Department of Chemical and Environmental Engineering University of Nottingham

BENZALDEHYDE PRODUCTION
GROUP 12
1) Adamu AbuBakar Rasheed - 010096 2) Cobham Emmanuel Itam 3) Nasir Muzaffar Kotriwala 4) Teh Yong Chuan
- 009390

Group Members:

- 005831 - 006379

Lecturers:

1) Prof. Dominic Foo 2) Dr. Denny Ng 3) Dr. Lam Hon Loong

Table of Content

1.0 2.0

Introduction Overview of Reaction Pathways 2.1 2.2 2.3 Chlorination of Toluene coupled with Hydrolysis of Benzal Chloride Liquid Phase Oxidation of Toluene Oxidation of Benzyl Alcohol

1 1 1 2 4 5 6 7 8 9

3.0 4.0 5.0 6.0 7.0

Reaction Path Selection Process Synthesis Process Flow Diagram (Liquid Phase Oxidation of Toluene) Hysys Simulation Diagram Mass Balance

References

10

1.0

Introduction

Benzaldehyde, the most valuable industrial aromatic aldehyde, is used as a flavouring agent for food and an intermediate for pharmaceuticals, dyes, perfume and flavouring chemicals. (Opgrande,J.W 2004) (Kantam,M.L., et al.2002).

2.0

Overview of Reaction Pathways

Liquid-Phase Air Oxidation of Toluene and Acid Hydrolysis of Benzalchloride, which are principally used by current industry to manufacture Benzaldehyde, along with the discontinued industrial process of Oxidation of Benzyl Alcohol to manufacture Benzaldehyde have been evaluated to manufacture 50,000 MTA of Benzaldehyde.(Ullmann, 2003)

2.1

Chlorination of Toluene coupled with Hydrolysis of Benzal Chloride

Overall Reaction

Reactivity of Chlorine molecule, facilitated by means of activation via light or heat, enables exchanging a hydrogen atom with the methyl molecule. Consequently, benzalchloride and benzylchloride are produced. Benzalchloride, the intermediate for hydrolysis in presence of presence of concentrated sulphuric acid, needs to be free from benzylchloride. (len1, 2008) The undesirable formation of benzylchloride can be minimized by the maintaining the chlorination temperature between 195-197oC at 1 atm. (len1, 2008). The recommended operating conditions for hydrolysis are 100-200oC at atmospheric pressure. (len1, 2008) Economical Potential C6H5CH3 + Cl2 + H 2O C6H5CHO + Kg mole 1 1 1 1 Mole Weight 92.14 70.91 18.02 106.12 Kg 92.14 70.91 18.02 106.12 Kg/Kg C6H5CHO 0.87 0.69 0.17 1.00 $/Kg 1.33 0.38 0 3.81 Table 1: Economic Potential of Chlorination of Toluene coupled with Hydrolysis. Price adapted from (ICIS, 2011) and (Creators, 2010) Gross Profit = [(3.81 x 1) + (0.11 x 0.69) (1.33 x 0.87) - (0.38 x 0.69)] x 1000 = $ 2466.60/tonne of benzaldehyde 2HCL 2 36.46 72.92 0.69 0.11

1|Page

Safety The chemicals involved are stable in terms of reactivity. Toluene is flammable and combustible. Chlorine gas is easily vaporised due to its low boiling point.(Vee Gee Scientific Inc., 2004) Environmental Impact All the raw materials and product found in this process are long-term biodegradable. Especially, toluene is dangerous to aquatic life in high concentration and fouling shoreline (Mark Van, et al., 1997). Furthermore, hydrochloric acid will accelerate the dissolution of mineral like carbonates and all aluminosilicates. Thus it contributes to the decay of buildings and structure (National Pollutant Inventory, 2011) Chlorine is extremely harmful to humans; may cause tracts burn, skin burn or eyes burn if contacted. (Matheson Tri-Gas, Inc., 2002) Dilute sulphuric acid, which isnt permitted to be flushed into water at large scale, is formed as a waste product in substantial quantities.(Ullman,2003)(Cartwright,2003)

2.2 Liquid Phase Oxidation of Toluene Overall Reaction

Adapted from (Hoorn, et al., 2005) Air oxidation of Toluene in liquid-phase is currently the worlds largest source of synthetic Benzaledyhde.(Opgrande,J.W 2004) Vapour-phase oxidation of Toleuene, the dominant

2|Page

process to manufacture Benzaldehyde in 1950-60s, isnt industrially important anymore. Instead, liquid-phase oxidation offers higher yields of Benzaldehyde and lower undesirable by-products of Carbon Monoxide and Carbon Dioxide relatively. (Opgrande,J.W 2004) Manganese(II) acetate, amongst various possible catalysts, has been selected to oxidize Toluene in liquid-phase. Bromide promoter, acetic acid solvent and Lewis Acid [stannous(II) chloride], which increases selectivity of Benzaldehyde, in the composite catalyst system facilitate higher Benzaldehyde yields, milder operating conditions [1200C, 70-400 psig] and cheaper catalyst costs in comparison to other catalysts respectively. 18% Single-pass Toluene conversion and 68% Benzaldehyde selectivity have been used in our analysis. (Chaudhari, et al., 2008) Economic Potential Since the side-reactions are not negligible selectivity of each product has been accounted for ascertaining the economic potential.(Chaudhari, et al., 2008) 18kg of Toluene would be consumed, when taking 100 kg Toluene as basis, as single-pass conversion is 18% . C6H5CH3 + O2 C6H5CHO + C6H5COOH + C6H5CH2OCOCH3 + C6H5CH2OH Mole (kmol) 1 1 1 1 1 1 Mole Weight 92.14 16 106.12 122.12 150.18 108.14 (kg/kmol) Selectivity 68 17 10.20 5.30 Weight (kg) 18 6.25 12.24 3.06 1.86 0.954 kg/kg 1.47 0.51 1 0.25 0.15 0.078 benzaldehyde $/kg 1.33 0 3.81 1.94 3.9 3.5 Table 2: Economy Potential for Liquid Phase Oxidation of Toluene. Price adapted from (ICIS, 2011) Gross Profit = [(3.81 x 1) + (1.94 x 0.25) + (3.9 x 0.15) + (3.5 x 0.078) (1.33 x 1.47) - 0] x 1000 = $ 3197.90/tonne of benzaldehyde. Safety Toluene must be prevented from undergoing exothermic polymerisation as it can lead to fire/explosion hazard. (Emerald, 2006) (Vee Gee Scientific Inc., 2004) Environmental Impact Minor emissions of Carbon monoxide and Carbon Monoxide occur. (Chaudhari, et al., 2008) Leakage of Toluene and Manganese(II) Acetate may harm aquatic life (Mark Van, et al., 1997), (Orica Chemicals, 2008). However, Manganese Acetate can be reused for the oxidation process instead of harmful disposal by recovering it via solvent extraction or distillation.

3|Page

2.3

Oxidation of Benzyl Alcohol

Overall Reaction

Adapted from (Satrio & Doraiswamy, 2000) Benzylchloride, in presence of sodium hydroxide, is hydrolysed to benzyl alcohol followed by further oxidation of the product, benzyl alcohol to benzaldehyde in the same reactor using sodium hypochlorite. (Satrio & Doraiswamy, 2000) Single-pass conversion and selectivity, under the recommended operating conditions are 90oC and 10 bars, are limited to 18.1% and 45.3% respectively. (Satrio & Doraiswamy, 2000) Economic Potential Since the side-reactions are not negligible selectivity of each product has been accounted for ascertaining the economic potential. Since 18.1% single-pass conversion of benzyl chloride occurs 18.1kg of toluene are assumed to be consumed taking 100kg of benzyl chloride as basis. C6H5CH2Cl + 1 126.58 18.1 2.21 NaOH 1 40.00 5.72 0.70 + NaOCl 1 74.44 10.64 1.30 C6H5CHO 1 106.12 45.3 8.20 1.00 + C6H5CH2OH 1 108.14 54.7 9.91 1.20 3.50

Mole (kmol) Mole Weight (kg/kmol) Selectivity Weight (kg) kg/kg benzaldehyde $/kg

1.97 0.65 0.24 3.81 Table 3: Economic Potential for Oxidation of Benzyl Alcohol Price adapted from (Seper, 2001), (ICIS, 2011) and (Johnston, 2010)

Gross Profit = [(2.21 x 1.97) + (0.65 x 0.7) + (0.24 x 1.3) - (3.81 x 1)-(3.5 x 1.2)] x 1000 = $ 2889.30/tonne of benzaldehyde

4|Page

Safety All chemicals involved in the reaction are combustible. Sodium hydroxide is very hazardous in case of skin contact (Sciencelab, 2010). Lastly, benzyl chloride is corrosive and inhalation of air containing benzyl chloride may cause lung burn (SEPA, 2011). Environmental Impact Sodium hydroxide, by virtue of raising the pH of aquatic environment, is very toxic to aquatic life. (Horizon, 2004)

3.0

Reaction Path Selection

Reaction Path Gross Profit ($/tonne) 1) Liquid Phase Oxidation of Toluene 3197.90 2) Chlorination of Toluene coupled with Hydrolysis of Benzal Chloride 2466.60 3) Oxidation of Benzyl Alcohol 2899.30 Table 4: Economy Potential Comparison between Various Processes. Considering the aforementioned factors, liquid phase oxidation of toluene is deemed to be the most appropriate reaction pathway for large-scale benzaldehyde manufacture. Firstly, liquid phase oxidation of toluene exhibits highest economy potential as shown in Table 4. Secondly, the 68 % selectivity of benzaldehyde significantly exceeds that achieved in oxidation of benzyl alcohol whilst roughly maintaining the same single-pass conversion[18%]. Furthermore, Benzaldehyde produced from chlorination process doesnt conform to food grade quality, thereby reducing the flexibility of demand for our benzaldehyde product. (Chaudhari, et al., 2008) Furthermore, the by-product of the Chlorination process, Hydrochloric Acid may potentially sell at depressed prices if theres abundant supply of Hydrochloric acid in our petrochemical complex.(Seider, et al. 2010) Higher capital and maintenance cost are required by the chlorination process in order to combat corrosiveness, which may potentially lead to emission of poisonous chlorine. Moreover, oxidation of alcohol employs Sodium Hydroxide, which is harmful to aquatic life if leaked. Furthermore, hydrochloric acid in chlorination of toluene may cause decay of building and structure. Conversely, Liquid phase oxidation of toluene, by producing only minor emissions of Carbon Monoxide and Carbon Dioxide, avoids substantial emissions of pollutant residues. Hence, its relatively the most environmental friendly process.

5|Page

4.0

Process Synthesis

The oxidation agent can theoretically be either pure Oxygen or Air. Air is selected as all industrial processes employing liquid-phase oxidation of Toluene use Air. Since the patent, relied upon in this study, doesnt report any adverse effect on the catalyst by use of Air it implies that the inert Nitrogen doesnt need to be removed before the reactor. (Chaudhari, et al., 2008) Moreover, the substantial amount of inert Nitrogen absorbs the heat generated by the exothermic oxidation reaction, thereby maintaining the reactor effluent temperature at a mild temperature of 135.8C. Air has been provided in excess in order to facilitate recycled Toluene to be completely consumed. Owing to unavailability of published kinetics data for the catalyst, used in this study, the Arrhenius graph couldnt be used to ascertain the favourable operating temperature range. Instead, personal judgement was used to ascertain the optimum combination of single-pass conversion and Benzaldehyde selectivity to be 18% and 68% from the various experiment results, which occur at 120C and 300 psig as reported in the patent. 76% Benzaledhyde selectivity was also reported. However, it wasnt selected since the single-pass conversion was limited to only 10% (Chaudhari, et al., 2008) Since the reactor effluent is distributed between liquid and vapour phases, partial condensation has been used after the reactor as liquid is easier to separate than vapour. The vapours of unconverted Oxygen and inert Nitrogen, collected by vapour recovery system, arent recycled as recycle costs arent economically viable considering that air is free of charge. Benzaldehyde produced from liquid oxidation of Toluene often contains minor odiferous impurities that discolour the product and are difficult to remove by distillation. (Ullmann,2003) These impurities have been removed by treating the impure benzaldehyde simultaneously with water and zinc powder followed by distillation. (Jongsma, C., 2008) A direct distillation sequence was used to recover the products as its generally considered to be the most desirable sequence. Slightly higher than atmospheric pressures, in order to avoid vacuum operation, were used in distillation columns as the boiling points of Toluene, Benzaldehyde and Benzoic Acid(110C, 179C and 249C) are widely spread at atmospheric pressure. The difficult separation of separating the relatively low output of Benzyl Alcohol and Benzyl acetate, which have boiling points of 205.4C and 212C , wasnt pursued owing to the capital-intensive nature. Catalyst is recovered for recycle by means of solvent extraction of the bottoms product of the last distillation tower (Chaudhari, et al., 2008). Prior to recycle of Toluene an adiabatic flash drum is used to remove in order to prevent vapour from entering the pump feeding Toluene to the reactor.The Benzaldehyde recovered is 98.6% pure, which exceeds the industrial specification of 98.0%.(Opgrande,J.W. 2004)

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BENZALDEHYDE: LIQUID PHASE OXIDATION OF TOLUENE

Air 101.3Kpa, 300C 735000Kg/h V-02 C-02 44.970C 2158Kpa E-05 135.8 C 2170Kpa
0

To Stack E-01 E-02 E-03 101Kpa

C-01

C-03 1200C 2170Kpa

44.970C 2158Kpa 25660kg/h

V-01 Impurities

300C 3051kg/h

By Products Storage

1200C 2172Kpa 61260kg/h HE-01

Reactor at 1200C and 2170Kpa

F-01

209.90C 118Kpa 1608kg/h P-07 E-11

Toluene Storage 30 C 2172Kpa 61260kg/h

0

44.970C 2158Kpa 101.3Kpa 21200kg/h 49830kg/h To Stack 300 C 40440kg/h E-06 P-01

Treatment to remove impurities causing discoloration before distillation

V-03

44.970C 120Kpa

E-12 Benzoic Acid Heated Storage Tank

CATALYST RECOVERY BY LLE

D-03

Benzaldehyde Storage Under Nitrogen Blanket

E-08

30 C 40440kg/h F-02

E-07

Heat in

184.8 C 118Kpa 6336kg/h P-02

115.30C 118Kpa 40440kg/h D-01 Heat in

R-03

300C 6336kg/h E-09 Heat in 256.60C 120Kpa 1608kg/h P-04 Heat out 228.40C 120Kpa 3051kg/h P-05 R-02 D-02

110.60C 120Kpa 49830kg/h

HE-02 LEGEND

Heat out 300C 1608kg/h E-10

R-01

Heat out

P-06 P-03

193.60C 122Kpa 9388kg/h

CCompressors HE- Heater RReboiler ECooler PPump DDistillation Column FFlash Drum VValve D-01 Toluene Column D-02 Benzaldehyde Column D-03 Benzoic Acid Column

To Stack too

QCool1 Air 1 Inter Cooler Compressor 2

QCool2 4 Inter Cooler 2 Qcomp3 QComp2 K-100 55 Inter Cooler 3

QCool3

Air to atmosphere Pressurised Air Catalyst Recovery Reactor Products Cooler 1 6 To Valve 1 Flash Flash Drum Q Cooler

VLV-102

to stack Qcond

V-100

Comp QComp-1 2

Toluene and Air

Condenser

Recyle toluene To recycle

Impurities E-01 10 7 Treatment of impurities causing discoloration before distillation Toluene Column Bottoms Benzaldehyde

HE-01

HE-02

Benzaldehyde to storage Cooler 2

Heat in

E-02 BZol and Bacetate Heat in 2 Benzaldehyde Column By Products HE-03 E-102 To Storage Cooler 3

Make-up Toluene Pump 1

QHeat 1 8

Toluene MIX-100 QP-1

Pressurised Toluene

Heater 1

Toluene to Reactor

gdfgd Valve 2 9 E-103 Benzoic Acid Column Heat in 3 Benzoic acid BZoic and Catalyst

Cooler 4

Liquid Liquid Separation

Benzoic Acid to storage

recycle Toluene

R
RCY-1

Mon Oct 24 21:18:11 2011

Case: H:\PSD\PSD CW\PSD COMPLETED SIMULATION GROUP 12.HSC

Flowsheet: Case (Main)

Material Streams Air Vapour Fraction Temperature Pressure Molar Flow Mass Flow Liquid Volume Flow Heat Flow C kPa kgmole/h kg/h m3/h kJ/h 1.0000 30.00 101.3 2.548e+004 7.350e+005 849.7 3.547e+006 Air to atmosphere Vapour Fraction Temperature Pressure Molar Flow Mass Flow Liquid Volume Flow Heat Flow C kPa kgmole/h kg/h m3/h kJ/h 10 Vapour Fraction Temperature Pressure Molar Flow Mass Flow Liquid Volume Flow Heat Flow C kPa kgmole/h kg/h m3/h kJ/h 0.0698 110.6 120.0 530.0 4.983e+004 55.37 2.204e+005 1.0000 44.97 2158 2.566e+004 7.464e+005 862.5 -2.935e+006 7 0.0000 204.6 2158 530.0 4.983e+004 55.37 9.239e+006 Toluene and Air 1.0000 115.3 118.0 446.2 4.044e+004 46.47 2.571e+007 1 1.0000 163.2 278.9 2.548e+004 7.350e+005 849.7 1.039e+008 Make-up Toluene 0.0000 30.00 101.3 230.1 2.120e+004 24.37 3.101e+006 Impurities 1.0000 204.6 2158 0.0000 0.0000 0.0000 0.0000 Benzaldehyde 1.0000 184.8 118.0 59.71 6336 6.046 -9.385e+005 Bottoms 0.0000 193.6 122.0 83.74 9388 8.899 -1.021e+007 8 0.0000 204.6 2158 530.0 4.983e+004 55.37 9.239e+006 Pressurised Toluene 0.0000 31.92 2172 667.2 6.126e+004 70.40 8.364e+006 To Flash 0.9798 44.97 2158 2.619e+004 7.963e+005 917.9 -9.731e+006 BZol and Bacetate 1.0000 209.9 118.0 10.86 1443 1.372 -2.025e+006 2 1.0000 120.0 276.9 2.548e+004 7.350e+005 849.7 7.101e+007 9 0.5127 123.7 120.0 530.0 4.983e+004 55.37 9.239e+006 Benzoic acid 0.0000 256.5 120.0 13.17 1608 1.481 -4.048e+006 3 1.0000 306.2 837.0 2.548e+004 7.350e+005 849.7 2.149e+008 4 1.0000 120.0 835.0 2.548e+004 7.350e+005 849.7 7.051e+007 to stack 1.0000 40.69 101.3 2.566e+004 7.464e+005 862.5 -2.935e+006 By Products 0.0000 228.4 120.0 24.03 3051 2.853 -6.640e+006 Recyle toluene 0.0167 30.00 108.0 446.2 4.044e+004 46.47 5.029e+006 Benzaldehyde to storage 0.0000 30.00 118.0 59.71 6336 6.046 -5.272e+006 55 1.0000 278.1 2172 2.548e+004 7.350e+005 849.7 1.924e+008 Pressurised Air 1.0000 120.0 2170 2.548e+004 7.350e+005 849.7 6.936e+007 recycle Toluene 0.0000 30.00 108.0 437.2 4.006e+004 46.03 5.066e+006 To Storage 0.0000 30.00 118.0 10.86 1443 1.372 -3.083e+006 Toluene to Reactor 0.0000 120.0 2170 667.2 6.126e+004 70.40 1.834e+007 To Stack too 1.0000 30.00 108.0 7.438 231.3 0.2703 -5.279e+004 BZoic and Catalyst 0.0000 30.00 120.0 13.17 1608 1.481 -4.701e+006 Products 1.0000 135.8 2170 2.619e+004 7.963e+005 917.9 8.769e+007 To recycle 0.0000 30.00 108.0 438.8 4.021e+004 46.20 5.082e+006 Catalyst Recovery 0.0000 30.00 120.0 0.0000 0.0000 0.0000 0.0000 Toluene 0.0000 30.00 101.3 667.2 6.126e+004 70.40 8.167e+006 Benzoic Acid to storage 0.0000 30.00 120.0 13.17 1608 1.481 -4.701e+006 6 0.9798 45.00 2168 2.619e+004 7.963e+005 917.9 -9.731e+006

Mon Oct 24 21:22:19 2011

Case: H:\PSD\PSD CW\PSD COMPLETED SIMULATION GROUP 12.HSC

Flowsheet: Case (Main)

Compositions Air Comp Mole Frac (Toluene) Comp Mole Frac (Nitrogen) Comp Mole Frac (Oxygen) Comp Mole Frac (BZal) Comp Mole Frac (BZoicAcid) Comp Mole Frac (BZ-Acetate) Comp Mole Frac (AceticAcid) Comp Mole Frac (BZol) Comp Mole Frac (H2O) 0.0000 0.0000 Air to atmosphere Comp Mole Frac (Toluene) Comp Mole Frac (Nitrogen) Comp Mole Frac (Oxygen) Comp Mole Frac (BZal) Comp Mole Frac (BZoicAcid) Comp Mole Frac (BZ-Acetate) Comp Mole Frac (AceticAcid) Comp Mole Frac (BZol) Comp Mole Frac (H2O) 10 Comp Mole Frac (Toluene) Comp Mole Frac (Nitrogen) Comp Mole Frac (Oxygen) Comp Mole Frac (BZal) Comp Mole Frac (BZoicAcid) Comp Mole Frac (BZ-Acetate) Comp Mole Frac (AceticAcid) Comp Mole Frac (BZol) Comp Mole Frac (H2O) 0.0088 0.0058 0.0000 0.0068 0.0117 0.0000 0.0554 0.0000 0.3630 0.0000 0.0001 0.0000 0.1641 0.0000 0.0117 0.0000 0.3630 0.0000 0.0001 0.0000 0.0001 0.0000 0.0001 0.0000 0.8229 0.0114 0.0021 0.1122 0.0249 0.0121 0.0000 0.0032 0.0088 0.0058 Toluene and Air 0.9770 0.0135 0.0025 0.0001 0.0000 0.0000 0.0009 0.2534 Benzaldehyde 0.0019 0.0000 0.0000 0.9864 0.0000 0.0000 Bottoms 0.0014 0.0000 0.0000 0.7093 0.1573 0.0766 0.0088 0.0058 0.0002 0.0033 BZol and Bacetate 0.0000 0.0000 0.0000 0.0459 0.0006 0.5905 0.0088 0.0058 Benzoic acid 0.0000 0.0000 0.0000 0.0000 0.9999 0.0001 0.0000 0.0032 By Products 0.0000 0.0000 0.0000 0.0208 0.5482 0.2670 0.0000 0.0068 Benzaldehyde to storage 0.0019 0.0000 0.0000 0.9864 0.0000 0.0000 To Storage 0.0000 0.0000 0.0000 0.0459 0.0006 0.5905 0.0000 0.0063 0.0000 0.0394 BZoic and Catalyst 0.0000 0.0000 0.0000 0.0000 0.9999 0.0001 0.0000 0.0063 Catalyst Recovery 0.0000 0.0000 0.0000 0.0000 0.9999 0.0001 0.0000 0.0041 Benzoic Acid to storage 0.0000 0.0000 0.0000 0.0000 0.9999 0.0001 0.0042 0.7841 0.2084 0.0000 0.0000 0.0000 7 0.8229 0.0114 0.0021 0.1122 0.0249 0.0121 0.0000 0.0000 Impurities 0.3302 0.3040 0.0963 0.0140 0.0007 0.0005 0.0000 0.0000 8 0.8229 0.0114 0.0021 0.1122 0.0249 0.0121 0.0000 0.0041 To Flash 0.0208 0.7684 0.2043 0.0023 0.0005 0.0002 0.0000 0.0000 9 0.8229 0.0114 0.0021 0.1122 0.0249 0.0121 0.0000 0.0000 0.0000 0.0000 to stack 0.0042 0.7841 0.2084 0.0000 0.0000 0.0000 Recyle toluene 0.9770 0.0135 0.0025 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 recycle Toluene 0.9929 0.0007 0.0001 0.0001 0.0000 0.0000 To Stack too 0.0453 0.7702 0.1452 0.0000 0.0000 0.0000 0.0000 0.0041 To recycle 0.9928 0.0007 0.0001 0.0001 0.0000 0.0000 0.0002 0.0033 Toluene 0.9953 0.0005 0.0001 0.0001 0.0000 0.0000 0.0002 0.0033 0.0000 0.7900 0.2100 0.0000 0.0000 0.0000 1 0.0000 0.7900 0.2100 0.0000 0.0000 0.0000 Make-up Toluene 1.0000 0.0000 0.0000 0.0000 0.0000 0.0000 Pressurised Toluene 0.9953 0.0005 0.0001 0.0001 0.0000 0.0000 2 0.0000 0.7900 0.2100 0.0000 0.0000 0.0000 3 0.0000 0.7900 0.2100 0.0000 0.0000 0.0000 4 0.0000 0.7900 0.2100 0.0000 0.0000 0.0000 55 0.0000 0.7900 0.2100 0.0000 0.0000 0.0000 Pressurised Air 0.0000 0.7900 0.2100 0.0000 0.0000 0.0000 Toluene to Reactor 0.9953 0.0005 0.0001 0.0001 0.0000 0.0000 Products 0.0208 0.7684 0.2043 0.0023 0.0005 0.0002 6 0.0208 0.7684 0.2043 0.0023 0.0005 0.0002

Mon Oct 24 21:23:56 2011

Case: H:\PSD\PSD CW\PSD COMPLETED SIMULATION GROUP 12.HSC

Flowsheet: Case (Main)

References
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17) MARK VAN MOUWERIK, L. S. M. D. S. W. B., 1997. Environmental Contaminants Encyclopedia. Toluene Entry, p. 7. 18) Mark Van, M., Stevens, L., Seese, M. D. & Basham, W., 1997. Environmental Contaminants Encyclopedia. Toluene Entry, p. 7. 19) MATHESON TRI-GAS, INC., 2002. Material Safety Data Sheet, NEW JERSEY: MATHESON TRI-GAS, INC.. 20) National Pollutant Inventory, 2011. Hydrochloric acid: Environmental effects. [Online] Available at: http://www.npi.gov.au/substances/hydrochloric-acid/environmental.html [Accessed 16 October 2011]. 21) Orica Chemicals, 2008. Material Safety Data Sheet, Melbourne: Orica Australia Pty Ltd . 22) Opgrande,J.W. 2004. Kirk-Othmer Encyclopedia of Chemcial Technology. Benzaldehyde 23) Pashkova, A. & Greine, L., 2011. Chemie Ingenieur Technik. Towards Small-Scale Continuous Chemical Production: Technology Gaps and Challenges, 83(9), pp. 1337-1342. 24) Satrio, J. A. & Doraiswamy, L., 2000. Two Step Process. Production of Benzaldehyde: A Case Study in a Possible Industrial, Issue 82, p. 48. 25) Sciencelab, 2010. Material Safety Data Sheet, Texas: Sciencelab.com, Inc. 26) Sciencelab, 2010. Material Safety Data Sheet Benzaldehyde MSDS, Texas: Sciencelab.com, Inc.. 27) Sciencelab, 2010. Material Safety Data Sheet Hydrochloric Acid MSDS, Texas: Sciencelab.com, Inc.. 28) Sciencelab, 2010. Material Safety Data Sheet Toulene MSDS, Texas: Sciencelab.com, Inc.. 29) SEPA, 2011. Sccottish Pollutant Release Inventory. [Online] Available at: http://apps.sepa.org.uk/spripa/Pages/SubstanceInformation.aspx?pid=24 [Accessed 22 October 2011]. 30) Seider,W.D. et al. 2010. Product and Process Design Principles. John Wiley & Sons. USA 31) Seper, K. W., 2001. Kirk-Othmer Encyclopedia of Chemcial Technology. Benzyl Chloride, Benzal Chloride, and Benzotrichloride. 32) Ullmann, F. E. B. A. H., 2003. Ullmann's Encyclopedia of Industrial Chemistry. Volume 6th. 33) Vee Gee Scientific Inc., 2004. Toluene Material Safety Data. [Online] Available at: http://www.ee.iitb.ac.in/~nanoe/msds/toluene.pdf. [Accessed 19 October 2011].