CHAPTER 4.

HEAT TRANSFER IN REACTORS

4.1Temperature change during reaction
All chemical reactions in principle by the nature of reaction are accompanied
evolution or absorption i.e., under this principle it is hard to assume a chemical
reaction that has a reaction heat of zero. Next figure shows schematic diagram of
temperature change during reaction in a batch and continuous operation.

Exothermic Exothermic
TR TR

Isothermal Isothermal
T To T TR
TR
Endothermic
Endothermic To
t V, L,W
Figure : Temperature change during reaction for batch & continuous operation
Change of temperature on the reacting fluid,
some times is Undesirable
e.g. for Exothermic rxn
 Undesirable temperature change causes

 Product decrease( equilibrium)

 low production rate
 fast rate of reaction(explosive)
 Damage the reactor
 Effect of cooling in Exothermic reactions

Poor cooling
Poor cooling

XA Moderate cooling
T Moderate Cooling

Strong cooling

To
Strong cooling

L, V, W L, V, W
Figure : The effect of cooling on the temperature and conversion
against the Length (L), Volume (V) or Weight of a catalyst (W)
4.2 Optimum temperature profiles for non- isothermal reactors

Undesirable temperature change causes unfavorable reaction condition we

need optimum temperature.

•Four core variables in reactor are

• temperature,
• Concentration / Conversion
• reaction rate and
• the size of the reactor,
These core variables (T, C, r, V) in a chemical reactor
influence the design and
operating performance

Since the temperature influences

the rate of reaction,
We should find the
the conversion
operating temperature in
the size of a reactor,
the reactor
 Optimum operating temperatures in the reactor
are those at which the chemical reactor shows an
economically justifiable maximum production
rate per unit length of reactor in terms of the
desired product.
Of course, our target in the design of a reactor,

 is to find the size of a reactor for a specified

conversion.
This is not also the end,
 we have further to consider if it is possible to
minimize the size of the reactor.
This means we have to establish, optimum
operational temperature range, which gives
maximum conversion, T(X), plausible (acceptable)
rate of reaction within the small size (length) of the
reactor. r(V)

We have to see r(V)

As an example, Looking to the design equation
X
A dX A
V F
R A,0  ( r )
0 A
 to determine the optimum temperature sequence,
 which minimizes the reactor volume or the
time of the reaction for a given conversion
 at the same time achieving the maximum rate
of reaction at all positions in the reactor.

r(T , C(X))

Different reactions give different solution.

4.2.1 Optimum operating temperature for irreversible reaction

Consider the reaction A P

The rate of disappearance of reactant A

r(T , X )  kC
A A
A(e-E RT ) C (1 - X )
A,0 A
 A(e-E RT ) f (X )
A
r(T , X ) A(e-E RT ) f (X )
A A
r r (a)
I II
r  f (T )
I
r  f (X )
II A
4.2.2 Optimum operating temperature for reversible reaction
Consider the reversible reaction,
A P

which has the rate of reaction function ability as

- E RT -1 - E -1 RT
r (T , X A )  A(e ) C A,0 (1 - X A ) - A (e ) C A,0 X A
- E RT 1 - E -1 RT
 A(e ) f ( X A ) - A (e )g( X A )

(b)
g(XA), E-1applies for the reverse reaction

The function g(XA) is always an increasing function and the

concentration of product increases with the conversion
In an endothermic reversible reaction,
since E > E-1,

the rate of forward reaction increases more rapidly with temperature

than that of reverse for any conversion, which brings that

the optimum operating temperature is the maximum

permissible temperature.

In an exothermic reversible reaction, E’ > E

Hence, the rate of reverse reaction increases more rapidly with

the temperature than that of the forward reaction.

4.3 Temperature effect on an adiabatic fixed - bed gas reactors

Gas/solid adiabatic catalyzed reaction is carried out in a plug

flow reactor,
 the reactants are fed continuously into one end of a
tube and
 the reactor products flow out at the other end.
During the reaction
if it is an exothermic reaction ,the temperature of the
gas stream will increase across the reactor length.
if it is an endothermic reaction, the temperature of the
gas stream will drop within the reactor length.
 A) Adding an inert gas or an excess of one of
the reactants to the reactor.

The addition of inert gas or excess reactant

 is used as heat sink by adsorbing high
exothermic heat.
Such method has disadvantage over the other methods because
of its requirement of a large size of the reactor to accommodate
both the reaction mixture and the inert or excess reactant.
Methods applied to extend the conversion to the desired level before
exceeding Tmax

B) Using indirect heat exchanger

In this method, the beds are sub-divided into two or more so that each bed
does not exceed Tmax.

To To T T

To

To T

X
T X
T ’

Figure : Cooling to the desired temperature by using indirect heat exchanger

in fixed bed reactors.
C) Direct cooling or quenching between two or more beds

This is used mostly in the case of

high exothermic reaction, i.e., for

too high temperatures and
 it is not useful through the usage of indirect heat
exchangers.
 Here one of the reactants is injected in cold stage
into the reaction stream between consecutive beds.
The following Figure shows such methods.
 D) Stepwise Quenching

This is similar to the previous method, but the

difference is that instead of sub-dividing the beds, it
will be carried out in the beds placed differently and
by using perforated tubes.
Disadvantage of this method over the previous one is
that it is somewhat sloppy and it is difficult to design
for. The following Figure depicts such a method
 4.4 Temperature effect on an autothermal reactor
 It is understood that when exothermic reactions
are conducted, there is enormous heat liberated
to the surroundings

This heat might be used for preheating the

reactant or for other industrial uses.
Why preheating the reactant?
Because at the starting the reaction, the reaction rate becomes so
low that it does not effectively start reaction in the vessel. For such
reasons, the reactant temperature is raised to the desired temperature, by
letting hot gas from the product mixture.
This phenomena is used in the auto thermal reactor.
A reactor system, in which the reacting mixture /product/ is
used to pre heat the feed (reactant) is called auto thermal
reactor.
It is to be noted here that the feed will not be preheated if no
conversion takes place.

Based on the range of reacting temperature auto thermal reactors

are working into two ways

i) Reactor with external heat exchanger tube between the product and the
feed.

ii) Reactor with internal heat exchanger tube between the product and the
feed
i)Reactor with external heat exchanger tube between
the product and the feed.
Here two separate units are installed namely
 the heat exchanger and

 the reactor.
 The feed is sent to get energy by counter current
heat exchanger.
 The heated feed are then sent to the reactor to
take reaction.
ii) Reactor with internal heat exchanger tube
between the product and the feed

 Here the heat exchanger is an

integral part of the reactor.
4.4.1 Design of an auto thermal adiabatic tubular
reactor with external heat exchanger tube between
the product and the feed

The main task here is

 to know the relationship between the
temperature rise in the heat exchanger and
 the inlet temperature of the reactor.
We have to consider separately the heat exchanger and the reactor

part.
Considering the reactor part, the energy balance will be reduced to equation
F C dT ( H )F dX UA(T  T )dV
R P R A,0 A S
for not having heat exchanger the equation becomes
FRC P,dT ( H R ) FA,0dX A

Integration for the reactor part

TE
R - H F X
 dTR
 
 

R A,0 AdX
 
 

= 
 

TF F C
R P 0
A
R
After integration, we obtain
E F FA,0
TR - TR = - H R  F C XA
R P
 or TRE - TR
F = T X
ad A -
FA,0
where Tad  - H R 
FRC P
Equation demonstrates that the temperature rise in the reactor,
TR , heat production is a linear function of conversion, XA
From the picture, it can be clearly seen that
TRE TRF = TR
-
E T F
TR = R, H
E
TR F = TH
Hence, equation can be rearranged
TRF, H - TH E = TH = TR = Tad X A
where
TH is the temperature difference available for heat transfer, which is
called heat removal
TR is the temperature rise in the reactor, which is called heat
production
or
Heat removal TH = Heat production TR
Equation demonstrates that the feed will not be
preheated if no conversion takes place
The heat balance of equation (3.11) for the heat exchanger part,
neglecting the reactor part, is reduced to
F C dT UA(T  T )dV
R P S
Integration gives
F C ( T E - T F)  UA(T F T E)
R P H H R, H H

TH E = TR F
We know that

TR, H F= TR E
Substituting and rearranging these, we get
F C
TR E - TR F = R P TR F - TH F
UA
 
Substituting equations and rearranging we obtain

 - H R FA,0 
R P R
UA

F C T F -T F
H  =  F C
 R P
 X A

Hence
TR F - TH F UA T X
= F C ad A
R P
These equation is demonstrated in two equations namely the left
side equation and the right side- equation
F T F UA T X
TR H F C ad A
R P
4.4.2 Design of an autothermal adiabatic multi-tube reactor with internal
heat exchanger tube between the product and the feed

The principle of such operation is that

 the cold feed passes nearby the reactor tubes, getting heat from
the reactor.
 The feed is then raised to a temperature in such a manner that
when it enters the reactor tube, the reaction temperature as well as
the rate is high enough for the operation.
 In the entrance of the reactor, there is a high temperature rise,
due to the heat generated by the reaction at a faster rate than
the heat exchange.
For the reaction mixture, which is carried out in the reactor, the energy
balance equation rearranged and becomes
 F C dT ( H )F dX U (T  T ) AdZ a)
R P,R R R A,0 A R H L

For the feed, which is preheated in the heat exchanger tubes, the
energy balance equation becomes

f F C dT U (T  T ) AdZ  0 b)
R P,R H R H L

where,
CP,R = constant, A is the total heat exchange area,  is the fraction of the feed
flowing through the heat exchanger, (1-) is the direct cold injection at the
entrance of the reactor and Z is the coordinate in the flow direction.
Equation (a) and (b) cannot be solved analytically only using
computer. Solution can be made analytically only for the fraction
of the feed flowing through the heat exchanger, f=1.

F C d (T - T )  (-H )F dX
R P,R R H R A,0 A c)

(-H R ) FA,0
TR - TH  dX A
FR C P, R d)

Hence, TR - TH Tad X A e)
 Taking equation
F C (T E - T F )  - U (T  T ) AdZ f)
R P,R H H R H L
Substituting modified equation (e) to equation (f) gives,
(-H )F X
F C (T E - T F )  - U A R A,0 A dZ
R P,R H H L F C
R P,R
(g)

T
F C (T E - T F )  - UA ad X dZ
R P,R H H L A (h)
or rearranging yields

F C (T E - T F ) T
R P,R H H - ad X dZ
UA L A

After integration between Z = 0 and Z = L, it become

F C (T E - T F ) T Z L
R P,R H H - ad  X dZ T X
UA L A ad A (i)
0
Generally, equation (i) demonstrates the following conditions
namely
T E- T F
H H is proportion to the heat taken by the feed before it
UA F C
R P,R enters into the reactor i.e., heat removal.

T X is the average driving force for the heat exchange,

ad A
where it is multiplied by a factor UA F C
R P,R
gives the total temperature increase i.e., heat
production
This is clearly seen in the next Figure that both the heat removal line as
well as heat production curve depends on the values of UA FR CP,R
• With too little and small heat exchange capacity, the
reactor entry temperature becomes too low and no
conversion results i.e., from Figure one can see that the
reactor is on the average in a stable operation.
• With optimum heat exchange capacity, it is possible to
obtain moderate conversions.
• With too much heat exchange capacity, the reaction
temperature is too high and equilibrium is adversely
affected. Based on this argument, it is desirable not to
make the heat exchange capacity much greater than
necessary .