11.8 Fixed bed reactor for styrene production (a) frtroduction Styrene is produced by catalytic dehydrogenation of ethylbenzene. The reaction is endo- thermic and reversible and takes piace with an increase in the number of moles. Con- sequently, the styrene conversion is favored by high temperatures, low pressures, and by dilution of the feed by means of an inert component, like benzene or more generally steam. The steam also serves as a heat cartier, reducing the temperature drop in adiabatic, operation. (b) Reactor The following data on the styrene reactor of the Polymer Corporation, Samia, Ontario, have been presented by Sheel and Crowe? Operating conditions Hydrocarbon flow: 4080 kg/h Sicam flow : 8160 keyh ‘Temperature of the superheated steam: Ty = 755°C Inlet temperature of the mixture: Ty = 650°C ‘Temperature at the reactor exit: 1, = 577°C Inlet pressure: 2.37 aim abs Reactor dimensions Diameter: 1.95 m Depth of catalyst bed: 1.61 m Additional data Catalyst equivalent diameter: d, = 0.005 m Void fraction of the bed: 2 = 0.455 Bulk density of the bed: pp = 1300 kg/m? (©) Kinetics Shee! and Crowe considered 10 reacting species. Six jinear independent stoichiometric equations are needed to describe the variation of the amounts of these species along the reactor. Reactions CoHs — CzHy St CyHy — CoH, + Ha C.Hs — CH; ——* C,H. + GH. CyHe — CyHy + Hy CoHy — CH, + CHy C,H. + HO co +3H, CH. +H,O ~—+ CO+3H, O'+H,0 —— CO,+H All reactions were assumed to be catalytic, Only the main reaction { was assumed to be reversible. The following rate expressions were proposed for the above reactions. eueeneTable 1 Rate equations and rave parameters Rate parameters . . mol Reaction Rate equation ! Tes E/RCK) 1 1.51286 10,925 2 5.6197 105 25,000 3 13446 11,000 4 9.3016 x 107! 12,500 5 15 = ksPwPou 6.3163 x 107? 7,900 6 16 = keoUT?)Pw Poo 1.6769 x 10° 8,850 p; fepresents the partial pressure of species i and p, is the total pressure. ‘The frequency factors and activation energies were determined by Sheel and Crowe from plant data. The equilibrium constant, K,, is taken to be 0.4 atm in the temperature range experienced in the reactor. (a) Reactor Model The reactor is assumed (o be adiabatic with plug flow. Axial dispersion can be ignored Any effect of limitations of mass or heat transfer inside the catalyst peilet is lumped into the rate constants given in Table 1, The catalyst activity is assumed to be constant. Use the conversion of ethylbenzene or water in the set of continuity equations. Use the Ergun equation to describe the pressure drop. (e) Physicochemical Data () Reaction Enthalpies These are fitted by means of linear equations (—AH;) = are given in Table 2 : + 5, T. The sets of (a;,b) Table 2 Coefficients in reaction en- thalpy equations i keal kcal Reaction 4) i ian — 28843 — 25992 12702 19602 50640 10802 Aanii) Heat Capacities These are calculated from Reid, Prausnitz, and Sherwood®. They are calculated in the form of quadratic functions of T. The coeficients are given in Table 3. + BT + CT? + DT? (kcal/kmol °K) Table 3 Cuetficients of the yuadratic equation ¢, = Species 4 B c D Mw LE 10.294 1,689 x 10°F = 1.149 x 10° 3.107 x 10 106.168 28 —6.747 ATL x 107! 9,609 x 107$ 2.373 x 10-8 104.151 38 8101 1.133 x 107) = 7.206 x 10°$ 1.703 x 10°F 78. 4 Tol ~5817 1.224 x 10°? 6.605 x 10°$ 1.173 x 10° 92.14I 5 CH, 0.909 3.780 x 107? 1.994 x 107 4.192 x 107? 28.054 6 CH. 4598 1.245 x 10 2860 x 10° 2.703 x 107% 16.043 7 HOW) 7.701 4.595 x 10S 2.521 x 10°F 0.859 x 107? 18.015 8 co 7373 0.307 x 10°? 6.662 x 10°S | 3.037 x 10° 28.010 9 CO; A728 1.784 x 107? 1.338 x 107? 4.097 x 10™? 44.010. 10 Hy 6483 2.215 x 10°) 3.298 x 10° 1.8% x 10-9 2.016 } R.C.Reid,J. M. Prausnitz. and T. K. Sherwood, The Properties of Gasesand Liquids 3rd ed.), MeGraw Hill, New York (1977), (iii) Viscosity The viscosity can be assumed to be that of steam al the reaction temperature (008 cp), (ie) Simularion Simulate tae profes of conversion ino styrene benzene, and toluene, and the remperature and pressuce profiles in the reactor,File Program Edit format Problem Exemples Window Help, Gee Se spec ms Boos | ar | sr eg Ge] ep | [KPa] Table Graph Beport [Differential Equations: & | Ausliony Equations: 85 [\7 Read fer solution eta) = rt db = AV FTO Jacx2yacz) = r2 + do = AY ETO Jacxayvacz) = 13 - db = AY ETO Jaioctvdi2) = ra 7 d= AY FTO lacxsyaiz) = rs * do = AY ETO Jaixeyvacz) = re * do ~ AY FTO 0 0 ° p40) = 0 0 ° kel * (BEB - (PES * PH/ Kp) 2 * PEB fa * PEB* PH ka * PW PET ks > PW" PM kG * (PT /T*3)* PW PCO Kkp= 04 |? Ecuaciones para k 41.5286 * exp(-10925 / T) 516197-5 * exp(-25000 / T) 1.3446 * exp(-11000 /T) 9.30 160-1 * exp(-12500 / T) 5 3163e-2 * expi-7900 / T) 9.676909 * exp(-8850 / 1) i?) ECUACIONES PARA PRESIONES:© POLYMATH 60 Professional Release - [Ordinary Differential Equations Solver] EE J File Program Edit Format Problem Examples Window Help toe & Bo | és ® war! |2? 4g @ Be] ® | [RKFAS I Table [7 Graph fh Report Differential Equations: 8 |Ausiliary Equations: 86 |W Ready for solution Pw = YW* PT PCO2 = YCO2* PT # FRACCIONES PARCIALES: IYTOL = FTOL / FT ET = FET/ FT LYM = EM / FT lYCO = FCO SFT. C02 = FCO2/ FT # ECUACIONES DE FLUJO FEB = FEBO - FTO* (x1 + x2+ x3) FES = FTO *x1 FH = FTO* (xt - x3 + 2* xd +3 * x5 + x6) FET = FTO* x2-0.5 * xd FTOL = FTO* x3 FM = FTO * (x3 - x5) FW = FWO - FTO * (x4 + x5 + x6) FCO = FTO * (xd + x5 - x6) FCO2 = FTO* x5 FT =FTO* (14 xt x24 1.5% xd 2% x8) # BALANCE DE ENERGIA Jd(T\/dlz) = (db * (rt * ht + 12* h2 + 13 *h3 + 14 *h4 +15 *hS + 16 * HG) / (G * Cp) T(0) = 923.15 # ENTALPIA DE REACCION ht = 120737 + (4.56 *T) h2 = 108802 + 2.95 *T h3 = 63171 + 13.19 *T ha = 82054 -8.83*T 4 (i Lat | REACTORES PROBLEMApol [No Tile 02:24pm. [07/12/2016 [CAPS [NUMDB File Program fait Format Problem fzmples Window Help DeBE| SRA As GHEE af! \z? Bd fers | CF dbe 7 Gah W Beni Uilert Eqn: 8 [dud Egan 5 Ready tin f= e0064-080°T b= 210978-1658°T hi =48017-1046°T (CP especin des conpoees (CPEB = 43.081 + 7TDEA*T- ABIES T+ 13016713) PUES (CPES= 28.40 +6KBE*T-40E-4°T*2+ 990068" 3) PUES (P= (90811 + 49E1°T-90HE4?T'2+ 71697789) PUB (CPTOL = (2436 + 51MES "T-2765E4 "72+ 4068 *T3)/PATOL (cPET= 815+ 1S66E-1°T- TES" 12+ 17856979 (PET (PU = (48247 + 621062 °T + ATES T° 2-LAMES ‘TFL CPW = 220 + S036" T+ 105 °742- 35866973) PL (CPCO= GOBUED- 129562" T + 27RHES*T'2-127168*T3)/PUCO cPCOD= (19781 + WED" T-SAUEE*T' 2 178E8°T" 3) PICO (PH = O18 + 927263"T- 165" T'2+ 7 BUEN 3) POH Clr especie aenein p= CPEB YEB+ CPES* YES + CPB“ YE + CPTOL*YTOL+ CPET*YET+ CPI" YM + CPWV*YW+ CPOO* YOO + CPCO2*YcO2+ CPH “YH ECUACIONES AUILARES = 106" D1" 2/4 FT = 0.13649 FW = 0.12582 FEED = 001067 {20-0 fish EFECTO DE LAPRESION PTA = 41-2) 23) * (175+ (160° (1-2) wa (6d (642) TES Pi)=237 W2= mA‘ eh al[Be Progam Edt Fomet Problem Gimpls \indow Hep OBBE|$GB2 AL GOOG O/! |e? SOM} free] Pla Bah Bent DielEgain 8 vgs Rehan SLE O24 t= 1300 . T= VALOR SUPUEST, BLSAR ECUACON DE SABE QUE i= 195 FT = 0139 FiO = 0.12582 =O006T 20)=0 b=t6t ; EFECTO DE LAPRESION arya }= (te) 249)1.5 + (10° (1-) i Bd *(642 el YES Pry)=297 aed isc = 103E3 n= 0005 G=a°W2 =m (A' gh yi=d4 Kf=PT! Pom) RT} R= O63 [Pmm= YEB* PNEB + YES* PUES + YH * Pu + YB" PMB + YET" PUET+ YTOL *PUTOL + YM*PM+ YWW*PMW + ¥CO* PCO + YCO2*PMCO2 PPUIEB = 10668 PPUIES = 104161 PuTOL= 42.41 PUIET=28(54 Puli’= 015 Puc = 24.010 Pucod=a4 000 [Lot PEACTORESPLBLEMApal oieFile Edit Window Help Os GSE|X BOA | mH % | POLYMATH Report Ordinary Differential Equations Calculated values of DEQ variables a 1.61 1.61 a 0.0350472 —_|0.0350472 a L801E13 (1.801613 a 0.0012289 —_(0.0012289 o 1326-14 (Lg2E14 oO ‘9.000508 |o.000508 oO 0.0004896 [00004896 851.4146 (923.15 851.4146 2312469 (2.37 2.312469 0.13649, 0.13649, 0.13649, a o.c048888 (0.004888 0.01067 (0.01067 0.01067 0.01067 0.12582 (0.12582 0.12582 (0.12582 0.13649 (0.13649 oi4i4i04 (0.414104 0.12582 (0.125684 9.12582 (0.125684 0.4 o4 o4 o4 1.108E-05 4.096-06 1.108E-05 _/4.09E-06 9.739E-17, 9.952E-18 '9.739E-17, 9.952E-18 '8.988E-06, (3.295E-06, 8.988E-06, 3.295E-06 1.224E-06 (3.914E-07, 1.224E-06 3.914E-07 1.021E-05 4.966E-06, 1.021E-05 '4.966E-06 LAS1E+0S =5.133E+04 L.L51E+05 '5.133E+04 (0.01067 0.0057204 0.01067 0.0057204 (t230pm [ormaveme|caPs [Nu po@ POLYMATH 6.0 P: @ File Edit Window Help a SE SBA wh | |\aeA!|B? (2a ven 0.0781742 (0.0404528 _0.0781742 _0.0404528 25FES oo 0 0.004782 0.004782 26 vH a 0 0.0345719 _0.0345719 7 re a 0 2458E-14 2458E-14 2s a 0 0.0001676 0.001676 29 o 0 L798E-14——1.798E-14 fo 0.9218258 0.887888 —_0.9218258 —_—0.8887888 faa 0 0 9.835E-05 9.835E-05 (32 o 0 0.006955 0,0006955, ba] 0.1852729 |0.0935477 __0.1852729 0.095477 joa o 0 6.925E-05 _6.925E-05 2s 0 0 0.9338161 _0.0338161 36. 0 0 0.0799481 _(0,0799481 Fd 0 0 1736613 (1.738E-13 38 0 0 0,0011852 0.011852 39 o 0 72E-13, 2.184727 2.055338 (2.184727 jan 0 0 0.016084 0.016084 az 0 0 2.509E-06 3. 1 9.31E-19 1.804E-17 aa o 0 1.774E-05 as, o 0 0.0782004 —_0.0782004 2.053E-06 3.187607 -2.053E-08 ——3.187E-07 a7 0 0 4.02E-13 4.02E-13 jas a 0 2.942613 2.941613 49 o 0 0.027408 0.027408 a 3.498E-19 2.366619 Bee ee Na File POLYMATH Report 02:32 pm. |07/12/2016 [CAPS [NUMLYMATH 6.0 Pr File Edit Window Help Osee6E\|s SOF | Me | |e A! |e? '52/Pco 0 0 4.102E-05, 4.102E-05. 0 9.0004897 9.0004897 -1.2496+05 —|-1.246E+05 -246E+05 “1.063E+05 — |-1.061E+05 .063E+05 6.446404 6.535E+04 6.446404 7.396404 7.AS4E+04 7.AS4E+04 “2.273E+05 |-2.261E+05 —-2.261E+05, B.S56E+04 = 3.6316+04 3.631E+04 106.68 106.68 106.68 104.151 104.151 104.151, 78.114 78.114 78.114 92.141 92.141 92.141 (28.054 28.054 28.054 16.043 16.043 16.043 18.015 18.015 18.015 28.01 28.01 28.01 44.01 44.01 44.01 2.016 2.016 2.016 3.117616 3.245294 3.117616 1.95 1.95 1.95 1300. 1300. 1300. 2.986484 2.986484 2.986484 0 0.011324 0.0011324 0 1.622E-08 1.622E-08 0 3.115€-08 2.464E-08 0.445, 0.445, 0.445 0.445 3.0E-05 3.0E-05 3.0E-05 3.0E-05 lan inns ans msi No File POLYMATH Report 02:33 p.m |O7/12/2016) CAPS [NUM$B?) at | BA! |e? 4.200084 4.071589 4.280044 4.071589 2.209973 (2.10162 (2.229073 2.10162 34 3a 3a 34 1.167894 1.150977 _—(1.167894—_1.150077 0.00314 0.08314 (0.08314 0.08314 1211742168028 (1.211742 ——*1.188028, 2931051 2.722911 2.831051 2.722911 2.667985 (2.553553 2.647985 2.553553 14.5204 (14.75162___(14.85224_14.75162. 2.596748 (2.500009 2.596748 2.500009 “2.aoie62 2.401062 2.110324 2.110924 2.276062 (2.276062 (2.646425 (2.646425 24.9963 (24.06112___24.94632___(24.06112 0.703224 0.703224 _0.7868379 __(0.7850272 1.47904 1,446383—(1.477904—_—1.448376, 1.136463 1.138463 (1.138863 1.138463, ifferential equations 2 d(xtyd(z) = r1* db* A/ FTO 2 dQa2)/d(Z) = r2* db * A/ FTO 3 d(x3)/d(Z) = 13 * db* A/ FTO d@xayd(z) = r4* db* A/ FTO 5 d(x5)/d(Z) = r5* db * A/ FTO 6 d(x6)/d(Z) = r6* db* A/ FTO 7 d(T)/a(z) = (db * (1 * hi +12 * h2+13* 3 +14 * h4 +15 * hS +16 * h6)) / (6* Cp) 8 d(PT)/d(Z) = (A - 2) / @* 3)* (1.75 +(150~ (1 - €) * vise) / (G* dp)) * (6 * 2) / dp) / 15 Exolicit equations No Fle POLYMATH Report (02:34 pm, [07/12/2016 | CAPS [NUM©@ POLYMATH 6.0 Professional Release - [Differential Equations Solut @ File Edit Window Help i ee |= F ary) = (db = (ra = hd +2 he += hata = hae B d(PT)/d(Z) = -(((1 - e) fe + 3) = (1.75 + (150 = (1- a) =v Explicit equations 2 Fro = 0.13649 2 FH = FTO = G39 4 2 = x4 +3 = 5 + XH) 3 FEBO = 0.01067 4 Fwo = 0.12582 S PT =FT0= xd to 4S = xt + 2 = x5) 6 Fw Fwo-Fro~ G4 + x5 + x6), 7 Kp=a0.4 8 ki = 1.5280 ~ exp(-10925 / T) 9 k2 = 5.0197e-5 ~ exp(-25000 / T) 10 k3 = 1.3446 = exp(-11000 / T) 11 k4 = 9.3016e-1 = exp(-12500 / T) 12 kS = 5.3163e-2 ~ exp(-7aa0 / T) 13 k6 = 1.6769e9 ~ exp(-8850 / T) 14 FEB = FEBO - FTO * (xl + x2 + x3) 15 YEB = FEB / FT 16 FES — Fro =a 17 VH = FHS ET is Fa = FTO > 49 FTOL = Fro = x3 20 FET = Fro ~ x2 - 0.5 = x4 21 yw = Pw/ FT 22 FM = FTO ~ (3-5) 23.YM = ems FT 24 FEB = YER ~ PT No File [POLYMATH Pleo [oza6om [ovfazoi6! cars [Mun2 A @ File Edit Window Help Oe HE tBR7\|Ad 25 FCO2= FID 5 26 YES = FES / FT 27 R= YH" =T 28 Ye = FB / FT 29 YTOL = FTOL/ FT 30 YET = FET/ FT 31 Pw="w* eT 32. PM = ¥M* PT 33 FCO = FTO * (xt +15 - 96) 34 12 =12* FEB 35 YCO = FOO / FT 36 PES = YES“ PT 37 rl. = ki ~ (PEB- (FES * PH / Kp)) 38 PE =YB* PT 39 PET = YET * PT 40 FTOL = YT0L* PT 41 =ka* PW? PET 4215 =15* PW? PM 43, PCO = YOO * FT 44 Yoo2 = F002 / FT 45 hi = -120737 + (-4.56*T) 46 h2 = -108802 +2.95 *T 47 ha = 53171 + 13.197 T 446 ba = 92054- 883° T 49 hs =-211979- 16.58 * T 50 he = 45217 - 10.46 *T ‘51 PMEB = 106.68,| @ File Edit. Window Help 2 ee 49 hs =-211979- 16.58 * T 50 hé = 45217 - 10.46 *T 51 PMEB = 105.68 52 PMES = 104.151 53 PNB = 78.114 54 PNTOL = 92.141 ‘55 PMET = 28.054 56 PNM = 16.043 ‘57 PMW = 18.015 58 PNCO = 28.010 59 PMCO2 = 44.010 60 PMH = 2.016 1 CPET = (3.905 +1,5665-1 * T - 8.3476-5 *T *2+1,755E-8 7 *3)/ PMET 62 DI=1.95 63 db = 1300 4 A=3.1416701%2/4 65 PCO2 = C02 * PT 66 r6=k6 * (T/T *3)* PW PCO 67 3 =k3 * PEB* PH 68 = 0.445 69 vise = 0,036-3 70 dp = 0.005 7A CPM = (19.247 +5.2126-2 *T + 1.19765 *T*2- 1.1318 * 7 *3)/ PMM 72 CPW = (32.236 + 1.923E-3 *T + 1.05SE-5 *T 2 -3,596E-9*T 3) / PMW 73m=3.4 74 CPCO = (30,8063 - 1,295E-2* T +2,7896-5 *T *2- 1.271E-8 *T*3)/ PMCO 75 R = 0.08314 76 CPCO2 = (19,791 + 7.342E-2* T - 5.6016-5 *T * 2+ L715E-8* 7 *3)/ PMCO2 No File POLYMATH Report 0236pm | 07/12/2016) CAPs [NUMWhe tat Wndow Hep G0 $2B7\As BEBE BA! 29 7h ép= 0005 Ti OM = (09.097 +52102°7 +1105 *T 82-18 *T 3) PM Te PW = (2.06 +1928E3°T + LOSES 72-3504" $3) AM Bm=34 4H CPCD = (B0MNER- 1.562 * T+ 2.785 *7*2-LIES*T 3) PCO BR= 004 5 PCO2 = (19701 +7302 *T- SES *T "2+ LTE *T 3) | FMC 77 PeB= (43001 + 207061 *T-4 8164 9041506773) Th CPS =(28.23 + 615861 °T- 404° *2+950168 °T 83) PMES 1138 +9297 L3HLES*T "2+ 768E9°T 3) Ba Pa = (au +408 T3482 47108783) Bi rToL = (2435 +5465 *T- 2.7684" 2491068 *T 3) PATOL 2 (p= CER“ + CHES “ES + CB * YH CTOL® YTOL + CPE “VET +CAM* YH+ CPU" YH +C2CD “YOO + CPeOD* YOUR + GH YH 1 Fm = 8 *PNED + YES * PES + YH* PUM + YB * PE + YET * ET = TOL * TOL + PU + YN * PY + YOO * PCD +YOOD* PCO Hf =FT*Pnm/(R*7) Bvz=m/ (Ard) Bod General outer eqns Humbrol equ Wimerofepet unos G6 Enysetine for Sioned AEE Seoseeneish OLN can rise 8 004 Dia ears potera gal oF POLSMUTH Reon (28pm [Oereani| CAPS