CN4121 Design Project Part II Interim Report

Team: 31 Group Members: Wan Chunfeng (Leader) Zhao Danqing Liu Qi Zhang Xibin Liu Shi Wang Yang Zheng Lu U083742L U083745W U083734M U083748E U083739W U083737X U083740M Fired Heater Ethylbenzene Reactor Diethylbenzene Reactor Benzene Column Ethylbenzene Purification Heat Exchangers & Flash Cooling Tower

Date of Submission: 16th February 2012

Project Overview In this project, an ethylbenzene (EB) plant using vapour phase alkylation of benzene and ethylene is designed. The process designed is benchmarked to the Mobil-Badger process except that AB-97 catalyst is used instead of ZSM-5 in the alkylation reactor and the operating conditions are changed accordingly. A detailed process flow diagram is attached in appendix A. Fresh benzene feed and recycled benzene from the benzene column are pressurized and vaporized before mixed with fresh ethylene feed. The feed mixture is sent to a three-stage-fixed-bed alkylation reactor with fresh ethylene quenching at every bed. The diethylbenzene (DEB) reactor takes in DEB from the EB column. The products of these two reactors are mixed and cooled. The mixture goes through a flash drum to remove ethane and unreacted ethylene before sent to the benzene column. Excessive benzene is collected as the top product and recycled in the benzene column. The bottom product is fed to EB column where EB is separated as the top product and further purified. The bottom product from EB column, the major component of which is DEB, is mixed with benzene and sent to the DEB reactor. Project Objectives The primary goal of this project is to design a plant that has an annual production capacity of 350,000 tonne EB with a purity of 98.5%. Profitability of the plant can be optimized by improving the efficiency of the raw material usage and energy utilization. The plant designed should also have the flexibility to tolerate variabilities in the feed compositions, product specifications and operating conditions. Another focus of this project is to select and size the major process equipment in order to maximize the productivity and minimize the installation and operating costs of the plant. With sustainability in mind, our design will also focus on minimizing the impact of this plant on the environment. Process Design Fired Heater: The fuel used in the fired heater is natural gas together with the off-gas from the flash. Air is preheated by the flue gas from the fired heater. The temperature of the cold flue gas is controlled to avoid dew point corrosion. A vertical cylinder fired heater with cross flow convection is chosen in this process. Benzene mixture and recycled DEB are pressurized to the reaction pressure and then sent to the fired heater. The fired heater is designed to fully vaporize the liquid feeds before they are sent to the vapour phase reactors. Ethylbenzene Reactor: Ethylene and benzene feeds are heated to 673K and 1000 kPa. The B/E ratio is maintained around 8 to ensure a high conversion of ethylene and to increase the total heat capacity of the reactants. As the reaction is exothermic, cold ethylene is used to quench the reaction at every stage in order to achieve a high conversion. The kinetics chosen is based on AB-97. This catalyst is found to be inactive to the ethane and toluene present in the feed stream. Therefore, both impurities are treated as inert in the current design. The designed reactor yields 97% ethylene conversion and an EB selectivity of 12.58 over DEB. Diethylbenzene reactor: DEB vapour and benzene vapour are mixed and fed to the DEB reactor. The molar ratio of benzene and DEB is kept around 6 to maintain a high DEB conversion. The reaction kinetics has been chosen based on ZSM-5 zeolite catalyst. A fixed

bed reactor, operated at 673K and 1000 kPa, is used in the current process and gives a 95% conversion of DEB. Heat Exchanger: Heat exchanging units are utilized to cool the hot products from the EB reactor and DEB reactor from 750K to approximately 350K and decrease their pressures to atmospheric pressure. Heat recovered from the hot products can be used to generate high pressure steam, which can be subsequently used in the reboilers. Alternatively, the heat recovered can be used to preheat the feed streams. Flash: The flash drum is designed to remove the majority of the ethylene and ethane in the product stream while to minimize the benzene loss. Currently a 3-stage fractionation column is used with the overhead condenser temperature above 310K. Therefore, cooling water can be utilized as the cooling agent in the condenser. The column has a benzene loss of 7-10 kgmole/hr, depending on separation pressure and temperature. Benzene Column: The benzene column takes feed from the flash drum. Most of the light components, namely unreacted ethylene and inert ethane, are removed in the flash drum. Therefore, benzene and EB can be regarded as the key components. 99.85% of the unreacted benzene is separated from the EB products and recycled; and more than 99.53% of the EB products are present in the bottom stream, which is to be further purified in the EB column. Currently a 15-stage distillation column is designed with the feed at the 4th stage, operating at 340K and atmospheric pressure. Ethylbenzene Purification: The bottom stream of the benzene column is sent to the EB column. The feed contains 84.03% EB with the balance being benzene, toluene and DEB. The key components in the EB column are EB and DEB. The EB column designed is able to achieve a 99.98% recovery of the EB product, which then goes through a 2 stage column to remove excessive toluene. More than 99.27% of the DEB product is recovered in the bottom stream and recycled to the DEB reactor. The current design of the EB column is a 15-stage distillation column with the feed at the 7th stage, operating at 414K and atmospheric pressure. Cooling Tower: Hot water at 318K from heat exchangers and condensers are to be cooled to 303K in the cooling tower. Water flow rate is roughly 2.562105 kgmole/hr based on energy balance. Wet-Mechanical draft-induced draft is chosen and a counter-flow flow pattern is used in the cooling tower. Mechanical draft has much larger capacity compared to natural draft. Induced draft gives a more stable performance than the forced draft. Counter-flow heat exchange is known to be more efficient than the cross-flow heat exchange Future Works In the future, our group will continue to optimize the operating conditions of all the process units to achieve optimal energy and raw material utilization efficiency. Designs of the process units, selection and sizing of the process equipment will be studied in detail in future works. Along the way, we will continuously review the novel and alternative technologies. More importantly, we will also discuss safety, health and environmental considerations in the design. Toward the end of this project, we will perform a thorough economic and profitability analysis of this plant design.

Appendix A: Process Flow Diagram

Fired Heater

EB Reactor

DEB Reactor

Heat Exchanger

Flash

Benzene Column

EB Column

EB Purification

Appendix B: Stream Table

Stream Number Vapour Fraction Temperature (C) Pressure (Kpa) Molar Flow (Kmol/hr) Mass Flow (Kg/hr) Flowrate in Kmol/hr Ethylene Ethane Benzene Toluene EB DEB Stream Number Vapour Fraction Temperature (C) Pressure (Kpa) Molar Flow (Kmol/hr) Mass Flow (Kg/hr) Flowrate in Kmol/hr Ethylene Ethane Benzene Toluene EB DEB

1 1 25 2000 497.5 14030 462.67 34.82 0.00 0.00 0.00 0.00 9 1 31.85 110 54.52 2050 10.61 34.92 8.99 0.00 0.00 0.00

2 0 25 110 450 35280 0.00 0.00 0.98 0.02 0.00 0.00 10 0 67.09 110 3838 314800 4.02 17.79 3294.83 9.82 453.18 57.86

3 1 400 1000 3410 265600 3.69 16.10 3379.84 8.84 1.94 0.00 11 0 60.17 110 3314 257900 4.02 17.79 3289.60 0.83 2.13 0.00

4 1 451.3 542.3 3456 279600 14.22 50.92 2959.27 8.84 390.95 31.57 12 0 140.5 110 523.1 56890 0.00 0.00 5.23 9.00 451.05 57.85

5 1 397.3 1000 436.3 37200 0.41 1.79 375.54 0.98 0.27 57.27 13 0 137.1 110 465.8 49190 0.00 0.00 5.23 9.00 450.99 0.55

6 1 397.7 1000 436.3 37200 0.41 1.79 344.56 0.98 62.23 26.29 14 0 187.1 110 57.36 7698 0.00 0.00 0.00 0.00 0.06 57.30

7 1 444.7 542.3 3892 316800 14.63 52.71 3303.83 9.83 453.18 57.86 15 0 128.3 110 52.88 5444 0.00 0.00 4.37 3.41 45.10 0.00

8 0.0079 70 180 3892 316800 14.63 52.71 3303.83 9.83 453.18 57.86 16 0 138.4 110 412.9 43750 0.00 0.00 0.00 0.01 0.99 0.00

Appendix C: References

1. Ali, N.E., Ashkan, Z.S., Seyyed, A.M., Faeze, A., Ahmad, S., Modification and Optimization of Benzene Alkylation Process for production of Ethylbenzen, Chemical Engineering and Processing 50 (2011) 3136. 2. Dimian, A.C., Baldea, C.S., Chemical Process Design: Computer-Aided Case Studies, Wiley-VCH, 2008. Chapter 15. 3. Ganji, H., Ahari, J.S., Farshi A., Kavavand M., Modeling and Simulation of Benzene Alkylation Process Reactors for Production of Ethylbenzene, Petroleum & Coal, 46 (1), 55-63, 2004 4. Hensley, J.C., Cooling Tower Fundamentals, Overland Park, Kansas USA: SPX Cooling Technologies, Inc., 2006. 5. Luyben, W., Design and Control of the Ethyl Benzene Process, AICHE J., March 2011, Vol.57, No.3. 6. Satendra, D., Shyam, G., Fired Heater in Chemical Process Industriess, CPEC News, 2000. 7. Seider, W.D., Seader, J.D. Lewin, D.R., Widagdo, S., Product & Process Design Principles, Wiley, 3rd Edition, 2010 8. Turton, R., Bailie, R.C., Whiting, W.B., Shaeiwitz, J.A., Analysis, Synthesis and Design of Chemical Process, Prentice Hall, 3rd Edition, 2009 9. You, H. Long, W., Pan, Y., The Mechanism and Kinetics for the Alkylation of Benzene with Ethylene, Petroleum Science and Technology, 24, 1079-1088, 2006. 10. Wankat, P.C., Separation Process Engineering, 2nd Edition, NJ: Prentice Hall, 2007. 11. Couper, J.R., Penny, W.R., Fair, J.R., Walas, S.M., Chemical Process Equipement: Selection and Design, 5th Edition, McGraw-Hill, New York, 2003.