ChE 471 Lecture 6 October 2005

Ideal Reactors and Multiple Reactions

Isothermal Operation

Selection of a proper flow pattern is the key factor in achieving desired selectivities and yields in
multiple reactions. For every multiple reaction system of known stoichiometry it is possible to
determine a priori which limiting flow pattern complete backmixing (CSTR) or no mixing
(PFR) will yield superior yields or selectivities. The consideration of yields often is more
important than reactor size in choosing the preferred reactor flow pattern.

From Lecture 1 we know that all multiple reaction systems can be represented by a set of R
independent reactions among the S chemical species present in the system:
S

ij Aj=0 for i = 1,2,3...R (1*)

j=1

These stoichiometric relationships allow one to relate moles produced (or depleted) of each
species to the molar extents of the R reactions:

R
F j = F jo + ij X& i (1)
i =1

The rate of reaction of each species is given through the rates of the R independent reactions, ri, i
= 1,2,R.
R
Rj = ij ri (2)
i =1

CSTR Ideal Stirred Tank Continuous Flow Reactor

Fjo Fj
Qo Q
V

The design equation (i.e., the mass balance for species j) can be written for R species, j =
1,2,3R:
R
Fjo Fj + ij riV = 0 (3)
i =1
for j = 1, 2,...R

1
ChE 471 Lecture 6 October 2005

If the reaction rate ri for each independent reaction i can be represented by an n-th order form, of
eq (4a)

S
ri = k i C j ij

(4a)
j =1

then at P = const, T = const, the rate of the i-th reaction, ri, can be represented in terms of molar
extents X& i of the reactions by:

ij
R
S
ij
F jo + ij X& i

ri = k i C tot
i =1
,o S R (4b)
j =1
Ftot ,o + ij X& i
j =1 i =1

where ij is the reaction order of reaction i with respect to species j, Ftot,o is the total initial
molar flow rate.

Substitution of equations (2) and (4b) into (3) results in set of R nonlinear equations in X& i .
Three types of problems described below arise:

a) Given the feed flow rates, reactor size V and rate forms for all reactions one can calculate
all the reaction extents X& i ' s and from equation (1) get the composition of the outlet
stream.

In addition, from Lecture 1, at P = const, T = const:

R S
Q = Qo 1 + ij X& i Ftot , o (5)
i =1 j =1

The exit volumetric flow rate can be computed and effluent concentrations calculated

Fj
Cj = (6)
Q

b) Given the feed molar flow rates and composition, and the desired partial composition of
the outflow, as well as the reaction rates, one can calculate the reactor size from equation
(3) and the composition of other species in the outflow.
c) Given molar feed rates and outflow molar flow rates for a given reactor size the rate of
reaction for each species can be found from equation (3).

2
ChE 471 Lecture 6 October 2005

PFR Plug Flow Reactor

Fjo Fj
Qo Q
V
The design equation (i.e. the differential mass balance for species j) can be written for R species

dF j R
= ij ri (7)
dV i =1
j = 1, 2, ...R

The initial conditions are

V=0 Fj = Fjo (7a)

Using equations (1) and (4b) the above set of R first order differential equations can be
integrated simultaneously and solved for X& i ' s as functions of V.

a) Given the feed flow rate and composition, and the form of the reaction rates, one could
determine what volume V is required to attain the desired product distribution.
b) Given the feed and reactor volume and reaction rate forms, one can determine the exit
product distribution.

Batch Reactor Autoclave of Constant Volume

The R species (for j=1, 2, 3..R) mass balances yield:

dn j R
= ij ri (8)
dt i =1

Initial conditions are:

t=0 nj = njo (8a)

Moles and extents are related by:

3
ChE 471 Lecture 6 October 2005

R
n j = n jo + ij X i (9)
i =1

For j = 1, 2, 3S

The rate form as a function of extents is given by

ij
R

s ij X i
ri = k i C joij 1 + i =1

(10)
n jo
j =1

s ij
R

ri = k i C jo + ij i (10a)
i =1
j =1

Xi
where i = (10b)
V

One can solve the set of R first order differential equations to calculate the product distribution in
time, or the desired time needed for a prescribed product distribution.

The above approach, while well suited for the computer, does not provide us with the insight as
to which flow pattern is better in a given process until we actually compute the answers for both
limiting cases.

In order to get better insight in the role of the flow pattern in product distribution in multiple
reactions we will consider some simple systems and use the notions of yields and selectivity.

Classification of Multiple Reactions

A + B = R
parallel
C + D = P
A+ B = R
competitive
A + 2B = S

A + B = R
consecutive (series reactions)
R=S

A + B = R
mixed reactions
R+ B = S

4
ChE 471 Lecture 6 October 2005

In Lecture 1 we have defined the various yields

R

P Rp ip ri
y = = R
i =1
{point (relative) yield
A RA r
iA ii =1

Point (relative) yield measures the ratio of the production rate of a desired product P and the rate
of disappearance of the key reactant A. Point yield is a function of composition and this varies
along a PFR reactor, varies in time in a batch reactor, and is a constant number in a CSTR.

P F FPo
Y = P {overall (relative) yield
A FAo FA

Overall (relative) yield gives the ratio of the overall product P produced and the total
consumption of reactant A.

In a CSTR the overall and point yield are identical.

P P
Y ( ) = y
A A

In a PFR the overall yield is the integral average of the point yield:
FAo
P 1 P
Y =
A FAo FA

FA
y dFA
A

Overall operational yield is also often used, defined as the number of moles of the desired
product produced per mole of key reactant fed to the system.

F F
@ = P Po
P
A FAo

The relationship to overall relative yield is obvious

@ = Y x A
P P
A A

where xA is the overall conversion of A

5
ChE 471 Lecture 6 October 2005

FAo FA
xA =
FAO

None of the above yields has been normalized, i.e., their maximum theoretical value may be
more or less than one as dictated by stoichiometric coefficients.

A normalized yield can be introduced by

P
y
P A
y =
A y P
max
A
P
where y max is obtained by assuming that only the reactions leading from A to R occur.
A
Point selectivity and overall selectivity measure the ratio of formation of the desired product and
one or more of the unwanted products, e.g.

P Rp F p F po
s = S=
U Ru Fu Fuo

A general rule:

P
dy
If > 0 PFR produces more P.
A
dC A

P
dy
If < 0 CSTR produces more P
A
dC A

P
If y is not a monotonic function of CA either reactor type may produce more P depending
A
on operating conditions. The case of monotonic point yield is illustrated below for the case with
A = 0.
P P
y y
A A

\ \ \ Area = Cp in PFR
Area = Cp in CSTR
CA CAo CA
CA CAo CA

6
ChE 471 Lecture 6 October 2005

R S
I. Liquid Systems or Gases With
i =1 j =1
ij =0

Competitive Reactions

a1A + b1B= p1P

a2A + b2B = s2S

Given the rate r1 = k1C A1 A C B1 B

r2 = k 2 C A 2 A C B 2 B

Point yield then is:

p1
P Rp p1 r1 a1
y = = =
A R A a1 r1 + a 2 r2 1 + a 2 r2
a1 r1
p1
P a1
y =
A 1 + a 2 k 2 C ( 2 A 1 A ) C ( 2 B 1 B )
A B
a1 k1

P p
y max = 1
A a1

P 1
y =
A 1 + 2 2 C ( 2 A 1 A ) C ( 2 B 1 B )
a k
A B
a1 k1

P
We want y to be as high as possible. This implies:
A

i) if 2 A < 1 A , 2 B < 1B , keep CA and CB as high as possible. PFR is better than

CSTR.
ii) if 2 A = 1A , 2 B < 1B , keep CB as high as possible. PFR is better than CSTR.
iii) if 2 A = 1A , 2 B > 1B , keep CB as low as possible. CSTR is better than PFR. Try
for yourself other combinations.

7
ChE 471 Lecture 6 October 2005

Example 1

A=P RP = 1.0 CA (kmol/m3s)

2A = S RS = 0.5 C A2 (kmol/m3s)

Determine Cp in a) CSTR, b) PFR. The feed contains CAo = 1 (kmol/ms), Cpo = 0.

Conversion of 98% is desired.

P Rp Rp 1
y = = =
A R A R p + 2 Rs 1 + C A
P P P
y max = 1 y = y
A A A

To keep point yield as high as possible, it is necessary to keep CA low everywhere. CSTR
will be better than PFR. Let us show this quantitatively.

a) CSTR

By setting the overall yield equal to the point yield we can solve for the exit concentration of
product P.
P Cp P 1
Y = = y =
A C Ao C A A 1+ CA

C Ao C A
Cp =
1+ CA
=
C Ao x A
=
1x0.98
1 + C Ao (1 x A ) 1 + 1 0.98
(
= 0.961 kmol / m 3 )

P Cp
Overall yield Y = = 0.980
A C Ao C A

@
P
Overall operational yield = 0.961
A

Required reactor size (space time)

C Ao C A C Ao x A
= = = 48.0( s )
RA C Ao (1 x A ) + C Ao
2
(1 x A ) 2

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ChE 471 Lecture 6 October 2005

b) PFR

Product concentration is obtained by integration of the point yield

C Ao C Ao
P dC A
Cp =
CA
y dC A =
A
1+ C
CA A

1 + C Ao 1+1
C p = ln = ln = 0.673(kmol / m )
3

1+ CA 1 + 1 0 . 98

P
Overall yield Y = 0.687
A

P
Overall operational yield @ = 0.673
A

C Ao C Ao
dC A dC A
Required reactor size =
CA
RA
=
CA
C A (1 + C A )

C Ao (1 + C A ) 1 + 1 0.98
= ln = ln = 3 .2 ( s )
C A (1 + C A ) (1 0.98)(1 + 1)

Plug flow reactor is considerably smaller but CSTR gives a better yield and higher
concentration of the desired product.

Example 2

A+B=P Rp = 1.0 CACB (kmol/m3s)

A+A=S Rs = 0.5 C A2 (kmol/m3s)

Given FAo = FBo = 1 (kmol/s; CAo = CBo = 1 (kmol/m3) CPo = CSo = 0 and desired
P P P
conversion xA = 0.98, determine C p , Y ,@ , S and required reactor space time for
A A S
a) CSTR, b) PFR.

P R Rp CB 1
y = p = = =
A RA R p + 2 Rs CB + C A 1 + C A
CB

9
ChE 471 Lecture 6 October 2005

To maximize point yield one should keep the reactant concentration ratio CA/CB as low as
possible everywhere.
R

Eliminate CB in terms of Cp and CA using C j = C jo + ij i i = 1, R

i =1
C A = C Ao 1 2 2
C P = C Po + 1

1
1 = C P C Po 2 = [C Ao C A C P ]
2

Now:

C B = C Ao 1 = C Bo C p

C S = C So + 2 = 0 +
1
2
[
C Ao C A C p ]
1
= [C Ao C A C Bo + C B ]
2

a) CSTR

P Cp P C Ao C p
Y = = y =
A C Ao C A A C Ao C p + C A

Solve for Cp

C p2 (C Ao _ C Bo )C p + C Bo (C Ao C A ) = 0
C Ao = C Bo = 1; C A = C Ao (1 x A ) = 1 0.98
C p2 2C p + 0.98 = 0

C p = 1 1 0.98= 0.859(kmol / m 3

C A = 0.02kmol / m 3
exit stream composition
C B = 0.141kmol / m 3

C S = 0.061kmol / m 3

P
Overall yield Y = 0.877
A

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ChE 471 Lecture 6 October 2005

P
Overall operational yield @ = 0.859
A
P Cp
Overall selectivity S = = 14.2
S Cs
Required Reactor Size

C Bo C B C Ao C B 1 0.141
= = = = 306( s )
RB C AC B 0.02 x0.141

b) PFR

dF p Rp P
= = y
dFA RA A

Since F j = QC j and Q = const

dC p C Bo C p
=
dC A C Bo C p + C A
at C A = C Ao , C p = 0

Rearrange:

dC A CA
+ = 1
dC p C Bo C p
d CA 1
=
dC p C C C C
Bo p Bo p

at Cp = 0 CA = CAo

Integrate from the indicated initial condition:

CA C C Bo C p
Ao = ln
C Ao C p C Bo C Bo

= 1 + ln(1 C p )(*)
CA
1 Cp

Substitute known quantities:

CA = CAo (1-xA) = 1-0.98 = 0.02 (kmol/m3)

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ChE 471 Lecture 6 October 2005

Solve for Cp by trial and error:

(C p ) = C p 0.98 (1 C p )ln(1 C p ) = 0
D (C p ) = 2 + ln(1 C p )

n +1
(C pn )
C =C n
Newton-Raphson Algorithm
D (C pn )
p p

This yields:

C p = 0.613 kmol / m 3

C A = 0.02 kmol / m 3
Exit stream composition
C B = 0.387 kmol / m 3
C s = 0.184 kmol / m 3

The last two concentrations above are evaluated using the stoichiometric relationship.

P
Overall yield Y = 0.626
A
P
Overall operational yield @ = 0.613
A

P
Overall selectivity S = 3.33
S

Required reactor space time:

C Bo C
Bo =1
dC B dC B
=
CB
=
R B C B =0.387 C A C B

From (*)

[
C A = (1 C p ) 1 + ln(1 C p ) ]
From stoichiometry

C B = C Bo C p = 1 C p
Thus
C A = C B (1 + lnC B )

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ChE 471 Lecture 6 October 2005

C Bo =1 1+ ln C
dC B Bo
e u
= = e u du
C B = 0.387 C B (1 + lnC B )
2
1+ ln C B

= e{E1 (1 + lnC B ) E1 (1 + lnC Bo )} = e{E1 (0.05) E1 (1)}

= 2.71{2.4679 0.2194} = 6.1( s )

where

e u
E1 ( z ) = du exponential integral
z
u

E1(z) values tabulated in M. Abramowitz & A. Stegun Handbook of Mathematical Functions,

Dover Press, N.Y. 1964.

Comparison of CSTR & PFR

Reaction System: A + B = P (desired)

A+A=S

Decision variables: xA = 0.98

F
M B / A = Bo = 1
FAo

Rate Form: r1 = 10 CACB (kmol/m3s)

r2 = 0.5 CA2 (kmol/m3s)

CSTR PFR Optimal Ideal Reactor

Operational yield 0.859 0.613 0.950
Overall selectivity 14.2 3.3 63.0
Reactor space time 306 (s) 6.1 (s) 150 (s)

The last column of the above Table was computed based on an ideal reactor model shown below.
We have B entering a plug flow reactor while FAo is distributed from the side stream into the
reactor in such a manner that CA = 0.02 kmol/m3 everywhere in the reactor.

FAo

PFR
FBo

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ChE 471 Lecture 6 October 2005

From the expression for the point yield

P CB 1
y = =
A CB + C A 1 + C A
CB

it is clear that one needs to keep CA low and CB high. With the constraint of FAo = FBo the above
ideal reactor accomplishes that requirement in an optimal manner.

Could such a porous wall reactor with plug flow be constructed? It depends on the nature of
the reaction mixture.

However, we learn from the above that with our choice of decision variables maximum
selectivity is 63, we can never do better than that! We also learn that a good reactor set up is a
cascade of CSTRs.

FAo

FBo

The total number of reactors used will depend on economics With 2 reactors we get selectivity
of over 20, with five we are close to optimum.

Examining the effect of decision variables we see that Cp increases with increased conversion of
A. For conversions larger than 0.98 the reactor volume becomes excessive.

If we took MB/A > 1 that would improve the yield and selectivity but at the expense of having to
recycle more unreacted B.

Let us ask the following question. How much excess B would we have to use in a PFR in order
Cp
to bring its overall selectivity to the level of a single CSTR i.e., S = = 14.2 at CAo = 1
Cs
(kmol/m3) and xA = 0.98. So the goal is to choose C Bo in order to get at the exit of plug flow:

Cp
= 14.2
Cs

From stoichiometry:

Cs =
1
2
[ ] 1
[ ] 1
[
C Ao C A C p = C Ao x A C p = 0.98 C p
2 2
]

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ChE 471 Lecture 6 October 2005

The prescribed desired selectivity is:

2C p
= 14.2C p = 0.859(kmol / m 3 )
0.98 C p
C s = 0.061(kmol / m 3 )

The integrated equation for PFR is:

CA C Cp
Ao = ln1
C Bo C p C Bo C Ao

The initial concentration of B is now the only unknown. Evaluate it by trial & error.

0.02 1 0.859
= ln1 gives
C Bo 0.859 C Bo C Bo

kmol
C Bo = 3.79
m3

Since CAo = l (kmol/m3), MB/A = 3.79 almost four times more B than A should be introduced
in the feed to get the selectivity in a PFR to the level of a CSTR.

A great excess of unreacted B has to be separated in the effluent:

CB = CBo Cp = 3.790-0.859 = 2.931 (kmol/m3)

Consecutive Reactions
aA = p1P
p2P = s S

Two basic problems arise:

a) conduct the reaction to completion,

b) promote production of the intermediate.

The first problem is trivial and can be reduced to a single reaction problem. Use the slowest
reaction in the sequence to design the reactor.

In order to maximize the production of intermediates PFR flow pattern is always superior to a
CSTR flow pattern.

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ChE 471 Lecture 6 October 2005

P Rp p r p 2 r2 p p r
y = = 11 = 1 2 2
A RA a r1 a a r1
P p
y max = 1
A a
P p r p k C
y = 1 2 2 = 1 2 2 P
A p1 r1 p1 k1C A

One needs to keep CA high and Cp/CA low which is best accomplished in a PFR.

Example 1
A=P r1 = 1.0 CA (kmol/m3s) = 1
P=S r2 = 0.5 CP (kmol/m3s) = 1

Starting with CAo = 1 (kmol/m3) and CPo = Cso = 0 find the maximum attainable CP in
a) CSTR, b) PFR.

We could continue to use the point yield approach.

CSTR Stirred Tank Reactor

P C 0.5C P
C P = y (C Ao C A ) = A (C Ao C A )
A CA

Solve for CP

C A (C Ao C A )
CP =
0.5(C Ao + C A )

Find optimal CA at which the CSTR should operate.

dC P
= 0 (C Ao 2C A )(C Ao + C A ) C A (C Ao C A ) = 0
dC A
C A2 + 2C Ao C A C Ao
2
=0
C Aopt = C Ao [ ]
2 1 = 0.414(kmol / m 3 )
0.414(1 0.414)
C Pmax = = 0.343(kmol / m 3 )
0.5(1 + 0.414)
C S = C Ao C A C P = 0.243kmol / m 3
P
Overall yield Y = 0.585
A

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ChE 471 Lecture 6 October 2005

@ = 0.343
P
Operational yield
A
P
Overall selectivity S = 1.4
S
Required reactor space time:

C Ao C Aopt C Ao C Aopt 1 0.414

= = = 1.4( s)
RA C Aopt 0.414

b) PFR Plug Flow Reactor

dC P P 0.5C P C A
= y =
dC A A CA

at CA = CAo, CP = 0

dC P 0.5 C p
= 1
dC A CA
d CP 1
==
dC A C A CA
CP
CA
[
= 2 C Ao C A ]
CP = 2 C A [C Ao CA ]
Find CA at the reactor exit by

dC P
= 0 C Ao 2 C A = 0
dC A
C Ao
C Aopt =
4
C Aopt = 0.25(kmol / m 3 )
[ ]
C Pmax = 2 0.25 1 0.25 = 0.5(kmol / m 3 )
C s = 1 0.5 0.25 = 0.25(kmol / m 3 )

P 2
Overall yield Y = = 0.667
A 3

@ = 0.5
P
Operational yield
A

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ChE 471 Lecture 6 October 2005

P
Overall selectivity S = 2.0
A

Required space time:

C Ao
dC A C
=
C Aopt
CA
= ln Ao = ln4 = 2ln2 = 1.39( s)
C Aopt

The same results can be obtained by using the design equations (i.e. mass balance)for P & A.

CSTR
C Ao C A C Ao
= CA =
CA 1+
CP C A C Ao
= CP = =
C A 0.5C P 1 + 0.5 (1 + )(1 + 0.5 )

dC p
= 0 gives opt = 1.4( s ), etc.
d

PFR
dC A
= C A C A = C Ao e
d
= 0, C A = C Ao = 1
dC P
= C A 0.5C P
d

=0 CP = 0
d 0.5
(e C P ) = C Ao e e 0.5 = C Ao e 0.5
d
C P = 2(e 0.5 e )
dC P
= 0 opt = 2ln 2, etc.
d

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ChE 471 Lecture 6 October 2005

Mixed Reactions

This is the most frequently encountered type of multiple reactions which can be viewed as a
combination of competitive and consecutive reactions. We can solve the problems involving
these reactions either by setting R design equations for R components or by utilizing the concept
of the point yield in simpler reaction schemes.

Example 1

2A + B = R -RA = 2k1 CA CB (kmol/m3min)

2B + R = S Rs = k2 CB CR (kmol/m3min)

k1 = 10 k2 = 1 (m3/kmol min). R is the desired product. Find CR in a) CSTR, b) PFR, when CRo
= Cso = 0. Decision variable CAo = CBo = 1 (kmol/m3).

We can write two point yields:

R R k C C k2CBCR 1 k2 CR
y = R = 1 A B = 1
A RA 2 k1 C A C B 2 k1 C A
k
C A 2 CR
R R k C C k2CBCR k1
y = R = 1 A B =
B R B k1 C A C B + 2 k 2 C B C R C + 2 k 2 C
A R
k1
R
The point yield y depends only on CR and CA and is simpler to use.
A

a) CSTR Stirred Tank Reactor

k
C A 2 CR
R k1
C R = y (C Ao C A ) = (C Ao C A )
A 2C A

C A (C Ao C A ) C (C C A )
CR = = A Ao
k k 1.9C A + 0.1C Ao
2 2 C A + 2 C Ao
k1 k1

Find optimum CA in a CSTR.

dC R k 2 k k 2
= 0 2 2 C A + 2 2 C Ao C A 2 C Ao =0
dC A k1 k1 k1

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ChE 471 Lecture 6 October 2005

C Ao
C Aopt =
k1
2 +1
k2
1
C Aopt = = 0.183(kmol / m 3 )
2 x10 + 1

0.183(1 0.183)
C Rmax = = 0.334 (kmol / m 3 )
1.9 x0.183 + 0.1

From stoichiometry

3 3
C B C Bo (C Ao C A ) + 2C R = 1 (1 0.183) + 2 x0.334
2 2
1 1
C S = (C Ao C A ) C R = (1 0183) 0.334
2 2
C B = 0.443(kmol / m ); C S = 0.0745(kmol / m 3 )
3

R R
Overall yield Y = 0.409; Y = 0.600
A B
@ = 0.334; @ = 0.334
R R
Operational yield
A B
R
Overall selectivity S = 4.48 = 4.5
S

Required reactor space time:

C Ao C A 1 0.183
= = = 5.0(min)
2k1C A C B 2 x1x0.183 x0.443

b) PFR Plug Flow Reactor

dC R R 1 k C
= y = + 2 R
dC A A 2 2 k1 C A
C A = C Ao ,C R = 0
d k2 1 k2
C A 2 k1 C R = C A 2 k1
dC A 2
k2 k2
1
2 k1
C C C A C Ao
2 k1
CA CA
0.95 0.05
CR = Ao A
=
k 1 .9
2 2
k1

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ChE 471 Lecture 6 October 2005

For optimal CA at reactor exit:

1

dC R k k2
1 2 k
= 0 C Aopt = 2 1
dC A 2 k1
1

C Aopt = (0.05) 0.95

= 0.0427(kmol / m 3 )

10.95 x0.0427 0.05 0.0427

C Rmax = = 0.427(kmol / m 3 )
1.9

3
C B = 1 (1 0.0427) + 2 x0.427 = 0.418(kmol / m 3 )
2

1
CS = (1 0.0427) 0.427 = 0.0517(kmol / m 3 )
2

R R
Overall yield Y = 0.446; Y = 0.734
A B
@ = 0.427; @ = 0.427
R R
Operational yield
A B
R
Overall selectivity S = 8.27 = 8.3
S

Reactor space time:

C Ao
dC A
=
CA
2C A C B.

From stoichiometry

3
C B = C Bo (C Ao C A ) + 2C R
2

but all along the PFR

C A0.05 C A
CR =
1.9

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ChE 471 Lecture 6 October 2005

C B = C Bo
3
(C Ao C A ) + 2 (C A0.05 C A )
2 1.9
2 2 0.05
C B = 1.5 C A + C A 0.5
1.9 1.9
C B = 0.447C A + 1.05C A0.05 0.5
1
dC A
= 0 .5 integrate numerically (2.759 min )
0.0427 0.447C + 1.05C A 0.5C A
2 1.05
A

Caution must be exercised when using the point yield concept and finding maximum
concentrations in mixed reactions. Sometimes formal answers will lie outside the
physically permissible range if the other reactant is rate limiting.

For example in Example 1 if we take

kmol kmol
CAo = 2 3 ; CBo = 1 3
m m

We are feeding the reactants in stoichiometric ratio for reaction 1.

Following the above described procedure in a CSTR we would find

C Ao
C A opt = = 0.366(kmol / m 3 )
2 x10 + 1
0.366(2 0.366)
C Rmax = = 0.668(kmol / m 3 )
1.9 x0.366 + 0.2

However these values are not attainable since from stoichiometry it follows that:

3
C B = 1 (2 0.366) + 2 x0.668 = 0.115 < 0
2

This indicates that B is not introduced in sufficient amount to allow the reactions to proceed to
that point.

If CBo = 1.115 (kmol/m3) then the above CR max can be obtained (theoretically) at CB = 0 and that
would require an infinitely large reactor.

Thus the maximum reactor size that is allowed would determine CBmin . Say CBmin =0.01
(kmol/m3) (99% conversion of B).

Calculate the resulting CA and CR from

22
ChE 471 Lecture 6 October 2005

4 2
C A = C Ao C R (C Bo C Bmin )
3 3
C A (C Ao C A )
CR =
1.9C A + 0.1C Ao

C A = 0.461(kmol / m 3 )
That yields: C R = 0.660(kmol / m 3 )
C S = 0.110(kmol / m 3 )

R R
Overall yield Y = 0.429; Y = 0.667
A B
@ = 0.330; @ = 0.660
R R
Operational yield
A B
R
Overall selectivity S = 6.0
S
Reactor space time:

2 0.461
= = 170min
2 x1x0.461x0.01

II. Systems with change in total volumetric flow rate ( A 0) gases

Same approach may be used but one needs to deal with X& i& extents rather than concentrations.
Use relationships from Lecture 1.

Summary

PFR promotes more reactions of higher order with respect to reactions of lower order.

CSTR favors reactions of lower order with respect to those of higher order.

In consecutive reactions better yields are achieved always in PFR than in a CSTR for an
intermediate product.

Select judiciously the objective function to be optimized.

Remember: Optimizing overall yield does not necessarily lead to the same result as maximizing
the production rate (or concentration) of the desired product or as maximizing selectivity.

Be aware of the relationship of the design equations and reaction stoichiometry.

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