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2. IDEAL - BATCH AND SEMI - BATCH REACTORS In batch reactor,

DESIGN ¾no material is supplied to or withdrawn from reactor
2. 1 The Ideal Batch Reactor during the reaction
A Batch reactor generally consists of a closed vessel ¾the reaction proceeds quickly at first, because of high
provided with a means of stirring and where the concentration of all reactants and
temperature is controlled. Figure 2.1 shows such type of ¾the composition is only a function of time.
reactor. ¾ due to the well mixing of the composition throughout the
vessel.The total mass of the reaction i.e., concentration
and temperature are identical over the reactor volume
The volume of the batch reactor is the space occupied by the
reacting mixture and it may vary during the course of reaction. In
gas phase, the volume may be varied as required to maintain the
pressure constant.
Cj

Figure 2.1 Typical batch reactor

CA,0 t=0
CA,0

XA
t=t1

t=t2
CA
CA,n t=tn

CA,end Over Reactor Volume

t
t1 t2 t Figure 2.4 The concentration inside the batch reactor
Figure 2.3 Variation of conversion
Figure 2.2 Variation of
with time in a batch Reactor
concentration with time in a
batch reactor

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2.1. 1 Design of batch reactors

Pressure
Movable It is important to note that we are dealing a process design
not a mechanical design.
Piston
Gauge

For process designing a reactor, we need a

material balance. Noting that in batch reactor, no
material enters or leaves the reaction mixture during the
I- Constant Volume II- Variable Volume course of reaction,
Figure
g 2.5 Batch reactor for g
gas p
phase reaction.
The material balance of equation (1.9) for
componentt A becomes
b ,
The general problem in designing a batch reactor Vf
¾ is to calculate the volume of the reactor for a certain average dn A
(2.1)
∫ rAdV =
rate of production. 0 dt
¾ The volume can be obtained from the required
We know from the condition that the reaction mixture is
degree of conversion and the corresponding time.
perfectly mixed and so no variation in the rate of reaction
¾ The reaction time of a batch reactor can
throughout the reactor volume takes place. Due to this, we
be determined by using material balance
can take rA out of the integral and we write the equation (2.1)
in the form

rAV f =
dn A (2.2) Equations (2.3) and (2.4) are the general design equations
dt showing, the reaction time required for either constant or
and for the disappearance of reactant A, variable volume in isothermal or non-isothermal
operation. Thus, the volume of reacting fluid and the
(− rA )V f = − dn A (2.2.1)
dt reaction rate remain under the integral sign, since they
By integration over the period of the reaction to a final mole, we both change as reaction proceeds
obtain the basic design equation for a batch reactor. Time involvement of the operation in batch reactor.
n A 1 dn In completing a batch process, four types of periods
tr = − ∫ A (2 3)
(2.3) are required.
required These are:
n A,0 V f ( − rA ) • Preparation time tch, during which a reaction is made
ready and fresh reactants are charged.
In a batch reactor, we are interested in determining how long • Reaction time, tr, during which the reaction proceeds to
we should keep the reactants in the reactor to achieve a the desired conversion.
certain conversion • Recovery time, td, during which the product is
X A dX discharged and return to the normal operating condition.
tr = n A,0 ∫ A (2.4) •Cleaning time, tcl , during which the reactor is cleaned.
0 V f ( −rA )

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The total time (cycle time), tc, is the time where one 1
1
(-rA) Equation (2.4.1)
operating cycle of a batch reactor is described. (-rA)V Equation (2.4)
Area = tr
tc = tch + tr + td + tcl (2.5) Area = tr CA,o

nA,o
The capacity of the batch reactor, which is the quantity
of the product obtained per unit time is reduced due to this XA,f XA
auxiliary time, and it is the major limitation of a batch XA,f XA
reactor especially when it is used for a bigger product operation.
Figure 2.6 Levenspiel Plots to find the reaction time
To carry out the integration of the design equation (2.4.1),
(2 4 1) Th integral
The i t l also
l can be
b evaluated
l t d using
i numerical
i l methods
th d
we need to know how the reaction rate (-rA) varies with the such as, Trapezoidal rule, Simpson's rule, Five-point
conversion of the reacting species quadratic formula.
As for an illustration, the so called Simpson's one-third rule to
Generally given (-rA)as a function of conversion evaluate the integral
(concentration), one can find the time of reaction and
eventually also the size of a reactor. We do this by X A, f
dX A ΔX ⎡ 1 4 1 ⎤
constructing the so called a Levenspiel plot = + +
∫
0 ( − rA ) 3
⎢
(
⎢⎣ A− r )( X A,0 ) ( − rA )( X A,1 ) ( − rA ) X
⎥
A, f ⎦⎥ ( )

Relevant in reactor design Step1 : We begin by applying our general mole balance
is a mathematical description that can predict reactor outlet equation to arrive at the design equation of the batch
concentration and temperature from reactor.
inlet concentration, rate of reaction and reactor Step2 : We determine the rate equation as the function of
dimensions. concentrations.
These equations by nature are complicated unless systematically Step3 : We change the concentration in terms of conversion
organized and solved. One way of solving such equations is by
using algorithm.
using stoichiometry relationship.
Step4 : Combine the steps 2 and 3 to obtain − rA = f (X A) ( )
Algorithm
g is a rule or calculation pprocedure for solvingg a Step5: Evaluate the integral using graphical, numerical,
mathematical problem that frequently involves extensive analytical, software package etc.
numerical operations.
Summarizing the algorithm for batch reactor design gives,
For an example, if we want to design isothermal batch reactor, the
algorithm steps will be as under:
9Mole Balance and Design Equation.
9Rate Law.
9Stoichiometry
9Combination
9Evaluation

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2.1.2 Heat Effect on the batch reactors

Changes of temperature during reaction are common in
Exothermic
reactors This happens deliberately (by heat exchange with the
surroundings) or by the nature of the reaction
The temperature change due to the nature of reaction
comes when the reaction takes place bond is breaking and Initial reaction Isothermal
forming and this is accompanied by the evolution(exothermic) or Temperature
absorption (endothermic) of heat.
Endothermic
Exothermic t
Reaction
T ∆HR = 0 Figure 2.11 Effect of temperature versus time in a batch reactor
In designing a non-isothermal reactor, basic design equations
Endothermic
i.e., rate laws and stochiometry relationship can be used
Reaction
from the mole balance design equation. The only thing
Conversion, XA we have to consider additionally is the change of
Figure 2.10 Temperature versus conversion in adiabatic reactors temperature during the reaction

Let us consider the following highly exothermic reaction carried Since k is a function of temperature and in adiabatic
C A ,o
adiabatically in a batch reactor
out yields reaction, temperature is changing during the course of
A→ B reaction i.e., k is also varying. This forces us not to take k
Our object is to calculate the reaction time for 60% conversion. outside the integral, hence the overall equation becomes,
• Mole balance design equation (2.4.1) gives,
X A, f X A. f
dX A dX A
tr = C A,O ∫ tr = ∫
0 − rA )
( 0 K o exp ⎜ 1 − 1 ⎟⎞⎤ (1 − X A )
⎡ E ⎛
• Rate Law, for first order reaction is ⎢ R ⎜ T T ⎟⎥
⎣ ⎝ o ⎠⎦
(− rA ) = kC A
• Stoichiometry To solve this equation, we need a relation of XA and T.
Liquid phase V f = V0 C A = C A,0 (1 − X A ) This type of problems forces us to use both the material and
• Combining and canceling the entering concentration energy balances. To calculate the heat effect in batch
X A, f reactor, we use the energy balance equation as it is
dX A
tr = ∫
0 k (1 − X A ) ⎡ dT
Recalling the Arrhenius equation ⎛ 1 1 ⎞⎤ mT C P + ΔH R (rV ) = KA(TS − T )
k = k0 exp ⎢ E ⎜⎜ − ⎟⎟⎥ dt
R⎝T T ⎠
⎣ 0 ⎦

4

(A) Isothermal Batch Reactor
Generally due to the nature of the reaction, during the
reaction, the heat is evolved or absorbed, thus it is
hard to imagine a chemical reaction that has a reaction heat
of zero.
Normally to bring in isothermal condition, the reaction is
brought immediately to that of the surrounding by cooling
(if the reaction is exothermic) or heating (if the reaction is
endothermic) i.e.,
i e the temperature of the reacting mixture is
maintained constant through out the course of reaction.
This happens with the assistance of the heat transfer
medium under perfectly stirring condition.
In isothermal operation, there is no change of reaction
temperature, i.e., constant temperature (dT = O). If the
reactor is to be operated isothermally, the rate of reaction can
be expressed as a function of concentration only, not as a
function of temperature, then
Ts
Temperature
Controller
Steam
The material balance can be rearranged
dX A
(− rA )VR = n A,0
dt
Combining the equations gives
dx
(− ΔH R )n A,o A = KA(T − TS )
dt
3/4/2010
The energy balance equation
ΔH R ( rV ) = KA(TS − T )
Looking to the above equation, the rate of heat
transfer value changes with the rate of reaction.
The rate of reaction is changing with temperature. The
change of temperature is controlled by the heat transfer
equipment, so as to maintain the rate of reaction constant.
The rate of heat transfer
Q = KA(TS − T )
- can be controlled by changing T
- by changing over-all heat transfer co-efficient K,
which is largely dependant on the agitator speed and
the viscosity of the liquid
(B) Non – isothermal Batch Reactor
This is sometimes called thermal reactors. Two cases
¾ Due to the nature of reaction, heat is absorbed or released,
¾ Deliberately heat is introduced or removed from the reactor,
which accounts for heat losses to the surrounding.
i.e the temperature is not constant and varies during the
course of reaction, then the rate of reaction will be a function of
temperature as well as conversion
(− rA ) = f (C , T )
Thus the design of non-isothermal reactors
requires simultaneous solutions of the material and energy
balance equations
There are a lot of questions to be answered to design
such type of reactors, such as type of materials of
construction, heat transfer equipment etc.
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The heat balance for non isothemal becomes, The Equation shows three variables,
dT 9time of reaction,
mT C P + ΔH R ( rV ) = KA(TS − T )
dt 9 conversion and
Taking as an example of a first‐order elementary reaction, 9 temperature.
the rate of reaction becomes, (− rA ) = kC A,0 (1 − X A ) The most important parameter is the reaction time or
and the rate constant is defined using Arrhenius Law, eventually the size of a reactor for a particular conversion
The time of a reaction required for a particular conversion
k = A exp .⎛⎜ −
E ⎞
⎟ involves simultaneous solutions of the material
⎝ RT ⎠
And rate as a function of both conversion and temperature X A. f
becomes dx A
tr = C A,0 ∫
(− rA )
(− rA ) = A exp⎜⎛ − E ⎞⎟C A,0 (1 − X A ) 0
⎝ RT ⎠ and energy balances
Substituting the rate equation to the energy balance for non- Simultaneous solution of material and energy balance in
isothermal operation gives, analytical form is difficult and numerical methods or analogy
simulation must be used. Analytical solution is possible by
= A exp⎜⎛ −
dT E ⎞
mT C P ⎟C A,0 (1 − X A )(− ΔH R )VR + KA(TS − T ) using the so called trial and error method
dt ⎝ RT ⎠

C. Adiabatic Operation mT C P dT = n A,0 (− ΔH R )dX A

¾Adiabatic reactors operate without any heat addition Equation Shows:
or removal •Time is not involved
¾Based on these facts adiabatic reactors are •Eliminates the need for simultaneous stepwise solution of
inexpensive and are used almost in all the industry. the mass and energy balances which was the case for
isothermal reaction
Adiabatic reactors can be used when: Differentiation of equation for the initial condition of X A ≈ X A,0
• The heat of reaction is low where desired conversion and
and T = TO and final condition of X A = X A, f and T = T
yield can be attained without excessive temperature change. f
•For high exothermic reaction, inerts or excess of one reactant mT C P (T − T0 ) = (− ΔH R )n A,0 (X A − X A.,0 )
can be added so that the desired conversion and yield are not
adversely affected by excessive temperature change. with the initial condition, X A,0 = 0 the equation can be rearranged
The energy balance for adiabatic batch reactor without heat (− ΔH R )n A,0 X A
T - T0 =
transfer equation becomes dT mT C P
mT C P = −ΔH R (rV ) Let (− ΔH )n
dt R A,0
ΔTad =
dT dX
mT C P = n A,0 (− ΔH R ) A mT C P
dt dt

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Where ΔTad
mT C P
is the adiabatic temperature rise of the reaction mixture. This b=
(− ΔH R )n A,0
adiabatic temperature rise indicates about how much the 1

temperature of the reaction mixture would rise if the reaction The sign of the slope depends on that of enthalpy change: (-)
is to proceed adiabatically to completion. exothermic,(+) endothermic
The relationship between the temperature and the
conversion in an adiabatic reactor gives. (a) Endothermic b) Exothermic
T − T0 = ΔTad X A
1

or M t i l
Material
T = T0 + ΔTad X A Material
balance
balance Energy
or 1 XA XA balance
XA = (T − T0 ) Energy
ΔTad
balance
For an assumption of C P , (− ΔH R ), ρ
are independent of temperature, conversion as a linear function
of temperature is shown in Figure ( 2.13 ). The straight line To To
described by equation (2.33.2) intersects the temperature axis T T
at point T = T0 and the slope of such curve becomes. Figure 2.13 Variation of conversion versus temperature

The adiabatic temperature rise is one of the most important

characteristics of the mixture. Isothermal
∆HR > 0 ∆HR < 0
‰ It's value depends on the initial composition (initial
condition) Increase Increase
‰The higher value of adiabatic temperature i.e., the inerts inerts
gradient rise is an indication of a stronger thermal effect
of the reaction mixture. XA
‰ These thermal effects can be subdued through the Decrease Decrease
dilution of the mixture or inerts inerts
‰ by addition of excessive amounts of some of the
reactants or inerts. This effect is shown in the Figure (2.14)

To T

Figure 2.14 The effects of addition of inerts to the reaction

mixture and the variation of conversion versus temperature in an
adiabatic operation.

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2.1.3 Available Technologies A batch reactor is usually This type of reactor is used especially for high corrosion
implemented in the industry for small scale operation, mostly materials. Table 2.2 gives the main characteristics of a standard
for testing new products that have to be fully developed and for reactors that are sold commercially. Figure 2.15 shows the
the processes that are difficult to convert to continuous illustrations of a simple batch reactor working in the industry.
operations. Table 2.2 Main characteristics of standard reactors available in the
The main advantage of batch reactor are market
¾ high conversion with a long time and
¾The equipment required to conduct a batch operation is
relatively simple and encompasses.
The disadvantage counts to high labor cost per unit
production and the difficulty in obtaining large scale
production
(A) Reactor
It is often a vertical cylinder with an elliptical bottom. The reactor
should be constructed in such a way that it can withstand vacuum
and some internal pressure. The material used for its
construction is generally suitable for various reactionary
processes. Most often used is a glass-lined steel vessel.

(B) Heat Exchanger

The heat exchanger can be located inside the reactor (coil,
Capacity 8 14 25 32 10 20 25 1 4 10 25 0.7
plates) outside it (conventional heat exchanger) or could be
(m3)
manufactured together with the reactor wall (double jacket).
Diameter 2 2.50 2.80 3.10 2.40 2.80 3.00 1.20 1.80 2.40 3.00 0.9 Figure 2.16 -2.18 illustrates different type of a reactor with heat
(m) exchange mechanism
Total weight 945 13,90 21,30 24,10 11000 1800 2180 1830 2500 5200 7900 800
(kg) 0 0 0 0 0 0

Exchange 18.6 26.6 40.0 45.6 19.8 33 38.8 4.45 10.9 11.15 19.5 3.4
area(m2) (1)
0 0
DE DE DE DE DE DE DE DE DE SE SE DE
Service 1.5 1.5 1.5 1.5 6 6 6 6 6 6 6 1.5
Pressure(bar
)

Material) AV AV AV AV AV AV AV AI AI AI AI V

DE = double jacket, SE = welded external coil, AV = glass-lined steel, AI = Stainless steel, V= Figure 2. 16 Batch reactor with double jacket
glass

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Figure 2.18 Batch reactor with double jacket and internal coil

Figure 2.17 Batch reactor with external heat exchange

(C) Stirrer 2.2 Ideal semi-batch reactor design

Stirrer is used to mix the reactor contents uniformly so that The semi-batch reactor is a tank type operated on a non-
the concentration remains the same throughout the reactor. steady flow basis. Semi-batch occurs when some reactants are
There are a number of stirrers used in the technology, such as charged into the reactor at time zero, while other reactants are
marine -, turbine-, vane disc-, paddle-, anchor-, double motion-, added during the reaction. Figure 2.17 illustrate typical semi-batch
etc. stirrers. The selection of stirrer type, its dimensions and reactor.
arrangement are dependant on the type of fluid in the reactor and
the stirring is achieved in the operation.
((D)) Auxiliaries CA,0
A0
Water, steam, or a heat transfer medium, electrical energy etc.
can be used in the operation
Cj

Figure 2.19 Semi-batch reactor

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Semi-batch reactor is inevitable when: dn j V

• It is essential to regulate the heat effect of high exothermic - = Fj,0 - Fj + ∫ r jdV
reaction. This can be achieved through regulating the rate of dt
addition of one of the reactants so that the energy evolution The mass balance for the reactant A after rearranging becomes
can be controlled. d (VC A )
= FA,0 - FA rA V
• To minimize unwanted side products by maintaining low dt
concentration of one of the reactants, where it is possible to This equation can be integrated with numerical procedure.
maximize the selectivity of the product especially in the liquid Analytical integral is possible for the case of constants of the
phase reaction. feed and exit rates of the feed composition; density and
• It is required to remove one of the products to increase the additional
dd l criteria is that
h it must be
b a first-order.
fi d
equilibrium of the reaction to the application of Le Chatelier’s d (VC A )
FV,0C A,0 - F C - r V =
principle V,f A A dt
For constant densities along constant flow rate
1.Material balance d (C A )
FV,0CA,0 - FV,0C A - rA V = V
For the semi-batch reactor design all the four terms in the dt
general mass balance of equation (1.9) may have to be ( )
or V
=
V d C A
considered. C A,0 - CA - rA
FV,0 FV,0 dt

Using the definition of space time, we have θF =

V For addition of a substance to a reactor causes to vary the
d (C A ) FV,0 volume of the reactor with time. The reactor volume at any time
C A,0 - CA - rAθ F = θ F can be found, using mass balance equation (1.9). The equation
dt
For a first-order reaction, the rate law is (−rA ) = kCA (1.9) can be further simplified for this condition as,
d (C AV )
We can combine the rate law and the above equation becomes FA,0 =
dC A dt d (C AV )
C A,0 - C A - kCAθ F = θ F Utilizing the definition of FA,O , we have FV,0 CA,0 =
dt dt
Dividing by θ F and rearranging gives, or d ( ρV )
ρ 0 FV,0 =
dC A ⎛ 1 ⎞ C A,0 dt
+ CA ⎜ + k⎟ =
dt ⎝θF ⎠ θF dV
This is the linear differential equation, which can be For a constant density system, ρ 0 = ρ we have FV,0 =
dt
integrated analytically. By doing so, we obtain variation of With initial condition V=VO at t=0, by integration gives volume as
concentration with time for a first-order reaction in semi-batch function of time for semi-batch operation,
operation ⎛ -1 ⎞
⎜ + k⎟ V = V0 + FV,0 t
CA =
C A,0
+ Ie ⎝ F
θ ⎠
⎛ 1 ⎞
θF ⎜ + k⎟
⎝θF ⎠

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2. Energy Balance
The energy balance for semi- batch operation can be written
using all items in energy balance of equation( 1.10.3), namely
dT
mT C P + ΔH R ( rV ) = ( H F − H E ) + KA(TS − T )
dt
or
dT
mT CP = −ΔH R (rV ) = FT CP (T0 − TR ) + KA(TS − T )
dt

The equation shows the variation involving both composition

and temperature as a function of time. Solving such equation
is problematic unless we have reduced the variables.

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