Johnson Olayiwola, Theodora Udabor, Norakmar Mohd Said, Rouvin Lazar, Muzal Shahabudin, Mohamed Abou-Rayyah Report 0: Process

Description

CENGMO11 Advanced Process Modelling & Design Group 1

Report 0 Process Description

Group Member Johnson Olayiwola Theodora Udabor Norakmar Hani Mohd Said Rouvin Raj Mark Lazar Muzal Shahabudin Mohamed Abou-Rayyah

Assigned Unit Unit 1: Acetic Acid Scrubber Unit 2: Acetic Acid Recovery Unit 3: CO2 Removal Column Unit 4: CO2 Solvent Recovery Column Unit 5: Light Ends Distillation Column Unit 6: Heavy Ends Distillation Column

Johnson Olayiwola, Theodora Udabor, Norakmar Mohd Said, Rouvin Lazar, Muzal Shahabudin, Mohamed Abou-Rayyah Report 0: Process Description

SUMMARY
The main objective of this report is to investigate and simulate the Vinyl Acetate Monomer (VAM) separation sections of the process plant. Furthermore, the units involved in the VAM separation process were identified and their operating conditions were obtained using ChemCAD. The plant is located in Hull, United Kingdom, commissioned by Bentham Chemicals Ltd. and manufactures 250,000 tonnes per year of vinyl acetate monomer, VAM (CH3COOCH=CH2 ) with a minimum purity of 99.95wt% from ethylene (C2H4), oxygen (O2), and acetic acid (C2H5OH). Based on (Luyben et. al., 2004), six units were used in the separation process. An acetic acid scrubber, an acetic acid recovery distillation column, a CO2 removal absorption column, a solvent recovery stripping column, a light end distillation column to remove the light by-products and a heavy ends distillation column to remove the heavy by-products. Using ChemCAD, preliminary simulations were carried out and the operating conditions obtained were presented along with brief descriptions and sketches of the units. The resulting VAM product successfully meets the required demand as well as specification, as do the other by-products.

Johnson Olayiwola, Theodora Udabor, Norakmar Mohd Said, Rouvin Lazar, Muzal Shahabudin, Mohamed Abou-Rayyah Report 0: Process Description

TABLE OF CONTENTS

1. Overall Plant Flowsheet .......................................................................................... 0 2. Description of Chemical Process Plant .................................................................. 1 3. Description of Individual Units................................................................................. 3.1 Acetic Acid Scrubber ........................................................................................... 2 3.1.1 Description .................................................................................................... 2 3.1.2 Sketch/ Operating Conditions........................................................................ 3 3.2 Acetic Acid Recovery...4 3.2.1 Description .................................................................................................... 4 3.2.2 Sketch/ Operating Conditions........................................................................ 5 3.3 CO2 Removal Column ......................................................................................... 6 3.3.1 Description .................................................................................................... 6 3.3.2 Sketch/ Operating Conditions........................................................................ 7 3.4 CO2 Solvent Recovery Column ........................................................................... 8 3.4.1 Description .................................................................................................... 8 3.4.2 Sketch/Operating Conditions......................................................................... 9 3.5 Light Ends Distillation Column ......................................................................... 10 3.5.1 Description .................................................................................................. 10 3.5.2 Sketch/ Operating Conditions...................................................................... 11 3.6 Heavy Ends Distillation Column ....................................................................... 12 3.6.1 Description .................................................................................................. 12 3.6.2 Sketch/ Operating Conditions...................................................................... 13 4. Conclusion .............................................................................................................. 14 5. References ............................................................................................................... 15

Johnson Olayiwola, Theodora Udabor, Norakmar Mohd Said, Rouvin Lazar, Muzal Shahabudin, Mohamed Abou-Rayyah Report 0: Process Description

1. OVERALL PLANT FLOWSHEET

Johnson Olayiwola, Theodora Udabor, Norakmar Mohd Said, Rouvin Lazar, Muzal Shahabudin, Mohamed Abou-Rayyah Report 0: Process Description

2. DESCRIPTION OF CHEMICAL PROCESS PLANT

General Plant Information The plant is located in Hull, United Kingdom and is producing 250,000 tonnes per year of vinyl acetate monomer, VAM (CH3COOCH=CH2 ) with a minimum purity of 99.95wt% from ethylene (C2H4), oxygen (O2), and acetic acid (C2H5OH). The plant will operate for 8000 hours in a non-shutdown year. Major shutdowns for maintenance purposes will be of a duration of 20 days and are required once every 2 years. By-products produced are water (H2O), carbon dioxide (CO2), heavy ends (ethylene acetate, p-hydroquinone) and light ends (methyl acetate). The reaction is irreversible and exothermic. In this report, only the separation section of the process is considered.

Plant Flow Sheet Description The overall plant flowsheet was based on that of (Luyben et. al., 2004) but changes are made, such as adding a complete CO2 removal system with a solvent recovery column. In addition, the hetero-azeotropic distillation column and decanter will not be taken into consideration design-wise.
The reactor outlet is separated into vapour (ethylene, carbon dioxide,VAM) and liquid (vinyl acetate, water, acetic acid) products. The vapour stream (Stream 1) enters Unit 1 (Acetic acid

scrubber) where VAM are recovered from ethylene and CO2 using water and acetic acid as the solvent. The gas outlet containing ethylene and CO2 (Stream 3) from Unit 1 is then sent to Unit 3 (CO2 removal absorption column) where CO2 is removed from ethylene using Methyl Diethanolamine (MDEA) and water as the solvent (Stream 5). The ethylene gas outlet is then recycled back into the system (Stream 7). Recovery of the solvent was carried out by Unit 4 (stripper column) using steam to remove the carbon dioxide. The MDEA/Water solvent was then recycled back into Unit 3 in Stream 11. The reactor outlet liquid stream and the liquid outlet from Unit 1 enters the hetero-azeotropic distillation column. The distillate which contains the organic products goes into two additional distillation columns; light end distillation column (Unit 5) and heavy end distillation column (Unit 6). Unit 6 removes heavy by-products such as p-Hydroquinone, water and ethyl acetate from VAM as the bottoms product (Stream 17) and Unit 5 removes the light by-products (methyl acetate) as distillate (Stream 13) from VAM (Stream 14). The bottoms product of the azeotropic distillation column (Stream 18) is sent to Unit 2 (acetic acid recovery distillation column) and acetic acid is recycled back into the system as the distillate (Stream 19) while the heavy components are removed as the bottoms product (Stream 20).

Johnson Olayiwola, Theodora Udabor, Norakmar Mohd Said, Rouvin Lazar, Muzal Shahabudin, Mohamed Abou-Rayyah Report 0: Process Description

3. DESCRIPTION OF INDIVIDUAL UNITS 3.1 UNIT 1: ACETIC ACID SCRUBBER (OLAYIWOLA, JOHNSON)
3.1.1 Unit Description Vinyl Acetate produced in the reactor is first separated using a flash vessel. The gas outlet from the separator is fed into an absorption column which recovers Vinyl Acetate from the gas mixture of CO2 and Ethylene. This allows the specified yield of Vinyl Acetate to be achieved and prevents build-up of vinyl acetate in the process. The Acetic acid scrubber is based on a typical countercurrent absorption column where is liquid solvent, in this case wash acid (Stream 1), is used to recover a gaseous component from the gas phase. The gas outlet (Stream 3) from the column will then become vinyl acetate lean and will be further purified to remove CO2 using a carbon dioxide recovery column. The liquid outlet (Stream 4) which is lean in Vinyl Acetate is then purified to me the specifications using distillation columns downstream. There is mass transfer to the liquid phase as the absorbant is soluble in the absorbent (liquid solvent) and this continues until equilibrium is reached between the rate of mass transfer from the gas phase and the rate of mass transfer into the liquid phase. The column has 12 stages with the Wash acid entering the column at stage 1 and the inlet gas stream entering as stage 12. The unit operates at 8 bar and between 27.2 oC and 30.3 oC. After the separation 95% of VAM is recovered in the liquid outlet (stream 4) that goes into the distillation columns for further separation. 3.1.2 Unit Sketch and Operating Conditions

Figure 1: Unit 1 Diagram

Johnson Olayiwola, Theodora Udabor, Norakmar Mohd Said, Rouvin Lazar, Muzal Shahabudin, Mohamed Abou-Rayyah Report 0: Process Description
Table 1: Data of associated streams with Acetic Acid Scrubber

Stream No. Stream Name

Temp C Pres bar Enth MJ/h Vapor mole fraction Total kmol/h Total kg/h Total std L m3/h Total std V m3/h Flowrates in kg/h Water Acetic Acid Oxygen Carbon Dioxide Vinyl Acetate Ethylene

1 Wash Acid (Acetic Acid & Water) 35.00 8.00 -63002.00 0.00 154.03 7500.00 7.15 3452.43 750.00 6750.00 0.00 0.00 0.00 0.00

2 Gas Inlet Stream 21.26 8.00 161340.00 1.00 4243.16 125000.00 339.57 95104.70 0.00 0.00 0.00 2500.00 7500.00 115000.00

3 Gas Outlet Stream 30.25 8.00 175320.00 1.00 4198.79 119931.79 334.01 94110.18 186.74 1318.84 0.00 2476.47 952.96 114996.78

4 VAM-rich liquid outlet stream 24.72 8.00 -76986.00 0.00 198.41 12568.25 12.71 4446.98 563.26 5431.16 0.00 23.53 6547.04 3.26

Table 2: Acetic acid scrubber operating details

Parameter Operating Temperature Operating Pressure Solvent Solute Number of stages Packing Type Packing Diameter (mm) Diameter (m) Height (m)* Stream 1 Feed Stage (from top) Stream 2 Feed Stage (from top)

Value 27.2 oC - 30.3 oC 8 bar Wash Acid (Water & Acetic Acid, 1:9) Vinyl Acetate 12 Raschig Rings 70 1.7 8.3 1 12

*A HETP value of 0.9m was used for Raschig Rings of 50mm diameter (Richardson, J. F. et al, 2002)

Johnson Olayiwola, Theodora Udabor, Norakmar Mohd Said, Rouvin Lazar, Muzal Shahabudin, Mohamed Abou-Rayyah Report 0: Process Description

3.2 UNIT 2 : ACETIC ACID RECOVERY (UDABOR, THEODORA)

3.2.1 Unit Description The purpose of this column is to separate and recover acetic acid from other, more heavy components (i.e Water, Ethyl Acetate, Ethylidene diacetate and P-hydroquinone; other trace components being neglected). The acetic acid exits at the top of the column with a minimum composition of 96.5% in the distillate stream and it is then recycled and used as a solvent (along with water) in the acetic acid scrubber absorption column. The heavies (i.e Ethylene Acetate) are removed from the system. The acetic acid is used in order to produce VAM. Thus, a high purity is required and this recycling also helps reduce costs in the production. 3.2.2 Unit Sketch and Operating Conditions

Figure 2: Unit 2 Diagram

Johnson Olayiwola, Theodora Udabor, Norakmar Mohd Said, Rouvin Lazar, Muzal Shahabudin, Mohamed Abou-Rayyah Report 0: Process Description

Table 3: Data of streams associated with acetic acid recovery column

Stream Temperature C Pressure (bar) Vapour Fraction Total Flow Acetic Acid Water Ethyl Acetate p-Hydroquinone Ethylidene Diacetate

18 90.00 2.00 0.00 27000 0.90 0.079 0.0050 0.099 0.0050

19 129.72 2.00 0.00 511.19 390.83 118.84 1.519 0.00338 0.00046

20 150.90 2.00 0.00 17.61 14.18 0.090 0.00056 2.43 0.92

Table 4: Acetic acid recovery column operating conditions

Parameter Design Temperature (C) Design Pressure (Bar) Diameter (m) Height (m) Number of stages Tray Type Tray Spacing Feed Stage (from top) Reflux ratio Condenser Duty (MJ/h) Reboiler Duty (MJ/h)

Value 90 2 1.98 14.93 18 Sieve Tray 0.6096 13 1.3 -17139.6 20001.3

Johnson Olayiwola, Theodora Udabor, Norakmar Mohd Said, Rouvin Lazar, Muzal Shahabudin, Mohamed Abou-Rayyah Report 0: Process Description

3.3 UNIT 3 : CO2 REMOVAL COLUMN (MOHD SAID, NORAKMAR)

3.3.1 Unit Description The purpose of this absorber unit is to remove carbon dioxide from the recycle gas stream containing ethylene to reduce the CO2 build-up circulating in the system. The presence of CO2 in the recycle gas stream into the reactor will also reduce the conversion rate and thus production of VAM. The removal will also ensure a lower throughput of materials which can improve the subsequent unit design. 30% Methyl diethanolamine (MDEA) and 70% water are used as the solvent (Alie, C.F., 2004) to remove the CO2 via absorption. Due to the corrosive nature of MDEA, this column will utilize Raschig Rings as packing. 3.3.2 Unit Sketch and Operating Conditions

Figure 3: Unit 3 Diagram

Johnson Olayiwola, Theodora Udabor, Norakmar Mohd Said, Rouvin Lazar, Muzal Shahabudin, Mohamed Abou-Rayyah Report 0: Process Description

Table 5:Data of streams associated with CO2 removal column

Stream No. Mass Flowrate (kg/hr) Temperature (oC) Pressure (bar) Vapor Fraction Enthalpy (MJ/h) CO2 Ethylene Water MDEA

3 124000 130.0 1 1 223030

5 25000 25 1 0 -307350

6 380677 96.7 1 0 -4449100

7 153634 70.2 1 1 -192930

8 351042 47.8 1 0 -4041000

11 355677 101.7 1 0 -414180

0.020 0.980 0.000 0.000

Component Mass Fraction 0.000 0.000 0.000 0.000 0.000 0.791 0.700 0.671 0.209 0.300 0.329 0.000

0.007 0.000 0.636 0.357

0.000 0.000 0.669 0.331

Table 6: CO2 removal column operating conditions

Parameter Number of Stages Column Pressure (bar) Design Pressure (bar) Packing Type Packing Diameter (mm) Diameter (m) Height (m)* Stream 6 Feed Stage Stream 3 Feed Stage

Value 4 1 1.1 Ceramic Raschig Rings 50 2.4 3.6 1 4

*A HETP value of 0.9m was used for Raschig Rings of 50mm diameter (Richardson, J. F. et al, 2002)

Johnson Olayiwola, Theodora Udabor, Norakmar Mohd Said, Rouvin Lazar, Muzal Shahabudin, Mohamed Abou-Rayyah Report 0: Process Description

3.4 UNIT 4: CO2 SOLVENT RECOVERY COLUMN (LAZAR, ROUVIN)

3.4.1 Unit Description The purpose of this absorption unit is to recover the methyl diethanolamine (MDEA) solvent used in the previous absorption column (Unit 3) in order to recycle it back into that column so as to essentially prevent wastage and reduce costs and to also ensure that the CO2 removed in the previous column meets the required specification. Steam has been chosen as a suitable solvent (Stewart and Lanning, 1994) to remove the MDEA via absorption. The amount of steam used in the inlet stream (Stream 9), as shown in Table 7, was determined by utilizing the Steam Rate Rule of 0.12 kg of Steam for every 1 litre of MDEA (Kohl and Nielsen, 1997). Due to the corrosive nature of MDEA, this column will utilize Raschig Rings as packing. In addition to that, a purge of 6% of the MDEA/Water recycle has been utilized in order to prevent any build-up of the solvent. 3.4.2 Unit Sketch and Operating Conditions

Figure 4: Unit 4 Diagram

Johnson Olayiwola, Theodora Udabor, Norakmar Mohd Said, Rouvin Lazar, Muzal Shahabudin, Mohamed Abou-Rayyah Report 0: Process Description
Table 7:Data of streams associated with solvent recovery column

Stream No. Mass Flowrate (kg/hr) Temperature (oC) Pressure (bar) Vapor Fraction Enthalpy (MJ/h) CO2 Ethylene Water MDEA

8 351042 47.8 1 0 -4041000 0.007 0.000 0.636 0.357

9 37875 150.0

10 10588 98.3

11 355676 101.7

21 378330 101.7 1 0 -4412600 0.000 0.000 0.669 0.331

22 22703 101.7 1 0 -264370 0.000 0.000 0.669 0.331

4 1 1 1 1 0 -501090 -129490 -414180 Component Mass Fraction 0.000 0.234 0.000 0.000 0.002 0.000 1.000 0.763 0.669 0.000 0.001 0.331

Table 8: Solvent recovery column operating conditions

Parameter Number of Stages Column Pressure (bar) Design Pressure (bar) Packing Type Packing Diameter (mm) Diameter (m) Height (m)* Stream 8 Feed Stage (from top) Stream 9 Feed Stage (from top)

Value 3 1 1.1 Ceramic Raschig Rings 50 1.37 2.7 1 3

*A HETP value of 0.9m was used for Raschig Rings of 50mm diameter (Richardson, J. F. et al, 2002)

Johnson Olayiwola, Theodora Udabor, Norakmar Mohd Said, Rouvin Lazar, Muzal Shahabudin, Mohamed Abou-Rayyah Report 0: Process Description

3.5 UNIT 5: LIGHT ENDS DISTILLATION COLUMN (SHAHABUDIN, MUZAL)

3.5.1 Unit Description The purpose of this unit is to eliminate the light ends impurities, which mainly consist of acetaldehyde and methyl acetate from the mixture of VAM and water. From the feed stream, the concentration of acetaldehyde and methyl acetate are 6% and 0.5% respectively. This unit will reduce the concentration of these components; the aim is to get most of the VAM as the bottom product with significantly low light ends concentrations. The components were separated into the top product, which mainly consists of acetaldehyde and methyl acetate and the bottom product, which consists of VAM and water. Initially, a shortcut column used in order to obtain the number of stages and feed stage before swapping the unit with an SCDS column for more accurate results. Then, the final product is reported after a balanced judgment between energy cost, capital cost, maintenance cost and higher purified VAM yields.

3.5.2 Unit Sketch and Operating Conditions A schematic diagram representing the column is shown below.

Figure 5: Unit 5 Diagram

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Johnson Olayiwola, Theodora Udabor, Norakmar Mohd Said, Rouvin Lazar, Muzal Shahabudin, Mohamed Abou-Rayyah Report 0: Process Description

Table 9: Data of streams associated with Light Ends column

Stream Temperature Pressure(bar) Vapour Fraction Total mass flowrate (kg/h) Mass Fraction Vinyl Acetate Water Acetalhyde Methyl Acetate

12 50.0 1.15 0 1000

13 47.0 1.15 0 307

14 79.0 1.15 0 693

0.915 0.020 0.060 0.005

0.780 0.00013 0.195 0.016

0.970 0.029 0.000 0.00005

Table 10: Operating conditions for the Light Ends Column

Parameters Number of stages Feed stage (from the top) Column Operating pressure Reflux ratio Condenser Duty (MJ/h) Reboiler Duty (MJ/h) Diameter (m) Height (m)

Value 20 5 1.15 bar 7.0 -1087.46 1130.13 0.6096 12.4

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Johnson Olayiwola, Theodora Udabor, Norakmar Mohd Said, Rouvin Lazar, Muzal Shahabudin, Mohamed Abou-Rayyah Report 0: Process Description

3.6 UNIT 6 : HEAVY ENDS DISTILLATION COLUMN (ABOU-RAYYAH, MOHAMED)

3.6.1 Unit Description
The last stage in the purification process of VAM is the heavy ends distillation column, which follows the light ends column. The purpose of this unit is to ensure the final pure product (VAM) is produced at a production rate of 250,000 tonnes/year and also meets the required specification, which is displayed in Table 11. The feed coming into this column contains VAM and the heavies: p-hydroquinone, water and ethyl acetate. This unit was modelled as an SCDS column in the ChemCAD simulation in order to accurately obtain the given specification at optimal conditions. The column was chosen with sieve tray internals due to the range of volumetric flowrates used in this column.
Table 11: Final product specifications of distillate stream (Stream 16)

Component Vinyl Acetate Water Ethyl acetate

Weight (%) 99.95 0.01 0.025

3.6.2 Unit Sketch and Design/Operating Conditions

.

Figure 6: Unit 6 Diagram

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Johnson Olayiwola, Theodora Udabor, Norakmar Mohd Said, Rouvin Lazar, Muzal Shahabudin, Mohamed Abou-Rayyah Report 0: Process Description
Table 12: Streams associated with Heavy Ends column data

Stream No. 15 Mass Flowrate (kg/hr) 33000 Temperature (oC) 145.1 Pressure (bar) 1.15 Enthalpy (Mj/h) -115200 Vapour mole fraction 1 Component Mass Fraction (%) Vinyl Acetate 0.993 P-Hydroquinone 0.0060 Water 0.0005 Ethyl Acetate 0.0005

16 31469 78.5 1.15 -50000 0.4 0.99975 0.00000 0.00000 0.00025

17 1531 78.9 1.15 -78500 0.000035 0.9885 0.0100 0.0083 0.0066

Table 13: Heavy ends distillation column operating conditions

Parameter Number of trays Feed tray (from top) Column Pressure (bar) Temperature of top product (oC) Temperature of bottom product (oC) Reboiler Duty (MJ/hr) Condenser Duty (MJ/hr) Reflux Ratio Tray spacing (m) Diameter (m) Height (m)

Value 18 16 1.15 68.2 152 8016 -23400 3.84 0.610 2.438 15.856

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Johnson Olayiwola, Theodora Udabor, Norakmar Mohd Said, Rouvin Lazar, Muzal Shahabudin, Mohamed Abou-Rayyah Report 0: Process Description

4. CONCLUSION
In conclusion, by using the ChemCAD simulation we have successfully simulated our distillation and absorption units to produce VAM and the other by-products that meet the required demand and specifications: 1. 251752 tonnes of VAM/year 250000 tonnes/year (Assuming the plant operates at an 8000 hours per year)
Table 14: VAM Product Specifications Met (Stream 16)

2.

Component VAM Water Ethyl acetate

Weight (%) 99.98 99.95 0 0.01 0.025 0.025

Lastly, it should also be noted that the operating conditions and internals of the units in this report are preliminary and, as such, are subject to change should there be infeasibility issues or other unforeseen difficulties that are possibly encountered as we progress to the more advanced stages of Unit Operation Modeling by using the gPROMS modeling software. However, having based our ChemCAD simulation on industrial practices (e.g. the Steam Rate Rule for Unit 4), we are confident that we have laid a steady foundation for our work in the future.

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Johnson Olayiwola, Theodora Udabor, Norakmar Mohd Said, Rouvin Lazar, Muzal Shahabudin, Mohamed Abou-Rayyah Report 0: Process Description

5. REFERENCES
1. Luyben, M. L., Tyreus, B. and Luyben, W.L., Plantwide control design procedure, AlChe. J., 43(12), pp. 3161- 3174. 2. Alie, C.F., CO2 Capture With MEA: Integrating the Absorption Process and Steam Cycle of an Existing Coal-Fired Power Plant, 2004, pp. 46. 3. Stewart, E. J. and Lanning, R.A., Reduce Amine Plant Solvent Losses, Part 2, Hydrocarbon Processing, June 1994, pp.189. 4. Kohl, A.L. and Nielsen, R.B., Gas Purification, 5th Ed., Gulf Publishing, Houston, Texas, 1997,pp.150. 5. Richardson, J.F.; Harker, J.H.; Backhurst, J.R. (2002). Coulson and Richardson's Chemical Engineering Volume 2 - Particle Technology and Separation Processes (5th Edition), Elsevier,2002, pp. 640.

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