Chapter-four.

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 To
TR
TR
Endothermic
Endothermic
t V, L,W
Figure : Temperature change during reaction for batch & continuous operation
If there is a chemical reactions, the following
changes occur :
Temperature,
conversion, and
reaction rate
Volume / Pressure

These are inter-related to each other

and are important parameters to the
size of a reactor and time
This relation also depends on the heat
liberated (exothermic) or heat absorbed
(endothermic) during the reaction.
Exothermic reaction in adiabatic reactor

X
TR

L, V, W
Figure : Conversion (X), Temperature (T) and the
Rate of reaction (r) versus the Length (L), Volume
(V) or Weight of a catalyst (W)
 Endothermic reaction in adiabatic reactor

TR

r
L, V, W

Figure : Conversion (X), Temperature (T) and the Rate of

reaction (r)versus the Length (L), Volume (V) or Weight of a
catalyst (W)
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
Hence, bringing the reactor in desirable
temperature (control), is vital and effected through
I. by Supply (endothermic) or withdrawal
(exothermic) of heat during the
reaction,
Q Q

(b)
(a)
Figure : Heating (a) or cooling (b) of the reactor for
endothermic or exothermic conditions to maintain
isothermal operation
Coolant

Heater

(a) (b)

Figure : Batch reactor with cooling (a) and with

heating (b)

Notice !!
Strong cooling / heating / also affects the path, irrespective
of whether it is strong or poor or medium cooling/ heating
Effect of cooling in Exothermic reactions
Poor cooling
Poor cooling

T XA
Moderate cooling
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)
Supply or Withdraw of heat during reaction is
controlled by the so called
 Heat Transfer Equipment and
 Heat Transfer fluid
Heat transfer fluid
As a heat transfer fluid, we prefer to use water.
If we use other fluids / Coolant, the more practical
difficulties may be encountered due to the
 Cost,
 corrosion,
 specific & latent heat etc.
Table : summarizes the heat transfer fluids /Coolant that are
commonly used, giving their working temperature range
Media Range Usage

Various -400C to Low temperature duties

Fluorocarbons +200C
NaCl - brine -200C to Low temperature duties,
+200C aqueous coolant
Water / Steam 00 C to Used as liquid phase or
2000C (10 liquid/vapor system
bar)
Heat-transfer 300C to Stable, low viscosity mineral oils
Oils 3200C for liquid circulation (e.g
mobiltherm 600)

Dowtherm A 200C to Diphenyl oxide as liquid or

4000C liquid/vapour system
Inorganic Salts 1500C to Mixture of sodium, nitrite,
4500C nitrate, and potassium nitrate
and also bringing the reactor in
desirable temperature is effected by

II by division of a fixed-bed reactor

into section with intermediate
cooling or heating of the mixture.
III. by addition of an inert compound,
or excess reactant for reducing
temperature changes.
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 reactor
 the size of a reactor,
 Adiabatic

T r

Non-Adiabatic

L T

Figure : Relationship between the temperature,

rate of reaction and the length
Looking to the above Figure, Generally, one
can see two conflicting situation in rxn:
high temperature offers high reaction
rate. This is positive
but
high temperature obtained with high
volume of reactor. This is negative

These are two conflicting situation !!!!!

Require optimum operating temperature
 Optimum operating temperatures in the reactor
are those at which the chemical reactor
shows an economically justifiable
Definition

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
 The minimum volume will be achieved

if the reaction rate is maximum at all

positions in the reactor

Therefore, Optimum operating temperature in the reactor at

any given position will be that for which the rate of reaction is
maximum at any conversion level.

Therefore, the rate of reaction

r[T,C(X)] is the basic information
 to the conversion, necessary to determine optimum
operating temperature in the
 to temperature,
reactor.
 to determine the optimum temperature
sequence,
We have to work

 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))
Attention not to forget that to achieve this
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 A
 r r
I II
r  f (T )
I
r  f (X )
II A
where f(XA) is usually a decreasing function of XA

From rII  f ( X A) a rise in the fractional conversion

brings about a fall in the rate of reaction.

Since E is positive
r  f (T )  A(e-E RT )
I
Temperature increasing, will increase the rate exponentially

This compensate the falling of the rate in rII i.e.,

the rate increases with the temperature at any
composition.
This is, therefore, to deduce that
the optimum operating temperature in the reactor
will be the highest temperature that is possible.
Of course, this conclusion has a limit due to
 the properties of the construction materials
and
 the formation of the side reactions.

For irreversible reactions, the drawn conclusion

applies for both endothermic and exothermic
reactions
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 ) CA,0 (1 - X A ) - A (e ) CA,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
 Exothermic
Endothermic
Energy of reactant molecule

E
E’

E E’

H  E - E'  0
R
H  E - E'  0
R

Distance along rxn path

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.
On the other hand, the equation (b) depicts that the reverse
reaction will be slow at low conversion, while the forward
reaction rate will be fast.
For the rate to be maximum at any conversion, the
temperature should be
 High at low conversion where predominantly the
forward reaction takes place
 Lower at high conversion, where the rate of the
reverse reaction is high.

Hence, for reversible exothermic reactions the optimum

operating temperature sequence is a changing temperature.
i.e., starting at high temperature and gradually changing to
a decreasing temperature.
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
 Exothermic Endothermic

Tmax
To
T

To

X
X

Figure : Temperature and Conversion behaviors in adiabatic

reactors.
High Temperature change in the reaction might exceed
workable temperature Tmax

Tmax

To

L, V, W
This High unworkable Temperature change causes

Unfavorable reaction condition

Practical difficulties may be encountered

 Hot spot if it is exothermic rxn
 Drop rate of rxn if it is endothermic
rxn
Lower equilibrium conversion
 Practical difficulties in an exothermic reaction, (hot spot)
 the heat generation along the tube is uneven and
 at the middle of the reaction it can exceed Tmax
(hot spot) so that the reactor is unworkable

FR,0 FR
T=200C T=3000C

As a solution
 The tube has to be very narrow
 Adding an inert gas or an excess of one of the
reactants to the reactor.
 A) Narrow the tube

 the tubes are usually very narrow to ensure a high

surface/volume ratio for heat transfer. Thus, in order to get
adequate reactor capacity at an acceptable pressure drop, the
industrial reactors must contain several thousands of such
tubes, built together in a single shell in which the coolant is
flowing.
 Gas inlet
Thermocouple

Baffles outlet

Gas outlet

Figure : Multi tube Fixed bed reactor

B) 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.
 Unfavorable reaction condition

Lower conversion

Endothermic rxn Exothermic rxn

XA,eq
XA,eq

XA

Isothermal
Isothermal
XA

T
T0 T0 T
 Methods applied to extend the conversion to the desired
level before exceeding Tmax
A) 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
T
Figure : Cooling to the desired, temperature by using
indirect heat exchanger in fixed bed reactors.
 To
Z=0 X3>X2>X1>

X3
T1
T1, X 1 T2
T2

X2
T3
T3 , X 2 T4 X1
T4
X1 T

Product Z=L
T5, X3

Feed

Figure : Cooling to the desired, temperature by using indirect

heat exchanger in fixed bed reactors.
B) 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.
 To

Quench To

Figure 4.13 Direct cooling between beds in fixed

bed reactor
 To Z=0

To
T1

Xeq
T1 X1

Z X

T2
X3
T2

T3 X2

T3 X2

X1
T4

T5

T To T
T5 Z=L
X3

Feed Product
C) 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
 Quench
Quench
O O O O O O
O O O O O O
O O O O O O
O O O O O O
O O O
O O O
D) Adding an inert gas or an excess of one of the
reactants to the reactor feed.
The addition of inert gas or excess reactant
 The reduced temperature in the
reaction plays advantageous role in
increasing the conversion.
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.
 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 preheat 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.
 THE TRF TRE
Feed
O O O O O O O
THF O O O O O O O
O O O O O O O
TR,HE O O O O O O O

Product TR,HF Reactor

Heat
Exchanger

TR,HF

TRE

∆TR
TR,HE
∆TH
TRF
TH E

THF

Distance
ii) Reactor with internal heat
exchanger tube between the product
and the feed
 Here the heat exchanger
is an integral part of the
reactor.
 Reactor

TH THE
E
o o o
o o o
o o o
o o o
o o o

Feed
THF
THF TRE

TRE
Heat exchanger
Product

Figure: Schematic diagram of internal heat exchanger for a

single reactor together with temperature distribution.
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 F C dT  (H ) F dX
R P, R A,0 A
Integration for the reactor part
TE X
-H
 
R  
F
R A,0 AdX
 

 dTR
=
 


 

TF F C A
R R P 0
After integration, we obtain
FA,0
TR - TR = - H R  F C X A
E F
R P
 or
TRE - TRF = Tad X 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
-
TR E = T F
R, H
TR F = TH E
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 feed will not be
that the
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
Integration gives R P S
F C ( T E - T F)  UA(T F T E )
R P H H R, H H
We know that
TH E = TR F

TR, H F= TR E
TH E = TR F
Substituting and rearranging these, we get

TR E - TR F = F C

R P TR F - THF
UA

Substituting equations and rearranging we obtain

 - H R FA,0 
R P R
UA
H
F C T F -T F  = 
 FRC P
 X A


Hence
TR F - = UA T X
TH F 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.
At the end of the reactor, where the reagents are becoming
depleted, the heat exchange overtakes the heat generation
and the gas temperature falls progressively to its entrance
value.

The most important parameters in designing such type

of reactor is to find
 the achievable conversion as well as
 the temperature control.
These parameters are found by combining material
and energy balances.
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
F C d (T - T )  (-H )F dX c)
R P,R R H R A,0 A
(-H R ) FA,0
TR - TH  dX A d)
Hence, FR C P, R

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

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 )
R P,R H H T
 - 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
UA
H  -
L
ad  X dZ  T
A ad
X
A
(i)
0