210 Chapter 8 FG P Reactor Regenerator Reactor / FG \ . J f ev | Regenerator x A F + A Stacked ype Side-by-Side ype F = Feed, P = Products, $= Steam, FG = Fle gas, A= Air Figure 8.6 FCCtype configuration and regenerator are separate vessels adjacent to each other. The Stacked or Orthoflow type reactor is mounted on the top of the regenerator. There have been many developments and modifications over the last few years to improve both performance and/or efficiency, or to develop special purpose FCC. The basic two types of FCC are shown in Figure 8.6 8.9. PROCESS DESCRIPTION ‘The process flow diagram for the side-by-side FCC unit is shown in Figure 8.7. Steam and VGO heated up to 316-427 °C (600-800 °F) are fed to the bottom of the riser, which is a long vertical pipe. The regenerated hot catalyst at 649-760 °C (1200-1400 °F) is also fed to the bottom of the riser. ‘The riser is the main reactor in which the endothermic reactions take place ‘The residence time in the riser is 210 s. At the top of the riser, the gaseous products flow into the fractionator, while the catalyst and some heavy liquid hydrocarbon flow back in the disengaging zone. Steam is injected into the stripper section, and the oil is removed from the catalyst with the help of some baffles installed in the stripper. The oil is stripped in this way from the catalyst and the spent catalyst is sent to the regenerator at a temperature oflui Catalytic Cracking zu Jesse 4b [ee — > i 8 cca Cyclone’ Seat ae pe Figure 8.7 Fluid catalytic cracking process flow sheet 482-538 °C (900-1000 °F). The coke in the spent catalyst, produced in the cracking reaction, is burned off in the regenerator by introducing excess air, which is used to ensure the efficient combustion of coke. The produced flue gas exits at the top of the regenerator. The hot flue gas contains carbon dioxide, carbon monoxide water and excess air at the regenerator tempera~ ture, These gases are sent to the power recovery unit to produce super- heated steam. The operation of the FCC remains in a steady state as long as a heat balance exists between the heat produced in the regenerator and the heat consumed in the reactor. In both the reactor and the regenerator, hydrocyclones are installed to catch any solid particles carried out in the overheated stream. The product gases from the reactor are sent to the fractionator which produces light gases, heavy gasoline (main product), light cycle gas oil (LCO), heavy cycle gas oil (HCO) and decant slurry. The light gases are sent to the gas concentration unit where flue gas, propane, butane, LPG and light gasoline are produced, ‘The operating conditions are usually adjusted to produce the maximum amount of gasoline from the VGO as shown in Table 8.4 (Parkash, 2003). The decant slurry from the bottom of the fractionator is a mixture of heavy aromatics and fine catalyst particles. These particles are formed during the circulation of the catalyst and are carried out to the fractionator. The filtered decant can be used as an aromatic solvent or recycled back to the riser with the HCO.22 Chapter 8 Table 8.4 Reactor and regenerator operating condition for max gasoline production (Parkash, 2003) Variable Reactor Feed Rate, MBPSD 40 Feed Temperature, “F 446 Catalyst/Oil Ratio 54 Catalyst Circulation Rate, tons/min 21.7 Catalyst Makeup Rate, tons/day 25 Riser Outlet Temperature, °F 991 Dispersion Steam, wt% feed 09 Stripping Steam, tons/ton catalyst 0.0213, Reactor Pressure, psig 30 Regenerator Pressure, psig 33 Regenerator Temperature, °F 1341 Flue Gas Temperature, °F 1355, 8.10. MODES OF FLUIDISATION IN FCC UNIT ‘The modes of fluidisation are used to operate the different parts of the FCC unit (Tominaga and Tameki, 1997). The regenerator is run at the higher velocity of the stable turbulent fluidisation. The line connecting the regenerator to the riser is carried out at the ‘bubbling fluidisation’ zone ‘The riser is operated at the ‘pneumatic transport’ zone, where the catalyst and products are carried out from the riser. In the stripper section, where steam is injected, the mode is ‘bubbling fluidisation’. The regenerated catalyst is transported back in the left line in a ‘pneumatic transport’ mode. The fluidisation modes are summarised in Table 8.5. 8.11. FCC YIELD CORRELATIONS ‘The yields of the products involved in fluid cracking are obtained by the regression of plant data compiled by Maples (1993) using a zeolite catalyst. The correlations given in Table 8.6 require target conversion (LV%), feed API and sulphur in the feed. Conversion is defined as the percentage of the oil fed that has been cracked into lighter fractions than gasoline and lighter products: conv%=( volume of oil feed ‘lume of eyclestock r Volume of oil feed ) 100 (8.12)Fluidised Catalytic Cracking 23 Table 8.5 Modes of fluidisation in FCC Location inFCC Regenerator Line for ca Riser Stripper Mode of fluidisation Turbulent fuidisation: to attain uniform burning temperature in bed. lyst transport Bubbling Suidisation from regenerator to riser Pneumatic transport: Catalyst and products are carried out thom riser. Plug flow has a few seconds of residence time. Bubbling Muidisation: St. stripper to vaporise and recover heavy oil and reduce coke formation, wn is injected in the Lift line from regenerator to Pneumatic transport, Table 8.6 FCC yield correlations Products Coke wt% LCO LV% Gases wt% Gasoline LV% iCy LV% nC, LV% Cy LW% Cy LV% C3 LW% HCO ‘We S in Gases We S in LCO Wes s HCO S in Coke" Gasoline API LCO API Correlation 0.05356 x CONV = 0.18598 x API + 5.966975 0.0047 x CONV? = 0.8564 x CONV + 53.576 0.0552 x CONV + 0.597 0.7754 x CONV = 0.7778. 0.0007 x CONV? + 0.0047 x CONV + 1.40524 0.0002 » CONV? + 0.019 x CONV + 0.0476 0.0993 x CONV = 0.1556 0.0003 x CONV? + 0.0633 x CONV + 0.0143 100 - CONV = (LCO LV) 3.9678 x (we S in feed) + 0.2238 1.04994 x (wt% S in feed) + 0.00013 S in feed) + 0.0135 wt S in feed — we S in gases — wt S LCO— wt% S HCO 0.19028 x CONV + 0.02772 x (Gasoline LV%) + 64.08 0.34661 x CONV + 1.725715 « (Feed API) * Assuming no sulphur in gasoline24 Chapter 8 The recycle stock is the portion of the feedstock which is not cracked to fractions lighter than gasoline. For example, for 75% conversion, the cycle stock is 25%, Example E8.1 A feed of 20,000 BPD of AGO (650-850 °F) having an API of 24 and a sulphur content of 0.2 wt, is mixed with another of feed of 15,000 BPD of VGO (850-1050 °F) that has an API of 15 and a sulphur content of 0.35 wt. They ire used ay a teed co FOC unit, Use dhe FCC correlations to find the material balance around the reactor unit. Assume a conversion of 75 LV%. Figure E8.1 shows the reactor input and output streams. Solution: AGO = 20000 (bbl/day) x 318.6 (Ib/bbl) x (1. day/24 h) = 265,000 Ib/h VGO = 15000 (bbl/day) x 338 (Ib/bbl) x (1 day/24 h) = 211250 Ib/h S in AGO = 265000 x 0.2/100 = 530 Ib/h Sin VGO = 211250 x 0.35/100 = 739 Ib/h S in feed = 1269/476250 x 100 = 0.266% Conversion = ((Vol. of feed - Vol. of cycle stock)/Vol. of feed) x 100 = 75% Cycle stock = unconverted portion below gasoline = (LCG + HCGO) = 25 API of mixture: Total feed = 476,250 Ib/h SG for AGO = 0.9099 and SG for VGO = 0.9659 2 5 ‘Then SG for mixed feed = 2°" __(@, 9999). 150 _(9,9659) 2H000-+ 15000 0000+ T5000 = 0.9339 regents | Cyl, R Gast NZ Spent Catalyst I AGO + VGO + Steam Figure E8.1 Reactor inputand outputstreamsFluidised Catalytic Cracking This gives feed API = 20.02 A summary of the feed mixture is shown in Table E8.1.1 Using the above data and the yield correl 235 jons from Table 8.6, the material balance and product properties can be calculated as shown in Table E8.1.2 Table E8.1.1 Feed properties Gases wt eLV% co LV% HGO wt% S in HS we% Sin LCO we% Sin HCO we% S in Coke wt% Gasoline API LCO API 53.576 0.0552 x (75) ~ 0.597 47 0.7754 x (75) — 0.7778 57.4 0.0007 x (75)? + 0.0047 x (75) + 5.7 1.40524 0.0002 x (75)? + 0.019 x (75) + 26 0.0476 0.0993 (75) — 0.1556 73 0.0436 x (75) - 0.8714 24 0.0003 x (75)? + 0.0633 x (75) + 64 0.0143 100-75 ~ 15.8 3.9678 x (0.266) + 0.2238 1.04994 > (0.266) + 0.00013 1.88525 x (0.266) + 0.0135 (1269 — 289 — 226 — 237)/29,813 1.734 =0.19028 x (75) + 0.02772 x (59.1) 514 + 64.08 0.34661 x (73) + 1.725715 x 85 (20.02) Stream) BPD API we S IbS/h AGO 20,000 24 02 530 vGO 15,000 15 0.35 739 20.02 1269 Table £8.1.2 Yields and properties of products Ibjh Coke wt% 0.05356 x (75) — 0.18598 x (20.02) 6.3 30,004 + 5.966975 LCO LV% 0.0047 x (75)? 0.8564 x (75) + 15.8 81,337 16,375 7735 22,356 6230 16,987 46,027 289 226 237 517236 Chapter 8 8.12. MATERIAL AND ENERGY BALANCES ‘The material and energy balance around the reactor and regenerator can be calculated by defining the input and output streams. 8.12.1. Material Balance 8.12.11. Reactor Material Balance ‘The input and output streams to the reactor (Figure 8.8) are: Reactor input: * Oil feed (VGO) to the riser: F (BPD) or ine (Ib/h) # Injection steam: S), (1b/h) © Regenerated catalyst: sax (Ib/h) Reactor output: ‘* Masses of products im;, as calculated from FCC yield correlations ‘These correlations require some feed properties such as: API, sulphur content and degree of severity expressed as conversion. # Spent catalyst circulation rate tmese (Ib/h) ‘* Steam present in cracked products, Sout (Ib/h) ‘Thus, a material balance around the reactor is » Ime = Sin ~ Meat = J hs + Sour = Mae (8.13) Flue gases Products 2 ya ay a - e ‘Og t 7 1 Q, i 1 ! 1 Sout, Q, I ‘neal 1 Sou, Qsout | |Regeneratorle M2] Reactor | | \ Ta {1 2 1 “A i “| K Exothermic — ry reactions 1 ~ 1 Endothermic | reactions Feed oil Sin, Asin m, Q, Figure 8.8. Inputand output streams for reactor and regenerator in FCC unitFluidised Catalytic Cracking 217 where p is the total number of vapour products and assuming Six does not condense and is present in the exiting vapour products at the same rate (Si) = Soue)- mj is the mass of each product that can be calculated using the FCC correlations. The produced coke is present in spent catalyst. Thus Meoke = Mscat — Mear Equation (8.13) can be rewritten as follows: my = > m+ Moke (8.14) ia 8.12.1.2. Regenerator Material Balance Regenerator input: © Spent catalyst circulation rate teas (Ib/h) # Air for coke burning mi, (Ib/h) Regenerator output: © Flue gases 1 (b/h) © Regenerated catalyst tea: (Ib/h) ‘Thus, the material balance around the regenerator produces: Iie Moar = YM Mo (8.15) a where 1 is the mass of each gas produced from the coke burning which may contain CO3, CO, H2O, SO2, No and Os (from excess air) 8.12.2. Energy Balance 8.12.2.1. Reactor Heat Balance Heat input: © Heat of feed oil Q;- (Btu/h) at inlet feed temperature (T)) ‘© Heat of steam injected Qs (Btu/h) at T, ‘* Heat of regenerated catalyst Qoar (Btu/h) at regenerator outlet temper- ature (Tic) Heat output ‘* Heat in vapour products, Q, (Btu/h) at reactor outlet temperature (Tr) ‘© Heat of spent catalyst Qoac (Btu/h) at Try238 Chapter 8 © Heat of exit steam Q.our (Btu/h) at Tre ‘Then the energy balance can be expressed as me Cpe Te = To} + el AH) + tMhea¢ Cr cat (Tires — To} ~ Sin Cp Ts = To) = (Te = To) mi Crs ~ teat Ch scat( Tit — To) + SourCps( Tr — To) (8.16) Since, Meoke = Mscat ~ Meae ANA Sj, = Sou, then equation (8.16) becomes. me Cps( Tr — To) + me( AH) + tex Coat Titeg — Te} + Sin p(T = Ti} = (Tr = To) mi Ces + coke Gr.coke( Tie — To) (8.17) 8.12.2.2. Regenerator Heat Balance Heat input: © Heat of spent catalyst Que (Btu/h) at Ty © Heat of input air for coke burning Q,i, (Btu/h) at Ty, © Heat of coke combustion qeoke (Btu/h) Heat output: © Heat of flue gas Qi, (Btu/h) at They © Heat of regenerated catalyst Quay (Btu/h) at Tiroy ‘Thus the heat balance around the regenerator can expressed as Ie Cp ail Tar — Ty) + Moke CP coke( Tr — To) + deoke a . . (8.18) = (Titeg — To) > MCo.g) + MearCr cae Theeg — Te) ‘ Example 8.2 Find the catalyst circulation rate for the FCC unit used in example E8.1 by carrying out a heat balance around the regenerator, A sketch of the stream flows, and temperatures around the regenerator is presented in Fig. E8.2.1 Data: Heat of combustion of coke, AHe = 0.393 x 10° kj/kmol, Chew = LID KI/kg.K, Cosie = 29.6 kJ/kmol.K, Cp, = 32.6 kJ/kmol.K, Cp.co, = 46.9 kJ/kmol.K, Crcoke = 21.1 kI/kg.K - Solution: Coke produced = 29,813 Ib/h = 13,551 kg/h (from example E8.1) Coke = 13,551 kg/h = 1129 kmol/h qeoke = 1129 (kmol/h) X 0.393 x 10° (kJ/kmol) = 443.8 x 10° (K/h)Fluidised Catalytic Cracking 219 M2, Meas Treg = 700 C Mecat + Moke Tooat= Ta = 520 0 Regenerator m Treg = 690 Figure E8.2.1 Regenerator Air required = Op required/0.21 Op required: C +0, —=CO, Oe required = 1129 kmol/h meo2 = 1129 kmol/h mg, = air required = 1129/0.21 = 5376 kmol/h myo = 5379 x 0.79 = 4247 kmol/h ‘Thus, the heat balance from equation (8.18) gives 5376 x 29.6(200 — 15} ~ may 1-11 x (520 — 15} ~ 13551 21.1 x (520—15) | 443.8 x 10® = (700 = 15)/1129 46.9 | 4247 > 32.6) | snes 1.11(690 15) 58 x 10° kg/h = 43.0 t/min = 0.717 t/s 8.13. KINETIC MODEL FoR FCC REACTOR ‘The FCC process involves a network of reactions producing a large number of components. Therefore, lumping models can be used to describe the reaction system in terms of the feed and a defined number of products, ‘Three, four and up to over ten lumps can be used theoretically. A three lump model (Figure 8.9) assumes that VGO produces two products: gaso- line and a combined product of gas and coke, where y refers to the mass fraction of each lump and k is the reaction rate constant. A more realistic model is the four-lump model (Figure 8.10) in which VGO produces gasoline, gas and coke. Assuming that the VGO cracking rate is second order and gasoline rate is, first order. The three and four lump models in Figures 8.9 and 8.10, respectively, are shown below. In these models the catalyst deactivation rate ¢) is considered equal for all reactions,220 veoy,) ——“* + Gasoline (y,) «6 he ‘Gas + Coke! Wa) Figure 8.9 Three-lump model veo yy) ——K2 _, Gasoline ys) Tet Coke (y4) Gas (ys) Figure 8.10 Four-lump model ‘Theee-lump model: for VGO dy; 5 P 2 n= a = -hiyié — byie = (kn + eid for gasoline dy 2 2 =p = kivid ~ kayad = (ki, ~ heya) for gas + coke dys 2 =a, = levis kn)d Four-lump model: for VGO Nd — kisyid — kaye avid — kayad — kad = (kyt kosya for gas dys 2 nap = (ken kayy )o Chapter 8 (8.19) (8.20) (8.21) (8.22) koaya) (8.23) (8.24)Fluidised Catalytic Cracking 221 Table 8.7 Experimental data at 548.9 °C and catalyst to oil ratio (C/O) = 4 (Ancheyta-Juarez and Murillo-Hernandez, 2000) Conversion VGO Gasoline (wt%) (wt%) (wt %) 82.38 17.62 54.16 7118 28.82 48.65 62.04 37.96 43.85 49.26 50.74 37.67 for coke dy, > aH (kuyt | kavr)o (8.25) Experimental data reported by AncheytaJuarez and Murillo-Hernandez (2000), which are shown in Table 8.7, can be used to evaluate the reaction rate constants Example £8.3, Use the experimental data given in Table 8.7 with @ equal to 1.0. Estimate the reaction rate constants for the three-lump model Solution: For a three-lump model and @ = 1 an pasty te (£8.3.1) dys . 2 E8.3.2) + (B8.3.2) Y _ (ey? oye) (E8.3.3) Initial conditions at = 0 are at yi = 1, yo = O and ys = 0. Initial guesses for ky, ko and k3 are assumed. Equations (E8.3.1), (E8.3.2) and (E8.3.3) are solved numer- ically in the Excel worksheet. The resulted values for y,, y2 and ys, at time corresponding to the space velocity in Table 8.7, are compared with the experimental composition listed in Table 8.7. The Solver in the Excel work~ sheet is used to minimise the difference by changing the values of ky, ky and ke ‘The resulting k values are ky = 23 bo!) ky = 3.1 bo! and ky = 7.5 hot Predicted yields are plotted as solid lines versus conversion in Figure E8.3. The experimental data are also plotted from Table 8.7 as symbols in the same figure.222 Chapter 8 = VGO x Gasoline © Gas+Coke — Predicted Yield, wit fraction 0 02 0.4 06 08 1 Conversion, wt fraction Figure E8.3. Experimental and predicted gas sas and coke yields 8.14. CONCENTRATION AND TEMPERATURE PROFILES IN THE RISER Itis possible to calculate the concentration profile for each component in the riser reactor by differential material balance in the riser. If the four-lump model discussed earlier is considered, it is possible to derive the following equation for each lump VGO, gasoline, gases and coke (Jia et al., 2003) For VGO [ki2 — kis + Realy (8.26) For gasoline p , , Pe (tay? = (kas + hes 01] (8.27) For gases (8.28) For coke (8.29)Fluidised Catalytic Cracking 223 Where A, = Cross-sectional area of the riser Hydrocarbon gases void fraction Hydrocarbon gases mass flow rate in the riser (kg/s) @ = Catalyse activity Density of gas phase in the riser (kg/m?) = = Axial distance in the riser (m) Numerical integration of equation (8.26) co (8.29) will give the yield profile of each component along the length of the riser. The value ¢, , Pg and nj, have to be updated along the length of the riser. Updating these values along the riser length can be carried out using the following equations: Peaetllg Pelle 8.30) Paea T Pout ™ where if = tlg/ttpy tg is the velocity of the gas (m/s) which is gas flow rate divided by riser cross-sectional area, 1, is the particle velocity in the riser and is defined as Uy = ———————_ 8.31 » Apel a The hydrocarbon gases flow rate is calculated from mg = mvcolyi | y2+ ys) 8.32) ‘The density p, has to be updated as a function of temperature change in the riser, which is calculated from a temperature profile generated from the energy balance equation The coke content of the catalyst C., varies with coking time according to Co = 2.43 x 107822? (8.33) And the deactivation function with respect to coke content can be determined: 1 1. 69.47(100: Coking time f, can be calculated at each riser interval as dtc AD! ao TS] RT Meal | = | mg. = Y4 Pea T i ¢ (8.34) ‘The energy balance equation gives224 Chapter 8 (ki2AHi2 + kisAHiy + kisAFhs)yt (Ro AHay + kesAHbs Jy (8.36) The boundary conditions are at > = 0, yr = 1, yo = ys = ys =0, Tr = To and 1, =0. Example £8.4 ‘The cracking of gas oil is carried out through a 33 m riser height with an 0.8 m inside diameter. Typical industrial FCC riser data (Ali and Corriou, 1997) are listed in Table E8.4.1 Kinetic and energy data (Abul-Hamayel, 2003) are listed in Table B8.4.2. Typical molec ities (Ahari et al., 2008) are given in Table E8.4.3. Solve the riser ma ar weights and heat capa m tration and temperature profile versus riser height id energy balance equations and plot the concen- Table £8.4.1 Typical FCC riser data Feed Catalyst flow Catalyst Feed Riser LD. Height flowrate rate temperature temperature _ pressure (m) (m) —_ (kg/s) (kg/s) (K) (K) (atm) O8 33 144 20 960 494 29 Table £8.4.2 Kinetic constants and energies for four-lump model at 823 K ka hes ky (wefrach) + — (wefrach) * —(wefrach) $y (h)* ey (h) 121 35 21 12 3 Ha (Keal) Hy (Keal/ Hy (Keal/ Hay (keal/ Hay (kal mol) mol) mol) mol) mol) 28 19 15, 34 30, Table £8.4.3 Kinetic constants and energies for four-lump model at 823 K Molecular weight (kg/kmol) ) (ike K) 333 33 106.7 KH 40.0 33 4 1.087 Z 1.087Fluidised Catalytic Cracking 225 Solution: Utilising the operating data the p, was calculated at initial conditions of temper- ature and pressure P(Mw) __2.9(333) RT 0.082(494) 3.84 kg/m? Gas velocity 4, was then calculated at pg At 2=0 of the riser n=Lp=y=ya=0 20 (1 + 0 + 0) = 20kg/s Ps 20 23.8405) 1.67 m/s Then 1, and 6, are calculated simultaneously as follows ees 36 O58) — 20} &= 23.8: 44)(36/(1 ‘The catalyst activity can be determined as 1 “1 -469.47(0.24302) Coking time /, can be calculated from equation (8.35) as en 0.5(8}(1.67/up) (E8.4.1) dz 0.082T, 29 144(1.67/up) | iS iz | Blan p08) Simple energy balance on the catalyst and the feed is performed to calculate the riser inlet temperature at z =0, T; = Ty = 821.8 K At yy = Land yy =0 [ke AHi2 + kuAHis +ksAHs)] (E8.4.2) -3)) Equations E8.4.1 and E8.4.2 should be solved numerically at boundary conditions of y and values of k and H from Table E8.4.2. Gas density is then calculated at the estimated riser temperature. Then the differential equations (8.26) to (8.29) are solved in Excel, using the Euler method. The procedure is repeated to calculate T, and 1, then the product compositions, Figure E8.4.1 shows the FCC riser composition profiles as a function of riser height. The Figure E8.4.2. emperature and activity. of cazalyst profiles are shown in226 Chapter 8 10 “VEO ost \? (3)Gases 2 06 2 (2)Gasoline 5 04 8 (4)Coke 02 , 0.0 |. o)0S~CS~*~«S SSCS Riser height (m) Reactor . effluent ol TSE Tt" [Separator x Catalyst Az < \ in —__> time in the riser time in separator Figure E8.4.1 Product concentration profiles along the riser 825 1.00 0.98 820 0.96 092 | 8 & E 810 0.90 8 & é 0.88 805 0.86 800 0.84 Riser height (rm) 1-2. Temperature and catalyst activity profile in the riser