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Problem set #2
k, h-1
0.044
0.301
1.665
(2) There are two reactors of equal volume available for your use: one a CSTR, the other a PFR.
The reaction is second order ( rA = kCA2 = kCA02(1 X)2), irreversible, and is carried out
isothermally
1
AB
There are three ways you can arrange your system:
(a) Reactors in series: CSTR followed by PFR
(b) Reactors in series: PFR followed by CSTR
(c) Reactors in parallel with half the feed rate going to each reactor after which the exit
streams are mixed.
(d) State which system will give the highest overall conversion and which system will
give the lowest overall conversion.
Solution
C
A0
A1
A2
CSTR:
PFR:
X1 = 0.5
X1 = 2/3
X1,ave = 0.5(0.5 + 2/3) = 0.5833
(d) State which system will give the highest overall conversion and which system will give the
lowest overall conversion.
System 2: highest conversion.
System 3: lowest conversion
0
10
0.2
16.67
0.4
50
0.5
50
0.6
50
0.8
12.5
0.9
9.09
What are the PFR and CSTR volumes necessary to achieve 40% conversion?
Over what range of conversions would the CSTR and PFR reactor volumes be identical?
What conversion can be achieved in a 10.5 L CSTR?
What conversion can be achieved if a 7.2 L PFR is followed in series by a 2.4 L CSTR?
What conversion can be achieved if a 2.4 L CSTRR is followed in series by a 7.2 L PFR?
Plot the conversion and rate of reaction as a function of PFR reactor volume up to a
volume of 10 L.
Solution
CSTR:
V=
(300)(0.4)
= 2.4 liters
50
PFR:
V = 7.2 liters
(b) Over what range of conversions would the CSTR and PFR reactor volumes be identical?
For a feed stream that enters the reaction with a previous conversion of 0.40 and leaves at any
conversion up to 0.60, the volumes of the PFR and CSTR will be identical because the rate is
constant over this conversion range
0.6
dX
FA0 ( 0.6 0.4 )
=
= VCSTR
rA
rA
(d) 60% conversion can be achieved if a 7.2 L PFR is followed in series by a 2.4 L CSTR.
(d) What conversion can be achieved if a 2.4 L CSTR is followed in series by a 7.2 L PFR?
90% conversion can be achieved if a 2.4 L CSTR is followed in series by a 7.2 L PFR.
(f) Plot the conversion and rate of reaction as a function of PFR reactor volume up to a
volume of 10 L.
X=0.1:.1:.9;Ai=X;
ira=[.1 .08 .06 .04 .02 .02 .02 .05 .08 .11];
Area=0;
for i=1:9
Area=Area+.5*(ira(i)+ira(i+1))*.1;
Ai(i)=Area;
end
Vol=300*Ai;
figure(2)
plot(Vol,X);grid on
xlabel('V(liter)');ylabel('X')
rate=1.0./ira(2:10);
figure(3)
plot(Vol,rate);grid on
xlabel('V(liter)');ylabel('Reaction rate (mol/L*min)')
(4) Consider an ideal batch reactor with the irreversible homogeneous reaction
1
A + 2B 3C + D
This liquid phase reaction has the rate equation
rA = kCA2CB CD-1
The reaction rate constant is k = 1.5 L/molhr at 350oK. The activation energy of the reaction is
100 kJ/mol. The initial concentrations are: CA0 = 2.0 mol/L, CB0 = 4.0 mol/L, CC0 = 0 mol/L, and
CD0 = 1.0 mol/L. We will neglect any reaction that takes place while the initial charge is being
added to the reactor, and while the reactor and contents are being heated to reaction temperature.
(a) How much time is required for the concentration of A to reach 0.10 mol/L if the reactor
run isothermally at 350oK? What is the concentration of C at this time?
(b) The reactor will be run isothermally at 350 oK. The concentration of A in the final product
must be less than 0.20 mol/L, and the molecular weight of C is 125. An average of 10
hours is required between the batches in order to empty and clean the reactor, and prepare
for the next batch. How large must the reactor be in order to produce 200,000 kg of C
annually (with 8000 hours per year of operation)?
(c) We want to produce 200,000 kg of C annually, with a final concentration of A of 0.20
mol/L or less. The only reactor available has a working volume of 1400 L. At what
temperature does the reactor have to be operated, if it is operated isothermally? Once
again, an average of 10 hours is required between batches to empty and clean the reactor,
and to prepare for the next batch.
Solution
(a) Time required for the concentration of A to reach 0.10 mol/L.
The fractional conversion of reactant A is defined as
X = (NA0 NA)/ NA0
Therefore the number of moles of A at any time, t, is given by
NA = NA0(1 X)
We now create a stoichiometric table for this batch system (A + 2B 3C + D).
Species
A
NA0
Number of moles at t = t
NA = NA0(1 X)
NB0
NB = NB0 2NA0X
NC = 3NA0X
ND0
ND = ND0 + NA0X
NT = NT0 + NA0X
Total
For liquid phase reaction, we can assume the volume V is constant. Dividing each term in the
second and third columns of the above table by V yields
Species
A
CA0
Number of moles at t = t
CA = CA0(1 X)
CB0
CB = CB0 2CA0X
CC = 3CA0X
CD0
CD = CD0 + CA0X
CT = CT0 + CA0X
Total
dX
= rAV
dt
dX
= kCA2CB CD-1
dt
CB0
CD0
dX
2 X
+ X
C
CA0-1 C A0
2
3ln(2 X) 2 + 3ln(2)
1X
2
2X
+
2 + 3ln(2)
1 X 1 X
2kCA0t = 3ln
(E-1)
k(T) = koexp
RT
350
R
k(350) = koexp
k (T )
E1
1 0.17295
=
= exp
= 0.1153
k (350)
1.5
R T 350
E1
1
= -2.1602
R T 350
= 1.79610-4
= 3.036710-3
T 350
T
T = 329.3oK
FA0
FB = FA0X
FC = 2FA0X
FT0 = FA0
FT = FA0(1 + 2X)
Total
FA 0 X
, where rA = kCA
rA
The total concentration at any point, CT, and at the entrance, CT0, to the reactor are given by
CT =
FT 0
P0
FT
P
=
and CT0 =
=
Q
Q0
Z 0 RT0
ZRT
FT P0 T
FT 0 P T0
FT
, therefore
FT 0
FA0 (1 X )
FA
(1 X )
=
= CA0
(1 + 2 X )
Q
Q0 (1 + 2 X )
CA =
The reaction rate constant k at 127oC can be evaluated with the gas constant R = 8.314 J/moloK
= 0.08205 Latm/moloK.
E 1
1
1
85,000 1
= 10-4exp
= 0.0443 min-1
8.314 323 400
R T1 T2
k2 = k1exp
The initial di-tert-butyl peroxide (A) concentration at 10 atm and 127oC is given by
CA0 =
10
PA0
=
= 0.305 mol/L
(0.08205)( 400)
RT
FA0 X
FA0 X (1 + 2 X )
(4.0)(0.95)(1 + 1.9)
=
=
= 16,312 L
kC A
kC A0 (1 X )
(0.0443)(0.305)(0.05)
dX
(1 X )
, we have
(1 + 2 X )
V=
FA 0
kC A0
V=
FA 0
kC A0
FA 0
X 1
V=
4.0
[ 20.95 3ln(1 .95)] = 2,098 L
(0.0443)(0.305)
FA 0
1 +2 X
[ 2 X 3 ln( X 1)] 0X
dX =
kC A0
1X
For the batch reactor, the reaction time to achieve 95% conversion is given by
V
dX
t = NA0 0 r V
A
If we assume constant volume V = V0 then the pressure will increase for isothermal system and
N A0 (1 X )
N
CA = A =
= CA0(1 X), we have
V0
V
dX
t = CA0 0 r =
k
A
t=
1
1
dX =
[ ln(1 X)]
k
1 X
1
[ ln(1 .95)] = 67.6 min
0.0443
The total cycle time is then tc = 67.6 + 660 = 428 min. Therefore we have 2460/412 3 runs
per day. The initial moles of di-tert-butyl peroxide fed to the reactor is
NA0 = 3600/3 = 1200 moles
The batch reactor volume is finally
V=
N A0
1200
=
= 3,935 L
C A0
0.305
kf
kb
C B CC
CA
= 0.025
( XC A0 )( 2 XC A0 ) 2
= 0.025
(1 + 2 X ) 2 C A0 (1 X )
With an initial concentration CA0 = 0.305 mol/L, we have
X340.3052 = 0.025(1 + 2X)2(1 X)
The above nonlinear equation can be solved with the Matlab function solve
solve('x^3*4*.305^2-.025*(1+2*x)^2*(1-x)')
The result is X = X eq = 0.512. For 95% of the equilibrium conversion X = 0.95X eq = 0.4864
V=
FA 0 X
rA
rA = kfCA0
kf
(1 X )
X
X2
CA0
(2CA0)2
(1 + 2 X )
(1 + 2 X )
KC
(1 + 2 X ) 2
C A0
1 4C A0 X 3
(1 X )
rA = kf
(1 + 2 X )
K C (1 + 2 X ) 2
rA = 0.0443
0.305
1 + 2 0.4864
1 (4)(0.305) 2 (0.4864)3
(1
0.4864)
.025 (1 + 2 0.4864) 2
rA = 5.035110-4 mol/L
The CSTR volume is then
V=
FA 0 X
(4.0)(0.4864)
=
= 3,864 L
rA
5.0351104
X
dX
C A0
where rA = kf
rA
(1 + 2 X )
1 4C A0 X 3
(1 X )
K C (1 + 2 X ) 2
dX
We can use the Matlab function quad to numerical integrate FA0 0 r . The Matlab function
A
FA0
pfrvol is written with f =
as follows:
rA
function f=pfrvol(x)
k=.0443;cao=0.305;Kc=.025;
ra=k*cao*(1-x-(4*cao^2*x.^3)./(1+2*x).^2/Kc)./(1+2*x);
f=4.0./ra;
The expression f must allow for the fact that X is a vector in the function. We now can use the
function quad to integrate
0.4864
fdX .
>> quad('pfrvol',0,0.4864)
ans =
5.6867e+002
Therefore the volume for the PFR is 569 L.
yA
0.5
0.333
0
Initial composition
yB
yC
0.5
0
0.667
0
0
1.0
Initial
200
300
200
Volume (cm3)
Final
150
233
293
Solution
K = 4.5914
Ks are constant for the three cases: equilibrium has been established.