‘Turton Appe_Partignd 5/11/12 82 12:21 a Page 82 [Appendix B Information forthe Preliminary Design of Fifteen Chemical Processes Table 8.3.3 Major Equipment Summary for Unit 400 (Continued) Pumps Poot AB 08 AB, Centrifugal electric drive (Centrifugal electric drive Stainless stect Carbon steel W=2.50 KW (actual) W=0.775 kW (actual) 80% efficient 80% efficient 02 A/B 405 A/B (Centrifugal /electic drive ‘Centrifugal electric drive Carbon ste! Carbon steel W= 1.33 KW (actual) W = 0825 KW (actual) 80% efficient ‘0% efficient 403 A/B 406 A/B (Centrifugal /electic drive (Centrifugal electric drive Carbon ste! Carbon stee! W= 03574 KW (actual) 0% efficient Reactors R401 R402 316 stainless steel, packed bed (Cylindrical catalyst pellet (1.6 mm 32:mm) Void fraction = 04 V225m° 9.26 m tall, 1.85 m diameter 316 stainless steel, packed bed Cylindvcal catalyst pellet (15 mm x 32.mm) V=25m 9.26 m tll, 1.85 m dlameter Towers T401 402 Carbon stee! Carban ste D=30m D=69m 61 sieve trays 158 bubble cap trays 54% efficient 55% efficient Feed on tray 31 Feed! on tay 78 Din tray spacing bin tray spacing sin weirs in weire Column height Coluian height =79 Vessels vant vv-s0s Carbon stl Horizontal Va268m° Carbon steel uD =3 Vas va02 Horizontal Carbon ste! UD=3 V=Sm +See Figure B3.1 and Table B31 for shell-aneltubeside pressures.Turton Apps Partl.gud $/11/12 12H ‘Appendix 8 Information forthe Preliminary Design of Fifteen Chemical Processes 33 The equilibrium calculation is given as CPCs CHSCaHy + Hy t oO i total =N'+1-+1 includes N moles of inert steam xP @-nw+iH a where Pis in bar. Equation (8.3.5) can be used to generate data for equilibrium conversion, x, versus P,T and N. ‘The kinetic equations are adapted from Snyder and Subramaniam [3]. Subscripts on 1 refer to reactions in Equations (B3.1)-(B.3.3), and the positive activation energy can arise from nonelementary kinetics its thought that perhaps these kinetics are an elemen- tary approximation to nonelementary kinetics. ry = 10177 10" exp —8) 36 70 13 2096 ef oan 7208 %:0" ro - 2) wos rea 1708 x 10h exp — 7” pa Pe 39) ‘where pis in bar, Tis in K, R = 1.987 cal/mol K, and r, is in mol/m-reactors, You should assume that the catalyst has a bulk density of 1282 kg/m’, an effective diameter of 25 mm, and a void fraction = 04. 8.3.3 Simulation (CHEMCAD) Hints Results for the simulation given here were obtained using SRK as the K-value and en- thalpy options in the thermodynamics package. B.3.4 References 1. Shiow-Shan Chen, “Styrene,” Kirk-Othmer Encyclopedia of Chemical Technology, online version (New York: John Wiley and Sons, 2006) 2. “Styrene,” Encyclopedia of Chemical Processing and Design, Vol. 55, ed. J.J. MeKetta, (New York: Marcel Dekker, 1984), 197-217. 3. Snyder, J. D, and B. Subramaniam, “A Novel Reverse Flow Strategy for Ethyl- benzene Dehydrogenation in a Packed-Bed Reactor,” Chem. Engr. Sci 49 (1994): 5585-5601ton_AppB_Parti.gyd $/21/12 12:21 AM Pas ‘Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 5 Table B.2.3 Major Equipment Summary for Unit 300 (Continued) Vessels v301 v-303 Carbon steet Carbon steet Horizontal Horizontal L/D=s L/D=3 Ve7m! Va77m Maximum operating pressure =250 KPa “Maximum operating pressure = 300 kPa v.302 v.s04 Carbon stel with 5S demister Carbon ste! Vertical Horizontal L/D=3 L/D=3 V=10m Ve62m ‘Maximum operating pressure = 250 kPa ‘Maximum operating pressure = 300 kPa 8.2.3. Simulation (CHEMCAD) Hints A. CHEMCAD simulation is the basis for the design. The thermodynamics models used were K-val = UNIFAC and Enthalpy = Latent Heat. It should be noted that in the simulation a component separator was placed after the high-pressure flash drum (V-302) in order to remove noncondensables from Stream 16 prior to entering T-301. This is done in order to avoid problems in simulating this tower. In practice, the noncondensables would be removed from the overhead reflux drum, V-308, after entering T-30L As a first approach, both towers were simulated as Shortcut columns in the main simulation, but subsequently each was simulated separately using the rigorous TOWER module. Once the rigorous TOWER simulations were completed, they were substituted. back into the main flowsheet and the simulation was run again to converge. A similar ap- proach is recommended. The rigorous TOWER module provides accurate design and simulation data and should be used to assess column operation, but using the shortcut simulations in the initial trials speeds up overall conversion of the flowsheet.. B.2.4 References 1, William J. Cannella, “Xylenes and Ethylbenzene,” Kirk-Othmer Encyclopedia of Chemi- cal Technology, online version (New York: John Wiley and Sons, 2006). 2. “Bthylbenzene,” Encyclopedia of Chemical Processing and Design, Vol. 20, ed. J. J MeKetta (New York: Marcel Dekker, 1984), 77-88, STYRENE PRODUCTION, UNIT 400 Styrene is the monomer used to make polystyrene, which has a multitude of uses, the ‘most common of which are in packaging and insulated Styrofoam beverage cups. Styrene . is produced by the dehydrogenation of ethylbenzene. Ethylbenzene is formed by reacting ethylene and benzene. There is very litle ethylbenzene sold commercially, because most ethylbenzene manufacturers convert it directly into styrene.‘Turton AppB_Partiged 5/11/12 12:21 aM Page 76 76 ‘Appendix B Information forthe Preliminary Design of Fifteen Chemical Processes B.3.1 Process Description [1, 2] ‘The process flow diagram is shown in Figure B3.1. Ethylbenzene feed is mixed with re- cycled ethylbenzene, heated, and then mixed with high-temperature, superheated steam. Steam is an inert in the reaction, which drives the equilibrium shown in Equation (B3.1) to the right by reducing the concentrations of all components. Because styrene formation is highly endothermic, the superheated steam also provides energy to drive the reaction. Decomposition of etinyllbenzene to benzene and ethylene, and hydrodealky- lation to give methane and toluene, are unwanted side reactions shown in Equations (8.3.2) and (B.333). The reactants then enter two adiabatic packed beds with interheating, ‘The products are cooled, producing steam from the high-temperature reactor effluent. ‘The cooled product stream is sent to a three-phase separator, in which light gases (hy- drogen, methane, ethylene), organic liquid, and water exit in separate streams. The hy- drogen stream is further purified as a source of hydrogen elsewhere in the plant. The benzene /toluene stream is currently returned as a feed stream to the petrochemical facil- ity. The organic stream containing the desired product is distilled once to remove the benzene and toluene and distilled again to separate unreacted ethylbenzene for recycle from the styrene product. CoHiCHs 9 CoHsCoH + Hy (631) there styrene —yrogen CoHHsCaHls > CiHg + CoH, (632) cuensene zene eliglne CoHsCaHy + Hy 4 CyHSCH, + CH, (633) titre hydrogen tolene mutha ‘The styrene product can spontaneously polymerize at higher temperatures. Because product styrene is sent directly to the polymerization unit, experience suggests that as long.as its temperature is maintained at less than 125°C, there is no spontaneous polymer- ization problem. Because this is less than styrene’s normal boiling point, and because low pressure pushes the equilibrium in Equation (B:3.1) to the right, much of this process is, run at vacuum. Stream tables, utility summaries, and major equipment summaries are given in Tables B3.1,B32, and B33, respectively B.3.2 Reaction Kinetics The styrene reaction may be equilibrium limited, and the equilibrium constant is given as Equation (B34). x= (tagne?) (e34) Ink = 15.5408 — where Tis in K and P is in bar.5/14/12 10:20 rage 77 orton Appl_Partl gud weiferg Moly sso00%g suaHKis oor TEE anblE oun dung dung dung ao so sre peed aptoos ont “en “peed ea Word BWSDRS O¥HORS GW etd ard s0r3 Von weg ang severeses vo twumeo rug dura "Smid 0) 29009 IEE sIPEEH sssuopuon smoqoy Sule nals estapueD iyegay cuonleg ey JessaduoD anit Bald Embed Prod sues RAN ‘sors “tors “cord ainakeard Ora Gra IPL @eIOrG 10RD. 0rASOra MOPS. GUS ZORA LON b— nTurton ApeB Parte’ 5/11/12 12:21 aM Page 78 78 ‘Appendix B Information forthe Preliminary Design of Fifteen Chemical Processes Table B.3.1_ Stream Tables for Unit 400 Stream Number i 2 3 a 5 Temperature °C) 1606S OSC Pressure (kPa) 200 momo aatz apc mole fraction a0 000m). Totalflow (kg/h) 130522239651 239651723597 Total flow (kl/hy —-12342—~=«224621-—=«BHDL_—«4OL630—— 01630 Component Flowrate kmoU/h) Water 00 0m ago 401630401630 Etylbenzene mm 23723730 Styrene am 006-0500 Hydrogen a0 = 0000) Benzene 1 1ztat0m0 Toluene 11a 0m a Ethylene a = 000mm Methane ao 000 00mm Stream Number 6 7 @ 9 10 | Temperature 0) 70 Soe UMS soi | | Pressure (kPa) 170.0 160.0 150.0 135.0 125.0 | apoe mole fraction 10 000100 it. | | romtnow (kg/h) 540450 780102 70102 700279102 | Towa ow (km/h) 300000322421 331728381728 Maa | Component Flowrates (kmoW/h) | | Water 0000 200000 © 3umn00 © sam000 smnan | Eylbenzene oo 223732381235 mR8 | styrene 00 005.9106. 9106 aan | Hydrogen 0.00 000 ©9069 906811938, Senaere oo aa Tolvene co =a Ethylene 00 = 0a? are Methane 000 0m) ast ost as (continued)ucton Appa _Partl.ged 5/11/12 12:21 a4 page 78 ‘Appendix B Information forthe Preliminary Design of Fifteen Chemical Processes Table B.3.1 Stream Tables for Unit 400 (Continued) Stream Number ase 8 “i Temperature (O) wo mo ”*~«SSSCSSC Pressure (KP) 100-50 Ow] Vapor mole fraction 100 = 100100 Toualflow (kg/h) 780102790102 T8026 SLISO Totafow (kmol/h) «3641336212020 300000 ‘Component Fowrates kmoV) Water 20000 300000 5000000030000 Eylberzene oss 1mzs8 102880] siyrne 12009 1007120090000 Hydrogen m938 3811938938000 Benzene 137177 ono | Totuene 18 1186 om] Eihylene ox = 0s. asta Methane oss 0880s asa ‘Stream Number 16 a7 18 19 20 | Temperature CO) So 9D S~SC | | Pressure Ps) eo 80 8080 | Vapor mole fraction 00 = 0mm, Tonlfow hgh) 237086 2595 234000999 Tas0TA Totaflow kmol/h) «206213810279 2008 | ‘Component Flowrates (kmol/h) | | Water Oe ee ee | Ethylbenzene 102.88 010 1027810273 0s | | Styrene 12008 0.00 12009 00 = 12003, | Hydrogen ce = 0mm mo | | Benzene 1713700 0m) a0 | Telune 186 186 ao 00 ano | iylene 00 = 0mm Methane co 0m 000 amo | [ Stream Number ee 23 mes | Temperature (°C) 138 65.0 022 910 9000 | | Pressure (kPa), 200.0 200.0 1400 200.0 4202.0 Vapor moe fraction ee | Total flow (kg/h) 12,507.1 54,0850 6 10.9129 18,3087 | Toial flv (kmol/h) 2908 3000.00 12020 102791016230Turton AppBParti.gid 5/11/22 12:21 AM Page 80 80 ‘Appendix 8 Information forthe Preliminary Design of Fifteen Chemical Processes Table B.3.1 Stream Tables for Unit 400 (Continued) Component Fowrates mol) Water oa 300000 000» om 0160 | Etnybenzene os = 0m om aso Styrene 12003000006) Hidrogen om 0m) 1938 0m). Benzene er Toluene om = 000 ©0000 | Ethylene om = 000 0x6. Methane om 0m 06s oma | [_Mehere 8c Stream Number 26 | Temperature °C) 700 Pressure (kPa) 20000 | Vapor mole fection 00 | Total fw hg) 205 Total ove fmol’ 34 ‘Component Flowrates (kmoV/h) | Water 0.00 | Eylenzone x0 | styrene 00 | Hytogen 00 Bente 197 | ‘Toluene 1.86 | Eylene 0 | Methane 00 | Table 8.3.2 _Utility Summary for Unit 400 [e401 £403 E406 E405 Uap biwohpsbiwlps ow | rosa kg/h 18ASTKg/—_SBSg/h 3.209.746 kg/h F406 £407 £408 £409 ow ps ow Ips BOOSITAg/h —_7SDAg/h 1105980 kg/h__21811 AgTurton Appe_Parti.ged 5/11/12 12:21 a4 Page 61 ‘Appendix B Information forthe Preliminary Design of Fifteen Chemical Processes Table B.3.3 Major Equipment Summary for Unit 400 || Compressors and Drives cot D401 AB Carbon steel Electric explosion proof We 13SkW W= 1367 kW 40% adiabatic efficiency 88% efficiency Heat Exchangen E01 06 Carbon steel Carbon ste! A= 260 me Azim Boling in shell condensing in tubes Process fluid in shel, cooling water in tubes 1 shell—2 tube passes 1 shell—2 tube passes Q=13550.Mi/h Q= 12951 Mh E102 E07 316 stainless steel Carbon seul A=26 mF A=6hn Boiling in shell, process fluid in tubes Steam in shel steam condensing in tubes 1 sholl—2 tube pases Desuperheater—steam saturated at 150°C 2822 MI/n 1 shell—2 tube passes E403 = 15782 Mn S16 stainless sto! 408 A= 157 me Carbon stect, Boing in shell, process din tubes Aa38h ne | 1 shell™2 tube pases Proces fui in shel cooling water inwubes | (244595 MI/h 1 Shll—2 tube passes Eo 6274678 Carbon steel E409 A702 me Carbon see! Boling in shel, process fu in tubes A= Wem 1 shell—2 tube passes Boling in shell, steam condensing in tubes | o=13.260ah7h Desuperheaterstesm saturated at 150°C | eos 1 sell—2 tube passes 316 stainless ste! = 45876 MI/h A= dem ow in shel, process id in tubes ‘shell? tube passes Q= 136600 Ma Fired Heater Hao. Fred heater refractory lined, stainles-stecl tubes Design Q=2363 MW Maximum Q= 2500 MW