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The highest conversion that can be achieved in

reversible reactions is the equilibrium conversion.


For endothermic reactions, the equilibrium conversion
increases with increasing temperature up to a
maximum of 1.0.
For exothermic reactions the equilibrium conversion
decreases with increasing temperature.

EXOTHERMIC REACTIONS
To determine the maximum conversion that can be achieved in
an exothermic reaction carried out adiabatically, we find the
intersection of the equilibrium conversion as a function of
temperature:
KC
Xe
1 KC
with temperature-conversion relationships from the energy
balance (eq. 1.46). For Ti0 = T0,
n T

iCpidT
i1 T0

T
0

HRx TR Cp dT
T

(1.57)

Graphical solution of equilibrium and energy balance equations


to obtain the adiabatic temperature and the adiabatic equilibrium
conversion Xe

EXAMPLE 1.5
For the elementary solid-catalyzed liquid-phase reaction:
A B
make a plot of equilibrium conversion as a function of
temperature. Determine the adiabatic equilibrium
temperature and conversion when pure A is fed to the
reactor at a temperature of 300 K.
Additional information:
H0A 298 K 40,000 cal mol

HB0 298 K 60,000 cal mol

Cp 50 cal mol.K

Cp 50 cal mol.K

K e 100,000 at 298 K

SOLUTION
Rate law:

CB
rA k C A
Ke

(a)

Equilibrium, rA = 0, so:
CBe
C Ae
KC

Stoichiometry (v = v0) yields


C A 0Xe
C A 0 1 X e
KC
Ke T
Xe
1 Ke T

(b)

Equilibrium constant:
0
HRx
K e T K e T1 exp
R

1 1

T1 T

0
HRx
HB0 H0A 20,000 cal mol

20 ,000 1 1

K e T 100 ,000 exp


1.987 298 T
T 298

K e T 100 ,000 exp 33.78

(c)

Substituting eq. (c) into (b)


100 ,000 exp 33.78 T 298 T
Xe
1 100 ,000 exp 33.78 T 298 T

(d)

T (K)

Ke

Xe

298

100000.00

1.0000

300

79835.65

1.0000

325

6042.58

0.9998

350

661.28

0.9985

375

97.20

0.9898

400

18.16

0.9478

425

4.13

0.8051

450

1.11

0.5257

475

0.34

0.2545

500

0.12

0.1058

For a reaction carried out adiabatically, the energy balance


reduces to

i C pi T T0 Cp T T0
HRx T

HRx T

50 T 300
X
2.5 10 3 T 300
20 ,000

T
300
350
400
450
500

Xe
0.0000
0.1250
0.2500
0.3750
0.5000

(e)

1.20

Ke T
Xe
1 Ke T

1.00

0.80
0.60
0.40

0.40

Cp T T0
Xe
HRx T
A

0.20
460

0.00
300

350

400

450
T (K)

500

550

600

For a feed temperature of 300 K, the adiabatic equilibrium


temperature is 460 K, and the corresponding adiabatic
conversion is 0.40.
Higher conversions than those shown in the previous figure
can be achieved for adiabatic operations by connecting
reactors in series with inter-stage cooling:

Increasing conversion by inter-stage cooling

EXAMPLE 1.6
What conversion could be achieved in Example 1.5 if two
interstage coolers were available that had the capacity to cool
the exit stream to 350 K? Also determine the heat duty of
each exchanger for a molar feed rate of A of 40 moles. Assume
that 95% of equilibrium conversion is achieved in each reactor.
The feed temperature to the first reactor is 300 K.

SOLUTION
In Example 1.5, for an entering temperature of 300 K the
adiabatic equilibrium conversion was 0.40.
For 95% of equilibrium conversion, the conversion exiting
the first reactor is 0.38.

The first reactor


The exit temperature from the first reactor is found from a
rearrangement of Equation (e):
X 2.5 10 3 T 300
T 400X 300 400 0.38 300 452

We now cool the gas stream exiting the reactor at 460 K


down to 350 K in a heat exchanger.

The gas stream is then sent to the second reactor.

The second reactor


T02 = 350 and X1 = 0.38
The energy balance leads to
T2 400 X2 X1 T0

T2 400 X2 0.38 350

Intersecting eq. (f) with eq. (d) yields in the maximum/


equilibrium conversion in the second reactor:
X e 0.61
2

95% of Xe2 = X2 = 0.58


The corresponding exit temperature is
T2 400 0.58 0.38 350 430

(f)

The third reactor


T03 = 350 and X2 = 0.58
The energy balance leads to
T3 400 X3 X2 T0

T3 400 X3 0.58 350

Intersecting eq. (g) with eq. (d) yields in the maximum/


equilibrium conversion in the second reactor:
X e 0.78
3

95% of Xe3 = X3 = 0.75


The corresponding exit temperature is
T3 400 0.75 0.58 350 418

(g)

1.20
1.00
0.80

X 0.60
0.40
0.20
0.00
300

350

400

450
T (K)

500

550

600

ENDOTHERMIC REACTIONS
Another example of the need for inter-stage heat transfer in a
series of reactors can be found when upgrading the octane
number of gasoline. The more compact the hydrocarbon
molecule for a given number of carbon atoms, the higher the
octane rating. Consequently, it is desirable to convert straightchain hydrocarbons to branched isomers, naphthenes, and
aromatics.
The reaction sequence is

The first reaction step (k1) is slow compared to the second


step, and each step is highly endothermic. The allowable
temperature range for which this reaction can be carried out
is quite narrow: Above 530C undesirable side reactions occur
and below 430C the reaction virtually does not take place. A
typical feed stock might consist of 75% straight chains, 15%
naphthas, and 10% aromatics.
One arrangement currently used to carry out these reactions
is shown in the figure below. Typical sizes of the reactors are
on the order of 10 to 20 m high and 2 to 5 m in diameter. A
typical feed rate of gasoline is approximately 200 m3/h at 2
atm. Hydrogen is usually separated from the product stream
and recycled.

V or W