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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 theProblems
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 = ksPywhere 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) isProblems
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 the348, 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.