Engineering Practice Ralph Levine ultiple CSTRs (continuous stirred-tank reactors) are 1 Jadvantageous in situations jbere the reaction is slow; two irmmiseibla liquids are presentand require higher agitation rates; or vis- cous liquids are present that require high agitation rates. Unlike in plug- flow reactors, agitation is easily avail~ able in CSTRs. In this article, batch and plugflow reactors are analyzed ‘and compared to multiple CSTRs. ‘The number of reactors required in a CSTR aystem is based on the con- version for each stage. When the final stage obtains the fraction of | vertad roaetant that ix equal sired final value from the plug-flow ‘ease, the CSTR system is complete, ‘The volumetric efficiency of mul- tiple CSTRa is expressed as 2 function of conversion per stage and gives the total conversion required. In this ar- ticle, we will apply this to reversible second-order reactions i 2nd-order,reversible reactions : ‘The first case presented here is a Kinetic prooess requiring a double ‘component (24) to be fed to a reactor, { and producing two products (@ and ' HD. The design may be calculated for { both CSTR and plug-flow reactors, de- termining the conversion in the first | CSTR Design | for Reversible Reactions Here, a design approach for continuous stirred-tank reactors is outlined for three cases of second-order reactions Kya GAtN= Can Can) “Product: Corand Cra Coz Mot CSTRs for Plug-low Multiple backmixed reactor Teactors | FIGURE 4. Conversion In plug-fow reactors and I cond order reactions Is shown. swith conversion per stage shown for the CSTR case | stage, the number of stages of equal volume, as well as the volumetric of ficiency of the OSTR stages and the plugflow reactor ‘The reactor design is developed by selecting a crnversion in the frst stage ‘Then, the second-stage conversion is ‘qual to that of the first stage, since it requires an equal volume. This pro cedure is continued until the fraction of reactant exiting each reactor stage reaches the desired value in the last slage, or slightly less than the plugilow case, as illustrated in Figure 1 ‘The kinetie rate conversion of a re versible bi-moleculae reaction at con stant: temperature and flowrate is rep- resented by Equation (1).The reaction is illustrated below (nomenclature is defines on p. 49. 2AOG+H orbs, —hyCCye @ by hy /K 7 (Car%,) (Co Cu) (2a) 2(C, ~ Cay} “(Cuxo~ Cre) Assume that @ and H compounds are not present in the feed. Therefore, Ogg | 46 CHEMICAL ENGINEERING WHZWTCHE.COM SEPTEMBER 2009, ‘and Cj are equal to zero, and the fol- lowing exproscions are true! Cap = Co, (2p) Cy =CaoX, . eo (Cuo%,)=(Cx-Cu) “Car” Cor ea ‘The ratio may be diffrent, as, for ex- ample, the concentration of G in the product may be five times that of #, However, we assume that the products, are equal (Cap= Cy Expressing reaction rate. The rate equation can be modified to include conversion and equilibrium constant terms, Substituting quations (1), and (2a) into Equation (1) give en expres: sion for rate, P= hyCig(t-XF = by K)(Cuo%) (a) ra, {500 (ab)Engineering Pract CSTR Design for Reversible Reactions Here, a design approach for continuous stirred-tank reactors is outlined for three cases of second-order reactions Ralph Levine ultiple CSTRs (continuous | stage, the number of stages of equal stirred-tank reactors) are advantageous in situations whare the reaction is slow; tivo immiseible liquids are present and require higher agitation rates; or vis- cous liquids are present that require high agitation rates. Unlike in plug- flow reactors, agitation is easily avail- able in CSTRs. In this article, batch and plugflow reactors are analyzed and compared to multiple CSTRs. ‘Tho number of reactors required in ‘CSTR system is based on the ean- version for each stage. When the final stage obtains the fraction of uncon verted reactant that is equal to the desired final value from tho plug-flow ‘ease, the CSTR aystem is eomplete. The volumetric officiency of mul- tiple CSTRs is exprossed as a function of conversion por stage and gives the total conversion required. In this ar- ticle, we will apply this to reversible second-order reactions. 2nd-order, reversiblereactions The first caso prosented here is a kinetic process requiring a double ‘component (2A) to be fed to a reaeton, fand producing two products, (@ and F). The design may be calculated for both CSTR and plug-flow reactors, de- termining the conversion in the first Plug-fow reactor Cm Cas Cio ‘Multiple backmixed reactors. FIGURE 1. ©: onversion in plug-low resctors and CSTRS for second order reactions Is shown here, ‘with conversion per stago shown for the CSTR case volume, as well as the volumotrie ef | I ficiency of the CSTR stages and the plugflow reactor. ‘The reactor design is developed by selecting a conversion in the first stage. ‘Then, the second-stage conversion is ‘equal to that of the first stage, sinee it requires an equal volume. This pro: cedure is continued until the fraction of reactant exiting each reactor stage reaches the desired value in the last stage, or slightly less than the plugflow case, as illustrated in Figure 1 "The kinetic rate emversion of a re versible biemolecular reaction at con- stant temperature and flovrrate is rep- resented by Bquation (1)."The reaction is illustrated below (nomenclature is, defined on p. 49. 2AoG+H (a) Aseume that Gand HT compounds are not present in the feed. Therefore, Cao 46 CHEMICAL ENGINEERING YWNALCHECOM SEPTEMGE 2008, and Cjzp are equal to zero, and the fol- lowing expressions are true: ap) (2e) Y= Cay* Coy ea) The ratio may be different, as, for ex ample, the concentration of G in the product may be five times that of HI. Hlowrever, we assume that the products, arg equal (Cgy= Cy). Expressing reaction rate. The rate equation cam be modified to include conversion and equilibrium constant terms, Substituting Equations (1), and (2@) into Equation (1) give an expres- sion for rate, r= gig 1 X,) ~(bo/B\(CaeX,)P (a) neil a fee =i} 2] (Be) ‘At equilibrium, the net reaction rate equals zero, 7 (S2)ie-an (4a) Using the quadratic equation, Equa- tion (4a) is simplified to Equation (4c). 4(K-ay/K .3K-1/K (ab) x 8K (K-1)/K- (te) ‘The quadratic equation can also be used to simplify Bquation (3), result ing in Equation (a), x, -2¢v4-4[t-(WK)] 1 R-D] 121 (JR) eave o (a) Tho reaction rate expression ean then bbo expressed as Equations (5b) and a, ~rohyCi(X, -X,) 6») BOX [-(X,/X,)] 60) Stirred reactor in a batch or plug. flow reactor. The bateh tenctr tase andthe eal continous plugfow eave are given in Hguaton (6) ‘The reaction time is ¢ for the batch cease, and Viv for the plugflow ease. Vo frat, Wg I oe 6 ‘Substituting Bquation (5¢) into (6) and rearranging, gives Equation (6a). ie, lacie) =f" er] j VAC, ToL /2.)] yy Volume of each CSTR stage. An ex pression for the first stage of a CSTR. isgiven in Equation (7). The first stage conversion, X;, occurs in each of the suovossive stages (Xp, Xp, and so on), and each has the same volume and re. action temperature, vx, ve, m ‘Substituting Equation (e) into (7) and rearranging gives Equation (7a), a Equation (7a) has only one indepen. dent variable (Vp Heath stnved tne tne stages to he of equal volume and volumetric orate, en theron A constant conversion per stage, That 'a omc stage, when at Bee oat of condition, has the same eonvmion from each tage, expessd ast Xy3%=%.. 2X, Number of stages. Conversion for stage 1 is expressed by equation (8), %=(Ceo-Cu)/Cun @ The equilibrium conversion is based on time to reach a net reaction rate of zero, which may be ealeulated by Equation (4b) or (9). X= (CoC) Cre Subtract Equation (8) from (8) and di vide by (9) to obtain Equations (10a) and (10b), @ XX = (Cy, Cy )/O yy oo XX Cy Cy, Xx, oe -C,, (10a) L(x Garde (10b) ‘The exit concentration, Cys, can be calelated from Equation (ib). Also, a) the exit concentration from the second ton (11), hase en each stge ex the same vohime and conditions, eae Continue this process for the nth stage to obtain the following equations. az) Total volume of all stages. Substi ‘tute Equation (7a) into (48a). Vn=n¥, asa) ¥ XX, oe TO TX) sb) 6, ase) CuO) xx, “toalt=(X,/,)] 1-(%,/%) By definition, C4q = Cal —¥7, where 4%} is the tlal convertion in'the nih stage or ths final deived conversion of the plug-fow reactor, By the method used to obiain Equation (10), the fl lowing equation is similariy derived. Substitution of Hguation (12b) into 286 gives Bguation (134). ¥, Flay la (X,/%)] xix, doe[-(¥,/28,)] 1-06.) aga) Volumetric efficiency Sinee Vpfo in Equation (130) is resi- dence time, as is Viv in Equation (6b), stage, C4g,can becaleulatod from Bquua- CHEMICAL ENGINEER for CSTRs, these terms are equiva ING YNWCHECOM SEPTEMBER 2009 47lent, The volumetric flowrate is the same in all eases (a batch operation for one complete reaction eycle). Thus, the ratio of comparison should be V for plugflow or batch operation (reaction volume and time only) compared to Vp for multiple CSTRs. This ratio (V V7), volumetzie effisieney is expressed. as Bquation (14), and is derived from ‘Equations (63) and (134). a,Cuo% YER Cy aa ~2,305 og 1-(%, %,/x,_loel-(%, 1-(6)%,) doal1-(%/,) (14a) ‘Volumetric efficiency is independent of the initial or final concentration ‘and velocity constant at constant ten perature, as well as overall conver- sion, It is dependent on only the ratio of the first stage conversion compared to the equilibrium conversion. Calcu- lations for Equation (lds) are shown, in Table 1. Reversible production of a dimer from two reactants ‘Another case exists, where wo com- ponents are roversibly reactod to form a single product, a dimer, rather than two produets (as shown in the react below). This ease is similar to the pre- vious case, but but with only one prod: ‘uct, as shown below in Equation (15) C+DeP ory C,Cy—hyC, saa CX, =Cy9 Cor = (16a) Cy =CaoX, (16b) rohyO [0 OX) an At equilibrium, the rate is zero. "TABLE |,VOLUMETRIC EFFICIENCY FOR EQUATION (144) v. 30a{1 (x, /2,) og (2/2, )] aad Ve X(%/%) Xie [Xe [-OGIX) _—_[loglI-OG7xI) [VAX [WIV or [or |o9 0.048 0.948 1.388 02 [07 [08 2.097 0.898 1275 os [or jor 0.155 332, cd oa [ov [oe 0.222 0.766 1095 os [07 jos 0.307 0.698 0.990 06 [or [oa 0.396 oat a7 o7 [or [oa 0523 sie (0787 os jo7 [oa 0.699 0.402 0.575 os [or [or =1.000 0256 0.366 ‘TABLE 1. For any ratio of conversion per stage to equilibrium conversion, this table provides the corresponding volumetric efficiency, based on Equation (14a) KC, )* wets ow asa) Using the quadratic equation, Baus: tion 8a) becomes (18) Mot f=] (MY oar KCy,* WUC x Km Wim 2 Using Bqvation (1) and (180), ano pression for Xs found M11)y +M iS yoy Equation (19a) ean be simplified to Equation (195) using the quadratic ‘equation. cash) Aci -{ 2 rohiCnX[L-(X/x,)] 180 Nlse nek) -in{1-(X,/X,) 20a) ‘The volume of each backmixed stage is equal Vi(heCooX)_— X, vy 1-(%/) 20D) 1-(%/x)=Geoe an ea1-(X,/%,) -p-(x/xyf (23) CHEMICAL ENGINEERING WHWW/CHE.COM SEPTEMBER 2000, ‘The volumetric efficiency is calculated as Equation (23). ’ Yr ‘ : (23) 2,303) 1-(X,/X, 2a aa adler dimer from twin reactants In another alternate but similar case Equation (15) is modified for doubl components that are reversibly re acted bo form a dimer, as shown in th reaction below. As in this last cas {here is only one product. 2AOP are pC yy) ~ RaCp (24 Oy =o, fe P= gC ug (1X) —( /K)(CaoX (26 arose XP RC) 11] (26 ‘At equilibrium, the rate i zero. O=XI-KCu)XA1 ate Using the quacratie equation, Bau: tion (27a) becomes (27b). p-YKC yy f(t KC,,) 4 en X, = YRC yy *y(1/KC yo) —1 i‘ =hCw'[1-(%/X)] og Por a plugilow roactor, the followin expression is truo,TABLE 1.VOLUMETRIC EFFICIENCY FOR EQUATION (14A) a bcsiesi OF EQUATIONS a{{ NOMENCLATURE Subscripts L——| pedese. a} © ial condion 2a, /5, tol. -0/)] sey os 128 ea id ope eering Practice EEE) a) Jara ae aye © Copcenraion. ‘A. For component A. 2(K-1)/K & Reaction ra © For component XIX [Xe TTX) [oat] [IVD | V/V eee Sooner D For component D Tent, Tho volumeirie flowrate is the | Foy Tog 3 0.046 0948 1.365 x, fea (ayaa yy K_ Equilibrio constant Equilibrio conditions same in all cases (a batch operation aor ames. iors 5 SR aR | Mel mole rt of 78 F Qyeral or Final canditions for ono complete reaction cycle). Thus, ||2__ | 0.7 Co 2AoGsH M Number of stages F Conditions for forward reaction forme ofeonparisor shouldbe V fr | [os [a7 [oa oa88 case [ve falas cna lugilow or batch operation {reaction 06 ~o222 0.766 7.095 1 Reaction time Hi For component H win and time nlp) compared te | [°4 [97 0301 Ce) ¥ Reactor vue 7 Any stoge inthe serie of reed stages Vp for multiple CSTRs. This ratio (W/ | [08 [0.7 Os x 7 ¥ Volumetic fowcate The ath stoge Vp), volumetric efficiency is expressed | [9.6 [0.7 04 0.398 O61) 0.873, % Conersion P For component P. as Equation (14), and is derived from | F>—)o7 03 ~os23 O56 0737 Conditions for reverse reaction i 7 Thou chal ogee Fans hn 0 ox jor fos aa ose ‘bal nag hel. 09 jor On 1,000 0.256 0.366 References % “TABLE For any loo conversion por lag 6 equ convraon this able * Lge hae tein bh Pov sa ing | Sac, (1 | TABLE Foray ae of are seb a onan) ee eee Fae weal ‘ae ee Ents icles te = ‘The volumetric efficioney is coleulated 3. Leo, , Now Desi Approach fr Masi Dey Balen, oe (i 1s sae se Bauaton Remy iste aa ere perr OG sears ety a (usa) Ha he Beg pat tose Ry al Using the quadratic equation, Equa- oa Eng duly 2, 1868 p46 iso," C*™ Sine Uaiverty made ae tion (18a) becomes (18b). (a3) Sfag yeaa. Pie eens ergy of Datawe Lovny cred a aa eee vfs (82) YO (KC y) 1 See SA | iad Pana niermace eve (14a) Mat, [ast a dave, Fo rine, R CSTR Bound fr fs fogs severa CS patente dane By wars, ar 1CaEa) wer, a aa HY Ol KG,.) A © bees py Meu | SS re ee dg oelt-(%,/X.)] x2 Se TT #/— 80) | reversible production ota 7 U ASria Sige! Ho td ro | : dimor from twin reactants (Cob) fst fy) 09 = Volumetric efficiency is independent | Using Equations (17) and (188), an ex | 5. other alternato but similar case, D /%,) of the initial or final concentration | pression for Xyis found. Eqoation (6) is modified for double Pena fd volocityeonstant at constant tem : Bonetee 0) 5 ead See he exrusen Deratare a6 well as overall comer | r=A,C3,X7-[MCU x, nat | Stentor dimer a5 sown in he sivon as Equation (30) The best way to heat and cool on Tes dependent o only the rato 7 Te y : f ; {rth fret stage conversion compared | Equation (19a) ean be simplified to | acuen Plow. Ut Oh ViCruhe __X,/%, [Ml the most corrosive materials. { the equilioam conversion Galeu- | Equation (19%) using the quadratic | ‘Here Ede} ; Tations for Equation (a) are showa | equation, : in Table 1 a crak, y hyp sy mat), (01) ay ; Reversible production of a KC, } WRC om (19b) =X, (25) (3 dimer from two reactants XX Sareea: i a donor eepeiii taupe ae rl (1-X,)'-(be/E\(Cuo%,) The volamotie efceney is found to | J NOt contro paments are revoriy reacd to arn : he volume thing conto single product, a dimer, rather than -(x,/x)] 190 (26a) er cahe: byopredt osha nth econ ofl) +3] ee corosives and high below), This eae ia similar tothe pre ved (x) purty materi beter ‘vious ease, but but with only ane pede ; ta[1-(X,/X,)]200 Pea eeueuune (6b) v ex ) (ee) | (82) fae a {us as shown below in Boat (8) [At equilibria, the rate is zero ant : The volume ofeach backnixd stage toe|t-(x, 2] las, Not stlcon carbide C+DeP CX, =Co9 C= CaoXy ‘At equilibrium, the rate is zero. CoCo —haC, as) (16a) (ah) x Ci |(0-X NM -¥)- ge an is equal, VilbeCao%, (20b) en 0=X2-(YRCn)X,+1 ata) Using the quadratic equation, Equa: tion (27a) becomes (27b). ao X,=1/KC,, 5 f(/6C,.) om X,=Y Hy Y(/RC uo) 1 —rakn'ft-(%/%)) apy 48 CHEMICAL ENGINEERING WHW.CHE.COM SEPTEMBER 2000 (22) } axpression is true, For a plugflow reactor, the following Tho last two cases proseniad here are reversible and have only one produc The differences hetween those cases are the values calculated based on fhe quadratic equation far both X. and 3 All second order reactions that are reversible and produce one or two products require the quarratie equa. tion fo the ealelation of X, and; for cach case. A summary of those efua- tions is presented in the box above. Mt Edited by Kate Toreawshi | or graphite units. Available with steel or non-metallic shells, diameters from 3° to 14* and metric designs, AMETEK heat exchangers Include TEMAVANS! nozzle and end connections, To learn more call (202) 456-4431 or visit: www.ametektpp.com Circle 27 on AMETEK wvoROPounten pRooUCTS 2 oF go to adlinks.che.com/23018-27 CHEMICAL ENGINEERING WIMWCHE.COM SEPTEMBER 2009 49