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# IDEAL REACTORS

(CHE 471)
M.P. Dudukovic
Chemical Reaction Engineering Laboratory
(CREL),
Washington University, St. Louis, MO
ChE 471: LECTURE 4 Fall 2003

IDEAL REACTORS

One of the key goals of chemical reaction engineering is to quantify the relationship between
production rate, reactor size, reaction kinetics and selected operating conditions. This requires a
mathematical model of the system, which in turn rests on application of conservation laws to a
well-defined control volume of the reaction system and on use of appropriate constitutive
expressions for the reaction rates. The concepts of ideal reactors allow us to quantify reactor
performance as a function of its size and selected operating conditions.

To illustrate this useful concept we deal here with a single, homogeneous phase, single reaction
at constant temperature. We introduce then the ideal batch reactor, and two ideal continuous
flow reactors. In each case we apply the conservation of species mass principle which states
(Rate of Accumulation) = (Rate of Input) (Rate of Output) + (Rate of Generation) (2-1)

Equation (2-1) is applied to an appropriately selected control volume, the largest arbitrarily
selected volume of the system in which there are no gradients in composition.

## 2.1 Batch Reactor

The ideal batch reactor is assumed to be perfectly mixed. This implies that at a given moment in
time the concentration is uniform throughout the vessel. The volume, V in the development
below is assumed equal to the volume of the reaction mixture. This is then equal to the reactor
volume VR in case of gas phase reaction but not in case of liquids (V< VR, then). The batch
reactor can be an autoclave of V = const (Figure 2.1-a) and a constant pressure, P = const)
(Figure 2.1-b) vessel. The former is almost always encountered in practice.

## Our goal is:

a) To find a relationship between species concentration (reactant conversion) and time on
stream.
b) To relate reactor size and production rate.

1
Let us consider a single irreversible reaction A P with an n-th order irreversible rate of
reaction
RA = kC An (2-2)

At t = 0 a batch of volume V is filled with fluid of concentration CAo. Reaction is started (nAo=
CAoVo). Find how reactant conversion depends on reaction time? Also determine the production
rate as a function of reaction time.

## We apply (eq 2-1) to reactant A:

dnA d(VCA )
0 0 + (RA V) = = (2-3)
dt dt

a) V = const b) P = const

## FIGURE 2-1: Schematic of Batch Reactors

2
In our case due to the fact that
j=1
j = 0 , V= const irrespective of the batch reactor type, so that

eq (2-3) becomes
dC A
= RA (2-4)
dt
dC n
A = ( RA ) = kC A ; t = 0 C A = CAo (2-5)
dt

## Separation of variables and integration yields:

CA
t
dC A 1 CAo dC A
dt = kC n = k C n (2-6)
o C A0 A CA A

2
CAo
t 1 C 1n
to= A
k 1 n CA
(2-7)
1
t0 =
k(1 n)
[C Ao C A ]
1n 1n

1n
C Ao
t=
k(1 n)
[
1 (1 x A ) ]
1n
(2-8a)

or
1
n1 [(1 x A ) 1]
1n
t= (2-8b)
k(n 1)CAo

Once order of reaction, n, is specified (as shown below for n=0, 1, 2, 1.5), the relation between t
n=0 n =1 n=2
CAo x A 1
t = ln
1 1 1 (2-9)
t= t= 1
k k 1 x A kC Ao 1 x A

1 1
n = 1.5; t= (1 x A ) 0.5 1
0.5k C Ao

mol FAo x A
FP =
S 1

## The production rate of P is given by:

(moles of P processed per batch)
FP = (2-10)
(reaction time + shut down time per batch)
C AoV x A C AoV x A
FP = = (2-11)
t + ts 1
n1 [
(1 x A ) ] + t s
1n

k(n 1)C Ao

NOTA BENE: Equation (2-11) is valid only for systems of constant density. Thus, it is valid
for all systems, gas or liquid, conducted in an autoclave at V = const (see
Figure 2-1a). It is also valid for gaseous systems with no change in the

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number of moles ( j = 0) conducted in P = const. system at T = const

(Figure 2-1b).
The first equality in equation (2-11) gives the general result, the second equality presents the
result for an n-th order irreversible reaction with resect to reactant A.

To use this equation the shut down time, i.e. the time needed between batches, ts, must be
known. Consider now the following second order reaction with stoichiometry A = P.
mol
RA = 0.1CA
2
L min

a) Find the batch reactor volume needed to produce FP = 38 kmol/min if reactor shut down
time is 60 minutes and the desired conversion is 0.95. Initial reactant concentration is
CAo = 1 (mol L).

Using the right form of equation (2-9) for n = 2 we get the reaction time.
1 1 1
t= 1 = = 190.0(min)
0.1 1 1 0.95 1 0.95

## Then, solving equation (2-11) for the volume we get

FP (t + ts ) 1.38(190 + 60) 3
V= = = 10,000L = 10m
C Ao x A 1x0.95

b) What is the maximum production rate, FP, achievable in the above batch reactor of
volume V=10m3 if ts, T, CAo all are fixed at previous values.

## Consider eq (2-11) for production rate as a function of conversion

CAoV x A 10 4 x A 10 3 x A
FP = = xA = x
1 xA 10 + 60 A
+6
+ t s 1 x 1 x
kC Ao 1 x A A A

2
3 x A (1 x A ) 3 xA xA
FP = 10 = 10
x A + 6(1 x A 6 5x A

4
This expression has a maximum which we can locate by differentiation
dFP
= 0 (1 2x A )(6 5x A ) + 5 (x A x 2A ) = 0
dx A
6 5x A 12x A + 10x 2A + 5x A 5x 2A = 0
2
6 12x A + 5x A = 0
6 36 30 6 6
x A1, 2 = = = 0.710
5 5
Clearly, the positive sign is not permissible as conversion cannot exceed unity. We need to
check whether the answer is a maximum or a minimum.
dFP
> 0 for x A < 0.710
dx A
dFP
< 0 for x A > 0.710
dx A
Maximum at xA = 0.710.
0.710 0.710 2 mol
FPmax = 10 3 = 84.0
6 5x0.710 min

84 38
An increase in productivity of x100 = 121% can be achieved at the expense of more
38
unreacted A to be recycled.

One must include the cost of separation into the real economic optimization.

## 2.2 Continuous Flow Reactors (Steady State)

2.2.1 Continuous Flow Stirred Tank Reactor (CFSTR or CSTR or STR)
The CSTR is assumed perfectly mixed, which implies that there are no spatial gradients of
composition throughout the reactor. Since the reactor operates at steady state, this implies that a
single value of species concentration is found in each point of the reactor at all times and this is

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equal to the value in the outflow. The outflow stream is a true representative of the reaction
mixture in the reactor.

FAO FA = FAo (1 x A )

CA
C AO

## FIGURE 2-2: Schematic of a Continuous Flow Stirred Tank Reactor (CSTR)

What does the above idealization of the mixing pattern in a CSTR imply? It postulates that the
rate of mixing is instantaneous so that the feed looses its identify instantly and all the reaction
mixture is at the composition of the outlet. Practically this implies that the rate of mixing from
macroscopic level down to a molecular scale is orders of magnitude faster than the reaction rate
and is so fast in every point of the vessel.

Then the mass balance of eq (2-1) can be applied to the whole volume of the reactor recognizing
that at steady state the accumulation term is identically zero. Again, taking a simple example of
an irreversible reaction A P application of eq (2-1) to reactant A yields:
FAo FA + ((RA)V=0 (2-12)

Molar flow rate of unreacted A in the outflow by definition is given by FA = FAo (1-xA) = Q CAo
(1-xA). The production rate of P is given by
FP = (R A )V = (R P )V (2-13)

## Reactor volume is given by eq (2-12)

FAox A QoC Aox A
V= = (2-14)
(R A ) (R A )

6
Reactor space time is defined by
V C Aox A
= = (2-15)
Qo (R A )

Using stoichiometry we readily develop the relation between production rate, FP, and reactor
volume, V.

Let us consider again the example of our 2nd order reaction, A = P, with the rate below:
n 2 mol
R A = kC A = 0.1C A
L min

Find CSTR volume needed to process FP = 38 mol/min. Suppose we choose again xA = 0.95 for
our exit conversion.

## From eq (2-13) we get

FP = 0.1 C 2Ao (1-xA)2 V

## And solving for volume V

FP 38 3
V= 2 2 = 2 = 152,000L = 152m
0.1C (1 x A )
Ao 0.1x1(1 0.95)
If we consider eq (2-13) it is clear that now the maximum production rate is obtained when the
reaction rate is the highest. That for n-th order reactions is at zero conversion. So the maximum
FP from VCSTR = 12,000 L is obtainable at xA = 0.

## FPmax =0.1 x 1 x 152,000 = 15,200 mol/min.

The penalty or this enormous production rate is that the product is at zero purity. Hence, the
separation costs would be enormous. The average rate in a CSTR is equal to the rate at exit
conditions.
( RA ) = ( R A ) exit = 0.1C 2Ao (1 x A )2exit = 0.1x1(1 0.95) 2 = 2.5 x10 4 ( mol / L min)

7
2.2.2 Plug Flow Reactor (PFR)
The main assumptions of the plug flow reactor are: i) perfect instantaneous mixing
perpendicular to flow, ii) no mixing in direction of flow

This implies piston like flow with the reaction rate and concentration that vary along reactor

C AO C AO

FAO FA = FAo (1 x A )
FAo dx A = ( R A )dV

## FIGURE 2-3: Schematic of a Plug Flow Reactor (PFR)

Since there are now composition gradients in the direction of flow, the control volume is a
differential volume V to which eq (2-1) is applied. Let us again use the mass balance on
reactant A

FA V FA V + V + RA V = 0 (2-16)
FA + RA V = 0
FA
lim = (lim )( R A )
V 0 V V 0

dFA
= ( RA ) (2-17)
dV

## Since FA = FAo (1 x A ) then dFA = FAodx A

so that
dx A
FAo = ( RA ) (2-18)
dV

## With initial conditions:

V=0 xA = 0 (2-19)

8
Upon separation of variables in (eq 2-18) and integration:
V xA
dx A
dV = F (R
o
Ao
A )
(2-20)
o

## For an n-th order reaction (with A = 0 ) we get

Q o [(1 x A ) 1]
xA 1n
F dx A
V = Aon
kC Ao
= n1
(1 x A ) n kC Ao (n 1)
(2-21)
o

## The expression for the PFR space time

V 1
= = n 1
Qo kC Ao (n 1)
[(1 x A )1n 1] (2-22)

is now identical to the expression for reaction time t in the batch reactor.
For the example of the second order reaction used earlier we get

xA xA
dx A FAo 1
V = FAo 2 2 =
kC Ao 1 x A o
2
o
kC Ao (1 x A )

FAo 1 FAo xA
V= 2 1 x A 1 = kCAo
2 1 x A
kCAo
FAo = Qo CAo
V 1 xA
= = (Same as the expression for reaction time t in the batch reactor)
Qo kC Ao 1 x A

Let us consider our example of the second order reaction and find the PFR volume needed to
produce FP = 38 mol/min
mol
( RA ) = 0.1CA
2

L min
mol
when C Ao = 1 and desired conversion xA = 0.95.
L
From stoichiometry it follows that
FP
FAo x A = FP FAo =
xA

9
Substitution in the expression for reactor volume (eq (2-21)) we get:
FP xA FP
V= =
2
kCAo xA 1 x A kCAo
2
(1 x A )
38
V= = 7,600L = 7.6m3
0.1x1(1 0.95)

The maximum production rate from that volume can be obtained at zero conversion
FP = kC 2Ao (1 x A )V
FPmax = 0.1x1x7600 = 760mol / min

FAo x A FP 38 3 mol
Average rate in PFR RA = = = = 5.0x10
V V 7,600 min
mol
( RA ) entrance = 0.1C 2Ao = 0.1 = 10 1
L min
mol
( RA ) exit = 0.1C 2Ao (1 0.95)2 = 2.5x10 4
L min)

Clearly there is a big variation in the reaction rate between the entrance and exit of the plug flow
reactor (PFR).

## 2.3 STY Space Time Yield

Volumetric Reactor Productivity - RVP

## Reactor volumetric productivity (RVP) is defined by:

FP
RP = (2-23)
V
For our 2nd order reaction example of stoichiometry A=P, RVP for the two continuous flow
reactors is:

## CSTR RP = (RP )exit = ( R A ) exit = kC 2Ao (1 x A )2 (2-24a)

FP 2
PFR RP = = kCAo (1 x A ) (2-24b)
V

10
For the same exit conversion
2
(R P )PFR kC Ao (1 x A ) 1
= 2 =
(RP ) CSTR kC Ao (1 x A )

At xA = 0.95
(RP ) PFR
= 20
(RP ) CSTR

## Indeed 20 x 7,600 L = 152,000 L

This is why higher CSTR volume is needed.
At xA = 0 ( RP ) PFR = (RP )CSTR

There is no difference!
Let us consider another example to illustrate some important points.

Ex: 2A + 3B = P + S stoichiometry
mol
r = 0.1C A C B2 - rate of reaction
L min
mol
C Ao = 2 and x A = 0.95 - are the feed reactant concentration and desired conversion
L
FP = 10 mol/min is the desired production rate

Assume first that we will operate at stoichiometric ratio so that CBo = 3 (mol/L). The reaction
occurs in the liquid phase so that A = 0 . Find the needed reactor volume.
a) Batch (ts = 60 min)
b
RA = 0.2CAo (1 x A )(C Bo CAo x A )2
a
2
3
RA = 0.2C3Ao (1 x A ) (1 x A ) 2
2
2
3
RA = 0.2C3Ao (1 x A ) 3
2

11
Reaction time is:
xA
1 dx A
t=
3
2 (1 x )3
o A
0.2C 2Ao
2
xA xA
1 g dx 1 1 1
t=
0.2x2 2 a
(1 x) 3 =
1.8 2 (1 x )2
o o

1 1 1 1
t= 1 = 1

3.6 (1 x A ) 2
36 (1 0.95)
3

t = 110.83 min
1
C Ao x A V 0.95xV
FP = 2 = = 10
t + ts 110.83 + 60
170.83x10
V= = 1,798 L = 1.8m3
0.95
b) CSTR
FAo FP
= - from stoichiometry
2 1
V x
= A - basic design equation (2-14)
FAo R A
FAo x A 2 FP 2FP
V= = =
RA ( RA ) 0.2CA C 2B
FP FP
V= 2 = 2
C 3 3 3 3
3
0.1CAo (1 x A ) Bo x A 0.1C Ao (1 x A )
CAo 2 2

10 10 1 3
V= 3 = 3 = 4,444(L ) = 44.4 m
0.1 2 9(1 0.95) 1.8 0.05
2
3 3
( RA ) = ( R A ) exit = 0.2 xC Ao (1 x A ) exit
3

2
= 0.2x2x9(1-0.95)3 = 4.5 x10-4 (mol/L min)

12
c) PFR
2FP
FAo = - from stoichiometry
xA
Basic design equation (2-21)
xA xA
dx A dx
V = FAo = FAo 2
o R A o 3 3
0.2C Ao (1 x) (1 x )2
2
xA
2FP dx 100 xA dx
V= 2 =
(1 x )3 18x 0.95 o (1 x )3
3 3 o
0.2C Ao x
2 A

100 1 1
V= 1
18x0.95 2 (1 x A ) 2

50 1 3
= 2 1 = 1,167(L ) = 1.17 m
10 0.95 (1 0.95)

Now the rate, at stoichiometric feed ratio, along the PFR as a function of conversion is
2
3 3
R A = 0.2C (1 x A ) 3 = 3.6(1 x A ) 3
2 Ao

## PFR reactor volume as function of conversion at stoichiometric feed ratio is

xA xA
2FP dx F dx
V=
3.6x A o (1 x) 3 = 1.8xP A (1 x)
o
3

Hence, the production rate from a given PFR volume as a function of conversion (at
stoichiometric feed rate) is
1.8x A V 3.6x A V
FPstoich = =
xA
1
(1dxx) 3 (1 x A ) 2 1
o

How much can we increase the production rate by doubling CBo to CBo = 6 (mol/L), i.e. by using
B in excess?

13
Now the rate as a function of conversion is:
2
C 3 3
2

R A = 0.2C (1 x A ) Bo
3
x A = 0.2x2 3 x (1 x )(2 x A )2
Ao
C Ao 2 2
R A = 3.6(1 x A )(2 x A )2

a) Batch
xA x
dx A 2 A dx
t = C Ao =
o
( RA ) 3.6 o (1 x)(2 x)2

## To integrate use partial fractions:

A B + Cx A(2 x ) 2 + (B + Cx )(1 x )
+ 2 = 2
1 x (2 x ) (1 x )(2 x )
4 A 4 Ax + Ax 2 + B Bx + Cx Cx 2 = 1
4A+B=1 4A-3A=1 A=1
-4A-B+C=0 -3A-B-0 B=-3A B=-3
A-C=0 C=A = 1
dx dx x3
(1 x)(2 x) 2 = +
1 x (2 x)2
dx

xA
dx 2x 1
= 2 dx 2 dx
o
1 x (2 x) (2 x)

1 xA
= ln(1 x) + ln(2 x)
2 x o
1 1
= l n (1 x A )+ 0 + ln (2 x A ) ln 2 +
2 x A 2

2 xA 1 2 2 xA xA
= ln + 1 = ln
2(1 x A ) 2 2 x A 2(1 x A 2(2 x A )

1 2 x A xA
t= ln
1.8 2(1 x A 2(2 x A ) x
A = 0.95

## 1 1.05 0.95 1 0.95

t= ln = ln10.5
1.8 2x0.05 2x1.05 1.8 2.1
t = 1.055 min Batch ill advised at these conditions since ts >> t!

14
1
C Ao x A V 0.95x1,798 mol
FPnew =2 = = 27.97
t + ts 1.06 + 60 min
FP 27.97 10
100 = 100 = 179.7%
FPold 10

## By operating at double the stoichiometric requirement of B we increase, at same xA, the

production rate of the batch reactor by 180%.

b) CSTR
2
RA = 3.6(1 x A )(2 x A )2 3.6(1 0.95)(2 0.95)
mol
RA = 3.6x0.05x1.052 = 0.19845
L min
R A 0.19845 mol
FPnew = R P V = V= 44,494 = 4,410
2 2 min
FP 4,410 10
100 = x100 = 44,000%
FPold 10

## In a CSTR we increase the production rate by 44,000%!

c) PFR
xA
dx
V = FAo
o
3.6(1 x)(2 x)2
Vx A 1.8x AV
FPnew xA = xA
2 dx dx

3.6 o (1 x)( x)
3 (1 x)(2 x) 3
o

1.8x A V
FPnew =
2 x A xA
ln
2(1 x A ) 2(2 x A )

1.8x0.95x1,167 1.8x0.95x1,167
FPnew = =
2 0.95 0.95 1.05 0.95
ln ln
2(1 0.95) 2(2 0.95) 0.1 2.10
FPnew = 1,051 mol / min

15
FP 1,051 10
x100 = x100 = 10,419%
FPold 10

## We present below these ratios of production rate obtainable at nonstoichiometric ratio of

C Bo C Ao = 2 (C Bo C Ao) stoich and at stoichiometric ratio of CBo/CAo = 3/2 for our example reaction.

## This ratio is:

For a PFR:
1.8x A V
2 xA xA 1
ln 1
FP(non stoich ) 2(1 x A 2(2 x A V (1 x A )2
= =
FP( stoich) 3.6x A 2 xA xA
1 2 ln
2
1 2(1 x A 2(2 x A )
(1 x A )

## Specifically for x A = 0.95 we get

1
FP(non stoich) 1 199.5
= 0.05 2 = = 105.0
FP(stoich) 1.05 0.95 0.75 ln10.5 0.45228045
2 ln 2 ln10.5
2x 0.05 2x1.05 2.10

For a CSTR
FP(non stoich) 3.6(1 x A )(2 x A )2 (2 x A )2
= = =
FP(stoich) 3.6(1 x A ) 3 (1 x A )2
2 2
2 0.98 FP( nonstoich) 1.05
= = 212 = 441
1 0.98 FP 0.05
( stoich)

Let us examine the situation when the reaction just considered occurs at P = const, T = const in
the gaseous phase. Then due to stoichiometry we have

2B + 3B = P + S
j = 1 + 1 2 3 = 3

16
Consider stoichiometric feed of reactants at CBo/CAo =3/2.
2
y Ao = = 0.4 ( A ) = 2
5
j 0.4 (3)
A = y Ao = = 0.6
( A ) 2
CBo 3
xA
1 x A CAo 2
C A = C Ao CB = CAo
1 0.6x A 1 0.6x A
2
3 3 (1 x A )3 (1 x A )3
RA = 0.2xCAo 2 (1 0.6x )3 = 3.6 3
A (1 0.6x A )

CSTR
( RA )
FP = V
2
2FP 2x10(1 0.6x0.95)3
V= =
RA 3.6(1 0.95)3
10 (1 0.57)3
V= 3 = 44,444x0.433 = 3,534(L)
1.8 0.05

## Tremendous reduction in required volume compared to the A = 0 case occurs!

PFR
xA xA
dx A 2Fp (1 0.6x)3 dx
V = FAo = o 3.6(1 x)3
o
RA xA
x A = 0.95 0.95 3
F (1 0.6x)3 10 1 06x)
V= P
1.8x A
0
(1 x) 3 dx =
1.8x0.95
0
1 x
dx

V = 125.6(L)

## Again a significant reduction in PFR reactor volume requirement is observed. Why?

17
2.4 Graphic Comparison of PFR and CSTR

V =
xA
FAo CSTR ( RA ) exit
V x Ao
dx A
=
FAo PFR o RA

The graphic representation of the above two design equations is represented below for an n-th
order reaction. Clearly, for fixed feed conditions and feed rate and for chosen desired conversion
the volume of the CSTR will always be larger than or equal to the PFR volume.

1
V
R A = area of box
FA o CSTR

V
= area under the curve
FA o PFR

xA

## FIGURE 2-4: Graphical Comparison of CSTR and PFR

18
Ideal Reactors and Multiple Reactions
Isothermal Operation
(CHE 471)
M.P. Dudukovic
Chemical Reaction Engineering Laboratory
(CREL),
Washington University, St. Louis, MO
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

## 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.

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

## 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

@ = 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

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

8
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

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
= = = = 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

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

11
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 )

12
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.

A+A=S

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

13
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

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

## 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.

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

Consecutive Reactions
aA = p1P
p2P = s S

## 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.

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 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.

## 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

16
ChE 471 Lecture 6 October 2005

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

= = = 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

17
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

18
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

19
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

20
ChE 471 Lecture 6 October 2005

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

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
= 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

## 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.

23
NONISOTHERMAL OPERATION OF
IDEAL REACTORS
Continuous Flow Stirred Tank Reactor
(CSTR)
(CHE 471)
M.P. Dudukovic
Chemical Reaction Engineering Laboratory
(CREL),
Washington University, St. Louis, MO
ChE 471 Fall 2005
LECTURE 7

## NONISOTHERMAL OPERATION OF IDEAL REACTORS

Continuous Flow Stirred Tank Reactor (CSTR)

T V T
To To
Fj
or Fj
Fjo, Qo Fjo, Qo
V

Tmo Tm Tmo Tm
Figure 1: Schematic of CSTR with jacket and coil
Assumptions:

Homogeneous system
s
a) Single Reaction A
j =1
j j =0

A CSTR is always assumed perfectly mixed so that the concentration of every species is uniform
throughout the reactor and equal to the concentration in the outflow. Due to assumption of perfect
mixing the temperature, T, throughout the reactor is uniform and equal to the temperature of the
outflow. The only difference between an isothermal CSTR treated previously and the general case
treated now, is that now we do not necessarily assume that reactor temperature, T, and feed temperature,
To, are equal.

## Two basic types of problems arise:

1. Given feed composition and temperature, rate form and desired exit conversion and temperature find
the necessary reactor size to get the desired production rate and find the necessary heat duty for the
reactor.

2. Given feed conditions and flow rate and reactor size together with cooling or heating rates,
determine the composition and temperature of the effluent stream.

To solve either of the above two problems we need to use both a species mass balance on the system and
the energy balance.

## Consider a single reaction

s

A
j =1
j j =0 (1)

or
aA + bB = pP (1a)

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Suppose the reaction is practically irreversible and the rate of reaction, which is a function of
composition and temperature is given by:

kmol
r = k o e E / RT C A C B 3 (2)
1424 3 123 m s

## Arrhenius concentration dependence

Temperature n-th order reaction n= +
Dependence of the rate

For a single reaction we can always eliminate all concentrations in terms of conversion of the limiting
reactant A (Lecture 1).

For liquids

j C jo
C j = C Ao M j / A x A ;M j / A =
A C Ao
For gases

M j / A j xA
A To P
C j = C Ao
1 + A x A TPo

where

A = y Ao
j

( A )

## The rate now becomes:

For liquids

( + )
r = k o e E / RT C Ao (1 x A ) M B / A b x A (3a)
a

For gases

b
(1 x A ) M B / A x A
T a
r = k o e E / RT o C Ao ( + )
+
(3b)
T (1 + A x A ) +

## (Rate of input ) (Rate of output )+ (Rate of generation by reaction)= 0 (4)

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## Apply equation (4) to mass of species A: (or to any species j)

FAo FA + A rV = 0; F jo F j + j rV = 0

FAo x A = arV = 0

C Ao x A = ar (5)

X& = rV (5a)

where
V
=
Qo

The energy balance of course cannot contain a generation term (in absence of nuclear reactions) and
hence can be written as:

s
~ s
~
F
j =1
jo H jo F j H j + q& = 0
j =1
(6)

kmol j
F jo - molar flow rate of species j in the feed
s
kmol j
Fj - molar flow rate of species j in the outflow
s
~ J
H j - virtual partial molal enthalpy of species j in the outflow mixture
kmol j
~ J
H jo - virtual partial molal enthalpy of species j in the feed
kmol j
J
q& - rate of heat addition from the surroundings i.e from the jacket or coil to the
s
reaction mixture in the reactor

The energy balance given by equation (6) is not general in the sense that the following assumptions have

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LECTURE 7

## Assumptions involved in deriving eq (6):

1. Potential energy changes are negligible with respect to internal energy changes.
2. Kinetic energy changes are negligible with respect to internal energy changes.
3. There is no shaft work involved i.e the only work term is the expansion (flow) work.

J
The virtual partial molal enthalpy, H j , is defined by:
mol j

s
~
m& tot H = F j H j
j =1

kg
m& tot - mass flow rate of the mixture
s
J
H - enthalpy per unit mass of the mixture
kg

In principle the virtual partial molal enthalpy can be evaluated by the following procedure (for gases):

H j (T , P, y j ) = H ofj + C * dT + [ H (T , P) H T , P] + [ H (T , P, y j ) H (T , P)]
T
~ *
~ jj ~ j ~ j ~ j ~ j
T*o

H - standard enthalpy of formation for species j at the pressure Po of standard state and temperature
~ f jo

## T (enthalpy of 1 kmole of pure j at To, Po)

o

C ~ f j*
dT - change in enthalpy of species j, if it behaved as an ideal gas, due to change in temperature
To

from standard state temperature T o to the temperature of interest T. C is the specific heat of j in ideal
~ p *j

gas state. In reality C pjo data for real gases obtained at atmospheric or lower pressures can be used.

C
*
H o+ f j*
dT = H ( T , P o ) enthalpy per mol of j for pure j, if it behaved like an ideal gas, at T and Po.
~ fj ~ j
To
Since enthalpy of an ideal gas does not depend on pressure this is also the enthalpy per kmol of j, if it
*
were an ideal gas, at T and P, H (T, P ).
~ j

*
H (T , P) H (T , P) = pressure correction factor i.e the difference between the enthalpy of j being a
~ j ~ j
*
real gas at T, P, ( H (T , P) and enthalpy of j being an ideal gas at T, P ( H (T , P) ).
~ j ~ j

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LECTURE 7

Frequently the pressure correction is read off appropriate charts and is given by:

H* H j
~ j ~

H j (T , P) H j (T , P) = Tcj
*

Tcj
~ ~

Tr ,Pr
Where

## Tcj critical temperature of species j.

H* H
~ j ~ T
is the correction read off the charts at appropriate reduced temperature Tr = T and
j
T
cj cj

P
reduced pressure Pr =
pcj

## Pcj critical pressure of species j.

Finally

H j (T, P, y j ) H j (T, P) = j is the correction factor which accounts for the nonideality of the
~ ~
mixture.
_________________________________________________________________________
For liquids (in a first approximation)

T
~
Hj =H o + C pj dT + j
~ fj
To

## Here we will assume:

Gases:

a. ideal mixtures j = 0
b. ideal gas behavior H = H *j
~ ~

Liquids:

a. ideal mixture j =0

Now the energy balance of eq (6) based on the above assumption can be written as

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LECTURE 7

s T

F C
j =1
jo
~
pj dT + H rT X& = q& (7a)
To

s T

F C
j =1
j
~
pj dT + H rTo X& = q& (7b)
To

where
s s T
H rT = j H + j C p j dT
~ f jo
j =1 j =1 To

## is the heat of reaction at temperature T.

Finally, in preliminary reactor design we assume that the heat of reaction does not vary much with
temperature

H r const H rTo H rT
and that some mean value of the specific heat can be used

C
To ~
pj dT = C
~
pj (T To )

## Equations (7) can then be written as:

F
j =1
jo C
~
pj (T To ) + H r X& = q&

or
C p Q(To T ) + ( H r )X& + q& = 0 (8)
where
F x C Q x
X& = Ao A = Ao o A
( A ) ( A )

H r
H rA =
( A )

## HrA - heat of reaction per mole of A.

C p Q(To T ) + ( H r )C Ao Qo x A + q& = 0 A
(9)
or
C p Q(To T ) + (H r )rV + q = 0 (9a)

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This final form of the energy balance resulting from all of the above assumptions can be interpreted as a
heat balance i.e as rate of input of sensible heat by the flowing stream minus rate of output of sensible
heat by exit stream plus heat generated by reaction plus heat added from the surroundings must add to
zero.

In addition we now need an energy balance on the jacket or coil and a constitutive relationship for heat
transfer rate, q& .

For a jacket at steady state (assuming that the jacket is well mixed too)

m Qm C p (Tm Tm ) q= 0
m o
(10)

m , Qm C p - are density, volumetric flow rate and mean specific heat of the fluid flowing through the
m

jacket.

## Tmo - inlet jacket temperature.

Tm exit jacket temperature.

Let
q& = UA(Tm T ) (11)

J
U o - overall heat transfer coefficient.
m3 Cs

From eq (10)

Tmo + mT
Tm = (12)
1+ m
where
UA
m =
m C pm Qm

dTm
= m (T Tm ) (13)
dz

## z = fractional length of the coil.

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LECTURE 7

Tm ( z ) = T + e m z (Tmo T ) (14)

For an n-th order irreversible reaction G(T) always has a sigmoidal shape and at high temperatures tends
to a horizontal asymptote CAo.

Finally, in dimensionalized form the two equations that have to be solved simultaneously are:

C Ao x A = a r (15)
~
To T + A a r (T Tmo ) = 0 (16)

## where r is given by equation (3) and

H r
A = A

C p

UA m C p Qm
= = m
for a jacketed reactor
1 + m m C p Qm + UA C pQ
m

=
m
(1 e m
) for a reactor with coil

UA UA
m = =
m C p m Qm C pQ

When we deal with problems of type 1, to find reactor size for given feed and product stream conditions
we use directly eq (15).

V CAo x A CAo x A
= = =
Qo ar RA

## Then calculate the desired heating or cooling rate from eq (16)

(
q& = C p Q(To T ) + H rA arV )

When we deal with problems of type 2 and try to find the operating conditions for a given reactor, then
we must solve eqs (15) and (16) simultaneously by trial and error for xA and T.

Sometimes we can solve explicitly for xA from eq (15) in terms of temperature xA = xA(T).

## Substituting this relationship into eq (16) we get

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LECTURE 7

To T + AarT (T Tmo ) = 0

rT indicates that the rate is now a function of temperature only since r (xA,T) = r (xA(T),T)

1+ To + Tmo
~ T ~ = ar
{ T = C Ao x A (15)
A A
123 G (T )
L (T )

Reactor operating temperature is given by the intersection of the straight line L(T) and curvilinear
function G(T).

For an n-th order irreversible reaction G(T) always has a sigmoidal shape and at high temperatures tends
to a horizontal asymptote C Ao .

For an endothermic reaction Hr > 0 A < 0 and line L has a negative slope.

L
C Ao
G
G
L C Ao x A
1+
slope =
C Ao x A A

T To + Tmo T
1+

## Several conclusions can be reached for endothermic reactions:

i) L & G can intersect at most once and for a given set of parameters only one steady state exists.
ii) For a given reactor and flow rate, fixed , given feed, To, and heating medium feed temperature,
Tmo , and given heat transfer properties, , the more endothermic the reaction, the larger A and
the smaller the slope of the L line, therefore the lower the operating temperature and conversion.
iii) For a fixed reaction, feed flow rate and composition and given reactor, fixed G curve, an increase
in feed temperature moves the L-line to the right while its slope remains unchanged. Hence, the
operating T and xA are increased.

For an exothermic reaction Hr < 0 and A > 0. The L-line has a positive slope.

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LECTURE 7

C Ao x A 3

G
L
1+
2 slope =
C Ao x A
A

To + Tmo T T
1+

## Several conclusions can be reached for exothermic reactions:

i) L & G can intersect sometimes at more than one place and for a given set of conditions, more
than one steady state may be possible.
ii) For fixed and reaction, fixed G, an increase in the feed temperature moves the L line to the
right increasing the operating T and xA. An increase in coolant Tmo has the same effect.
iii) For a fixed and reaction, fixed G, , an increase in heat removal, increase in , rotates the
A
L-line in the counterclockwise direction and moves the intercept at the abscissa to the left if
To > Tmo or to the right if Tmo > To .

For exothermic reactions it is important to calculate the adiabatic temperature rise and the maximum

## Maximum fractional temperature rise is also called the Prater number, .

= = (20)
To To
Now let us consider a number of simple illustrative examples.

Example 1.

## The following information is given.

Irreversible reaction A R
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LECTURE 7

mol
RA = e 25e 20,000 / RT CA
L min
mol
C Ao = 1 To = 350 K = 77 C
o o

L
cal
H R A = 100,000
mol A
cal
C p = 500( o )
LC

CSTR

a. Isothermal. Find reactor space time needed for xA = 0.9 at 350K and heat to be removed.

C Ao C A C Ao x A 1x0.9 0.9
= = = =
RA RA 25

20 , 000
1.987 x 300
0.0233
e e
= 38.59 = 36 min
q& = Q C p (T To ) + X&H R
X& = FAo x A = Q C Ao x A (H R A )

cal
q& = QC p (T To ) + QC Ao x A (H R A )
min

q& cal
= C p (T To ) + C Ao x A (H R A ) = 1x0.9( 100,00)0 = 90,000cal / L to be removed.
Q L
mol
Note that the reaction rate at 350K is only 0.0233
L min

## Find for xA = 0.9.

Q C p (T To ) = (H R A )QC Ao x A
( H )C
T = To +
RA Ao
xA
C p
100,000 x1
T = 350 + 0.9 = 530 K (257 o C )
500

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LECTURE 7

C Ao C A C Ao x A 1x0.9 0.9
= = = 25 20,000 / 1.987 x 530 =
RA RA e e 407
= 2.21x10 3 min = 0.133s

Note that at 530K the reaction rate has increased by orders of magnitude to

mol
R A = 407
Lmin

Nonisothermal

## Find , q& / Q given desired x A = 0.9 and desired T = 400 K .

C Ao x A 0 .9 0 .9
= = = = 1.06 (min )
RA
20 , 000
0.849
e 25 e 1.987 x 400

q&
= C p (T To ) + C Ao x A ( H RA )
Q
= 500(400 350) + (90,000)
= 25,000 90,000 = 65,000cal / L

## Note the value of the rate which is

kmol
R A = 0.849
c min

Example 2

A well stirred bench scale reactor (CSTR) is used for a first order exothermic reaction A R
(practically irreversible) under the following conditions:

= 1.0(min)
CAo = 1.0(mol / liter) ; To = 350K
UA C Q
Tmo = 350K ; = 1.0 = m pm m
m C pm Qm + UA C p Q
K lit (H R A )
A = 200 =
mol C p

20, 000
mol
r = e 25e RT
CA
lit min

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LECTURE 7

## a) Find the operating temperature and exit conversion.

b) How many steady states are possible under these conditions?
c) What is the maximum adiabatic temperature rise?
d) How would you change some of the operating conditions (Tmo, To, ) in order to operate at a unique
e) What start up program should one use in order to have the reactor settle in the steady state of high
conversion?

Solution
Solve simultaneously eqs (15) & (16)

C Ao x A = ar = k 0 e E1 / RT C Ao (1 x A ) (15)
k0 = e 25 E = 20,000 cal / mol

1+ To + Tmo
~ T ~ = a r = k 0 e E / RT C Ao (1 x A ) (16)
A A

## Eliminate xA from (15).

k 0 e E / RT
xA =
1 + k 0 e E / RT
Substitute into eq (16)

1+ To + Tmo k o e E / RT C Ao
~ T ~ =
A A 1 + k 0 e E / RT
14442444 3 144 244 3
L G

## Substitute in the values of parameters:

20,000
exp
1+1 350 + 1x350 1.9877T
T = x1x1
200 200 20,000
1 + exp25
1.987T
20,000
exp25
1.987T
0.01T 3.5 = (*)
20,000
1 + exp25
1.987T
Solve * by trial and error for T. Then obtain the corresponding conversion by:

20,000
exp25
1.987T
xA = (**)
20,000
1 + exp25
1.987T
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LECTURE 7

## We can also represent equation (*) graphically as shown below:

Example 1
1

0.9

0.8

0.7

0.6
XA

0.5

0.4

0.3

0.2

0.1

0
320 340 360 380 400 420 440 460 480 500
Temperature, K

## Figure 4: Operating points for the CSTR of Example 2.

Figure 5 on next page shows the dramatic temperature excursions that the reactor can experience during
start-up before it settles to a steady state.

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LECTURE 7

Error!

## Figure 5: Transient CSTR operation for Example 2

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LECTURE 7

a) There are three intersections of the L and G line indicating 3 possible steady states.

T = 353K
(1)
x A = 0.03
T = 408K
(2)
x A = 0.576
T = 439K
(3)
x A = 0.886

## Tad max = A CAo = 200x1 = 200K

c)
d) Increase To or Tmo to bypass the lower bump in the curve. Increase if possible.
e) See attached Figure 5.

Reversible Reactions

## For endothermic reactions, Hr > 0 , equilibrium conversion increases with increased

temperature.

xA
xAe
II
III
I

T
Figure 6: Equilibrium conversion as function of temperature for endothermic reactions.

In region III the reaction can be considered practically irreversible. In region II xAe rises with
increase in T.

For endothermic reactions the maximum permissible temperature is always the optimal
temperature for maximizing conversion or production rate from a given CSTR.

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LECTURE 7

The net rate of an endothermic reaction at fixed composition always increases with increased
temperature.

s s
r = k10 e E1 / RT C j k 20 e E2 / RT C j
j j

j =1 j =1

since E1 > E 2

## For exothermic reactions, Hr < 0 , equilibrium conversion decreases with increased

temperature.

xA
xAe
II
III
I

T
Figure 7: Equilibrium conversion as function of temperature for exothermic reactions.

## Again in region I the reaction is practically irreversible. In region II it is reversible.

xA

r = 0.01

r = 0.02
r=0

r = 0.04

0.06

T
Figure 8: Conversion temperature relation at fixed rates for exothermic reactions.

Now we notice that at fixed composition, fixed xA, the net rate of reaction has a maximum at a
certain temperature, Tm. Below that temperature the rate is lower and above it, it is lower. The
reason for this is that E1 < E2.

On the above diagram we can pass a line - - - called the locus of maximum rates or a Tm line.
For a given conversion the Tm line defines a temperature at which the rate is maximum and vice
versa at every T the line defines an xA a which the rate is maximum.

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LECTURE 7

We should always select To, Tmo, in such a manner as to make sure that we operate on the Tm
line.

r dx
= 0 from A =0
T
r
dT

aA+bB=pP

## and the rate is given by

r = k10e E1 / RT CA CB k20 e E 2 / RT Cp

Assuming further that we deal with liquids and that CAo and CBo are given while Cpo = 0

p
(
x Ae ) p
p a b a
K c = C Ao b
(A)
a C Bo
(1 x Ae ) b
x Ae
C Ao a
Assuming an ideal solution

Gro

Kc = e RT
(B)

## Using (A) and (B) we can calculate xAe as a function of temperature.

The given rate form, if it is to be viable in the vicinity of equilibrium, must satisfy the following
constraint:

Cp
q p
= Ca p b
CA CB eq CA CB

r
The locus of maximum rates i.e the Tm-line can be obtained by = 0 which results in
T

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LECTURE 7

( E 2 E1 ) / R
T = Tm = (C)
p
xA
k 20 E 2 a
ln CAo ( )

k E C b
10 1 (1 x A ) Bo x A
CAo a

For a desired conversion eq (C) gives the temperature Tm at which the rate is maximum.
Substituting that conversion and temperature into the equation for the rate produces the
maximum rate

Example 3 - CSTR

A R
Gro298 = 2,500cal / mol
H ro298 = 20,000cal / mol = const
C p = 2,000(cal / lit ) = const
12,500 1
k1 = 5110
x2 3 e RT (min )
8

k10

mol
C Ao = 2
lit

f) Find he optimal size CSTR necessary to achieve a production rate of FR=100 (mol/min)
at xA = 0.9. If the reactor is to be operated adiabatically find the necessary feed
temperature.
g) If the feed is available only a T = 298K how should one operate? Can one maintain the
desired production rate and conversion?
h) How should 2 CSTRs in series be operated to minimize the total reactor volume and
keep FR and xA at desired levels. Feed is at 298K, T = 350Kis not to be exceeded.

Solution

## Find equilibrium constant at 298K

Gro298 2,500
K 298 = exp = exp = 68.2
1.987 x 298
RT

## Find equilibrium constant as a function of temperature using Vant Hoffs equation

d ln K Hr
=
dT RT 2
H r 1 1

10.065
K T = K 298 e R 298 T
= 1.461x10 13 exp
T

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LECTURE 7

## Find equilibrium conversion variation with temperature:

10,065
1.461x10 13 exp
x Ae =
KT
= T
1 + KT 10,065
1 + 1.461x10 13 exp
T

T 298 300 310 320 330 340 350 360 370 380
x Ae 0.986 0.982 0.949 0.870 0.720 0.512 0.311 0.169 0.094 0.045

## Find the locus of maximum rates

Tm =
(E 2 E1 ) R
=
10,065
k E xA x
ln 20 2 30.51 + ln A
k10 E1 1 x A 1 xA

xA 0.94 0.95 0.9 0.85 0.8 0.6 0.4 0.2 0.1 0.01
Tm 287 301 308 312 316 326 334 346 356 388

Plot the equilibrium line, xAe, and the locus of maximum rates, Tm, in order to graphically
interpret some of the later results.

Tm
1

0.8
xA xAe
0.6

0.4

0.2

## 280 290 300 320 340 360 380 400 T

a. At x A = 0.9 T = Tm = 308K

## The rate at the operating point is:

12, 500 32, 500

r = 5 10 8 e 1.987 308
2 (1 0.9) 3.422 10 21 e 1.987 308
2 0.9
mol
r = 0.815
lit min

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LECTURE 7

## From the design equation (balance on R)

100
= 1227 (lit )= 1.23 m 3
FR FR
V= = =
RR r 0.815
V = 1.23 m 3

H rA
To T + A (VA )r = 0 = = 10
Cp
To = T A CAo x A = 308 10 2 0.9 = 290K

For adiabatic operation the feed temperature would have to be 290K. The same result is

## To = 298K To1 = 290K T = 308K

(
q = Q C p To To =
1
) FR
CA o x A (
C p To To
1
)
100 cal
q = 2000 (298 290)= 8.889 10 5
2 0.9 min

## ii) Introduce the feed at 298K and cool the reactor

To = 298K T = 308K

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LECTURE 7

q = Q C p (To T )+ ( H rA )CA o Q x A

C p (To T )+ ( H r ) FR
FR
q =
CA o x A
2000
(298 308) + 20,000 = 8.889 10 5
cal
q = 100
2 0.9 min

The cooling rate requirement is the same, as it should be as there is no work term in the energy
balance. But it is easier to remove heat from the higher reactor temperature.

iii) Operate adiabatically with the new feed temperature while maintaining the previous feed
100
rate FA o = ; FA o x A = FR
0.9

FAo 100
Qo = =
C Ao 1 .8

Now we must find the new operating point by a simultaneous solution of the species and
energy balance.

C Ao x A = r
~
To T + r = 0

Since we need adiabatic operation by combining the above two equations we get the
relationship between conversion and temperature
~ ~
T = To + r = To + C Ao x A
T = 298 + 10 2 x A = 20 [14.9 + x A ]

## Substituting into the first equation we get:

12, 500

32, 500
1.987 20 [14.9 + x A ] 1.987 20 (14.9 + x A ) 1227 1.8

2 x A = 5 10 e
8
2 (1 x A ) 3.4 10 e 21
100

314.5 817.8
14.9 + x A

11.043 10 (1 x A )e
9 14.9 + x A
6.810 x A e
21
xA = 0

## x A = 0.88 T = 315.6 = 316 K

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LECTURE 7

The purity (conversion) has been reduced somewhat from the required 90%.

## 12, 500 32, 500

r = 510 e 8 1.987 315.6
2 (10.88) 3.4 10 e
21 1.987 315.6
20.88
mol
r =0.0786
lit min

100 mol
FR = FAo x A = 0.88 = 97.8
0.9 min

## and production rate has dropped very little.

iii) We could operate the reactor adiabatically with the new feed temperature and maintain (via
a controller) fixed exit composition at x A = 0.9 which would require adjusting the feed
rate.

Now
~
T = To + A C Ao x A = 298 + 20 1.8 = 316 K
x A = 0.9

## The new rate is:

12, 500 32, 500

r = 5 10 e
8 1.987 316
2 (1 0.9) 3.4 10 e 21 1.987 316
2 0.9
mol
r = 0.023
lit min

## The production rate now drops to

mol
FR = r V = 0.023 1227 = 28.2
min

This is too high a penalty to pay for maintaining purity i.e. keeping x A = 0.9 constant!

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ChE 471 Fall 2005
LECTURE 7

C. For minimum total reactor size we must find the minimum of the following expression

1 + 2 x A1 0.9 x A1
= +
CA o rm1 rm f
12, 500 32, 500

rm1 = 10 e 9 1.987 Tm
(1 x ) 6.8 10
A1
21
e
1.987 Tm1
x A1

10,065
With Tm =
x A1
30.51 + ln
1 xA
1

## rm f = 0.0818 (mol lit min )

d +
By taking 1 2
= 0 one gets by trial and error
d x A1 Ao
C

x A1 = 0.72 mol
rm1 = 0.5
Tm1 = 320 K lit min

## For the first reactor

FA o x A1 100 0.72
V1 = = = 160 liters
rm1 0.9 0.5

## For the second reactor

V2 =
(
FA o x A f x A1 )= 100 (0.9 0.72) = 244.5 lit
rm f 0.9 0.0818

## The graphical representation of the above system is shown below

24
ChE 471 Fall 2005
LECTURE 7

1
To = 298K 306 320 304 308
0.8
xA
q&1 V1 q& 2 V2

0.4

0.2
To

## Preheat the feed from 298K to 305.6K 306K

100 cal
q&1 = Q C p (305.6 298) = 2000 (305.6 298) = 8.44 10 5
0 .9 2 min

## Cool the stream from 1st reactor to 304.4K 304

700 cal
q& 2 = Q C p T = 2000 (320 304.4 ) = 1.73 10 6
0 .9 2 min

It should be noted that the above calculations can be made easier with a little analytical work to
obtain an expression for the maximum rate as a function of conversion. This is done by
substituting the Tm values

Tm =
(E 2 E1 ) R
k E xA
ln 20 2
k10 E1 1 x A

## for temperature T in the rate expression

(R )A m = rm = k10e E1 R Tm
CA o (1 x A ) k 20 e E 2 R Tm
CA o x A

If we recall that e a ln b = e ln b = b a
a

We get:

E2 E2

( A)
E1
k E E 2 E1 k E E 2 E1 1 x E 2 E1
rm = k10 10 1 k20 10 1 CA o
k 20 E 2 k 20 E 2
E1

(E 2 E1 )
xA

25
ChE 471 Fall 2005
LECTURE 7

## In our particular example the above expression reduces to:

rm = 3.22 (1 x A )
1.625 0.625
xA

Another variation on the above problem is to have two equal size CSTRs in series. For
maximum production rate then under conditions 1 = 2 we must find x A1 that satisfies

x A1 x A 2 x A1
=
rm1 rm 2

## This happens at x A1 = 0.75 so V1 = V2 = 205 liters

In summary the following types of problems may be encountered:
~
I. Given V , Q, To , Tmo , Qm , , q& , find x A and T. This is equivalent to determining the
performance of an existing reactor or of one that is contemplated by design engineers.
In this case species mass balance and energy balance are solved simultaneously.
~
II. Given To , Tmo , , FR and x A determine the required V and desired operating T.

## This is the typical design problem.

III. Production rate is specified. Exit conversion and temperature can be selected
together with V in order to optimize some profit function.

## We have not touched here on two very important problems.

- transients in a CSTR
- control of a CSTR around an unstable steady state.

26
ChE 471 Fall 2005
LECTURE 7

## Extension to Multiple Reactions

One should keep in mind that yields and selectivities can be affected dramatically by the choice
of operating temperature when activation energies of various reactions are different.

## The problems consist of

a. Finding the optimum temperature for a desired product distribution irrespective of space
time requirements.

b. Finding an optimal temperature for a given reactor (given ) which maximizes the
production of the desired product.

## The equations to be solved are given R independent reactions among S species

v
j =1
ij Aj = 0 i = 1, 2, ...... R

F jo F j + v ij ri V = 0 (1)

j = 1, 2, ...... R

or
R

v [Xij i ri V ]= 0
i=1

## X1 ri V = 0 for i = 1, 2, 3...R (1a)

and

(F )
s
~ ~
jo H jo F j H j + q& = 0 (2)
j =1

Equation (1) represents independent R species balances and eq (2) is the energy balance based on
assumptions of

## a) no work other than flow work

b) negligible changes in potential and kinetic energy

## If we assume further c) ideal gas behavior d) ideal mixture

27
ChE 471 Fall 2005
LECTURE 7

s To s T
jo ~ fj ~ p j j ~ fj ~ p j + q = 0
F H + C dT F H + C dT
j =1 T0 j =1 T0
s To s R T
F jo C~ dT v ij H~ fj + C~ p j dT ri V + q = 0
j =1 T pj j =1i=1 To

s To R

F C jo
~
dT v ij H ri V + q = 0
~ rTi
(2a)
j =1 T pj i=1

## Where H rTi is the heat of reaction of reaction i at temperature T.

If we further assume e) constant heats of reaction and f) constant mean specific heats we get

R
C p Q (To T )+ ( H r ) ri V + q = 0
i
(2b)
i=1

28
ChE 471 Fall 2005
LECTURE 7

PROBLEMS

A R

## The reaction rate is given by:

= k1 C A k 2 C R (mol lit s )

k1 = exp 7
83,000
10 s
3
( )
1

RT

k 2 = exp 18
167,400
10 s
3
( )
1

RT

Note: the activation energies are given in (J/mol) use the value of the gas constant accordingly.

## The heat of reaction is:

H r = 80,000 ( J mol )

## Specific heat of the reaction mixture is:

C = 40 (J mol K )
~ p

## Assume that these are constant.

1. The above reaction occurs in the liquid phase. The pressure is high enough so that the
liquid will not volatize in the permissible temperature operating range which is: 300 to
900K.

## Qo = 100 (lit s ); C Ao = 1 (mol lit ) ; To = 300 K

You have a V = 100 liters CSTR reactor. How would you operate this CSTR in order to
maximize the production rate of R?.

## a) What is FR (mol s ) -maximum production rate?

b) What are x A & T -operating conditions?
c) What is the heat duty for the system?
d) Sketch your system and location and heat duty of all heat exchangers, if any.

29
NONISOTHERMAL OPERATION OF
IDEAL REACTORS
Plug Flow Reactor
(CHE 471)
M.P. Dudukovic
Chemical Reaction Engineering Laboratory
(CREL),
Washington University, St. Louis, MO
ChE 471 Fall 2005
LECTURE 8

## NONISOTHERMAL OPERATION OF IDEAL REACTORS

Plug Flow Reactor

To T To T
Fjo, Qo Fj

Tm,Qm Tm Tm Tmo
Assumptions:

1. Homogeneous System
2. Single Reaction

## Two types of problems:

1. Given desired production rate, conversion and kinetics and other parameters, determine the
required reactor size, heat duty and temperature profile.
2. Given reactor size, kinetics, etc., determine the composition of the exit stream.

s

A
j =1
j j =0 (1)

## with the rate given by

s s
E1 / RT j E 2 / RT j
r = k10e Cj k20 e Cj (2)
j =1 j =1

with

j
Mj / A x
A A To P
C j = CAo (3)
1 + A xA TPo

The mass balance in the reactor for species j can be written as:

dF j
= jr (4)
dV

v = 0 Fj = Fjo (4a)

1
ChE 471 Fall 2005
LECTURE 8

or

dx A
FAo = ( v A ) r = RA (4)
dV

V =0 xA = 0 (4a)

The energy balance based on (a) negligible changes in potential and kinetic energy and (b) no work
other than flow work is

d s
FjH j +
qv = 0 (5)
dV j =1

V = 0 F j H1 = F jo H jo (5a)

Based on further assumptions of (c) ideal mixtures and (d) ideal gases one gets:
s s
dF j
F j C H
dT
+ qv = 0 (6a)
~ pj dV j=1 ~ j dV
j=1

Using the idea of (e) mean specific heats which are constant and (f) constant heat of reaction, one gets

dT
(Q )C p + (H r )r + qv = 0 (6)
dV

Q =
mtot is the mass flow rate which is constant

J
qv is the rate of heat addition per unit reactor volume
m3 s

The simplest constitutive relationship for the rate of heat exchange is:

## qv = Uav (Tm T ) (7)

m2
av 3 - area for heat transfer per unit reactor volume
m

## The equations to be solved simultaneously are:

dx A
Fao + Ar = 0 (A)
dV

2
ChE 471 Fall 2005
LECTURE 8

qv
dT 647 48
QC p m (H r ) r + U av (T Tm ) = 0 (B)
dV
qv
647 48
dTm
mQm m C p m U av (Tm T) = 0 (C)
dV

## V = V; (Tm = Tmo for countercurrent flow) (D)

and

du dp
G + +F = 0 (E)
dz dz

G = u - mass velocity

P = pressure

V
z= - axial distance
A

Q
u= - velocity
A

## A cross sectional reactor area

F frictional losses

Equation (E) is the momentum balance. However this equation is usually solved separately and a mean
pressure is selected for evaluation of gas concentrations in eq (3).

For gases the use of mass fractions, wj, and extent per unit mass, ' ' is recommended. (See lecture 1).

## The equations can then be written as:

d ' '
G =r (8)
dz

dT
G = ' ' r + q'v' (9)
dz

## z= 0 ' ' = 0, T = To (10)

3
ChE 471 Fall 2005
LECTURE 8

Hr qv
'' = ; q
''
v = (11)
Cp Cp

## where the rate is expressed by:

s

j =1
j

s m j T P 1
r = k10eE1 / RT
C joj 1 + j tot o s
F jo TPo 1 + M
j =1

j avo
j=1

s v j
mbot ' ' To P
j
j 1
Cjo 1 + j
E2 / RT
k20e (12)
j =1
Fjo TPo 1+ ( )
y Mavo ""
Mav o - average molecular weight at feed conditions

m Mj
tot
=
F jo w jo

## For liquids one can write

d
=r (13)
d

dT
= r + qv (14)
d

= 0 ; = 0 ; T = To (15)

Hr qv Q' '
= ; qv = = v (16)
C p C p

## where the rate is given by

s s
( ) ( )
j j
r = k10e E1 / RT
C jo + j k 20e E 2 / RT
C jo + j (17)
j =1 j =1

4
ChE 471 Fall 2005
LECTURE 8

z V
= = - residence time along the reactor.
u Q

From eqs (8) and (9) or (13) & (14) we can always get the following relationship between temperature
and extent
z
1 ''
G o
T = To + +
'' ''
qv dz (18a)

or

T = To + + qv d (18b)
o

For adiabatic operation (q'v' = 0, qv = 0 ) this yields the equation of the adiabatic line, i.e extent and
temperature satisfy the relationship below at any and every point of the reactor

T = To +
'' ''
(19a)

T = To + (19b)

The maximum fractional adiabatic temperature rise is given by the Prater number just like in the case of
a CSTR.

= =
(Hr )CAo (20)
To ( A )To C p
Basic types of problems

## 1. The temperature in the reactor is prescribed

a. T(z) = To isothermal reactor. Integrate (8) or (13) and find extent along the reactor. From
eq. (9) or (14) find the heat addition/removal requirement along the reactor and the overall
heat duty for the reactor.

b. T(z) specified. Integrate (8) or (13) find (z). Use (z) and T(z) in eq (9)or (14) to get qv (z)

## 2. The heat addition (removal) rate is prescribed

a) Adiabatic operation. T = To + ' ' ' ' or T = To + . Substitute into eq (8) or (13) and
integrate

5
ChE 471 Fall 2005
LECTURE 8

b) Heat duty is prescribed. q'v' (z) or qv (z ) prescribed. Simultaneously integrate (8) or (9) or
substitute
z
1 ''
T = To + + qv dz into (8) and integrate.
'' ''

Go

## 3. Rate of heat addition (removal) controlled by another equation

qv = Uav (T Tm )

a) Tm = const. Integrate eqs (8) and (9) or eqs (13) and (14) simultaneously.
This is the case when reactor tubes are immersed in boiling medium or condensing medium.

## b) Tm determined with T and by equations (A) to (E).

dTm
Gm = m 'm (Tm T )
dz
Ua Q
m = vm Gm = m m
Cp m Am

Note: With cocurrent cooling a PFR can be kept isothermal with countercurrent cooling it cannot in the
case of n-th order reactions. Prove that for an exercise.

There is always a unique steady state in a PFR. Main problem with PFRs is:

## hot spot formation

parametric sensitivity and temperature runaway.

Classical example of temperature runaway presented by Bilous & Amundson (AIChE J., 2, 117 (1956).

## PFR cooled from the wall t constant Tm = Twall.

6
ChE 471 Fall 2005
LECTURE 8

440

342.5

420

337.5
400

T
380

360

335
340 330

320
320
310
Tm = 300
300
0 10 20 30

A hot spot is formed due to a very small change in wall temperature. The system shows extreme
parameter sensitivity.

Reaction runaway is the phenomenon when a small change in feed concentration, temperature, flow rate
or in coolant temperature triggers a dramatic change in he temperature profile and leads to runaway
reactions and explosions. Exact criteria for runaways are difficult to develop.

## Approximate criteria are given on the enclosed graph..

Example 1
A reversible first order reaction (considered earlier in a CSTR) is now to be per formed in a PFR.

A R (liquid phase)

k1 = 5x10 8 e 12,500 / RT (min1 )
k 2 = 3.4x1021 e 32,500 / RT (min1 )
Hr = 20,000 cal / mol G298
o
= 2,500 cal / mol
C p 2,000 (cal / lit oC)
CAo = 2 (mol / lit)

7
ChE 471 Fall 2005
LECTURE 8

If the feed rate is Q = 100 (lit/min) and the PFR size is V = 1,500 (lit):

## b) determine conversion in an adiabatic reactor if the feed is at i) 0C, ii) 20C,

c) if the maximum permissible temperature is 80C determine the optimal temperature profile along
the reactor necessary to maximize exit conversion.

d) If the desired conversion is 85% find the minimum reactor volume and the desired heat removal
rate along the reactor. Permissible temperature range is 0 to 100C.

Solution

## a) For an isothermal reactor only the mass balance has to be solved

Ax
V dx
= = CAo A
Qo o
rA
rA = k1CA k 2 CR = CAo[k1 (1 x A ) k2 x A ]

rA = k1CAo1 x A A
x ( 1 x Ae ) k
sin ce k 2 = 1 =
(
k1 1 x Ae )
x Ae K x Ae
k1CAo K k1
(rA ) = (x Ae x A ) x Ae = =
x Ae 1 + K k1 + k2
(rA ) = (k1 + k2 )CAo (x Ae x A )
1
xA
1 x

dx A
= = ln

Ae

k1 + k 2 o x Ae x A k1 + k 2 x Ae x A

## Solve for conversion

1
x A 1 exp(k1 (1 + ) )
K
k 1500
= x Ae 1 exp 1 = = 15 min
x Ae 100

8
ChE 471 Fall 2005
LECTURE 8

## We get the following results:

T K k1 xae xa
273 1494 0.0498 0.999 0.526
283 407 0.112 0.998 0.813
293 121 0.239 0.992 0.965
303 40 0.486 0.975 0.974
313 13.5 0.943 0.931 0.931
323 5.0 0.755 0.833 0.833
333 2.0 3.149 0.662 0.662
343 0.81 5.46 0.448 0.448
353 0.35 9.17 0.262 0.262
363 0.16 15.0 0.139 0.139
373 0.08 23.8 0.071 0.071

## Same as equilibrium conversion

The reactor space time is so large that above 50C practically equilibrium conversion is obtained.

## a) The adiabatic operating line is

T = To + ACAo x A
HrA 20,000 lit oC
A = = = 10
C p 2,000 mol

CAo = 2
mol
lit
T = To + 20 x A

## Substitute this relationship into the mass balance and integrate:

dx A
CAo = ( k1 + k 2 ) CAo( x Ae x A ) = k1CAo ( k1 + k 2 ) CAo x A
d
= 0 xA = 0
E / RT E / R( T + 20 x )
k1 = k10e 1 ad = k10 e 1 o A
E / R( T +20 x )
k 2 = k20 e 2 o A
K k1
x Ae = =
1 + K k1 + k 2

## dx A E / RT (To + 20 x A ) E1 / R (To+20 x A ) E / R(T +20 x A )

= k10 e 1 k10e + k20 e 2 o xA
d
=0 xA = 0

9
ChE 471 Fall 2005
LECTURE 8

dx A 8

12, 500
1.987( To +20 x A )
8

12, 500
1.987( To +20 x A ) 21

32,500
1.987( To +20 x A

= 5x10 e 5x10 e + 3.4x10 e xA
d
= 0 ; xA = 0

## Alternatively we could solve by trial and error the following integral:

xA
dx
= 15 =
12, 500
1.987(To + 20 x )

12,500
1.987( To +20 x )

32,500
1.987( To +20 x )

o 8
5x10 e 5x10 e
8
+ 3.4x10 e
21
x

We find:

i) To = 0C = 273 K xA = 0.78
Tadiabatic = 15.7K = 16K T = 289 K
ii) To = 20C = 293 K xA = 0.94 = xAe
Tadiabatic = 18.8 = 19 K T = 292 K

c) In order to maximize conversion at given space time we should follow the line of maximum
rates.

( E 2 E1 / R) 10, 065
Tm = =
k 20 E 2 xA x
ln + ln 30.51 + ln A
k10 E1 1 xA 1 x A

Since maximum permissible temperature is 80C (353 K) we have to preheat the feed to 33 K, cool the
reactor and keep it isothermal a 353 K until the locus of maximum rate is reached and then run along the
locus of maximum rates.

The intersection of the isothermal line T = 353 K and the Tm line determines up to which point the
reactor has to be run isothermally.

10,065
T = 353 = Tm =
x
30.51+ l n A
1 x A

10,065 353x30.51
exp
353
xA = = 0.119
10,065 353x30.1
1+ exp
353

10
ChE 471 Fall 2005
LECTURE 8

1
0.119
dx 1 x Ae
= = ln
k1 + k2 o
(x Ae x A ) (k1 + k2 ) x Ae x A

## At 80C (353 K) from the table given earlier

1 0.262 = 0.017(min)
= ln
9.17(1+
1
) 0.262 0.119
0.35

The isothermal operation should occur in the very entry section of he reactor. After that the Tm line
should be followed.
12 ,500 32,500

dx A 1.987Tm 1.987Tm
= 5x108 e (1 x A ) 3.42x1021 e xA
d
10,065
Tm =
x
30.51 + ln A
1 x A
= 0.017 x A = 0.119

Desired result at = 15

## xA=0.988 Texit = 288K

Really one should preheat only to adiabatic line. Adiabatic line should end at T = 353 K, xA = 0.119.
Hence, the fluid must be preheated up to To = T ACAo x A = 353 20x0.119 = 350K

xA

x Ae

## a. Isothermal. Solid lines are operating lines for = 15 min

11
ChE 471 Fall 2005
LECTURE 8

xA

x Ae

xA

Tm

x Ae

Tmax

## c. Operating along the locus of maximum rates

d) Permissible temperature range is 0C to 100C. We want minimum reactor size for xA = 0.85.
Preheat to 100C, run along the locus of maximum rates
x A = 0.85
dx
=
12 ,500
1.987Tm

12,500
1.987Tm

32, 500
1.987Tm

o 8
5x10 e 8
5x10 e + 3.4x10 e
21
x

10,065
with Tm =
x
30.51 + ln A
1 x A
= 1.8min Thus with Q = 100 lit/min we need only V = 160 liters

The desired temperature profile along the reactor is presented in the enclosed graph. The heat removal
per unit volume is

12
ChE 471 Fall 2005
LECTURE 8

q
= C p (To T ) + (H r )CAo x A
Q
= 2, 000(100 T ) + (20, 000x2)x A

This curve is also presented in the figure. The total heat density is:

q
= 2,000(100 70) + 40,000x0.85
Q tot
= 1.56x105 (cal / lit)

7
With Q = 100 lit/min qtot = 1.56x10 (cal / min)

For comparison, if cooling failed and reactor ran adiabatically with To = 100C one would get

## Extension to Multiple Reactions

s

A
j =1
ij j =0 i = 1,2,...R (1)

R
dFj
+ ij ri = 0 j = 1,2,...R (2)
dV i=1
or
R
dXi R
ij + ij ri = 0
i =1 dV i=1
(2a)
dX
i + ri = 0
dV

(
d Fj H j )+ q = 0 (3)
v
dV

V = 0 ; Fj = Fjo ( Xi = Xio ) ; H j = H jo

With the usual assumptions made about the energy balance (see the lecture on CSTR) one gets:

13
ChE 471 Fall 2005
LECTURE 8

( )
s R
dT
Fjo C + HrTi ri + qv = 0 (4)
~ pj dV i =1
j =1

## The equations to be solved for a set of multiple reactions are:

dXi
+r = 0 i = 1,2...R (A)
dV i

( )
R
dT
C pQ + Hri ri + qv = 0 (B)
dV i=1
V = 0 ; Xi = Xio T = To
Q = const

s s
E1i / RT ij E2 i RT
ri = k i10e Cj ki 20e C j ij (C)
j =1 j=1

with
R

ij Xi

1+ i =1
T Fjo
C j = Cjo o (D)
o T
R s

ij Xi

1+ i =1 j=1
Fbot o

## The constitutive relationship for qv is:

qv = Ua v (Tm T )

a) Tm= const

## b) Tm is governed by another D.E.

dTm
m mQm C p m qv = 0 (E)
dV

## V=V Tm = Tmo (countercurrent flow)

14
ChE 471 Fall 2005
LECTURE 8

Problems

A R
Consider the reaction introduced in he last lecture

R=k1CA-k2CR (mol/lit s)

83,700
k1 = exp 7 x10 3 (s-1)
RT

167, 400 -1
k2 exp18 10 (s )
3

RT

Hr = 80,000 (J / mol)
C = 40(J / mol K)
~ p

## Activation energies given in joules.

1. The above reaction occurs in liquid phase! Permissible temperature range of operation is 300 <T <
900 K.

Feed conditions:

## Qo = 100 (lit/s) ; To = 300 K ; CAo = 1(mol/lit)

You have a V = 100 liters PFR. How would you operate this reactor if the only objective is to
maximize the production rate of R.

## b) What are final x A and T .

c) What is the profile of heat addition or removal for every 10% of reactor volume.

d) What is the overall heat duty for the reactor and any heat exchangers preceding it.

## Qo = 100(lit / s) at To = 300K, Po = 24.6 atm

The feed is 50%A, 50% inerts. Permissible temperature range is 250< T < 900 K. Pressure is
constant in the reactor. Gases start to condense below 250 K. Desired conversion is 85%.
15
ChE 471 Fall 2005
LECTURE 8

a) What reactor volume is needed if you operate along the locus of maximum rates?

## c) What is the production rate of R?

3. For the above problem what would FR and xA be if you had a reactor (PFR) of V = 100 liters
available?

4. Suppose that the reactor can only be operated adiabatically and the desired conversion is 85%.
Minimize the required reactor size.

## c) What is the heat duty?

16
WALL COOLED TUBULAR
REACTORS: AVOIDANCE OF HOT
SPOTS
(CHE 471)
M.P. Dudukovic
Chemical Reaction Engineering Laboratory
(CREL),
Washington University, St. Louis, MO
ChE 471 Lecture 9 Fall 2005

## WALL COOLED TUBULAR REACTORS: AVOIDANCE OF HOT SPOTS

The pioneering work of Bilous and Amundsen (AIChE J. 2, 117, 1956) showed that a plug flow
reactor (PFR) cooled from the wall can exhibit extreme parametric sensitivity to small changes in
the wall temperature or heat transfer parameters. Their observation is sketched in Figure 1
below:

1 300 oC
440
2 320 oC
420
3 330 oC
400
4 335 oC
380
5 337.5 oC
360 5
4
340
3
320 2
1
300
0 10 20 30

(s)

## FIGURE 1: Temperature Profiles in a Wall Cooled Tubular Reactor as a Function of Wall

Temperature

Clearly a small variation in the wall temperature of 2.5 C (from 335C to 337.5 C) caused an
80C local rise in reactor temperature! This 'hot spot' generation can lead to reactor runaway for
many reasons. Undesirable reactions of high activation energy can take off at this elevated
temperature, vapor formation can cause increased pressure, rate of reaction may reach extreme
values, etc. Therefore, it is imperative to operate the wall cooled tubular reactor in such a
manner that it does not exhibit such extreme parametric sensitivity and, hence, is not prone to
runaway.

To identify the parameter space for safe operation one starts with the mass and energy balance
for the reactor. Assuming for simplicity, constant volumetric flow rate, Q = const., and a single
simple irreversible reaction, A products, the governing equations are:

## Mass balance on species A:

dx A ( R A )
= (1)
d C Ao

1
ChE 471 Lecture 9 Fall 2005

Energy balance (assuming constant average physical properties and constant heat of reaction):

= (H rA )(RA ) Uav (T Tw )
dT
Cp (2)
d

## The initial conditions are:

= 0 x A = 0, T = To (2a)

## In the above equations:

=
V
(min ) is the space time measured from the reactor entrance as reactor internal
Q
volume V is also measured from the entrance.

mol
CAo 3 = molar feed concentration of A
m
( )
kg / m 3 = fluid density
C (J / kg K )
p
o
= mean specific heat of the reaction fluid
J
H rA = heat of reaction per mole of A
mol A
mol A
RA 3 = rate of reaction of A
m min
T(K) = temperature in kelvin
xA = conversion of A
J
U 2 = overall heat transfer coefficient
m K min

(
av m 2 / m 3 = ) 4
dt
= area for heat transfer per unit internal reactor volume

## Tw (K) = coolant (wall) temperature

To (K) = inlet feed temperature
dt (m) = tube (reactor) diameter

To simplify the algebra, but without loss of generality of the result to be derived, we will take
To= Tw thus assuming the inlet and wall temperature to be the same.

We can now divide eq (2) by eq (1) and rearrange the result to get:

dT H rA CAo 4U (T To )
=
dt C p (RA )/ CAo
(3)
dx A Cp

2
ChE 471 Lecture 9 Fall 2005

Let us define the characteristic reaction time based on the value of the reaction rate at the feed
conditions of concentration and temperature:

C Ao C Ao
R = = (4)
( R A )o k o e E / RTo C Ao n
Here we have assumed for simplicity an n-th order irreversible reaction and ( R A )o means that
we evaluate the rate at feed conditions of concentrations and temperature.
We also have a characteristic heat transfer time:

dt C p
h = (5)
4U

R 4U CAo
=N= =
h (RA ) dt C p
(6)
o
and

=
(H )C rA Ao
(7)
C p To

## Equation (3) now becomes (recall we assumed To = Tw )

dT T To
= To
(RA )/ (RA )o
(8)
dx A

This last expression contains the dimensionless rate of reaction, ( R A ) / ( R A )o , which for an n-
th order irreversible reaction can be written as:

(R ) = k e E / RT
CAn
E To
1
(1 x )
RTo T n
=e
A o

(R ) ke E / RTo n A (9)
A o o CAo

E
= (10)
RTo

## and dimensionless temperature is conveniently defined by:

T To
= (11)
To

Upon substitution of eqs (9), (10), (11) into equation (8) we get:

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ChE 471 Lecture 9 Fall 2005

d
= / 1+ / (12)
e ( )
(1 x )
n
dx A
A

S = = (13)

## We can rewrite eq (12) as:

d n / 1+ / )
= e (
/ 1+ / . )
(1 x A ) e ( (1 x A )
n
(14)
dx A

Since the term on the right hand side of eq (14) that multiplies the term in the brackets is always
positive the sign of the derivative of the dimensionless temperature with respect to conversion,
d
i.e sgn , depends on the terms in the brackets in eq (14). By taking the coolant temperature
dx A
d
Tc to be equal to the feed temperature To, we have assured that > 0 and temperature rises
dx A
with conversion. This is obvious by observing and plotting the terms in the brackets in eq (14).
Physically this tells us that if we try to cool an exothermic reaction with the coolant at feed
temperature, unless the characteristic heat transfer time is infinitesimal in comparison to
characteristic reaction time, i.e , or stated differently the heat removal rate is infinitely
faster than the heat generation rate by reaction at the feed (wall) temperature, then the reactor
temperature must rise with conversion. We can allow for this but we want to know what values
of parameters , , will keep that temperature rise within safe limits.

We can think of the first exponential term in the brackets of eq (14) as the heat generation term
by reaction and the second as the heat removal rate. Indeed heat generation term has an
Arrhenius dependence on temperature, heat removal rate is linear in temperature. Now the heat
generation term is difficult to plot as a function of dimensionless temperature because of the
presence of the (1-xA)n conversion dependent term. We would need to integrate eq (14), save
values of xA vs and then we could plot the terms in brackets of eq (14) against . However,
since we are interested in preventing excessive maximum temperatures in the reactor, we can
take a conservative approach by assuming the worst possible scenario. In the n-th order reaction
(n > 0) the rate of heat generation is being slowed down as conversion increases with as the
(1-xA)n term becomes smaller and smaller at increased conversion. The worst possible scenario
is then if the heat generation rate (and hence the rate of temperature rise) is not affected by
increased conversion. This is the case of zeroth order reaction.

For a conservative approach assume n = 0 and now consider the term in the brackets of eq (14)

4
ChE 471 Lecture 9 Fall 2005

F ( ) = e / (1+ / ) = y1 ( ) y 2 ( ) (15)

Clearly, as = 0, y1 (0) = 1; and as , y1 e and y1 is bounded. At the same time, as
= 0, y 2 (0) = 0; and as , y2 is unbounded. Thus, y1 ( ) is a sigmoidal (S-shape)
curve and y 2 ( ) is a straight line through the origin as shown in Figure 2.

Depending on the value of the ratio of the two dimensionless groups / the three scenarios
depicted in Figure 2 may occur.

1
y1 ( )
2 3

y 2 ( ) e

y1 ( )

1 , 2 ,3
are y 2 (0) for

decreasing

## FIGURE 2: Sketch of y1 ( ), y 2 ( ) of Eq. (15)

The three straight lines in Figure 2 represent y 2 ( ) at three different values of the parameter
/ . Please, recall that at / our y 2 ( ) would be a vertical line guaranteeing = 0 ,
i.e T = To = Tw. For the three scenarios depicted above

> > (16)
1 2 3
and the rate of cooling decreases as we go from case 1 to case 3. Also remember that the value
d
of at which y1 ( ) = y 2 ( ) signifies F ( ) = 0 i.e. = 0 and yields the maximum
dx A
temperature that is observed in the reactor at such conditions. So, in case of rapid heat removal
rate (Case 1) the maximum temperature max 1 is relatively small and of no concern. At the

5
ChE 471 Lecture 9 Fall 2005

certain lower value of heat transfer rate than in case 1, y 2 ( ) not only intersects but is a tangent
of y1 ( ) (Case 2). In this case the maximum temperature max 2 is still tolerable but any
further, even very small, decrease in / would lead to an excessive maximum temperature as
depicted in Case 3 where clearly max 3 is a hot spot to be avoided.

## y1 ( ) = y 2 ( ) which yields max (17a)

and
dy1 dy 2
for avoiding the hot spot (17b)
d max d max

This means that at the maximum temperature, max , the slope of the heat generation line, y1 ( ) ,
must be less than the slope of the heat removal line, y 2 ( ) . The condition at which the slopes
are equal corresponds to using the equality sign in eq (17b) and is illustrated by line 2 in Figure
2. This defines the maximum allowable maximum temperature max 2 . Beyond this point
excessive hot spots may arise.

## We now apply eq (17a) and (17b) to eq (15) to get

e / (1+ / ) = (18a)

and

1
e / (1+ / ) (18b)

2

1 +

/(1+ / )
By eliminating e in equation (18b) in terms of , as per eq (18a), and by using the

equality sign in eq (18b), we can develop an equation for the maximum permissible temperature.
Do that for an exercise by solving the resulting quadratic equation for max . Substitution of the
result for max in the inequality of eq (18b) determines the parameter space that guarantees the
absence of hot spots. The result is not pretty looking.

To get a clear and easy formula to remember an approximate analytical solution is developed via
/(1+ / )
a conservative approach in which one replaces e by a rising exponential e . This is
' T
equivalent to replacing k=koe-E/RT, i.e the Arrhenius temperature dependence with k = k o e
'

dk dk '
and demanding that at T = To, k = k' and = at T = To i.e at that point of T = To both
dT dT

6
ChE 471 Lecture 9 Fall 2005

/(1+ / )
functions are equal and their derivatives are equal. Indeed e and e have the same value
and the same value of the first derivative at = 0 . In Figure 3 we sketch the approximation of
y1 = e /(1+ / ) with e

e
e (1 + ) y1
e

Figure 3: Approximation of the Arrhenius dependence of the rate constant with an exponential
function.

Since we are interested in limiting the max the two curves are pretty close for small . Clearly,

if we replaced y1 ( ) with e in Figure 2 we would lose the intersection with y 2 ( ) for Case 3
but this is not of concern since we are not interested in > max 2 , and for Case 2 the intersection

of y 2 ( ) with e is close to that of y 2 ( ) with y1 ( ) in Figure 2. The advantage of this
approximation is that the criteria of equations (17a) and (17b) applied to

y1 ( ) = e and y 2 ( ) = yield

e = (19a)

and

e (19b)

## From which it follows:

max = 1 (20)

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ChE 471 Lecture 9 Fall 2005

Substitution of this into the inequality described by eq (19b) yields the parameter space that
guarantees absence of hot spots

e (21)

Replacing the above dimensionless quantifies in terms of actual physical variables we get from
eq (20) the maximum permissible temperature that can be tolerated in absence of hot spots

1
Tmax + 1To (22)

From eq (21) we get the conditions that the system parameters must satisfy to guarantee absence
of hot spots.

4 U R To2
e
(k oeE / RTo CAo
n
)
(H rA )E dt (23)

## where R is the ideal gas constant in proper units.

This equation is usually written in terms of tube diameter that will guarantee absence of hot spots
by providing sufficient heat transfer area per unit volume

4U RTo e1
2

dt (24)
E (H rA )k oeE / RTo CAo
n

Clearly, other permutations of eq (23) are possible. Given kinetic and reaction parameters, feed
temperature and tube diameter one can calculate the maximum permissible feed concentration
that guarantees safe operation, etc.

Approximate analysis, using the approximate exponential dependence of the rate constant, but
accounting for the effect of reactant depletion, is possible for an n-th order reaction and yields
the following result which is a little less conservative than equation (23).

e
(25)
1 + 2.703n 2 / 3 2 / 3

This result is due to Chandler Barkelew, Chem. Engr. Progress Symp. Ser. No. 25, Vol. 55, p. 37
(1959) and is one of the most useful expressions for nonisothermal tubular or batch reactors.

The graph showing the parameter space that is safe, based on Barkelew's and similar criteria, is
appended as Figure 3.

8
ChE 471 Lecture 9 Fall 2005

## Figure 3: Runaway diagram

9
SAFE OPERATION OF TUBULAR (PFR)
(CHE 471)
M.P. Dudukovic
Chemical Reaction Engineering Laboratory
(CREL),
Washington University, St. Louis, MO
ChE 471 Lecture 10 Fall 2005

## SAFE OPERATION OF TUBULAR (PFR) ADIABATIC REACTORS

In an exothermic reaction the temperature will continue to rise as one moves along a plug flow
reactor until all of the limiting reactant is exhausted. Schematically the adiabatic temperature
rise as a function of space time, measured from the reactor entrance, takes the form shown in
Figure 1.

Tinf

T0

## FIGURE 1: Temperature as a function of space time in an adiabatic PFR with

exothermic reaction.

( )
H rA C Ao
Tad = To 1 + = To [1 + ] (1)
C p To

is often excessive for highly exothermic systems ( large) and needs to be avoided. In such
situations the old rule of thumb suggests that we should operate in such a way that the inflection
dT
point, i.e. the point of maximum temperature rise , is never reached. This implies that
d max
we operate with < * where * is the value of space time at which the inflection point
d 2T
2 = 0 occurs.
d

1
ChE 471 Lecture 10 Fall 2005

Let us now develop a convenient and simple formula for use by practicing engineers which
would guarantee safe operation. Consider an n-th order irreversible reaction:

R A = k o e E RT C Ao (1 x A )
n n
(2)

At adiabatic conditions temperature and conversion are related by the adiabatic line equation

T = To (1 + x A ) (3)

## If we define, as in the case of wall cooled reactors, the dimensionless temperature by

T To
= (4)
To

then conversion in Eq. (3) can be expressed in terms of dimensionless temperature as:

xA= (5)

where

= (6)

with

= E RTo (7)

## The rate of reaction evaluated at adiabatic conditions in terms of dimensionless temperature is

obtained by using the adiabatic line eq (5) to replace conversion. The result is:

( R A )ad = ( R A )o e ( + )
1 (8)

## where the rate evaluated at the feed condition is:

( R A )o = k o e E RTo C Ao
n
(9)

Cp
dT
d
(
= H rA ) ( R )

## Written in terms of dimensionless temperature it becomes:

2
ChE 471 Lecture 10 Fall 2005

d
n
( + )
= e 1 (11)
d R

## where the characteristic reaction time is:

C Ao
R = (12)
( R A )o
The initial condition is

=0 =0 (13)

We can rewrite Eq. (11) in the most compact way by defining the Damkohler number as the ratio
of characteristic process time and reaction time, i.e.

( R A )o
Da = = (14)
R C Ao

## Equation (11) and initial condition (13) become:

d
n
( + )
= e 1 (15)
d (Da )

At Da = 0 =0 (16)

Now we want to have the reactor short enough (limit the conversion achievable) so that we can
d 2
keep the inflection point = 0 out of the reactor i.e. we do not let it occur in the reactor.
d 2

d 2
=0 (17)
d (Da )
2

## which results in an equation for = inf yielding:

inf =

2n
[ 2
]
+ 4n ( + ) 2n ; n 0 (18a)

## inf = , n=0 (18b)

3
ChE 471 Lecture 10 Fall 2005

The result for the zeroth order reaction, eq (18b), can be obtained by applying the LHospital rule
to eq (18a). A better approach is to notice that for n = 0 equation (15) indicates that
d d (Da ) > 0 always, so that there is no inflection point as the rate of temperature rise keeps
rising until all reactant is depleted. Then at x A = 1 , from eq (5) it follows that max = and

We can integrate the differential equation (15) by separating the variables to obtain the critical
value of Da * and, hence, of *

Da * inf ( + )
e
Da = d (Da ) = d
*
(19)

n

1
0 0

Clearly for given values of parameters , , = , and reaction order n, we can evaluate inf
from eq (18a) and then calculate the value of Da * by numerically evaluating the integral in eq
(19).

Using then the definitions of Da and we get the criterion for safe operation Da < Da *
which can be expressed as:

k o e E RTo C Ao
n
( H ) E
rA
*

Da * (20)
R C p To
2

To get a convenient, easy to remember value of Da * , the following approximations are often
made. First, the Arrhenius dependence of the rate constant on temperature is replaced by an
exponential dependence, in effect

( + )
e e (21)

Substituting this approximation in eq (15) yields via eq (17) to a new approximate value of the
temperature at inflection point

## Substituting eq (21) and eq (22) into eq (19) yields

n
e
(Da ) *
app = d = n e
eu
n u n du (23)

n

1
0

4
ChE 471 Lecture 10 Fall 2005

The final approximation (which is conservative in nature as it assumes the worst possible case of
zeroth order reaction) ignores the slowdown of the temperature rise due to the consumption of
the reactant, which is the same as taking n = 0 in eq (23).

This yields

(Da ) *
app , 0 = e e
u
du = e e u ( )
0
(24)
[e ]
0
= e
1 =1 e
=1 (for large enough )

## For highly exothermic reactions 10 and clearly (Da * )app , o = 1 .

Substituting this into eq (20) gives the conservative criterion for safe operation.

It is constructive to note that this same equation (20a) with time t replacing

k o e E RTo C Ao
n
( H ) E t *

<1
rA
(20a)
R C p To
2

is used to determine the so called time of no return or time to explosion in batch systems. This
time to inflection point t * may be very long for low To but becomes quite short if the system of
high activation energy is exposed to higher To . Hence, chemicals that may be safe to store at
25C may be explosion prone if exposed to 40 50C!

## The mass balance for an irreversible n-th order reaction is:

C Ao x A = ( R A ) (25)
The adiabatic equation relates conversion and temperature
T To
xA =
( )
H rA C Ao C p
(26)

## Upon substitution of dimensionless temperature we get from eq (25)

n
1 ( + )
= e 1 (27)
Da n
let

G ( ) = e ( + )
1 (28a)

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ChE 471 Lecture 10 Fall 2005

L ( ) =
1
(28b)
Da n

We know from before that G is a sigmoidal curve in and represents heat generated by reaction.
L is the heat removal rate (i.e., heat removed by sensible heat of the fluid that flows through the
CSTR).

We know that up to three intersections are possible between G and L lines. To avoid the
intersection leading to excessively high temperatures we must assure that intersections at low
temperatures are available. The last permissible operating condition is the one when line L is
also tangent to curve G as schematically shown in Figure 2.

1 2 3
G ( )
L( )

1 2 = * 3

## (Da )1 < (Da )2 < (Da )3 (29)

While operating adiabatic temperatures at 1 and 2 are acceptable, 3 represents too large a
temperature jump. Hence, we must assure that the L line always intersects the G line at its lower
temperature branch. The critical point is reached when L is also tangent to the G line.

## For safe adiabatic operation we therefore require

6
ChE 471 Lecture 10 Fall 2005

L=G (30)

dL dG
(31)
d d

Applying the above to eqs (28a) and (28b), and using the equality sign in eq (31), we get the
equation for the maximum permissible temperature max perm = * . The critical value of the space
time * can be obtained from the critical value of Da * , which in turn results from substituting
the expression for * into eq (30).

( + )
To get a simple, easy to remember expression, usually we again replace e with e . This
yields

* =
1 n + 1 ( n + 1) 4
2
(32)
2

The negative sign in front of the square root needs to be taken as we are interested in the lower of
the two temperatures at which the L line could be tangent to the curve G. Then equation (30)
yields:

n
*
(Da ) = 1 e
* *
*
(33)
app

Da * e 1 (34)

k 0 e E RTo C Ao
n
( H ) E e
rA 1
(35)
R C p To
2