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CHAPTER 5

Non- isothermal reactor design


5. HEAT TRANSFER IN REACTORS
5.1Temperature 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 Endothermic
TR 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
N-1
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

(a) (b)

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 00C to Used as liquid phase or
2000C (10 liquid/vapor system
bar)
Heat-transfer 300C to Stable, low viscosity mineral
Oils 3200C oils 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
5.2 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
operating
 The conversion 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
Definition
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 N-2
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
 to the conversion,
information necessary
to determine optimum
 to temperature, operating temperature
in the reactor
We have to work 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))
Attention!!! not to forget that to achieve this
different reactions give different solution.
5.2.1 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 r  f ( X ) a rise in the fractional conversion
II A
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
5.2.2 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
Energy of reactant molecule Exothermic
Endothermic

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.
Next Figure shows the operating line for minimum
reactor size.
 In the figure, the net rate from the equation (b)
is plotted versus temperature; each curve
corresponds to a constant conversion.
 An optimum operating temperature is
determined by counting the maxima and is
shown by the dashed lines.
 Establishing of the optimum operating
temperature, encounters technical
difficulties and expensive costs are involved.
 Thus it is difficult to implement in the industry.
 Since most of the industries these days are
working with gas phase in the presence of a
catalyst, it is much simpler from a technical point
of view, to let the reaction proceed adiabatically.
X4> X3 > X2 etc

X1 =0
r
X2
X3
X4

T
Figure : Optimum Operating Temperature sequence for an
exothermic reversible reaction.
5.3 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
T

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
FR,0 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.
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’
X
T
T T

Figure : Cooling to the desired, temperature by using


indirect heat exchanger in fixed bed reactors.
X3>X2>X1>
To Z=0

T1, X1 T1 X3
T2

T
2
T X2
T3, X2
T4 T
4
3 X1

X1

Z=L T
T5, X5
Product

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

T5 X3 Z=L T To T

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.
5.4 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.
THE TRF TRE
Feed OOOOOOOOOOOOOO
OOOO
THF OOOOOOOOO

TR,HE OOOOOOOOO

0
Product TR,H F
Heat Exchanger 0
Reactor
O

TR,HF
0

0 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

THE THE
o o o
o o o
o o o
o o o
o o o

Feed
THF TRE
THF

TRE Heat exchanger


Product
Figure: Schematic diagram of internal heat exchanger for
a single reactor together with temperature distribution.
5.4.1 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
FRCP,dT  (H R ) FA,0dX A
Integration for the reactor part
TE
-H F X A
 
R 


 dTR R A,0 dX
 

= 
 

TF F C A
R R P 0
After integration, we obtain
FA,0
E F
TR - TR = - H R  XA
FRCP
or
-
TRE - TR
F
= Tad X A
where FA,0
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 = TRF, 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 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
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
F C
TR - TR = R P TR F - TH F
E 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 TR F - T F and the
H
UA T X
right side equation F C ad A
R P
TR F - TH F
and
UATad
FT C P
XA Heat production
curve
UA T X
F C ad A
R P

Heat removal line


TRF-THF

T HF T RF
The left side of equation is simply the temperature
rise in the heat exchanger

TR F - H
T F

This temperature rise of the feed stream is the


heat taken up in the heat exchanger and is equal
to the right side of the equation.

This also can be translated as the temperature


rise in the reactor multiplied by the factor
In practice this factor is often greater than 1
UA
F C
R P
The right side of equation simply implies the heat
production by conversion. Both terms can be plotted
separately as a function of the reactor inlet
temperature T F
R

Heat production curve is influenced by the quantity


of space time or residential time. Assuming the
volume of a reactor for a single operation is fixed, the
space time is inversely proportional to the flow
rate. The heat production curves reach a horizontal
level at high temperatures, where the conversion
is complete. This level depends on the residence
time in the reactor
5.4.2 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 
FRC P, R
dX A d)
Hence,
TR - TH  Tad X A e)
Taking equation
F C (T E - T F )  - U(T T ) AdZf)
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 (g)
R P,R H H L F C
R P,R
T
F C (T E - T F )  - UA ad X dZ (h)
R P,R H H L A
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 )
R P,R H H T Z L
 - ad  X dZ  T X
UA L A ad A (i)
0
Generally, equation (i) demonstrates the
following conditions namely
T E- T F is proportion to the heat taken
H H by the feed before it enters into
UA F C
R P,R the reactor i.e., heat removal.

T X is the average driving force for


ad A the heat exchange, where it is
multiplied by a factor UA FR CP,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
(TH E - TH F ) Situation 1 2 3
Tad  X A 
UA FT C P UA 1.6 2.0 4.0
FT C P

1 2
3
Heat Removal Heat Production

THE TRF
• 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
Example 5.1 A first - order autothermal gaseous
reversible reaction, of constant density,
A P
is carried out in a plug flow reactor. Experimental data is
given,
(-rA )  k1CA - k -1CP

k1  0.02 exp(- 29300 ), s -1


RT
K eq  0.061 exp(16700 3
) , mol/m . s
RT
At 873 K, Keq = 0.61; while at 473 K, Keq = 4.3
Using the symbol FA,0, CA,0 and knowing that the
maximum permissible temperature is 873 K, and CP,0 =
0, Calculate the optimum temperature profile and
the required volume of a reactor for a 60%
Example 5.2 A multi-tube reactor is used for the first-
order reaction,
A B
The rate constant k = 6.624 x 108 exp(- 44.9 /RT). The feed
charged to the reactor is composed of inert, which has CA0 =
1.8x103 mol/m3, CI,0 = 10.8 x103 mol/ m3,. The heat of reaction
(ΔH R ) = -44.8 kJ/mol. The heat of capacity, CP,A = 6.2 J / mol. K,
CP,I = 5.5 J / mol. K as 10 tubes of length of 4.4 m and
diameter 0.08 meter are necessary for the reaction. The
cooling water is available at T = 293 K and CP,W = 4.19 kJ /
kg.K. The flow rate of the cooling water is 4320 kg / h
and heat transfer coefficient is 1152 kJ /m2 .h .K.
Determine the conversion, the cooling
temperature of the water and the temperature of
the reaction as a function of the length of the
reactor