate pressure drop, thermodynamic and physical properties and mass and
energy transfer coefficients. A kinetic model to describe the chemical transformations must also
be specified, as well as the quantity of catalyst and its characteristics.
73
Conclusions
In the present chapter the state of the art and motivation of the work are presented. The car fuels
used in engines with internal combustion originate from distillate fractions obtained by crude-oil
processing and possess usually an octane number under the interval of values required (87–93).
The octane number enhancement by using tetra-ethyl-lead as fuel additive induces great
pollution problems, the toxic effect of Pb aerosols in exhaust gases being well known. The
replacement of tetra-ethyl-lead started to be effective along with the introduction of
environmental protection restrictions in USA by “Clean Air Act Amendments” (CAAA) in 1990.
To cover the octane deficit appeared by tetra-ethyl-lead banning, the only solution accepted at
refineries level was the usage of tertiary ethers derived from olefins C5-C7, among which the
most spread is methyl-tert-butyl-ether (MTBE). The aliphatic tertiary ethers with practical use
contain in their molecule two alkyl groups, one tertiary (tert-butyl or tert-amyl) and the other
primary (methyl, ethyl, and rarely isopropyl) (e.g. MTBE, ETBE, TAME, TAEE). Nowadays,
TAME is one of the most used compound as gasoline additive and its synthesis is studied in
more detail in this thesis.
TAME is produced by reaction of methanol with the tertiary olefins contained in the C5 fraction
obtained from the oil catalytic cracking, i.e. 2-methyl-1-butene and 2-methyl-2-butene.
Therefore, there are two eterifications reactions, one for each olefin, and a third reaction of
isomerization between both olefins. The reactions only take place when catalized and the
isomerization is faster than the eterifications. The 2-methyl-1-butene is more reactive than the 2-
methyl-2-butene. The reaction is exothermic and a little excess of methanol is employed to avoid
the dimerization and polymerization of the alkenes. The most used catalysts are Amberlyst 16,
Amberlyst 35, Purolite-type catalysts, a.s.o. This introductory chapter provided details related to
physical and chemical properties of TAME, the environmental impact of its employment as
gasoline additive, the industrial synthesis procedures, thermodynamics and kinetics of the
synthesis process. A detailed literature survey was presented in this chapter, covering many
aspects describing the synthesis particularities.
Reactive distillation was proved to industrially provide the most efficient processes for TAME
production. The most known technology of this type is CDEtherol. Several advantages of this
process are that a very high conversion is attained, the heat of reaction is used directly for the
distillation, high reaction rates as the mixture is keep at its boiling point, better temperature
control, avoidance of azeotropes, etc. Although some commercial simulators provide the
possibility to calculate the reactive distillation, this process has not a very spread use in the
industry because there are not systematic methodologies for its computation, analysis and design.
74
In the present work, TAME synthesis by catalytic distillation is studied with the aim to get some
new highlights based on new contributions to the methodology to study this kind of systems. The
mathematical models already used for the design calculations of reactive distillation units are of
different complexities.The simplest ones are based on a total thermodynamic equilibrium
assumption. However, these proved to be too approximate. Intermediary complexity models
assume achievement of liquid – vapour equilibrium, considering the chemical transformation
kinetics. The most accurate models consider the kinetics of both liquid – vapour mass transfer
and chemical transformation.These are of higher complexity and include a high number of
parameters whose values are different to determine with necessary accuracy. Therefore, the
intermediary complexity models seems to be the adequate / rational ones, especially for
conceptual design purpose.
75
Chapter 3
The kinetics of TAME synthesis on solid acid catalysts
3.1. Experimental study of isoamylenes etherification with methanol
As presented in previous section, there is an important number of papers on thermodynamics and

kinetics of TAME synthesis scheme. The purpose of this study is to bring new contributions to
these topics, answering some questions to subjects not yet tackled such as to elucidate the
kinetics of TAME synthesis from C5 fraction of FCC enriched with isoamylenes, as obtained in
an oil refinery with Amberlyst35 used in practice. Experimental study targets the following
objectives suggested by further applications in reactive distillation:
• Role of temperature on reaction system (experiments are performed at 60–70–80–90 oC);
• Role of catalyst particles dimension using sieved fractions of catalyst at different
temperatures (d < 0.63 mm, 0.63 < d < 0.8 mm, 0.8 < d < 1.0 mm);
• Role of isoamylenes on process kinetics using C5 fraction enriched with 2M2B (25%,
30%, 35%, 40%).
The experimental program is presented in the next Table 3.1. Main parameters considered in
coding the experiments are:
• temperature – Temp. ºC
• alcohol to isoamylenes ratio – MeOH:IA
• initial concentration of isoamylenes in reaction mixture – IA0 (%)
• concentration of catalyst added to reaction mixture (gcat/gmixture)
The details about experiments are given in Annex as well as on CDROM.
3.1.1. Materials and method
The reactants used were methanol anhydrous 99.8% (Sigma-Aldrich) and C5 fraction
from FCC with a content of 18 – 22% (wt) active isoamylenes for the etherification reaction, 2-
methyl-1-butene (2M1B) and 2-methyl-2-butene (2M2B), in a molar ratio of approximately 2:1.
The AMBERLYST-35 ion-exchange resin produced by Rohm and Haas was used as
catalyst. It has the following physico-chemical characteristics (as specified by the producer):
- acidity, mgH+/g = 5.2
- microspheres (granules) dimension (diameter), mm = 0.4÷1.2
- pores volume, mL/g = 0.41
- average pores diameter, nm = 20
76
- specific area, m2/g = 44
- moisture retention = 55%
Table 3. 1 Experimental plan

No. Scope Temp. (ºC) MeOH:IA C5 Fr. (g) MeOH (g) IA0 (%) Cat. (g) Notes
1 Role of 60 1.1:1 100 10 19.6 5
2 temperature 60 1.1:1 120 12.5 19.9 6
3 60 1.1:1 120 12.5 19.9 6
4 70 1.1:1 100 10.0 19.6 5
5 70 1.1:1 120 12.5 19.9 6
6 80 1.1:1 100 10.0 19.6 5
7 80 1.1:1 120 12.5 19.9 6
8 80 1.1:1 120 12.5 19.9 6
9 80 1.1:1 120 12.5 19.9 6
10 80 1.0:1 120 12.0 21.0 3.5
11 80 1.0:1 120 12.0 21.0 3.5
12 80 1.1:1 120 12.5 19.9 6
13 90 1.1:1 100 10.0 19.6 5
14 90 1.1:1 120 12.5 19.9 6
15 90 1.1:1 120 12.5 19.9 6
16 90 1.1:1 120 12.5 19.9 6
17 120 1.1:1 120 12.5 20.0 2.65
18 Role of particle 90 1.15:1 120 12.5 19.5 6
19 dimension 80 1.15:1 120 12.5 19.5 6
20 d<0.63 mm 90 1.15:1 120 12.5 19.5 6
21 80 1.0:1 120 12.0 21.0 3.5
22 90 1.15:1 120 12.5 19.5 6
23 90 1.15:1 120 12.5 19.5 6
24 0.63<d<0.80 mm 80 1.15:1 120 12.5 19.5 6
25 80 1.0:1 120 12.5 21.0 6
26 70 1.0:1 120 12.5 21.0 6
27 80 1.0:1 120 12.0 21.0 3.5
28 90 1.15:1 120 12.5 19.5 6
29 0.80<d<1.0 mm 80 1.15:1 120 12.5 19.5 6
30 80 1.15:1 120 12.5 19.5 6
31 90 1.15:1 120 12.5 19.5 6
8 g excess
32 Role of IA 80 1.15:1 109 15.4 25 6
2M2B
15 g excess
33 initial 80 1.15:1 99.5 18.1 30 6
2M2B
21.8 g excess
34 concentration 80 1.15:1 90 20.7 35 6
2M2B
28 g excess
35 80 1.15:1 81.4 23.1 40 6
2M2B
21.8 g excess
36 80 1.15:1 90 20.7 35 6
2M2B
77
Before use, the catalyst was washed with a few bed volumes of demineralised water, until
the effluent is clear and neutral. Dry ion exchange resins can be obtained by first displacing the
moisture with a few bed volumes of a hydrophilic solvent such as methanol or isopropanol and
then drying under vacuum for 24 h at 100 oC.
The operating temperatures were in the range 60oC to 90oC, and operating pressures were
higher than 10 bar. The catalyst quantity/concentration used in a batch was 6 g. The methanol
quantity was so calculated to correspond to a ratio of 1.1:1 methanol to isoamylenes. Some
experiments were also performed with MeOH/isoamylenes ratios of 1.15:1 and 1:1.
3.1.2. Set-up description
The main equipment is the reactor of autoclave-type, model BERGHOF SS316TI (Figure
3.1). The batch set-up for kinetic and thermodynamic studies (Figure 3.2) consists mainly of a
reactor (R), two thermostats (UT1 and UT2) and a gas-chromatograph for samples analysis.
The It is provided with a thermostatic jacket coupled to the apparatus delivering thermal
agent (thermostats) by threaded fittings. Inside, the autoclave presents a stainless steel enclosure
resistant at high pressure, in which a Teflon recipient can be introduced for performing the
synthesis reaction. Mixing the reaction mass is performed using a pallet stirrer driven through a
magnetic coupling by an AGM engine.
The main characteristics of the autoclave are the following:
- volume, mL max. 800
- maximum pressure, bar 200
o
- maximum temperature, C 230
- external diameter, mm 92
- internal diameter, mm 64
- height PTFE insert, mm max. 261
The autoclave is provided with the following joints:

Cover (lid):
- valves for gases inlet and vent
- pressure sensor and safety disk
- manometer and safety valve
- thermocouple
- samples fitting
The jacket presents fittings for:
78
- inlet thermal agent hot/cold
- outlet thermal agent hot/cold
The AGM engine is connected to the magnetic couple of the stirrer by a system of cardanic-type
joints, which permit to centre the rotation movement of the stirrer.
The stirrer engine is provided with a speed regulation system and a display which indicates the
speed value.
Coupling entrainment stirring Valves for gases inlet/vent
Manometer
Autoclave lid
Closing system
PTFE inside
Stainless steel body
Figure 3. 1 Autoclave-type reactor of the etherification plant
The thermostat UT1 delivers and controls the heating oil is of JULABO ME-12 type. It
presents a 12 litre capacity tank, in which the thermal agent is stored, and a body made of a
command block and a thermal agent delivery pump. The thermostat is provided also with a
system of programming the operating temperature, of alarming in case this one is exceeded or in
case the liquid level in the tank decreased, and of transmitting the temperature value to a
computer.
Thermostat UT2 delivers and controls the reactor cooling agent is of LAUDA RE112
type. It is provided with a 12 litres capacity thermal agent storage tank and a block of command
and pumping the cooling agent.
The set-up presents three main circuits:
79
- Thermal agent circuit is made of pipes which connect the two thermostats to the
autoclave jacket by inlet-outlet thermal agent lines. For cooling or heating the thermal
agent, the circuit is provided with two 3-way ball valves on the panel to switch the
circulation of cold or hot agent through the autoclave jacket.
- Inert gas circuit, necessary to reactor purge and to establish the proposed operating
pressure, connects the pressure reducer mounted on the gas cylinder and the
autoclave. The circuit also contains two needle valves for fine-tuning of pressure, one
situated on the panel and the other on the autoclave lid.
- Gases and vapours exhaust circuit in the autoclave is connected to the purge line, the
escapement of safety valve and safety disk, which are linked by a cross-type
connection. From here, only one exhaust line goes out, directed towards the exterior
of the laboratory, gases and vapours being purged into the atmosphere.
The purge line is used for reducing the operating pressure or in case of depressurising
during set-up shut-down. The exhaust of gases or of vapours is made manually, by actuating a
needle valve situated on the reactor lid.
The safety valve, placed on the autoclave lid, is regulated to open in case of accidental
pressure increase in the domain 155 – 206 bar.
The safety disk is provided for limit situations in which the pressure suddenly increases
to high values and the safety valve does not cope with the fast escapement of over-pressure. The
safety disk mounted on the autoclave breaks at maximum pressure of 250 bar.
For an optimum tracking of operating parameters, the set-up was endowed with a data interface.
This permits the transmission of temperature and pressure values, determined by sensors in
direct contact with the working environment, to a computer on which the momentary parameters
are registered and presented as a value or as a graph.
The rotation speed of the stirrer is a very important parameter for kinetic and
thermodynamics determinations. Its value is displayed continuously on the mechanical stirrer
drive module.
To increase the accuracy of sampling and analysis (avoiding losses of light volatile
compounds), the set-up was provided with a sealed system which connects the sampling device
to the VARIAN 3800 chromatograph, where analysis of the reaction mixture is performed at pre-
established intervals.
80
Purge Purge
Nitrogen
500
rpm AGM
5
PC 1 GC
4 TT
6
3
2 M
∼ PT
1 7
TT1 ∼
TT 80 OC
TT2
TT3
IF TT4
PT1
UT 1 R
PC 2
∼
UT1 – Heating circuit 1 – Sampling fitting
TT 20 OC UT2 – Cooling circuit 2 – Escapement fitting safety valve
R – Reactor autoclave 3 – Escapement fitting safety disk
IF – Data interface (Analog/numeric 4 – Nitrogen inlet
UT 2 GC – Chromatograph convertor) 5 – Purge gases
AGM – Stirring engine 6 – Thermocouple
PC1,2 – Computers 7 – Pressure sensor
Figure 3. 2. Batch plant scheme for kinetic studies
81
3.1.3. Sample analysis
The analysis are performed in a gas chromatograph (GC) model VARIAN GC3800
equipped with a FID detector and with a CP - SIL5CB –type GC column with the following
characteristics: length 50 m, diameter 0.32 mm, film width 0.4 µm. The carrier gas is hydrogen.
The volume of sample injected is 1 µL. During the experiments, the response factors were
checked using calibration solutions. All compounds were calibrated to obtain quantitative results.
The main components of C5 cut from FCC light gasoline from catalytic cracking are C5
hydrocarbons with high volatilities from isopentane range. For this reason, the current set-up for
the etherification of reactive olefins is provided with an automatic sampling system direct line
from the reactor to gas chromatograph, based on a liquid valve mounted on the VARIAN 3800 –
type chromatograph . This is a 4-ways VALCO valve for liquids driven by the chromatograph
via a pneumatic actuator. All the lines are stainless steel, carefully sealed to prevent any loss of
light compounds.
A FID detector is used, i.e. the detector receives a signal that is integrated in an Area which
is usually directly proportional to carbon number of moles burned. The proportionality constant
is known as Response Factor (RF) and, along with the retention time, is characteristic to each
chemical component. Although all the chromatograph variables and column operation are kept
fixed, the Response Factor can change slightly from one sample to another. To avoid these
variations, an internal reference standard is used. For concentrated mixtures, it is easier to
determine ratios of RFs, used to calibrate the GC according to the ratio of number of moles (n)
versus ratio of areas (A). Instead of usual procedure to calibrate the GC with binary mixtures of
samples that do not accurately reproduce the behaviour of the complex mixture used, the initial
weight of methanol is used as reference calibration parameter, the quantity of isopentane (iC5) as
internal reference standard and the other values of RFs are obtained according to stoichiometry.
The calibration curve of MeOH and iC5 would be:
AMeOH RFMeOH nMeOH

= ⋅ (III. 1)
AiC 5 RFiC 5 niC 5
As the iC5 is an inert that is not reacting, its number of moles and its chromatographic
area are constant during the experiment. The number of moles of iC5 and the response factors
can be placed together in a constant. Therefore, equation (III.1) can be written:
AMeOH RFMeOH AMeOH
= ⋅ nMeOH where nMeOH = K ⋅ (III. 2)
AiC 5 RFiC 5 ⋅ niC 5 AiC 5
82
The area corresponding to each chemical component is determined by gas
chromatograph. The value of K from equation (III.8) is calculated easily at the initial point:
AiC 5
K = nMeOH
0
⋅ 0
(III. 3)
AMeOH
0
where nMeOH is the stoichiometric number of MeOH moles added initially to the probe.
Substituting the calculated value of K at the initial time to the equation (III.2), the
number of moles remaining in the reactor are directly calculated from the ratio of areas of MeOH
and iC5 determined by gas chromatograph.
Once the number of moles of MeOH is determined, the number of moles of TAME is
calculated according to the stoichiometry (equation III.4):
nTAME = nMeOH
0
− nMeOH (III. 4)
A similar expression as equation (III.2) is used for the mixture TAME – iC5. The values
of the areas are determined experimentally by the gas chromatograph and number of moles of
TAME is calculated from equation (III.4). As the iC5 is an inert, the ratio appearing in the
equation (III.5) must be constant. Slight variations on this value are attributed to experimental
error.
ATAME RFTAME
= = ct (III. 5)
nTAME ⋅ AiC 5 RFiC 5 ⋅ niC 5
The ratio of the RFs for MeOH and TAME can be also determined, the value should be
constant but slight variations are attributed also to experimental error.
AMeOH
RFMeOH A
= TAME = ct (III. 6)
RFTAME nMeOH
nTAME
The C5 fraction is used instead of pure components for getting as close as possible to the
industrial problem. It is assumed that initial quantity of isoamylenes is not known. This value
can be estimated using the initial conditions (equation III.5) and the conditions after a time t
(equation III.6). Both equations allow calculating the initial number of moles of isoamylenes:
0
nIA RF A0
t = 0; = iC 5 ⋅ 0IA (III. 7)
niC 5 RFIA AiC 5
For an arbitrary time t, can be written:
83
0
nIA − nTAME RFiC 5 AIA
t = t; = ⋅ (III. 8)
niC 5 RFIA AiC 5
Consequently,
nTAME
0
nIA = (III. 9)
A0 ⋅ A
1 − iC0 5 IA
AIA ⋅ AiC 5
For each experimental point, it is possible to calculate from (III.9) a different value of
initial moles of IA, due to the experimental errors, therefore the average of all the results is used
0
as initial value ( nIA ). The number of moles of IA at any time can be calculated from the
stoichiometry of the reaction (equation III.10). Assuming initially there is no TAME in the
feedstock:
nIA = nIA
0
− nTAME (III. 10)
The area of IA is the sum of two areas: the area of 2M2B and of 2M1B. As both isomers
are chemically very similar, it is assumed that both have the same RF. From the equations
(III.11) and (III.12) can be determined the equation (III.13) for the number of moles of 2M2B
and 2M1B.
n2 M 1B A2 M 1B
= (III. 11)
n2 M 2 B A2 M 2 B
n2 M 2 B + n2 M 1B = nIA (III. 12)
nIA
n2 M 2 B = and n2 M 1B = nIA − n2 M 2 B (III. 13)
A2 M 1B
1−
A2 M 2 B
The number of moles of inert is unknown. However, there are a lot of some other inerts,
more than 40 components, whose sum of area is almost double iC5 area. The areas of iC5 and
other inerts are nearly a constant value.
niC 5 = AiC 5 and ninerts = Ainerts (III. 14)
Once the number of moles is determined for all the components, the molar fractions can
be calculated by equation (III.15). The results of the mole fractions include the error due to
unknown quantity of inert moles.
ni
xi = (III. 15)
nTOTAL
84
niC 5 + nin AiC 5 + Ain
xir = ≈ (III. 16)
nTOTAL ATOTAL
But mass of each individualised component can be calculated according to its molecular
weight (MW). This equation is not used for the inerts (iC5 + others) as the MW of inerts is not
known. So, it can be written:
mi = MWi ⋅ ni
where i = MeOH, TAME, 2M1B, 2M2B (III. 17)
The advantage of using mass fractions eliminates the error introduced by the assumption
that the number of moles is proportional to the area of chromatogram. As total mass of the C5
fraction ( mC0 5 fr ) added to the reactor is known, mass of inert can be calculated as mass of 2M1B
and 2M2B known at the initial time. On the other hand, total mass of inert is constant during all
the experiment. So, mass of inert can be calculated by equation (III.18).
minert = mC 5 fraction − m20M 2 B − m20M 1B

(III. 18)
Once the mass for all the components in the mixture is determined, miC5 mass fraction for
all the components can be determined according to equation (III.19), with mTOTAL = mC0 5 fr + mMeOH
0
mi
% mi = ⋅ 100
mTOTAL (III. 19)
In this way, using the initial mass of MeOH and C5 fraction, the areas from the gas
chromatograms and the stoichoimetry of the reaction, it is possible to calculate the mass fraction
of all the components of interest (i.e. MeOH, 2M1B, 2M2B and TAME) for some reaction
scheme.
3.1.4. Operating Procedure
3.1.4.1. Set-up start-up
Preparation of the set-up for start-up

- It is checked that all the fittings on the autoclave lid are tightened, so that the system
tightness is assured;
- It is checked that all the valves are closed, including the ones on the thermal agent circuit;
- The ventilation system of the set-up is started;
85
- It is checked if the stainless steel inside or the PTFE recipient are empty and clean.
Introduction of the catalyst and alcohol

- The pre-established quantity of catalyst is measured and introduced in an especially-made
PTFE capsule, the capsule is closed and mounted into autoclave PTFE lid (in the inlet
corresponding to the nitrogen admission valve);
- The desired quantity of alcohol is also measured and introduced in the autoclave;
- The C5 fraction corresponding to the established molar ratio is measured and quickly
introduced into the autoclave;
- The autoclave is closed and the two screws are tightened.
Checking the tightness and system inertness
- The quick connections to the autoclave lid are set up (the nitrogen feed line to the purge
valve and the corresponding ones for safety valve and rupture disk);
- It is checked if the valve on the low pressure part of the pressure reducer mounted on the
nitrogen cylinder is unscrewed;
- The valve on the cylinder is open and the valve for pressure regulation on the reducer is
pressed until a pressure of 15 barg is reached;
- The pressure transducer is connected to electrical network;
- The valve on the nitrogen line (placed on the panel) is open as well as the one for nitrogen
admission into autoclave, located on the lid (purge valve), waiting to reach a pressure of
10-12 barg inside the autoclave (the value on the display is checked);
- The valves on the nitrogen line and on the lid are closed and it is checked if the pressure in
the autoclave remains constant during 30 minutes;
- In case the pressure decreases, all the joints on the autoclave lid and the panel valves are
checked with soap foam. The leakiness found is fixed after a previous pressure vent;
- After fixing the leakiness found, the nitrogen line is disconnected from the purge valve and
the purge joint is connected; the purge valve is open on the autoclave and the pressure
inside is exhausted until a value of 6-7 barg is reached;
- The purge valve is closed. The purge line is disconnected and the nitrogen line is coupled
again to the purge valve. The nitrogen valve on the panel and then the one on the autoclave
are open and so that the pressure slowly increases inside up to 10-12 barg;
- The two nitrogen valves are closed and the system is purged as previously described up to
a pressure value of 6-7 barg;
86
- The nitrogen admission operation and the purging are repeated three times and finally
nitrogen is introduced until a desired value of pressure is reached;
- All the valves are closed after system inertness is performed; the nitrogen admission line is
connected to the nitrogen valve and the purge line to the purge valve.
3.1.4.2. Experimental procedure
The thermostats, the stirrer, the computer for monitoring the operating parameters and the
VARIAN chromatograph are startup;
- The parameters transmitter is connected to the computer by USB interface;
- The temperature on JULABO thermostat is programmed at the pre-established operating value
+ 10 – 12oC (to recover the losses on the circuit);
- The hot thermal agent circuit is connected by positioning the two actuators of the 3-way;
- Stabilization of the desired operating temperature inside the autoclave is monitored; in case it is
needed, the temperature of the thermal agent circulating inside the jacket is increased or
decreased;
- The pressure value in the autoclave is monitored during heating and the excess pressure is
exhausted by opening the purge valve;
- When the operating temperature and pressure are reached, the stirrer is started up and the
rotation speed is adjusted to 500 rpm. Previous experiments evidenced that over 500 rpm, the
influence of external diffusion is negligible. This stirring intensity was found also adequate by
Ruhko and Krause (1995) in a similar study.
- The nitrogen admission valve on the panel and then the one on autoclave lid are open. Due to
the nitrogen pressure accumulated in the catalyst capsule, its lid is broken and the catalyst is
discharged in the liquid mixture of reactants;
- Catalyst discharge represents the “0” moment of the experiment and from this point, the
experimental time is monitored.
- During the test, the temperature and pressure values are monitored and maintained constant.
Error for temperature measurement is ± 0.1 oC and for pressure ± 0.01 bar.
- For sampling and chromatographic analysis during the experiment, the procedure involves the
following steps:
• A program for sampling and samples analysis during the experiment is established (in the
first hour the chromatographic analysis was performed at intervals of 15 minutes, in the
second hour at interval of 30 minutes, and then, until the thermodynamic equilibrium is
reached, the interval of sampling and analysis is of one hour);
87
• The automatic sampling line (autoclave – chromatograph) is made of the line autoclave –
chromatograph liquid valve – purge – nitrogen injection line. On this circuit, there is a 3-way
valve which allows to empty the sampling line in the autoclave by blowing with nitrogen and
to purge the gas sampling line through another valve;
• Before the automatic sampling, the 3-way valve is shifted on the nitrogen blowing line to
blow back the liquid on the sampling line into the autoclave. The nitrogen admission valve
on the panel is open and the pressure in the autoclave is monitored (the pressure increase
must be of maximum 2 barg);
• The nitrogen admission valve is closed and the 3-way valve is shifted from sampling line to
purge position. The purge valve on this circuit is kept open until drops of liquid arrive to a
collecting vessel;
• The purge valve on this line is closed and sample is injected into the chromatograph
automatically;
• For each sampling and sample analysis, the procedure to follow is the same as described
above.
- The duration of the experiment will be chosen in function of the desired goal; it may vary
from 3 hours up to 12 – 14 hours, depending on operating parameters.
At the end, the reactor is cooled and the set-up is shut down following a suitable pre-
established procedure.
3.1.5. Experimental results
3.1.5.1. Influence of reaction temperature
The influence of the reaction temperature has been tested performing experiments at four
reaction temperatures: 60oC, 70oC, 80oC and 90oC. In each experiment, 120g of C5 fraction, 12.5
g of MeOH and 6 g of catalyst Amberlyst-35 have been charged into the autoclave. The results
of these experiments are presented in Figure 3.3.
The curves indicate an expected result that as the reaction temperature increases, the reaction rate
increases as well. At 60oC a slower increase is noticed compared to the experiments performed at
70, 80 and 90oC. The difference between the results obtained at 80oC and 90oC is not of great
magnitude, the curves follow almost the same trajectory. This happens as consequence of
internal diffusion influence on the process kinetics stronger at 90oC. The maximum mass fraction
obtained is decreasing with the temperature increase due to temperature influence on the
equilibrium isoamylenes conversion.
88
18
16
14
fraction, %
12
mass wt% 60C
10 70C
TAMETAME
80C
8
90C
6
0
0 100 200 300 400 500 600
Time, min
Figure 3. 3 Time evolution of TAME concentration at different temperatures. The initial content
of reaction mixture was 120g C5 fraction, 12.5 g MeOH and 6 g catalyst Amberlyst-35 (unsieved
catalyst grains)
3.1.5.2. Influence of catalyst grain size
The influence of catalyst granule size has been studied in a series of experiments
developed at 80oC and 90oC, since it is thought that at these temperatures, the influence of mass
transfer inside the catalyst particle may become significant. Three classes of grain dimensions
were tested, corresponding to the intervals 0.8 – 1 mm, 0.63 – 0.8 mm and grains smaller than
0.63 mm. Figures 3.4 and 3.5 illustrate the experimental results at the analysed temperatures for
the granule size intervals studied. The initial quantities of reactants and catalyst for these
experiments are as follows: 120 g of C5 fraction, 12.5 g of MeOH and 6 g of catalyst Amberlyst-
35. The curves in Figure 3.4 are obtained for the experiments performed at 80 oC. The results
represented for experiments performed on catalyst grains in the interval 0.8 – 1 mm and 0.63 –
0.8 mm almost overlap. These indicate that the difference between the results of the experiments
performed on unsieved catalyst grains and sieved ones (sizes of grains smaller than 0.63 mm,
0.63 < d < 0.8 mm, and 0.8 – 1 mm) is around 11 %. The curves represented in Figure 3.5 are
obtained for experiments performed at 90oC. These show that the difference between the results
corresponding to different catalyst grain sizes is much greater than those obtained at 80oC. This
fact can be explained by the increase of the reaction rate which occurs when increasing the
reaction temperature from 80oC to 90oC. In consequence, it can be noticed that the catalyst grain
dimensions determine a slow-down due to the limitation induced by internal diffusion. In this
case, the influence of the catalyst grain dimensions on the internal diffusion cannot be neglected.
89
20
18
16
14
80C unsieved
TAME wt %
12 80C 0.8-1
10 80C 0.8-1
80C 0.63-0.8
8
80C <0.63
6
4
2
0
0 20 40 60 80 100
Time, min
Figure 3. 4. Experimental results at 80oC for various granule sizes
18
16
14
12
TAME wt %
10 90C unsieved
90C 0.8-1
8 90C <0.63
6
4
2
0
0 50 100 150
Time, min
Figure 3. 5. Experimental results at 90oC for various granule sizes
90
From the diagrams presented in Figures 3.4 and 3.5 it can be observed that the internal
diffusion influence on the overall process kinetics begins to be significant over 80oC. Below this
temperature, the decrease of isoamylenes conversion due to this factor is approximately 11%, a
level having the same order of magnitude as the error in the measurements of effective diffusion
coefficients in the porous catalyst matrix. Consequently, in the kinetic studies developed in the
next section will be considered unsieved catalyst data obtained at temperatures up to 80oC.
The same approach was followed by Rihko and Krause (1995) in a study of TAME
synthesis over a catalyst having the same acidity as the one used in this work.
3.1.5.3. Effect of isoamylenes concentration
For influence of isoamylenes (IA) concentration investigation on process kinetics, several

experiments are performed with C5 fraction (20.7% IA) and C5 fraction enriched with IA (adding
2M2B), but keeping the same methanol to IA ratio (1.15:1). Three enriched C5 fractions are used
in this aim containing 26.12% IA, 36.16% IA and 41% IA respectively. The experiments were
performed at 80oC, due to the presumption that the effect of catalyst grain dimensions can be
neglected at this reaction temperature. The quantities of reactants used for these experiments
were varied accordingly, in order to maintain the same initial reactants ratio MeOH/Isoamylenes.
In the experiment with no isoamylenes enrichment, 120g of C5 fraction, 12.5 g of MeOH and 6 g
of catalyst Amberlyst-35 were used. When the C5 fraction containing 26.12% isoamylenes was
used, the initial quantities of reactants become: 109 g of C5 fraction (8 g of isoamylenes added)
and 15.4 g of MeOH. In case of the C5 fraction containing 36.16% isoamylenes, the initial
quantity of C5 fraction used was 90 g (21.8 g of isoamylenes added) and 20.7 g of MeOH. For
the C5 fraction containing 41% isoamylenes, the initial quantities of reactants become: 81.4 g of
C5 fraction (28 g of isoamylenes added) and 23.1 g of MeOH. Figure 3.7 illustrates the results of
these experiments, presenting the effect of isoamylenes concentration on the maximum
concentration of TAME obtained. In the case of experiments performed with no enrichment in
isoamylenes of the C5 fraction, the maximum mass fraction of TAME that can be obtained is
around 15% compared to 25% that can be reached in case of 41% enrichment in isoamylenes of
the C5 fraction, but these values are relative to the dilution of the reaction medium. All the curves
obtained reflect the dilution relative to each experiment. More diluted is the reaction medium,
the reaction rate is slower. This result is highlighting a positive order of isoamylene
concentration in the etherification rate expression. Therefore, it is demonstrated that the
isoamylene molecules do not compete with methanol in the adsorption of the acid sites of the
catalyst.
91
30
25
20
TAME wt %
no enrichment
26.12%
15
36.16%
41%
10
0
0 50 100 150 200 250
Time, min
Figure 3. 6. Effect of isoamylenes concentration in the C5 fraction at 80oC.
3.2. Modelling reaction kinetics for TAME synthesis
Kinetic models are built including some parameters to be determined by processing

experimental data. The kinetic model consists of dependent variables (y) vector predicted by a
model vector function. The arguments of this function are vector of independent variables (x)
and vector of parameters (p).
Kinetic models can be:
• Algebraic
y = f ( x, p ) (III. 20)
• Differential – generally as ordinary differential equations (ODE)
dy
= f ( x, p ) (III. 21)
dΘ
where Θ = time, length, mass, volume, a.s.o.
If the model is partial differential equations (PDE), it can be transformed into ODE type
model by discretisation. Dependent variables usually correspond to concentrations or molar or
mass amounts for batch or semi-batch reactors, or concentrations or molar flows or mass flows
for plug-flow reactors or fixed bed reactors.
The dependent variable values ŷ are measured experimentally in different experimental
conditions, i.e. for different values of independent variable vector x. Regression analysis purpose
is to determine the values of parameter vector p giving good agreement between values
measured experimentally of dependent variable ŷ and model predicted values y. Usually,
92
independent variables are time, concentration, pressure, temperature. Kinetic models parameters
could be rate constant, chemical equilibrium constant, mass/heat transfer coefficients. They
present a non-linear dependence in the kinetic model. This is the reason for using mainly non-
linear regression techniques.
As already underlined in the previous section, the conditions in liquid phase for
etherification reaction are highly non-ideal (Colombo et al, 1983, Rihko et al, 1994), it is
recommended to use activities in kinetic equations. In the calculations of activities, we used the
classical UNIFAC method, as described by Reid et al. (1986), and the group contribution values
published therein (see Appendix I).
The GC diagrams did not evidence significant concentration of heavier products in the
final reaction mixture, so that the only reactions considered are those of etherification and
isomerization. These correspond to the reaction network presented in Figure 2.9 (see Chapter 2),
which gives rates of formation for each component:
rM = −r1 − r2 (III. 22)

r1B = − r1 − r3 (III. 23)
r2 B = −r2 + r3 (III. 24)
rT = r1 + r2 (III. 25)
where r1, r2 represent the reaction rates for etherification of 2M1B and 2M2B respectively, r3 –
reaction rate for 2M1B isomerization.
Kinetic models can be developed starting from mechanistic models of chemical reactions
presented in Chapter 2. Experimental data can validate a specific kinetic model by simulation of
experimental reactor. Among the published kinetic models presented in Chapter 2, the most
realistic appear to be the model of Rihko et al (1995, 1997), who developed a rate expression
based on heterogeneous ER mechanism.
3.2.1. Comparison of experimental results with values calculated based on

kinetic models published in literature
In the first step, we compare the prediction of the Rihko et al (1995, 1997) model with
our experimental data. The expressions for the reaction rates defined by relations (III.26) –
(III.28):
93
⎛ aT ⎞
k1aM a1B ⎜1 − ⎟
r1 = ⎝ K1aM a1B ⎠ (III. 26)
⎛ KT ⎞
⎜ aT + aM ⎟
⎝ KM ⎠
⎛ aT ⎞
k2 aM a2 B ⎜1 − ⎟
r2 = ⎝ K 2 aM a2 B ⎠ (III. 27)
⎛ KT ⎞
⎜ aT + aM ⎟
⎝ KM ⎠
⎛ 1 a2 B ⎞
r3 = k3 a1B ⎜1 − ⎟ (III. 28)
⎝ K 3 a1B ⎠
For the temperature dependence of equilibrium constants K1, K2, K3, the model uses the
expressions, proposed by Rihko and Krause (1995):
K 1 = exp(− 8.3881 + 4041.2 T ) (III. 29)
K 2 = exp(− 8.2473 + 3225.3 T ) (III. 30)
K 3 = exp(− 0.1880 + 833.3 T ) (III. 31)
For the adsorption constant of methanol, Rihko et al. (1997) provide the expression:
KT
= 0.1405 − 0.00061⋅ (T − 334 ) (III. 32)
KM
In order to express the rate constants and the adsorption constants, a modified
Arrhenius-type equation (III.33 – III.35) is recommended. In this case, the model parameters are:
three rate constants at the average temperature (A1, A2, A3), and three activation energies (E1, E2,
E3). The following relations can be written:
⎛ E1 ⎞
k1 = A1 ⋅ exp ( − E1 ⋅ z ) , where A1 = A1,0 exp ⎜ − ⎟ (III. 33)
⎝ RTmean ⎠
⎛ E2 ⎞
⎝ RTmean ⎠
⎛ E3 ⎞
⎝ RTmean ⎠
94
KTM = 0.1405 ⋅ exp(4464.677 ⋅ z1 ) (III. 36)
1 ⎛1 1 ⎞
z= ⋅ ⎜⎜ − ⎟ (III. 37)
R ⎝ T Tmean ⎟⎠
1 ⎛⎜ 1 1 ⎞⎟
z1 = ⋅⎜ − (III. 38)
R ⎝ T Tmean,1 ⎟⎠
where KTM is the methanol adsorption constant, R=8.314 J/mol·K, Tmean = 343 K and Tmean,1 =
334 K.
The constant rates Ai,0 at the average temperature (343 K) and the activation energies Ei
for this model obtained by Rihko et al (1995, 1997) are given in Table 3.2.
Table 3. 2. Parameters of the model used for calculating the theoretical values (Rihko et al
(1995, 1997))
⎡ mol ⎤ ⎡ J ⎤
Reaction Ai,0 ⎢ ⎥ Ei ⎢
⎣ s ⋅ g cat ⎦ ⎣ mol ⎥⎦
2M1B + MeOH Ù TAME 0.286 72 600
2M2B + MeOH Ù TAME 0.125 94 100
2M1B Ù 2M2B 0.107 81 600
In order to calculate the predictions of kinetic model of Rihko et al (1995, 1997) for this
experimental working conditions, the mass balance equations used in the mathematical model of
the batch process are described by equation (III.39):
dξ i
= mcat ⋅ ri ; i = 1,2,3 (III. 39)
dt
where ξ – reaction extent; mcat – weight of catalyst; t – reaction time.
The equations of UNIFAC model are added to the kinetic model to calculate the activity
coefficients, together with equations to calculate molar fractions (III.40 – III.44) and conversion
(III.45) as a function of initial number of moles (n0) and molar extent of reactions (ξ1, ξ2, ξ3):
n 0,2M1B − ξ 1 − ξ 3
x 2M1B =
n 0, total − ξ 1 − ξ 2
(III. 40)
n 0,2M2B − ξ 2 + ξ 3
x 2M2B = (III. 41)
n 0, total − ξ 1 − ξ 2
95
n 0, MeOH − ξ1 − ξ 2
xMeOH = (III. 42)
n 0, total − ξ1 − ξ 2
n 0, TAME + ξ1 + ξ 2
xTAME = (III. 43)
n 0, total − ξ1 − ξ 2
n 0,inert
xinert = (III. 44)
n 0, total − ξ 1 − ξ 2
ξ1 + ξ 2
X = (III. 45)
n0 ,2 M 1B + n0 ,2 M 2 B
The capability of the kinetic model proposed by Rihko et al (1995, 1997) to predict our
experimental data was measured by simulating this mathematical model implemented in
MATLAB. Independent variables considered are: feed compositions and operating temperatures
for the range of experiments.
The kinetic model proposed by Rihko et al (1995, 1997) considered as catalyst Amberlyst
16. As experiments in this work are performed with Amberlyst 35, correction factors are
introduced for including the differences in catalyst acidity. These factors, amplifying the
reported reaction rates for different published kinetic models, represent the ratios between the
acidity (exchange capacity) of Amberlyst-35 catalyst, used in present studies, and the acidity of
the ion exchange resin catalysts used to obtain the above kinetic model (i.e. to transform the
units of rate constants from kmol/(kg·dry cat·h) to kmol/(eq H+ ·h)).
As result of simulation, the parity diagram in Figure 3.7 is obtained. It can be seen that
most of the points are concentrated above the main diagonal, which indicates that the
conversions reported by the kinetic model proposed by Rihko et al (1995, 1997) are greater than
the ones obtained in present experimentally study. Only in a small number of points, both
calculated and experimental conversions are coincident, but the deviation provided by the kinetic
model with parameters from Rihko et al (1995, 1997) is always positive. This is determined by
the model parameters, not by experimental error. In addition, the differences between the
calculated and experimental errors cannot be attributed to the influence of internal diffusion, as it
is estimated at less than 11% deviation. Figure 3.8 illustrates the deviation provided by Rihko et
al (1995, 1997) kinetic model with original parameters, versus our experimental data. Therefore,
a new adjustment of kinetic model parameters is needed, to obtain appropriate fitting for
experimental results of this study.
96
3.2.2. Parameters estimation for the kinetic model proposed
The samples analysed from TAME synthesis reactor for various operating conditions
(various temperatures, various catalyst sieved fractions, and various isoamylenes concentrations)
allow to calculate the experimental conversion. Based on this data, new values for the kinetic
model parameters are obtained using an application developed in MATLAB software. Built-in
function, lsqcurvefit, representing an implementation of Levenberg-Marquardt optimisation
algorithm for least square method of nonlinear parameters estimation is used. The kinetic model
described in the previous section is implemented as a subroutine containing reaction rate
expressions.
Calculated IA conversion
Experimental IA conversion
Figure 3. 7. Parity diagram experimental conversion – calculated conversion

using kinetic model proposed by Rihko et al (1995, 1997)
As starting values, the program uses initial estimates, introduced by the user, for searched kinetic
parameters. Once determined kinetic model parameters, it is possible to simulate the theoretical
conversion, according to previously described method (§ 3.2.1.) The simulation is performed for
the model of reactor used in experimental arrangement.
For each iteration, lsqcurvefit function estimates new values of kinetic parameters vector,
and consequently, new values for model predicted conversion. To improve the fitting quality,
new parameters values are obtained minimizing the performance function based on the sum of
97
the squared differences between the calculated and experimental conversion values, χ given by
relation (III.46), using a multivariable optimization technique (Levenberg-Marquardt algorithm)
with adaptive random search, as mentioned above.
N exp
χ= ∑ (X
i =1
calc − X exp ) 2 (III. 46)
IA conversion
Time, h
Figure 3. 8. Variation in time of the experimental and calculated conversions
The measured conversions are calculated based on experimental data. The strong non-
linear dependence of the process model in respect with unknown parameters makes necessary
close approximation values to ensure convergence.
The chemical equilibrium constants are calculated from the equations (III.29 – III.31)
(Rihko et al, 1995).
The estimation of kinetic parameters is high degree of complexity, from mathematical
point of view, due to big number of parameters and highly non-linear nature of the model. The
initial points are of great importance in this type of computation.
The lsqcurvefit function in MATLAB requires an initialization value but also the lower and
upper bounds where to perform parameters value search both for activation energies and for pre-
exponential factors. For identifying precisely the search space, important expertise is requested
for search region identification. In literature the correlated values can be found, but not the
criteria or method to specify the search region.
98
For this application, a criterion is proposed for identifying the search zone. Considering the
relation between the activation energies of forward and backward reactions and the reaction
enthalpy of forward transformation ( Δ R H = E1 − E2 and Δ R H = H f ,TAME − H f , MeOH − H f , IA ) , the
lower limit for activation energy in the search region can be from zero to the enthalpy of
reaction, depending if the direct or inverse reaction is taken into account. The upper limit for the
energy of activation should not be greater than the enthalpy of formation of the reference
reactant since this value corresponds to the situation when all the molecular bounds are broken.
For TAME synthesis process, this means that the energy of activation for the isomerization
should be smaller than 35300 kJ/kmol, when 2M1B transforms into 2M2B and for the
etherification reactions should be smaller than 236240 kJ/kmol when MeOH reacts with 2M1B
(these enthalpies of formation are reported to gas phase).
Both reactions pass by the same intermediate
Ea1 Ea2
Ea3 2-methyl-1-butene / -35.300

2-methyl-2-butene / -41.800
Enthalpy of reaction
for the isomerization
Methanol / -200.940
Enthalpy of
formation in gas TAME / -305.400
phase
(kJ/kmol)
Figure 3. 9. Energy of reactions scheme for the TAME synthesis
However, substracting the enthalpy of vaporization values for liquid phase can be calculated.
The enthalpy of formation in gas phase should be already a high enough value.
On the other hand, both etherification reactions pass by the same intermediate, therefore
the difference between the activation energy for both etherification reactions must be exactly the
enthalpy of reaction for the isomerization (figure 3.9) i.e. 6300 kJ/kmol. This fact is very
important, because the number of parameters to correlate decreases from 6 to 5 as both energies
of activation for the etherification reactions become linked.
The pre-exponential factors Ai (i = 1, 2, 3) at temperature T, the pre-exponential factors
Ai at average temperature 343 K (Tmean) and the activation energies Ei, obtained from solving the
99
previously described algorithm for kinetic parameters estimation, are given in Table 3.3.
The parity diagram experimental conversion – calculated conversion, using the above
described method, is illustrated in Figure 3.10 and corresponds to a correlation coefficient r2 =
0.96 and the error function χ = 0.14. It can be noticed that the points are simmetrically arranged
around the main diagonal, fact suggested also by the low value of the sum of square deviations
(error function χ) for a number of 132 experimental pointsand the average predicting error of
0.032. Consequently, the adequacy of this model to experimental data is good and it could be
used for estimative design calculations.
Table 3. 3. Estimated parameters of the kinetic model
⎡ mol ⎤ ⎡ mol ⎤ ⎡ J ⎤
Reaction A0i ⎢ ⎥ Ai ⎢ ⎥ Ei ⎢
⎣ s ⋅ g cat ⎦ ⎣ s ⋅ g cat ⎦ ⎣ mol ⎥⎦
2M1B + MeOH Ù TAME 3.49·1012 0.475 ± 0.006 107830 ± 212.8
2M2B + MeOH Ù TAME 2.41·1012 0.036 ± 0.0004 114130 ± 225.22
2M1B Ù 2M2B 1.12·10-3 0.552 ± 0.016 5664 ± 2363
The values of activation energies for the etherification reactions are very close, whereas
the value of the isomerisation reaction is very small compared the other two activation energies,
as presented in Table 3.3.
Figure 3. 10. Parity diagram experimental conversion – calculated conversion

100
Therefore, this result is consistent with the kinetic model proposed by Oost and
Hoffmann (1996) who assumed that the etherification reactions can be lumped together, and the
isomerisation reaction reaching instantaneously chemical equilibrium. Therefore, the kinetic
model proposed by Oost and Hoffmann (1996) and later used by Thiel et al. (1997) is further
implemented for the calculation of residue curve maps, for feasibility analysis of TAME
synthesis in Chapter 5 of this thesis.
Conclusions
In this chapter, an experimental study of the TAME synthesis process kinetics was performed.
The purpose of this study was to evaluate the quality of the published kinetic models and to bring
original contributions to these results, answering some questions to subjects not yet tackled such
as to elucidate the kinetics of TAME synthesis from C5 fraction of FCC enriched with
isoamylenes, as obtained in an oil refinery with Amberlyst35 used in practice. Experimental
study targets the following objectives suggested by further applications in reactive distillation:
• Role of temperature on reaction system (experiments are performed at 60 – 70 – 80 – 90
o
C);
• Role of catalyst particles dimension using sieved fractions of catalyst at different
temperatures (d < 0.63 mm, 0.63 < d < 0.8 mm, 0.8 < d < 1.0 mm);
• Role of isoamylenes concentration on process kinetics using C5 fraction enriched with
2M2B (25%, 30%, 35%, 40%).
The operating pressures were higher than 10 bar assuring practically total condensation of
isoamylenes. The experimental set-up developed for these studies is especially designed to
assure that the objectives proposed can be reached with a high precision. The experiments
performed at four reaction temperatures 60oC, 70oC, 80oC and 90oC in the presence of unsieved
catalyst Amberlyst-35 indicate that at T > 80 oC, although the etherification rate is increased, the
chemical equilibrium limitation becomes significant. The difference between the results obtained
at 80oC and 90oC is not of great magnitude, the curves follow almost the same tendency and the
maximum mass fraction of TAME that can be reached in the two cases is very similar. The
influence of catalyst granule size has been studied in a series of experiments developed at 80oC
and 90oC. Three classes of grain dimensions were tested, corresponding to the intervals 0.8 – 1
mm, 0.63 – 0.8 mm and grains smaller than 0.63 mm. The results obtained at 80oC permits us to
consider that the influence of the grain dimension on internal diffusion can be neglected at this
value of temperature, with errors smaller than 11%. However, the results obtained indicate that at
T > 80 oC, the catalyst grain dimensions determine a significant slow-down of the internal
diffusion. Therefore, at a reaction temperature higher than 80 oC, the influence of the catalyst
101
grain dimensions on the internal diffusion cannot be neglected. The influence of isoamylenes
concentration was studied at 80oC. In the experiments performed, the isoamylenes concentration
varies from no enrichment up to 40% enrichment. The results indicate that more diluted is the
reaction medium, the reaction rate is slower.
A kinetic model for the synthesis of TAME was also proposed by adapting the one
proposed by Rihko et al (1995). The kinetic equations corresponding to the considered model are
expressed in terms of components activities and assume that the adsorbed methanol molecules
are predominant with respect to other adsorbed species. The composition measurements have not
evidenced significant concentration of isoamylene oligomerization products in the reaction
mixture, so that the only reactions considered are those of etherification and isomerisation. The
capability of the kinetic model Rihko et al (1995, 1997) to predict the experimental composition
changes was tested by simulating the experimental conditions. The results of the simulation
show that all the points are concentrated above the main diagonal, which indicates that the
kinetic constants obtained by Rihko et al (1995, 1997) overestimates conversion of isoamylenes.
Therefore, a new correlation of kinetic model parameters is needed to obtain a new kinetic model
fitting the experimental points obtained. The activity coefficients are calculated using UNIFAC
thermodynamic model and the results are correlated to the kinetic model of Rihko et al (1995,
1997). The model parameters are regressed in MATLAB and a parity diagram is used to
visualize the correlation of the results. The parity diagram illustrates that the points are well
arranged around the main diagonal, fact suggested also by the sum of square deviations (error
function χ) which has a small value: 0.14 for 132 experimental points, a correlation coefficient r2
=0.96 and the mean predicting error of 0.032. The adequacy of this model to experimental data
is good and it could be used for estimative design calculations.
102
CHAPTER 4
Experimental study of vapour liquid equilibrium data
4.1. Experimental device
4.1.1. Description of the dynamic vapour liquid equilibrium (VLE) apparatus
The VLE apparatus produced by Fischer Model: D-53340 Type 0413-0120-00 Basic Unit shown
in Figures 4.1 and 4.2 is a single piece of glass, but several zones dedicated to several functions
can be identified: boiler, Cottrell pump, adiabatic chamber, condenser, sampling, back flowing
circulation and mixer.
Figure 4.1. Dynamic VLE apparatus used in the experimental work
103
Figure 4. 2. VLE apparatus scheme
104
VLE apparatus components
1. Magnetic stirrer
2.1 Mixing chamber
2.2 Tower mantle (option)
2.3 Control pump with silvered vacuum jacket
2.4 Circulation heater (glass tube)
2.5 Discharge valve
2.6 Sample take-off nozzle for vapour phase
2.7 Temperature measuring nozzle
2.8 Cooler for liquid phase
2.9 Stop value for receiver change under vacuum and overpressure (liquid)
2.10 Sample take-off nozzle for liquid phase
2.11 Stop valves
2.12 Cooler for vapour phase
2.14 Sample take-off nozzle for liquid phase
2.15 Feed nozzle
2.17 Stop valve for receiver change under vacuum and overpressure (vapour)
2.19 Vacuum or pressure compensation line
2.20 Aeration valves
2.21 Temperature measuring nozzle
3. Stirrer magnet
4. Receiver glasses
5. Hose connection with screw cap GL 14
6. Pt-100 sensor 170 mm
7. Valve caps
8. Solenoid coils
8.1 Distance holder
8.2 Screw cap
9. Immersion heater
10. Valve rod (liquid phase)
11. Valve rod (vapour phase)
12. Feed burette
12.1 Feed nozzle for feed burette
12.2 Stop valve for feed burette
12.3 Aeration valve for feed burette
13. Stam of precision valve
14. Precision valve
15. Stop plug with safety screwing
16. Connecting piece
16.1 ground-in ball and socket joint
17. Pt-100 temperature sensor 50 mm
18. Glass connection for vacuum resp. overpressure
20. Basic mounting frame
20.1 Support for stirrer drive
105
Figure 4. 3. VLE apparatus control panel
VLE apparatus components
30.1. Digital temperature display for circulation evaporator/vapour phase, reversible
30.2 Digital display of the unit pressure, reversible to vacuum/pressure
30.2.1 Change-over switch of the pressure display range mbar/bar
30.3 Capacity controller circulation evaporator heating
30.4 Capacity controller circulation line heating
30.5 Capacity controller circulation tower mantle
30.5.1 Control light tower mantle
30.6 Adjuster pressure/vacuum stabilizer
30.6.1 Control light pressure/vacuum stabilizer
30.7 Change-over switch temperature display
30.8 Operating key discharge valve vapour phase
30.9 Operating key discharge valve liquid phase.
30.10 Mains switch vacuum pump
30.11 Mains switch
30.12 Limit controller evaporator temperature
30.12.1 Control light limit controller
Boiler: The energy to form the vapour phase is provided in this zone. Evaporation takes place in
the crown between a cylindrical immersion heater and the glass wall of the apparatus. The heater
is teflonated with some rugosity grains to assure a uniform distribution of bubble formation
points. Sometimes, when the samples are kept for some hours inside the boiler at room
temperature, the heater does not provide anymore a constant stream flow of bubbles. The crown
is a quite narrow section to assure that all the liquid gets properly heated. At the lower part of the
boiler, there is a valve to empty the apparatus and a lid that fixes the heater by the base. At the
upper part of the boiler, there is a Pt-100 thermometer to check the temperature of the circulating
106
fluid. The superheating of the liquid and the occurrence of a concentration gradient in the flask
contents is avoided by comparing this temperature and the temperature inside the adiabatic
chamber. The liquid flow rate must be high enough and the vapour flow rate low enough to
assure that the composition in the liquid phase composition is not changing too much in all its
recirculation. The charge quantity is around 100 mL, but the optimum level of liquid is around 1-
2 cm above the immersion heater (in some circumstances to assure an enough liquid circulation
can be above).
Crottell pump (or vapour lift pump): This zone assures an intimate mixing between the liquid
and the vapour to ensure equilibrium. Once the mixture is heated, vapour is flowing up by means
of a Crottell pump. The pump is already inside the adiabatic chamber. The vapour bubbles
ascending stream is stirring thoroughly and entrain an appreciable amount of liquid along the
Cottrell tube, so that a mixture of vapour and liquid is ejected onto the temperature measuring
point. The density of the hot mixture with vapour is lower than the density of the colder mixture
in the mixer. The level becomes higher in the side of the boiler than at the side of the mixer. The
liquid flows in a thin film until superheat is dissipated and its true boiling temperature can be
measured. The liquid overflows form the side of the boiler and returns to the side of the mixer.
This technique has one disadvantage: the pumping rate depends on the heat input. Sometimes,
the pumping rate of liquid is not suitable but the vapour flow rate is already enough. To
overcome this disadvantage, the ebullometer can be fed with a higher volume of mixture. In this
way the liquid level increases in the side of the mixer but also in the side of the Cottrell pump
increasing the obtained flow rate. Some other options to increase the flow rate of liquid are by
increasing the stirring speed in the mixer or by lowering the temperature of the mixer side. An
increase of the heat in the reboiler will increase the liquid flow rate but also the vapour flow rate.
The vapour flow rate must be fixed to about 30 drops per minute at the dropping point. The
hydrostatic pressure head, due to the Cottrell pump and boiler, has no influence on the
temperatures and pressures measured, provided the experiment is properly performed.
Adiabatic chamber: In the adiabatic chamber is practically achieved the VLE equilibrium, the
vapour and liquid in equilibrium being split there. To assure that it is adiabatic, there is a vacuum
jacket to avoid heat losses by conductivity and convection. When the mixture is above 100 oC,
the heat radiation losses become appreciable. To avoid it, the external glass is mirrored and a
mantle whose temperature can be regulated is surrounding this chamber. The temperature of the
mantle must be a few degrees below the boiling temperature inside the adiabatic chamber
(approx. 3-5oC below). A partial condensation on the walls of the adiabatic chamber would
produce an erroneous result. To avoid the entrainment of droplets by the vapour or partial
107
evaporation of sprayed liquid, a deflector is present. However, if the vapour flow rate were very
large, the entrainment would occur.
Condenser: Once separated the liquid and vapour phases, the liquid flows downwards passing
the sampling point to the mixer and the vapour passes through a settling chamber, is totally
liquefied in a condenser and flows downwards passing the sampling point and to the mixer
where gets mixed again with the liquid. The temperature of the condenser fluid must be low
enough to assure a total condensation of the vapours. In this way, the vapour composition and
the composition of the condensed liquid are equal. A heating band can be used when the vapours
can solidify. The returning tube from the vapour passes at the back of the boiler and receives
heat from it, it is recommended to put some isolating material between the boiler and the
returning tube of the vapour. To avoid that vapours from the condensate liquid reach back to the
adiabatic chamber, a siphon is present in the tube of the liquid at the exit of the adiabatic
chamber.
Sampling: The sampling is necessary in order to determine the chemical compositions of the
liquid and vapour phases in equilibrium. Some apparatus are equipped with an automatic
sampling system using suspended rods operated with electro valves; this is useful when it is
operated far from the atmospheric pressure. The quantity of sample collected is quite high and
the equilibrium is slightly disturbed. When possible, it is recommended to extract the samples
with a gas tight syringe from the dropping points using a large enough needle to reach from the
lid with silicone septum to the dropping point. Change the septa before each experiment. When
evaporation of the sample is suspected, the syringe and vials can be cooled in an ice bath. Some
inserts can be used inside the vials to reduce the quantity of sample taken with the syringe from
1.5 mL to 0.5 mL. But if the samples are very volatile or if the analysis apparatus, e.g. gas
chromatograph, is available to perform the analysis immediately after sampling, then it is
recommended to use a gas tight syringe of 1 microliter and inject it directly to the gas
chromatograph. The gas chromatography presents a very high sensibility and works well,
however, some authors use flow refractometers for this purpose avoiding the need of sampling.
The refractometer can be used only when the refractive indices of the components differ
substantially. The main difficulties encountered in sampling are due to the disturbance of
equilibrium by the withdrawal of samples, evaporation of the sample or contamination of
samples. It is important to take care not to contaminate the samples during withdrawal. It would
be recommended to use two different syringes, one for the vapour phase and another for the
liquid. The cleaning of the syringe is performed with a volatile component, it can be done with
acetone, but it is important to identify a priori where it would appear in the chromatogram. The
syringe must be dried with compressed air after being several times cleaned with acetone. If the
108
boiling point of the components is low, such as the acetone, then it is not necessary to clean with
acetone and they can be dried directly with the compressed air. If the samples are withdrawn
with a syringe of 1 microliter, then the syringe can be cleaned directly by pumping with the
syringe several times in the sampling point of the chromatograph. A special advantage of the unit
is the possibility of a direct gaseous sample take-off in the vapour phase via a further sample
take-off point in case of e.g. mixtures with occurring miscibility gaps.
Mixer: A magnetic stirrer assures the composition homogeneity of the mixture recycled to the
boiler. Great fluctuations of the composition could affect the equilibrium. The minimum stirring
speed, when the samples are hot, can be sometimes too high and the solution is to correlate the
distance between the magnetic stirrer and the teflonated bar. If the temperature in the mixer and
in the reboiler would be equal, then the Cottrell pump will not work properly. The Cottrell pump
is working because the heat introduced to the liquid in the reboiler is eliminated by the walls of
the mixer and other parts of non isolated places; therefore, the external temperature influences
the apparatus regulation. A cooler around the mixer is useful for a better controllability of the
apparatus but it is not implemented in the commercial ones. A cooler around the tube where the
vapour returns to the mixer can be useful for volatile components to avoid vapours going back
from it.
4.1.2. Operation and experimental procedure
The apparatus start up can take about 2h, a constant temperature for at least 30 min is an
indicator that the steady state is reached. At the beginning, the pressure increases due to the
vapour formation. The flow rate of liquid and vapour are smaller at the beginning and when the
apparatus reaches a steady temperature, both increase. If the change of composition inside is not
too big, each 10-30 min the steady state conditions for the next sample can be reached. A
summary of the operation is as following:
1. Switch on the refrigeration
2. Ensure that the valve used to empty the reboiler is closed and that the reboiler resistance
is well screwed. Change the sampling point septum.
3. Bring ice for the cool trap of the vacuum pump and also to chill the syringes when the
chemical compounds are very volatile.
4. Pick up the chemical compounds required for the experiment.
5. Fill up the ebullometer by the upper part lid of the mixer with a small funnel. During the
filling, let open some other lid to allow the air exit, e.g. a sample point lid. The volume
used is around 100 mL, but it is not necessary to measure it exactly. When the apparatus
reach steady state, it is re-correlated. The optimum level is around 1 or 2 cm above the
109
immersion heater, but it is regulated according to the required flow rate of liquid phase.
Care must be taken to not be higher than the sampling point.
6. Ensure that all the lids are closed before heating, but that the automatic release of
pressure is working well. Keep under close surveillance while the pressure is increasing
due to the initial generation of vapour. (Instead of automatic release of overpressure, it is
also possible to let it open to the atmosphere in some point over the condensers to let the
air escape but not the vapours, but when the pressure gets stable, it must be closed again).
7. Switch on the main button and regulate the heating power of the heater (usual values are
between 40 and 60%). The power must be lower or higher depending on the heat of
vaporization of the components. To accelerate the heating process, an initial higher
power can be used.
8. The vapour pressure generated increases the pressure inside the apparatus when it is
hermetically closed. The automatic valve releases the pressure, or one of the lids above
the condensers is let opened or the pressure can be released manually.
9. The time to reach a uniform and stable temperature is quite large, and it can take more
than 2 hours.
10. Switch on the chromatograph and the computer controlling it. Open the chromatograph
control program to charge method operation parameters.
11. Start the FID flame, the GC ignites easily if only the H2 and air are open. Let it stabilize
around half hour.
12. Verify the previous calibration apparatus with a mixture of known composition.
13. Mix well to assure that the sample is uniform. If the injection is performed manually, a 1
microliter syringe must be used. The ratio of number of moles from each sample
(calculated using the corresponding molecular weights), divided by the ratio of the areas
obtained from the GC analysis gives the calibration.
14. Take a sample from the pure component introduced in the ebullometer and analyze it to
ensure that it is not contaminated.
15. Regulate the ebullometer. The pressure can be adjusted around atmospheric pressure
(1013.2/3 mbar) with a syringe of 10 mL (introducing or extracting air). The liquid flow
rate must be high, whereas the condensed vapour flow rate must be low about 30
drops/minute. When regulating the heating power, then the vapour flow rate is controlled
(and also the liquid one). When regulating the volume of sample inside the ebullometer,
mainly the liquid flow rate is regulated. The speed of the stirrer can also affect the liquid
flow rate. When some regulation is performed, the pressure will be also affected.
110
16. When the pressure is stable for some time, check the boiling point of the pure component
to match its known value.
17. Add the quantity indicated of the second compound (the approximate quantity required
for a given molar fraction jump can be estimated in base a simplified mass balance of the
system). To decrease the level in the ebullometer, it can be done with the electro valve of
the liquid arm.
18. Once the temperatures are stable, take note of the vapour and liquid temperatures, both
must be close but the one used in the calculations will be the one of the vapour. When the
boiling temperature is higher than 100oC to avoid heat losses by radiation, the mantle
must be regulated at a temperature 3-5oC below the boiling point.
19. Sample with the 1 microliter syringe from the liquid and analyze it in the chromatograph.
20. Sample with the 1 microliter syringe from the vapour and analyze it in the
chromatograph.
21. Transfer the data obtained from GC and process them to check the correctness of the
obtained point. Perform some replicas of the point analysed by repeating sampling,
analysis and data processing.
22. Represent the obtained points on a Txy and a xy graphic.
23. Repeat the last steps from the point 17 on until you reach around a little bit more than the
half of the xy diagram. From this point, it is easier to start for the opposite pure
component. Both half curves will join in the middle of the graphic.
24. At the end, close the apparatus at the inverse order followed to switch them on. First the
ebullometer, then the thermostatic bath of the refrigeration when no more vapours are
going out from the heater. The oven, injector and detector of the chromatograph must be
let get cool around room temperature before closing them.
25. For high boiling components, the ebullometer must be cleaned using acetone. 110 mL of
acetone are charged inside the ebullometer after it is again closed. The heater is switched
on and the acetone is let to flow inside the apparatus for some time. When the
components used are very volatile, it is not required to use acetone.
26. It is not recommended to let the ebullometer filled from one day to another.
27. Once determined the entire VLE curve, the experimental data obtained can be introduced
into a commercial simulator to correlate to some thermodynamic model and to check
their thermodynamic consistency. The experimental results can be compared with the
results obtained by some predictive methods such a UNIFAC or COSMO-SAC.
111
4.1.3. Considerations related to the experimental error
Finally the following considerations were taken into account when the ebullometer was used, in
order to minimize the measurement errors:
- Avoid to take the sample from the reboiler, only from the dropping points ;
- Avoid liquid entrained by the vapour, using the right flow rates of vapour and liquid ;
- Avoid a bad isolation;
- Avoid insufficient time for reaching the equilibrium;
- Avoid a too long sampling time. The analysis was made with a gas tight syringe of 1
microliter with a short sampling time;
- Avoid the large samples which destabilize the system. It was taken just 1 microliter for
direct injection;
- vapour flow is not the same for all the points. It was regulated with the heating power to
the recommended flow rate.
- vapour flow is important compared to the liquid one. The liquid / vapour flow rates were
regulated with the heating power, the level of liquid inside the apparatus and the
temperature on the walls of the mixer.
- Avoid bad calibrations.

Some of these effects are still present in some of the actual machines. However, the values are
close to the equilibrium, but the equilibrium is never totally reached because by definition to
reach the equilibrium there must be an infinite time of contact of the liquid with the vapour. If
literature data is compared, variations of approx. 10 % can be found between the authors, but this
depends on the considered system.
4.2. Materials
The compounds used to perform the experimental work are listed in Table 4.1:
Table 4.1. Raw materials for VLE experiments

Component Reference Purity
2-methyl-1-butene (2M1B) 66035-50ML purum, ≥97.0% (GC) (FLUKA)
2-methyl-2-butene (2M2B) 86262-250ML-F purum, ≥95.0% (GC) (ALDRICH)
Methanol (MeOH) 322415-2L anhydrous, 99.8% (SIGMA-ALDRICH)
Tert-amyl-methyl-ether 283096-500ML 97% (ALDRICH)
(TAME)
Isopentane (i-C5) 59070-1L puriss. p.a., ≥99.5% (GC)
(SIGMA-ALDRICH)
112
4.3. Gas chromatograph analysis
A microlitre of every sample is injected in a gas phase chromatograph HP 5890 Series II. It is
equipped with an automatic injector of sample, a flame ionisation detector and a capillary
column Supelco (PTE-5 2-4159, 30 m x 0.52 mm internal diameter, 1 micrometer of the
thickness of the phase). The carrier gas is the helium. The control of the pressure is electronic
and the integration of the chromatograms is made by the software ChemStation, implemented on
a computer linked to the chromatograph. When using the following parameters: fixed
temperature of 90 ºC and pressures (bars): inlet A = 0.69; channel C = 1.03 (hydrogen); channel
E = 1.22 (helium), there were not detected any superpositions of the signal and the picks were
well separated.
The calibration allows the knowledge of the ratio between the response factors of the
constituents (RF) which joins the pick’s areas (a) with the mass fractions (x) using the following
expression :
Apic1 RF1 x 1 m1
⋅ = = (IV. 1)
Apic 2 RF2 x 2 m2
The mass fractions ratio x 1 x 2 is equivalent to the weight ratio m1 m2 which is known and
measured by a precision balance. The ratio RF1 RF2 is obtained from the regression slope
Apic1 Apic 2 versus x1 x 2 . The deviation at the origin (the bias), is very small and we ignore it.
The molar fraction of the constituents is obtained from the molecular mass (Mw) with the
following expression:
A1 ⋅ RF1 ⋅ Mw2
A2 ⋅ RF2 ⋅ Mw1
x1 = (IV. 2)
A ⋅ RF1 ⋅ Mw2
1+ 1
A2 ⋅ RF2 ⋅ Mw1
The relation (IV.1) shows that the ratio of the areas of the binary mixture’s picks studied on the
chromatogram varies in a linear way with the ratio of their weight. Fixing the origin at zero and
using a precision balance (accuracy 0.0001 g), we obtain a regression coefficient superior of
0.9998 for the calibration. The error is negligible compared to the error of Ebullometer in degree
of reaching the equilibrium.
After verifying that the behaviour is linear over the whole range of the composition considered in
this work, different calibrations of the line were performed during the analyses using three points
for refining the results. Sometimes, the line of calibration may be slightly outside the confidence
interval at 95%, but this error remains negligible when compared with the errors of Ebullometer.
113
4.4. Experimental results of the binary vapour liquid equilibrium
4.4.1. 2-methyl-2-butene/Methanol
The vapour liquid equilibrium data measured for the binary system methanol/2-methyl-2-butene
are presented under the form of y-x diagram and T-xy (boiling diagram). The binary system
methanol / 2-methyl-2-butene presents a non ideal behaviour with the presence of a minimum
boiling azeotrope at a composition around 0.78 2-methyl-2-butene (Figure 4.4) and a
temperature around 33oC (Figure 4.5). The mixture does not present phase split in the liquid
phase. The experimental results obtained are in accordance with the experimental results
available from the literature (Ogorodnikov et al, 1960; Reichl et al, 1998; Rihko-Struckmann et
al, 2000) (Figure 4.6).
1
0.9
0.8
0.7
0.6
0.5
y
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x
Figure 4.4. VLE 2-methyl-2-butene (1) / methanol (2), x-y diagram (P=1013 mbar)
70
65
60
Temperature (C)
55
50
45
40
35
30
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x, y
Figure 4.5. VLE 2-methyl-2-butene (1) / methanol (2), Txy diagram (P=1013 mbar)
114
1
0.9
0.8
0.7
This work
0.6
Rihko-Struckmann 2000
0.5 Reichl 1998
y
Ogorodnikov 1960
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x
Figure 4.6. VLE 2-methyl-2-butene (1) / methanol (2), x-y diagram from data available in the
literature (P=1013 mbar)
In the range of molar fractions 0.05 – 0.2 of 2M2B, the experimental values for the vapour phase
mole fractions reported in literature are slightly lower than the ones obtained in this thesis. For
example, the liquid phase mole fraction 0.12 of 2M2B corresponds to a value of 0.66-0.67
vapour phase mole fraction 2M2B as reported by Rihko-Struckmann (2000), while in this work
the value is 0.73. Rihko-Struckmann (2000) made two replicas of this point obtaining the same
result. In this thesis, a much larger set of experimental points were measured and all the results
around this point follow a clear tendency. As it is not feasible to get compositions richer than the
equilibrium ones, it can be assumed that these points are beyond the capabilities of the
ebullometer of Rihko-Struckmann (2000). Usually when the liquid and vapour have not enough
time to attain the equilibrium because of the limitations of the ebullometer, then the curve
appears cut at the points where the difference between liquid and vapour compositions is
maximum (at corner of the curve). This fact is due to the difficulty to reach the equilibrium. This
is just an assumption, however to verify its validity requires the availability of more points from
Rihko-Struckmann et al (2000) in this zone. Concerning the experimental values that define the
azeotropic composition, all the authors (Rihko-Struckmann et al (2000), Ogorodnikov et al.
(1960), Reichl et al (1998)) identify it to a 2M2B molar fraction between 0.78 and 0.79. Rihko-
Struckmann et al (2000) identify it at a higher position whereas Ogorodnikov et al. (1960) locate
the azeotrope between our results and the ones of Rihko-Struckmann et al (2000). However, all
of them are reported very close. When the temperatures are compared, they are very coincident
for the vapour phase but for the liquid phase, the results reported by Rihko-Struckmann et al
115
(2000) are about 0.5oC over the temperature reported in this thesis and from the other authors
(Figure 4.7).
70
65
60
Temperature (C)
This work
55 Rihko-Struckmann 2000
Reichl 1998
50 Ogorodnikov 1960
45
40
35
30
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x, y
Figure 4.7. VLE 2-methyl-2-butene (1) / methanol (2), Txy diagram from data available in the
The experimental liquid phase activity coefficients are calculated using AspenPlus, introducing
the experimental data and using vapour pressure correlations available in AspenPlus database for
the extended Antoine equations. Ideal behaviour of vapour phase was considered. The values
obtained are shown in figure Figure 4.8 a.
30 4
28
26 3
24
22 2
activity coefficient
2M2B
ln(gama1/gama2)
20 MeOH
18 1
16
0
14
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
12 -1
10
8 -2
6
4 -3
2
0 -4
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 x1
x1
b)
a)
Figure 4.8 VLE 2-methyl-2-butene (1) / methanol (2),

a) experimental activity coefficients, b) Herington consistency test (P=1013 mbar)
The activity coefficient of each component is the unity for the pure substance and it increases
exponentially as the component becomes mixed with the other component due to the non-
116
idealities of the system. Both curves are asymmetric and the one of methanol increases more
abruptly, this fact making the azeotrope closer to the pure 2M2B side. According to the
Herrington thermodynamic consistency test (Herrington, 1951), by representing the logarithm of
the activity coefficients ratio as a function of 2M2B fraction in liquid phase, the positive and
negative areas (around zero) must be equal within an error of maximum 10 %. For our
experimental data, the two areas differ by ~ 6.8% (Figure 4.8b), so that the consistency test is
fulfilled.
From the original experimental data and using thermodynamic models implemented in
AspenPlus, various models are tested for identifying which provides the best correlations. The
calculus is performed in AspenPlus. From the Figure 4.9 can be observed directly that the Van
Laar model is not able to correlate this system because it does not take into account the influence
of the temperature on the activity coefficients. In the systems without liquid-liquid equilibrium,
the Wilson model usually provides very good correlations but for this particular case this is not
fulfilled. The NRTL and UNIQUAC models provide the best correlations, being the
recommended models for this binary mixture. It is interesting to notice that from a molar fraction
of 2M2B from 0.2 to 0.9, the temperature of the corresponding vapour composition is close to
the azeotropic composition. Although this behaviour is typical when there is liquid-liquid
equilibrium, it was noticed experimentally that the mixture was totally miscible.
70 1
65 This work 0.9

Wilson
Van Laar 0.8
60
NRTL
0.7
Temperature (C)
UNIQUAC
55
0.6 This work
50 0.5 Wilson
y
Van Laar
45 0.4 NRTL
UNIQUAC
0.3
40
0.2
35
0.1
30 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x, y x
Figure 4.9 VLE 2-methyl-2-butene (1) / methanol (2), correlation of the experimental data to
several thermodynamic models (P=1013 mbar)
The comparison of the results from predictive models with the experimental results is shown in
figure Figure 4.10. COSMO is an ab initio model being based only on the molecular structure
and not on any experimental data. Qualitatively the results predicted are quite good without any
liquid liquid equilibrium, the main deviations are of 5oC in the temperatures of the liquid phase
and the position of the azeotrope is displaced 0.1 units. As it is usual, the predictions of the group
contribution methods such as UNIFAC are better correlated than the COSMO as they are based
117
on experimental data results. However, the UNIFAC predicts a liquid-liquid equilibrium that
does not exist, but the azeotropic composition is in good agreement with the experimental
results. The prediction provided by the UNIFAC Dortmunt does not indicate the liquid-liquid
equilibrium but the azeotropic composition is a bit higher than the experimental one, around
0.795, and the vapour compositions are slightly lower than the experimental ones. Nevertheless,
as a prediction, the results are quite good for the UNIFAC Dortmund.
70 1
0.9
65 This work
UNIFAC 0.8
60 COSMO
0.7
Temperature (C)
UNIFAC Dortmund
55 0.6
This work
50 0.5
y
UNIFAC
0.4 COSMO
45 UNIFAC Dortmund
0.3
40
0.2
35
0.1
30 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x, y x
Figure 4.10 VLE 2-methyl-2-butene (1) / methanol (2), predictions compared with the
experimental data (P=1013 mbar)
Finally, the experimental data is compared with the VLE obtained from the Aspen database
using the Wilson and NRTL models (Figure 4.11).
70 1
65 0.9
This work
60 WILSON Aspen
0.8
Temperature (C)
NRTL Aspen 0.7

55
0.6
50 0.5
y
45 0.4
This work
40 0.3 WILSON Aspen
NRTL Aspen
0.2
35
0.1
30 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x, y x
Figure 4.11 VLE 2-methyl-2-butene (1) / methanol (2), comparison of Aspen database with the
It should be noticed that using this readily available database, the deviation from the
experimental results are similar to use directly a predictive model such as the UNIFAC
Dortmund. These graphics are just included in order to highlight the importance of perform a
bibliographic search and/or experimental determination before assuming that the parameters in a
simulator database must be suitable for our purposes.
118
4.4.2. 2-methyl-2-butene / TAME
The VL equilibrium data measured for the binary system 2M2B/TAME are presented under the
form of y-x diagram and T-xy (boiling diagram). The shapes of these curves are indicating a
behaviour close to that of an ideal mixture, without azeotropes or important pinch zones (Figure
4.12). Usually when the components are chemically similar and/or their boiling points have a
difference higher than 30oC, the type of graphics are obtained are as in Figure 4.13.
1
0.9
0.8
0.7
0.6
0.5
y
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x
Figure 4.12. VLE 2-methyl-2-butene (1) / TAME (2), x-y diagram (P=1013 mbar)
90
80
Temperature (C)
70
60
50
40
30
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x, y
Figure 4.13 VLE 2-methyl-2-butene (1) / TAME (2), Txy diagram (P=1013 mbar)
There are only few experimental data available in the open literature related to this system, a
possible reason being the difficulty to have the substances with a very high purity. The published
boiling point of pure TAME is around 86.3oC and that of pure 2M2B is of 38.5oC. The
119
experimental values obtained in this thesis are 85oC for TAME and 35.9oC for 2M2B. This may
be explained by the purities of TAME and 2M2B used in the experiments which are of 97% and
≥95.0% respectively. The boiling point of TAME obtained by Reichl et al (1998) is at 85.9oC
and of 2M2B is at 37.95oC, which are closer to the boiling points of pure components suggesting
the availability of substances with higher purity (Figure 4.14). Unfortunately, Reichl et al (1998)
determined only 5 experimental points for this system (Figure 4.15).
1
0.9
0.8
0.7
0.6
0.5 This work
y
Reichl 1998
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x
Figure 4.14. VLE 2-methyl-2-butene (1) / TAME (2), x-y diagram from data available in
90
80
This work
Reichl 1998
Temperature (C)
70
60
50
40
30
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x, y
Figure 4.15. VLE 2-methyl-2-butene (1) / TAME (2), Txy diagram from data available in the
120
The VLE experimental procedure is performed in two series, each one starting from pure
components and following the curve up to the middle of the diagram. The coincidence of both
half series in the middle also is an argument that the experiments are performed with good
precision. All the experimental points determined by Reichl et al (1998) are obtained in the half
graphic starting from pure 2M2B, but the other half graphic remains undetermined.
The experimental points of Reichl et al (1998) can be correlated to an ideal behaviour with a
volatility coefficient of 4.56 (Figure 4.16). The volatility coefficient for TAME obtained for the
experimental points from this thesis would be around 6. But from the complete system can be
observed that the behaviour is not totally ideal as the curve is not totally symmetric, the mixtures
richer in 2M2B are slightly more distanced from the diagonal than the mixtures richer in TAME.
This aspect can be observed also in the experimental activity coefficients (Figure 4.17). Using
the same scale than for the previous binary system, all the points are around 1, but with a zoom
on the activity coefficient axis, it is observed that there is a slight deviation from 1. The vapour
pressure values are used for the calculation of the experimental activity coefficients. As the
experimental boiling point of TAME is not matching the one of the pure component, then all the
experimental activity coefficients have some error. It can be observed that for pure TAME the
experimental activity coefficient is not at value of 1. Although all the points of the logarithm of
the activity coefficients ratio are close to 0, all the values are positive. This fact generates a
nonzero result and consequently the thermodynamic consistency test is not satisfied. The value
for the consistency test is of 74%, which is above the tolerance of 10%.
1
0.9
0.8
0.7
0.6
0.5
y
This work
0.4 Reichl 1998
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x
ideal mixtures (P=1013 mbar)
121
1.5 1.5
1.4
2M2B
1.3 TAME 1
1.2
ln(gama1/gama2)
0.5
1.1
1
0
0.9 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
0.8 -0.5
0.7
0.6 -1
0.5
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 -1.5
x1 x1
Figure 4.17. VLE 2-methyl-2-butene (1) / TAME (2), a) experimental activity coefficients, b)
Herington consistency test (P=1013 mbar)
When the experimental data is correlated to several thermodynamic models (Figure 4.18), it is
observed that the Van Laar is not fitting the data and that all the other models provide a very
similar quality of correlation. The correlations are not very satisfactory as the theoretical values
line is always at the same side of the experimental points and not passing in the middle of them.
100 1
90 This work 0.9

Wilson
Van Laar
0.8
80 NRTL 0.7
Temperature (C)
UNIQUAC
70 0.6
0.5 This work
y
60 Wilson
0.4 Van Laar
NRTL
50 0.3 UNIQUAC
0.2
40
0.1
30 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x, y x
Figure 4.18 VLE 2-methyl-2-butene (1) / TAME (2), correlation of the experimental data to
All the three estimation methods evaluated provided very similar results (Figure 4.19), the ones
of COSMO being between the results provided by UNIFAC and UNIFAC Dortmund, offering a
very good prediction. When the Tx-y diagram is observed, the UNIFAC provides a better
correlation to experimental data for mixtures richer in TAME and the COSMO and UNIFAC
Dortmund provide better correlation to experimental data for mixtures richer in 2M2B. The
results of the predictions are closer to the experimental points from Reichl et al (1998) assuming
a more ideal behaviour of the mixture than the results of the present thesis. The prediction using
the UNIFAC Dortmund is very close to the curves correlated using the thermodynamic models
(Wilson, NRTL or UNIQUAC). This system is not implemented in the Aspen Plus database,
therefore the experimental data obtained cannot be compared with the VLE obtained from the
simulation environment database.
122
90 1
0.9
This work
80 UNIFAC 0.8
COSMO
UNIFAC Dortmund 0.7
Temperature (C)
70
0.6
60 0.5
y
This work
0.4 UNIFAC
50 COSMO
0.3 UNIFAC Dortmund
40 0.2
0.1
30 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x, y x
Figure 4.19 VLE 2-methyl-2-butene (1) / TAME (2), predictions compared with the experimental
data (P=1013 mbar)
4.4.3. 2-methyl-1-butene / TAME
When the VLE curve approaches pure TAME, the experimental points are not reaching the pure
TAME corner (Figure 4.20). The boiling temperature of TAME at 82.3oC instead of the 85oC as
obtained in the previous experiment indicates that perhaps the ebullometer did not have enough
time to reach equilibrium (Figure 4.21). Therefore, the first 5 points, up to mole fraction of 0.075
2M1B should be disregarded. The behaviour of this system is quite ideal. However, there are not
many available experimental data in the literature. The experimental values obtained by Everson
et al. (2001) are slightly closer to the diagonal (Figure 4.22).
1
0.9
0.8
0.7
0.6
0.5
y
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x
Figure 4.20. VLE 2-methyl-1-butene (1) / TAME (2), x-y diagram (P=1013 mbar)
123
90
80
Temperature (C) 70
60
50
40
30
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x, y
Figure 4.21 VLE 2-methyl-1-butene (1) / TAME (2), Txy diagram (P=1013 mbar)
1
0.9
0.8
0.7
0.6
0.5
y
0.4
This work
0.3
Everson 2001
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x
Figure 4.22 VLE 2-methyl-1-butene (1) / TAME (2), x-y diagram from data available in the
In their study, Everson et al. (2001) do not indicate the boiling temperature obtained for the pure
substances (Figure 4.23). However, according to the tendency of the curves, it seems they
reached quite low values, this suggesting a higher degree of contamination than for the
substances used during the experimental work of this thesis. The points of Everson et al. (2001)
can be correlated quite well to an ideal mixture with a volatility coefficient of 5.7. The points of
124
this thesis are more distant from the diagonal and would correspond to a volatility coefficient
around 7.6.
90
80
This work
Everson 2001
Temperature (C)
70
60
50
40
30
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x, y
Figure 4.23 VLE 2-methyl-1-butene (1) / TAME (2), Txy diagram from data available in the
It can be observed that the behaviour is not totally ideal as the curve is not totally symmetric, the
mixtures richer in TAME are at a greater distance from the diagonal than the mixtures richer in
2M1B (Figure 4.24). This aspect can be observed also in the experimental activity coefficients
(Figure 4.25). Using the same scale than for the previous binary system, all the points are around
1, but with a zoom on the activity coefficient axis, it is observed that there is a linear slight slope.
The vapour pressure values are used for the calculation of the experimental activity coefficients.
As the experimental boiling point of TAME is not matching the one of the pure component, then
all the experimental activity coefficients have some error. It can be observed that for pure TAME
the experimental activity coefficient is not at value of 1. Although all the points of the logarithm
of the activity coefficients ratio are close to 0, all the values are positive. This fact generates a
nonzero result and consequently the thermodynamic consistency test is not satisfied. The value
for the consistency test is of 69 %, which is above the tolerance of 10%. The deviation is similar
to the one observed in the previous system which also contains TAME.
When the data is correlated to thermodynamic models, all the models are very close to each other
(Figure 4.26). The boiling point of pure TAME is higher than the one reported by experimental
points due to the impurities in the TAME solution used and to the insufficient time of apparatus
stabilisation. The vapour compositions correlated are closer to the xy diagram diagonal than the
experimental points.
125
1
0.9
0.8
0.7
0.6
This work
0.5
y
Everson 2001
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x
ideal mixtures (P=1013 mbar)
1.5 1.5
1.4
1.3 2M1B
1
TAME
1.2
ln(gama1/gama2)
0.5
1.1
1
0
0.9 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
0.8 -0.5
0.7
0.6 -1
0.5
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 -1.5
x1 x1
Figure 4. 25 VLE 2-methyl-1-butene (1) / TAME (2), a) experimental activity coefficients, b)

90 1
0.9
80 0.8
0.7
Temperature (C)
70
0.6
0.5
y
60 This work
0.4 Wilson
This work Van Laar
50 0.3
Wilson NRTL
Van Laar UNIQUAC
0.2
40 NRTL
UNIQUAC 0.1
30 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x, y x
Figure 4. 26 VLE 2-methyl-1-butene (1) / TAME (2), correlation of the experimental data to
126
1
90
0.9
80 0.8
0.7
Temperature (C)
70
0.6
0.5
y
60
0.4 This work
UNIFAC
50
This work
0.3
COSMO
UNIFAC 0.2 UNIFAC Dortmund
COSMO
40
UNIFAC Dortmund 0.1
30 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x, y x
Figure 4.27 VLE 2-methyl-1-butene (1) / TAME (2), predictions compared with the experimental
data (P=1013 mbar)
Using estimation models, the estimated vapour compositions in the xy diagram are closer
to the diagonal than the experimental ones (Figure 4.27), similar to the correlated functions
obtained. The predictions of COSMO are between the predictions using UNIFAC and UNIFAC
Dortmund, although all of them are very close to each other. The UNIFAC model is which is
closer to the experimental data.
4.4.4. Isopentane / methanol
This experiment is focused on data for dilute solutions and near the azeotrope. Except some
erroneous punctual values such as 0.767 molar fraction of i-pentane, the rest of data follow a
curve which suggests an easy separation because the vapour compositions are very far from the
diagonal in the x-y diagram (Figure 4.28).
1
0.9
0.8
0.7
0.6
0.5
y
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x
Figure 4.28 VLE isopentane (1) / methanol (2), x-y diagram (P=1013 mbar)
127
75
65
Temperature (C) 55
45
35
25
15
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x, y
Figure 4.29 VLE isopentane (1) / methanol (2), Txy diagram (P=1013 mbar)
However, a minimum boiling azeotrope is detected at a temperature of 24oC and i-pentane molar
fraction of 0.88 (Figure 4.29). A lot of precautions had been taken during the manipulation of the
samples due their low boiling point, such as freezing the gas tight syringe before using it. A
possible evaporation can affect the samples compositions providing vapour compositions poorer
in i-pentane.
1
0.9
0.8
0.7
0.6
0.5
y
This work
0.4
Ogorodnikov 1960
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x
Figure 4.30 VLE isopentane (1) / methanol (2), x-y diagram from data available in the literature
(P=1013 mbar)
128
The azeotropic composition found in this thesis is around 0.88 molar fraction of i-pentane.
Rihko-Struckmann et al (2000) and Ogorodnikov et al (1960) obtained the azeotropic
composition a bit lower at 0.85 molar fraction of i-pentane (Figure 4.30). When representing
graphically the experimental data obtained by these authors, a rather small difference can be
noticed in terms of position relative to the experimental points determined in this thesis, being
closer to the lowest compositions obtained in the present experimental work. Although the
difference is not important, the vapour compositions obtained are richer in volatile than the ones
available in literature. The values found in literature fill the gap of values present in this thesis
and are in a very good accordance with the experimental values obtained (Figure 4.31). The
values of the experimental activity coefficient and of the consistency test are in accordance to a
non ideal system, fulfilling the thermodynamic consistency test (Figure 4.32).
When the experimental data are correlated to thermodynamic models, the worst
correlation is depicted, as in the previous binary systems, for the Van Laar. UNIQUAC does not
provide satisfactory results because it predicts a liquid-liquid equilibrium which was not
observed during the experimental work. NRTL fits without the liquid phase split but the best
fitting is provided by Wilson thermodynamic method. The fitting is slightly improved if the non-
ideal behaviour of i-pentane in the vapour phase is taken into account instead of the ideal one.
The Wilson fitting completed with an equation of state with Henry’s law (HF) is also shown.
75
65 This work
Ogorodnikov 1960
Temperature (C)
55
45
35
25
15
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x, y
Figure 4.31 VLE isopentane (1) / methanol (2), Txy diagram from data available in the literature
(P=1013 mbar)
129
140 5
4
120
3
100
ln(gama1/gama2)
80 1
0
60
iC5 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
-1
MeOH
40
-2
20 -3
-4
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 -5
x1 x1
Figure 4.32 VLE isopentane (1) / methanol (2), a) experimental activity coefficients, b)
75 1
0.9
This work
65 Wilson 0.8
Van Laar
This work
NRTL 0.7
Temperature (C)
55 Wilson
UNIQUAC
0.6 Van Laar
WILSON-HF
NRTL
45 0.5
y
UNIQUAC
WILSON-HF
0.4
35
0.3
25 0.2
0.1
15 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x, y x, y
Figure 4.33. VLE isopentane (1) / methanol (2), correlation of the experimental data to several
thermodynamic models (P=1013 mbar)
Comparing the experimental results with the estimation models, the UNIFAC predicts a liquid-
liquid equilibrium that does not exist experimentally (Figure 4.34). The UNIFAC Dortmund
provides the best for mixtures rich in methanol and the COSMO provides the best correlation for
the azeotropic point and the range rich in i-pentane. It is remarkable that for this range, COSMO
provides a better estimation than the group contribution methods.
75
1
0.9
65 This work
UNIFAC 0.8
COSMO
Temperature (C)
55 UNIFAC Dortmund 0.7

0.6
45
0.5
y
This work
0.4 UNIFAC
35
COSMO
0.3
UNIFAC Dortmund
25 0.2
0.1
15 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x, y x
Figure 4.34. VLE isopentane (1) / methanol (2), predictions compared with the experimental
data (P=1013 mbar)
130
Finally, the experimental data is compared with the VLE obtained from the Aspen database
using the Wilson and NRTL models (Figure 4.35). The Wilson model is not able to simulate
liquid-liquid equilibrium and as NRTL model parameters implemented show a liquid phase split,
the conclusion that the system presents a liquid phase split could be erroneous. Apart from the
liquid-liquid equilibrium, the Txy diagram curves are very different for both models in the zone
between the azeotrope and pure i-pentane. These graphics are just included in order to highlight
the importance of performing a bibliographic search and/or experimental determination before
assuming that the parameters in a simulator database must be suitable for our purposes.
75 1
0.9
65 0.8
This work
WILSON Aspen
0.7
Temperature (C)
NRTL Aspen
55
0.6 This work
WILSON Aspen
0.5
y
45 NRTL Aspen
0.4
35 0.3
0.2
25
0.1
15 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x, y x, y
Figure 4.35 VLE isopentane (1) / methanol (2), comparison of Aspen database with the
4.4.5. Summary of the performances of different thermodynamic model
As a summary, there is not detected experimentally liquid-liquid equilibrium for any of the
studied binary systems although some predictions or simulator database values indicate this split.
The systems containing TAME and 2M2B or 2M1B behave quite ideally. The systems
2M2B/MeOH and iC5/MeOH present minimum boiling azeotropes.
The models evaluated for the calculation of liquid activity coefficients are Van Laar (1910),
Wilson (1964), NRTL (Renon et Prausnitz, 1968) and UNIQUAC (Abrams et Prausnitz, 1975).
For the gas phase the best fitting was obtained considering the ideal gas equation, except for the
system iC5/MeOH where a slightly better correlation was obtained considering the Henry’s law
in the vapour phase.
In order to make some calculus for a distillation process it is necessary first to establish a model
that correlates the experimental data and also that can describe the relation between the
dependent and independent variables. The difference between an experimental value and a fitted
one gives the deviation of the model for that point. This difference is called the residual. The
software calculates the parameters of each model using the method of least squares. To
131
determine which model correlates best the experimental data, the root mean square error for the
temperatures ( ΔT ) is used, according to the following expression:
∑ (T exp,i − Tcalc ,i )
ΔT = i =1
, where N – number of experimental points (IV. 3)
N
The calculations were performed using ASPEN Plus. The Van Laar model provides the
worst correlation in all the cases according to the root mean square error for the temperatures
(Figure 4.36). From the average temperature deviation, the Van Laar correlation is worst in most
of cases except for the 2M1B/TAME where the correlated Txy curve is closer to the
experimental temperatures and for the iC5/MeOH where it correlates an inexistent LLE. All the
other models provides a similar correlation, the UNIQUAC is slightly worst than the NRTL or
Wilson. Some systems are better correlated with NRTL and some others with Wilson, but both
models provide generally very good correlation. The fitted parameters are given in Table 4.2 and
the corresponding standard deviations in Table 4.3 together with the maximum deviations of
temperature. The average temperature deviation between the fitted and the experimental values is
shown in Figure 4.37.
3.5
2.5
2
ΔT,K
1.5
TAME-2M2B
0.5
TAME_2M1B
0 MeOH-2M2B
Wilson MeOH-iC5
VanLaar
NRTL
UNIQUAC
Figure 4. 36 Thermodynamic model correlation for each binary system. Root mean square error
for the temperatures.
132
Table 4. 2. Estimated thermodynamic models parameters.
2M2B/MeOH 2M2B/TAME 2M1B/TAME iC5/MeOH
bijcma 7.491E+2 1E+04 4.011E+01 8.607E+02

Van Laar
bjicma 8.381E+02 -3.799E+01 1E+04 9.290E+02
ΔT 0.3956 2.5396 0.1049 -0.0174
bijcma -5.043E+2 3.949E+02 3.611E+02 -6.063E+02

Wilson
bjicma -1.125E+03 -1.012E+03 -2.721E+03 -1.013E+03
ΔT 0.2401 1.2983 0.6334 0.0320
bijcma 7.743E+02 -3.310E+02 8.766E+02 9.817E+02
bjicma 4.868E+02 4.575E+02 -4.543E+02 6.741E+02

NRTL
α cma 0.3974 0.358038 0.3000 0.4645
ΔT 0.0345 1,4595 0.8867 0.1699
bijcma -7.615E+02 -4.719E+02 -5.519E+02 -8.479E+02

UNIQUAC
bjicma 5.716 2.769E+02 2.810E+02 -8.9354
ΔT 0.0329 1.2845 0.7791 -0.3896
2.5
1.5
ΔT,K
0.5
TAME-2M2B
0
TAME_2M1B
-0.5 MeOH-2M2B
Wilson MeOH-iC5
VanLaar
NRTL
UNIQUAC
Figure 4. 37 Average temperature deviation.

133
Table 4. 3 Maximum error temperature prediction for the estimated parameters.
2M2B/MeOH 2M2B/TAME 2M1B/TAME iC5 /MeOH
bijcma 22.65 0 7.85 19.62

Van Laar
bjicma 52.16 17.46 0 31.70
ΔT -3.6 6.0 4.6 -8.3
bijcma 32.96 18.16 14.66 12.34

Wilson
bjicma 319.08 174.25 0 30.45
ΔT -5.3 5.2 3.9 -5.6
bijcma 100.00 0 171.27 27.62
bjicma 51.07 158.98 44.81 16.58

NRTL
α cma 0.0382 0.16 - 0.0102
ΔT -4.8 4.2 4.3 -5.3
bijcma 64.95 59.16 81.42 24.14

UNIQUAC
bjicma 11.26 18.96 19.95 5.27
ΔT -4.7 5.2 4.0 -6.1

The experimental data obtained is in good agreement with the literature data available. The
thermodynamic consistency tests are satisfied for most of the systems except when the
component TAME is present. The TAME boiling point is quite different from the pure
component boiling point. The consequence is that the thermodynamic consistency test fails due
to the non-matching vapour pressure for this component. UNIFAC predicts erroneously the
presence of liquid-liquid equilibrium for the systems 2M2B/MeOH and iC5/MeOH. Without the
prediction of liquid phase split for the 2M2B/MeOH system, UNIFAC would provide the best
correlation. For the ideal systems, all of the models are quit close and the COSMO predicted
curve is usually between the curve predicted by the UNIFAC and UNIFAC Dortmund. For the
non ideal systems, some experimental points are best predicted by one model or another. For
instance, for the iC5/MeOH system, the UNIFAC Dortmund provide the best prediction when the
mixtures are rich in methanol but the COSMO provides a better estimation when the mixtures
are rich in i-pentane. For the 2M2B/MeOH system, the UNIFAC Dortmund provides in all the
range of values better predictions than the COSMO.
134
Conclusions
The vapour liquid equilibrium experimental data for several mixtures related to TAME synthesis
have been determined using a Labodest-type ebullometer. The samples analysis has been
performed by gas chromatography with a FID detector. The binary mixtures studied are the
following:
• 2M2B - methanol
• 2M2B - TAME
• 2M1B - TAME
• isopentane – methanol.
The response factor ratios of the chromatograms are linear. The data obtained in this thesis are in
good agreement with the data available in literature. The predictions using the UNIFAC,
UNIFAC Dortmund and the ab initio method COSMO are quite satisfactory when compared to
the experimental data. Although in some cases is predicted a liquid immiscibility, it was not
observed experimentally. The Herrington consistency test is used to choose the model for the
vapour phase; this showed that the ideal gas model is satisfactory. The mixtures with an ideal
behaviour in liquid phase (TAME and isoamylenes) show a higher sensibility to satisfy the
thermodynamic consistency test. The experimental data is correlated and compared to several
thermodynamic models using AspenPlus (Van Laar, Wilson, NRTL and UNIQUAC). The worst
correlation is obtained for Van Laar because it does not take into account the influence of the
temperature on the activity coefficient.
135
CHAPTER 5
Feasibility, analysis and simulation of TAME synthesis-separation
process
In the previous chapters the problem, the state of the art and the thermodynamic data
related to the TAME synthesis chemical system are presented. The kinetics and the vapour liquid
equilibrium data have been determined experimentally and regressed. The aim of the present
chapter is to study and provide new theoretical insights in the process of industrial TAME
manufacture based on thermodynamic data.
The chapter is divided into several sections. Firstly, the reactive residue curve maps
(RRCM) are presented as a tool to understand the behaviour of the systems based on basic
thermodynamic data. A program to calculate reactive residue curve maps (RRCM) taking into
account the reaction kinetics have been implemented. The absence of information about the
separation difficulty in the residue curve maps is overcome in the present thesis by the use of the
number of transfer units. The residue curve maps are the basis for the sensitivity analysis of the
flow rates in the stream purities using simplified models, such as the infinite/infinite analysis.
This is extended in this thesis to kinetically controlled reactions. The process is also evaluated
from the economical and environmental point of view. In this aim, an original and simple cost
function is proposed. The environmental evaluation is performed using the Waste Reduction
Algorithm (WAR) and the Environmental Performance Index is calculated. Rigorous simulations
corroborate the feasibility of the process.
In summary, the goal is to provide an early stage proposal and evaluation of
environmental process schemes, taking into account its techno-economical viability. The method
is structured from fast to rigorous calculations to discard as soon as possible the unfeasible
processes (Figure 5.1).
The methodology to follow consists of several steps for identification of conditions to be
fulfilled and for further decision-making:
- Market demand and basic economic feasibility: identify if there is a market demand to
transform a chemical compound into another. Determine if the price of the obtained products is
higher than the reactants. (Data required: reactants and product prices).
- Basic physical feasibility: determine if the proposed process schemes are feasible according to
the infinite/infinite analysis based on the residue curve map (Data required: kinetic data and
vapour-liquid equilibrium data).
136
- Technical feasibility: determine by rigorous simulation if the proposed process schemes are
feasible.
Figure 5.1 Systematic procedure of the methodology proposed and used.
137
- Techno-economic model with CO2 capture feasibility: determine if the proposed process
schemes are feasible when the energy consumed comes from a coal thermal plant with 95% of
CO2 capture and the investment costs are taken into account
- Environmental Performance Index (EPI) ranking: identify the feasible processes with a higher
EPI, suitable for a more detailed study.
5.1. Market demand and basic economic feasibility

The solution of octane number enhancement by using tetra-ethyl-lead as fuel additive induces
great pollution problems, the toxic effect of Pb aerosols in exhaust gases being well known. The
replacement of tetra-ethyl-lead started to be effective along with the introduction of
environmental protection restrictions in USA by “Clean Air Amendment” (CAAA). To cover the
octane deficit appeared due to tetra-ethyl-lead elimination from cars gasoline, the only solution
accepted at refineries level was the usage of tertiary aliphatic compounds C5-C7. TAME appears
from a market demand of gasoline additives more environmentally friendly than the ones based
on lead. A more detailed discussion about the statement of the problem and the use of TAME is
provided in the Introduction chapter.
A worldwide oil processing capacity of 3 650 Mt/y where 20% of oil is transformed into
gasoline to be further reformulated is assumed. It is considered that raw gasoline contains 11%
TAME; this represents a world production of ~ 10 kt/h.
As the process is already industrially in use, the market and the profitability are assured as stated
in the chapter about the reaction kinetics. TAME can be substituted in the future by some other
chemical compounds but the methodology developed in the present thesis can be applied to any
other case, for this reason a general view is provided.
5.2. Basic physical feasibility

The feasibility is based on the information provided by the residue curve maps. Therefore, the
residue curve maps and the computer implementation are discussed in this section. The
infinite/infinite analysis is used to check the feasibility based on the residue curve map
information and the sensitivity analysis of several variables is calculated.
5.2.1. Introduction to Residue Curve Maps: Theory and Practice

The increasing processing power provided by the computers allows nowadays performing
calculations faster, more efficiently and with lower errors. Complex systems of equations can
be converged sometimes with success and obtain solutions that fulfil the mass and energy
balances. More rigorous is the model, more parameters are required to define exactly the system
138
behaviour. Despite this fact, when the problem is approached only the main chemical
components and its basic thermodynamic data are known. At this early stage, an overall view
and understanding of the system behaviour is desired instead of a wide list of parameters. For
this reason, the residue curve maps that will be introduced in this chapter are the first approach to
face a distillation system because they just depend on basic thermodynamic data. The residue
curve maps are for the chemical engineer what are the streets maps for a taxi driver. It is possible
to go without maps but without a very good knowledge and previous experience there, more
turns around will be performed before reaching the goal.
The representation and graphical visualization of the chemical components in the composition
space is a powerful tool for the analysis and interpretation of systems behaviour. The topological
analysis of the thermodynamics is based on the classical works of Schreinemakers (1901) and
Ostwald (1902) that linked the vapor liquid equilibrium of a ternary mixture with the behavior of
the residue curves. Some years later, Wade and Merriman (1911) introduced the definition of
maximum and minimum boiling azeotropes. The residue curve (Doherty et al., 1979) is defined
as a set of the liquid compositions followed by the residue in the still of a Rayleigh distillation as
the evaporation advances in time. The Rayleigh distillation is an open simple batch distillation
with a single theoretical stage (Rayleigh, 1902) (Figure 5.2). An initial amount of a liquid
mixture with a specified initial composition is brought to its boiling point at a given pressure by
heating. By further heating, the liquid is vaporized and the more volatile components removed
from the system. The output vapor is assumed to be in equilibrium with the liquid phase.
Because the vapor is enriched with the more volatile species, the least volatile species are
enriched in the residue.
Figure 5.2 Rayleigh distillation scheme
For a ternary mixture, the evolution of the residue composition is then plotted on a Gibbs
diagram and a curve is drawn through the composition points taken, giving a residue curve.
When several residue curves are plotted together, they form a Residue Curve Map. In the Gibbs
triangle, each vertex represents a pure component. The edges of the triangle correspond to binary
139
mixtures and each point inside the triangle stands for a certain ternary composition. The
compositions can be expressed in mass or mole fractions. By definition, residue curves do not
intersect. Therefore, there are no closed cycles. Figure 5.3 shows the residue curve map for a
ternary system as illustrative example of their aspect.
Figure 5.3 Residue curve map example. (TAME synthesis at Da=1, P=1 bar;
from Moreira Duarte, 2006).
Matsuyama and Nishimura (1977) investigated and classified all feasible topologies of residue
curve maps. In order to introduce the reader, some definitions about the topology of the residue
curve maps are introduced in this paragraph. Doherty and Perkins (1978) proved that the residue
curve on each point is unique if it is not a singular point, consequently, residue lines cannot cross
each other. In addition, there are some points from which diverge or converge families of residue
curves. These are some of the so-called singular points. The points from where diverge some of
the residue curves are called unstable nodes and the points to where converge some of the
residue curves are called stable nodes. There is a third kind of singular point where some of the
residue curves converge and some others diverge; these are called saddle points. The
mathematical interpretation will be provided later in this chapter but here a qualitative
interpretation is provided.
The singular points correspond to compositions for which although a higher volume of vapour
is retrieved from the system, the liquid composition remains the same. This happens for the pure
140
components and for the azetropic compositions in non reactive systems because the liquid and
vapour compositions are equal. When a reaction is present, then the topology of the residue
curve map changes. For instance, in reactive systems, the azeotrope formed by two reactants can
react and the corresponding singular point present in the non reactive systems can be no longer
present in the reactive system. On the other hand, due to the reaction, new type of singular points
corresponding to some reactive azeotropes can appear in the residue curve map.
A more general definition of azeotrope given by Prigogine and Defay (1967) is more suitable: it
is a state in which there is mass transfer at the interface, while the compositions of both phases
remain constant. It is not required for both phases to have the same composition. For the isobaric
case, there are only isolated singular points.
For a constant pressure, the temperature always increases along a residue curve, because the
liquid phase depletes in the more volatile components. Therefore, the boiling temperature of the
residue increases. If the boiling points are plotted over the composition space giving a
temperature surface, the unstable nodes represent the local minimum of this surface while the
stable nodes represent the local maximum of this surface. The globally lowest (highest) boiling
point is always at an unstable (stable) node. The representation of the boiling point temperatures
provides a graphic which reminds of a topographic map, but when they are plot together with the
residue curves these are not following the obtained valleys and top ridges (Rev, 1992). Valley
floors and top-ridge lines in the T(x) surface may be utilized to identify ternary azeotrope points
(Swietoslawski, 1963).
The set of residue curves that diverge from the same unstable node and converge to the same
stable node defines a distillation region. If there are more than one node of the same kind
(stable or unstable), there will be at least as many simple distillation regions as nodes. The
residue curve that separates two simple distillation regions is called a boundary line. At least one
of the ends of a residue curve boundary must be a saddle.
Previously, a global vision of the residue curve maps and its topology is provided. The
usefulness of the residue curves comes from the fact that the variation against time of the residue
composition, in the still of a simple distillation, is matching the compositions along the length of
a packed distillation column at infinite reflux flow rate. It is important to notice that it
corresponds to an infinite reflux flow rate and not to an infinite reflux ratio or total reflux. These
two situations represent two very different scenarios.
At total reflux, no distillate flow rate is collected and all the vapour condensed in the top of the
column is returned at a finite flow rate. On the other hand, an infinite reflux flow rate means that
the liquid and vapour flow rates descending and ascending respectively in the column have an
infinite flow rate in respect with the distillate flow rate, the latter having a non-zero value. The
141
consequence of this assumption is that the feed position has no influence on the column. The
feed, as the distillate and bottoms flow rates, have a non-zero values infinitely smaller than the
vapour and liquid flowrate inside the column so that the feed effect is negligible in the column
profile. This allows a first plot of the residue curve map and, in a second step, an analysis
considering the compositions of the input and output flows to and from the distillation column.
Usually, when a column profile is represented graphically in a ternary diagram, a certain
deviation of the column profile towards the feed composition is observed. Due to the infinite
reflux flowrate assumption, the residue curves do not deviate to the feed and therefore they are a
limit condition and not a real situation. As the reflux used in the column becomes higher, the
column profile gets closer to the residue curve. The deviation of the column profiles or residue
curves represented on a ternary diagram are according to the chemical affinity. For instance,
when the curves are near a triangle vertex corresponding to a pure component, the curves deviate
towards the triangle edge defined by this component and the chemical component with higher
chemical affinity with it. This fact can be useful for selecting components for an extractive
distillation. However, the main use of the residue curves is concerning the feasibility of a
separation.
If there is a residue curve running between two compositions in the residue curve map, it means
that a distillation column that collects these compositions by the distillate and bottoms is
feasible. The feed composition must fulfil the mass balance and graphically it means that the
point corresponding to the feed must be over the straight line defined by the distillate and
bottoms composition. The lever rule can be applied to determine the correspondent flow rates.
The existence of the residue curve assures that this separation is feasible in a distillation column
with an infinite reflux, or in a distillation column with a high enough reflux. One of the
nowadays drawbacks of the residue curve maps is that they provide the feasibility of the
separation but not the difficulty of the separation. From the residue curve map, the feasibility can
be assured but not the technical feasibility because it could be feasible with a too high reflux or
number of stages, which would be economically unviable.
It should be noticed that the residue curve maps provide a necessary but not sufficient condition
of feasibility. When a process is feasible according to the residue curve maps, then it is feasible
with an enough number of stages and reflux; nevertheless, a feasible process can appear as
unfeasible according to the residue curve maps. For instance, using a double feed, the column
profile between both feeds can show a trajectory almost perpendicular to the residue curves and
separations unpredicted by the residue curves can be attained. This deviation comes mainly from
the assumption of infinite reflux flow rate, and not from the multiple feed; a multiple feed
column with a high enough reflux flow rate would behave as predicted by the residue curves.
142
According to the residue curves map feasibility, a separation is only feasible when both the
distillate and bottoms are inside the same distillation region. The feed can be present in a
different distillation region when the boundary is curved, having to fulfil the mass balance, but it
must not be on the same residue curve with distillate or bottoms. However, the residue curve
regions boundaries can be crossed by a rectification as is pointed out by Doherty and Perkins
(1978). It is because the tie lines are always tangent to the residue lines at the liquid point and the
boundaries are usually curved. But an appreciable crossing of the boundaries can be found just in
very rare cases such as in boundaries between two saddle points (Rev, 1992).
5.2.2. Mathematical model for the (reactive) residue curves

Assuming that there are M reactions in the liquid phase, described stoichiometrically by the
equations:
Nr Np
  ir , j Air    ip , j Aip for j=1…M (V. 1)

ir 1 ip 1
where ir and ip are the component index for reactants and products, Nr and Np are the total
number of reactants and products, j is the reaction index, M is the number of reactions in the
system,  i, j is the stoichiometric coefficient of the component i in the reaction j and A is the
molecular formula of the component ir or ip. The rate expression is assumed to have the form:
Nr Np
r j  k f , j  a ir ir , j  k r , j  a ip ip , j
 
(V. 2)
ir 1 ip 1
kf,j, is the forward reaction rate constant, kr,j is the reverse reaction rate constant, and air and aip
represent the liquid phase activities of the components. The same equations are valid for
products and reactants, therefore the overall index i will be used instead of ir and ip.
The activities are usually expressed as function of molar fractions (xi) and activity
coefficients γi:
ai   i  xi (V. 3)
Writing the component mass balances in the still of a simple distillation with chemical reaction
(Figure 5.2):
d H  xi  M
 V  y i   i , j  r j  H (V. 4)
dt j 1
143
where H is the liquid molar holdup, xi is the molar fraction of component i in the liquid phase, t
is the time, V is the vapour flow rate, yi is the molar fraction of component i in the vapour phase
and the reaction rate rj has as units moli/(molholdup·s).
dxi dH M
H  xi   V  yi   i , j  rj  H (V. 5)
dt dt j 1
The overall mass balance, a linear combination of partial mass balances, is:
M N
dH
 V   T , j  r j  H where  T , j   i , j (V. 6)
dt j 1 i 1
substituting the overall mass balance (V.6) in the component mass balance (V.5):
dxi  M
 M
H  xi   V   T , j  rj  H   V  yi   i , j  rj  H (V. 7)
dt  j 1  j 1
By rearranging the last equations:
dxi M M
H  V   xi  yi    i , j  rj  H  xi   T , j  rj  H (V. 8)
dt j 1 j 1
and dividing by V:
H dxi H M H M
   xi  yi     i , j  rj  xi    T , j  rj (V. 9)
V dt V j 1 V j 1
or:
H dxi H M
   xi  yi      i , j  xi  T , j   rj (V. 10)
V dt V j 1
Finally, substituting the value of rj, the next equation for each component is obtained:
H dxi H M  Nr  k Np 
 xi  yi    k f , j   i , j  xi  T , j     air ir , j  r , j a
 ip , j
  for i=1,…,N (V. 11)
V dt V j 1  ir 1 kf ,j
ip

 ip 1 
The expression of chemical equilibrium constant Kj(T) is obtained when rj=0:
144
Np
a
 ip , j
ip , eq
kf,j N
  ai ,ieq, j 
 ip 1
K j (T )  Nr
(V. 12)
kr , j
a
i 1  ir , j
ir , eq
ir 1
In the previous expression, N is the total number of components (Nr+Np) and, by convention, the
stoichiometric coefficient ij is negative for the reactants and positive for the products. The value
of the chemical equilibrium constant can be introduced in the residue curve differential
equations:
H dxi H M  Nr  1 Np 
 xi  yi    k f , j   i , j  xi  T , j     air ir , j  a
 ip , j
  for i=1,…,N (V. 13)
V dt V j 1  ir 1 Kj
ip
 ip 1 
In the expression appearing in equation (V.13), there are two factors affecting the direction taken
by the residue curve. The reaction (REA) and the separation terms (SEP):
SEP  xi  yi (V. 14)
H M  Nr  1 Np 
  k f , j   i , j  xi  T , j     air ir , j  a
 ip , j
REA   (V. 15)
V j 1  Kj
ip
 ir 1 ip 1 
The H/V ratio is expressed in units of time. When the value of H is much higher than V, the
situation corresponds to an elevated “hold up” versus the vapour flow rate (V) and the reaction
approaches the equilibrium. On the contrary, when H is very small compared to V, the term of
the reaction becomes negligible and the expression becomes as that of distillation without
reaction. A change of variable for t is usually applied providing a dimensionless time. The
(reactive) residue curve map represents the evolution of the liquid composition, but the time is
not appearing explicitly in the diagram. Therefore this change of variable is “changing the time
scale” but not the liquid composition evolution (relative position) of each residue curve.
d  V  H dt (V. 16)
dxi H M  Nr  1 Np 
 xi  yi    k f , j   i , j  xi  T , j     air ir , j  a
 ip , j
 ir 1  (V. 17)
d
ip
V j 1  Kj ip 1 
Another point is that the reaction rate can be reported to units of catalyst weight or to the number
of active sites in the catalyst. This second option, also applied by Thiel et al (1997) is followed in
this thesis:
145
dxi H M m  Nr  1 Np 
 xi  yi    k f , j   i , j  xi  T , j   cL cat0   air ir , j  a
 ip , j
  (V. 18)
d
ip
V j 1 H  ir 1 Kj ip 1 
where H0 is the initial molar hold up, cL represents mean acid group concentration on catalyst
and mcat represents the mass of catalyst and kf,j is the kinetic constant expressed as 1/(time · acid
group).
The residue curve equation (V.18) can be also expressed in terms of Damkhöler number (Da)
defined as:
cL  mcat H 0 cL  mcat  k f T *
Da  k f T *   0  (V. 19)
H0 V V0
where kf(T*) is a reference rate constant value, conveniently selected and V0 is the initial molar
vapour flow rate. In this thesis, in order to provide results that can be easily compared with the
existing literature data, a kinetic constant calculated at 333 K is used such as Thiel et al. (1997).
dxi
 xi  yi
d
(V. 20)
H V0 H0 1 M
m  Nr  1 Np 
  k f , j   i , j  xi  T , j   cL cat0   air ir , j  a
 ip , j
  Da  0   
H cL  mcat k f T * j 1 H  ir 1
ip
V Kj ip 1 
simplifying
dxi H V0 1 M  Nr  1 Np 
  k f , j   i , j  xi  T , j     air ir , j  a
 ip , j
 xi  yi   Da  0   (V. 21)
d V H k f T * j 1  ir 1 Kj
ip
 ip 1 
Assuming H/V=Ho/Vo:
dxi M kf,j  Nr  1 Np 
 xi  yi  Da     i , j  xi  T , j     air ir , j  a
 ip , j
 (V. 22)
d j 1 k f  T *
 Kj
ip
 ir 1 ip 1 
This is the expression used in this thesis for the calculation of the reactive residue curves. Note
that the expression of kinetics in terms of the active centres of catalyst instead of the catalyst
weight is changing the definition of the Da number, but not the general expression as was
previously obtained, the residue curve expressions remaining the same. An equivalent expression
using the direct kinetic constant at the minimum temperature would be feasible but to keep the
coherence with the existing literature, as already indicated, in this work the same reference
temperature as Thiel et al (1997) at 333 K is used.
146
The kinetic constant and reaction equilibrium constant depend on the boiling point temperature
of the mixture. The boiling point temperature (Tb) and the vapour composition are related to the
liquid composition. As phase equilibrium is assumed, yi can be evaluated from the modified
Raoult law and the condition of concentrations sum to unity in the vapour phase:
 i  xi , Tb   pisat Tb x

yi  i for i=1,…,N (V. 23)
p
N
1   yi (V. 24)
i 1
That combined lead to:
N  i  xi , Tb   pisat Tb x

0  1  i (V. 25)
i 1 p
This expression is calculated using a software with an equation solver. The system formed by the
previous equation and the differential equations of the residue curves provides the mathematical
model to solve. The differential equation is solved numerically and the liquid compositions
obtained must be normalized at each step.
5.2.2.1. Residual Curves and Number of Transfer Units (NTU)

The residue curve maps are widely used because they provide fast insights into the distillation
processes such as chemical affinity between components, distillation regions, the presence of
azeotropes and boundary lines are easily identified. The inclusion of a quantification of the
separation difficulty in the residue curve maps is proposed for first time on the studies derived
from the present thesis to contribute to the enhancement of the residue curve map tool.
It is traditional for chemical engineers to model packed columns through the concept of Number
of Transfer Units (NTU) according to a dimensionless expression (Taylor and Krishna, 1993).
The NTU necessary for a given separation depends only on the composition column profile and
it does not depend on the characteristics and performance of the packing.
The mass balances around a section of differential height (z) at an arbitrary position z in a
packed distillation column results in the following equations. For the vapour phase:
i |z i |z z  N iV  a  A  z (V. 26)
147
where the positive direction of z is given by the direction of liquid flow, a is the interfacial area
between liquid and vapour phases per unit volume, A is column cross section area, υi is the molar
flow rate of component i and N iV is the molar flux for the i component from the vapour phase.
Passing from small increments to differential equations, taking z approaching zero, the
following partial and overall mass balances are obtained:
di
 N iV  a  A where 1 = 1, 2, …, N
dz
The overall molar flow rate of vapour phase is the sum of component flow rate: V  i .
Summing up, one obtains:
dV
  N tV  a  A (V. 27)
dz
Where N tV is the total vapour flux up the column. The molar flux for each component has a
diffusive component (J) and a convective one:
N iV  J iV  yi  N tV (V. 28)
As i  V  yi and assuming equimolar transfer N tV  0 , the vapour molar balance becomes:
d yi dV
V  yi    J iV  a  A  yi  N tV  a  A where i = 1, 2, …, N (V. 29)
dz dz
In view of equation (V.28), the right members on both sides of equation (V.29) cancel each other
and we get:
d yi
V   J iV  a  A (V. 30)
dz
The molar flux relation is the following:

J V  ctV   K OV   y  y  (V. 31)
where ctV is the vapour molar density, KOV is the overall mass transfer coefficient, y is the vector
of vapour concentration in equilibrium with the liquid and y is the vector of vapour concentration
148
in direct contact with the liquid. This rate relation introduced in the differential mass balance
gives:
V
dy
dz
 
 ctV   K OV   y  y  a  A (V. 32)
The packed characteristics can be introduced in the overall number of transfer units (NTU) for
the vapour phase defined as:
NTU T  ctV  K OV  a  Lc  A V (V. 33)
where Lc is the total column height.

Replacing NTU in the previous equations, one obtains:
d y NTU T
  ( y  y) (V. 34)
dz Lc
z
and defining   as dimensionless space coordinate, the following expression is obtained:
Lc
d yi
d

 NTU T  yi  yi  (V. 35)
The difference between y and y is the driving force for the components transfer from the liquid
phase to the vapour phase, Lc represents the overall packing height. This expression is used when
the total number of transfer units along the overall height of the column is fixed. The number of
transfer units at each value of ζ is:
NTU  NTU T   (V. 36)
In this way, the dependence of the composition versus NTU is:
d yi
 yi  yi (V. 37)
dNTU
For a non-reactive distillation column, the mass balance on the rectifying section is:
V  yi  L  xi  D  xiD (V. 38)
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where V is the vapour flow rate, L is the liquid flow rate and D is the distillate flow rate.
Assuming infinite reflux flow rate, L and V are infinite meanwhile D is a finite number.
L D
yi   xi   xiD (V. 39)
V V
lim L D 
yi    xi   xiD  (V. 40)
L, V    V V 
Then D/V=0 and applying the Hôpital rule,
yi  xi (V. 41)
And the NTU expression becomes, in the case of infinite reflux, the following equation:
dxi
 xi  yi (V. 42)
dNTU
The similitude of this equation with the residue curve expression without reaction is obvious.
The dimensionless time of the residue curve can be directly related to the number of transfer
units (NTU).
d  dNTU (V. 43)
The coincidence of the residue curve profile with the profile of a packed column with infinite
reflux flowrate was demonstrated by several authors (Van Dongen and Doherty, 1985; Laroche
et al, 1992). This coincidence is what makes the residue curves useful to check the feasibility of
distillation systems. In the studies for this thesis, the dimensionless time of the residue curves has
been identified as the NTU. This is one of the main contributions of the present thesis as this fact
has important implications. The residue curve maps are just used to check the feasibility of
separation systems but as it is related to the NTU, it means that it is also possible to quantify how
difficult is the separation.
dNTU 1
 (V. 44)
dxi xi  yi
The value of NTU necessary to change the concentration of a component between xi0 and xi is:
150
xi
dxi
NTU   x  yi
xi ,0 i
(V. 45)
As all the residue curves from the same distillation region depart and reach the same singular
points, then all of them must have the same NTU. This fact is obvious as at the nodes xi=yi and
NTU is infinite.
A similar equation for NTU dependence of composition can be also determined for reactive
systems. The molar balance for the rectifying section of a reactive distillation column is:
M
V  yi  D  xiD  L  xi  H   i , j  rj (V. 46)
j 1
where H is the liquid hold-up in the rectifying section and rj is the reaction rate in rectifying
section. The overall molar balance is:
M N
V  D  L  H   T , j  rj where  T , j   i , j (V. 47)
j 1 i 1
From the last two equations:
 M
 M
 D  L  H    T, j  r j   yi  D  xi
D
 L  xi  H    i , j  rj (V. 48)
 j 1  j 1
From these equations, one obtains:
D D H M
 xi  xi    i , j  rj
L L j 1
yi  (V. 49)
D H M
 1    T , j  rj
L L j 1
As L is infinite and D is a finite number, then D/L=0 and H/L corresponds to the residence time
(τ) on the column section:
M
xi     i , j  rj
j 1
yi  M
(V. 50)
1     T , j  rj
j 1
Notice that the overall molar balance in the rectifying section becomes independent of distillate
composition withdrawal. Assuming that the distillate composition is close to xi composition, then
151
rj can be calculated for an xi composition. Otherwise, an average reaction rate for the overall
section must be calculated and the method would lose its simple form. The retention time is
linked to the height of the column for which rj is calculated. Therefore, assuming an average
reaction rate, the retention time will be changing along the column profile depending on
initialization point.
d yi dy dxi
 i (V. 51)
dNTU dxi dNTU
From equations (V.37) and (V.51) results:
 M

dxi
 xi      i , j  rj  
d y 
1
  yi 
j 1
 i
 (V. 52)
dNTU  M
  dxi 
 1      T , j  rj 
 j 1 
For the case of simple distillation and for first order reactions without variation of number of
d yi
moles,  ct  1 , the equation (V.51) being written as:
dxi
dxi
 yi  xi
dNTU (V. 53)
d yi
For systems of reactive distillation, the expression  ct and is more complex. The present
dxi
d yi
study is focused on the simplified case where  ct  1 . In this case, equation (V.52)
dxi
becomes:
M
xi     i , j  rj
dxi j 1
 yi  M (V. 54)
dNTU
1     T , j  rj
j 1
This expression obtained combining the definition of NTU and the molar balances, assuming
infinite reflux flow rate and the hypothesis that the input-output stream compositions do not
affect the RRC compositions, is quite different from the expression obtained by a molar balance
on a Rayleigh distillation:
152
dxi H M
 xi  yi     i , j  xi  T , j   rj (V. 55)
d V j 1
The expressions (V.54) and (V.55) differ by:
 2 M M M 
    T , j  rj    i , j  rj   T , j  rj  xi  
 j 1  j 1 j 1  (V. 56)
  M
 
  1     T , j  rj  
 
  j 1  
Notice that when there is no reaction term, both expressions become equivalent. When the total
number of moles are not changing due to reaction stoichiometry  T , j  0 , then both expressions
are also equal and the NTU can be also identified with the dimensionless time of the reactive
residue curve expression. In this case, the H/V term from the Rayleigh distillation can be
identified with the retention time in the reactive distillation column τ. According to this fact, it
must be reconsidered if it useful to define a Da number instead of using directly H/V as a
variable. As already discussed, the Da number substitutes the H/V ratio, but it requires the
introduction of some new assumptions such as H/V = constant and a new parameter
corresponding to a kinetic constant which depends on a reference temperature whose value is not
clearly established. When  T , j  0 , the expressions become different. This difference is
evaluated later for TAME synthesis. However, in the present thesis, the expression derived from
a Rayleigh distillation including reaction is used following the same expression as in the existing
literature for the analysis of the system. Krolikowski (2006) proves that even the assumption that
a residue curve can predict the behaviour of a full reflux column via distillation boundaries (Van
Dogen and Doherty, 1985) can be inaccurate.
In summary, from the above discussion some new points of view about the residue curve maps
are introduced such as to use the integral results in a NTU map in addition to the differential
results in a residue curve map in order to provide additional information about the difficulty of
the separation. The NTU and the residue curve expression are equivalent, except when the
number of moles is not constant due to reaction stoichiometry.
5.2.2.2. Singular Points

At the beginning of the chapter, the singular points are qualitatively defined and classified as
stable nodes, unstable nodes and saddles. In the previous section, mathematical expressions for
the residue curve maps are provided. Therefore, the singular points can be defined also in a
mathematical way.
153
The singular points can be expressed mathematically such as a non-evolution point in the residue
curve map and according to the derived Rayleigh expression:
dxi H M
 0  xi  yi     i , j  xi  T , j   rj (V. 57)
d V j 1
yi  xi     i , j  xi  T , j   rj
H M
(V. 58)
V j 1
And for the obtained NTU expression is:
 M 
 xi     i , j  r j 
 
d xi 
 0   yi 
j 1 
(V. 59)

dNTU   M 
1     T , j  r j 
  
  j 1 
 M   M 
yi  1     T , j  r j    xi     i , j  r j  (V. 60)
 j 1   j 1 
In both cases, when there is no reaction (rj=0), the singular points correspond to the situation
when the liquid and vapour compositions have the same composition and, in this case, it is not
possible to distil further. This happens for pure components and azeotropes. In the presence of a
reaction, the non-evolution points become placed differently in the reactive residue curve map.
In this case, the composition of the phases can differ due to the effect of the reaction. The
composition changes due to mass transfer are compensated by the composition changes due to
the reaction. The compositions that provide a non-evolution point are called reactive azeotrope.
However, when the number of moles change due to reaction stoichiometry, as in the case of
TAME synthesis, then the mathematical definition of the singular points becomes different.
The position of the singular points in the reactive residue curve map depends on the
thermodynamic data, on one side the vapour liquid equilibrium and on the other side the reaction
kinetics. For a mixture of several chemical components, the vapour liquid equilibrium data
depends on the pressure of the system and the reaction extent depends on the pressure and the
retention time. The pressure is a distillation process variable, which determines the boiling point
of the mixture and the vapour liquid equilibrium composition. The reaction rate and chemical
equilibrium depend on reaction temperature, while the boiling point temperature in a reactive
distillation column changes according to the liquid composition. Therefore, the position of the
singular points for a given chemical mixture depends just on the retention time and pressure. In
154
most cases, atmospheric pressure is chosen to avoid the need of pressurizing equipment, but in
some cases where the compounds are very volatile, such as in the TAME synthesis, the pressure
becomes an important design and operation variable. The retention time is rather a consequence
of the column design. Very high retention times mean that the process is limited by separation
and the reaction approaches the chemical equilibrium, while very low retention times results in
little to no reaction occurring. The maximum retention time is infinite and the minimum is zero.
The exact position of the singular points depends on the value given to the retention time or Da
related parameter. However, each singular point should define a unique curve on the reactive
residue curve map when the pressure or Da values change.
5.2.3. Implementation of the reactive residue curve maps calculation

In this section, the previously discussed model is implemented. A qualitative general overview of
this implementation is provided at the beginning followed by a more detailed discussion of the
program.
The main program is divided into four main sections and calls two subprograms (MATLAB
functions). The main sections are the following:
1. Input of the process design and thermodynamic data
2. Exploration of the map topology. Generate a thick and uniform mesh grid on the map and
determine for each point of the mesh the boiling point and the driving force for the
separation. The results obtained can be used as additional information in the background
of the curves.
3. Generate the residue curves.
4. Integrate the residue curves to obtain the Number of Transfer Units (NTU).
The two subprograms used are:
1. Calculus of differential equations for the residue curves
2. Determination of the vapour liquid equilibrium data (VLE).
5.2.3.1. Data Input

The data input can be divided in two main categories:
1. Thermodynamic and kinetic data;
2. Process design data.
The inputs needed to calculate the thermodynamic and kinetic data are:
1. Ideal gas constant value (in coherent units) R;
2. Extended Antoine Equation Parameters to calculate vapour pressures;
3. Chemical equilibrium data;
155
4. Kinetic data.
The VLE model parameters are introduced in a file depending on the subprogram calculating the
VLE. Although it would be advisable to have all the input data together, several models can be
implemented to calculate the vapour liquid equilibrium and each one has its own parameters. For
this reason, it was preferable to let this thermodynamic data in the VLE calculation subprogram
instead than in the main program that is more general. It must be taken into account that there are
commercial programs able to perform the thermodynamic calculations that can be used as
already implemented functions in the main commercial programs such as MATLAB or EXCEL.
The process design data that influence the residue curve maps are only two:
1. the pressure;
2. the retention time or Damköhler number.
The input data is placed in a first position in order to make it easy for the users to find the data to
be introduced, when new conditions or reaction system is studied.
5.2.3.2. Exploration of the map topology

Generate a thick and uniform mesh grid on the map and determine for each point of the mesh the
boiling point and the driving force for the separation. The results obtained can be used as
additional information in the background of the curves. As it is a different stage from the residue
curves calculation, the results are saved and loaded again when residue curves at previously
calculated conditions are determined. The steps to follow are:
1. Determine the boiling point of the pure compounds at the pressure P
2. Check if the exploration has been previously done, if it already exists load the data and
go to the next step. (The boiling points of the pure components could be also saved but as
the calculation time is not too large, they can be recalculated).
3. Give the compositions to generate the uniform grid.
4. Provide an initialization temperature, e.g. using the boiling point of the pure components.
5. Calculate the boiling point at each mixture composition and the activity coefficients.
6. Calculate the vapour pressure at each mixture composition for each component.
7. Calculate the vapour composition and activities at each mixture composition.
8. Calculate the chemical kinetic constants, the reacted moles rij and the liquid composition
corrected with the reaction term involved in the relation (V.54).
9. Calculate the driving force as the distance between the vapour composition and the liquid
composition corrected with the reaction term.
10. Save the boiling point and driving force corresponding to each composition.
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5.2.3.3. Residue curve calculation
The reactive residue curves are obtained by solving the differential equations (V.54). The initial
point for each differential equation must be provided as an input. How many and which reactive
residue curves are suitable to visualize properly the system is a difficult task. Some zone can
become empty and some other too crowded of curves. One way to generate the initial points for
the differential equations can be from generating a contour of isotherm or of the driving force
and use some points of it to generate the reactive residue curves. However, it is difficult to set it
in a general way and finally the more satisfactory choice is to select it by a mouse click on the
residue curve map, with the driving force in the background as a guide. The program prompts to
plot a reactive residue curve; in affirmative case appears the map and the user can choose where
to click and plot it. Immediately, it is calculated and appears on the map and the program
prompts for a new curve to be added to the map. The steps followed to plot each reactive residue
curve are the following:
1. Provide input composition from where starts the reactive residue curve calculation.
2. Calculate the boiling point and activity coefficients for the input composition.
3. Integrate the differential equations (V.54) forward and backward from the input point
(using the MATLAB function ode15s and a subprogram is used for this purpose) and
store the values  xi , t obtained.
4. Join both sets of values  xi , t .
5. Calculate composition values defining the vapour composition and reaction term for each
of the solutions.
6. Plot the reactive residue curves.
5.2.3.4. Number of Transfer Units calculation

The composition profile of a reactive residue curve does not depend on the starting point of the
curve; only the scalar independent variable that corresponds to the dimensionless time or NTU of
the residue curve equation depends on this starting point. Common criteria for the starting point
of each residue curve must be provided. When several residue curves overlap when approaching
a stable node, all of them should have the same NTU at the same points of the overlapping
curves zone. This is achieved once the residue curve is generated; a common initial composition
is calculated for all them by fixing the same distance to the stable node. The residue curves
should not be generated from the overlapping zone, as the residue curves would depend on very
small variations in the starting and calculated compositions. This criteria works well except in
the cases when the residue curve pass through a pinch zone. In this case, the visualization of the
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NTU change is not easy, as they are not aligned. Therefore, a different criterion to start the
integrations should be used. A compromise solution is to use the fixed distance criteria when the
chemical reaction is controlling the reactive residue curves and to use the maximum driving
force as initial point when the separation is controlling. The total number of NTUs is determined
by counting the steps from each side to their crossing. The steps followed for the NTU
determination are:
1. Change the first random time used to initiate the calculation of the reactive residue curve
for an initial time to calculate NTU following a certain coherent criteria.
2. Adjust a function around the initial point and interpolate the compositions and time, so
that the initial point is defined with enough precision to get all the overlapping curves
with the same NTUs
3. Adjust functions and interpolate the rest of points in order to get the compositions for all
NTUs numbers
4. Plot all the NTUs values.
5.2.3.5. Implementation of the residue curve map model to the TAME case
Mathematically, the residue curves can be calculated for any number of chemical compounds
but, unfortunately, only three chemical compounds can be represented in a bidimensional surface
using a Gibbs diagram. Two compositions are independent and the third is dependant due to the
condition of summation to one. There is a large list of chemical compounds in TAME synthesis
but the main ones that are the directly involved in the reaction are: the C5 fraction from FCC unit
which contains 18-22% reactive isoamylenes (2-methyl-2-butene and 2-methyl-1-butene),
methanol and TAME. As it has been already indicated, the number of independent compositions
in the Gibbs diagram must be only two. In this case, it is assumed that the isomers 2-methyl-2-
butene and 2-methyl-1-butene are in chemical equilibrium. This chemical equilibrium equation
relates the two compositions. In this way, only two independent compositions are obtained since
the other two are fixed by the chemical equilibrium and the summation of compositions to one.
Both compositions of 2-methyl-2-butene and 2-methyl-1-butene are taken into account in the
thermodynamic compositions but when they are represented in the Gibbs diagram, they are
lumped together. The idea of lumping the compositions of 2-methyl-2-butene and 2-methyl-1-
butene was already used by Thiel et al (1997). This works well in this case because both
components are chemically and thermodynamically similar and usually are fed in equilibrium in
the column. The kinetic expression implemented is according to Oost and Hoffmann (1995).
Generalized Langmuir-Hinshelwood rate expressions were formulated for the heterogeneously
catalyzed etherification. Since there are three reactions taking place simultaneously, three
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coupled chemical equilibrium constants have to be considered. Rihko et al. (1994) proposed the
following expressions (T in K):
- TAME synthesis from 2M1B: K a,1  1.057 10 4 exp4273.5 T 
- TAME synthesis from 2M2B: K a ,2  1.629 104  exp  3374.5 T 
- isoamylenes isomerisation: K a ,3  K a ,1 K a ,2
The kinetic model of this global reaction is formulated according to Oost and Hoffmann (1995):
a 1 aTAME 
r1,2  r1  r2  k f ,12   2 M 1B   2  (V. 61)
a
 MeOH K a ,1 aMeOH 
and the reaction rate constant is given by the following Arrhenius equation:
 1 1 
k f ,12  1  K a ,3 T    2.576  exp  10.764 103     [mol/s eq] (V. 62)
  T 333.15  
The thermodynamic model used to calculate the vapour liquid equilibrium is the UNIFAC
method implemented in MATLAB. Figure 5.4 shows a snapshot of how the initial point used to
calculate a residue curve is selected. The interactive interface allows a free choice of the starting
compositions allowing to select the position and number of residue curves according to the
needs. The free choice of the residue curves location provides a map without gaps, improving the
appearance of most of the available residue curve diagrams. All the nodes are calculated, even
when they are outside of the physical meaning zone.
Figure 5.4 Screen snapshot of the implemented user interface for initial concentration selection
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5.2.4. Reactive residue curve maps calculated for TAME
The industrial interest for TAME synthesis is at pressures around 4 or 6 bar. Thiel et al (1997)
provided the results at 1 and 10 bar. The present study is focused on the pressure values relevant
to industrial application. The residue curve maps for several Da at 4 bar are shown in Figures 5.5
– 5.8 and at 6 bar in Figures 5.9 - 5.12.
Figure 5. 5 Reactive residue curve map at p = 4 bar and Da = 10-4
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Figure 5.6 Reactive residue curve map at p = 4 bar and Da = 10-3
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The presence of singular points in the obtained reactive residue curve maps divides the
composition diagram into separate distillation regions by introducing distillation separatrix,
which connects two singular points in the composition space.
In the diagrams presented in Figures 4.8 to 4.12 (except 4.12), four singular points are depicted.
The stable nodes are associated to pure MeOH vertex and to a ternary azeotropic mixture
MeOH-TAME-IA. The unstable node is represented by the binary azeotrope MeOH-IA, which
changes its location, leaving physical meaning range. This moves towards the mole fractions
MeOH – IA equal to 1:1 due to the reaction stoichiometry. The saddle node is represented by the
binary azeotrope TAME-MeOH at Da values of 10-4 and 10-3 and by the ternary azeotrope
TAME-MeOH-IA at Da values of 10-2 and 10-1. Additionally, another unstable node is expected
far outside of the physical meaning range, suggested by the orientation of the residue curves near
pure TAME vertex. A reactive residue curve may follow the map edges only if both components
defining the edge do not react and any of them doesn’t decompose. In the present case, two of
the edges include TAME which decomposes due to reaction reversibility. Therefore, TAME
vertex does not act as a singular point and this situation supports the mathematical existence of
the expected unstable node.
162
163
164
The singular points detected define several separatrices: from the unstable node to the saddle
point, from the saddle point to the stable nodes, from the ternary stable node to the IA vertex and
from the saddle point to the expected unstable node mentioned above. Therefore, the diagrams
composition spaces are divided into several distillation regions.
The change of location and composition for all the singular points detected (except pure MeOH
vertex) is due to the influence of operating conditions (pressure) and chemical reaction (Da
number). The unstable node is enriched in MeOH as the pressure increases. At low Da values
(10-4 and 10-3), it is represented by the binary azeotrope MeOH-IA. At higher Da values (10-1),
the unstable node moves out of the physically relevant composition space. This fact was also
described by Thiel et al. (1997) although its position was not indicated. The saddle point gets
richer in MeOH as the pressure increases from 4 to 6 bar and Da = 10-4. However, for Da = 10-2,
the saddle point gets poorer in MeOH.
For low Da value, the boundary lines diverging from the ternary stable node are close to the pure
TAME vertex and approach the chemical equilibrium curve when Da and pressure increase.
TAME decomposes due to the reaction reversibility and it is noticed that this tendency increases
with the increase of pressure and Da. The boiling point of the mixture and the reaction
temperature and rate are related to pressure values as well. Due to the exothermic characteristic
of the TAME-synthesis, the chemical equilibrium curve is shifted towards the reactants MeOH
and IA when pressure increases from 4 to 6 bar.
The diagram at Da=10-1 and 4 bar presents a different topology (Figure 5.12). In this case, the
ternary stable node is not present. Consequently, the saddle point and the corresponding
boundary lines are neither present. Thiel et al. (1997) reported the same behaviour for Da=1 and
1 bar, where the stable node disappears and every trajectory runs into the collecting trajectory
which is the only remaining separatrix in the composition space. Other residue curve map
topologies such as with three stable nodes are not detected in the operating conditions considered
in the present study.
5.2.5. Number of transfer units in the residue curve maps calculated for
TAME
The information provided by residue curve map is supplemented with more details related to the
number of transfer units (NTU) to quantify the difficulty of separation. NTU depends only on the
column profile and it does not depend on the characteristics and performance of the packing. As
the composition profile of a packed column at infinite reflux corresponds to a residue curve map,
the NTU can be calculated according to the residue curve map results.
165
For kinetically controlled reactive distillation columns, the reaction is taken into account for the
NTU calculation as it is also considered in the reactive residue curve maps. The expression for
the NTU is:
xf
dxi where i=1..N-1; j=1..M (V. 63)
NTU    M  
Da
  i , j  xi j   rj  x, p    
x0
 y  x, p    xi 
 
 k f T   j 1  

For the case of reactive distillation, the driving force is represented by the difference between the
vapour composition in equilibrium with the bulk liquid (y) and the bulk liquid composition (xi)
plus the reaction term. The driving force between the vapour (y) and the corresponding bulk
liquid (xi) can be increased or decreased by the reaction term. In some cases, the non-reactive
driving force (yi-xi) can be cancelled by the reaction, producing the so-called reactive azeotropes.
Figures 5.13 to 5.20 illustrate the residue curve maps for TAME synthesis at 4 and 6 bar, which
are the pressures of industrial interest. The background represents a visual expression of the
driving force. In this way, the pinch zones where the separation is more difficult are easily
identified. It is important to notice that the presence and situation of the pinch zones follow the
evolution of the nodes with the reaction. The chemical equilibrium curve, separatrix and nodes
are indicated in the maps to provide complete information. A transfer unit is required to move
from one circle to the next on the residue curves. The black circles indicate the points of the
residue curves with highest driving force. When a greater number of residue curves are plotted, it
can be observed that the black circles approach each other defining a curve, the next whiter
circles define a new curve and so on towards the stable and unstable nodes. Only a few curves
are presented because they approach very much one to the other in some zones and the circles
information is more difficult to be discerned. The pinch zones generated by the saddle points
produce a minimum in the driving force. Therefore, if the saddle compound is not the product to
be collected, the residue curves passing through the saddle points should be avoided and the
more straightforward residue curves are preferable.
The reactive distillation for the TAME synthesis must contain a non-reactive section at the lower
part of the column to avoid de decomposition of TAME to its reactants. The reactive residue
curve map section at the right side of the equilibrium line contributes to the formation of TAME
meanwhile the section at the left side decomposes TAME. For Da equal to 10-4 and 10-3, the
highest driving force is at the left side of the chemical equilibrium. For Da equal to 10-2 the
maximum driving force is around the chemical equilibrium and therefore this Da is preferable to
lower ones.
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Figure 5.13. Number of transfer units in the residue curve map at p = 4 bar and Da =10-4
Figure 5.14 Number of transfer units in reactive residue curve map at p = 4 bar and Da =10-3
167
Figure 5. 15 Number of transfer units in reactive residue curve map at p = 4 bar and Da = 10-2
Figure 5.16 Number of transfer units in reactive residue curve map at p = 4 bar and Da = 10-1
168
169
Figure 5. 19 Number of transfer units in reactive residue curve map at p = 6 bar and Da = 10-2
Figure 5.20 Number of transfer units in reactive residue curve map at p = 6 bar and Da =10-1
The pressure also influences the number of NTU and the position of the chemical equilibrium.
As the increase of pressure from 4 to 6 bar is small, the increase in the NTU required is not
appreciable (Figure 5.21 and 5.22). Due to the exothermic characteristic of the TAME synthesis,
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the chemical equilibrium curve is shifted towards the reactants MeOH and IA when pressure
increases. This fact is appreciable in the Figures 5.13 to 5.20 when the pressure changes from 4
to 6 bar. At 6 bar the number of reactive NTU is smaller than at 4 bar, but the number of non
reactive NTU increases.
From the obtained results, it would be possible to propose a feasible column profile: (a) At 4 bar
Figure 5.15, following the reactive residue curve from the IA/MeOH azeotrope until the black
circle near the chemical equilibrium line and near the composition 0.3 MeOH and 0.3 IA
(NTU=4). (b) At 4 bar Figure 5.21, following the residue curve from a white circle near the
composition 0.3 MeOH and 0.3 IA until pure TAME is reached (NTU=3). Therefore the process
is feasible with a reasonable NTU at 4 bar, a non reactive section at the bottom and a reactive
section with a Da=10-2.
From these maps results, it can be concluded that the Da is recommendable to be higher than
0.01 for the TAME reactive distillation.
Figure 5.21 Number of transfer units in reactive residue curve map at p = 4 bar and Da = 0
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Figure 5.22 Number of transfer units in reactive residue curve map at p = 6 bar and Da = 0
5.2.6. Comparison of the reactive residue curves with the reactive distillation
column profile at infinite reflux for the TAME synthesis
Figures 5.23 to 5.28 show the reactive residue curve maps described by differential equations
(V.55) and the column profiles for an infinite reflux packed column calculated by equations
(V.54). When comparing the residues curves with the column profiles, it is observed that the
behaviour is quite similar at low H/V values. The reason is that the reaction term is small
compared to the separation term. The main difference is that for the residue curves the TAME
singular point moves towards the middle of the graph due to the reaction and for the column
profiles becomes outside the graph. The main implication of this fact is that the reactive column
bottoms can be composed of a TAME/methanol mixture free of the volatile isoamylenes. Both
models show that as the retention time H/V increase, then the maximum purity of TAME that
can be collected at the bottoms decreases due to its decomposition.
The results presented for low values of H/V ratio are not realistic, but they are presented in this
work for illustrative purposes of the computation method.
For middle values of H/V, the differences between both models become more obvious (Figure
5.27). The unstable node goes out of the graph in both models but its position is different. The
profiles rich in isoamylenes tend for both models to the same boundary. But for the column
profiles rich in methanol it is observed a maximum concentration of TAME in the middle of the
172
column which decreases and reaches a bottom composition with less volatile isoamylenes. The
point of enrichment in TAME of the profiles coincides with the boundary line of the residue
curves at this value of H/V.
(continuous line) for the TAME reactive distillation at 1 bar and a value of H/V = 0.0001 s
The most interesting results are for very high retention times H/V (Figure 5.28). The reactive
residue curves show that the simple Rayleigh reactive distillation tends to behave just like a
simple reactor when the reaction term is predominant over the separation term. A section of the
residue curve follows the chemical equilibrium. But the reactive distillation column profiles at
infinite reflux behave quite different than a simple reactor although a part of the column profile
can be at chemical equilibrium. For mixtures rich in isoamylenes, the column profile contains an
almost constant quantity of isoamylenes and the TAME is collected at the bottoms and the
methanol at the top, both of them mixed with a great quantity of isoamylenes. For mixtures with
less isoamylenes, the bottoms collected are a mixture of isoamylenes and TAME free of
methanol but part of the column profile is in chemical equilibrium. In a limit situation, when the
column profile follows the chemical equilibrium curve, methanol is collected at the top of the
column, while towards the lower part of the column, the profile moves away from chemical
equilibrium and a mixture of isoamylenes and TAME is collected at the bottom. TAME
concentration is lower than the maximum to be obtained when the reaction reaches the chemical
equilibrium (thicker line in Figure 5.28).
173
(continuous line) for the TAME reactive distillation at 1 bar and a value of H/V= 0.001 s
MeOH
TAME IA
174
MeOH
TAME IA
MeOH
TAME IA
(continuous line) for the TAME reactive distillation at 1 bar and a value of H/V = 1 s
175
MeOH
TAME IA
(continuous line) for the TAME reactive distillation at 1 bar and a value of H/V = 100 s
5.2.7. Analysis of the system
5.2.7.1. Simplification of the rigorous mathematical model

In the previous sections, the usefulness of the residue curves is stated. Their usefulness is
provided by the fact that a section of residue curve approaches the composition column profile of
a packed column operated at infinite reflux flow rate. Notice that a column at infinite reflux
exhibits infinite internal flows while the feed and product flowrates are not zero, which is
different from total reflux. The effect of time on the variation of the composition in the residue
of a simple distillation is analogous to the effect of the number of transfer units on the variation
of composition in a packed column operated at infinite reflux. Therefore, a packed column
distillation separation profile is feasible when there is a continuous residue curve linking its
bottom and distillate compositions. The existence of the residue curve implies the feasibility of
the separation when a high enough reflux and number of transfer units are used. Notice that it is
a necessary but not sufficient condition: the existence of the residue curve assures the feasibility.
If there is no residue curve does not assure that the separation is not feasible at lower reflux
values, e.g. double feed columns. The use of the residue curves allows the simplification of the
mathematical model in the analysis of the process and decrease the number of degrees of
freedom.
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The number of degrees of freedom in a distillation column using the MESH model at fixed feed
conditions are five, usually in the process simulators are used the following: reflux, feed stage,
number of stages, pressure and distillate flow rate. The pressure usually is fixed at the
atmospheric value, although it can be optimized for energy savings such as to adjust the boiler or
condenser temperatures at the utilities available in the plant or to integrate energetically with
other streams. For instance, in the case of TAME, the column is pressurized to avoid a costly
refrigeration system at the condenser. The feed stage and number of stages are input parameters
for calculation reasons because they are discrete variables but certainly, these are not really
design parameters: the design parameters are the product purities desired. The reflux is neither a
parameter known a priori, what we want is to work at conditions that provide the minimum
costs. To perform a sensitivity analysis of the distillate flow rate variable, all these other
variables must be fixed.
There is the danger that if the reflux or number of stages is fixed under their minimum values,
the desired purity is not attainable. Instead of using an arbitrary value for them, assuming them at
infinite value simplifies greatly the mathematical resolution model. Therefore, assuming the
reflux as infinite then the column profiles can be calculated independently of the feed
composition or position. As stated previously, the shape of the residue curves is independent of
the feed, distillate or bottoms composition. The residue curves calculated are general and valid
for any input/output streams. The infinite reflux assumption simplifies also the feed stage
variable. If the number of transfer units or number of stages is also fixed to infinite, then the
mathematical model becomes dependent only on pressure and distillate flow rate. In case of a
reactive distillation taking into account the kinetics, there will be an additional variable such as
the hold up time in the stages. For an infinitely long column, the profile must reach a pinch. If a
column of infinite length is operated at infinite reflux, then the pinch must be a singular point in
the residue curve map.
The analysis of the process assuming infinite reflux and infinite number of stages is known as
infinite/infinite (∞/∞) analysis. Therefore, the ∞/∞ analysis is defined as a framework that
predicts possible product paths of a distillation column based on residue curve map information
only. A product path is obtained by the continuation of solutions found by varying, for example,
the distillate flow rate D from 0 to its maximum, the feed flow rate F. From the above
discussion, the next three rules must be fulfilled when the path is calculated:
- Distillate and bottom compositions must be linked in a continuous manner by a column profile
composed of one or several residue curve sections, e.g. reactive and non reactive sections
(feasibility):
177
- At least one of the residue curves composing the column profile must contain at least one
singular point (infinite/infinite assumptions)
- The distillate, feed and bottoms must fulfil the mass balances, graphically this means that they
are aligned.
For kinetically controlled reactions, the following points should be taken into account:
- Avoid reactive residue curve sections where the formation of products is unfavourable;
- The feed for the mass balance is the feed to the column approaching chemical equilibrium
(pseudo-feed). For kinetically controlled reactions, the distillate, pseudo-feed and bottoms must
be aligned and the pseudo-feed must be aligned with the feed and reaction difference point. The
pseudo-feed indicates the reaction turnover, in other words, the reaction extent inside the reactive
distillation column.
There are three basic possible profiles for a ∞/∞ column (Bekiaris et al., 1993) which are shown
in Figure 5.29:
Type I. The column profile is a type I profile if the distillate composition xD is at the unstable
node (L in this case). The column profile starts at L and follows the indicated residue curve until
it is at xB that is collinear with xF and xD. For a different split D/F, the profile would follow a
different residue curve.
Type II. The column profile is a type II profile if the bottom composition xB is at the stable node
(H in this case). The column profile starts at an arbitrary point xD that is collinear with xF and xB
and follows the indicated residue curve until it is at the stable node (H in this case).
Type III . The column profile is a type III profile if the profile contains at least one saddle (the I-
H azeotrope in this case). The column profile starts either at the edge of the triangle or on a
residue curve boundary, as in this case. It follows the residue curve boundary, passes the I-H
azeotrope, and ends somewhere at the binary I-H edge.
Figure 5.29 Three possible ∞/∞ column profiles
178
5.2.7.2. The infinite/infinite analysis and the reactive residue curve maps
A useful tool used at the early stages of design to perform input-output analysis related to
distillation process systems is the infinite/infinite analysis which is based on residue curve maps.
Infinite reflux and infinite number of stages are the simplifying hypotheses that have inspired the
name of the  /  analysis. This analysis was firstly proposed by Petlyuk and Avetyan (1971),
but with a low impact on the scientific community outside USSR. The potential of this analysis
was rediscovered by Bekiaris et al. (1993) which lead it to a great grade of maturity (Bekiaris
and Morari, 1996a), it was extended to heterogeneous systems (Bekiaris et al., 1996b), hybrid
distillation columns with reactive and non reactive sections (Güttinger and Morari, 1999a,b) and
its potential in process synthesis to find and rank feasible separation schemes according to the
energetic consumption (Ulrich, 2002) has been studied. It is able to take into account the energy
savings in the first steps of designing a distillation process and it can be used to evaluate new
opportunities for the existing distillation systems. Barbosa and Doherty (1987a,b) and Doherty
(1990) developed reactive residue curves in transformed coordinates. Ung and Doherty (1995)
proposed a lever rule using this reduced coordinate space. In this reduced coordinated space
based on reaction invariant compositions, it is not possible to fix the advance of the reaction to
other values provided by the reaction equilibrium and mass balance. Hauan, Omtveit and Lien
(1996), Hauan, Werterberg and Lien (1999a) introduced the reaction difference point. They
showed that reaction moves in the composition space along straight lines, all of which pass
through this same difference point behaving similarly to a difference point for an extractive
distillation column (Hoffman, 1964). Lee et. al. (2000) introduced the concept of pseudo-feed
and how it may be used to formulate a lever rule for the mass balance. The use of the pseudo-
feed concept joint with the infinite/infinite analysis extends the capabilities of this analysis to
solve reactive distillation systems taking into account the reaction kinetics. Venimadhavan et al.
(1994) studied the effects of kinetics on reactive distillation residue curve maps. They tracked
the singular points as a function of the Damköhler number (Da) which is the ratio of a
characteristic residence time to a characteristic reaction time. At large Da, the reaction achieves
equilibrium on every reactive stage, and at lower Da, the column is kinetically controlled.
The applicability of the infinite/infinite analysis as a tool for an early oriented energy
consumption minimization is extended in this thesis to kinetically controlled reactions in reactive
distillation columns including also hybrid configurations. For the hybrid configuration is used
the approximate method (only one pinch on column profile) proposed by Güttinger (1999b). The
analysis is applied graphically on the reactive residue curve maps determined by Thiel et al.
(1997).
179
Two binary azeotropic points were detected: between the olefin (IA) and the alcohol (MeOH), an
unstable node, and between the ether (TAME) and the alcohol, a saddle point. These two points
are linked by a distillation boundary, separatrix. Consequently, there are two different stable
nodes in the system: pure MeOH and pure TAME. If, in addition, the operating pressure p is
varied, the following statement is valid: with increasing p, both azeotropic points move towards
pure MeOH.
For the residue curve maps of reactive distillation for TAME-synthesis, the operating pressure p
is discussed as second parameter besides the Damköhler number Da. The diagrams were
calculated by Thiel et al. (1997) using different operating pressures: p = 0.1 MPa and p = 1 MPa.
The Damköhler number Da is enhanced starting with the value 10-4, via Da = 10-3 to Da = 1.
From the residue curve maps published by Thiel et al. (1997) can be seen that at a low
Damköhler number Da = 10-4, the separation term is still dominating over reaction term, so that
two stable nodes in MeOH and nearby TAME are developed. A slight enhancement of Da leads
to Da = 10-3. This case is qualitatively similar to the previous case except for the fact that the
lower stable point has discharged from the TAME-vertex. If Da is increased to Da = 1, reaction
term is strong in comparison with the separation one. Consequently, one stable node disappears
and every trajectory runs into the collecting trajectory that is the only remaining separatrix in the
composition space. This separatrix is near the chemical equilibrium line and ends in the MeOH
vertex.
By raising the operating pressure p, from the results of Thiel et al. (1997) a new behaviour of the
system can be studied. A new saddle point appears, with the consequence that at Da = 10-4 and p
= 1.0 MPa, three stable points exist. It is remarkable, as in addition to the stable node in MeOH
vertex and in the region between chemical equilibrium and TAME vertex a third stable point is
built in the isoamylene (IA) vertex. This circumstance is surprising as IA is the light-boiling pure
component of the system. Thus, the statement that it is possible to enrich the highest volatile
component above a certain pressure and a certain magnitude of REA is correct.
It is shown above that two different kinds of saddle points can appear, caused by the combination
of distillation and chemical reaction. The crucial parameters for occurrence and position of these
saddles in residue curve maps are the Damköhler number Da and the operating pressure p. At an
operating pressure p = 0.1 MPa the line of chemical equilibrium lies near the product TAME and
the temperature profile is continuously rising from pure IA (right margin of figure) to pure
MeOH (left margin of figure). Raising the pressure leads to an enhancement of the temperature
in the still and because of the exothermic characteristic of the TAME-synthesis, the line of
chemical equilibrium is shifted towards the reactants MeOH and IA. The closer the line of
chemical equilibrium gets to the line of the binary mixture MeOH/IA, the more the binary
180
azeotropic point between MeOH and IA has an influence on the shape of the line of the boiling
temperature. This leads, for adequately high pressure, to the formation of a minimum boiling
temperature azeotrope between MeOH and IA.
An adequately high pressure can lead to the formation of a saddle point in the region of high
mole fraction of reactant isoamylene. It can be explained by the existence of a temperature
minimum along the line of chemical equilibrium, which has been moved near the binary
isoamylene-methanol azeotrope.
5.2.7.3. Application of the infinite/infinite analysis to non-chemical

equilibrium systems
The application of the infinite/infinite analysis is not straightforward for the chemical non-
equilibrium systems because the advance of reaction is an unknown parameter. As compared
with the analysis assuming feed at chemical equilibrium, in this study the feed is not at chemical
equilibrium, the infinite/infinite hypothesis lets one degree of freedom without being fixed, and
the feed point can be in any position over a line defined by the stoichiometry of the reaction
(Figure 5.30)
(0.5; 0.5)
Figure 5.30. Possible feed locations
In order to apply the infinite/infinite analysis, a pseudo-feed composition is assumed to express

the reaction extent along the column. The overall column mass balances for a non reactive
system where the lever rule is applied are:
F  DB
(V. 64)
F  xiF  D  xiD  B  xiB
181
Next, it is considered the following reversible reaction for an ideal mixture, where reactants A1
and A2 convert into product B1. It is assumed that A1 is light, A2 intermediate and B1 heavy in
terms of their volatilities, A1 and A2 forming a stoichiometric mixture.
A1  A2  B1 (V. 65)
In the case of TAME synthesis, A1 = Isoamylenes, A2 = Methanol, B1 = TAME.

This reaction takes place inside the reactive distillation column. The reaction is catalytic and
therefore, the extent to which it occurs on any tray can be defined. A feed stream containing
species A1 and A2 enters the column. The total and component material balances around the
column are presented in equations (V.66).
F  D  B   νi  ξ
i (V. 66)
F  x  D x  B x  νξ
i
F
i
D
i
B
In equation (V.66),  ν is
i
i the sum of the stoichiometric coefficients of the reactants and
products, where the coefficients of the reactants are taken as negative and those of the products
as positive since the reaction consumes the reactants and generates the products. Hence, we have
 ν as minus one (= -1 + - 1 + 1) for the above reaction. ξ is the total molar turnover of the
i
i
reaction (as a flowrate in mol/time), for the specified reaction.

From equation (V.66), if the term DxiD  BxiB is combined as  D  B  xiF * , by performing the
substitution in equation (V.66), the following relation (V.67) is obtained. xiF * is the pseudo-feed
composition,  D  xiD  B  xiB   D  B  , and δR is the reaction difference point, that is  i  i

i
(Hauan et al., 1999a). In equation (V.57), xiF * is the vector combining the distillate and bottom
composition vectors and can be called a pseudo-feed composition vector since it is the linear
combination of the distillate and bottoms product streams.
 i 
xiF  xiF *
i
 (V. 67)
DB xiF   R
Conceptually, the reaction in the column converts the feed stream F into the pseudo-feed stream
F*. Then, we obtain the distillate product D and the bottom product B from the pseudo-feed F*.
The location of the real feed composition xF (Figure 5.31), according to relative amounts of
182
(D+B) and ν ξ
i
i using the lever rule is on the straight line between the pseudo-feed (xF*) and
reaction difference point (δR = [1, 1, -1]T), because the total sum of stoichiometric coefficients
 ν is negative. Another important implication is the linearity of composition change from feed
i
i
to pseudo-feed for a cascade system with reaction and separation (Hauan et al., 1999). Hence, the
extent of the linear shift from the real feed to the pseudo-feed is that of net overall reaction in the
column.
MeOH δ=[1,1,-1]
)
+B
(D
xF
iξ
Συ
xB
D
xF*
B xD
TAME IA
Figure 5.31 The illustration of the reactive lever rule in composition space.
The lever rule can be applied for the resulting pseudo feed composition, distillate and bottoms
compositions. For the mass balances with the reaction term, the lever rule is not fulfilled but the
reaction term can be moved to the left side of the equations resulting:
F   νi  ξ  D  B
i (V. 68)
F  x  νi  ξ  D  x  B  x
i
F
i
D
i
B
Making a change of variable, the feed flowrate F and the feed composition xiF can be
transformed into the pseudo-feed indicated with F* and xiF * respectively, according to the
following equations:
F *  F   νi  ξ
i (V. 69)
F*x i
F*
 FxiF  νi  ξ
In this case, the system of equations for the column mass balances becomes:
183
F*  D  B
(V. 70)
F * xiF *  D  xiD  B  xiB
After the calculations, the real compositions and flowrate of the feed can be obtained by
applying equation (V.69).
Using equations (V.70), the lever rule is fulfilled, the expressions of it being as follows:
B xiD  xiF * B xiD  xiF * D xiF *  xiB

 F*  
D xi  xiB F * xiD  xiB F * xiD  xiB (V. 71)
Hence, we will apply graphically the lever rules from the equations (V.67) and (V.71) to solve
each of the mass balances:
c
B x x D F*   xiF  xiF *
i
 i i i
 F
D x xi
F*
i
B
DB xi   R (V. 72)
For illustration purposes of the method, all the residue curve maps obtained by Thiel et al. (1997)
are taken for further study, considering that the pseudo-feed composition is equal to the
corresponding chemical equilibrium composition. The reason of this choice is to fulfil the
condition that when all the feed is collected from one column end then it is collected at chemical
equilibrium and the entire column works just like a reactor. However, any other pseudo-feed not
over-passing the chemical equilibrium would be feasible as it is also calculated later.
A stoichiometric feed of both reactants without containing any product will react inside the
column until a desired conversion; if the infinite/infinite analysis is applied directly to this feed
composition, it is equivalent to consider that there is no advance of the reaction and in this case,
the reactants are simply separated by a binary distillation (Figure 5.32). Then, the pseudo-feed
must not be understood as the feed composition to the column, it must be considered as a
measure of the advance of the reaction in the column.
Figure 5.32 Mass balance for simple binary distillation

184
5.2.7.4. Results of the infinite/infinite analysis to kinetically controlled reactive
distillation for TAME synthesis
For comparison, the analysis is applied both to non reactive distillation columns and to reactive
distillation columns. For the non reactive columns, it is supposed a configuration containing a
pre-reactor which reaches the chemical equilibrium composition that is fed to the distillation
column. The crude feed is fixed at the stoichiometric composition of reactants: 1:1. For easier
comparison, the pseudo feed to the reactive distillation column is fixed to the value of reaction
turnover obtained in the traditional scheme of reactor and distillation column. The influence of
the pressure is evaluated at 1 bar (case study 1 in Table 5.1) and 10 bar (case study 2 in Table
5.1) and several values of Da number are evaluated in the reactive distillation column: 0.0001;
0.001 and 1. The influence of reaction turnover variation is evaluated at 1 bar using the same
pseudo-feed as previously at 10 bar (case study 3 in Table 5.1).
Table 5.1. Case studies used in the infinite-infinite analysis for traditional system reactor +
distillation column at stoichiometric feed
xiF *
Case Pressure Pseudo-feed at
(pseudo-feed composition)
study (bar) chemical equilibrium
IA MeOH TAME
1 1 0.2 0.2 0.6 Yes
2 10 0.344 0.344 0.312 Yes
3 1 0.344 0.344 0.312 No
The continuation paths satisfying the required conditions of the infinite/infinite analysis are
determined and the bifurcations diagrams are calculated to provide information on the influence
of the pressure and the Damköhler number on the presence of multiple steady states and the
purities attained on the streams. The bifurcation diagrams illustrate the influence of the output
flowrates on the distillate and bottoms composition. At the value B/F=0, all the feed is recovered
by the distillate and the distillate has the same composition as the pseudo-feed. At the value B/F
= 1, all the feed is recovered in the bottom of the column which has the same composition as the
pseudo-feed. The feasibility and the influence of the bottoms flow rate on the distillate and
bottoms purities for each one of the evaluated situations is detailed in the following paragraphs.
The first system evaluated is a traditional system of a reactor followed by a distillation column at
1 bar (Figure 5.33). The reactor is fed with a stoichiometric mixture of the reactants methanol
(MeOH) and isoamylenes (IA) indicated in the continuation diagram as xF. According to the
stoichiometry of the reaction, the differential point δR is obtained. The composition at the exit of
185
the reactor must be on the straight line defined by δR and xF; the composition at the exit of the
reactor is indicated as the pseudo feed to the reactive distillation columns with an asterisk (xF*).
1
0.9
0.8
0.7
Comp. Distillate
0.6 Distillate
MeOH
0.5
Distillate
0.4 TAME
Distillate
0.3
IA
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
0.9
0.8
0.7
Comp. Bottoms
0.6
Bottoms
0.5 MeOH
Bottoms
0.4
TAME
0.3 Bottoms
IA
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
MeOH δR=[1, 1, -1]
)
+B
(D Saddle node
Stable node
xF Unstable node
xD
xF*
xB
TAME IA
P=1 bar and real-feed composition at the corresponding chemical equilibrium at 1 bar.
186
There are several scenarios where the compositions of the reactor exit can be located. The
residue curve map is divided in two distillation regions by a boundary line. The azeotropic
composition of methanol and isoamylene is the unstable node from where all the residue curves
depart.
Some of the residue curves converge to the stable node of the methanol in the upper distillation
region and some other residue curves converge to the TAME vertex in the lower distillation
region. If the reaction extent produces a composition of xF* in the upper region, then it is not
possible to collect pure TAME at the column bottoms: there is no residue curve from the upper
region that reaches pure TAME.On the other hand, if the extent of reaction is big enough inside
the reactor and the composition at the exit of the reactor is on the lower distillation region, then
there is an optimal value of bottoms flow rate that provides pure TAME at the column bottoms.
According to the lever rule, at higher reactor conversion then higher pure TAME flow rate can
be collected at the bottoms. The maximum conversion inside a reactor is limited by the chemical
equilibrium; in this case its value using as a calculation basis one mole of crude feed is 0.39.
Figure 5.33 shows this optimal case when the composition at the exit of the reactor is at chemical
equilibrium. It is observed that at the highest bottoms flow rate that produces pure TAME, there
is some TAME that is lost by the distillate due to the presence of the boundary line.
Nevertheless, as the distillate composition is depending on the pressure and the reaction kinetics,
in order to be able to make comparisons of the effect of each variable we will keep the
stoichiometric feed to the reactor. The conclusions derived from the other figures (Figures 5.34 –
5.43) are presented in the next paragraphs. When the column profile is of type II, the situation
corresponds to low values of B/F, in this case the bottom composition is constant at the pure
TAME for the non-reactive systems. The column profile type II for reactive distillation systems
produces a bottom composition corresponding to the ternary azeotrope (IA-MeOH-TAME); the
ternary azeotrope becomes poorer in TAME when the Da number increases. When the Da
number equals to 1, then the ternary azeotrope disappears and pure methanol is obtained in the
bottom of the column. Hence, as the Da number increases, the TAME purity in the bottom
decreases and its maximum value is obtained at higher values of bottom flowrate B/F. Therefore,
the highest bottom flowrate collecting pure TAME is obtained by the traditional reactor and
column system. In the type II profiles, the TAME composition in the distillate decreases until a
value around 0.1, while the isoamylene and methanol composition increases for most of the
cases. Da=1 and P=1 bar is one of the exceptions, in this case the TAME is collected by the
distillate while the methanol is obtained at the bottom of the column; the TAME composition in
the distillate stream increases until a maximum value around 0.7; at the same time the
isoamylene composition also exhibits an increasing tendency.
187
1
0.9
0.8
0.7
Comp. Distillate
0.6 Distillate
MeOH
0.5
Distillate
TAME
0.4
Distillate
0.3 IA
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
0.9
0.8
0.7
Comp. Bottoms
0.6
Bottoms
0.5 MeOH
0.4 Bottoms
TAME
0.3
Bottoms
0.2 IA
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
MeOH δR=[1, 1, -1]
)
+B
(D
Saddle node
Stable node
xF
Unstable node
xD
xF*
xB
TAME IA
0.0001, P=1 bar and real-feed composition at the corresponding chemical equilibrium at 1 bar.
188
A similar behaviour can be noticed in the case of Da=0.001 and P=10 bar, but here the main
component in the distillate is the isoamylene and not TAME, which only increases until around
0.3. For a Da=0.0001 and P=10 bar, it is observed that the composition of isoamylene in the
distillate remains constant in this segment of bifurcation diagram.
When the column profile is of type III, the TAME composition begins to decrease due to the
presence of the methanol collected in the bottoms instead of being in the distillate. In the case of
Da=1 and P=1 bar, TAME changes from being recovered mainly in the distillate to being
recovered at a similar purity in the bottoms.The methanol composition decreases in distillate and
bottom while the isoamylenes composition increases. An important aspect is that a multiplicity
zone around B/F=0.5 is clearly defined for the case of Da=0.0001 and P=10 bar. The multiple
steady state has three branches: two stable and one unstable. The difference in methanol in the
distillate between the upper branch and lower branch is around 0.1. The convergence of a
commercial simulator in a multiplicity zone is very complicated and the column presents the risk
to change its operation from one branch to the other. Usually, the multiplicities zones must be
avoided if there are not great advantages to operate on the domain defined by them. In the case
of P=1 bar, there are multiplicities noticed when the column profile changes from type II to type
III, for Da= 0.001 and 0.0001 (B/F = 0.61 and 0.64 respectively). These multiplicities are quite
small but they are just near the values that maximize the TAME production and separation. In
this case, it can be recommended to work on the multiplicities zone. Due to the multiplicity, the
isoamylenes are absent in the bottom stream or they are present in a low concentration.
When the column profile is of type I, the distillate is at the azeotropic composition of isoamylene
and methanol. This azeotrope is sensitive to the operating pressure and the methanol purity on
the distillate changes from 0.20 at 1 bar to 0.36 at 10 bar. The concentration of methanol remains
constant at the bottoms while the isoamylenes increase their concentration provoking a further
decrease of TAME concentration in the bottom. In the case of P=1 bar and Da= 1, pure
isoamylenes are recovered on the distillate; its composition increases in the bottom while the
methanol and TAME compositions decrease.
From the results obtained, it can be observed the influence of the pressure on the TAME
synthesis. For the non-integrated reactor and column systems, the optimum B/F at 10 bar is 0.26
while at 1 bar is 0.60, while the TAME lost in the distillate compositions at 10 bar is 0.03 and at
1 bar is 0.1. The optimum B/F is considered to be the value that allows a maximum purity of
TAME with smaller losses of TAME in the other stream. Qualitatively, the pressure does not
influence the traditional system. On the other hand, for the reactive distillation system, the
pressure has a great influence on the results. At Da=0.0001, the P=1 exhibits a small multiplicity
while the multiplicity at P=10 atm is very pronounced. At Da=0.001, the bifurcation analysis is
189
qualitatively similar to the obtained at Da=0.0001 at P=1 bar; on the other hand, at P=10 bar and
Da=0.001, the results of the analysis are qualitatively more similar to the ones obtained at P= 1
bar and Da=1. For Da=1 at P=10 bar, the bifurcation analysis can not be performed because the
pseudo-feed is on the boundary line.
One of the main conclusions that can be obtained from the infinite/infinite analysis is that when
the Da increases then the purity of the main product TAME decreases on the bottom stream; at
high values of Da=1, TAME can be recovered in the distillate instead of the bottom. Then, from
the results obtained, it does not seem too much advantageous to use an entire reactive distillation
in contrast with using the traditional system of a reactor followed by a distillation column. From
this point of view, a hybrid reactive distillation column could be a more advantageous solution.
Up to this point, it has been considered that the pseudo-feed composition was in the chemical
equilibrium of the corresponding pressure. The pseudo-feed composition is not defined in one
fixed point, but it is situated on a locus defined over a line of compositions according to the
crude feed and stoichiometry of the reaction. Therefore, in order to be able to compare the
influence of this pseudo-feed composition, it has been fixed at the value corresponding to the
higher chemical equilibrium pressure. This allows us to study the influence of the same pseudo-
feed at different pressure and the influence of the same pressure with a different pseudo-feed.
When the comparison is made at the same pressure (P= 1 bar) with a lower conversion in the
column, the bifurcation diagrams are qualitatively quite similar, but there are some remarkable
differences as the type III region is situated in a larger zone of the bifurcation diagram and the
multiplicities becomes smaller. The most different diagram is at Da=1: the type III profiles
region becomes narrower. The decrease of conversion on Da=1 at the bottom leads to the result
that the composition of TAME is lower and in a sharpest shape at the maximum. The effect in
the distillate is that the isoamylenes become the predominant component in the distillate
compositions instead of the TAME; the TAME composition presents a sharper maximum when
the profile changes from type II to type III, the methanol composition is very low not only for
profile type I but also for type III. In the bottoms, the methanol presents a sharp maximum at the
change from profile III to I.
When the study is made at two different pressures (P=1 bar and P=10 bar) at the same
conversion in the column, the bifurcation diagrams show some remarkable differences. These
differences are not remarkable for non-reactive systems, but for the reactive distillation systems,
the differences are significant. For a Da=0.0001 and P=10 bar, the presence of multiple steady
states was on a quite big region; for Da=0.0001 and P=1 bar, the presence of multiplicities was
smaller but clearly observed; for P=1 bar and the same pseudo-feed composition used for P=10
bar then the multiple steady states disappears completely.
190
1
0.9
0.8
0.7
Comp. Distillate
0.6
Distillate
MeOH
0.5
Distillate
0.4 TAME
0.3 Distillate
IA
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
0.9
0.8
0.7
Comp. Bottoms
0.6 Bottoms
MeOH
0.5
Bottoms
0.4 TAME
0.3 Bottoms
IA
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
MeOH δR=[1, 1, -1]
)
+B
(D
Saddle node
xF Stable node
Unstable node
xD
xF*
xB
TAME IA
Figure 5.35 Bifurcation diagram of distillate compositions for the TAME synthesis at Da=0.001,
191
1
0.9
0.8
0.7
Distillate
0.6 MeOH
Comp. Distillate
Distillate
0.5 TAME
Distillate
0.4
IA
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
0.9
0.8
0.7
Bottoms
Comp. Bottoms
0.6 MeOH
0.5 Bottoms
TAME
0.4
Bottoms
0.3 IA
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
MeOH
)
D+B
(
Saddle node
xF
Stable node
Unstable node
xB
xF*
xD
TAME IA
192
1
0.9
0.8
0.7
0.6
Comp. Distillate
Distillate
0.5 MeOH
Distillate
0.4
TAME
0.3 Distillate
IA
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
0.9
0.8
0.7
Comp. Bottoms
0.6 Bottoms
MeOH
0.5 Bottoms
TAME
0.4
Bottoms
IA
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
MeOH δR=[1, 1, -1]
)
D+B
(
xF Saddle node
Stable node
xD Unstable node
xF*
xB
TAME IA
193
1
0.9
0.8
0.7
Comp. Distillate
0.6 Distillate
MeOH
0.5
Distillate
0.4 TAME
Distillate
0.3 IA
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
0.9
0.8
0.7
Comp. Bottoms
0.6
Bottoms
0.5 MeOH
Bottoms
0.4 TAME
0.3 Bottoms
IA
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
MeOH δR=[1, 1, -1]
)
D+B
(
Saddle node
xD
xF Stable node
Unstable node
xF*
xB
TAME IA
0.0001, P=10 bar, real-feed composition at the corresponding chemical equilibrium at 10 bar.
194
1
0.9
0.8
0.7
Comp. Distillate
0.6
Distillate
MeOH
0.5
Distillate
0.4 TAME
0.3 Distillate
IA
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
0.9
0.8
0.7
Comp. Bottoms
0.6
Bottoms
0.5 MeOH
0.4
Bottoms
TAME
0.3
0.2 Bottoms
IA
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
MeOH δR=[1, 1, -1]
)
+B
(D Saddle node
xB Stable node
xF
Unstable node
xF*
xD
TAME IA
195
1
0.9
0.8
0.7
Comp. Distillate 0.6

Distillate
0.5 MeOH
0.4 Distillate
TAME
0.3
Distillate
IA
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
0.9
0.8
0.7
Bottoms
MeOH
0.6
Comp. Bottoms
Bottoms
0.5
TAME
0.4
Bottoms
IA
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
MeOH δR=[1, 1, -1]
)
+B
(D Saddle node
Stable node
xF
Unstable node
xD
xF*
xB
TAME IA
Figure 5 40 Bifurcation diagram of distillate compositions for the TAME synthesis at Da=0,
196
1
0.9
0.8
0.7
Comp. Distillate
0.6 Distillate
MeOH
0.5
Distillate
TAME
0.4
Distillate
0.3 IA
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
0.9
0.8
0.7
Comp. Bottoms
0.6 Bottoms
MeOH
0.5
Bottoms
0.4 TAME
0.3 Bottoms
IA
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
MeOH δR=[1, 1, -1]
)
+B
(D Saddle node
Stable node
xF Unstable node
xF* xD
xB
TAME IA
197
1
0.9
0.8
0.7
0.6
Distillate
Comp. Distillate
MeOH
0.5
Distillate
TAME
0.4
Distillate
0.3 IA
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
0.9
0.8
0.7
0.6
Bottoms
Comp. Bottoms
MeOH
0.5
Bottoms
0.4 TAME
0.3 Bottoms
IA
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
MeOH δR=[1, 1, -1]
)
+B
(D
xF Saddle node
Stable node
xF* xD Unstable node
xB
TAME IA
198
1
0.9
0.8
0.7
Distillate
0.6
Comp. Distillate MeOH
0.5 Distillate
TAME
0.4
Distillate
0.3 IA
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
0.9
0.8
0.7
Comp. Bottoms
0.6 Bottoms
MeOH
0.5
Bottoms
0.4 TAME
0.3 Bottoms
IA
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
MeOH δR=[1, 1, -1]
)
xB
D+B
(
Saddle node
xF Stable node
Unstable node
xF*
xD
TAME IA
199
On the other hand, for Da=0.001 at P=10 bar there were not multiplicities detected and for P=1
bar with the same pseudo-feed there is a small bifurcation zone detected when the profile
changes from type II to III. It is also remarkable that for Da=1, there was no solution for P=10
bar, but it is feasible for P=1 bar. The shape of the bifurcation diagrams remains qualitatively
quite similar when the pseudo-feed changes, but the effect of the pressure has a high impact over
the system due to the influence on the azeotropic compositions, providing qualitatively different
results.
5.2.7.5. Results of the infinite/infinite analysis to kinetically controlled hybrid

reactive distillation for TAME synthesis
In the last section it was seen that due to the reaction on the entire column, TAME decomposes
to methanol and isoamylene and pure TAME can not be obtained at the bottoms. The use of a
hybrid column with a reaction section at the upper part and a non-reactive section at the lower
part could give the benefits of both kinds of operations (reaction and separation). It was seen in
the last section that with a non-reactive column is possible to reach pure TAME at the bottoms
and with a reactive column, the azeotrope in the distillate can disappear. The same resolution
procedure applied to the last section can be used for hybrid distillation columns. In this case,
there is not a unique residue curve from the distillate to the bottoms; the column profile would be
defined by two residue curves: at the lower part of the column a non-reactive curve and a
reactive curve at the upper part of the column. Both residue curves must intersect in order to
have a feasible column profile. According to Güttinger (1999), the approximate method that
requires only one pinch point for the entire column is applied in this study. For the hybrid
systems evaluated, there are not multiplicities. Figure 5.44 shows the analysis of a hybrid column
with a Damköhler number of 0.0001 and 10 bar. In the hybrid column it is possible to reach pure
TAME at the bottom but the reaction only changes the position of the boundary line increasing
the quantity of TAME in the distillate. Due to the complexity of the hybrid graphics that
superpose the non-reactive in green colour with the reactive in red colour, it will be explained in
more detail the fulfilment of the feasibility conditions.
At the right side of Figure 5.44, when B/F is maximum, all the pseudofeed is collected at the
bottoms, the bottoms composition coincides with the pseudo-feed and the distillate corresponds
to the azeotrope methanol isoamylene. An increase of the bottoms flow rate leads to the
compositions described by the orange line. In this case, the profiles contain the pinch point of the
azeotrope methanol-isoamylene, which is the unstable node of three distillation regions on the
reactive residue curve map. All the profiles situated in the left side of the discontinuous line
indicating the chemical equilibrium converges to this azeotrope.
200
1
0.9
0.8
0.7
Distillate com p.
0.6
Distillate MeOH
0.5 Distillate TAME
Distillate IA
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
0.9
0.8
0.7
Bottom s com p.
0.6
Bottoms MeOH
0.5 Bottoms TAME
Bottoms IA
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
MeOH δR=[1, 1, -1]
Saddle node
) Stable node
+B Unstable node
(D
xF
xD
xF*
xB
TAME IA
distillation column, at Da=0.0001, P=10 bar and real-feed composition at the corresponding
chemical equilibrium at 10 bar.
201
A condition of feasibility states that a part of the column profile must be on the zone where the
reaction generating the product takes place. All the non-reactive residue curves diverge from the
azeotrope methanol-isoamylene that is in the reaction zone where the formation of product takes
place. This fact assures that any non-reactive residue curve reaches the zone where the reactive
curves converge to their unstable node. When the bottoms composition does not contain
isoamylenes and the bottoms flow rate is increased, then the bottoms compositions follows the
edge of the triangle towards pure TAME, while the distillate follows the reactive boundary line.
Both lines are indicated on the continuation diagram by blue lines. The column profile follows
the triangle edge methanol-TAME until the saddle point of the non-reactive map for this mixture,
then follows a very short distance the non-reactive boundary line indicated in green until the
reactive boundary line in red is met, which is then used to reach the reactive saddle point. We are
following a path against the direction of the residues curves, towards the unstable node. The
presence of the saddles on the profile and the existence of residue curves from the bottoms to the
distillate assure the feasibility. Finally, the distillate composition moves towards the pseudo feed,
while the bottoms composition is pure TAME. This last movement is indicated in violet; as the
distillates are on the distillation region of the stable node (TAME) for the non-reactive map, the
existence of residue curves from the distillate to the bottoms is assured. It is important to notice
that a pseudo feed at the left side of the reactive equilibrium curve could not be reached because
all the column profile would be in regions where the formation of product TAME is not
favourable. In Figure 5.45 there are some points that are a clear example of the fact where all the
requirements are fulfilled but all the profile is on the unfavourable zone of formation of TAME.
The part of continuation path in colour violet and the last small section of the blue one run over
the reactive boundary until the non-reactive boundary and to the non-reactive azeotrope. The
profiles contain a pinch, the lever rule is satisfied and there is a feasible profile from the distillate
to the bottoms but any part of the profile is not favourable to form TAME. In this situation, it can
be used a pseudo feed enriched with isoamylene as was explained at the last section for the non-
reactive column. In this way, it would be possible to collect pure TAME at the bottoms and the
azeotrope methanol with isoamylene on the distillate. Figure 5.46 for a Damköhler of 1 shows
that although the Damköhler increases similar results are obtained. Figure 5.47 shows that the
pressure has an important role in the process and with a Damköhler equal to 1 and 1 bar is not
feasible to obtain the pure TAME because the unstable node for the reactive residue curve map is
pure isoamylene. According to the results obtained, using a stoichiometric crude feed to the
system, the worst results are obtained by the use of an entire reactive distillation column because
TAME decomposes before being collected at the bottoms and it is not possible to collect pure
TAME.
202
1
0.9
0.8
0.7
Distillate Comp. 0.6
Distillate MeOH
0.5 Distillate TAME
Distillate IA
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
0.9
0.8
0.7
Bottoms Comp.
0.6
Bottoms MeOH
0.5 Bottoms TAME
Bottoms IA
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
MeOH δR=[1, 1, -1]
Saddle node
Stable node
+ B)
(D Unstable node
xB
xF
xF*
xD
TAME IA
distillation column, at Da=0.001, P=10 bar and real-feed composition at the corresponding
203
1
0.9
0.8
Distillate Comp. 0.7
0.6
Distillate MeOH
0.5 Distillate TAME
Distillate IA
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
0.9
0.8
0.7
Distillate Comp.
0.6
Bottoms MeOH
0.5 Bottoms TAME
Bottoms IA
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
MeOH δR=[1, 1, -1]
Saddle node
+ B) Stable node
(D Unstable node
xB
xF
xF*
xD
TAME IA
distillation column, at Da=1, P=10 bar and real-feed composition at the corresponding
204
1
0.9
0.8
0.7
Distillate Comp.
0.6
Distillate MeOH
0.5 Distillate TAME
Distillate IA
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
0.9
0.8
0.7
Bottoms Comp.
0.6
Bottoms MeOH
0.5 Bottoms TAME
Bottoms IA
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
B/F
MeOH δR=[1, 1, -1]
)
+B Saddle node
(D
Stable node
xF Unstable node
xB
xF*
xD
TAME IA
distillation column, at Da=1, P=1 bar and real-feed composition at the corresponding chemical
equilibrium at 1 bar.
The hybrid column with a non-reactive section at the bottoms overcomes this limitation and
reports some advantages as the use of the heat of reaction in the distillation column and
205
simplifies the system, as the reactor is not required anymore. The presence of some small
proportion of TAME product at the distillate is not a problem as it can be recycled to the system
jointly with the non-reacted components. The presence of TAME in the distillate can be avoided
by increasing the content of isoamylene in the feed of the column in order that the distillate
reaches the azeotropic mixture isoamylene-methanol instead of the boundary line. Then pure
TAME is collected at the bottoms and the azeotrope of methanol and isoamylene at the distillate.
The excess of isoamylenes in the distillate depends on the start-up of the distillation column. The
distillate composition is mixed with the crude stoichiometic feed that provides the feed of the
reactor. The lever rule is also fulfilled for mixing streams. From the representation of the
bifurcation diagram are not observed multiplicities. The calculations of the bifurcation and
continuation diagrams presented in the previous paragraphs are referencing the distillate flow
rate to a crude feed without the recirculation of the distillate. When a recirculation of the
distillate with TAME is taken into account for the traditional system of at 1 bat at the optimal
point, the value reported of D/F is of 0.146, a value smaller than the one obtained by using an
excess of isoamylene in the distillate that leads a value of 0.306. When the recirculation of the
distillate with TAME is considered for the system at 10 bar, the value of D/F becomes 1.385
versus a value 1.286 obtained by the excess of isoamylene on the column feed. The traditional
system of reactor and distillation column at 1 bar (Figure 5.48) provides a lower recirculation
distillate flow rate than the system at 10 bar (Figure 5.49) because the advance of reaction to
produce TAME in the reactor is higher. The hybrid reactive distillation column is able to
overcome the equilibrium limitation of the reaction and a total conversion is attainable (Figure
5.50). Figure 5.51 shows the relation between the distillate flow rate and the advance of reaction
according to the feed to the reactor or the overall feed to the reactive distillation column. For the
traditional system of reactor and column at 1 bar, 10 bar and the reactive hybrid column, the
main difference is noticed in regard of the advance of reaction that can be achieved. Taking into
account that B/F is constant and equal to 0.5 for all the situations with recycle stream, for low
reaction conversions the distillate flow rate is huge in relation to the bottoms flow rate of
product. At low advance of reaction, any small increase on the advance of reaction leads to an
important decrease of the recycled flow rate and the energy requirements. At high advance of
reaction, the benefits of a small increase on the advance of reaction leads to poor improvements.
The advance of reaction in the traditional system depends on the temperature of the reactor, at
higher pressure considered leads to higher boiling point and higher temperatures. The decrease
of the temperature in order to push the equilibrium constant to form a higher quantity of TAME
can lead to lower reaction kinetics. At the hybrid reactive distillation, the chemical equilibrium is
not a restriction, seems the best option from operational, and energetically point of view.
206
MeOH δR=[1, 1, -1]
MeOH δR=[1, 1, -1] MeOH δR=[1, 1, -1]
)
+B
+B
)
(D +B
(D
(D
xF xF xF
xD xD xD
xF* xF* xF*
xB xB xB
TAME IA TAME IA TAME IA
MeOH δR=[1, 1, -1] MeOH MeOH

δR=[1, 1, -1] δR=[1, 1, -1]
) ) )
+B +B +B
(D (D (D
xF xF xF
xD xD xD
xF*
xF*
xB xB xB
xF*
TAME IA TAME IA TAME IA
Figure 5.48 Hybrid reactive distillation column overcoming chemical equilibrium
207
(IA; MeOH; TAME; W/F)
xD MeOH δR=[1, 1, -1]

(0,80;0,20;0;0,3)
)
+B
1 bar
(D
xF xFR 1 bar xF* xF
xFR
(0,31;0,07;0,62;0,7)
(0,57;0,43;0;1,3)
(0,50;0,50;0;1,0)
(0;0;1,00;0,5)
xD
xB xF*
xB TAME IA
Figure 5.49 Classical system of reactor and distillation column at 1 bar using an excess of
isoamylene on the reactor feed.
xD MeOH δR=[1, 1, -1]

(0,64;0,36;0;1,3)
)
+B
(D
10 bar
xF xFR 10 bar xF* xF
xFR
(0,46;0,26;0,28;0,7)
(0,58;0,42;0;2,3)
(0,50;0,50;0;1,0)
xD
(0;0;1,00;0,5)
xF*
xB
xB xB TAME IA
Figure 5 50 Classical system of reactor and distillation column at 10 bar using an excess of
isoamylene in the reactor feed.
208
xD MeOH δR=[1, 1, -1]
(0,55;0,45;0;0)
total
reflux
+B)
10 bar (D
xF xF
xD
(0,50;0,50;0;1,0)
(0;0;1,00;0,5)
xB
xB TAME xF* IA
Figure 5.51 Hybrid reactive distillation column at 10 bar using an excess of isoamylene in the
column feed
10
9
R+D at 10 bar
8 RD at 10 bar
R+D at 1 bar
7
6
D/F
0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5
R/FR
Figure 5.52 Influence of the reaction extent on the performance of various process
configurations
209
5.3. Technical assessment
In the previous section, the infinite/infinite analysis has been extended to chemical non-
equilibrium systems by the use of a pseudo-feed that is related to the overall advance of reaction
on the column. A type of multiplicity has been detected by the infinite/infinite analysis; this
multiplicity depends on the Da number, at Da=0 and Da=1 there are not multiplicities while
some multiplicities are observed when the Da number varies between 0 and 1. The reactive
distillation columns for TAME synthesis show some multiple steady states in some of the
bifurcation diagrams. These multiple steady states should be avoided to improve the control of
the system and avoid convergence problems in the rigorous simulations by changing the Da
number, the column pressure or the pseudo-feed composition. The traditional system of a reactor
followed by a distillation column has been compared to the use of an entire reactive distillation
system. The traditional system configuration is more advantageous than the reactive distillation
system because pure TAME can not be obtained in the column bottoms due to its decomposition
in methanol and isoamylenes. When the boundary line is close to the residue curve map edge as
at 10 bar, it is preferable to introduce stoichiometric feed at the reactor and recycle the non
reacted components with some of the TAME product than use an excess of isoamylene to avoid
this presence. When the boundary line is more distant from the edge as happens at 1 bar, it is
preferable to use the excess of isoamylene to avoid the presence of TAME in the distillate. In the
traditional system of reactor and column, to maximize the advance of reaction and minimize the
recycle flow rates of the distillate of the column, the temperature of the reactor must be kept at
low values. The hybrid reactive distillation columns overcomes the limitation of the chemical
equilibrium and pure TAME can be collected using a non-reactive section at the bottoms. The
heat of the reaction is used directly by the reactive distillation column. From the results, it seems
as a promising alternative the use of a hybrid reactive distillation column with a total reflux to
avoid the recycle of reactants and reach a total conversion. The infinite/infinite results are used
as a basis for the rigorous simulation of the reactive distillation columns and for the
environmental and economical evaluation according to Klemeš et al. 2007 in the present section.
5.3.1. Rigorous simulation of the reactive distillation column alternatives for

TAME synthesis
The ∞/∞ analysis is also useful to evaluate new alternatives for an existing process and to
propose energy efficient alternatives by process integration. An approximation used in the
literature is that the energy required in the reboiler is proportional to the distillate flow rate
determined by the analysis. As mentioned previously, most of the energy consumed by the
distillation columns is due to the reboiler; a vapour flow rate proportional to the reboiler duty
210
and constant along the column (according to the McCabe-Thiele hypothesis) is collected in the
condenser. Applying a mass balance at the condenser and using the definition of reflux ratio, the
heat in the reboiler is proportional to the distillate flow rate, reflux and the heat of vaporization
of the mixture. As a first approximation, only the distillate flow rate is considered (V.73) The
heat of vaporization is not constant along the column and the reflux is also a relevant parameter,
therefore the main results obtained from the ∞/∞ analysis must be followed by more rigorous
calculations.
Qreboiler   V  H R    D   r  1  H R  D (V. 73)
where H R represents the reaction enthalpy.

The heat in the reboiler cannot be determined by the ∞/∞ analysis; therefore, the rigorous
simulation of the systems is required. A distillation column of one hundred stages with the feed
plate in the middle is used to determine the minimum reflux. The minimum number of stages is
estimated by integrating the inverse of the modulus of the vector between the liquid and vapour
composition in equilibrium, along the column profile composition accordingly to the number of
transfer units. From the simulation results of the large distillation column, the reboiler duty is
estimated according to an optimum reflux equal to 1.2 times the minimum reflux. The energy
cost for each system is evaluated considering the cost of a coal thermal plant with CO2 capture
(Klemeš et al., 2007), which would be able to satisfy the energy demand for the selected process
when it would be implemented at international scale. For the estimation of the process
investment cost, it is considered that the investment costs are proportional to the quantity of steel
needed to construct the distillation column, according to the procedure described by Bonet et al.,
2008.
The analysis is applied to different distillation column configurations both non-reactive and
reactive (Figure 5.53). A traditional system consisting of reactor and distillation column, as well
as a totally reactive and a hybrid reactive distillation columns are evaluated and compared in
terms of energy savings, with the aim to collect pure TAME at the end of the process and to
recycle the non-reacted components (Figure 5.53a). Stoichiometric and non-stoichiometric feeds
are investigated at 1 and 10 bar. As TAME synthesis reaction is exothermic, the heat generated is
directly used for the energy requirements of the distillation column, decreasing the energy
consumption of the system.
The distillate flow rate is calculated easily from the ∞/∞ analysis, but the heat in the reboiler
cannot be determined, therefore the simulation of the systems is required. The rigorous
simulation of these situations, at their optimal distillate flow rates obtained from the ∞/∞
211
analysis, is performed to rank the results according to the energy required by the column
reboiler.
D D D
F F
F FR F*
B B B
(a) (b) (c)
Figure 5.53 Classical system of reactor and distillation column (a); whole reactive distillation
column (b); hybrid reactive distillation column (c).
The rigorous simulations of the five situations previously discussed, at their optimum distillate
flow rates, are presented to verify and rank the results according to the energy required by the
column reboiler. The heat in the reboiler cannot be determined by the ∞/∞ analysis, therefore the
simulation of the systems is required. A reflux value of 1.2 times bigger than the minimum
reflux is fixed for the distillation columns. A concentration-based kinetic model proposed by
Subawalla and Fair (1999) is used because the Aspen simulator does not allow implementing the
kinetic model based on activity coefficients, such as the kinetic model proposed by Oost and
Hoffmann (1995) and used by Thiel et al. (1997) to generate the residue curve maps. The details
of the system streams are shown in Table 5.2 and the reactor and columns characteristics are
given in Table 5.3. The systems tabulated are all with recycle streams.
The first case tabulated is a stoichiometric crude feed to the system, which is mixed with a
recycle stream containing some TAME and stoichiometric mixture of reactants. When it is fed to
the reactor, a pseudo-feed is obtained with a content of TAME according to the extent of
reaction. The TAME is collected pure at the bottom of the column and the distillate is recycled;
the TAME content in the distillate is determined by the presence of the boundary line. The
second case tabulated is a stoichiometric crude feed to the system, which is mixed with a recycle
stream containing the methanol-isoamylene azeotrope. When it is fed to the reactor, a pseudo-
feed is obtained with a content of isoamylene higher than for the first case, according to the
extent of reaction. The TAME is collected pure at the bottom of the column and the distillate is
recycled. The third case tabulated (reactive distillation) is the hybrid column with the non
212
reactive section at the bottom of the column. There is no additional reactor used and the reaction
takes place inside the distillation column. TAME is collected at the bottom of the column and it
would be desirable that there will not be any distillate flow rate to be recycled. However, the
simulations of the column at total reflux encounter problems of numerical convergence.
Therefore, the results obtained for the reactive distillation system require further improvement.
Nevertheless, the results obtained are sufficiently meaningful to verify the feasibility of the
hybrid configuration of the reactive distillation column proposed and to re-confirm that the
reactive distillation process is more advantageous than the others due to the integration of
processes (reaction and distillation) within the same equipment.
Table 5.2 Flow rates of the selected alternatives obtained by simulation.
Stoichiometric feed Non-stoichiometric Reactive

to column feed to column distillation
1 bar 10 bar 1 bar 10 bar 1 bar
F IA 0.5000 0.5000 0.5000 0.5000 0.5000
MeOH 0.5000 0.5000 0.5000 0.5000 0.5000
TAME 0.0000 0.0000 0.0000 0.0000 0.0000
kmol/s 100.0 100.0 100.0 100.0 100.0
FR IA 0.4710 0.4827 0.5870 0.5810 0.5103
MeOH 0.4707 0.4827 0.4130 0.4190 0.4902
TAME 0.0293 0.0173 0.0000 0.0000 0.0097
kmol/s 140.32 222.67 141.18 216.38 107.43
F* IA 0.2000 0.3440 0.3600 0.4550 -
MeOH 0.2000 0.3440 0.0910 0,2450 -
TAME 0.6000 0.3120 0.5480 0.3010 -
kmol/s 90.32 172.67 91.19 166.38 -
B IA 0.0000 0.0000 0.0010 0.0010 0.0010
MeOH 0.0010 0.0010 0.0000 0.0000 0.0000
TAME 0.9990 0.9990 0.9990 0.9990 0.9990
kmol/s 50.00 50.00 50.01 50.00 50.00
D IA 0.4480 0.4840 0.7980 0.6500 0.5867
MeOH 0.4470 0.4840 0.2020 0.3500 0.2523
TAME 0.1050 0.0320 0.0010 0.0000 0.1696
kmol/s 40.32 122.67 41.18 116.38 6.45
213
Table 5.3 Comparison of the distillation columns and reactors for several schemes
Stoichiometric feed Non-stoichiometric Reactive

to reactor feed to reactor distillation
1 bar 10 bar 1 bar 10 bar 1 bar
D/F 0.4032 1.2267 0.4118 1.1638 0.0644
T (K) – Distillate 309.1 382.0 305.4 380.3 309.2
r (reflux ratio) 0.5393 2.1625 0.7267 0.70311 14.7159
Conversion in reactor or RD 73.42 45.67 70.79 46.29 92.94
column %
Qreboiler (kJ/kmol of feed) 22290 100603 22654 49715 20373
Qcondenser (kJ/kmol of feed) 20151 95680 20088 44546 31319
Number of stages 42 36 19 38 15*
Feed stage 31 20 9 13 2
Qreboiler /(  D  ( r  1)   H R ) 1.17 0.84 1.04 0.82 1.06**
Q reboiler / Q condenser 1.11 1.05 1.13 1.12 1.05
* reactive stages from 2 to 6 with residence time of 0.5 h. Not optimized.

** obtained considering the heat generated by reaction = 26800 kJ/kmol (Rihko et al. (1994))
The equation (V.73) is fulfilled for the hybrid reactive distillation column when the heat
generated by the chemical reaction is taken into account. The deviation from the values obtained
by simulation, introduced by the simplifications used in the ∞/∞ analysis (the heat of the reboiler
is proportional to the distillate flow rate) shows that the reboiler duty is not directly proportional
to the distillate flow rate, but for the evaluated cases, it was obtained that a lower distillate flow
rate leads to a lower reboiler duty (Ulrich, 2008).
The increase of the pressure in the traditional system of reactor and column does not show any
advantage: it requires a compressor, thicker walls and more stages in the distillation column and
higher recycle flow rate. This corresponds to higher energy demand in the reboiler and higher
costs. At 1 bar, the stoichiometric feed to the reactor leads to a lower energy consumption than
the non-stoichiometric one, but it requires the usage of a higher number of stages. The process
intensification achieved by the hybrid reactive distillation column demands a shorter column,
and in the same time, the recycle streams are minimized or even avoided. The heat of the
reaction is used directly in the column, decreasing consequently the reboiler duty. The reactive
distillation is able to overcome the chemical equilibrium limitations and it is the most
advantageous alternative.
214
The hybrid reactive distillation column results are presented in detail. Figure 5.54 illustrates the
column composition profile. The first six stages are reactive and the remaining nine stages
towards the bottom are non-reactive (where TAME product is purified). The temperature profile
has a maximum slope on stage 9 that could be suitable to be taken into account for control
purposes (Figure 5.55). The sharp increase of temperature from the stage 1 to 2 is explained by
the change of composition caused by chemical reaction.
1
0.9
0.8
0.7
0.6 IA
0.5 MeOH
xi
0.4 TAME
0.3
0.2
0.1
0
0 2 4 6 8 10 12 14
Stage number
Figure 5.54 Hybrid reactive distillation column compositions profile
360
355
350
345
340
T (K)
335
330
325
320
315
310
305
0 2 4 6 8 10 12 14
Stage number
Figure 5.55 Hybrid reactive distillation column temperature profile
215
Figure 5.56 shows that the reaction takes place mostly where the feed is introduced on stage 2.
For stages 4 to 6, the reaction molar extent is negligible or even negative in stage six (due to
TAME decomposition), but a reduction of the reactive zone arises convergence problems.
Finally, in the Figure 5.57, the internal flow rates present mostly constant molar overflow, except
stage 2 which accommodates the feed to the column and where the heat of reaction produces a
sudden increase of the vapour flow rate.
50
40
TAME generation (kmol/s) .
30
20
10
0
0 2 4 6 8 10 12 14
-10
Stage number
Figure 5.56 Distribution of the reaction extent in the hybrid reactive distillation column.
120
100
Flow (kmol/s) .
80
60
40
L
20
V
0
0 2 4 6 8 10 12 14
Stage number
Figure 5.57 Internal hybrid reactive distillation column flow rates.
216
5.3.1.1. Error Analysis of the obtained results
The ∞/∞ analysis is based on the information provided by the residue curve maps and its errors
depend on the data used to calculate the residue curve map: binary vapour-liquid equilibrium and
kinetic data. The validity of the assumptions that the reboiler duty is equal to the condenser duty
or, equivalently, to a constant vapour molar overflow and heat of vaporization is verified. The
proportionality of the reboiler duty and the distillate flow rate used in the early-stage energy
evaluation is also discussed. The rigorous simulation results present also some unavoidable
errors due to the MESH model and to simplifying assumptions.
The mass balances obtained from analysis are exact for zeotropic mixtures. For azeotropic
mixtures sometimes the boundary lines were approximated to straight lines leading to errors but
in our case we took into account the boundary line trajectory. The analysis was based on the
residue curve maps and the errors of the maps were not presented explicitly in the analysis. The
errors related to the calculation of the residue curve map are not provided (Thiel et al., 1997).
When vapour liquid equilibrium data from different authors are compared, the errors can be
around 10%.
A potential source of error was to assume that the reboiler duty is equal to the condenser duty.
When the error of this assumption was evaluated using the results of the rigorous simulation, the
confidence interval of the error was up to 20% for a probability of 95% using Student’s t-
distribution. Table 5.2 shows that the approximation to consider equality of reboiler duty with
the condenser duty is satisfied; the average value obtained for the ratio reboiler duty / condenser
duty with a confidence interval of 95% is 1.09±0.05. The application of equation (V.73) also
satisfies the equality of the ratios, but the interval of 95% confidence is wider: 0.99±0.19. Figure
5.58 shows the regression of the vapour flow rate entering the condenser and the reboiler duty.
The slope of the correlation is 26.13±2.87 kJ/kmol (confidence interval of 95%) which
corresponds to an average enthalpy of vaporization for the evaluated mixtures.
The assumption that the distillate flow rate is proportional to the reboiler duty is difficult to
validate because the number of cases presented in this work was too small and not enough
representative to obtain statistically precise values of the errors. A greater number of solved
cases should be performed to get more accurate error estimation. Figure 5.59 shows that the
energy requirements related to the reflux are of the same order as the ones related to the distillate
condensation. For the hybrid reactive distillation, the reboiler duty is 20373 kJ/kmol as compared
with the condenser duty of 32847 kJ/kmol, the difference of 12474 kJ/kmol being covered by the
heat of reaction.
These error evaluations are based on the rigorous simulation results, but these simulations also
contain some errors, for instance, the heat losses through the column walls are neglected. The
217
validation of theoretical results in reactive distillation is not usually performed by pilot plant
experiments due to the elevated operational costs and to generated residues. Sometimes, the
results obtained by using commercial simulators are applied to design the industrial column
considering an error tolerance of 10%. In general, the optimum operation cost region is a flat
zone and the adjustment of the reflux ratio of the column allows a final adjustment to the desired
purities.
In conclusion, the level of the overall error for this method could be appreciated around 20 %,
which is acceptable for an early-stage analysis.
120000
y = 2.6420E+04x
R2 = 9.7717E-01
80000
Q reboiler
(kJ/kmol)
40000
0
0 1 2 3 4 5
D/F·(r+1)
Figure 5. 58 Correlation between reboiler duty and vapour flow rate.
120000
 ·r·D/F
Non-stoichiometric feed to reactor 10 bar
 ·D/F
Non-stoichiometric feed to reactor 1 bar
100000
Stoichiometric feed to reactor 10 bar
Stoichiometric feed to reactor 1 bar
80000
 ·D/F·(r+1)
Hybrid reactive distillation*
60000
40000
20000
0
20373 22290 22654 49715 100603
(32847) Q reboiler
(kJ/kmol)
Figure 5.59 Influence of distillate flow rate and reflux on reboiler duty.
218
5.3.2. Rigorous simulation taking into account the presence of isopentane
inert
The TAME synthesis shows that an entirely reactive distillation column is not suitable due to the
TAME decomposition, but if a non-reactive stripping section is used, then the resulting hybrid
reactive distillation column is the most advantageous alternative. From the results obtained by
rigorous simulation, it can be concluded that the recommended configuration among the systems
analysed for TAME synthesis is the hybrid reactive distillation column, which provides an
energy saving in the reboiler of 10%, in comparison with the traditional system at 1 bar from
which the azeotrope methanol – isoamylene is collected in the distillate. It has been observed in
the column profile that the reaction takes place just in a few plates. The isoamylene contains
several compounds from de C5 fraction; one of the main ones is the isopentane. This component
was not taken into account in the previous sections as otherwise it would not be possible to plot
the residue curve maps in two dimensions to visualize it properly. The isopentane forms a
minimum boiling azeotrope with the methanol. Therefore, the unstable node of the system is this
azeotrope avoiding the total conversion of the methanol. Around a quarter of the distillate
composition is methanol. The presence of the volatile compound does not affect the results
commented previously for the bottoms. Pure TAME is the stable node of the non-reactive
residue curves. Therefore, reactive distillation with isopentane separates the isopentane/methanol
azeotrop from pure TAME at the bottoms. The lower part of the column must be non-reactive
and the upper part to separate the azeotrope from the rest can be non-reactive. Therefore, the
reactive section should be a few stages above the feed stage to put in contact the volatile
isoamylenes with the refluxed methanol. The pure isopentane is a saddle node and therefore its
concentration will be higher in the middle of the column. A divided wall column is proposed to
collect isopentane in a side stream.
The etherification reactions are typically chemical equilibrium limited and face challenges with
product purification. They are carried out commercially using either large excess of one of the
reactants, or by removing one of the products continuously in a reactive distillation column
(RDC). In this work, the possibility to operate the reactive distillation process in a dividing wall
column (RDWC) apparatus for TAME synthesis, using ion exchange resin Amberlyst 35, as
catalyst, was studied using process simulator ASPEN-HYSYS. The main objective in choosing
of this operation is to get a high isoamylene-to-TAME conversion and a high purity of TAME
product and also to recover and recirculate the excess of reactant MeOH. Analysis of RCM (built
in ASPEN-DISTIL™) (Doherty and Malone, 2001) is used in process topology synthesis.
Flowsheet simulation of RDWC is not very easy with commercial software (as ASPEN-
HYSYS™) due to difficulties to adapt existing modules to needed topology. RDWC is modelled
219
considering four zones: the prefractionator, hosting reactive packing, (modelled with back flow
cell model (BCM) with forward flow of liquid and back flow of vapour), upper separation zone
in prefractionator (modelled as absorber standard unit), separation zone in the prefractionator
below the reaction zone (modelled also as absorber standard unit) and finally upper, right side
and lower DWC separation zone (modelled together as standard distillation column), as in Figure
5.60. The flowsheet includes as well as some additional units for mixing and conditioning of
feedstock streams and pre-reactor. Reporting system of this CAPE tool allow performance
assessment of each analysed topology. RDWC topology presented in Figure 5.60 can be in
principle a candidate process structure to produce TAME at industrial scale. The kinetic model
implemented is published by Bumbac et al (2007), valid for Amberlyst 35 catalyst, and the
thermodynamic model is NRTL. Feed composition (mole fraction) is : 0.6437 - i-C5, 0.0661 -
2M1B, 0.0756 - 2M2B, 0.0000 – TAME and 0.2146 – MeOH. For implementation in Aspen-
HYSYS, the scheme shown in Figure 5.60 is used. The pre-fractionator has 15 theoretical trays
and 30 theoretical trays (without reboiler and condenser) in right side of RDWC wall. Sulzer
structured packing Melapack/Katapack is considered for column capacity calculations.
COND PRODUCT
TO BE RECYCLED
PDZ DWC separation

separation zone
(absorber standard
PDZ PDZ
DWC separation
the prefractionator
reaction CDZ INERTS standard
(back flow cell
FEED distillation
column
PDZ PDZ
separation zone
(absorber standard
PDZ DWC separation
PDZ – pure distillation zone; MAIN PRODUCT

REB
CDZ – catalytic distillation zone;
Figure 5. 60. Flowsheet scheme for RDWC
Product streams show good separation for targeted compounds (distillate 72% mol i-C5, 27.3%
MeOH and 0.7% isoamylenes), side stream 93.2% mol i-C5 and bottom stream 99.9% mol
TAME). Isoamylenes to TAME conversion is 90.6%. Of course, further purification of products
can be setup in other units. Maximum operating temperature in reaction zone is 70 oC at 2.5 bars.
Composition profiles in RDWC upper, right and bottom zones are presented in Figure 5.61
220
showing that separation objectives are reached. i-C5 composition present strong variation mainly
in dividing wall right side neighbourhood, with maximum in that region. TAME is progressively
accumulating in RDWC bottoms.
Reactive prefractionator composition

Reaction zone
1
0.8
i-C5
mole fraction
0.6 2M1B
2M2B
0.4 TAME
MeOH
0.2
0
1 5 9 Feed 13
Tray number (no 1 in top of

prefractionator, 4-8 reactive trays)
Right side of RDWC wall composition

Side Draw
1
0.9
0.8
0.7 i-C5
m ole fraction
0.6 2M1B
0.5 2M2B
0.4 TAME
0.3 MeOH
0.2
0.1
0
0 10 20 30
No of tray (0 is condenser)
Figure 5. 61. Liquid phase composition profiles in the RDWC
5.4. Economical assessment
5.4.1. Basic economic feasibility

A basic economical rule to provide an economically feasible process is that the price of the
products must be higher than the cost of reactants. The reactions and processes that do not satisfy
221
this premise must be disregarded. In this step of analysis, a thorough search must be performed
to identify the prices for the analysed system components. When the chemical components prices
are available, the income is calculated based on the difference between economical values of
products and reactants.
As a fine chemical compound, TAME has a high added value. Its price is higher than the
reactants (the isoamylenes available in the refineries from the C5 fraction and methanol), a bulk
reactant of low value, assuring the basic economic feasibility.
5.4.2. Economical comparison of the reactive distillation alternatives

The chemical engineer needs a quick and rough economical evaluation to decide between
alternative designs and optimize the operating parameters from early stages of design. The
ability to find reasonable optimum operating conditions of a complex distillation system within a
short period is difficult due to a huge mathematical computing effort required and mathematical
convergence difficulties. This work proposes a simplified cost function taking into account the
main parameters to which are proportional the capital and operational costs. The goal is not to
provide an exact cost estimate in some currency units, but to provide an optimal operational
window defined by a percentage over the minimum cost value.
Cost estimation is a specialized profession. The expenses necessary for preparing an estimated
cost with an accuracy of ± 5% are about 2 per cent of the total project cost (Sinnott et al, 1999).
The chemical engineer, however, needs a quick and rough economical evaluation to decide
between alternative designs and optimize the operating parameters from early stages of design.
The preliminary estimates have accuracy typically ±30 % and this accuracy increases to ±10-15
% at the authorization estimates (budgeting).
The total cost is the sum of investment and operational costs. The amortization of the investment
costs must be divided to the recovery period before being added to the operational costs.
Therefore, the investment costs vary depending on marginal conditions, e.g. the period of
depreciation or the consideration of calculated interest, which influences the exact optimum
parameters conditions.
As a reasonable simplification, similar weighting between operating and annualized investment
costs can be chosen (Bauer and Stichlmair, 1998). However, after the optimization, Frey et al
(1997) obtained that the investment costs were about twice the operational costs. Several
optimizations of the same system can provide different optimal conditions. These apparent
contradictory results are consequence of the difficult cost evaluation. Several simplifications are
assumed, local minimum can be present and it is difficult to assure that the overall minimum is
obtained. Preliminary estimations have low accuracy and the overall cost usually is a function
222
with a quite flat minimum that with small variations can provide quite different optimum
conditions. Cardoso et al (2000) used simulated annealing and the results present costs of 15.04
and 15.05·106 USD/year for a distillation column with 7 and 8 trays, respectively at pressures of
1 and 15 atm. The authors concluded also that several feasible designs could be found from 5 to
17 trays with objective functions within 1% of the lowest cost.
Therefore, an estimation of an accurate cost is a tough task but, fortunately, most of the chemical
engineering systems present flat minimum cost regions. An optimum operating window for the
main variables of a distillation process is useful to provide reasonable values in the early stages
of design and a better understanding of the process in the last stages of accurate cost estimation
and optimization.
A compilation of cost data from various sources shows that the next expression can be used for
preliminary investment cost estimates (Sinnott et al, 1999):
Ce  C  S n
(V. 74)
where Ce represents the purchased equipment cost, S represents the characteristic size parameter,
C is a cost constant and n is the index for the type of equipment.
A mathematical deduction leads to the main process parameters influencing the characteristic
size parameter and operating costs of distillation systems (Bonet et al., 2006). The operational
costs (Co) are proportional to the vapour flow rate inside the column. Applying mass balance in
the condenser, the vapour flow rate is related to the distillate flow rate (D) and the reflux ratio
(r). The investment costs (Ce) are proportional to the steel required in the column shell and to the
thickness of the walls. This leads to the proportionality with the pressure (P), the height of the
column, the number of stages (N), the column diameter and the vapour flow rate. The cost
expressions are expressed with the proportionality constants (C1 and C2) as in the following
equations, where Fc represents the crude feed:
D (V. 75)
C o  C1   (r  1)
Fc
P D
Ce  C2   N   ( r  1) (V. 76)
Patm Fc
Equation (V.75) is adapted to the shape of equation (V.74) to provide an equipment cost
equation taking into account the size of the distillation column.
223
n
 P D 
C e  C    N   ( r  1)  (V. 77)
 Patm Fc 
The overall cost is the sum of operational costs and investment costs corrected by some marginal
factors, such as the depreciation period, which are included in a constant:
n
C  P D  D
COV     N   (r  1)   C1   (r  1) (V. 78)
C deprctn  Patm Fc  Fc
The exact cost depends on the exact value of the constants that depend on the fluctuations of the
steel costs (C), energy costs (C1) and of company politics (Cdeprctn). For sake of simplicity, a cost
proportional to the total cost is proposed:
n
COV C  P D  D
    N   (r  1)    (r  1) (V. 79)
C1 C1  C deprctn  Patm Fc  Fc
n
 P D  D
COV  K    N   (r  1)    (r  1) (V. 80)
 Patm Fc  Fc
The process parameters appearing in the expression (V.80) can be calculated from shortcut
methods such as the infinite/infinite analysis (Bonet et al, 2007, Plesu et al 2008) and a stage-by-
stage calculation from the feed plate to the distillate and to the bottoms. The values for K and n
are estimated from ideal binary mixtures in the present work. The obtained cost function is used
in the illustrative example providing the percentage of cost above the minimum cost calculated.
The constants K and n depend on equipment type and therefore a distillation column separating
ideal binary mixtures is used to determine them. Both the purity of heavy component in the
bottoms and the purity of the light component in the distillate are fixed at 0.99. The feed
composition and the volatility coefficient are the two variables remaining that will be studied and
used for the determination of the cost expression parameters. Figure 5.62 shows that using a
reflux 1.3 times the minimum reflux and fixing the cost expression parameters at K=1.8 and
n=0.54, the equipment and operational costs are quite similar for any value of feed composition
and for any volatility coefficient. However, Figure 5.63 shows that the minimum costs are lower
than the costs where the operational and equipment costs are equal. The reason is that the
equipment cost decreases more abruptly and with higher slope than the smooth increase of the
operational costs. It is noticeable that the optimum cost is very sensitive to small changes of the
relative volatility. This behaviour is consequence of the flat minimum cost region and of the
number of stages, which is a discrete variable. Therefore, the value of 0.54 for the constant n is
224
acceptable but the constant K should be twice higher, in this way the results are in accordance
with Frey et al. (1997) and the rule of thumb that the optimal reflux is around 1.3 times the
minimum reflux (Figure 5.64).
Figure 5. 62 Operational and investment costs for ideal mixtures assuming K=1.8 and n=0.54.
Figure 5. 63 Operational and investment costs crossing point for ideal mixtures assuming K=1.8
and n=0.54.
225
Figure 5. 64 Operational and investment costs crossing point for ideal mixtures assuming K=3.6
and n=0.54.
According to the results, the following cost function is adjusted:
0.54
 P D  D
C OV  3.6   N  (r  1)    (r  1) (V. 81)
 Patm Fc  Fc
Table 5. 4 Overall cost comparison of the several alternatives

Process scheme P (bar) D/Fc rmin N Total cost, Cov
Stoichiometric feed 1 0.4032 0.54 42 23
Non stoichiometric feed 1 0.4118 0.73 19 16
Stoichiometric feed 10 1.2267 2.16 36 203
Non stoichiometric feed 10 1.1638 0.70 38 139
Hybrid RD 1 0.0644 14.63 15 19
Applying this formula, assuming that the reflux is 1.3 times the minimum reflux, it seems
preferable to use 1 bar than 10 bar and the non stoichiometric feeds are preferable to the
stoichiometric feeds (Table 5.4). The best options for which a more detailed study would be
required are the hybrid reactive distillation and the non stoichiometric feed at 1 bar.
5.4.3. Techno-economic model with CO2 capture feasibility

The next step is the techno-economical model. This step gives us an idea of the costs associated
to each alternative. In contrast to the previous steps, a negative result does not mean that the
process is not suitable, it can simply suggest that the process is not enough optimised. The
methodology proposes to evaluate the process economical viability comparing main indexes to
nowadays industrially used alternatives, which are taken as reference system. Process operation
cost evaluation is based on the assumption that required energy is provided by a coal thermal
226
plant with 95% CO2 capture (Klemeš et al., 2007). Therefore, the link between the total energy
requirements and the energy costs is the following:
Operational cost (M$/y)  7.7258  0.1690  Qreboilers (MW) (V. 82)
For the reference system, investment cost depreciation is assumed to be equal to the process
operation cost (Bonet et al., 2006). For the process alternatives schemes, investment cost is
assumed proportional to the quantity of steel involved in distillation columns construction.
For the reference system (the process scheme nowadays in use or what it is considered the best):
Amortization of investment cost (M$/y)  Operation cost (M$/y) (V. 83)
For all the schemes:
Amortization of investment cost (M$/y) ~ P  N min  D  (rmin  1) (V. 84)
The expenses represent the sum of operation process costs and investment costs. The cost of
reactants is not taken into account since it is a fixed term defined by the purity and flowrate of
the product desired. The economical viability is quantified with simple models assuming that a
coal thermal plant whose CO2 emissions are mostly captured (Klemeš et al., 2007) provides the
energy. The results for TAME synthesis using this model is shown in table 9.
Table 5. 5 Results for the TAME synthesis (for 2.656 TAME Mt/h)
P Q reboilers Energy cost Total cost
Process scheme D/Fc rmin N
(bar) (MW) (M$/y) (M$/y)
Stoichiometric feed 1 0.4032 0.54 42 359 68 137
Non stoichiometric 1 0.4118 0.73 19 365 69 105
feed
Stoichiometric feed 10 1.2267 2.16 36 1.620 281 15.347
Non stoichiometric 10 1.1638 0.70 38 800 143 4.274
feed
Hybrid RD 1 0.0644 14.63 15 328 63 100
5.5. Environmental performance assessment

Direct or indirect CO2 emission minimisation for energy intensive processes is a priority for
reducing their environmental impact. For distillation, this issue is observed redesigning the
separation processes to improve the energy efficiency as stated in the previous section.
Sustainability requests as well to enhance the usage of environmentally friendly products and to
227
ensure good economic effectiveness. Advanced process integration methodologies such as for
total site integration (Klemeš et al., 1997), for industrial utility systems integration (Varbanov et
al., 2005) or for waste and renewable energy integration (Perry et al., 2008) are used to save
energy. Reactive distillation combines process integration and process intensification
overcoming chemical equilibrium limitations, saving energy and ensuring economic
effectiveness by reduced capital investment. Environmental performance is based on potential
environmental impact (PEI), emissions, resource and energy conservation factors. PEI is
obtained using waste reduction (WAR) algorithm as evaluation tool.
Using the results from the previous sections of the analysis and simulation, the environmental
performance is evaluated with well-known Waste Reduction (WAR) algorithm developed by
Cabezas et al. (1999). This algorithm is used by several authors to complete their process
simulations, e.g. Iancu et al. (2001), or incorporated into conceptual process design (Seay and
Eden, 2009). Some applications are reported in literature (Cardona et al., 2004). A techno-
economical viability evaluation of processes involving process integration takes into
consideration calculation of potential environmental impact.
A great number of good quality data collected is required to apply a Life Cycle Assessment, but
these data requirements are usually simplified, the Environmental Performance Strategy Map is a
possible solution (De Benedetto and Klemes, 2009). When we want to compare industrial
processes treating the same input (reactants) streams and providing the same output (products)
streams, the system boundaries become fixed and their environmental impact depends only on
the process itself. In this case, the proposed methodology is suitable. The only data required for
the study is the vapour liquid equilibrium (e.g. UNIFAC), the reaction kinetics or equilibrium,
the world production estimation and the price of reactants and products. The normalized impact
scores computed for different categories of potential environmental impact of the compounds
involved in the case studies are presented in Table 5.6.
5.5.1. Environmental Performance Index (EPI) ranking

In the last step of the methodology proposed, the potential environmental impact (PEI) of the
alternatives is evaluated based on Waste Reduction algorithm (WAR) (Cabezas et al., 1999). The
data related to toxicology and physical properties for the evaluation of impact scores is taken
from the database based on the study of Heijungs et al. (1992). WAR GUI software developed
by US Environmental Protection Agency (US EPA) contains incorporated the above-mentioned
database. Main individual potential environmental impact categories are (units of Impact/kg of
product):
- human toxicity potential by ingestion (HTPI) ,
228
- human toxicity potential by inhalation or dermal exposure (HTPE),
- ozone depletion potential (ODP),
- global warming potential (GWP),
- acidification potential (AP),
- photo oxidation chemical potential (PCOP),
- aquatic toxicity potential (ATP)
- terrestrial toxicity potential (TTP) are calculated.
Table 5. 6 Normalised impact scores for different categories of potential environmental impact
for the compounds involved in the case studies (source: WAR GUI software)
Normalized impact score
Compound
HTPI HTPE TTP ATP GWP ODP PCOP AP
MeOH 0.0626 0.0011 0.0626 0 0 0 0.2462 0
TAME 0.2340 0.0028 0.0007 0 0 0 0.5230 0
isoamylenes 0.2630 0 0.0264 0 0 0 4.61 0
CO2 0 0 0 0.0002 0 0 0 0
Coal energy 7.83·10-5 1.22·10-6 7.83·10-5 2.65·10-4 2.03·10-9 1.93·10-4 7.07·10-8 5.98·10-3
A coal thermal plant is considered in the WAR software, without CO2 capture, unlike the techno-
economical evaluation made in the previous step of our methodology. The comparison of the
alternative processes is based on the Environmental Performance Index (EPI) (Ramzan et al.,
2008). EPI takes into account the individual potential environmental impacts calculation (PEI)
from the WAR results, the energy consumption, the resource conservation and the fugitive
emissions index. The parameters taken into account for the PEI calculation are related to mass
flow rate of the main product in kg/h (Mp). The weight factors and equations used at this stage
are the ones proposed by Ramzan et al. (2008):
4
PEI  (V. 85)
EPI  Ec  Er  E f
Where Ec, Er and Ef are calculated as follows:
Energy consumption index : Ec  H/M p (V. 86)
where H represents the total energy consumed by the reboilers in MJ/h
Resource conservation index : Er  M r /M p (V. 87)
229
where Mr represents the total mass flow rate of inputs to the system in kg/h
Fugitive emission index : E f  7 10-4  Fi (V. 88)
where Fi is the sum of mass flow rates fed to the columns of the system in kg/h.
.
The resource conservation factor is alike for the distillation processes with fixed input and output
compositions and flowrates. The hybrid reactive distillation scheme provides the lowest fugitive
emissions factor. It was obtained that the energy consumption factor is the most critical
parameter in the environmental performance index (Table 5.8).
Under all the environmental aspects evaluated, the use of the hybrid reactive distillation column
instead of the traditional process of reactor and distillation column offers a cleaner and more
sustainable process scheme among the alternatives studied. The WAR algorithm is a commonly
used tool to evaluate the impact focused on the chemical manufacturing. The Life Cycle
Assessment (LCA) covers a wide scope taking into account the life cycle of the product but
requires a high number of data gatherings (raw material acquisition or pre-chemical
manufacturing stage, post-chemical manufacturing stage, product distribution, product use and
disposal or recycle, the effect of the emissions in the air, water and soil and the impact on the
receptors). The WAR algorithm results are in accordance with the LCA only when both are
applied to an overall process path involving the same reactants and the same final products. Each
stage of a multi-stage process has a lower environmental impact than the overall process. The
results related to energy consumption factor and PEI follow the same pattern for most of
distillation processes due to the high influence of energy consumption upon the distillation
schemes.
Table 5. 7 Individual total PEI for each TAME process alternative (PEI/kg product)*.
HTPI HTPE TTP ATP GWP ODP PCOP AP
Stoichiometric 1.56·10-6 2.80·10-3 1.56·10-6 5.29·10-6 2.59·10-2 4.06·10-11 1.41·10-9 1.20·10-4
feed 1bar
Non -6
stoichiometric 1.59·10 2.80·10-3 1.59·10-6 5.39·10-6 2.59·10-2 4.13·10-11 1.44·10-9 1.22·10-4
feed 1bar
Stoichiometric 7.07·10-6 2.80·10-3 7.07·10-6 2.40·10-5 2.59·10-2 1.83·10-10 6.38·10-9 5.40·10-4
feed 10bar
Non -6
stoichiometric 3.50·10 2.80·10-3 3.50·10-6 1.18·10-5 2.59·10-2 9.06·10-11 3.16·10-9 2.66·10-4
feed 10bar
Hybrid RD 1.43·10-6 2.80·10-3 1.43·10-6 4.85·10-6 2.59·10-2 3.72·10-11 1.29·10-9 1.09·10-4
1 bar
*
From TAME synthesis until its combustion.
230
One of the main issues in the evaluation of fugitive emissions is the presence of distillation
column vents. According to US EPA, 0.7 kg volatile components are assumed to escape in the
environment for each 1000 kg throughput. It was observed that the global warming potential is
the most critical parameter in the potential environmental impact determination (Table 5.7)
which is similar for all the evaluated alternatives
Table 5. 8 Factors for EPI determination of TAME process

Total PEI Energy EPI (Environ-
Resource Fugitive
(Potential consumption mental
conservation emissions
Environmental factor Performance
factor factor
Impact) (MJ/kg) index)
Stoichiometric 4.48·10-3 20.0 1 1.39 1.79·10-1
feed 1bar
Non
stoichiometric 4.48·10-3 20.3 1 1.48 1.76·10-1
feed 1bar
Stoichiometric 4.51·10-3 90.3 1 1.39 4.32·10-2
feed 10bar
Non
stoichiometric 4.49·10-3 44.6 1 1.47 8.50·10-2
feed 10bar
Hybrid RD 1 4.48·10-3 18.3 1 0.70 2.00·10-1
bar
Conclusions
A method from fast analysis to rigorous simulations have been proposed and applied to TAME
synthesis. The approach takes into account technical, economical and environmental aspects.
Considering basic thermodynamic data, the reactive residue curve maps have been calculated
using MATLAB software. An original user-friendly interface has been implemented to represent
the desired residue curves. One of the main drawbacks of the residue curve maps is that,
although are useful to check the feasibility, these do not provide any hint about easiness of
separation. Therefore, a new parameter based on the number of transfer units is also included in
the residue curve map information. For a non-reactive system, the number of transfer units of a
packed column operated at infinite reflux flow rate is directly linked to the dimensionless time of
a Rayleigh distillation. The number of transfer units depends only on the composition column
profile and it does not depend on the characteristics and performance of the packing.
For non-reactive systems, the compositions followed by the residue in the still of a Rayleigh
distillation match with the compositions in the column profile of a packed column operated at
infinite reflux flow rate. This assumption is valid for any distillation system but it is not true for
reactive distillation taking into account kinetics where the number of moles changes due to the
reaction stoichiometry. This difference becomes more evident for high retention times in the
231
column. The Rayleigh distillation for high retention times behaves like a simple reactor leading
the composition at chemical equilibrium. On the other hand, the infinite reflux flow rate column
shows a different behaviour being able to be collected a bottoms composition free of methanol
and a distillate free of TAME.
The infinite/infinite analysis is useful to perform a sensitivity analysis of the flow rate effect on
the product concentrations to search multiplicities and understand the systems behaviour. The
use of this analysis has been extended to kinetically controlled systems. It has been successfully
applied to TAME synthesis, also using a hybrid reactive distillation column.
The TAME synthesis is rigorously simulated and optimized under several process schemes: a
classical scheme of reactor and separator and reactive distillation column, and different feed
conditions: stoichiometric feed, non stoichiometric feed and presence of isopentane inert.
To compare and optimize the schemes, a new approach for cost comparison is proposed. The
originality of the approach is that it is based on the input parameters used in the simulations and
the goal is not to obtain cost estimation but a value useful for comparison. A quantification of
costs is performed in a second step by using a techno-economic model considering CO2 capture.
Finally, the environmental performance of the schemes has been evaluated using the data
obtained in the previous calculus and simulations. The environmental performance is based on
the potential environmental impact, emissions, resource and energy conservation factors. The
potential environmental impact has been calculated using the waste reduction algorithm as
evaluation tool. For industrial processes treating the same input (reactants) streams to provide the
same product, the system boundaries become fixed and their environmental impact depends only
on the process itself. Therefore, a good comparison of alternatives can be performed without
requiring the great amount of data for a life cycle assessment.
232
CHAPTER 6
CONCLUSIONS
This thesis presents the results of an experimental and theoretical research performed in the field
of Modelling and simulation of continuous catalytic distillation

processes, being focused on the synthesis of tert-amyl-methyl-ether (TAME), an ecological
fuel additive.
The original contributions of the present thesis are:
- A detailed literature survey in the field of ethers synthesis by the addition of alcohols to tertiary
olefins.
- A critical analysis of kinetic models proposed in literature and information related to chemical
equilibrium in liquid phase, specific to TAME synthesis.
- Development of an extensive experimental program to study the kinetics of isoamylenes
etherification with methanol over the Amberlyst35 catalyst. The influence of various parameters
on reaction system kinetics was evaluated: temperature (experiments performed at 60 – 70 – 80 –
90 oC), catalyst particles dimension (using granulometric fractions of catalyst obtained from
sieved catalyst d < 0.63 mm, 0.63 < d < 0.8 mm, 0.8 < d < 1.0 mm), and isoamylenes
concentration in initial C5 fraction (adding 2M2B, the initial IA concentrations obtained were
25%, 30%, 35%, 40% IA).
- The experiments were carried out on an experimental setup particularly adapted for kinetic
studies, having as main component a stainless steel autoclave provided with automatic injection
of liquid samples in gas chromatograph.
- The study of the limitative effect of internal diffusion on TAME synthesis kinetics with
commercial Amberlyst 35 catalyst. The experiments with various catalyst particles dimensions
highlighted the existence of a certain influence of internal diffusion on process kinetics, but not
greater then the uncertainty existing at the determination of effective coefficients for diffusion in
granule porous structure. Consequently, using the experimental data obtained, with unsieved
catalyst, the parameters of the kinetic model were determined, including in their value a certain
effect of internal diffusion on process kinetics.
- Adapting the kinetic model proposed by Rihko et al (1995, 1997) to the TAME synthesis with
Amberlyst35 catalyst. The parameters of the model were estimated based on experimental data
obtained in this thesis. For this purpose, an original application was developed in MATLAB for
kinetic model parameter estimation using MATLAB toolboxes. The values of reaction activation
energies were calculated considering the existing thermodynamic relations and restrictions. The
233
agreement between the Rihko model predictions after parameters estimation and experimental
data is very good. The adequacy is highlighted by a high correlation coefficient and by relatively
small intervals for model parameters estimation, for a 95% confidence level.
- Development of an extensive experimental program for vapour-liquid equilibrium
measurement for binary systems of compounds presents in the reaction system specific to TAME
synthesis (2M2B-MeOH, 2M2B-TAME, 2M1B-TAME and iC5-MeOH, respectively). The
boiling curves (Txy), experimentally obtained, are in good agreement with data existing in
literature and supplement these databases, especially for the systems containing TAME. These
thermodynamic data are used for validation of activity coefficients calculation methods,
considered in process kinetic modeling.
- The quality of experimental results was confirmed by comparison with data available in
literature and by comparison with predictions of various thermodynamic models adequate for
hydrocarbons – ethers mixtures. The comparison of experimental data with classical
thermodynamic models predictions (UNIFAC, UNIQUAC, NRTL, Wilson) presents good
agreement.
- A methodology and a computer tool was proposed to evaluated the feasibility of reactive
distillation process, considering technical, economical and environmental impact aspects. The
tools used with this purpose are: reactive residue curve maps, infinite / infinite analysis, process
simulators, cost evaluation using simplified models and the evaluation of environmental impact
with WAR algorithm based on Environmental Performance Index (EPI). The introduction of the
number of theoretical units, necessary for liquid separation, into the equation of residual curves
and the inclusion of this information into the residual curve maps. This is important as it gives
details regarding the difficulty of separation (not included in the classical methodology currently
in use).
- An algorithm and a program to build residual curves were developed to be used also for
systems of reactive distillation and for classical distillation systems. The original application
implemented in MATLAB provides an interactive interface which permits the exploration of
diagram topology and the calculation of desired residual curves. Within the same application, the
number of transfer units (NTU) calculation was also implemented. For illustration, residual
curves diagrams were represented in this thesis for different values of operating pressure and for
different values of Damkhöler (Da) number in the field of interest for industrial applications.
These diagrams were modified inserting the NTU concept to evaluate the process feasibility
based on reactive distillation principle, pointing out in the same time the degree of difficulty of
separation.
234
- A new approach for evaluation of feasibility for reactive distillation process was proposed
based on infinite / infinite analysis. This provides information related to feasible operating
conditions, detects multiple steady states regions and identifies the possible purities for all the
streams, considering certain operating conditions. The infinite / infinite analysis, as preliminary
analysis tool, is extended in this thesis to systems with chemical reaction. The results of the
analysis are used for rigorous simulation of feasible topologies for TAME synthesis process.
- As a continuation to TAME synthesis process feasibility analysis, a simplified cost function
was proposed to compare and optimize feasible topologies. The evaluation of various topologies
based on original cost indicators and environmental impact (evaluated with WAR algorithm)
highlighted the performances and advantages of hybrid reactive distillation process for TAME
synthesis case.
The quality of the results obtained in this Thesis is supported by 17 publications and scientific
communications, out of which 8 in peer-reviewed journals (two in journals with impact factor
greater than 2.2).
235
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255
Appendix I. Thermodynamic models for estimation of physico-chemical
properties
NRTL Model
NRTL model (Non-random two-liquids) developed by Renon and Prausnitz in 1968 is an extension
of the local composition concept which considers the random character of interactions (Syed et al.,
2000; Ferreira and Loureiro, 2004).
∑x τ G j ij ji 
x j G ji  ∑ xmτ mj Gmj 

ln γ i = j
+∑ τ ij −
m
 (1)
∑x G k
k ki j ∑ x k Gki 
k 
∑k xk Gkj 

where
Gij = exp ( −α ijτ ij )
bij
τ ij = aij + + eij ln T + fijT (2)
T
αij = cij + dij (T − 273.13 K )
aii = bii = cii = dii = 0
The model needs the knowledge of binary interaction parameters τij. These can be found in
databases or can be determined by regression of experimental data. The coefficients τ ij express the
differences between interaction energies τ ji = ( g ji − gii ) / R ⋅ T . The parameters Gij consider the
non-random character of this kind of interactions: Gij = exp ( −α ijτ ij ) Parameter αij can be treated as
an adjustable parameter, even if usually it has a fixed value. There are a few recommendations:
• α = 0.20 for saturated hydrocarbons with unassociated polar species
• α = 0.30 for non-polar components, as well as for water.
• α = 0.40 for saturated hydrocarbons
• α = 0.47 for alcohols
NRTL model proved able to predict in many applications the non-ideality of liquid phase with
enough precision.
256
UNIQUAC Model
The UNIQUAC (UNIVERSAL QUASI-CHEMICAL) model was developed by Abrams and

Prausnitz in 1978 (Syed et al., 2000, Rihko et al., 1995). Unlike NRTL model where the local
volume fraction is used, the UNIQUAC model uses the local surface area fraction θij . Each molecule
is characterized by two structural parameters: r the relative number of molecule segments (volume
parameter) and q the relative surface area (area parameter). The values of these parameters were
obtained in some cases by statistic calculation. There is a special UNIQUAC form for systems
containing alcohols, where a third parameter q ' can lead to a significant increase of accuracy. In the
UNIQUAC model, the excess free Gibbs energy is the sum of two contributions. The first
contribution is the combinatorial part representing the influence of structural parameters, such as the
volume parameter (r) and the shape (q). The second contribution is the residual part, which
considers the interaction energy between segments. Parameters r and q can be calculated from other
two dimensions, the van der Waals area AW and van der Waals volume VW. This information is
usually stored in databases for pure component properties. UNIQUAC model has two adjustable
parameters, τ ij and τ ji . These can be considered constant or temperature dependant.
ln γ i = ln γ iC + ln γ iR (3)
with
φi z θ φ n
ln γ iC = ln
xi
+
2
⋅ qi ⋅ ln i + li − i
φi xi
∑x
j =1
j ⋅lj (4)
 
   θ jτ ij 
ln γ = qi 1 − ln ∑ θ jτ ji  − ∑
R
(5)
 
 j ∑ θ kτ kj 
i
  j
k 
bij
τ ij = aij + (6)
T
⋅ (ri − qi ) − (ri − 1) ,
z
li = z = 10 (7)
2
xjq j x jq j
θj = ;φj = (8)
∑xqi i ∑xq i i
Despite the apparent complexity, UNIQUAC model is a robust computation method.
257
UNIFAC Model
UNIFAC method represents a version of UNIQUAC method in which both the combinatorial and
the residual terms are computed from group contributions (while in UNIQUAC method, the residual
term is computed based on interaction parameters obtained from experimental data).
The activity coefficients are computed as the sum of two free terms, the combinatorial and the
residual term, respectively, with similar equations as the one previously described in the case of
UNIQUAC model (equations 3, 4, 6 – 8).
Parameters rj and qj can be computed from information related to molecular structure, using group
contributions:
rj = ∑ν
k
( j)
k Rk ; q j = ∑ν k( j ) Qk
k
(9)
Rk Qk – k structural group contributions; ν k( j ) - number of k groups in molecule j.

The values of group contributions (Rk, Qk), which appear in the computation of activity
coefficients for the components involved in the specific reaction system for tertiary ethers synthesis
are presented in Table 1.
According to this method, γi is computed from relation (3), together with an additional
equation specific to the computation of residual term:
ln γ iR = ∑ν ( ) ln Γ
j
j
i
j − ln Γ(j ) 
i

(10)
 
   θ Ψ 
ln Γ j = Q j 1 − ln 

∑ θ m Ψ mj  −

∑m ∑mθ n Ψjmnm  (11)
 m 
 n 
where
ν (ji )
- number of j groups contained in species i;
Γj
- activity coefficient of group j in the mixture;
Γ(j )
i
- residual contribution of group j activity coefficient in a fluid containing only species i.
X m Qm
θm = - surface fractions represented by group m; (12)
∑ n
X n Qn
258
∑ν ( j)
m xj
=
j
Xm - molar fraction of group m in the mixture (13)
∑∑ν
j n
( j)
n xj
 a 
Ψ mn = exp  − mn  (14)
 T 
amn - groups interaction parameters, specific to the method (Table 2).
Table 1 Rk and Qk parameters

Grupul CH3 CH2 CH=C C CH3–OH CH3O
Rk 0.9011 0.6744 0.8886 0.2195 1.4311 1.1450
Qk 0.848 0.540 0.676 0 1.432 1.088
Table 2. Binary interaction parameters

Grup CH3 CH2 CH=C C CH3–OH CH3O
CH3 0 0 86.02 0 679.2 251.5
CH2 0 0 86.02 0 679.2 251.5
CH=C -35.36 -35.36 0 -35.36 787.6 214.5
C 0 0 86.02 0 679.2 251.5
CH3–OH 16.51 16.51 -12.52 16.51 0 -128.6
CH3O 83.86 83.86 26.51 83.86 238.4 0
259
UNIFAC-Dortmund Model
UNIFAC-Dortmund method represents a version of UNIFAC method, improved by researchers at

University of Dortmund. The activity coefficients are computed from equation (15) in which:
Table 3. Values of the interaction parameters amn
CH3 CH 2 CH C C CH 2 CH C OH
O CH2
CH3 0 0 0 0 86.02 86.02 251.5 986.5
CH 2 0 0 0 0 86.02 86.02 251.5 986.5
CH 0 0 0 0 86.02 86.02 251.5 986.5
C 0 0 0 0 86.02 86.02 251.5 986.5

C CH 2 -35.36 -35.36 -35.36 -35.36 0 0 214.5 524.1
CH C -35.36 -35.36 -35.36 -35.36 0 0 214.5 524.1
83.36 83.36 83.36 83.36 26.51 26.51 0 237.7

O CH2
OH 156.4 156.4 156.4 156.4 457.0 457.0 28.06 0
 φi  φi 
ln γ iC =1 − φ i′ + ln φ i′ − 5 qi 1− + ln   (15)
 θi  θi  
ri3 4 ri qi
θ i′ = ; φi = ; θi = (16)
∑
j
x j rj3 4 ∑ j
x j rj ∑
j
xj qj
The term ln γ iR is computed from previous equations. The computation of parameter ψnm is
based on an operating temperature dependent equation:
 a + b T + c nm T 2 
Ψ nm = exp  − nm nm  (17)
 T 
260
WILSON Model
For a binary mixture, the equation used to compute the activity coefficients is as follows (Sandler,
1999):
 Λ12 Λ 21 
ln γ 1 = − ln ( x1 + Λ12 x2 ) + x2  −  (18)
 x1 + Λ12 x2 Λ 21 x1 + x2 
The model contains two parameters, Λ12 and Λ21, which can be computed from
experimental data. For a multicomponent mixture, the equation to compute activity coefficients is
as follows:
 n  n x j Λ ij
∑
ln γ i = 1 − ln  x j Λ ij  − ∑ n
(19)
 j =1  j =1
∑x Λ
k =1
k jk
In equations (18) – (19), parameters Λij are computed from the equation (Reid et al., 1987:
V jL  ∆ λij 
Λ ij = exp −  (20)
Vi L  RT 
V jL - molar volume of pure liquid i; ∆ λij - energy parameters characterizing the interaction of
molecules i and j.
261

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UNIVERSITY “POLITEHNICA” of BUCHAREST

Faculty of Applied Chemistry and Material Sciences

MODELLING AND SIMULATION OF CONTINUOUS CATALYTIC

A Thesis submitted to the

for ACADEMIC TITLE OF DOCTOR

Alexandra Elena BONET RUIZ

SPECIALITY: CHEMICAL ENGINEERING

under the supervision of

Professor Grigore BOZGA

CHAPTER 1 Introduction............................................................................... ………………..1

Appendix 1……………………………………………………………………………………. 256

Figure 3. 1 Autoclave-type reactor of the etherification plant...................................................... 79

Table 2. 1. Allowed concentration limits for reformulated gasoline compounds......................... 14

Survey regarding the catalytic distillation technique and synthesis

2.1. The principle of reactive distillation and its technical importance

2.2. The importance of tertiary aliphatic ethers C5-C7. Legislation aspects

m e til te rt-b u til e te r ( M

te rt-a m il m e til e te r ( (TAME)

Figure 2. 2 Main tertiary ethers used at industrial scale

Table 2. 1. Allowed concentration limits for reformulated gasoline compounds

Table 2. 2 Allowed concentration limits for ethers used in gasoline

Table 2. 3. Worldwide tertiary ethers production in year 2000 (Pääkkönen, 2003)

Table 2. 5. Typical composition of C4 fraction from pyrolysis units

Table 2. 6 Typical composition of C4 fraction from catalytic cracking units

Table 2. 7 Typical composition of C5 fraction from catalytic cracking units

2.2.2. Synthesis methods for C5-C7 aliphatic tertiary ethers series

Figure 2. 3 Generation of tertiary alcohols by hydration of olephins

C5H10 + C5H10 C10H20

Tert-amyl alcohol (TAA) Ethanol Tert-amyl ethyl ether (TAEE)

Industrial technologies for tertiary ethers synthesis

Procedure Application Description Company

Fixed bed trifunctional catalyst reactor

Two fixed bed adiabatic reactors, placed in

MTBE, TAME, Extended layer adiabatic reactor, followed

Two fixed bed reactors, followed by

Tert-amyl-methyl-ether (TAME) is a stable compound. Random polymerization like peroxide

Table 2. 9 TAME composition produced in European Union

- butyl tert-butyl ether 0.06%

Physico – chemical properties

Table 2. 10 Physicochemical properties of tert-amyl methyl ether

Flash point - 11 oC CHEMSAFE , 1994;

Does not have oxidizing prperties due to

Viscosity 0.50 mm2/s at 40 oC Stephenson, 1992;

Production capacities at European level

TAME started to be used as an important compound in production of commercial gasoline at the

Table 2. 11 Companies producing TAME with capacities of over 1000 t/year

Figure 2. 4. Amounts of product used in various fields

Table 2. 13 The amount of TAME consumed in different EU countries in 2002

Greece Finland France Italy Holland Spain United

Figure 2. 5 The amount of TAME consumed in different EU countries

TAME synthesis processes

Figure 2. 6 Main reactions for obtaining TAME

Figure 2. 7 Secondary reaction – dimerization of isoamylenes

Figure 2. 8 Secondary reaction – etherification (dehydration) of methanol

Modelling of thermodynamic equilibrium

 ir , j represents the stoechiometric coefficient of component i in reaction r, in phase j.

i j  ipure liquid T , p 0   RT ln  xij  i j  (II. 4)

and for non-condensable compounds in liquid phase (according to Henry law):

Table 2. 14 Thermodynamical data for the participants in the reaction

v H 0 kJ/mol 37.52 26 27.0 35.3

cp (liq) kJ/(mol·K) 0.0816 0.1569 0.1523 0.2192

reaction in gaseous phase can be calculated according to equation II.14:

where γ represents the activity coefficient.