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342 Selectivity and Optimization Considerations in the Design of Isothermal Reactors determine the relative costs of operating in the separation and recycle mode cis @ ris the costs of utilizing the second stage plug flow reactor and the attendant separation costs necessary to obtain the final product. LITERATURE CITATIONS 1. Levenspiel, O., Chemical Reaction Engineering, Second Edition, pp. 166-167, Wiley, New York, copyright © 1972. Used with permission. 2. Denbigh, K. G.,and Turner, J.C. R., Chemical Reactor Theory, pp. 123-124, Cambridge University Press, Cambridge, 1971 3. Trambouze, P. J., and Pitel, E. L., AICHE J., § 384) 1959, 4. Denbigh, K. G.. Chem. Eng. Sei, 17 5. Levenspiel. ©., op. cit, p. 180 Levenspiel, ©., op. cit.,p. 181 1961 6. 7. Levenspiel, ©., op. cit., pp. 186-192 8. Levenspiel, O., op. cit. p. 189 9, Levenspiel, O., op. cit., pp. 191-192. 10. Denbigh, K. G., and Turner, J.C. R., op.cit.,p. HS. 11, Denbigh, K.G., and Turner, J.C. R., op. cit. p. 114, 12, Baeyer, A., Ann, Chem. Pharm., 103 (178), 1857. 13. Walles, W. E,, and Platt, A. E., dnd. Eng. Chem., 59 (6), p.41, 1967. PROBLEMS 1. Your plant has two liquid streams available containing solutes that are not profitably mar- ketable at the present time, The first contains solute A, the second solute B. Two possible reactions may occur between these species. The stoichiometric equations and rate expressions are given below. A + B- V (valuable product) ry = kyCyCgCh? + kaCyCy A+ B+ U (undesired byproduct) ty = kyCaCn (a) You have two beakers containing samples of the two streams and desire to carry out a small-scale laboratory experiment in which you maximize the formation of V. In what manner would you carry out this experi- ment; that is, how would you mix the re- actants and at what rate? (b) If you desire to produce V in a flow reactor, what type of reactor and operating condi- tions do you recommend? (c) If the activation energies for the rate con- stants k,, ky, and k, are 30, 25 and 25 kJ/ mole, respectively, what additional state- ment can you make regarding recommended operating conditions’? 2. Consider the following chlorination of ben- zene reaction system of elementary reactions. Cl, + CoHy “> CoH,Cl + HCI Cl, + CHCl C.H,Cl, + HCI Assume that chlorination of dichlorobenzene does not occur to an appreciable extent. Mono- chlorobenzene is the desired product. (a) Obtain an equation that relates the concen- tration of monochlorobenzene to the con- centration of benzene, assuming that only benzene and chlorine are present initially: (1) Fora CSTR. (2) For a batch reactor. (b) Utilizing this information, for each of the above cases (I and 2) in order to minimize the rate of production of dichlorobenzene relative to the rate of production of mono- chlorobenzene, would you want a high or low conversion of benzene? Prove this math- ematically for each of the following cases. ky > ke ky = ka ky ks > ka and that, ky = 45 x 10 e-45:8007 soe~t ky = 2.57 x 108e~20100/T goo kg = 7 x 108e7 151007 gee~ where T is expressed in degrees Kelvin (2) If the reaction at 2500 °K may be con- sidered as occurring at constant volume, determine the times corresponding to the two maxima, Note that the time in the plasma jet will be exceedingly small. (©) Roughly what fraction of the methane is converted to acetylene at 2500 °K if the contact time in a plasma jet is that corre- sponding to the maximum in acetylene concentration? 8. Consider the sequential first-order reactions Av 3 w where V is the desired product. These liquid phase reactions are to be carried out in a cascade of two equal volume CSTR's in series. If the reactors are to be sized so as to maximize the concentration of species V in the effluent from the second reactor, determine the reactor volumes necessary to process 500 gal/hr of feed containing 6 moles/gal of species A. No V or W is present in the feed. What fraction of the A ends up as V? The rate constants ky and kz are both equal to 0.5 hr. 9. A sequential isomerization reaction is be- lieved to be characterized by the following mech- anistic equations ASBSC These reactions are being studied in a series combination of two CSTR's. Each of these re- actors has a volume of 2 liters. Liquid is being fed to the first reactor at a rate of I liter/min. This liquid contains only pure A and the solvent. The inlet concentration of A is 2 g moles/lter. Under the conditions of operation, k; = 0.5 min”! and k, = 0.25 min“, Both reactors op- erate at the same temperature. (a) What is the composition of the effluent from the first reactor? Include all species of interest. (b) Repeat part (a) for the second reactor. 10. Kostyuk, Belen’ku, and Tezhneva [Kinetics and Catalysis, 10 (53), 1969] have studied the Problems acid catalyzed decomposition of p-diisopropyl- benzene dihydroperoxide in ethyl acetate solu- tion. The stoichiometric equations for the two consecutive reactions that occur are: O--OH a~ 345 + CH,COCH, (acetone) OH Cy So + CH,COCH, CH,—C—CH, ou OOH (hydroquinone) Both reactions are first-order in catalyst con- centration and in the reactant involved. If one incorporates the catalyst concentration into the rate constants k, and k,, the following values are typical of the results reported by these in- vestigators at 40 °C. 0.95 ky = 3.6 x 1074 sec”! Both reactions take place in liquid solution. If one desires to carry out these reactions in a con- tinuous stirred tank reactor, determine the space time corresponding to a maximum yield of p-hydroxycumyl hydroperoxide. If the initial p-diisopropylbenzene dihydroperoxide concen- tration is 10 moles/m3, what are the concentra- tions of the various species in the effluent? UL. Vaidyanathan and Doraiswamy [Chem. Eng. Sci., 23 (537), 1966] have studied the cat- alytic partial oxidation of benzene in a composi- tion range where the reactions of interest all follow pseudo first-order kinetics. The pertinent stoichiometric equations are CoHe + 30: > C,H,O, + 2CO, + 2H,0 CyHO; + 30, + 4CO, + HZ0 CoH, + $0, + 6CO, + 3H,0 The corresponding rate expressions are ry = kyPy ry = kpPu 13 = ksPy where Py refers to the partial pressure of ben- zene and P, to that of maleic anhydride. If one is interested in designing a reactor for maleic anhydride (CjH,O3) production, deter- mine the reactor space time for a PFR that maximizes the concentration of this species in the effluent. Start by deriving equations for Pp, Py, and Peo, as functions of the space time. At 350 °C, the values of the rate constants are: ky = L141 x 107? ky = 2.468 x 10°? }g moles/(hr-g catalyst-atm) ks = 0.396 x 10°* Under optimum conditions at this temperature, what fraction of the inlet benzene ends up as maleic anhydride? What is the yield of maleic anhydride based on the amount of benzene reacted? Neglect volumetric expansion. 12. The following reaction sequence takes place in the liquid phase in a continuous stirred tank reactor. by ky A+B+C+2D The feed concentration of A is C4o, and the reactions may be assumed to be irreversible re- actions proceeding by this mechanism. No B, C, or D are present in the feed. If the input volumet- ric flow rate is ¥ and the reactor volume is Vp, derive equations for the effluent concentrations of B,C, and D. If species B is the desired product, determine the space time that corresponds to the maximum production of B. 13. Ziegler-Natta catalysts are used commer- cially for the production of stereoregular poly- mers, especially isotactic polypropylene and high-density linear polyethylene. The resultant polymers have number and weight average molecular weights (7, and MM,,, respectively) that are defined as ee oy M and Optimization Considerations in the Design of Isothermal Reactors and a) where N, is the number of molecules containing n monomer units M is the molecular weight of the monomer, (The summations extend from n = 2ton = ©.) Keii [Kinetics of Ziegler-Natta Polymerization, Kodansha, Tokyo, 1972] has noted that under steady-state reaction conditions, the number of polymer molecules with degree of polymeriza- tion n desorbing per unit catalyst surface area in unit time may be written as Tgesorprion = kaN of (In) where k, = desorption rate constant (assumed to be independent of n) No = number of active sites per unit surface area 0, = fraction of the sites covered by a polymer with degree of polymerization n Reattachment of the n-mer does not occur. If the reaction occurs by the so-called Rideal mechanism the net rate at which a polymer with degree of polymerization n is produced is given by k,NoPO,-1 — ky NoPO, (vy) where the rate constant for the reaction of gas phase monomer with adsorbed n-mer (k,) is as- sumed to be independent of n and where P is the gas phase monomer pressure. If the rate at which monomer is adsorbed to initiate polymerization is given by bNor (1 =r ) Vv) Pat and if the average rate of polymerization (R) is Problems taken as the rate of disappearance of monomer e_dN, R La show that the average rate of polymerization is given by _ NokikaP?(2ks + k,P) (K.P + kakaP + ka) The breadth of the molecular weight distribu- tion may be measured by the ratio M,/M,. Show that this ratio is given by where By considering the limits of 1/7 as zero and infinity corresponding to infinitely rapid desorp- tion or slow reaction and very slow desorption or rapid reaction, respectively, show that M, 1<—*<2 << which is a rather narrow molecular weight distribution. 14. The following reactions take place in the liquid phase in a continuous stirred tank reactor operating at steady state. A+B3C wo C+4A>D (i) Under the conditions of operation, reaction I is, first-order in species B and is characterized by a rate constant equal to 15 ksec™'. Reaction I] is first-order in species C and is characterized by a rate constant equal to 3 ksec™!. A stream con- taining 2.0 kmoles/m? of A and 0.5 kmoles/m? of Bis available at a rate of 0.75 m?/ksec. 347 (a) Derive equations for the effluent concentra- tion of each species in terms of the rate constants k, and ky, the reactor volume, the initial volumetric flow rate, and the initial concentrations of species A and B. (b) What reactor volume will give the highest concentration of species C in the effluent stream? What will this concentration be? 15. An autocatalytic reaction is to be carried out in aqueous solution in two identical continuous stirred tank reactors operating in series. The reaction stoichiometry is A>B while the reaction rate expression is r= kC,Cy If the system is to operate isothermally at 50°C where the reaction rate constant is equal to 0.9 m*/kmoleksec, determine the reactor vol- ume necessary to achieve an overall fraction conversion of 0.80. Species A is to be fed at a rate of 0.3 mole/sec and an initial 4 concentra- tion of 2 kmoles/m?. 16. An autocatalytic reaction represented by the mechanistic equations A+RERER ie is being carried out in two identical stirred tanks operating in series. The reaction is reversible and exothermic. The reaction stoichiometry is AR Two hundred and twenty-five pound moles of liquid A at 70 °F are fed to the first reactor each minute, The fraction of the inlet A converted to R in the first reactor is such that the effluent from the first reactor leaves at 85 °F. The temperature of the stream leaving the second reactor is 100 °F. ‘The mole density of A in the entrance stream is 1.5 Ib moles/ft?. The following table provides some informa- tion about the temperature dependence of the 348, Selectivity and Optimization Considerations in the Design of Isothermal Reactors, rate constants k; and k_, in units of cubie feet per pound mole per minute. Temperature CF) k koa 70 055 » 85 290 0.078 100 2 0.625 If the reactor volume is 50 f1°, determine the composition of the stream leaving each reactor. 17. Consider the following combination of reactors. fy = 0.25 este PFR It has been suggested that the following liquid phase reaction be carried out in this reactor network. A+B+C The reaction rate expression for this stoichio- metric equation is r= kC,Cp The feed to the CSTR contains a concentration of A of 2.0 kmoles/m’, while neither species B or C is present in this stream, Both reactors operate isothermally at the same temperature. Steady-state operation may be assumed. The CSTR and the PFR each have a volume of 0.1 m®. The rate at which A is fed to the first reactor is 150 kmoles/ksec. Note that this is an autocatalytic reaction in which a product acts as a catalyst for subsequent reaction. (a) If the fraction conversion leaving the CSTR is 0.25, what is the reaction rate constant? (b) What is the effluent composition from the second reactor? (c) Ithas been suggested that the rate of produc- tion of species C by this network can be increased by operating the first reactor at a fraction conversion of 0.45. To what value must the input feed rate of A be changed under these operating conditions? Will the rate of production of species C by this com- bination of reactors be increased under these circumstances? The composition of the feed- stream is to remain unchanged.

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