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IV. HEAT TRANSFER IN REACTORS Several

(a)
means are available
(b)
to conduct the reaction in a
reactor, in desirable temperature, amongst which are:
All chemical reactions in principle are accompanied by
evolution or absorption i.e., under this principle it is hard to I.Supply (endothermic) or withdrawal (exothermic) of heat
during the reaction, as shown in the Figure 4.2 and Figure 4.3
assume a chemical reaction that has a reaction heat of
zero. Figure 4.1 shows schematic diagram of temperature II.Addition of an inert compound, or excess reactant for
change during reaction in a batch and continuous operation reducing temperature changes.
III.Division of a fixed-bed reactor into adiabatic section
with intermediate cooling or heating of the mixture.
Exothermic Exothermic Q Q

Isothermal Isothermal
T To T To
Endothermic
Endothermic (a) (b)

v Figure 4.2 Heating (a) or cooling (b) of the reactor for

t endothermic or exothermic conditions to maintain isothermal
Figure 4.1 Temperature change during reaction for batch & continuous
operation operation

Table 4.1 summarizes the heat transfer fluids that are commonly
used, giving their working temperature range
Coolant
Heater Media Range Usage

Various -400C to Low temperature duties

Fluorocarbons +200C
NaCl - brine -200C to Low temperature duties, aqueous
(a) (b)
+200C coolant
Figure 4.3 Batch reactor with cooling (a) and with heating (b) Water 00C to 2000C Used as liquid phase or
For endothermic and exothermic reactions, the heat (10 bar) liquid/vapor system
liberated or absorbed during the reaction is controlled by the so Heat-transfer Oils 300C to Stable, low viscosity mineral oils
called Heat Transfer Equipment with heat transfer fluid 3200C for liquid circulation (e.g
mobiltherm 600)
As a heat transfer fluid, we prefer to use water. If we use
other fluids, the more practical difficulties may be encountered Dowtherm A 200C to Diphenyl oxide as liquid or
due to the reasons of cost, corrosion, specific & latent heat 4000C liquid/vapour system
etc. Inorganic Salts 1500C to Mixture of sodium, nitrite,
4500C nitrate, and potassium nitrate

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Temperature, conversion, and reaction rate are inter- X

related to each other and to the size of a reactor. This
relation also depends on the heat liberated (exothermic) or heat
absorbed (endothermic) during the reaction.
The effect of temperature can easily be demonstrated in an
adiabatic flow reactor. Such reactor is simple to analyze due to T
the fact that the energy balance can be solved without r
reference to the mass balance X L, V, W
T
Figure 4.5
Fi 4 5 Conersion
C i (X),
(X) temperature
t t (T) and
d rate
t off reaction
ti (r)
()
VS the length (L), volume (V) or weight of catalyst (W) for an
r endothermic reaction.
It is to be clear that the heat absorbed or released by
reaction can enormously change the temperature of the
L, V, W reacting fluid, and this is controlled by the cooling or
Figure 4.4 Conversion (X), Temperature (T) and the Rate of heating medium. This cooling medium also affects the
reaction (r) versus the Length (L), Volume (V) or Weight of a path, irrespective of whether it is strong or poor or medium
catalyst (W) for an exothermic reaction. cooling. Figure 4.6 demonstrates such effect

4.2 Optimum temperature profiles for

non-isothermic reactors
Poor cooling Poor cooling Looking the relationship between temperature, reaction rate and
the size of the reactor, one can see high temperature favors the
XA Moderate cooling high reaction rate and contrary to this, high temperature requires
T Moderate Cooling
high volume or reactor. The general shape of rate and length of
Strong cooling the reactor versus temperature plot is shown in Figure 4.7
To Strong cooling
Adiabatic
L V,
L, V W L, V, W
T r
Non-Adiabatic
Figure 4.6 The effect of cooling on the temperature and
conversion against the Length (L), Volume (V) or Weight of a
catalyst (W)
L T
Figure 4.7 Relationship between the temperature, rate of reaction
and the length

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The above variables that influence the design and operating
performance of a chemical reactor can be termed as optimum
variables. Since the temperature influences the conversion,
the rate of reaction, the size of a reactor, we set this as a
core variable and should find the optimum operating
temperature
Optimum operating temperatures 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
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, in what
operational temperature range, a given reaction can be
operated to have the maximum conversion and a plausible
rate of reaction within the small size (length) of the
reactor.
Optimum operating temperature for irreversible reaction
Consider the reaction A P
The rate of disappearance of reactant A
r (T , X A ) = A(e-E RT ) C A,0 (1 - X A )
= A(e-E RT ) f (X A )
where f(XA) is usually a decreasing function of XA
Since E is positive, a rise in the fractional conversion brings
about a fall in the rate of reaction. This could be compensated
p
by raising the temperature of the operation i.e., the rate
increases with the temperature at any composition. This is,
therefore, to deduce that the optimum operating
temperature 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
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Looking to the design equation dV dX
=
FA,0 (-rA )
¾The minimum volume will be achieved if the reaction rate is
maximum at all positions in the reactor.
¾The optimum operating temperature at any given position
will be that for which the rate of reaction is maximum at any
conversion level.
¾ Therefore, the related rate of reaction corresponding to
the conversion, temperature, r(T,X) is the basic information
necessary to determine optimum operating temperature.
¾Generally to determine the 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. Here, different cases may be analyzed for distinction
Optimum operating temperature for reversible reaction
Consider the reversible reaction,
A P
which has the rate of reaction functionability as
-1
r (T , X A ) = A(e-E RT ) CA,0 (1 - X A ) - A1(e-E RT ) C A,0 X A
-1
= A(e-E RT ) f ( X A ) - A1(e-E RT ) g ( X A )
g(XA), E-1applies for the reverse reaction
The function g(XA) is always an increasing function since the
concentration of product increases with the conversion
In an endothermic reversible reaction,
since E > E-1, the rate increases with temperature for any
conversion, which brings that for an endothermic reversible
reaction, the optimum operating temperature is the
maximum permissible temperature.
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For an exothermic reversible reaction, where E-1 > E, the

rate of reversible reaction increases more rapidly with the
temperature than that of the forward reaction. On the other
hand, the equation (4.2) depicts that the reverse reaction will X1 X4> X3 > X2 etc
be slow at low conversion, while the forward reaction rate will X2
be fast. r X3
X4
For the rate to be maximum at any conversion, a high
temperature is used at low conversion where predominantly
the forward reaction takes place and is the lowest at high
conversion, where the rate of the reverse reaction is high. T
Generally, we can see here, for reversible exothermic
reactions the optimum operating temperature sequence is a Figure 4.8 Optimum Operating Temperature sequence for an
changing temperature i.e., starting at high temperature exothermic reversible reaction.
and gradually changing to a decreasing temperature. Figure
4.8 shows the operating line for minimum reactor size. An
optimum operating temperature is determined by counting the
maxima and shown by the dashed lines

4.3 Temperature effect on an adiabatic fixed -

bed gas reactors
Gas/solid catalyzed reaction is carried out in a plug flow
reactor, where the reactants are fed continuously into one end of
a tube and the reactor products flow out at the other end.
During the reaction, heat is liberated or absorbed
This happens in such manner that if an exothermic reaction is
run into an adiabatic fixed bed reactor, the temperature of the
gas stream willill increase from the inlet towards
to ards the outlet.
o tlet
On the other hand in an adiabatic fixed bed reactor of an
endothermic reaction, the temperature of the gas stream will
drop within the reactor length
Tmax
To
T
To
X X
Figure 4.9 Temperature and Conversion behaviors for Exothermic
(a) and Endothermic (b) reaction in adiabatic reactors.
In an exothermic reaction, the heat generation along the tube
is uneven and at the beginning of the reaction it can
exceed Tmax so that the reactor is unworkable. To avoid
such events, the tube has to be very narrow. Using narrow
tube ensures a high surface/volume ratio for heat transfer.

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In order to get adequate reactor capacity at an acceptable
pressure drop, one can use in the industry several thousand
tubes built together in a single shell in which the coolant is
flowing. Figure 4.10 demonstrates such an unit
Gas inlet
Thermocouple
Baffles outlet
If the reaction temperature exceeds Tmax before the desirable
conversion, then the following methods may be applied to
extend the conversion to the desired level.
A) Using indirect heat exchanger
In this method, as illustrated in the figure 4.11, the beds are
sub-divided into two or more so that each bed does not
exceed Tmax.
To T T
To

To
To T

T X
T
Gas outlet
Figure 4.11 Cooling to the desired, temperature by using
Figure 4.10 Multi tube Fixed bed reactor 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
To Z=0 of the reactants is injected in cold stage into the reaction
stream between consecutive beds. Figure 4.13 shows such
T1, X1
T1 X3 methods.
To
T2
T
2
T3, X2
T4
T3
T4
X2
X1

T5, X5 Z = TLo T5 T
Product

Feed X1

Quench To

Figure 4.13 Direct cooling between beds in fixed bed reactor

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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. Figure 4.15
depicts such a method
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 is used as heat
sink by adsorbing high exothermic heat. 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.
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.
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.
It is to be noted here that the feed will not be preheated if
no conversion takes place. Figure 4.15 illustrates schematic
diagram of such a system together with the path of temperature
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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. In the reaction there is a critical
temperature, known as initiation temperature, where the
reaction rate becomes so low that it does not effectively
start reacting 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..
ii) Reactor with internal heat exchanger tube
between the product and the feed
The auto thermal behavior of a fixed bed adiabatic reactor
in which the reacting mixture preheat the feed can take place
in a single tube or multi-tube reactor. Here the heat
exchanger is an integral part of the reactor. Figures 4.16
and 4.17 show the schematic diagram of internal heat exchanger
for a single and multi tube reactors together with temperature
distribution.
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.
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We have to consider separately the heat exchanger or

TRE - TR
F
= ΔTad X A
and the reactor part. -

Considering the reactor part, the energy balance will be reduced where FA,0
ΔTad = (- ΔH R )
to equation (3.11) FRC P
FR C P dT = (− ΔH R ) FA,0 dX A + KA(TS − T )dV
Equation demonstrates that the temperature rise in the reactor,
for not having heat exchanger the equation becomes ΔTR , heat production is a linear function of conversion, XA
FR C P, dT = ( − ΔH R ) FA,0 dX A From the picture, it can be clearly seen that
Integration for the reactor part TRE T F = ΔTR
- R F
E
TR E = TR,H
(- ΔH R )FA,0 X A
T
R

∫dTR = ∫dX A TR F = TH E
FRC P
Hence, equation can be rearranged
F
T 0
R

After integration, we obtain

F TRF, H - TH E = ΔTH = ΔTR = ΔTad X A
F =
TRE - TR (- ΔH R ) A,0 X A
F C
R P

where Substituting and rearranging these, we get

ΔTH is the temperature difference available for heat
transfer, which is called heat removal
F C
(
TR E - TR F = R P TR F - TH F
KA
)
ΔTR is the temperature rise in the reactor, which is Substituting equations and rearranging we obtain
( )
called heat production ⎛ (- ΔH R )FA,0 ⎞
T F - TH F = ⎜⎜
FRC P
⎟⎟ X A
or KA R ⎝ FRCP ⎠
Heat removal ΔTH = Heat production ΔTR Hence
TR F - TH F = KA ΔTad − X A
Equationdemonstrates that the feed will not be FR C P
preheated if no conversion takes place The left side of equation is simply the temperature rise in the
The heat balance of equation (3.11) for the heat exchanger part, heat exchanger T F - T F This temperature rise of the feed
neglecting the reactor part, is reduced to R H
FR C P dT = KA(TS − T ) dV stream is the heat taken up in the heat exchanger and is
Integration gives equal to the right side of the equation. This also can be
FRC P ( TH E - TH F ) = KA(T F R, H − T E H ) translated as the temperature rise in the reactor multiplied
We know that by the factor KA In practice this factor is often greater
TH E = TR F FRC P
than 1
TR, H F= TR E
TH E = TR F

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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 TR F
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.
complete This level depends on the residence
time in the reactor
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,
t th
there i a high
is hi h temperature
t t rise,
i d
due t the
to th heat
h t
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 Taking equation A
reactor, the energy balance equation rearranged and becomes FR C P, R (TH E - TH F ) = - K (TR − TH ) dZ
A L
− FR C P, R dTR + (− ΔH R ) FA,0 dX A = K (TR − TH ) dZ Substituting modified equation (4.11.1) to equation (4.12) gives,
L
For the feed, which is preheated in the heat exchanger A (-ΔH R ) FA,0 X A
FR C P, R (TH E - TH F ) = - K dZ
tubes, the energy balance equation becomes L FR C P, R
ΔT
A
f FR C P, R dTH + K (TR − TH ) dZ = 0 FRCP, R (TH E - TH F ) = - KA ad X AdZ
L L
where,
or rearranging
g g yields
y
CP,R = constant,
t t A is i the
th total
t t l heat
h t exchange
h area, ƒ is
i the
th
fraction of the feed flowing through the heat exchanger, (1-ƒ) is FRC P, R (TH E - TH F ) ΔTad
the direct cold injection at the entrance of the reactor and Z is the = - X AdZ
coordinate in the flow direction
KA L
After integration between Z = 0 and Z = L, it become
FR C P, R d (TR - TH ) = (-ΔH R ) FA,0 dX A
(-ΔH R ) FA,0
TR - TH = dX A FRC P, R (TH E - TH F ) ΔTad Z = L
FR C P, R = - ∫ X AdZ = ΔTad X A
Hence, KA L 0
TR - TH = ΔTad X A

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Generally, equation (4.14) demonstrates the following conditions

namely •With optimum heat exchange the reaction
TH E - TH F is proportion to the heat taken by the feed temperature is too high & equilibrium is adversely affected.
KA FRC P, R before it enters into the reactor Based on this argument, it is desirable not to make the
i.e., heat removal. heat exchange capacity much greater than necessary.
ΔTAD X A is the average drawing force for the heat
exchange, where it is multiplied by a factor
KA FR C P, R gives the total temperature
increase i.e., heat production.
This is clearly seen from the Figure 4.21 that both the heat
removal line as well as heat production curve depends on the
values of KA FR C P, R
• With too little and small heat exchange capacity, it is
possible to obtain moderate conversions.
•With too much heat exchange capacity, the reactor
entry temperature becomes too low and no conversion
results i.e., from the Figure 4.21, one can see that the
reactor is on the average is in a stable operation.