MODELING A N D SIMULATION O F CATALYTIC

DISTILLATION FO R ESTERIFICATION O F ACETIC

ACID WITH M ETHANOL U SIN G A S P E N P L U S

A DISSERTATION
Submitted in partial fulfillment of the
requirements for the award of the degree
of
MASTER OF TECHNOLOGY
in
CHEMICAL ENGINEERING
(W ith S pecialization in C o m pu te r A ided P rocess P lant Design)

By
NAGESHW AR REDDY K

^ R A LU a ,

■ACC No.
-O
Date.

6/

DEPARTMENT OF CHEMICAL ENGINEERING

INDIAN INSTITUTE OF TECHNOLOGY ROORKEE
ROORKEE -247 667 (INDIA)
JUNE, 2011
 CANDIDATE’S DECLARATION

I hereby declare that the work, which is being presented in the dissertation entitled
“M O D E L I N G AND SIMULATION OF CATALYTIC DISTILLATION FOR
ESTERIFICATION O F ACE T I C ACID W I T H M E T H A N O L USING A S P E N PLU S ”,
in the partial fulfillment of the requirements for the award of the degree of Master of
Technology in Chemical Engineering with specialization in “Computer Aided Process Plant
Design”, and submitted to the Department of Chemical Engineering, Indian Institute of
Technology Roorkee, Roorkee, is an authentic record of my own work carried out during the
period from July 2010 fo June 2011 under the guidance of Dr. Surendra kumar, Professor,
Department of Chemical Engineering, Indian Institute ofTechnology Roorkee.

I have not submitted the matter, embodied in this dissertation for the award of any other
degree.

Date:

Place: IIT Roorkee ( N A G E S H W A R R E D D Y K)

CERTIFICATE

This is to certify that the above statement made by the candidate is correct to the best of my
knowledge and belief.

Dr. Surendra kumar 1

Professor
Department of Chemical Engineering
Indian Institute ofTechnology Roorkee
Roorkee-247667 (India)
 ACKN O W LED G EM EN T

I wish to express m y sincere gratitude to m y guide, Dr. Surendra kumar, Professor,

Department of Chemical Engineering, Indian Institute of Technology Roorkee, who’s
strengthening presence was a source of great inspiration for the successful completion of this
dissertation report. I also want to express m y gratitude to, Dr. (Mrs) Shashi, Associate
Professor, Department of Chemical Engineering, Indian Institute of Technology Roorkee for
their useful guidance. Their constant guidance, useful criticism and constant help in the hours
of need have been immensely useful.

Thanks are due to Dr. Indra Deo Mall, Professor and Head of the Department, Department
of Chemical Engineering, Indian Institute of Technology Roorkee, Roorkee, for providing
various facilitiesduring this dissertation.

I am greatly indebted to m y friends and all others for their enthusiastic support,

encouragement and help, made me come up with this report.

Above all, I want to express m y heartiest gratitude to all m y family members for their love,
faith and support for me, which has always been a constant source of inspiration

( N A G E S H W A R R E D D Y K)
 ABSTRACT

The present investigation pertains to a theoretical study of simulation of

multicomponent catalytic distillation column. In this it was studied that the reaction and
separation are in one column with 25 stages included reboiler and condenser for synthesis of
methyl acetate by using A S P E N R A D F R A C column for two feed set up and also studied
about the complex modelling concepts ofreactive distillation by using catalyst.

In present investigation, the rate kinetics has been assumed to be pseudo

homogeneous model for simulation. Further, the comparison of this model has been done
with the data ofPopken, T, et al (2001). Finally the effect of design variables namely - reflux
ratio, feed tray location, start of reactive section andendof reactive section, and
thermodynamic models on composition ofM e O A c profiles on column is studied.

By using M E S H equations with the rate kinetic model equation for synthesis of
methyl acetate, mathematical model has been developed. The developed model has been
validated by comparing the composition profile in the liquid phase and variation of methanol
conversion haying the reflux ratio with the experimentaldata of Popken et al (2001).
Comparison shows the deviation of simulation results with the experimental results. Avg.
maximum deviation is found to be 30% in composition profiles, and maximum deviation is
v
found to be 14 % in variation of methanol conversion with reflux ratio.

In the above mentioned design variables, the reflux ratio, feed tray locations, end of
reactive stage and thermodynamic model have most significant effect on the methanol
conversion and methyl acetate composition in the distillate and the remaining column.
 CONTENTS

Page No.

C A N D I D A T E ’S D E C L A R A T I O N i

ACKNOWLEDGEMENT ii

ABSTRACT iii

CONTENTS iv

LIST O F FIGURES vi

LIST O F T A B L E S vii

C H A P T E R 1: I N T R O D U C T I O N 1

1.1.W h y RD? 2
1.2.Comparison of Processes in Conventional
Distillation and R D 4
1.3 .Advantages of Reactive Distillation 6
1.4.Some Boundaries and Difficulties in R D „7
1.5. Introduction of Synthesis of Methyl Acetate 7
1.6.Objective of Thesis 8

C H A P T E R 2: L I T E R A T U R E R E V I E W 9

2.1. Development of catalytic distillation for

Synthesis of Methyl Acetate 9

2.2. Vapor-liquid equilibrium for multi component distillation 22

2.2.1. Thermodynamic models 22

2.2.2. Ideal Vapor-Liquid Equilibrium 23

2.2.3. Non Ideal Vapor-Liquid Equilibrium 24

2.3*. Calculation of Activity Coefficient 24

2.3.1. Wilson Model, 1962 25

2.3.2. N R T L Model, 1986 25

2.3.3. U N I Q U A C Model, 1975 26

2.3.4. U N I F A C model, 1975 26

 2.4. Rate kinetics in Catalytic distillation 29

2.5. Modelling of catalytic distillation column 33

2.5.1. The Equilibrium Model 33

2.5.2. Non-Equilibrium or Rate-Based Model 35

2.5.3. N E Q modeling o f R D 38

2.5.4. Dynamic Non-Equilibrium stage

Model (homogeneous) 39

2.5.5. Heterogeneous equilibrium stage model 40

2.5.6. Heterogeneous Non- Equilibrium model 41

C H A P T E R 3: Simple Modeling of Catalytic Distillation Column 43

3.1. Assumption for modeling of catalytic distillation 43

3.2. Assumption for simulation 43

3.3. Modeling equations 44

C H A P T E R 4: R E S U L T S A N D DISCUSSION 47

4.1. Model validation 48

4.1.1. Validation of liquid phase composition

Profile for two feed set up 48

4.1.2. Variation of Methanol conversion with

Reflux ratio using two feed set up 48

4.2. Effect ofvariables 48

4.2.1. Effect of reflux ratio 49

4.2.2. Effect of feed tray locations 50

4.2.3. Effect of starting of reactive zone 51

4.2.4. Effect of end of reactive zone 51

4.2.5. Effect of thermodynamic model 51

C H A P T E R 5: C O N C L U S I O N A N D R E C O M M E N D A T I O N S 60

REFERENCES 62

ANNEXURE-A: SIMULATION RESULTS 66

v
 LIST OF FIGURES

Figure No. Description Page N o.

Figure 1.1 Processing schemes for a reaction sequence A + B C + D where C 3

and D are both desired products
Figure 1.2 Processing schemes for the esterification reaction 4
MeOH + HOAc <-> MeOAc+ H zO
Figure 1.3 Reactive distillation concept for synthesis o f MTBE from .the acid- 5
catalysed reaction between MeOH and iso-butene
Figure 2.1 Equilibrium stage m odel with feed stream and side stream 34.
Figure 2.2 N on-equilibrium stage m odel with feed stream and side 36
streams
Figure 3.1 Schem atic diagram o f j th equilibrium stage 44
Figure 3.2 R AD FR A C colum n used as C D column in aspen plus 44
Figure 4.1 Liquid phase com position profile for synthesis o f methyl 52
acetate using two feed set up.
Figure 4.2 Conversion versus R eflux ratio for synthesis o f m ethyl 53
'acetate using two feed colum n
Figure 4.3 : C om position o fM eO A c in distillate vs R eflux ratio for two 54
feed set up
Figure 4.4 M eO A c Com position on trays for different N fl using two 55
feed set up with N f2= 20
Figure 4.5 M eO A c Com position on trays for different N f2 using two 56
feed set up with N fl =5
Figure 4.6 Variation o fM eO A c Com position with start o f reactive 57
section (Nrs ) using two feed setup(N re=19).
Figure 4.7 Variation o f methyl acetate( com position on trays for 58
different Nre stages with N rs=10 for using tw o feed set up.
Figure 4.8 Variation o fM eO A c com position on trays for different 59
thermodynamic models
 LIST OF TABLES

Table No Description Page No

Table 2.1 Details ofdifferent catalyst used for synthesis ofmethyl acetate 12

Table 2.2 Parameters and Residual Errors of the Different Kinetic Models 30
Used to Fitthe Experimental Data

Table 2.3 Parameters and Residual Errors of the Different Kinetic Models 31
Used to Fitthe Experimental Data with Amberlystl 5 as the
Catalyst

Table 4.1 Operating parameters oftwo feed column 47

Table 4.2 Range ofprocess variables using in two feed stage 49

Table A.l Composition data for Figure 4.1 66

Table A.2 M e O H Conversion Data for Figure 4.2 67

Table A.3 MeOAc liquid composition Data in distillate for Figure 4.3 68

Table A.4 MeOAc Composition Data for Figure 4.4 69

Table A.5 MeOAc Composition Data for Figure 4.5 70

Table A .6 MeOAc Composition Data for Figure 4.6 71

Table A.7 MeOAc Composition Data for Figure 4.7 72

Table A .8 MeOAc Composition Data for Figure 4.8 73

 CHAPTER 1

IN T R O D U C T IO N

Reactive distillation or catalytic distillation process has been installed in many industries
in now-a-days. In this unit two functional works are included one as a reaction and another one is
separation process. By using this unit in industries can reduce the capital cost of equipments by
eliminating the two equipments in (reactor & distillation) industries. The concept of reactive
distillation was applied in the late 1920’s to esterification processes (Keys, 1932). The industrial
application of reactive distillation did not take place before 1980’s. Reactive distillation term
describes both catalytic and non-catalytic distillation. Operation of non-catalytic reactions in R D
is very difficult for separation of compounds. Catalytic distillation is two types one is
heterogeneous and another one is homogeneous reactions. Heterogeneous reactions are operated
easily to compare with the homogeneous reaction in catalytic distillation unit; in homogeneous
catalyst reactions in R D unit separation of catalyst take place is difficult. In this paper we discuss
about simulation and modeling of catalytic distillation for a synthesis of methyl acetate from
methanol and acetic acid. The first patents date back to the 1920s (Backhaus, 1921, 1922,
1923a,b). Early journal articles are by Keyes (1932), Leyes and Othmer (1945a, b), Schniep,
Dunning and Lathrop (1945), Berman, Melnychuk & Othmer (1948b) and Berman et al. (1948a).
The first publications deal mainly with homogeneous self-catalyzed reactions such as
esterifications, trans-esterifications, and hydrolysis. Heterogeneous catalysis in R D is a more
recent development and was firstdescribed by Spes (1966).

Reactive distillation deals with many reactions in now a day. There are many process
examples are available like as esterification, trans-esterification, hydrolysis, etherification,
hydrogenation, dehydrogenation, alkylation, metathesis and disproportionation, hydration and
dehydration, carbonylation, production of polymers, chlorination/amination, synthesis of
carbonates etc.

In this paper, we discuss about esterification of acetic acid and methanol to from methyl
acetate in catalytic distillation. They are many papers were published on esterification process
since 1920’s.RD process effect by many factors like as in conventional distillation are reflux
ratio, distillate flow rates, feed tray location, total number of stages and new factors are start of
reactive section and end of reactive section will studied for different feed configurations(single
feed and double feed).

“The versatility of the fractionating column in the dual role of continuous reactor and
separator as applied to chemical processing iswell established.”
-Berman, Isbenjian, Sedo! and Othmer (1948a).
The quote was more than six decades ago! It provides an interesting historical perspective
because in more recent times we have seen an explosion of interest in the subject of reactive
distillation, and a veritable plethora of papers have appeared in the last 20 years alone. W e start
with why we need R D or catalytic distillation.

1.1 W hy RD? :
Let us begin by considering a reversible reaction scheme: A + B <-> C + D where the
boiling points of the components follow the sequence A, C, D and B. The traditional flow-sheet
for this process consists of a reactor followed by a sequence ofdistillation columns; see Fig. 1(a).
The mixture of A and B is fed to the reactor, where the reaction takes place in the presence of a
catalyst and reaches equilibrium. A distillation train is required to produce pure products C and
D. The un reacted components, A and B, are recycled back to the reactor. In practice the
distillation train could be much more complex than the one portrayed in Fig. 1(a) ifone or more
azeotropes are formed in the mixture. The alternative R D configuration is shown in Fig. 1(b).
The R D column consists of a reactive section in the middle with nonreactive rectifying and
stripping sections at the top and bottom. The task ofthe rectifying section is to recover reactant B
from the product stream C. In the stripping section, the reactant A is stripped from the product
stream D. In the reactive section the products are separated in situ, driving the equilibrium to the
right and preventing any undesired side reactions between the reactants A (or B) with the product
C (or D). For a properly designed R D column, virtually 100% conversion can be achieved.

2
 O
?
cs
iD
Ui
c

s
a

Ia
A,B— M cc
5

D
TW?
o
<£
c

3
tt

(a) Conventional process (b) Reactive distillation

Figure 1.1Processingschemes forareactionsequence A + B <->C + D where C and D areboth desiredproducts,

(a)Typical configurationofaconventional process consistingofareactorfollowed by a distillationtrain,(b)The
reactive distillation configuration. The components A, C, D and B have increasing boiling points. The reactive
sectionsareindicatedbygridlines,Adaptedfrom StichlmairandFrey(1999).

3
1.2 Comparison of Processes in Conventional Distillation and RD:
Examples forthe benefits ofR D using in some process:

1. The acid catalyzed reaction was traditionallyM e 0 H + H 0 A c < r J> M e 0 A c + H 20

carried out using the processing scheme shown in Fig. 2(a), which consists of one reactor and a
train of nine distillation columns. In the R D implementation (see Fig. 2(b)) only one column is
required and nearly100% conversion of the reactant is achieved. The capital and operating costs
are significantly reduced (Siirola, 1995).

MeOH HAc MeO A c

Catalyst J MeAc

Reactoi AcO H

MeOH

1 T

i^Pi

h 2o Water

(a) Conventional process (b) Reactive distillation

F ig u re 1.2 P rocessin g schem es fo r the e ste rifica tio n rea ctio n M e O H + H O A c <r-> M e O A c + H 20 . (a)

C o n v e n tio n a l p ro ce ssin g schem e co n sistin g o f on e reactor fo llo w e d b y n in e d is tilla tio n co lu m n s, (b) T h e reactive

d is tilla tio n co n fig u ra tio n . T h e re a ctiv e section s are in dica te d b y g rid lin e s. A d a p te d fro m S iir o la (1995).

2. For the acid catalysed reaction between wo-butene and methanol to form methyl te r t -butyl

ether: wo-butene+MeOH ^ MTBE, the traditional reactor-followed-by-distillation concept is

particularly complex for this case because the reaction mixture leaving the reactor forms three
 minimum boiling azeotropes. The R D implementation requires only one column to which the
butenes feed (consisting of a mixture of n-butene, which is non-reactive, and /'so-butene which is
reactive) and methanol is fed near the bottom of the reactive section. The R D concept shown in
Fig. 3(a) is capable of achieving close to 100% conversion of z'so-butene and methanol, along
with suppression of the formation of the unwanted di methyl ether (Sundmacher, 1995). Also,
some ofthe azeotropes in the mixture are “reacted away” (Doherty& Buzad, 1992).

3. For the hydration of ethylene oxide to mono-ethylene glycol: E 0 + H 2 0 — ►EG, the R D

concept, shown in Fig. 3(b) is advantageous for two reasons (Ciric & Gu, 1994). Firstly, the side
reaction E O + E G — ► D E G is suppressed because the concentration of E O in the liquid phase is
kept low because of its high volatility. Secondly, the high heat of reaction is utilised to vaporise
the liquid-phase mixtures on the trays. To achieve the same selectivity to E G in a conventional
liquid-phase plug-flow reactor would require the use of 60% excess water (Ciric & Gu, 1994).

butcne JWo

PCH
Ca{O H )j

M eOH

rt-ta u te n s
i-buffine J|

L i v e s -le a m

M TEE PG, j
HaO. 4
(d) Ij
F ig u re 1.3 (a) R e a c tiv e d is tilla tio n c o n c e p t fo r syn th e sis o f M T B E fro m the a cid -ca ta ly se d re a ctio n betw een M e O H

and iso-butene. T h e butane feed is a m ix tu re o f re a c tiv e iso -bu tene and n o n -re a ctiv e «-butene. (b ) R e a c tiv e

d is tilla tio n co n ce p t fo r the h y d ra tio n o f e th yle n e o x id e to e th yle n e g ly c o l, (c) R e a c tiv e d is tilla tio n co n c e p t fo r

re a ctio n b etw een ben ze n e and p ro p e n e to fo rm cum ene. (d ) R e a c tiv e d is tilla tio n c o n c e p t fo r re a ctio n p ro d u c tio n o f

p ro p y le n e o x id e fro m p ro p y le n e c h lo ro h y d rin s and lim e . T h e re a ctiv e se ctio n s are in d ica te d b y g rid lin e s

5
4. In several alkylation reactions, aromatic + olefin y * alkyl aromatic are best carried out using
the R D concept not only because of the shift in the reaction equilibrium due to in situ separation
but also due to the fact that the undesirable side reaction, alkyl aromatic+olefin dialkyl
aromatic, is suppressed. The reaction of propene with benzene to form cumene, benzene +
propene cumene (Shoemaker & Jones, 1987; see Fig. 3(c)) is advantageously carried out in a
R D column because not only is the formation of the undesirable di-isopropyl benzene
suppressed, but also the problems posed by high exothermicity of the reaction for operation in a
conventional packed-bed reactor are avoided. Hot spots and runaway problems are alleviated in
the R D concept where liquid vaporisation acts as a thermal flywheel. The alkylation of is o -

butane to wo-octane, wo-butane + n -butene wooctane is another reaction that benefits from a
R D implementation because in situ separation of the product prevents further alkylation: is o -

octane+w-butene (Doherty & Buzad, 1992).

5. The reaction between propylene chlorohydrin (PCH) and Ca(OH )2 to produce propylene oxide
(PO) is best implemented in an R D column, see Fig. 3(d). Here the desired product PO is
stripped from the liquid-phase by use of live steam, suppressing hydrolysis to propylene glycol
(Bezzo, Bertucco, Forlin & Barolo, 1999)

1.3. A dvantages of R eactive D istillation:

1. Higher conversion for equilibrium limited reaction due to increase in the reaction. This
increase in the conversion results in reducing forward rate i.e. shifting of equilibrium to the
right side of recycling to a great extent.
2. Simplification (or) elimination of the separation system can lead to significant capital
savings.
3. Improved selectivity is obtained because of removal of the products from the reaction zone
and preventing them to undergo further reaction to give various by products.
4. Heat integration benefits are obtained, because the amount of heat generated in exothermic
reaction can be utilized for the vaporization ofthe mixture.

6
 5. Catalytic distillation is particularly advantageous when reactor products, i.e. products and
reactants can form several azeotropes with each other’s,which require additional costs for
separation.
6. Significantlyreduced catalystrequirements forsame degree ofconversion.
7. Reduced formation ofbyproducts.
8. Avoidance ofhotspots and runaways using liquidvaporization asthermal flywheel.
9. Increasedspeed and improved efficiency.

1.4. Some Boundaries and Difficulties in RD:

Against the above-mentioned advantages of RD, there are several constraints and
foreseen difficulties(Towler & Frey, 2000):
1. Volatility constraints. The reagents and products must have suitable volatility to maintain
high concentrations ofreactantsand low concentrations ofproducts inthereactionzone.
2. Residence time requirement. Ifthe residence time for the reaction is long, a large column
size and large tray hold-ups will be needed and itmay be more economic to use a reactor-
separatorarrangement.
3. Scale up to large flows. It is difficult to design RD processes for very large flow rates
because ofliquiddistributionproblems inpacked RD columns.
4. Process conditions mismatch. In some processes the optimum conditions oftemperature and
pressurefordistillationmay be farfrom optimal forreaction and viceversa.
5. Understanding of the separation function in reaction zone leads to complex interactions
between vapor-liquid equilibrium, vapor-liquid mass transfer, intra catalyst diffusion (for
heterogeneously catalyzedprocesses) and chemical kinetics.

1.5. Introduction of Synthesis of Methyl Acetate:

Esterification ofmethanol and acetic acid to form methyl acetateperformed intwo phase
catalyst (heterogeneous and homogeneous). The synthesis ofmethyl acetate from methanol and
acetic acid using structured catalyst packing Katpack-S with abmerlyst-15 as heterogeneous
catalyst has been studied by experimentally by Popken et al. (2001). Methyl acetate synthesis
through reactive distillation has been studied by Agreda et al. (1990), Kerul et al. (1998), and
Bessling et al. (1998). There are more papers are published on synthesis of methyl acetate in
different aspects.

M e O H + H O A c ^ M e O A c + H 20

The esterification of methanol and acetic acid to form methyl acetate is a reversible
equilibrium controlled reaction. Itis exothermic reaction. W e have different type of rate kinetics
model equations for heterogeneous catalyst reaction, such as adsorption base kinetic model, and
pseudo homogeneous kinetics model. This reaction occurs only in liquid phase in reactive
distillation. There occur two azeotrope mixtures in this reaction. There are different feed set-ups
used for reactive distillation: one feed and two feed set up used for synthesis of methyl acetate.
In two feed set up heavy weight compound to feed at the top of the column and lower weight
compound fed into bottom of the column, in this process acetic acid feed into the column. The
reactive or catalytic distillation unit divided has four zones such as, rectification zone, extractive
zone, reactive zone, and striping zone. W e can simulate the catalytic distillation model as a user
model on aspen plat form.

1.6 Objective of Thesis:

To develop a model for esterification process of methanol with acetic acid in

heterogeneous catalytic distillation and by using this model, to simulate the catalytic distillation
by using Aspen plus R A D F R A C for two feed set up column. Also to study the effect of
variables namely-reflux ratio, feed tray location, start of reactive zone, and end of reactive zone,
and thermodynamic models on the composition profiles of compounds in the column for pseudo
homogeneous kinetic model.

8
 CHAPTER 2
L IT E R A T U R E R E V IE W

2.1. Development of catalytic distillation for synthesis of Methyl Acetate:

Popken et al. (2001): In this paper three different setups were used to perform reactive
distillation experiments for the synthesis and hydrolysis of methyl acetate using the structured
catalytic packing Katapak-S with an acidic ion-exchange resin (Amberlyst-15) as the
heterogeneous catalyst. Those three different setups were as follows: one-feed and two-feed
setups for the methyl acetate synthesis and another two-feed setup for the hydrolysis reaction.
Moreover, studied the influence of several variables, such as reaction kinetics, separation
efficiency, residence time distribution, and heat loss, on the simulation results and most
important was the use of adequate reaction kinetics, that was, an adsorption-based kinetic model
that took into account the selective swelling of the polymeric catalyst. By using tin's model the
synthesis as well as the hydrolysis experiments could be simulated within experimental accuracy.
With pseudo homogeneous kinetics, only the experiments performed for the synthesis of methyl
acetate could be modeled. Also, an equilibrium stage model is capable of describing the
experiments in the packed column when the reaction kinetics, separation efficiency, and heat loss
of the column were taken into account. A large number of experiments for various experimental
setups performed in order to develop a reliable framework for simulating reactive distillationthat
was capable of modeling the methyl acetate synthesis as well as the hydrolysis reaction with the
required accuracy. It was shown that only with an adequate expression for the rate of the
chemical reaction experiments could be described within the experimental accuracy when
compared experimental results with simulation results using the Aspen R A D F R A C model. Also
found that the equilibrium-stage concept was sufficient to model the column behavior. However,
the heat loss of the mini-plant column, which could be measured easily with the required
accuracy, had to be included in the simulation. The residence time distribution had no significant
influence. The difference in the composition profile obtained by assuming ideally mixed
equilibrium stages or a cascade of two or more ideally mixed tank reactors per equilibrium stage
was negligible.
Taylor, R and Krishna, R. (2000): The design and operation issues for reactive distillation
systems are considerably more complex than those involved for either conventional reactors or
conventional distillation columns. In this paper, itwas discussed that the introduction of an in
situ separation function within the reaction zone led to complex interactions between vapor-
liquid equilibrium, vapor-liquid mass transfer, intra-catalyst diffusion (for heterogeneously
catalyzed processes) and chemical kinetics. Such interactions had been shown to lead to the
phenomenon of multiple steady states and complex dynamics, which had been verified in
experimental laboratory and pilotplant units. The development ofmodels that had been used for
design ofreactive distillation columns was traced and suggested future research directions. Also
discussed the complexity of reactive distillation process installing, and explained the neediness
of reactive distillation compare with conventional reactor-distillation process by giving some
process examples. Moreover, developed steady state and dynamic models for equilibrium and
non equilibrium stage reactive distillation and also gave the conceptual design procedure for
estimating reactivezone height, column diameter, and reflux ratio for packed catalystdistillation.
The information of different type of design methods for reactive distillation, such methods was
conceptual method, graphical method, and design via optimization method was given.

Bao et al. (2002): Described the industrial catalytic-distillation process for the production of
methyl tert -butyl ether (MTBE) from methanol and isobutylene was simulated by developing the
process model as a user modular on Aspen plus platform. The model utilized the Aspen plus
system and retained the characteristics of the self-designed model, which had been verified:in
various scale-up processes. The experimentally determined reaction kinetics was applied in the
model. NRTL and Redlick-Kwong-Soave equations were selected for the vapor-liquid
equilibrium calculation. The NRTL binary interaction parameters were estimated from the
experimental data ofthe two-component vapor—liquid equilibrium. Two typical industrial plants
forthe MTBE production, one using the loose-stack-type package technology and the otherusing
the bale-type package technology inthe catalytic-distillation column, were chosen as the sample
i ,t
processes to demonstrate the validity ofthe model. Also, the flow sheet simulations of the two
industrial plants were done on Aspen plus platform, in which the simulation of tlie catalytic-
distillation column used the developed user modular from the advantage ofthe strong database,
flexible simulation functions and optimization tools ofthe Aspen plus system, while retainingthe

10
ch aracteristics o f the p rev io u s v e rifie d m od e l. T h e flo w sheet sim u la tio n s o f the tw o industrial

plants, u sin g the loose-stack-typ e package and the ba le-type package te ch n o lo g ie s in the

ca ta ly tic-d istilla tio n c o lu m n , were sim u lated on the A s p e n p lu s platform . T h e results show ed that

fa ir agreem ents betw een the calculated and operatin g data w ere obtained. T h e y d e ve lop e d the

m o d e l equations fo r m u lti co m p o n e n t ca ta lytic-d istilla tio n from fu nd am en tal approach and

co n secu tiv e relationship s, and explained the b e h a v io r o f system , its id ea l o r n o n -id e a l and

fo rm a tio n o f azeotrope m ixtures. T h is p ap e r g ave the co n ce p t to rem ove the sid e reactions in

system b y m a in ta in in g o f a ppropriate feed m o la r ratio, b y u s in g this concept; they reduced the

b yp ro d u cts fo rm a tio n in the system , and to get a p p ro x im a te ly 100% o f co n v e rsio n o f reaction

and separation o f d esired product. T h is pap er ex p la in e d b r ie f study o f flo w sheet d ra w in g for

user m o d e l o f ca ta lytic d istillatio n . They g ave concentration o f co m p o u n d s .profiles and

tem perature p ro file s fo r e a ch e q u ilib riu m stage.

H iw a le et a L (2004): In this paper, the in fo rm atio n about p u b lica tio n and patents in last 30 years

on histogram s. T h is article review s the v e ry recen t app lication s and serves as a su pp lem ent for

the exhaustive re v ie w on this su bject b y S h a rm a and M a h a ja n i (2003). N o t o n ly fu rn ish ed the

in fo rm a tio n o n the o n g o in g research in the e x istin g ap p lica tion s but also elaborated the n e w ly

d isco v e re d a p p lica tio n s su ch as m anufacture o f p h en o l, lin e a r a lk y l benzene, carbonates,

ch lo ro sila n e d e riv a tiv e s and ch ira l ch em ica ls. M u lt ip le reactions in R D , fa ilu re o f R D in som e

cases and new R D co n fig u ra tio n s to in crease the o v e ra ll y ie ld s are so m e o f the additional aspects

b e in g covered . In this pap er gave the cla rity in fo rm a tio n o f w h ich type o f reactions are operated

in reactive d istilla tio n co lu m n . T h e y ex plain e d som e processes w h ic h can operate in reactive

d istillatio n , su ch as esterification, trans-esterificatidri, h y d ro ly sis , eth erificatio n, hydrog en a tio n ,

dehydrogenation , a lk y la tio n , m etathesis and d isp ro p o rtio n a tio n , h y d ra tio n and d ehydration,

ca rb o n yla tio n , p ro d u ctio n of p o ly m e rs, ch lorin ation /am ination , synthesis o f ' carbonates,

m isce lla n e o u s reactions su ch as p ro d u ctio n o f p h e n ol, p ro p y le n e o x id e process, 2 ,2 ,6 ,6 -

tetram ethyl p ip e rid in e .etc,. In th is paper d iscu sse d flo w sheet o f re a ctive d istilla tio n in p ro cess

in d u stiy g iv e n fo r above process, and gave the co lle cte d in fo rm atio n o f p rocesses co n ve rsio n

w ith d iffe re n t catalyst used b y d iffe ren t authors. A c c o r d in g to o u r re a ctio n m eans esterification

o f acetic a cid w ith m ethan ol to fo rm m e th y l acetate w ith presence o f d iffe re n t catalyst w as g iv e n

b e lo w table.

11
 Table 2.1 Details o f different catalyst used for synthesis of methyl acetate.

Reaction T y p e o f catalyst Rem arks on motive References

and achievements

A cetic acid +methanol = M U LT IP A K H ig h conversion Gorak and Hoffm ann (2001)

M ethyl acetate +water M U LTIP A K 82.7% conversion Kolodziej et al. (2001)

KATAPAK- 97.1% conversion, Popken et al. (2001)

S, A m ber lyst-15 97.5% purity

\
The application domain o f reactive distillation is increasing fast and will continue to

remain on the rising trend. In the last few years, reactive distillation has entered in the well-

established technologies for the manufacture o f carbonates, phenols, and linear alkyl benzenes
etc. It also seemed to be a promising technology in the lucrative business o f chiral chemicals and

to some extent in the production o f organ silicon derivatives. The idea o f coupling more than one

reaction in a single column is taking shape especially for various hydrogenation, reactions.
However, the recent work for some reactions, if not many, has revealed the important limitations
o f RD especially when the side products are formed at high temperatures near reboiler or

because o f the depletion o f one o f the reactants in the reactive zones. Though there is a scope to

overcome this limitation by a prudent choice o f operating parameters, this may be considered as

an important threat to conventional reactive distillation column and modifications like stripped or

rectified RD units, side reactor concept are likely to be inevitable in future.

Chandakar et al. (2007): This paper dealt with the development o f a mathematical model for

esterification o f acetic acid with methanol by using a packed column with two different feed

setups: a single feed column and a two feed column. The reaction kinetics assumed to be
heterogeneous, also included the solution technique for the solution o f the model. An in-house

code in C++ developed to solve the model equations. Further, the comparison o f the model had

been done with available experimental data. Finally me effect o f design variables namely- reflux
ratio, feed tray location, and start o f reactive section had been studied.

12
 M o r e o v e r , stud ied an e ffect o f v a r io u s v a ria b le s fo r e ste rifica tio n o f m etha n ol w ith

a ce tic a cid in ca ta ly tic d is tilla tio n c o lu m n w ith o n e fee d setup c o n ta in in g 10 stages and tw o feed

setup c o n ta in in g 25 stages and also stud ied the e ffe c t o f v a ria b le s w as an attem pt to a ch ie v e the

h ig h e r c o n v e rs io n and better separation. So th e o b je ctiv e o f th is stud y w a s to in crease the

0
co n cen tra tio n o f m e th y l acetate o n the d istilla te and in crease m ethan ol co n v e rsio n . T h e range o f

the d esig n and p ro ce ss v a ria b le s selected w as g iv e n as C h a n d ra k a r (2004).

T h e c o m b in a tio n o f re a ctio n and d is tilla tio n h e lp e d in a c h ie v in g p ro d u cts o f h ig h e r

p u rity and h ig h e r co n v e rs io n o f reactants as co m p a re d to o ld c o n v e n tio n a l p ro ce sse s. A s sh o w n

in this stud y it is p o s sib le to o b ta in as h ig h as 95 % p ure m e th y l acetate and co n v e rs io n o f 90 %

in a c a ta ly tic d is tilla tio n c o lu m n . H o w e v e r, i f th e re a ctio n and d is tilla tio n are ca rried o u t in

separate e q u ip m e n t, the m a x im u m a ch ie v a b le extent o f co n v e rsio n is g iv e n b y the liq u id p hase

e q u ilib riu m con straint. The m ath e m a tica l m o d e l .develop ed sh o w n sa tisfa cto ry results in

sim u la tin g a ca ta ly tic d is tilla tio n c o lu m n fo r the e ste rifica tio n o f m e th a n ol w ith a cetic a cid . T h e

results w ere fo u n d in g o o d agreem ent w ith e x p e rim e n tal results o f P o p k e n et al. (2001).

M a x im u m d e v ia tio n fo u n d was 17 %. T h e m o d e l and co m p u ta tio n a l tech n iq u e had a lso been

su cc e ssfu l in d e te rm in in g the e ffe ct o f v a rio u s d e sig n v a ria b le s n a m e ly re flu x ratio, fe e d plate

lo ca tio n , start o f rea ctiv e stage o n c o m p o s itio n in d istillate and m ethan ol c o n v e rs io n in ca ta ly tic

d istilla tio n c o lu m n .

Q i et al. (2 0 0 2 ): R e a c tiv e d is tilla tio n is a h y b rid p ro ce ss w h ere c h e m ic a l re a ctio n and

d istilla tiv e sep aration are p e rfo rm e d in sin g le e q u ip m e n t. E v e n th o u g h re a ctiv e d is tilla tio n c o u ld

in crease the se le c tiv ity o f the d e sired p ro d u ct b y th e se le ctive re a ctio n this is n o t a lw a ys true as

sh o w n in th is w o rk . A stu d y on the M T B E re a ctio n system u s in g tw o co u p le d re a ctive

d istilla tio n c o lu m n s to separate a C 4 c ra c k m ix tu re w as ca rrie d out, w h ere m ethan ol as reactive

entrain er and M T B E as in term ed iate p ro d u ct. In the first c o lu m n , isobutene and m ethan ol reacted

to fo rm M T B E h en ce separating the inert C 4 co m p o n e n t, w h ile in the se con d c o lu m n M T B E

sp lits b a c k to m ethan ol and isobutene. M e th a n o l w as re c y c le d b a c k to the M T B E fo rm a tio n

c o lu m n and isobu ten e w a s o btain ed as a p ro d u ct. T h is c o u p le d p ro ce ss w ith d ire c t re c y c le o f

m eth a n ol w as p o s sib le o n ly i f n o side reactio ns o c c u r. W h e n the sid e reactio ns w ere taken into

a ccou nt, b y p ro d u c ts su ch as d i isobutene, d i m e th y l ether and w ater w o u ld be p ro d u ce d so that

h ig h e r p u rity m e th a n o l c o u ld n o t be o btain ed at the b o tto m o f the s p littin g c o lu m n . T h e o u tlet o f

13
the splitting column must be firstly separated rather than being recycled directly to the formation

column. Moreover, an attempt had been made to show how the selectivity of the desired product

isobutene could be critically influenced by the operating parameters such as the reflux ratio. If

the reflux ratio increased, a high quantity of di isobutene and di methyl ether would be obtained

which seriously affects the selectivity of isobutene. The influence o f operating parameters was

investigated by using a continuation method, which shows that bifurcation behavior could appear

in both MTBE formation and decomposition process.

This paper concluded the following matter; a system of coupled reactive distillation

columns was studied for the MTBE system, taking the influence o f side reactions into account.

The objective was to obtain high purity products isobutene and n-butene from a feed o f a closely

boiling butenes mixture. If side reactions are not considered, high purity n-butene as one final

product and MTBE as an intermediate product are obtained from the MTBE formation column.

The second final product isobutene and the reactive entrainer methanol leave the top and the

bottom of the MTBE splitting column in high purity, respectively. The bottom product stream of

the splitting column was directly recycled to the formation column. However, the system

behavior changed considerably if side reactions were taken into account. In this case, the

byproducts di isobutene, di methyl ether and water affect the purity o f the products, especially in

the splitting column. The bottom product stream of the splitting column has to be separated in

order to recycle the reactive entrainer methanol. Stein et al. (2000a, 2000b) proposed a coupled

reactive distillation scheme where side reactions were suppressed as far as possible and the in

avoidable byproducts are removed from the system veiy efficiently. Bifurcation analyses show

that multiple steady states exist in the formation as well as the splitting columns. In the formation

column, the multiplicity regions were near to the optimum operating parameters. In the splitting

column, the bifurcation behaviors with reflux ratio propose the operating parameters to obtain

high selectivities of isobutene and methanol. In the future, the dynamic behaviors of the single

columns and the coupled column system would be investigated. Based on these dynamic

analyses, optimal control strategies would be proposed'.

Bessling et al. (1998): The production of methyl acetate in a reactive distillation process -prior

art for 15 years - is often used as an example to study the basic phenomena o f reactive

distillation. The present paper dealt with a theoretical and experimental analysis of methyl

14
acetate synthesis in a re a ctive d istilla tio n c o lu m n . A d esign m ethod based o n the interpretation o f

reactive d istilla tio n lin e diagram s was used to id e n tify the m a in process param eters and to

p ro v id e a foun dation fo r ex p e rim e n tal in vestig ation . T h e s ig n ific a n t in flu e n ce o f the re flu x ratio

on the c o n v e rsio n in the c o lu m n w as sh o w n b y m in i pla n t experim ents u s in g supported ion-

ex ch an g er in the fo rm o f R a s c h ig ring s as a heterogeneous catalyst. T h e s e experim ents

dem onstrate the ca talytic q u a lity o f th is p a c k in g m aterial. T o sim u late the reactive d istilla tio n

c o lu m n w ith a s im p le stage-to-stage m ethod, the separation e ffic ie n c y o f the ca ta lytic rin g s was

investigated. C o m p a ris o n o f experim ental and sim u la tio n results revealed that a s im p le m o d el

based on the assu m ption o f sim u ltan eou s c h e m ic a l and phase e q u ilib riu m described the

experim ental data q uite w e ll o v e r a w id e range o f re flu x ratios. F u rth erm o re, sim u la tio n results

sh o w ed that the co n v e rsio n depends less o n the n u m b e r o f re a ctive stages than o n the use o f tw o

feed stages.

In this co n trib u tio n the hetero g eneo usly ca ta lyze d p ro d u ctio n o f m e th y l acetate in a

reactive d istilla tio n c o lu m n w as an a lyzed b y th eo retical and experim ental investigations. A s

sh ow n b y the expe rim e n tal in vestig ation s and rig o ro u s sim u la tio n s, a sim p le a n a lysis o f reactive

d istilla tio n line d iagram s a c c o rd in g to the design m ethod o f B e s s lin g et al. (1998) p re d icts the

b e h a v io r o f the h ig h ly n o n -id e a l m ethyl acetate system in a re a ctive d istilla tio n co lu m n quite

w e ll. B e sid e s, the m ethod sh ow s w h eth er reactive d istilla tio n w ill be e ffic ie n t and h o w a reactive

d istilla tio n co lu m n sh o u ld be co n fig u re d . T h is m etho d appears to be an e x ce lle n t to o l fo r

fe a s ib ility studies and fo r the design o f reactive d istilla tio n processes.

T h e sig n ific a n t in flu e n ce o f re flu x ratio o n co n ve rsio n that was p ro v e d in this w o rk is

im portant fo r the d e sig n and co n tro l o f reactive d istilla tio n c o lu m n s p ro d u c in g m e th y l acetate:

the ch o ic e o f an o p tim a l re flu x ratio saves capital in vestm e n t and energy co n su m p tio n .

T h e decrease o f co n v e rsio n outside the o p tim a l re flu x ratio range w as m a in ly based on

d istilla tio n effects, e.g. p o o r separation in the re c tify in g section o f the c o lu m n b e io w m in im u m

re flu x and e n rich m e n t o f an azeotrope in the top p ro d u ct at h ig h re flu x ratios.

A s im p le m o d e l w h ich is based o n ch e m ica l e q u ilib riu m in the re a ctiv e section and vap o r-

liq u id e q u ilib riu m o n a ll trays is s u ffic ie n t to d e scrib e m e th y l acetate p ro d u ctio n o v e r a w id e

range o f re flu x ratios. E ffe c ts o f c h e m ic a l rea ctio n k in etics o n ly b e co m e sig n ific a n t at h ig h e r

re flu x ratios in co m b in a tio n w ith a d e cre a sin g re sid ence tim e o f the reactants. N ear-to tal

15
c o n v e rsio n req u ires a co n sid e ra b le in crease in the n u m b e r o f re a ctive stages in the reactive

d is tilla tio n co lu m n . H o w e v e r, the in crease in m a x im u m c o n v e rsio n w ith in cre a s in g n u m b e r o f

rea ctive stages is lo w .

P ro p e r lo ca tio n o f the feed stages is v e ry im p ortant fo r h ig h c o n v e rs io n in m e th yl acetate

p ro d u ctio n . A s u ffic ie n t c o n v e rs io n is o n ly p o s s ib le w ith a d o u b le feed strategy. T h e h ig h

c o n v e rsio n and n e g lig ib le b y -p ro d u c t fo rm a tio n , a ch ie v e d in o u r exp e rim en ts, dem onstrate the

a p p lic a b ility o f ca ta ly tic I C V T rin g s fo r the p ro d u c tio n o f m e th y l acetate. In a d d itio n th ey have

h ig h sep aration e ffic ie n c y . B e c a u s e o f th e ir lo w p ro d u ctio n costs the c a ta ly tic I C V T ring s

p ro v id e an in teresting a lternative to h o m o g e n e o u s p ro cesses and also to structure ca ta ly tic

p a c k in g .

P o p ke n e t a l. (2 0 00 ): In th is p a p e r the rea ctio n k in e tics and c h e m ic a l e q u ilib riu m o f the

re v e rs ib le e ste rifica tio n o f m e th a n o l w ith a ce tic a c id w e re in vestig ated . T h is system w as o f

m a jo r im p o rta n ce as a m o d e l re a ctio n fo r re a c tiv e d istilla tio n . T h e re a ctio n had been ca ta ly ze d

both h o m o g e n e o u sly b y a ce tic a cid it s e lf and h e te ro g e n e o u sly b y an a c id ic io n -e x c h a n g e resin

(A m b e rly st-1 5 ). T h e c h e m ic a l e q u ilib riu m c o m p o s itio n w as m easured fo r v a rio u s tem peratures

and starting c o m p o s itio n s o f the reactants and p rod ucts. K in e t ic in fo rm a tio n w as ob ta in e d at

tem peratures betw een 3 0 3 .1 5 and 3 43.15 K. at v a rio u s starting c o m p o s itio n s c o v e rin g

co n cen tra tio n ranges fro m the sto ic h io m e tric re g im e to the d ilu te re g io n s. B o th the e ste rifica tio n

and the h y d r o ly s is rea ctio n w e re in vestig ated to y ie ld a m o d e l w h ic h w as a p p lic a b le fo r a n y

starting co m p o s itio n . T h e h o m o g e n e o u s re a ctio n had b een d e scrib e d w ith a s im p le p o w e r-la w

m o d e l. T h e use o f a ctiv itie s in the k in e tic m o d e l instead o f m o le fra ctio n s results in a m u c h

s m a lle r re sid u a l error. T o co m p a re p se u d o -h o m o g e n e o u s and adso rp tio n -based k in e tic m o d e ls

fo r the h e tero g e n e o u sly ca ta ly ze d reaction, in d e p e n d en t b in a ry liq u id ad so rp tio n experim ents

w ere used to fit the ad so rp tio n constants to k e e p the n u m b e r o f a djustable p aram e ters the sam e

fo r ea ch m o d e l. T h e use o f a ctiv itie s instead o f m o le fractio n s results in a s lig h t im p ro v e m e n t o f

the k in e tic m o d e l o n ly , w h ile in co rp o ra tin g a d so rp tio n in fo rm a tio n into the k in e tic m o d e l results

in a m u c h better fit. T h e c h e m ic a l e q u ilib riu m c o m p o s itio n ca lc u la te d fro m the k in e tic m o d e l

w as in a greem en t w ith the m easured c h e m ic a l e q u ilib riu m .

T h e d e sig n o f rea ctiv e d is tilla tio n c o lu m n s requires re lia b le k in e tic data b e sid e s oth er

in fo rm a tio n , lik e p hase e q u ilib riu m data, c h e m ic a l e q u ilib riu m data, tra n sp o rt p ro p e rty data, o r

16
the various pure com ponent properties. In this w ork, kinetic expressions for the methyl acetate

system are presented w ith parameters fitted to a fairly large database covering both the

esterification and the hydrolysis reaction. F o r the homogeneous reaction, the kinetic fit is

im proved by using activities instead o f m ole fractions. T h e reaction follow s a rate expression

that suggests catalysis b y m olecular acetic acid instead o f by solvated protons. T h is was

consistent with the results from W illia m so n and H insh elw ood (1934). T h e magnitude o f the

homogeneous reaction rate showed that this reaction could be neglected in reactive distillation

colum ns, unless v e iy high liqu id holdups were present.

F o r the heterogeneously catalyzed reaction, the use o f activities alone in a pseudo

homogeneous m odel im proves the fit only slightly. T a k in g the liquid-phase non-ideality into

account was ob viou sly not sufficient to describe the heterogeneous kinetics. T h e interaction

between the solid catalyst and the reactants had to be considered in the m odel. Despite the fact

that a precise and therm odynam ically consistent treatment o f systems in vo lv in g sw elling ion-

exchange resins was not available, a good fit o f the kinetic experiments could be obtained using

an adsorption-based m odel. F o llo w in g the concept o f Son g et al. (1998) independent adsorption

experiments were used to determine the adsorption equilibrium constants w hich were then

incorporated into the kinetic expression. Including adsorption inform ation led to a m uch better

description o f the kinetic results. B y using an adsorption expression based on adsorbed mass

instead o f adsorbed amount results in further im provem ent o f the fitting result. T h e adsorption

based kinetic m odel could easily be incorporated into com m ercial simulators. A d d itio n a lly, this

m odel provided better agreement between kinetics and therm odynamics (chem ical equilibrium )

than the pseudo-homogeneous m odel.

G o r a k and H o ffm a n n . (2001): C atalytic D istilla tio n can im prove process design; the design o f

colum n internals requires special attention. T h e catalytic packing M U L T I P A K facilitates

effective catalysis, high separation efficiency, and a w ide loading range simultaneously. In this

w ork the m ain characteristics o f M U L T I P A K -pressure drop, loading range, and separation

efficien cy were determined experim entally. The developed non-equilibrium stage m odel

developed reflects the com plexity o f catalytic distillation processes and com prises correlations

describing pressure drop and separation efficie n cy o f M U L T I P A K as a function o fth e operating

17
conditions. T h e m odel had been im plem ented in the sim ulation environm ent A sp e n C usto m

M o d e le r, and the sim ulation results were com pared w ith experim ental data for the synthesis o f

m ethyl acetate. T h is m odel reflected the process behavior, but differences between simulated

results and experim ental data co u ld still be observed.

T h e new type o f catalytic p acking M U L T I P A K that show ed a w ide loading range

com bined w ith high separation e fficie n cy and catalytic activity had been presented in this article.

T h e m ain p ack in g characteristics pressure drop and separation e ffic ie n c y had been determined

experim entally fo r the w hole lo a d in g range and com pared with data fo r conventional structured

packings taken from literature. T h e pressure drop o f M U L T I P A K co u ld be estimated w ith the

h ydrau lic m odel o f R o c h a et al. (1996), but new m odels considering the special hydrod yn am ic

beh avior o f catalytic packings were necessary to reflect the p ackin g characteristics w ith good

accuracy and to p ro vid e inform ation about the scale-up behavior. A correlation fo r mass transfer

coefficients in both phases was presented that represents the experim ental data w ith good

accuracy.

Exp erim en ts had been perform ed in a pilot-scale reactive distillation co lu m n to

investigate the beh avior o f a continuous process. A rigorous d ynam ic m odel based on the

M a x w ell-S tefa n approach to describe mass transfer between phases had been m od ified and

im plem ented in the sim ulation environm ent A s p e n C u sto m M o d e le r. Steady-state sim ulations for

the process o f methyl-acetate synthesis had been perform ed and com pared with experim ental

data. It was show n that the m odel is able to reflect the process behavior, but deviation was.

observed between experim ental and theoretical conversion and purity. H o w eve r, by

im plem enting the reaction kinetics and the hydrod yn am ics o f the catalytic packings in the

process sim ulation, their in fluence on design aspects o f reactive distillation colum ns were taken

into account.

i
S c h o e n m a k e rs a n d B e sslin g . (2003): R ea ctive and catalytic distillation has attracted g ro w in g

interest, both in industry and in scientific research. T h is contribution gives an overview w ill o f

the tools that are available today and the m ethods that have now been introduced into the

industrial practice in a large ch em ical com pany. A process synthesis gives good qualitative

reference points. S im u la tio n tools have been developed w h ich are m ain ly equilibrium -based.

18
H o w e v e r, fu rth er steps are nece ssa ry o n the w a y to im p le m e n ta tio n in an in d u stria l plant. T h e

sc a le -u p fro m the m in i pla n t used fo r the e x p e rim e n ta l v a lid a tio n o f a n e w p ro ce ss is w e ll k n o w n

fo r c o n v e n tio n a l d istilla tio n , b u t c o m p lic a te d b y several facts fo r re a ctiv e d is tilla tio n s p e c ific a lly

in the ca se o f h etero g eneo us ca talysis. T o o v e rc o m e these p ro b le m s re fe re n ce p la n t e x p e rie n ce

o n an in d u stria l sca le is n e ce ssa ry o r--/ if n o t a v a ila b le - w ili re q u ire future research. O th e r

o p tio n s both fo r h o m o g e n e o u s and h e tero g eneo us c a ta ly sis are p o s sib le and w ill b e d iscu ssed in

the co n trib u tio n . A tte n tio n is d ra w n to the fa ct that a c o m b in a tio n o f rea ctio n and d istilla tio n

does n o t n e c e ssa rily h a v e to be operated in a c o lu m n . F o r s lo w e r reactio ns a b ro a d range o f

e q u ip m e n t not n e c e ssa rily c o n ta in in g co lu m n s can b e used.

In the case o f c o n v e n tio n a l d istilla tio n , a s u ffic ie n t b o d y o f k n o w le d g e has b een acq u ired

to e n a b le the tasks in p ro ce ss syn th esis, d e sig n and sca le -u p to be so lv e d q u ic k ly in m a n y cases

O n d r e y ,G .( 1 9 9 6 ) .F o r re a ctiv e d istilla tio n , th e m ethod s o f d e sig n and syn th e sis have been

d e v e lo p e d to a co n sid e ra b le extent, p a rtly w ith the a id o f the m a n y a n a lo g ie s to d istilla tio n . A

m a jo r fo c u s o f research and d e v e lo p m e n t in future years sh o u ld b e the sca le -u p o f rea ctio n

co lu m n s. In a d d itio n the m e th o d o lo g y to c h o o s e the best e q u ip m e n t w ill h a v e to be im p ro v e d . In

the expert co m m u n ity , o n ly co lu m n s are o fte n seen as a p o ssib le c h o ice . W o r k w ill h a v e to be

d on e to ensure that the b e n e fit o f c o m b in in g re a c tio n and d is tilla tio n can b e e n jo ye d to the fu ll

b y e m p lo y in g the m o s t su itab le e q u ip m e n t w as w o rk e d out.

E l le n b e r g e r a n d K r i s h n a . (1 99 9 ): S tru ctu re d p a ck e d c o lu m n s, in w h ic h the ca talyst p articles

are en clo se d w ith in w ire g au ze e n v e lo p es ("sa n d w ich e s” ), are p ro m is in g reacto r co n fig u ra tio n s

fo r rea ctiv e d istilla tio n and h y d ro co n v e rsio n s. B y a llo w in g p re fere n tia l ch a n n e ls fo r the gas and

liq u id phases, co u n ter-cu rre n t o p e ra tio n is a ch ie v e d e v en fo r m illim e te r size d ca talyst p articles

w ith o u t the p ro b le m o f flo o d in g . In th is p a p e r the results o f a c o m p re h e n siv e e x p e rim e n tal study

o f the h y d ro d y n a m ic s o f structured p a c k e d c o lu m n s o f 0.1 and 0 .2 4 m d ia m e te r w ere reported.

T h e pressure d ro p w as fo u n d to in crease s h a rp ly w h e n the su p e rfic ia l liq u id v e lo c it y e x ceed s a

certain th resh o ld v a lu e . T h is th re sh o ld co rre sp o n d s to the situation in w h ic h a m a x im u m flo w o f

liq u id in the p a c k e d ch a n n e ls w as re a lize d a n d the excess liq u id flo w s th ro u g h the "open"

ch a n n els. T h e liq u id flo w in the o pen ch a n n e l ca u sed a sharp rise in the p ressure d ro p . A m o d e l

w as d e v e lo p e d to d e scrib e the h o ld u p o f liq u id in the o pe n ch a n n e ls. W ith in cre a s in g liq u id flo w

19
rate, the p ressu re d ro p w as fo u n d to in crea se e x p o n e n tia lly w ith the liq u id h o ld u p w ith in the

o p e n ch a n n els. L iq u id p hase re sid e n ce tim e d istrib u tio n studies le d to the c o n c lu s io n th at there is

a g o o d e x ch a n g e o f the liq u id p hase in sid e and o u tsid e the p a c k e d ch a n n e ls. T h e re sid e n ce tim e

d istrib u tio n c o u ld b e d e scrib e d b y an a x ia l d is p e rs io n m o d e l. C o m p a re d w ith a tric k le bed

reactor, the results o f th is stu d y sh o w e d that a structured p a c k e d c o lu m n h a d a m u c h la rg er

o p e ra tin g w in d o w at a m u c h lo w e r p ressure d ro p .

C o u n te r-c u rre n t o p e ra tio n o f gas and liq u id phases is im p o rta n t in m a n y c a ta ly tic

p ro cesses su ch as re a c tiv e d istilla tio n . A s d isc u ss e d b y K r is h n a and S ie (1 99 4 ) there w ere m a n y

s ig n ific a n t advantages w ith co u n te rcu rre n t o p e ra tio n fo r h y d ro -tre a tin g o p e ra tio n s, w h ic h are

c la s s ic a lly , c a rrie d o u t in co -cu rre n t d o w n flo w tr ic k le beds. T h e w o rk d e scrib e d in th is p a p e r

co n c e rn s the h y d r o d y n a m ic s and m ix in g ch a ra cte ristics o f stru ctu red c a ta ly tic a lly p a c k e d bed

reactors, o p e ra tin g in co u n te rcu rre n t flo w o f gas a n d liq u id . T h e p re ssu re d ro p , liq u id h o ld u p and

liq u id p hase re sid e n ce tim e d istrib u tio n o f c a t a ly tic a lly structured p a c k e d c o lu m n s o f 0.1 and

0 .2 4 m d ia m e te r w ith co u n te r-cu rre n t f lo w o f gas and liq u id w as studied. T h e pressure d ro p in

su ch structured co lu m n s w as a b o u t three ord ers o f m a g n itu d e lo w e r th an that o f c o n v e n tio n a l

H u s s et a l. (2002): W e d e scrib e a h ie ra rc h y o f m e th o d s, m o d e ls , and c a lc u la tio n te ch n iq u e s that

su p p o rt the d e sig n o f re a c tiv e d is tilla tio n c o lu m n s . T h e m o d e ls re q u ire in c re a s in g ly so p h istica ted

data needs as the h ie ra rc h y is im p le m e n te d . T h e a p p ro a ch is illustrated fo r th e p ro d u c tio n o f

m eth y l acetate b e ca u se o f its c o m m e r c ia l im p o rta n c e , and b eca u se o f the a v a ila b ility o f adequate

p u b lis h e d d ata fo r c o m p a ris o n . In the lim it o f re a c tio n and p h a se e q u ilib riu m , it w as sh o w e d that

(1) the ex iste n ce o f b o th a m in im u m and a m a x im u m re flu x , (2) there is a n a rro w ra n g e o f re flu x

ratios that w ill p ro d u ce h ig h c o n v e rs io n s and h ig h p u rity m e th y l acetate, and (3) the e x iste n ce o f

m u ltip le steady states th ro u g h o u t the entire ra n g e o f fe a sib le re flu x ratios. F o r fin ite rates o f

re a ctio n , (4) that the d e sire d p ro d u c t c o m p o s itio n s are fe a sib le o v e r a w id e range o f re a ctio n

rates, up to and in c lu d in g re a ctio n e q u ilib riu m w a s fo u n d , and (5) that m u ltip le steady states d id

n o t o c c u r o v e r the ra n ge o f re a lis tic re flu x ra tio s, t u t th ey w e re fo u n d at h ig h re flu x ratios

o u tsid e the ran ge o f n o rm a l o p e ra tio n . Our ca lc u la tio n s w ere in good a greem en t w ith

e x p e rim e n ta l results reported b y B e s s lin g et al., (1 9 9 8 )

20
 A h ie r a r c h y o f m e th o d s a n d m o d e ls fo r th e d e s ig n a n d s im u la t io n o f a re a c tiv e d is t illa t io n

c o lu m n f o r th e p r o d u c t io n o f m e t h y l acetate w e re e x p lo r e d . A l s o , fo u n d th at w h e n a s s u m in g

re a c tio n e q u ilib r iu m , it w a s p o s s ib le to d e s ig n a c o lu m n o p e r a tin g w ith s t o ic h io m e t r ic fe e d s a n d

p r o d u c in g h ig h - p u r it y m e th y l a ce tate as d is tilla te , a n d w a te r as b o tto m p ro d u c t. F o r th e re a c tiv e

e q u ilib r iu m c o lu m n , a n o p t im u m v a lu e f o r th e r e f lu x ra tio , p r o d u c in g a d e s ig n w ith th e m in im u m

n u m b e r o f sta g e s w a s fo u n d . W it h a h ig h e r o r lo w e r r e f lu x ra tio , th e n u m b e r o f sta g e s re q u ire d

in c re a s e d . T h e fe a s ib le ra n g e o f r e f lu x ra tio s w a s s m a ll, a n d the fe a s ib le ra n g e d e cre a s e s w ith

in c r e a s in g p re ss u re .

We v e r if ie d th e e q u ilib r iu m d e s ig n w it h a k in e t ic s im u la tio n o p e r a tin g near th e

e q u ilib r iu m lim it . S e n s it iv it y s tu d ie s o n th is k in e t ic m o d e l re v e a le d a re g io n o f m u lt ip le s te a d y

states a ro u n d th e o p t im u m v a lu e o f th e r e f lu x ra tio . T h e tw o ste a d y states p r o d u c e d n e a r ly th e

s a m e c o n v e r s io n , b u t h a v e q u ite d iffe r e n t te m p e ra tu re a n d c o m p o s it io n p r o file s .

W it h a k in e t ic m o d e l, a f e a s ib ilit y a n a ly s is w a s p e rfo rm e d a n d d e te rm in e d th a t th e d e s ire d

p ro d u c ts w e re fe a s ib le o v e r a w id e ra n g e o f D a m k o h le r n u m b e rs , i.e ., o v e r a w id e ra n g e o f

re a c tio n rates, liq u id h o ld u p s , p r o d u c t io n rates a n d c a ta ly s t c o n c e n tra tio n s . T h i s in fo r m a t io n w a s

u s e d to d e v e lo p a c o lu m n d e s ig n w ith re a lis t ic v a lu e s fo r th e se d e s ig n v a r ia b le s .

S e n s it iv it y c a lc u la t io n s f o r v a r io u s D a m k o h le r n u m b e rs s h o w e d th at th e c o n v e r s io n d ro p s

o f f s h a r p ly w h e n o p e r a tio n m o v e s a w a y fr o m t h e o p t im u m r e f lu x ra tio . F u r th e r m o r e , w e fo u n d

th at in c r e a s in g th e D a m k o h le r n u m b e r y ie ld s a n in s ig n if ic a n t in c re a s e in c o n v e r s io n o r o p e r a tin g

ra n g e .

F in a l ly , th o se s im u la tio n s w e re c o m p a r e d to p u b lis h e d e x p e r im e n ta l re s u lts f o r a re a c tiv e

d is t illa t io n c o lu m n p r o d u c in g m e th y l acetate. T h e fin d in g s m a tc h th o se in B e s s lin g et a l., (1 9 9 8 )

q u ite c lo s e ly .

A lt h o u g h th is s y s te m is a c o m m o n ly u s e d e x a m p le f o r re a c tiv e d is t illa t io n re s e a rc h , and

is o n e o f th e b e st e x a m p le s o f the b e n e fits o f u s in g re a c tiv e d is t illa t io n t e c h n o lo g y , w e s h o u ld

n o te th a t it h a s s o m e u n iq u e c h a ra c te ris tic s . It w a s th e o n ly s y s te m o f th e f a m ily o f a cetate

e s t e rific a t io n re a c tio n s th a t h a d n o h ig h e r o r d e r a z e o tro p e s o r li q u id - liq u id re g io n s . T h e re la t iv e

b o ili n g p o in ts o f th e c o m p o n e n ts m a k e th e a c e tic a c id a c a n d id a te f o r u s e as an e x tr a c tiv e a gen t.

T h e e x tr a c tiv e - re a c tiv e n a tu re o f th is c o lu m n p ro d u c e d a n a r ro w o p e r a tin g ra n g e .

J
21
2.2. Vapor-liquid equilibrium for multi component distillation:

F o r m ulti-com ponent m ixture, graphical representation o f properties cannot be used to

determine equilibrium -stage requirements. A n a ly tic a l com putation procedures m ust be applied

w ith therm odynam ic properties depending o n temperature, pressure and phase com position,

these equations tend to be com plex. Nevertheless the equations are w id e ly used fo r com puting

phase equilibrium ratios (K-values), enthalpies and densities o f m ixture over a w ide range o f

conditions. V a p o r liqu id equilibrium calculations are usually carried out for separation processes

w ith several versions. T h e prediction o f m ixture vapor-liquid equilib rium is m ore com plicated

than prediction o f pure com ponent. Phase e q uilibrium relation is one o f the fundamental

properties w hich are necessary for the separation processes, and useful equation have been

proposed for expressing relation. E fficie n t design o f distillation equipm ent requires quantitative

understanding o f vapo r-liqu id eq uilibrium in m ulti com ponent m ixture as expressed through

vapor phase fugacity co efficien t and liq u id phase activity coefficients.

2.2.1. Thermodynamic models:

T o describe the phase eq uilibrium o f a system o f N c com ponents at a temperature T and

pressure P, the vapor phase fugacity is equal to the liq u id phase fugacity fo r every com ponent

i= l, 2, 3 Nc

T h e vapor phase fugacity can be written in terms o f the vap o r phasefiigacity co efficien t <T>i ;

vapor m ole fraction yt ; and total pressure P as follow s.

fi = y f o P '

A ls o the liquid phase fugacity can be written in terms o f liqu id phase activity co efficien t y„
.liquid m ole fraction x,t and liqu id phase properties f as follow s.

fi = XiYifi
22
W h ere,/is calculated using the equation:

y i f p _

ft = o r ^ ' e x p ~^T— -]

A t e q u ilib r iu m ,

Y iP r*xi
yi =

W h e re , €>, is g iv e n b y the e q u a tio n ;

$i K,(P - P f
<I>f“ eXP ^ RT ^

A t lo w p re ssu re s, v a p o r p h a se s u s u a lly a p p ro x im a te id e a l gases fo r w h ic h

<f>. = <x>fa t= l a nd P o y n t h in g fa c to r w h ic h is re p re se n te d b y th e e x p o n e n tia l d iffe r s fr o m u n ity b y

o n ly a fe w parts p e r th o u sa n d . F in a lly , w e g et

n psat
yi = — *i

2.2.2. Id eal V ap or-L iq u id E q u ilib riu m : -

Vapor liq u id e q u ilib r iu m is one o f the m ost im p o rta n t fu n d a m e n ta l p ro p e rtie s in

s im u la tio n , o p t im iz a tio n a n d d e s ig n o f a n y d is t illa t io n p ro c e s s. T h e m ix tu re is c a lle d id e a l i f

b o th liq u id a n d v a p o r are id e a l m ix tu re s o f id e a l co m p o n e n ts , th u s in the v a p o r p h a se the p a rtia l

p re ssu re o f c o m p o n e n t Pt is p ro p o rtio n a l to its m o le fra c tio n in the v a p o r p h a se a c c o r d in g to

D a lt o n ’ s la w : P£ = yj P

V
T h e e q u ilib r iu m re la tio n s h ip fo r a n y c o m p o n e n t is d e fin e d as, K, - —
x,

F o r id e a l m ix tu re the K v a lu e c a n b e p re d ic te d fr o m R a o u lt ’ s la w , w h e re .

v. P sa'
*, P

23
2.2.3. Non Ideal V apor-L iquid E quilibrium :

For non-ideal mixture or azeotropic mixture additional variable /[(activity coefficient)

appears invapor-liquid equilibrium equation.

Where, y t represents degree ofdeviation from reality.

Wheny* = 1, the mixture issaid to be ideal which simplifies the equation to Raoult’s law.
For non-ideal mixture y* =£ 1, exhibits either positive deviation from Raoult’s law (/* > 1), or
negative deviation from Raoult’s law (Yi < !)•

2.3. C alculation o f A ctivity C oefficient:

The prediction of liquid phase activity coefficient is most important for design calculation
of non-ideal distillation. Before calculating vapor-liquid equilibrium of non-ideal mixture, the
activity coefficient of each component must be calculated. There are several excess energy (gE)
models to calculate the activity coefficient for multi component systems, the most important
models are of (Wilson, NRTL, UNIFAC, and UNIQUAC). In all these models, the model
parameters are determined by fittingthe experimental data ofbinary mixtures.

Each one of these models has advantages and disadvantages. There is no general model
which has a good representation of all azeotropic mixtures. The selection of appropriate model
for a given mixture is based on three characteristics, which are temperature, pressure and
composition. Ifinappropriate model isselected, the design and simulation ofthe process will not
work well.

24
Wilson and Deal (1962) used the following equation to calculate the liquid phase activity
coefficient.

The Wilson model has the disadvantage that itcannot predict vapor -liquid equilibrium when two
liquids existinthe liquid phase

2.3.2. N R T L M od el, 1986:

The NRTL (non-random, two liquid model) was developed by Renon and Prausnitz
(1968). This model uses three binary interaction parameters for each binary pair in multi
component mixture-pairs. For Nc components system, itrequires Nc (Nc -l)/2 molecular binary
pair. This equation is applicable to multi component vapor-liquid, liquid-liquid, and vapor-
liquid-liquid systems.

The main equation used to calculate liquid phase activity coefficient for NRTL model is
(Sim Basis 2003).

\
m j tn mj

In Yi =

*=1

The NRTL group interaction parameters are defined in literature (Gmehling etal. 1977).

2.3.3. U N IQ U A C M odel, 1975:

Abrams and Prausnitz (1975) developed the UNIQUAC (UNIversal QUAsi Chemical)

25
The combinational part basically accounts for non -ideality of a mixture arising from differences
in size and shape of constituent molecular species; whereas the residual part considers the
difference between inter-molecular and intra molecular interaction energies. The two-parameter
UN IQUAC equation gives a good representation of the vapor-liquid equilibrium of binary and
multi component mixtures (SimBasis 2003).

( NC \
Inr f = - q , In X 6-J p + Nc
/ 7
■=
/=1'

Values for parameters are given by Gmehling et al., (1977-1984).

2 .3 .4 . U N IF A C m o d e l, 1975:

The UNIversal Functional Activity Coefficient (UNIFAC) method is a semi-empirical

system for the prediction of non-electrolyte activity estimation in non-ideal mixtures. UNIFAC
uses the functional groups present on the molecules that make up the liquid mixture to calculate
activity coefficients. By utilizing interactions for each of the functional groups present on the
molecules, as well as some binary interaction coefficients, the activity of each of the solutions
can be calculated.

The UNIFAC model splits up the activity coefficient for each species in the system into two
components; a combinatorial y c and a residual component y R . For the /thmolecule, the activity
coefficients are broken down as per the following equation:

Iny i = Iny f + In yf

In the UNIFAC model, there are three main parameters required to determine the activity for
each molecule in the system. Firstly there are the group surface area R and volume contributions
Q obtained from the Van der Waals surface area and volumes. These parameters depend purely
upon the individual functional groups on the host molecules. Finally there is the binary
interaction parameter xy, which is related to the interaction energy £/,■ of molecular pairs

26
(equation in "residual" section). These parameters must be obtained either through experiments,
via data fittingor molecular simulation

Combinatorial component:

The combinatorial component of the activity is contributed to by several terms in its equation
(below), and isthe same as forthe UNIQUAC model.

0
Wif z Vi 0£ n
V>iST'
ln y ‘ = ln Ti + 2 q‘ to Wt + L‘ ~ ^ Z XlLl
i

0j and cpiare the molar weighted segment and area fractional components for the i,hmolecule in
the total system and are defined by the following equation; Li is a compound parameter of r, z
and q. z is the coordination number of the system, but the model is found to be relatively
insensitive to itsvalue and isfrequently quoted as a constant having the value of 10.

9i = Z
Ylj71=*l x*j Ha j ; 0 i = ZY i *j =} i' *7 j '7j ) L i = \£- “ 1);Z = 10

ri and qi are calculated from the group surface area and volume contributions R and Q (Usually
obtained via tabulated values) as well as the number of occurrences of the functional group on
each molecule v* such that:

it ii

ri = v k R k ;q t = ^ v k Q k
k=1 k=l

Residual component:

The residual component of the activity y R is due to interactions between groups present in the
system, with the original paper referring to the concept of a "solution-of-groups". The residual
component of the activity for the ilh molecule containing n unique functional groups can be
written as follows:

27
 n
Iny/* = ^ \ £ ) P n I ,f t - l n rj-0
k

W here,

4 ° = the activity o f an isolated group in a solution con sistin g only, o f m ole cu le s o f type

.. .. nm
m m

Qm^m
&m ZnQnXn

iumn Unmi Yij VmXi

W
~mn = ce rt >’• AXm =
2 jln V ]nXj

28
2.4. R ate kinetics in Catalytic distillation:

K in e t ic rate equation fo r synthesis o f m ethyl acetate is depends on catalyst nature

(hom ogeneous catalyst o r heterogeneous catalyst).

A g r e d a et al. (1990) described the d evelop m e n t o f rate equation fo r p ro d u ctio n o f high

m ethyl acetate v ia counter current reactive d istillatio n w ith usin g H 2 S O 4 as hom ogeneous

catalyst.

CH3COOH+CH3OH o CHjCOOCH3 + h 2o

T h e d evelop ed rate equation is:

C HOAc C MeOH
r = k exp
yR T y K
W h ere

k —k x{ X H iS 0 ^) + k2 ( X H ^s o ^) fo r X HS0 <0.004

and k = k3~k4exp for ^ 0004

* ^ -0 .0 0 4

Popken et a l (2000) investigated the rate kin e tics fo r synthesis o f m eth y l acetate w ith

h o m o gen eou sly u sin g acetic a cid as s e lf catalyst and heterogeneously b y an a c id ic ion-exchange

resin (A m b e rly st 15).

® H o m o g e n e o u s R e a c tio n :

T h e kin etic equation fo r the reaction fo r the catalyzed b y acetic acid is expressed as:

1 dx-
r ~ "77 = a H 0Ac (^ 1 a H O Aca MeOH ~ ^-1 a M e O A c ® H zo )
vt at
W h ere at is a ctiv ity o f co m p o n en t i.

i. e. <*i = Y f t

29
 Table 2.2 Parameters and Residual Errors of the Different Kinetic Models Used to Fit the
Experimental Data without Catalyst Added:

Mean reative
error (%)
Exponent Activities s"1 Ea,i Ea,-i

(kJ.mol"1) s'1 (kJ.mol1)

! 0.5 Ideal 4.9 6.57E04 J% ' 60.4 I.02E07 79.1 ,,

‘ I: '.': '•
.5 UNIQUAC 4.0 1.30E05 61.6 1 .00E07 82.2

1
f * -1 Ideal 3.1 2.54E06 62.5 . ’ 1.00E0T 77.3 .,
|U‘ ,;.4 •• . ’f•' ilf

1 UNIQUAC 2.2 5.11E05 63.5 9.83E06 80.2

,, v*3
. 1.406 • Ideal ' 2.2 2.42E06 67.3- ' 9.27E06 1 75.8
|. -■

1.056 UNIQUAC 2.2. 6.06E05 63.8 9.84E06 80.0

• Heterogeneous catalyst reaction :

Reaction catalyzed by Amberlystl 5 described with both pseudo homogeneous model and
with adsorption-based model.

Pseudo homogeneous model:

1 1 dnt u _
r ~ , — K ]a H O A ca M eO H IC - i a M e 0 A c C l H 2 0

Adsorption-based model:

1 1 d rij & H Q Ac a M eO H a M e O A c a H 7Q

mcat Vi d t (a H0Ac + ® M eO H ^ M eO A c + ^ I f 20 )

a\ = - LJ-
M,

30
2.5. Modeling of catalytic distillation column:

A reactive distillatio n p ro b le m can be studied using different approaches in clu ding :

feasibility, sim ulation, m od eling , design and experim ental studies in the laboratory and the p ilo t

plant. A co m b in atio n o f a ll o f these m ethods gives rise to the m ost accurate solution to the

problem . O ne v e ry im portant aspect o f pred ictin g the beh avio r in these system s is the m odel used

to design and sim ulate the reactive distillatio n process. A n effective w ay o f d eco m p o sin g the

m o d e lin g aspects o f reactive d istillation in vo lv e s the fo llo w in g classificatio n o f the m odels

existing fo r d istillation w ith reaction (B au r, 2000):

I. Steady-state e q u ilib riu m stage m odel.

II. D y n a m ic e q u ilib riu m stage m odel.

III. Steady-state n o n -e q u ilib riu m stage m odel;

IV. D y n a m ic n o n -e q u ilib riu m stage m odel;

V. Steady-state non -equ ilibriu m ce ll m od e l, that accounts fo r staging o f t h e v ap o r

and liq u id phases inside the colum n.

T w o prim ary approaches available in the literature fo r m o d e lin g reactive distillation

colum ns w ill be taken up.

I. E q u ilib riu m stage m odel.

II. N o n -e q u ilib riu m stage m odel.

2.5.1. The Equilibrium Model:

T h e eq u ilib riu m stage m od e l assumes that the vap or and liq u id stream leaving a given

stage are in therm odynam ic eq u ilibriu m w ith one another (K rish n a and T a y lo r, 1985). A

schem atic diagram o f an e q u ilib riu m stage is show n in V a p o r from the stage b e lo w and liqu id

from the stage above are brought in to contact on stage together with any fresh o r re cycle feeds,

the v a p o r and liq u id streams leaving the stage are assum ed to be in e q u ilib riu m w ith each other.

33
 F ig u r e 2.1 E q u ilib r iu m stage m o d e l w ith feed stream and side stream

T h e equation s o n the e q u ilib riu m stage m o d e l are a lso k n o w n as M E S H b e in g a cro n ym :

» T h e M equations are the m aterial balance equations.

• T h e E e q uation s are phase e q u ilib riu m relations.

• T h e S equations are su m m a tio n equations.

• T h e H equations are heat (enthalpy) equation.

dtn r c
1 - L M + r M + F j - S ’ - V j - L , - S' + X E V , „ RmJe,
dt n=l /=1
din x r
— ^ L = Lj-lx,J. l + VM y,Jtl + FJzIJ-(.S'j + V ^ j - ( L j + S ‘)X,J + 2> ,
ut m=i
y ,j = Ki j xi j

2 X ,= 1

L - ,
;=1
dE r0
- + = LM hH + Vm H m + Fj H f j - L, h , - S > , +
al m-l/=1

The (m j) is the h o ld -u p o n the stage j . W ith v e iy fe w exceptions, m j is co n sid e re d to be

the h o ld -u p o n ly o f the liq u id , it is, h o w e ve r, im p ortant to in clu d e the h o ld up o f v a p o r phase at

34
high er pressure. T h e term ^
’ J^ v imRmjej is the rate o ft h e disappearance o fth e total m oles due
m=1/=1
to any m reaction o f the stage j. v,-m represents the stoichiom etric co efficien t o f com ponent i in

reaction m and ej, represents the reaction volum e.

T h e E equations are phase eq u ilib riu m relations, the com positions o f the stream leaving

stage are in therm odynam ic eq uilibrium . Therefo re, the m ole fractions o f com ponent i in the

liq u id and v ap o r streams leaving stage j b y th e e q u ilib riu m relationship are show n in above

equations

T h e S equation are sum m ation are two equations arise from the necessity that m ole

fraction o f all com ponents, in either liqu id o r v a p o r phase, sum to unity.

T h e enthalpy balance is given above, in that the left side represents the accum ulation o f

enthalpy on stage. It represents the total enthalpy o f stage, but fo r the reason given above this

w ill no rm ally be the liqu id phase enthalpy. A t steady state condition, all terms p er time equal to

zero.

So m e authors in clu d e additional equation in their (m ostly unsteady state) m odels, for

exam ple pressure drop, controller equations, and so on.

2.5.2. Non-Equilibrium or Rate-Based Model (NEQ Model).

A non -equ ilibriu m ( N E Q ) or rate-based m odel em ploys a transport phenom enon approach and

the film m odel description fo r p redictin g the m ass transfer rates. It assum es eq u ilib riu m is

established at the interface between v ap o r and liq u id phases. T h e m odel equation fo r a generic

stage j (T he N E Q stage m ay represent a tray or section o f p ack in g colu m n ) and com ponent i m ay

be represented based on conventional distillation equation that incorporate the ch em ical reaction

term (T a y lo r and K rish n a , 1985). A schem atic representation o f the N E Q stage is show n in

F ig u re 2.2.

35
 Figure 2.2 Non-equilibrium stage model with feed stream and side streams.

The component molar balance for the vapor and liquid phases is

Where N/j is the interfacial mass transfer rate, and is the product of the molar flux and the net
interfacial area. The overall molar balances are obtained by summing above equation over the
total number(c) of components in the mixture. The N j , j is obtained from the Maxwell-Stefan
equation modified as follows:

xf j 9/j.jj _ v 1xu N kj ~ x kJN IJ

c'jik'^cOj

With a similar relation for the vapor phase, the k,J represents the mass transfer coefficient of the
i-k pair in the liquid phase; this coefficient is estimated from information on the corresponding
Maxwell-Stefan diffusivity using the standard procedures discussed in Taylor and Krishna
(1993). ‘a’ is the interfacial area. Only c-1 of above equation are independent .the mole fraction
of the last component is obtained by summation equations for both phases. The enthalpy
balances for both vapor and liquid -phases are:

36
 Vj^ - V jH j +FJH I j -E'j - Q ^ 0
L j ^ - L j h j + F ^ - E ’ -Q ^ O

T h e interphase energy transfer rates Ej (equal in both phases) have co n d u ctive and co n ve ctive

contributions

, dTl
E\ = ,a ------ +
—h,a
drj

W ith a sim ila r relation for the v a p o r phase, h‘j \s the heat transfer c o e fficie n t in the liq u id -p h a se .

T h e co n d u ctive contributions are ignored in som e m o d e lin g studies.

A t the vap o r- liq u id interface, w e assum e phase eq u ilib riu m

yu , = V u

W h ere the su bscrip t I denotes the e q u ilib riu m co m po sition s and K i j is the vapor- liq u id

eq u ilib riu m ratio for co m p o sitio n o f the tem perature , pressure and co m p o sitio n o f the interface

from appropriate th erm odyn am ics m odels.

In addition to above equations, we have the sum m ation equations fo r the m ole fractions in vap o r

and liq u id phase and equations o f co n tin u ity o f flu x e s o f mass and energy across the interface i s :

K j
= N >,
'J

H e a t flu x ,

Ev.
hj

Furtherm ore, in the N E Q m o d e l w e take account o ft h e pressure drop across a stage

P y - P y - l- ( A P y - i) = 0

W h ere pj a n d pj.] are the stage pressures and (A p y_,) is the pressure drop p er tray from stage j-1

to stage j. T h e pressure drop o v e r the stage is considered to be a fu nctio n o f t h e stage flo w s, the

p h ysica l properties and the hardw are design.

37
2.5.3. NEQ modeling of RD:

B u ild in g an N E Q m odel o f a reactive separation process is not as straightforward as it is for the

E Q stage m odel in w h ich we sim p ly (or not so sim p ly ) add a term to account fo r reaction to the

liquid-phase material balances. F o r a reactive separation process, w e first need to kn o w whether

the reaction is heterogeneous or hom ogeneous.

F o r hom ogeneous systems the com ponent m o la r balance for the liquid-phase becom es

Lj XU - LH XKj-l ~ K j ~ K j - X \m R™,jej = 0
m=1
W h ere Rmj is the rate o f reaction m on stage j. v,> represents the stoichiom etric co e fficie n t o f

com ponent i in reaction m and Sj represents the reaction volu m e on stage j . F o r hom ogeneous

reactions this is given b y the total liquid hold-up on stage j and, in an N E Q m od el, is obtained

d irectly from the colum n internals specifications and appropriate hydrod yn am ic correlations.

I f it is su fficie n tly rapid, the reaction w ill also take p lace in the liqu id film adjacent to the phase

interface, and v e iy fast reactions m ay o ccu r o n ly in the film . In either case tlie continuity

equations for the film are required fo r taking into account the effect o f the reaction on the

interphase mass transfer rates. T h e com bined set o f M S and continuity equations u su a lly m ust be

so lved nu m erically.

T h e phase e q u ilib riu m equations for the interface m a y need to be m o d ifie d for the influence o f

additional species on the therm odynam ic properties at the interface.

F o r a heterogeneous reaction, there are two options for the description o f the reaction term. T h e

sim plest approach is to treat the reaction pseudo-hom ogeneously, w hereby catalyst d iffu sio n and

reaction is lum ped into an overall reaction term. F o r heterogeneous reactions that are m odeled in

this w ay the liquid-phase material balance is as g iven above and £} is given b y the total amount

o f catalyst present on the stage under consideration. In this case, one o n ly needs to specify

catalyst mass and activity. A m ore rigorous approach w o u ld in v o lv e the use o f the dusty flu id

m od el discussed above i f the catalyst is porous, o r reaction at the surface i f not. In this case one

also needs inform ation about the catalyst geom etry (surface area, m ean pore diameter, etc). In

either case it is unnecessary to a llo w fo r reaction in the vapo r-liqu id film and the vapo r-liqu id

transport equations are exactly as g iv e n above.

38 ,
2.5.4. Dynamic Non-Equilibrium stage model (homogeneous):
B a u r R . a n d K r is h n a R . (2001) developed a d yn a m ic non equilibrium stage m odel fo r reactive

distillation. D y n a m ic behaviour on stage is determined b y storage capacity (or) accum ulation, o f

mass and energy in the v ap o r and liqu id phase. B o th the vapor and liqu id phases on the stage are

assumed to be w ell-m ixed. T h e tim e rate o f change o fth e num ber o f m oles o f com ponent i in the

vapor (Miv) and liqu id (Mi1) phase on stage j are given b y the fo llo w in g balance equations:

dM^: v v „
-Vjyj + K j< j-N ljii = 1,2, c

dMf, ,, , ,
- f - ~ Lh xh - L j Xj + F iJ ziJ + N , j + Y t vi * Rk j s j
at jt=i

W here JV,, y is the interfacial mass transfer rate. A total r chem ical reactions take place in the

liq u id phase and Rkj is the rate o f reaction k on stage j, v,> represents stoichiom etric coefficient

o f com ponent i in reaction k and Ej represents the volum etric liqu id hold- up on stage j.

O v e r all m olar balance equation:

d M y, y * „

^
d L M -LI+F }+t N ^ t t \ A A
Ul k=1 i=l k=\
i ■

T h e m qle fraction o f the vap or and liqu id phases are calculated from the respective phase m olar

hold-ups

Mjt, M j-.

O n ly c-1 o f these m ole fractions is independent because the phase m ole fractions sum to unity.

i = 1

ti = 1
, , ■ .

T h e energy balance for vap or and liquid phases are written in terms o f energy “ hold ups” in

vapor and liqu id phase on stage j:

39
 jpV cV py
-~ L -V — _l-F v H vf - E v - O v
d: 'm ; 1 > < Uj

dFL Fl Fl
— L = L j ,— ^ - L , — -1r + F j H ' f + E'; - Q'j
dt j 1M ‘ j j j J

The energy hold-ups are related to corresponding molar hold-ups via the stage enthalpies

Ej = H jM '] ;E j = H j M j

2.5.5. Heterogeneous equilibrium stage model:

Jie Bao et al (2002) developed equilibrium model for a catalytic distillation process for the
MTBE from methanol and isobutylene. The model equations based on equilibrium stage j are as
follows:
Mass balance equation:
djEjXj,)
' ~ Lj_\Xj_t l + Vj+IyJ+Ij LjXjj Vjyjj + FljZIjj + tsRj(
dt

Where FIj and Zlj are feed stock flow rate and composition at stage j respectively. ARj, is

consumption rate for component i at stage j.

Reaction equations:
' v ^
l-exp -(^ + ^ 2)77-
VL J
Where V c is the catalyst volume, V l the liquid volumetric flow rate flowing through the catalyst
and V t ( = V l / V c) is the catalyst space velocity, meaning the liquid volumetric rate flowing
through per volume unit of solid catalyst.

l-e x p
k .+ L (N C 2 - N C I +1).KS.aLkJ_i pj

Where pj is the liquid molar density, k the layer of catalyst package at stage j (1 < k < KS), a is
the contacting efficiency of liquid to catalyst, and 5 is the reaction efficiency in the catalyst
package.
Vapor-liquid equilibrium equation:

y > j= K u xu
Where j is the vapor- liquid equilibrium coefficient for component i at stage j.

40
Component summation equations:
C C
Yj x>j = x and 2 > u =1
i=i
E n th a lp y bala n ce equations:

Z h iw e n Q i et al. (2002) presented steady state n o n e q u ilib riu m m od e l fo r catalytic distillatio n.

T h e m ass transfer between liq u id and v a p o r phases are characterized b y the h eig h t o f transfer

un it ( H T U ) .

Several assum ptions have been m ad e fo r d e v e lo p in g m odel.

• K in e t ic a lly co n tro lle d reactions have been considered.

e Feed s enter into the co lu m n as saturated liq u id s at the operatin g pressure.

• T h e co lu m n operates w ith a total condenser.

• R ea ctio n s o n ly o cc u r in liq u id phase.

• M a s s transfer in sid e the catalyst is neglected so that we use quasi-ho m o g eneo us rate

expression.

I f the height o f the co lu m n is sp e cifie d , the n u m b e r o f transfer units ( N T U ) can b e determ ined. In

the fo llo w in g , the m o d e l equations fo r the j th transfer u n it are given, w here the in dex j counts

dow nw ards.

L iq u id phase co m p o n e n t m ass balance:

V a p o r phase co m p o n en t m ass balance:

41
Total mass balance of liquid phase:

Lh - li + =0
1=1

T o ta l energy balance:

V L E relationship:

h jfu P u
y<j p

Sum m ation conditions:

NC NC
Z x , tJ = 1 and £ y UJ = 1
/=! i=1
W here, i= l,2 ,...N C ; j= 0 ,l,..., N T U + 1 , j= 0 means the condenser, j = N T U + l the reboiler ; 1=1, 2,

3..., represents the reaction number; vf/is the stoichiom etric co efficien t o f com ponent i in

R eaction I;
vT , is the m ole change o f reaction I ; Hj, hj, and hfj are enthalpies o f v ap o r and liqu id

phases and the feed, respectively; Ecaij is the am ount o f catalyst at stage j , w h ich is defined b y

cat ® c a t P 'c a fic a t^ c

42
 CH APTER 3

Simple M odeling o f Catalytic Distillation Column

3.1. Assumption for modeling of catalytic distillation:

° R e a ctio n o ccu rs in so m e stages and separation.

• V a p o r - li q u id e q u ilib riu m reached in each stage.

• C o lu m n operates at steady state.

• H e a t losses fo r the w a ll o f the co lu m n are n e g lig ib le .

• H e a t o f m ix in g fo r v a p o r and liq u id phase are n e g lig ib le .

• C h e m ic a l reactions take p la ce o n ly in liq u id p hase reaction.

• T h e heat o f reaction is n e g lig ib le as co m pa re to enthalpy o f v a p o r and liq u id phase.

3.2. Assumption for simulation:

• A l l stream s are fed into the c o lu m n as saturated liq u id s.

0 A s s u m e d Pseud o ho m o gen eou s reaction o c c u r in reactive zo n e

• Phase e q u ilib riu m o ccurs on each stage.

• C o lu m n operates 'at steady state.

• T h e a ctiv ity o f the com ponents in the liq u id phase is calculated w ith the N R T L m od e l.

• C o lu m n operatin g pressure is 1.017 bar.

• N o sid e reaction o ccurs in reactive zone.

0 C o n d e n se r operates at total condenser.

N th stage is re b o ile r and 1 a stage is condenser.

43
3.3. M odeling equations:

T o ta l bala n ce on j 1*1e q u ilib riu m stage

*ij-i Vjyu

. Ih
J sa

L x V y
j y j« y+i

F ig u re 3.1 S ch e m a tic d ia gra m o f j th e q u ilib riu m stage

F ig u r e 3.2 R A D F R A C c o lu m n used as C D c o lu m n in aspen plus.

44
Over all material balance:

L n = Vn +i + Y j Fic-D
<t=1
Component material balance on jth stage:

Lj - 1Xi, j - 1+ Vj + iy<. j * i —LjXi, j —Vjyi, j + FjXf, <,j + ARi, j = 0

(1< j> A^-l)
M ij = 0
(j < nrsORj > nre)
Fj = 0(y * nflORj * nfl)
Viyw - Loxi,o - Dxi.o = 0(J = 0)
Ln - ix/, n - 1 - VNyi, n —Bxi. k= 0(J = N)

Rate kinetics:
Rate equation written as
f ij =-kj (xoj X , j - ( X 2J X 3 J / kej)) (i =0 or 1)
nj = kj (x0j xij-(x2jx3j/kej)) (i =2 or 3)
ARi,j —tjLj - in, j
kj and kej ar function of temperature.

Vapor-liquid equilibrium:
y ij~ KijXjj

v frjpi.j
K i, j = -----------
P ‘J
P ij calculated from'Antoine equation and y ij are calculated form NRTL model
Component summation:

(=0 1=0

Enthalpy balance:

Enthalpy balance on the j thplate,

Lj -\hj-\ + Vj +1Hj +1—LjHj + Fjhf, j + VjHj = 0

The variation of enthalpy with temperature has been incorporated by use of following
correlation.
 CHAPTER 4

RESULTS AND DISCUSSION

T h e m athem atical m odel in chapter 3 is used to solve fo r the synthesis o f methyl acetate

by using pseudo hom ogeneous rate kinetics m odel for tw o feed set up. W e sim ulate this m odel

by using A sp e n R A D F R A C . W e use the fo llo w in g operating parameter taken from Popken et al

(2001). In the fo llo w in g sections, m odel v a lid ity and effect o f variables nam ely - r e flu x ratio,

feed tray locations, start o f reactive zone and end o f reactive zone, and therm odynam ic m odels

effect on the com position o f m ethyl acetate.

T a b le 4.1 O p e r a t in g p a ra m e te rs o f two feed co lu m n

Param eter V a lu e

T o ta l num ber o ftra y s(in c lu d in g reboiler 25

and total condenser)

R e flu x ratio 2 .1

O perating pressure (Pa) 101700

Feed rates(mol/hr)

F HOAc 30.8

F MeOH 32.2

D istilla te rate 30.1.

Feed tray

N fl 5

N f2 20

R eactive stage

Start o f reactive stage (Nrs) 10

E n d o f reactive stage(Nre) 19

C o lu m n diameter(m) 0.05

Feed tem peratures^C) at 1 atm

T HOAc 2 1 .1

T MeOH 2 0 .1

47
4.1. Model validation:

A n a ly z in g the m o d e l o f catalytic d istilla tio n co lu m n is done fo r the synthesis o f

m eth yl acetate b y u sin g A S P E N R A D F R A C sim u lator. W e sim u late the reactive zo ne based on

pseudo ho m o gen eou s rate k in etic m o d el. S im u la tio n results g iv e n in A n n e x u re - A and has been

com pared w ith experim ental results o f P o p k e n et al, (2001).

4.1.1. Validation o f liquid phase com position profile for two feed set up:

F ig u r e 4.1 sh ow s the liq u id phase co m p o s itio n p ro file as obtained b y sim u la tio n o f tw o

feed co lu m n and experim ental result o f P o p k e n et al, (2001). T h is d iagram re v e l the variation

betw een experim ental result and sim u la tio n results. T h e average o f m a x im u m d eviatio n w ith the

experim ental results is fo u n d to be 30%.

4.1.2. Variation o f M ethanol conversion with Reflux ratio using two feed set

up:

F ig u re 4.2 show s the variation m ethanol co n ve rsio n w ith re flu x ratio as obtained b y

sim u la tio n o f p seud o hom ogen eou s m odel and experim ental results o f Popken (2001).

O b se rv a tio n o f th is fig u re e x p lain s som e v a ria tio n s is o cc u r betw een experim ental results and

sim u la tio n results. T h e m a x im u m d eviatio n is fo u n d to be 14%.

4.2. E ffect of variables:

In the fo llo w in g sections, w e study th e effect o f v a ria b le s n a m e ly - R e flu x ratio, feed

tray lo ca tio n , start o f reactive section and end o f reactive section, and th e rm o d yn a m ic m o d e ls on

the co m p o sitio n o f m e th yl acetate o n trays and distillate, and co n v e rsio n o f m ethan ol b y u sin g

A s p e n R A D F R A C sim u lator. In the table 4.2, g iv e n the range o f p rocess variables fo r a n a ly z in g

catalytic d istilla tio n usin g tw o feed set up.

48
 Table 4.2 Range of process variables using in two feed stage

Variables Range
Reflux ratio 0.5 to 5.0
Feed tray location
Nfl (Acetic Acid) 2 to 10
Nf2(Methanol) 19 to 23
Start of reactive stage 5 to 15
End of reactive stage 16 to 23

4.2.1. E ffect o f reflu x ratio:

Figure 4.2 shows the effect of reflux ratio on methanol conversion for (D/F=.48 and
Fh o a c ~ F M eO H = 3 2.5 mol/hr) using two feed set up. A close observation of the figure gives
following details about optimum operating conditions.

• Methanol conversion initially increases then decreases with increase in reflux ratio.
• Methanol conversion is high when reflux ratio is 1.6 to 2.1 for two feed set up.
• At low reflux ratio (0.5 to 1.2) insufficient separation of the products from the reactive
zone limits the conversion of methanol.
• At high reflux ratios, the reactants are separated too effectively from each other, thus
limiting conversion is observed.
® For optimum reaction conditions, the concentrations of both the reactants must be high in
reactive zone.
• If a high reflux ratio is used methanol leaves the column with the distillate,
Because of methyl acetate/methanol azeotrope is enriched at top ofthe column.

49
 F ig u r e 4.3 show s the e ffe c t o f re flu x ratio o n m e th y l acetate c o m p o s itio n in d istillate u s in g tw o

feed set up. A clo s e an a lysis o f th is fig u re g iv e s f o llo w in g details:

• M e t h y l acetate c o m p o s itio n in distillate in itia lly increases w ith in crease in re flu x ratio.

• M e t h y l acetate co m p o s itio n in distillate is decreases w ith increase after re flu x ratio o f

1.6.

4.2.2. Effect of feed tray locations:

F ig u r e 4.4 S h o w s the effect o f a ce tic a c id fe e d tray ( N f l ) lo ca tio n o n liq u id phase m ethyl

acetate c o m p o s itio n on each tray o f ca ta lytic d is tilla tio n c o lu m n u s in g tw o feed set up. A c lo s e

e x a m in a tio n o f t h e fig u re re v e l that

• M e t h y l acetate c o m p o s itio n in tray ju s t a b o ve the feed tray N f l increase a b ru p tly that w ith

respect to feed tray.

• M e t h y l acetate c o m p o s itio n o n the d istilla te in itia lly in creases w ith in cre a s in g N f l and

then decrease w ith in cre a sin g N f l .

• A t lo w N f l =2 there is n o re ctifica tio n se c tio n and o n ly extractive section in the top and

separation o c c u r o n ly d ue to that and a ce tic a c id leaves the c o lu m n w ith distillate.

• As. N f l in creases fro m 2 to 5 separation ab o ve the reactive section o ccu rs due to

extractive and re c tifica tio n sectio n the m eth y l acetate c o m p o s itio n in the d istillate

increases.

e A ft e r N f l =5, the extractive section b e co m e shorter and d ue to this m e th y l acetate

c o m p o s itio n in d istillate decreases.

F ig u r e 4.5 S h o w s the effect o f m ethan ol fe e d tray (N f2 ) lo ca tio n o n liq u id p hase m ethyl

acetate c o m p o s itio n on each tray o f ca ta lytic d is tilla tio n c o lu m n u sin g tw o feed set up . A c lo s e

e xam in atio n o f t h e fig u re re v e ls that

• M e th y l acetate c o m p o s itio n in the trays in re c tifica tio n section , in distillate and in? the

bottom ch anges is n e g lig ib ly w ith in crease in N£2 fro m 19 to 21.

• A fte r N£2=21 the m eth yl acetate c o m p o s itio n in trays in re ctifica tio n section and

d istillate decreases w ith increase N f2 .

9 R e m a in in g trays m e th y l acetate c o m p o s itio n decreases w ith increase in N£2.

50
4.2.3. Effect of starting of reactive zone:

F ig u re 4.6 sh ow s the effect o f start o f re a ctive stage (N rs) k e e p in g end o f re a ctiv e stage

(N re ) constant o n m e th yl acetate liq u id p hase c o m p o s itio n o n each tray o f ca ta ly tic d istilla tio n

c o lu m n u s in g tw o feed set up. In th is fig u re e x p la in s fo llo w in g details.

• T h e re is s lig h tly ch ang e in co m p o s itio n o n each tray o f d istilla tio n co lu m n bu t it

co m p a ra tiv e ly the changes are n e g lig ib le .

4.2.4. Effect of end of reactive zone:

F ig u r e 4.7 S h o w s the e ffect o f end o f re a ctiv e stage (N re ) k e e p in g start o f re a ctiv e stage

(N rs) con stan t on m e th y l acetate liq u id phase c o m p o s itio n on each tray o f rea ctive d istilla tio n

c o lu m n u s in g tw o feed set up. A clo s e study o f fig u re revels fo llo w in g points

• F r o m N re = 18 to 23 the ch ang e in re c tifica tio n section, bottom and in d istillate is

n e g lig ib le and in re m a in in g section m e th yl acetate co m p o s itio n is increases w ith increase

the end o f rea ctive stage .

• The c o m p o s itio n o f m e th yl acetate in d istillate and re m a in in g section increases w ith

in crease reactive zo n e in strip p in g se ctio n (bottom side) and u n ch an g ed in bottom

p ro d u ct(is a lm o st z ero M e O A c co m p o sitio n ).

4.2.5. Effect of thermodynamic model:

F ig u re 4 .8 S h o w s the effect o f th e rm o d y n a m ic m o d els on m e th yl acetate liq u id phase

c o m p o s itio n in each tray o f ca ta lytic d istilla tio n co lu m n fo r u sin g tw o feed set up . T h is e x p lain s

the fo llo w in g details:

• N e g lig ib le changes in re ctifica tio n se ctio n and co m p o s itio n increases distillate

. . re sp e c tiv e ly for, U N I F A C , U N I Q U A C , W I L S O N and N R T L .

• D iffe re n t c o m p o s itio n variation s are o c c u r in the m id d le o f c o lu m n betw een feed trays

and n o changes in strip p in g sections and bottom product.

51
 M e O A c c o m p o s it io n

0 0.1 0.2 0.3 0.4 0.5 ‘ 0.6 0.7 0.8 0.9 1

Stage N o .

F ig u r e 4.1 L iq u id p h a se c o m p o s itio n p r o file fo r s y n th e s is o f m e th y l acetate u s in g tw o fe e d set

up .

52
F ig u r e 4 .2 C o n v e r s io n v e rsu s R e flu x r a t io fo r s y n t h e s is o f m e th y l a c e ta te u s in g tw o fe e d

c o lu m n

53
 Reflux ratio

F ig u r e 4.3 C o m p o s it io n o f M e O A c in d istilla te vs R e f lu x ratio fo r tw o feed set up

54
 Stage No.

55
F ig u re 4.5 M e O A c C o m p o s itio n o n trays fo r d iffe re n t N C u sin g tw o feed set u p w ith N f l =5.

56
F ig u r e 4 .6 V a r ia t io n o f M e O A c C o m p o s it io n w ith start o f re a c tiv e se ctio n ( N r s ) u s in g tw o feed

se tu p (N re = 1 9 ).

57
F ig u re 4.7 V a ria tio n o f m eth yl acetate co m p o sitio n on trays for d ifferent N re stages w ith N rs= 10

fo r u sin g tw o feed set up.

58
 MeOAc composition
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
No
Stage

F ig u r e 4.8 V a ria tio n o f M e O A c co m p o s itio n on trays fo r d iffe re n t th e rm o d y n a m ic m od els.

 C H A PT E R 5

CO N CLU SIO N S AND R EC O M M EN D A TIO N S

C o n c lu s io n s :

F o llo w in g C o n c lu s io n s ca n be m a d e u p o n s im u la tio n results:

• B y a ssu m in g p se u d o h o m o g e n e o u s rate k in e tic m o d e l, s im u la tio n is ca rrie d o u t in

A spen R A D F R A C fo r ca ta ly tic d is tilla tio n and results o b ta in e d sh o w n d e v ia tio n s

w ith e x p e rim e n ta l results o f P o p k e n et al (2001). A v g . M a x im u m d e v ia tio n in

c o m p o s itio n is fo u n d to be 30% and is larg e d ue to in the s o lu tio n strategy and

in s u f fic ie n t in p u t d ata a b o u t liq u id h o ld up.

• M a x im u m c o n v e rs io n o f m e th a n o l in tw o feed set u p o c c u rs b e tw ee n the r e flu x ratio

o f 1.5 to 2.1 and at lo w re flu x ratio v a ria tio n in c o n v e rs io n o f m e th a n o l is m o re than

that o f h ig h re flu x ratio.

• T h e lo c a tio n o f fe e d tray a lso effects the c o m p o s itio n o n each tray as sh o w n in F ig u r e

4 .4 and F ig u r e 4.5. Start o f re a c tiv e stage e ffe cts ch a n g e s the c o m p o s itio n to be lo w

o n e a ch tra y a n d the e nd o f re a c tiv e se c tio n ch a n g e s the c o m p o s itio n le v e ls o n the

trays to b e h ig h

® A s s u m in g th e rm o d y n a m ic m o d e l a lso e ffe c ts the results o f s im u la tio n .

Recommendations:

F o r a ccu ra te result, the fo llo w in g a ssu m p tio n s and s p e c ific a tio n s s h o u ld be co n sid e re d :

• In th is stu d y, v a p o r and liq u id has b e e n a ssu m ed to be in e q u ilib riu m w ith e a ch

o th e r o n e a ch stage, w h ic h is n o t in actual case. S o fu rth e r stu d y can b e d e v e lo p e d

b y ta k in g a n o n - e q u ilib riu m m o d e l.

» D y n a m ic s im u la tio n m a y g iv e re su lts a ccu ra te ly.

• M o r e o v e r , m o re a ccu ra te results can b e o b ta in ed p ro v id e d the data o f c o n ta c t tim e

o f liq u id w ith catalyst, o r liq u id h o ld o n trays is a v a ila b le .

• T h e e ffe c t o f s id e re a ctio n s o n the c o m p o s itio n o f p ro d u cts in b o tto m and d istilla te

ca n be a n a ly z e d to ru n the m o d e l e ffe c tiv e ly .

60
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2 7 . P o p k e n T . , S te in ig e w e g S ., a n d G m e h lin g J., “ S y n th e s is a n d h y d r o ly s is o f m e th y l acetate b y

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fr o m C 4 C r a c k F r a c tio n s b y C a t a ly t ic D is t illa t io n P ro c e s s e s ” , S e p . P u r if. T e c h n o l. V o l . 2 6

N o . 2 -3 , 147-163 (2 00 2 ).

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3 6 . S o n g , W .; V e n im a d h a v a n , G .; M a n n in g , J. M . ; M a lo n e , M . F .; D o h e r ty , M . F . M e a s u re m e n t

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3 9 . S te in , E ., K ie n le , A , S u n d m a c h e r, K . C h e m . E n g . 107 (2 0 0 0 b ) 6 8 - 7 2 .

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4 4 . W illia m s o n , A . T . ; H in s h e lw o o d , C . N . T h e K in e t ic s o f E s te r ific a tio n . T h e R e a c tio n b e tw e e n

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1145.

65
 AN NEXU RE-A

SIM U LATIO N RESULTS

T a b le A .1 C o m p o s it io n d a ta f o r F ig u r e 4.1

Stage Exp. Exp. Exp. Exp.

No. M eO H HOAc M eO Ac h 2o M eOH HOAc M eO AC H 20

1 0.007373 0.000578 0.976165 0.015884 0.107 0 0.887 0.016

2 0.003778 0.003966 0.983985 0.008271

3 0.002629 0.019535 0.972093 0 .005744

4 0.002733 0.094001 0.897265 0.006002

5 0.003585 0.375661 0.611899 0.008855

6 0.004996 0.375524 0.605983 0.013497 0.034 0.082 0.84 0.044

7 0.006238 0.375409 0.599968 0.018386

8 0.00735 0.375291 0.593647 0 .02 3 71 2

9 0.008369 0.375073 0.586832 0 .029726

10 0.00933 0.374352 0.579531 0 .036787 0.107 0.327 0.502 0.064

11 0.011084 0.374034 0.570528 0.044354

12 0.013147 0.37373 0.559533 0.05359

13 0.015676 0.373422 0.545423 0 .065479
14 0.01894 0.37289 0.526355 0.081815
15 0.023471 0.370937 0.499386 0.106206 0.285 0.215 0.219 0.281
16 0.030643 0.362508 0.459821 0.147028
17 0.045365 0.32896 0.396443 0.229232
18 0.088396 0.209352 0.250403 0.451849

19 0.213183 0.028844 0.052553 0.705419 0.571 0.061 0.015 0.363

20 0.533747 0.01775 0.008118 0.440384

21 0.527896 0.018101 0.001827 0.452176

22 0.494671 0.019438 0.00038 0.485511
23 0.400669 0.024493 6 .4 3 E-0 5 0.574773
24 0.226931 0.035849 6 .9 7 E -0 6 0.737213 0.246 0.066 0.002 0.686
25 0.078891 0.042553 4 .4 5 E -0 7 0.878556 0.07 0.104 0.002 0.824

66
 Table A.2: MeOH Conversion Data for Figure 4.2

Reflux ratio Theoretical MeOH Conversion Exp. MeOH Conversion using

using Double feed Double feed

0.5 0.590008 0.678

1 0.761264 0.868

1.2 0.812889

1.4 0.860705

1.5 0.886507

1.6 0.912273

1.7 0.933476

1.8 0.93787

2 0.938493 0.878

2.1 0.938021

2.5 0.934286

3 0.927179

3.5 0.918152

4 0.907545

4.5 0.895577 0.748

5 0.882552

67
Table A.3: MeOAc liquid composition Data in distillate for Figure 4.3

R e f l u x ra tio M e O A c in d is t illa t e u s in g tw o fe e d se t u p

0 .5 0 .6 1 4 4 5 7 6 8

1 0 .7 9 2 9 5 5 9 7

1.2 0 .8 4 6 7 4 6 0 3

1.4 0 .8 9 6 5 6 4 4 8

1.5 0 .9 2 3 4 4 2 8 4

1.6 0 .9 5 0 2 8 3 9 3

1.7 0 .9 7 2 3 7 0 2

1.8 0 .9 7 6 9 4 7 9

2 0 .9 7 7 5 9 6 1 8

2.1 0 .9 7 7 1 0 4 1 5

2 .5 0 .9 7 3 2 1 3 3 5

3 0 .9 6 5 8 0 9 7 3

3 .5 0 .9 5 6 4 0 5 7 4

4 0 .9 4 5 3 5 5 6 2

4 .5 0 .9 3 2 8 8 6 1 1

5 0 .9 1 9 3 1 5 5 4

68
 Table A.4: MeOAc Composition Data for Figure 4.4

Stage N o . N f l =2 N f l =5 N f l =7 N f l =9 N f l= 1 0

1 0.92549 0.976165 0.971641 0.964331 0.959349

2 0.634691 0.983985 0.985031 0.98078 0.977584

3 0.631003 0.972093 0.989394 0.987333 0.985182

4 0.627304 0.897265 0.987775 0.989644 0.988093

5 0.6235 0.611899 0.972491 0.989803 0.98904

6 0.619484 0.605983 0.896269 0.986717 0.988717

7 0.615128 0.599968 0.609456 0.97097 0.985493

8 'f- 0.610283 0.593647 0.601904 0.894186 0.969749

9 0.604822 0.586832 0.594079 0.605557 0.892768

10 0.598902 0.579531 0.58591 0.595858 0.603101

11 0.59113 0.570528 0.576282 0.585106 0.591433

12 0.581458 0.559533 0.564811 0.572764 0.578394

13 0.568892 0.545423 0.550402 0.557749 0.562878

14 0.55183 0.526355 0.531284 0.538371 0.543223

15 0.52774 0.499386 0.50466 0.51202 0.516907

16 0.492344 0.459821 0.466139 0.474715 0.48016

17 0.432624 0.396443 0.405412 0.417287 0.424488

18 0.274098 0:250403 0.266424 0.287532 0.30032

19 0.061434 0.052553 0.058928 0.068628 0.075391

20 0.010208 0.008118 0.00928 0.01113 0.012475

21 0.002444 0.001827 0.002118 0.002595 0.00295

22 0.000554 0.00038 0.000447 0.00056 0.000646

23 0.00011 6 .4 3 E -0 5 7 .7 4 E -0 5 0.0001 0.000118

24 1.49E-05 6 .9 7 E -0 6 8 .6 9 E-0 6 1.19E-05 1.45E-05

25 1.09E-06 4.45 E -0 7 5 .8 2 E -0 7 8.51 E -0 7 1.09E-06

69
 Table A.5: MeOAc Composition Data for Figure 4.5

Stage N o . NG=19 N £2= 20 N f2 = 2 1 N f2 = 2 2 N f2 = 2 3

1 0 .9 7 6 1 8 7 0 .9 7 6 18 0 .9 6 7 8 0 9 0 .8 8 8 1 8 3 0 .8 3 6 0 0 3

2 0 .9 8 3 9 9 7 0 .9 8 3 99 3 0 .9 7 9 2 7 9 0 .9 0 0 6 4 0 .6 6 3 2 9 9

3 0.9721 0 .9 7 2 0 9 7 0 .9 6 9 0 2 5 0 .8 9 5 4 5 6 0 .2 3 5 583

4 0 .8 9 7 2 7 2 0 .8 9 7 2 6 9 0 .894301 0 .7 9 5 1 5 2 0 .0 9 3 9 5 7

5 0.611911 0 .6 1 1 9 0 7 0 .6 0 7 2 7 3 0 .4 6 0 6 3 8 0 .0 7 7 0 2 6

6 0 .6 0 6 0 0 2 0 .6 0 5 9 9 6 0 .5 9 8 8 2 2 0 .3 3 2 5 8 4 0 .0 7 6 213

7 0 .5 9 9 9 9 4 0 .5 9 9 9 8 7 0 .5 8 9 8 5 2 0 .2 0 6 6 0 8 0 .0 7 5 9 4 8

8 1 0 .5 9 3 6 8 4 0 .5 9 3 6 7 4 0 .5 7 9 8 1 7 0 .1 3 2 8 3 4 0 .0 7 5 8 5 7

9 0 .5 8 6 8 8 3 0 .5 8 6 87 0 .567961 0 .1 0 1 8 4 7 0 .075821

10 0 .5 7 9 6 0 2 0.579581 0 .5 5 3 2 5 6 0 .0 9 0 5 6 8 0 .0 7 5 7 9 9

11 0 .5 7 0 6 4 6 0 .5 7 0 5 9 8 0 .5 3 1 1 1 6 0 .0 8 6 4 5 9 0 .0 7 5 7 6 5

12 0 .5 5 9 7 7 5 0.559631 0 .4 9 5 4 7 8 0.08501 0 .0 7 5 7 1 6

13 0 .5 4 6 0 1 9 0 .5 4 5 5 5 7 0 .4 3 4 5 9 5 0 .0 8 4 4 3 7 0 .0 7 5 6 2 7

14 0.5 2 8 0 1 3 0 .5 2 6 53 0 .3 4 0 7 6 4 0 .0 8 4 0 7 2 0 .0 7 5 4 4 9

15 0 .5 0 4 1 1 6 0 .4 9 9 5 8 7 0 .2 3 5 8 8 8 0 .0 8 3 5 7 6 0 .0 7 5 075

16 0.4 7 2 6 2 5 0.46 0 .1 5 8 4 3 2 0 .0 8 2 4 8 7 0 .0 7 4 1 9 8

17 0 .4 2 6 2 0 .3 9 6 5 5 0 .1 1 3 5 4 0.0 7 9 38 0 .0 7 1 7 6 5

18 0.296301 0.25.0399 0 .0 7 3 3 2 7 0.0 6 7 4 7 5 0 .0 6 2 9 2

19 0.1 1 4 5 8 5 0 .0 5 2 5 3 8 0 .0 1 6 6 8 9 0 .0 2 5 0 1 2 0 .0 2 8 3 4 7

20 0 .0 3 1 6 2 8 0 .0 0 8 11 5 0 .0 0 1 30 3 0 .0 0 2 1 7 9 0 .0 0 2 6 7 8

21 0 .0 0 7 3 8 9 0 .0 0 1 8 2 6 0 .0 0 0 1 9 0 .0 0 0 2 5 6 0 .0 0 0 3 0 5

22 0 .0 0 1 5 4 9 0 .0 0 0 3 8 4 .0 3 E -0 5 4 .3 6 E -0 5 4 .2 3 E -0 5

23 0.0 0 0 2 6 3 6 .4 3 E -0 5 7 .0 4 E -0 6 1 .0 1 E -0 5 7 .4 2 E -0 6

24 2 .8 5 E -0 5 6 .9 6 E -0 6 8 .0 4 E -0 7 1.7 8 E -0 6 1 .5 7 E -0 6

25 1 .8 2 E -0 6 4 .4 5 E - 0 7 5 .5 2 E -0 8 2 .1 5 E - 0 7 2 .4 5 E -0 7

70
 Table A.6: MeOAc Composition Data for Figure 4.6

Stage N o . N rs= 5 N rs= 6 N rs= 1 0 N rs= 1 3 N rs= 1 5

1 0 .9 7 6 50 4 0 .9 7 6 50 2 0.976165 0.975025 0 .97299
2 0.9 8 4 11 6 0.984123 0.983985 0.98342 0.98 2 37 2
3 0.972183 0.972175 0.972093 0.971741 0.971081
4 0 .897412 0 .8 9 7 34 6 0.897265 0.89 6 95 6 0.89 6 35 9

5 0.61 2 04 8 0.611898 0 .6119 0.611623 0.61 0 93 6

6 0.6 0 6 19 2 0.6 0 6 1 6 2 0.6 0 5 98 4 0.6 0 5 6 2 7 0.60 4 66 9
7 0.6 0 0 2 2 4 0.60 0 19 8 0.599969 0.5 9 9 61 7 0.598483
8 0.5 9 3 94 9 0.593931 0 .593649 0.593375 0.5 9 2 16
9 0.58 7 13 5 0 .587128 0 .586836 0.5 8 6 6 3 7 0.585441
10 0.579471 0 .579479 0 .579535 0 .5 7 9 0 5 4 0.577988

11 0 .570508 0 .570537 0.570535 0.570151 0.56 9 31 7

12 0.55955 0 .559607 0.559545 0.5 5 9 3 1 9 0.558691
13 0.5 4 5 48 0 .545567 0 .545442 0.54608 0 .5 4 4 96 4
14 0.526463 0.5 2 6 57 7 0.526383 0 .527 0.52648
15 0.4 9 9 56 0 .4 9 9 68 4 0 .4 9 9 42 2 0 .5 0 0 0 9 6 0.50 1 49 8
16 0.4 6 0 06 0 .4 6 0 15 7 0.45 9 85 6 0 .460719 0.46 2 35 9

17 0 .396685 0 .396692 0 .396486 0 .397834 0.400311

18 0.25 0 19 8 0.250078 0.250441 0.253288 0.25 8 59 7
19 0.0 5 2 46 9 0.052413 0 .052552 0.0 5 3 62 4 0 .0 5 5 71 6
20 0.0 0 8 1 1 4 0.008101 0.0 0 8 11 8 0.0 0 8 29 9 0 .0 0 8 66 4
21 0.00183 0 .001826 0 .001827 0.001868 0.00 1 95 4
22 0.0 0 0 38 2 0.00038 0.00038 0.000388 0 .0 0 0 40 6

23 6 .5 1 E -0 5 6 .4 8 E -0 5 6 .4 3 E -0 5 6 .5 4 E -0 5 6 .8 3 E -0 5
24 7 .1 1 E -0 6 7 .0 6 E -0 6 6 .9 7 E -0 6 7 .0 6 E -0 6 7 .3 7 E -0 6
25 4 .5 6 E -0 7 4 .5 2 E -0 7 4 .4 5 E -0 7 4 .5 2 E -0 7 4 .7 7 E -0 7

71
 Table A.7: MeOAc Composition Data for Figure 4.7

Stage
N o. Nre=16 Nre=17 Nre=18 Nre=19 Nre=20 Nre=21 Nre=22 Nre=23

1 0.846586 0.894145 0.967879 0.976166 0.978179 0.978979 0.979419 0.979636

2 0.747278 0.910315 0.979321 0.983986 0.985079 0.985509 0.985745 0.985861

3 0.35404 0.908516 0.969052 0.972093 0.972798 0.973076 0.973227 0.973301

4 0.125122 0.819283 0.894326 0.897266 0.89795 0.898219 0.898366 0.898438

5 0.084971 0.494156 0.607315 0.611901 0.612986 0.613417 0.613652 0.613767

6 0.080041 0.383215 0.598889 0.605985 0.607647 0.608302 0.608661 0.608836

7 0.07845 0.250193 0.589953 0.599969 0.60227 0.603172 0.603666 0.603906

8 0.07792 0.155858 0.579972 0.593648 0.596696 0.597879 0.598528 0.598843

9 0.077714 0.111594 0.568212 0.586831 0.59079 0.592308 0.593141 0.593544

10 0.077581 0.094653 0.553724 0.579528 0.584602 0.58652 0.587569 0.588075

11 0.077365 0.088376 0.532132 0.570522 0.57719 0.57966 0.581006 0.581652

12 0.07697 0.086025 0.497868 0.559524 0.568467 0.571697 0.573436 0.574268

13 0.076061 0.084835 0.439845 0.54541 0.557786 0.562089 0.564395 0.565482

14 0.073523 0.083483 0.349176 0.526339 0.544175 0.550086 0.553205 0.554654

15 0.064175 0.080196 0.242716 0.499373 0.526253 0.534603 0.538941 0.540906

16 0.027951 0.067806 0.156144 0.459809 0.502341 0.514434 0.520588 0.523278

17 0.002609 0.024473 0.086957 0.396436 0.470634 0.488859 0.497743 0.50145

18 0.0003 0.00211 0.017886 0.250398 0.423282 0.45702 0.471411 0.476955

19 4.34E-05 0.00025 0.00142 0.052549 0.289411 0.394214 0.433164 0.446501

20 8.51E-06 4.44E-05 0.000212 0.008118 0.10899 0.248911 0.349143 0.38973

21 2.48E-06 1.18E-05 4.80E-05 0.001827 0.028976 0.104533 0.247733 0.355161

22 6.98E-07 3.03E-06 1.02E-05 0.00038 0.006252 0.025615 0.097115 0.252262

23 1.79E-07 6.89E-07 1.77E-06 6.43E-05 0.00106 0.004461 0.019004 0.082785

24 3.67E-08 1.18E-07 2.02E'07 6.97E-06 0.000113 0.000477 0.002065 0.009829

25 5.45E-09 1.38E-08 1.39E-08 4.45E-07 7.11E-06 2.97E-05 0.000128 0.000611

72
 Table A.8: MeOAc Composition Data for Figure 4.8

S ta g e N o . W ILS O N N R TL U N IQ U A C U N IFA C

1 0 .9 7 6 1 6 5 0 .9 5 5 7 3 9 0 .9 8 2 4 1 9 0 .9 9 0 0 1

2 0 .9 8 3 9 8 5 0 .9 6 8 0 1 4 0 .9 8 8 8 6 0 .9 8 8 0 8 6

3 0 .9 7 2 0 9 3 0 .9 6 2 6 7 5 0 .9 7 8 4 0 3 0 .9 7 2 2 3 8

4 0 .8 9 7 2 6 5 0 .8 9 2 3 3 1 0 .9 0 0 0 6 4 0 .9 0 1 5 5 2

5 0 .6 1 1 8 9 9 0 .6 1 4 9 7 6 0 .6 2 0 4 4 4 0 .6 1 4 1 6 8

6 0 .6 0 5 9 8 3 0 .6 0 8 3 8 5 0 .6 1 8 2 5 4 0 .6 0 9 3 3 9

7 0 .5 9 9 9 6 8 0 .6 0 2 1 8 4 0 .6 1 5 6 3 4 0 .6 0 3 4 6 1

8 0 .5 9 3 6 4 7 0 .5 9 6 0 2 7 0 .6 1 2 2 0 4 0 .5 9 6 1 6 6

9 0 .5 8 6 8 3 2 0 .5 8 9 6 9 4 0 .6 0 7 6 6 2 0 .5 8 7 0 6 3

10 0 .5 7 9 5 3 1 0 .5 8 3 2 8 6 0 .6 0 2 2 0 7 0 .5 7 6 1 4 3

11 0 .5 7 0 5 2 8 0 .5 7 5 9 0 6 0 .5 9 4 8 4 3 0 .5 6 1 2 9 3

12 0 .5 5 9 5 3 3 0 .5 6 7 3 9 8 0 .5 8 5 8 2 7 0 .5 4 2 1 8

13 0 .5 4 5 4 2 3 0 .5 5 7 0 4 7 0 .5 7 4 2 0 9 0 .5 1 7 1 6 8

14 0 .5 2 6 3 5 5 0 .5 4 3 6 9 5 0 .5 5 8 2 4 6 0 .4 8 4 0 7 9

15 0 .4 9 9 3 8 6 0 .5 2 5 3 7 2 0 .5 3 4 4 6 8 0 .4 4 0 7

16 0 .4 5 9 8 2 1 0 .4 9 8 3 7 8 0 .4 9 5 2 8 6 0 .3 8 6 0 4 4

17 0 .3 9 6 4 4 3 0 .4 5 3 2 0 7 0 .4 2 1 5 4 8 0 .3 1 8 3 9 5

18 0 .2 5 0 4 0 3 0 .3 3 0 7 7 5 0 .2 3 7 0 5 8 0 .1 8 3 1 3

19 0 .0 5 2 5 5 3 0 .0 7 8 8 9 6 0 .0 3 9 4 9 6 0 .0 3 2 6 4 7

20 0 .0 0 8 1 1 8 0 .0 1 2 0 8 7 0 .0 0 5 4 0 7 0 .0 0 4 9 8 1

21 0 .0 0 1 8 2 7 0 .0 0 2 5 9 4 0 .0 0 1 0 9 1 0.001119

22 0 .0 0 0 3 8 0 .0 0 0 5 1 4 0 .0 0 0 2 0 2 0 .0 0 0 2 3

23 6 .4 3 E - 0 5 8 .3 5 E - 0 5 2 .9 1 E - 0 5 . 3 .7 7 E - 0 5

24 6 .9 7 E - 0 6 8 .0 8 E - 0 6 2 .3 2 E - 0 6 3 .5 7 E - 0 6

25 4 .4 5 E - 0 7 3 .8 8 E - 0 7 1.01 E - 0 7 1 .5 5 E - 0 7

73