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Ideal Reactors and Multiple Reactions Isothermal Operation: 0 For I 1,2,3... R
Ideal Reactors and Multiple Reactions Isothermal Operation: 0 For I 1,2,3... R
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
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 + ∑υ 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 = ∑ υij ri (2)
i =1
Fjo Fj
Qo Q
V
The design equation (i.e., the mass balance for species j) can be written for R species, j =
1,2,3…R:
R
Fjo − Fj + ∑ υij 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
α
(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:
α ij
⎛ R ⎞
S
∑ ij ⎜
⎜ F jo + ∑ υ ij X& i ⎟
⎟
ri = k i ∏ C tot
α i =1
,o ⎜ S R ⎟ (4b)
j =1
⎜⎜ Ftot ,o + ∑∑ υ ij X& i ⎟⎟
⎝ j =1 i =1 ⎠
where α 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.
⎛ R S ⎞
Q = Qo ⎜⎜1 + ∑∑υ 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
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
= ∑ υ ij ri (7)
dV i =1
j = 1, 2, ...R
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.
dn j R
= ∑ υ ij ri (8)
dt i =1
3
ChE 471 Lecture 6 October 2005
R
n j = n jo + ∑υ ij X i (9)
i =1
For j = 1, 2, 3…S
α ij
⎛ R
⎞
s ⎜ ∑υ ij X i ⎟
ri = k i Π C joij ⎜1 + i =1 ⎟
α
(10)
⎜ n jo ⎟
j =1 ⎜ ⎟
⎝ ⎠
s α ij
⎛ R
⎞
ri = k i Π ⎜ C jo + ∑υ ij ξ i ⎟ (10a)
⎝ i =1 ⎠
j =1
Xi
where ξ 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.
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
⎛P⎞ Rp ∑ υ ip ri
y⎜ ⎟ = = R
i =1
{point (relative) yield
⎝ A ⎠ − RA − υ 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.
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
@ ⎛⎜ ⎞⎟ = Y ⎛⎜ ⎞⎟ x A
P P
⎝ A⎠ ⎝ 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.
⎛ 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
εA = 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 ∑∑υ
i =1 j =1
ij =0
Competitive Reactions
⎛P⎞ p
y max ⎜ ⎟ = 1
⎝ A ⎠ a1
⎛P⎞ 1
y⎜ ⎟ =
⎝ A ⎠ 1 + 2 2 C (α 2 A −α1 A ) C (α 2 B −α1 B )
a k
A B
a1 k1
⎛P⎞
We want y ⎜ ⎟ to be as high as possible. This implies:
⎝ A⎠
7
ChE 471 Lecture 6 October 2005
Example 1
⎛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⎠
C Ao − C A C Ao x A
τ= = = 48.0( s )
− RA C Ao (1 − x A ) + C Ao
2
(1 − x A ) 2
8
ChE 471 Lecture 6 October 2005
b) PFR
⎛ 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 τ= ∫
CA
− RA
= ∫
CA
C A (1 + C A )
⎛ C Ao (1 + C A ) ⎞ ⎡ 1 + 1 − 0.98 ⎤
τ = 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
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
1
ξ1 = C P − C Po ξ 2 = [C Ao − C A − C P ]
2
Now:
C B = C Ao − ξ1 = C Bo − C p
C S = C So + ξ 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⎠
10
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
τ = = = = 306( s )
− RB C AC B 0.02 x0.141
b) PFR
dF p Rp ⎛P⎞
= = − y⎜ ⎟
dFA RA ⎝ A⎠
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
CA C ⎛ C Bo − C p ⎞
− Ao = ln⎜⎜ ⎟⎟
C Ao − C p C Bo ⎝ C Bo ⎠
= 1 + ln(1 − C p )(*)
CA
1− Cp
11
ChE 471 Lecture 6 October 2005
φ (C p ) = C p − 0.98 − (1 − C p )ln(1 − C p ) = 0
Dφ (C p ) = 2 + ln(1 − C p )
n +1
φ (C pn )
C =C − n
Newton-Raphson Algorithm
Dφ (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⎠
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 )
12
ChE 471 Lecture 6 October 2005
C Bo =1 1+ ln C
dC B Bo
e −u
τ= ∫ = e ∫ u du
C B = 0.387 C B (1 + lnC B )
2
1+ ln C B
where
∞
e −u
E1 ( z ) = ∫ du exponential integral
z
u
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
13
ChE 471 Lecture 6 October 2005
⎛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 CSTR’s.
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
]
14
ChE 471 Lecture 6 October 2005
2C p
= 14.2⇒C p = 0.859(kmol / m 3 )
0.98 − C p
C s = 0.061(kmol / m 3 )
The initial concentration of B is now the only unknown. Evaluate it by trial & error.
0.02 1 ⎛ 0.859 ⎞
− = ln⎜⎜1 − ⎟⎟ 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.
Consecutive Reactions
aA = p1P
p2P = s S
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.
15
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 Cβ
y ⎜ ⎟ = 1 − 2 2 = 1 − 2 2 αP
⎝ 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) α = 1
P=S r2 = 0.5 CP (kmol/m3s) β = 1
Starting with CAo = 1 (kmol/m3) and CPo = Cso = 0 find the maximum attainable CP in
a) CSTR, b) PFR.
⎛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 )
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:
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⎠
17
ChE 471 Lecture 6 October 2005
⎛P⎞
Overall selectivity S ⎜ ⎟ = 2.0
⎝ A⎠
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
τ= CA =
CA 1+τ
CP C Aτ C Aoτ
τ= CP = =
C A − 0.5C P 1 + 0.5τ (1 + τ )(1 + 0.5τ )
dC p
= 0 ⇒ gives τ opt = 1.4( s ), etc.
dτ
PFR
dC A
= −C A C A = C Ao e −τ
dτ
τ = 0, C A = C Ao = 1
dC P
= C A − 0.5C P
dτ
τ =0 CP = 0
d 0.5τ
(e C P ) = C Ao e −τ e 0.5τ = C Ao e −0.5τ
dτ
C P = 2(e −0.5τ − e −τ )
dC P
= 0 ⇒ τ opt = 2ln 2, etc.
dτ
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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
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).
⎛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⎠
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
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⎠
C Ao − C A 1 − 0.183
τ= = = 5.0(min)
2k1C A C B 2 x1x0.183 x0.443
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
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⎠
From stoichiometry
3
C B = C Bo − (C Ao − C A ) + 2C R
2
C A0.05 − C A
CR =
1.9
21
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
τ = 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.
⎛ kmol ⎛ kmol
CAo = 2⎝ 3 ⎞⎠ ; CBo = 1⎝ 3 ⎞⎠
m m
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).
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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
τ= = 170min
2 x1x0.461x0.01
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.
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.
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