Learning Objectives

Upon completion of this unit, you should be able to define, in words, the following terms:
semi-batch operation
Upon completion of this unit, you should be able to perform the following specific tasks
and be able to recognize when they are needed and apply them correctly in the course of a
more complex analysis:
identify circumstances where semi-batch reactor operation might be advantageous
formulate mole balance design equations for a semi-batch reactor
solve the semi-batch reactor design equations and use the results to perform a requested
engineering task
 Semi-Batch (Semi-Flow) Reactor
A batch reactor where some reactant flows in or some product flows out
while the batch is processing
Neutralization of an acid with a base
Add base slowly to batch of acid in order to control the rate at which heat is released
Reversible esterification
Allow one product to boil off allowing the reaction to reach higher conversion than in a
closed batch process
If species are boiling off, the composition of the leaving vapor is related to
the composition of the liquid, e. g. by Raoults law or Henrys law
Unlike common batch reactors, often the fluid volume is not constant
Use the appropriate equation of state to re-write the derivatives of fluid volume and pressure in
terms of the moles in the reactor and the temperature

As one might expect, the design equations for a semibatch reactor can be generated by
modification of the batch reactor design equations.
 Semi-Batch Design Equations
Mole balance
i is the net molar rate of flow of
species i into the reactor
may be a function of time

Energy balance

The semi-batch reactor design equations are ordinary differential equations, and they
are solved in the same manner as the batch reactor design equations. A mole balance is
written for every reactant and product along with an energy balance, and the resulting
set of ordinary differential equations is solved numerically. To do so, the initial values
of the independent and dependent variables must be specified along with the final value
of either the independent variable or one of the dependent variables. In addition, code
must be provided that is given values for the independent and dependent variables and
that uses them to evaluate the differential equations being solved
 Selectivity and Yield
Instantaneous Overall
Selectivity:
 Selectivity and Yield
Instantaneous Overall
Selectivity:

Yield:
 Selectivity and Yield
Instantaneous Overall
Selectivity:

Yield:

desired product , rD k1C A C B

2
Example:
undesired product , rU k 2C A C 2B
 Semibatch Reactors
Semibatch reactors can be very effective in maximizing selectivity in liquid phase reactions.
The reactant that starts in the reactor is always the limiting reactant.

Three Forms of the Mole Balance Applied to Semibatch Reactors:

1. Molar Basis:
 Semibatch Reactors
Semibatch reactors can be very effective in maximizing selectivity in liquid phase reactions.
The reactant that starts in the reactor is always the limiting reactant.
 Semibatch Reactors
Semibatch reactors can be very effective in maximizing selectivity in liquid phase reactions.
The reactant that starts in the reactor is always the limiting reactant.

Three Forms of the Mole Balance Applied to Semibatch Reactors:

1. Molar Basis:

2. Concentration Basis: dN A d C A V dC dV dC
V A CA V A 0CA rA V
dt dt dt dt dt
 Selectivity and Yield
Instantaneous Overall
Selectivity:

Yield:

desired product , rD k1C A C B

2
Example:
undesired product , rU k 2C A C 2B

To keep the selectivity of the desired products high with respect to the undesired
products carry out the reaction at high concentrations of A and low
concentrations of B. If the reactor is liquid phase, a high selectivity can easily
be achieved using a semibatch reactor in which B is few slowly to A.
 Semibatch Reactors
Semibatch reactors can be very effective in maximizing selectivity in liquid phase reactions.
The reactant that starts in the reactor is always the limiting reactant.

Three Forms of the Mole Balance Applied to Semibatch Reactors:

1. Molar Basis:

2. Concentration Basis: dN A d C A V dC dV dC
V A CA V A 0CA rA V
dt dt dt dt dt

3. Conversion:
 Semibatch Reactors
Semibatch reactors can be very effective in maximizing selectivity in liquid phase reactions.
The reactant that starts in the reactor is always the limiting reactant.

Three Forms of the Mole Balance Applied to Semibatch Reactors:

1. Molar Basis:

2. Concentration Basis: dN A d C A V dC dV dC
V A CA V A 0CA rA V
dt dt dt dt dt

3. Conversion:

For constant molar feed:

For constant density:
 Semibatch Reactors
The combined mole balance, rate law, and stoichiometry may be written in terms of number of moles,
conversion, and/or concentration:
 Semibatch Reactors
The combined mole balance, rate law, and stoichiometry may be written in terms of number of moles,
conversion, and/or concentration:
Conversion Concentration Number of Moles
dX rA
V
dV N A 0
N A NB
k V
V V
NA 0
kN A 0 1 X N B

VN A 0
 Semibatch Reactors
Polymath Equations:
Conversion Concentration Moles
d(X)/d(t) = -ra*V/Nao d(Ca)/d(t) = ra - (Ca*vo)/V d(Na)/d(t) = ra*V
ra = -k*Ca*Cb d(Cb)/d(t) = rb + ((Cbo-Cb)*vo)/V d(Nb)/d(t) = rb*V + Fbo
Ca = Nao*(1 - X)/V ra = -k*Ca*Cb ra = -k*Ca*Cb
Cb = (Nbi + Fbo*t - Nao*X)/V rb = ra rb = ra
V = Vo + vo*t V = Vo + vo*t V = Vo + vo*t
Vo = 100 Vo = 100 Vo = 100
vo = 2 vo = 2 vo = 2
Nao = 100 Fbo = 5 Fbo = 5
Fbo = 5 Nao = 100 Ca = Na/V
Nbi = 0 Cbo = Fbo/vo Cb = Nb/V
k = 0.1 k = 0.01 k = 0.01
Na = Ca*V
X = (Nao-Na)/Nao
 Semibatch Reactors
C C
rA k CA CB C D
KC
 Semibatch Reactors
C C
rA k CA CB C D
KC

At equilibrium, -rA=0, then

 Semibatch Reactors
C C
rA k CA CB C D
KC

At equilibrium, -rA=0, then

Xe

X
X

t
The hydrolysis of acetic anhydride, reaction (1),
(CH3CO)2O + H2O 2 CH3CO2H
can run away thermally in a batch reactor [1], but this can be prevented using
semi-batch operation [2]. Suppose the rate can be described using a rate
expression that is first order in acetic anhydride with a pre-exponential factor of
1.192 x 1015 min-1 and an activation energy of 97,600 J mol-1. The heat of reaction
may be taken to be constant and equal to -58,615 J mol-1. The reacting fluid in the
semi-batch reactor for the process is cooled by an external fluid uniformly
maintained at 60 C; the product of the heat transfer area and the heat transfer
coefficient, UA, equals 260 cal min-1 K -1. The reactor operates at atmospheric
pressure and initially contains 67 cm3 of water, 283 cm3 of acetic acid (the solvent
and product) and 0.30 cm3 of sulfuric acid at 60 C. The heat capacity of the fluid
in the reactor may be taken to be constant and equal to 2.68 J cm-3 K-1. Acetic
anhydride at 21 C is fed to the reactor at a rate of 64.5 cm3 min-1 for the first 5.5
minutes of operation, after which the reaction continues in batch mode. The
solution may be assumed to be ideal with a constant density. Plot (a) the
concentration of acetic anhydride in the reactor as a function of processing time.

References Cited [1] R. Haldar, D.P. Rao, Chem. Eng. Technol., 15 (1992) 34-38.
[2] R. Haldar, D.P. Rao, Chem. Eng. Technol., 15 (1992) 39-43.
The reaction between A and B produces the desired product, D according to reaction
(1), but B also decomposes according to reaction (2), generating the undesired
product U. The reactions take place in solution, and the heat of reaction is so small
that the reactions are effectively isothermal. Reaction (1) is first order in each of the
two reactants, second order overall. Reaction (2) is second order in B. At the process
temperature the rate coefficient for reaction (1) is 8 x 10-3 L mol-1 min-1 and that for
reaction (2) is 4 x 10-3 L mol-1 min-1. A 2000 L stirred tank reactor will be used,
taking its feed from one solution containing A at a concentration of 3 mol L-1 and
from a second containing B at a concentration of 1 mol L-1. Compare the selectivity
(mol D per mol U) that will result from a batch process charged with 500 L of the A
solution and 1500 L of the B solution to a semi-batch process where the reactor is
charged with 500 L of the A solution at which time the B solution flows into the
reactor at a rate of 150 L h-1. In both cases, allow the reaction to proceed to a 95%
conversion of B; in the semi-batch system, this may require stopping the flow when
the reactor contains 2000 L of solution and allowing it to continue to react as a batch
reactor until the desired conversion is reached.

A+BD (1)

2BU (2)