C H A P T E R

4
Batch Reactor

O U T L I N E

4.1. Isothermal Batch Reactors 142 4.4. Numerical Solutions of Batch

Reactor Problems 165
4.2. Batch Reactor Sizing 155
4.5. Summary 172
4.3. Non-Isothermal Batch Reactors 159
Problems 173

The batch reactor is the generic term for a type of vessel widely used in the process indus-
tries. Batch reactors are used for a variety of process operations such as solid dissolution,
product mixing, chemical reactions, crystallization, liquid/liquid extraction, and polymeri-
zation. In some cases, they are not referred to as reactors but have a name that reflects the
role they perform (such as crystallizer or bioreactor).
A typical batch reactor consists of a tank with an agitator and integral heating/cooling
system. These vessels may vary in size from less than 1 L to more than 15,000 L. They are
usually fabricated in steel, stainless steel, alloys, glass lined steel, glass, Plexiglas, china,
brick, cement, plastics, and even wood. Liquids and solids are usually charged via connec-
tions on the top cover of the reactor. Vapors and gases also discharge through connections
on the top. Liquids and solids are usually discharged out of the bottom.
The advantages of the batch reactor lie with its versatility. A single vessel can carry out
a sequence of different operations without the need to break containment. This is particularly
useful when processing multiple feedstocks, toxic, or highly potent compounds or producing
different unrelated products.
Commonly seen batch reactors are pots (in the kitchen e cooking), frying pans, pickling
jars, beakers and test tubes (in chemistry laboratories), anaerobic digestion pits, to name
a few. Batch reactor is an idealized reactor such that there are no inlets to or outlets from
the reactor. Furthermore, in this text, we assume that the reaction mixture is well mixed all
the time inside a batch reactor. Therefore, the temperature and concentrations are uniform

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142 4. BATCH REACTOR

inside the reactor at any given instant in time. However, the concentration and/or tempera-
ture can vary with time. This idealization makes the batch reactor analysis far simpler as now
one need not to consider the locality of contents inside the reactor. This is one type of reactor
that is frequently used in laboratories and classrooms.

4.1. ISOTHERMAL BATCH REACTORS

Figure 4.1 shows a schematic of a batch reactor. Mole balance for a given species j inside
the reactor leads to
dnj
0
0 þ rj V ¼ (4.1)
dt
which leads to
dnj
rj V ¼ (4.2)
dt
which is the general mole balance equation for a batch reactor.
For a single reaction that is carried out in a batch reactor, there is only one independent
concentration or reaction mixture content variable and all other concentrations can be
related through stoichiometry as shown in Chapter 3. Without loss of generosity, let us
use component A as the key component of consideration. Equation (4.3) applied to
species A gives
dnA
rA V ¼ (4.3)
dt
If we use fractional conversion as the independent variable, Eqn (4.3) is reduced to
dfA
rA V ¼
nA0 (4.4)
dt

C, T

C, T

C, T

FIGURE 4.1 Schematic diagram of a batch reactor.

 4.1. ISOTHERMAL BATCH REACTORS 143
which can be rearranged to yield

V0 dfA
dt ¼ CA0 (4.5)
V
rA

Since the total amount of mass is not changing with reaction or temperature and mass ¼ rV,
we have

r dfA
dt ¼ CA0 (4.6)
r0
rA

The density is a function temperature and pressure. For condensed phase reactions, the
density can be considered as constant. As we encounter liquid or liquidegas phase reactions
quite often, constant density or constant volume batch reactors have been studied
extensively.
For a single-phase reaction mixture or for a condensed reaction mixture, if the effective
reactor volume or density is constant, Eqn (4.3) can be reduced to

dCA
rA ¼ (4.7)
dt

which is a commonly used equation. In fact, Eqn (4.7) has been abused in many situations by
many people unintentionally. Now we know that this equation is only valid for constant
density or constant volume batch reactors.
In order to solve for a batch reactor problem, one needs to solve for a differential equation
like Eqns (4.3), (4.6), or (4.7). For example, Eqn (4.6) can be integrated to yield

ZfAf
r dfA
tf ¼ CA0 (4.8)
r0
rA
0

In general, the rate of reaction is a function of concentration and temperature. From

Chapter 3, we learned that the stoichiometry can be applied to relate the amount of every
species in the reaction mixture. The amount change of a component participating in the reac-
tion divided by its stoichiometric coefficient is the universal extent of reaction for a single
reaction. The stoichiometry can be written in a batch reactor as

dnj dnA
¼ ¼ rV (4.9)
nj nA

Equation (4.9) can be integrated to give

nj
nj0 nA
nA0
¼ (4.10)
nj nA
144 4. BATCH REACTOR

As the stoichiometrical coefficients are true constants for a given reaction, the total number of
moles in the reactor can be computed by adding the number of moles for all the components
(species) up. That is
 
P
NS PNS nA
nA0
n ¼ nj ¼ nj0 þ nj
j¼1 j¼1 nA
(4.11)
nA
nA0 X NS
¼ n0 þ nj
nA j¼1

Letting nS be the total stoichiometric coefficients, i.e.

X
NS
nS ¼ nj (4.12)
j¼1

We obtain
nS
n ¼ n0 þ ðnA
nA0 Þ (4.13)
nA

While the above derivation is concise, we often tabularize the stoichiometry to gain a thor-
ough understanding of the stoichiometry for every species, either be those involved in the
reaction or those that are not participating in the actual reaction. The stoichiometry is shown
in Table 4.1.
The concentration can be related to the number of moles in the reactor through
nj
nj nj0 þ ðnA
nA0 Þ
nA
Cj ¼ ¼ (4.14)
V V
which can be further reduced to
 
r nj r
Cj ¼ Cj0 þ CA
CA0 (4.15)
r0 nA r0

TABLE 4.1 Stoichiometry of a Reaction System in a Batch Reactor

Species Initial Change At time t

A nA0 nAenA0 nA
n
nA0 nA
nA0
j nj0 nj
nj0 ¼ nj A nj ¼ nj0 þ nj
nA nA
. . . .
NS
P NS
P
nA
nA0 nA
nA0
Total n0 ðnj
nj0 Þ ¼ nS nj ¼ n0 þ nS
j¼1 nA j¼1 nA
 4.1. ISOTHERMAL BATCH REACTORS 145
The reaction mixture density is a function of temperature, pressure, and concentration/
composition. For isothermal operations, r is constant for reactions involving condensed
matter (liquid or solid) only. For ideal gas, the reactor volume, pressure, and temperature
are related through the ideal gas law
pV ¼ nRT (4.16)

That is
 
RT RT nS
V ¼ n ¼ n0 þ ðnA
nA0 Þ (4.17)
p p nA

Using the fractional conversion fA, Eqns (4.14) and (4.17), respectively, are reduced to
nj
nj0
nA0 fA
nA
Cj ¼ (4.18)
V
 
RT nS
V ¼ n0
nA0 fA (4.19)
p nA

Therefore, one can conveniently working with nA, CA, or fA in solving batch reactor problems.
For constant volume batch reactors,
ZCAf ZCA0
dCA dCA
tf ¼ ¼
rA
rA
CA0 CAf
(4.20)
ZfAf
dfA
¼ CA0

rA
0

We see in this chapter that isothermal constant density reactions are more easily solved than
other types of reactions.

Example 4-1. A reaction,

A ! products r ¼ kCO
A
RA
(E4-1.1)
is being carried out isothermally in a constant volume batch reactor. Initially, the reactor is
charged with A at a concentration of CA0. Determine the concentration of A in the reactor
as a function of time.
Solution. To start, let us draw a sketch to illustrate the problem as shown in Fig. E4-1.1. Mole
balance of reactant A inside the reactor leads to
0 0
In – Out + Generation = Accumulation
dnA
rA V ¼ (E4-1.2)
dt
146 4. BATCH REACTOR

t = 0, CA = CA0

A
…
t = t, CA

FIGURE E4-1.1 A schematic diagram of the batch reactor.

Since the volume is constant (constant volume batch reactor), Eqn (E4-1.2) is reduced to
dCA
¼ rA (E4-1.3)
dt
Applying the rate law,
rA ¼ vA r ¼
kCO
A
RA
(E4-1.4)

Substitute the rate expression, Eqn (E4-1.4), into the reduced mole balance Eqn (E4.1-3),
one obtains
dCA
¼ rA ¼
kCO
A
RA
(E4-1.5)
dt
Separation of variables,
dCA
¼
kdt (E4-1.6)
CO
A
RA

And integrate:
ZCA Zt
dCA
¼
kdt (E4-1.7)
CO
A
RA

CA0 0

If ORA ¼ 1, i.e. for a first-order reaction, we have

ZCA Zt
dCA
¼
kdt (E4-1.8)
CA
CA0 0

which can be integrated to yield

ln CA jC t
CA0 ¼
ktj0
A
(E4-1.9)
 4.1. ISOTHERMAL BATCH REACTORS 147
Thus,
ln CA
ln CA0 ¼
kt (E4-1.10)
Equation (E4-1.10) can be rearranged to yield
CA ¼ CA0 expð
ktÞ (E4-1.11)
That is, the concentration of A decreases exponentially in a batch reactor for a first-order
reaction.
If ORA s 1, Eqn (E4-1.7) is integrated to yield
C
C1
O RA  A

A
¼
ktjt0 (E4-1.12)
1
ORA CA0
Thus,
C1
O
A
RA

C1
O
A0
RA
¼
ð1
ORA Þkt (E4-1.13)

Equation (E4-1.13) can be rearranged to yield

h i 1
CA ¼ C1
O
1
ORA
A0
RA

ð1
ORA Þkt (E4-1.14)

That is, the concentration of A decreases following a hyperbolic path for an ORAth-order
reaction.
Fig. E4-1.2 shows the plots for the concentration of A as a function of time. One can
observe that the concentration drops down quicker for a lower order reaction than a higher
order reaction. This is due to the fact that at low concentrations, higher order reactions are
slower than lower order reactions.

Example 4-2. Variable Volume Batch Reactor. A gaseous reaction

A ! B þ C r ¼ kC2A ;
with k ¼ 0.1 mol
1·L·s
1

CA0

CA

ORA > 1

ORA = 1
ORA < 1
0
0 O RA-1
k CA0 t

FIGURE E4-1.2 Concentration of A as a function time t for an ORAth-order reaction in a constant volume batch
reactor.
148 4. BATCH REACTOR

is occurring in an isothermal constant pressure batch reactor. The reactor is charged initially
with pure A at 1 bar and 373 K. Determine the time required for the reaction volume to
expand by 50%, i.e. V/V0 ¼ 1.5.
Solution. A sketch of the batch reactor is shown in Fig. E4-2.1. The stoichiometry of the reac-
tion system is given by
A ! B þ C
t ¼ 0 : nA0 0 0 þÞ ¼ nA0
t ¼ t : nA nB nC þÞ ¼ nT
nA nA0
nA nA0
nA þÞ ¼ 2nA0
nA

Assume ideal gas law applies. The volume of the reaction mixture and concentration of A
in the reactor are given by
nT RT 2nA0
nA
V ¼ ¼ V0 (E4-2.1)
P nA0
pA nA P nA
CA ¼ ¼ ¼ CA0 (E4-2.2)
RT nT RT 2nA0
nA
Based on Eqn (E4-2.1), we obtain
nA V
¼ 2
(E4-2.3)
nA0 V0
Thus, the extent of reaction is dependent on the volume expansion. Mole balance of A in the
reactor gives
dnA
0
0 þ rA V ¼ (E4-2.4)
dt

P = 1 bar

t = 0:
pA = P = 1 bar
pB = p C = 0
V = V0

A, B, C
T = 373 K

FIGURE E4-2.1 A schematic diagram of a constant pressure batch reactor.

 4.1. ISOTHERMAL BATCH REACTORS 149
Substituting the rate expression into the mole balance equation, we obtain
dnA
¼ rA V ¼
kC2A V ¼ kCA nA (E4-2.5)
dt
Substituting Eqn (E4-2.2) into Eqn (E4-2.4), we obtain
dnA n2A
¼
kCA0 (E4-2.6)
dt 2nA0
nA
Separation of variables,
2nA0
nA
dnA ¼
kCA0 dt (E4-2.7)
n2A
Integration between t ¼ 0 and t ¼ t, we obtain
2nA0 2nA0 nA

þ
ln ¼
kCA0 t (E4-2.8)
nA nA0 nA0
which is reduced to
nA0 nA0
kCA0 t ¼ 2
2
ln (E4-2.9)
nA nA
Substituting Eqn (E4-2.3) into Eqn (E4-2.9), we obtain
 
2 V

2 þ ln 2

2
V=V0 V0
t ¼ (E4-2.10)
kCA0
Thus, the time required for 50% expansion of the reactor volume is given by
   
2 V 2 V

2 þ ln 2

2 þ ln 2

2
V=V0 V0 2
V=V0 V0
t ¼ ¼
kCA0 P
k
RT
2

2 þ lnð2
1:5Þ
¼ 2
1:5 s ¼ 405:3 s

3
1  105
0:1  10 
8:314  373

Therefore; it takes 405:3 s for the reactor volume to expand 50%:

Example 4-3. Concentration profile for a series reaction. For the following elementary reac-
tion system
k1 k2
A ! B ! C
Find the change of concentrations of A, B, and C as a function of time starting with pure A
initially at CA ¼ CA0 in a constant volume isothermal batch reactor.
150 4. BATCH REACTOR

t = 0, CA = CA0,
CB = 0,
CC = 0
A B C

A,
B, t = t, CA,
C CB,
CC

FIGURE E4-3.1 A schematic diagram of the batch reactor.

Solution. This is a set of two reactions occurring in series. Figure E4-3.1 shows a sketch of the
reactor system. Mole balance for species j leads to

dnj
¼ rj V (E4-3.1)
dt
Since the volume is constant, we have

dCj
¼ rj (E4-3.2)
dt
We next find the rates of reaction. Applying Eqn (3.66), we obtain

rA ¼ n1A r1 þ n2A r2
(E4-3.3)
¼
r1 ¼ k1 CA

rB ¼ n1B r1 þ n2B r2
(E4-3.4)
¼ r 1
r 2 ¼ k1 C A
k2 C B

rC ¼ n1C r1 þ n2C r2
(E4-3.5)
¼ r 2 ¼ k2 C B
Substituting Eqn (E4-3.3) into Eqn (E4-3.2), we obtain

dCA
¼ rA ¼
k1 CA (E4-3.6)
dt
Separation of variables and integration,

ZCA Zt
dCA
¼
k1 dt (E4-3.7)
CA
CA0 0
We obtain
CA
ln ¼
k1 t (E4-3.8)
CA0
 4.1. ISOTHERMAL BATCH REACTORS 151
or
(E4-3.9)
CA ¼ CA0 exp ð
k1 tÞ

Substituting Eqns (E4-3.9) and (E4-3.4) into Eqn (E4-3.2), we obtain

dCB
¼ rB ¼ k1 CA
k2 CB ¼ k1 CA0 e
k1 t
k2 CB (E4-3.10)
dt
which can be rearranged to yield

ek2 t dCB þ k2 CB dt ¼ ek2 t k1 CA0 e
k1 t dt (E4-3.11)
or

ek2 t dCB þ CB dek2 t ¼ d CB ek2 t ¼ k1 CA0 eðk2
k1 Þt dt (E4-3.12)
Integration of Eqn (E4-3.12) yields
8
< k1 C ½eðk2
k1 Þt
1; k2 s k 1
k2 t A0
CB e ¼ k2
k1 (E4-3.13)
: k 2 ¼ k1
k1 CA0 t;
Thus, the concentration of B in the isothermal constant volume reactor is given by
(E4-3.14)
8 k1
< CA0 ðe
k1 t
e
k2 t Þ; k2 s k 1
CB ¼ k2
k1
: k 2 ¼ k1
k1 CA0 te
k1 t ;

The concentration of C can be obtained either by substituting Eqns (E4-3.14) and (E4-3.5)
into Eqn (E4-3.2) or via stoichiometry. Since there is only A in the reactor initially, the total
concentration of A, B, and C is not going to change with time based on the stoichiometry
as given by the series reaction (all the stoichiometry coefficients are unity). Thus,
CC ¼ CA0
CA
CB (E4-3.15)

which gives
k1 e
k2 t
k2 e
k1 t
CC ¼ CA0
CA0 (E4-3.16)
k1
k2
Figure E4-3.2 shows the change of concentrations with time based on Eqns (E4-3.9),
(E4-3.14), and (E4-3.16). One can observe that there is a maximum for concentration CB
that changes with k1 and k2. This maximum can be obtained by setting

dCB 
0 ¼ ¼ rB ¼ k1 CA
k2 CB
dt tm
(E4-3.17)
k1
¼ k1 CA0 e
k1 tm
k2 CA0 ðe
k1 tm
e
k2 tm Þ
k2
k1
152 4. BATCH REACTOR

k1t
0 1 2 3 4 5
1.00

0.75 A B
Ci/CA0
0.50 a) k2 = 0.1 k1

0.25
C
0.00 1.00

b) k2 = 0.2 k1 0.75

Ci/CA0
0.50

0.25

1.00 0.00

0.75
Ci/CA0

0.50
c) k2 = 0.5 k1

0.25

0.00 1.00

0.75

Ci/CA0
d) k2 = k1 0.50

0.25

1.00 0.00

0.75
Ci/CA0

0.50 e) k2 = 2 k1

0.25

0.00 1.00

0.75

Ci/CA0
f) k2 = 5 k1 0.50

0.25

1.00 0.00

0.75
Ci/CA0

0.50
g) k2 = 10 k1

0.25

0.00
0 1 2 3 4 5
k1t

FIGURE E4-3.2 Variation of concentrations with reaction time for series reactions.
 4.1. ISOTHERMAL BATCH REACTORS 153
TABLE 4.2 Reaction Residence Time Requirement and Concentration Profile for Single Reactions in an
Isothermal Constant Volume Batch Reactor for Some Simple Kinetic Models

1. Zeroth order: A / products; r ¼ k

t ¼ ðCA0
CA Þ=k; CA ¼ CA0
k t

2. First order: A / products; r ¼ k CA

t ¼ lnðCA0
CA Þ=k; CA ¼ CA0 expð
k tÞ

3. Power-law kinetics: A / products; r ¼ kCnA

C1
n
A0
CA
1
n
  1
n
1
t ¼ ; CA ¼ C1
n
A0
1
n kt
ð1
nÞk

4. Bimolecular: A þ B / products; r ¼ kCA CB

 
1 1 1 CA0
t ¼
; CA ¼ CB ¼ ; if CA0 ¼ CB0
k CA CA0 1 þ kCA0 t

1 CA0 ðCA þ CB0
CA0 Þ CA0 ðCB0
CA0 Þ

t ¼ ln ; CA ¼ ; CB ¼ CB0
CA0 þ CA
kðCB0
CA0 Þ CA CB0 CB0 exp½kðCB0
CA0 Þt
CA0

5. Autocatalytic: A þ R/2 R þ products; r ¼ k CA CR

1 CA0 ðCA0 þ CR0
CA Þ CA0 ðCA0 þ CR0 Þ

t ¼ ln ; CA ¼ ; CR ¼ CA0 þ CR0
CA
kðCA0 þ CR0 Þ CA CR0 CA0 þ CR0 exp½kðCA0 þ CR0 Þt

kCA
6. Unimolecular catalytic: A / products; r ¼
KA þ CA
 
1 C
t ¼ KA ln A0 þ CA0
CA
k CA

kC2A
7. Unimolecular catalytic: A / products; r ¼
KA þ CA
 
1 CA0 KA KA
t ¼ ln þ

k CA CA CA0

8. First-order reversible: A % B; r ¼ kf CA
kb CB
 h  i 
1 kf CA0
kb CB0 kf CA0
kb CB0 exp
kf þ kb t þ kb CA0 þ CB0
t ¼ ln   ; CA ¼
kf þ kb kf þ kb CA
kb CA0 þ CB0 kf þ kb

CB ¼ CA0 þ CB0
CA

kðCA
CB =KC Þ
9. Catalytic first-order reversible: A % B; r ¼
1 þ KA CA þ KB CB
       
KC KA
KB ð1 þ KC ÞCA0
ðCA0 þ CB0 Þ
t ¼ KA
KB CA0
CA þ 1 þ CA0 þ CB0 KB þ ln
kð1 þ KC Þ KC ð1 þ KC ÞCA
ðCA0 þ CB0 Þ
CB ¼ CA0 þ CB0
CA

(Continued)
154 4. BATCH REACTOR

TABLE 4.2 Reaction Residence Time Requirement and Concentration Profile for Single Reactions in an
Isothermal Constant Volume Batch Reactor for Some Simple Kinetic ModelsdCont’d

10. Reversible decomposition: A % B þ C; r ¼ kf CA
kb CB CC

qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
A; b ¼ kf þ kb ð2CA0 þ CB0 þ CC0 Þ  ½kf þ kb ð2CA0 þ CB0 þ CC0 Þ2
4kb2 ðCA0 þ CB0 ÞðCA0 þ CC0 Þ

 
a
b
að2kb CA0
bÞ exp t
bð2kb CA0
aÞ
2 ð2k CA0
aÞð2kb CA
bÞ 1 2
t ¼ ln b ; CA ¼  
a
b ð2kb CA0
bÞð2kb CA
aÞ 2kb a
b
ð2kb CA0
bÞ exp t
ð2kb CA0
aÞ
2

CB ¼ CA0 þ CB0
CA ; CC ¼ CA0 þ CC0
CA

11. Reversible codimerization: A þ B % C; r ¼ kf CA CB
kb CC

rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
h  i2
A; b ¼ kf ðCA0
CB0 Þ
kb  kf CA0
CB0
kb þ 4kf kb ðCA0 þ CC0 Þ

 
a
b
Að2kf CA0
bÞ exp
t
bð2kf CA0
aÞ
2 ð2kf CA0
aÞð2kf CA
bÞ 1 2
t ¼ ln ; CA ¼  
b
a ð2kf CA0
bÞð2kf CA
aÞ 2kf a
b
ð2kf CA0
bÞ exp
t
ð2kf CA0
aÞ
2

CB ¼ CB0
CA0 þ CA ; CC ¼ CA0 þ CC0
CA

12. Reversible bimolecular: A þ B % C þ D; r ¼ kðCA CB
CC CD =KC Þ

qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
a ¼ KC ðCA0
CB0 Þ
2CA0
CC0
CD0 ; A; b ¼ a  a2 þ 4ðKC
1ÞðCA0 þ CC0 ÞðCA0 þ CD0 Þ

2KC ½2ðKC
1ÞCA0
a½2ðKC
1ÞCA
b

t ¼ ln ;
kðb
aÞ ½2ðKC
1ÞCA0
b½2ðKC
1ÞCA
a
 
a
b
A½2ðKC
1ÞCA0
b exp
kt
b½2ðKC
1ÞCA0
a
1 2KC
CA ¼  
2ðKC
1Þ a
b
½2ðKC
1ÞCA0
b exp
kt
½2ðKC
1ÞCA0
a
2KC

CB ¼ CB0
CA0 þ CA ; CC ¼ CA0 þ CC0
CA ; CD ¼ CA0 þ CD0
CA

 4.2. BATCH REACTOR SIZING 155
which can be rendered to
k1 k1
k1 CA0 e
k1 tm ¼ k2 CA0 e
k2 tm (E4-3.18)
k2
k1 k2
k1
or
(E4-3.19)
lnðk2 =k1 Þ
tm ¼
k2
k1

and the corresponding concentration of B is given by

 
k2 (E4-3.20)
k2 k2
k1
CBmax ¼ CA0
k1

One can observe that at short times, the formation of intermediate product is noticeable. The
time at which maximal concentration of B occurs decreases with increasing k2. However, at long
timescale, only the formation of the final product C is important and the series reaction may be
simplified to a first-order reaction from reactant A to product C if timescale is long. The reaction
rate constant can be approximated by the smaller of the two for the approximate reaction.
When simple kinetics is combined with constant volume or constant density for single
reactions in a batch reactor, closed form analytic solutions are usually easy to achieve. A
list of some of these cases is shown in Table 4.2.
While simple problems can be solved by hand, this last example showed how tedious for
even a simple problem could be. At this point, one can appreciate that an automatic inte-
grator is helpful in solving batch reactor problems. There are many software programs one
can use for integration: Maple, Mathcad, Matlab, to name a few. We have also supplied
a visual basic code that can run in Microsoft Excel. This is a good option as Microsoft Excel
can be applied to solve most of the programs a process engineer encounter when an auto-
matic integrator is added. The excel visual basic program provided is ODExLims. We shall
discuss the solution in Numerical Solutions of Batch Reactor Problems.

4.2. BATCH REACTOR SIZING

We have learned now how to compute the required reaction time for a given reaction
kinetics to proceed onto a desired reaction extent (or conversion). How big a reactor do we
need to carry out the bioprocess? To do this, let us look at Fig. 4.2 to find the answer.
Mass balance of the raw materials leads to
V V
Q ¼ ¼ (4.21)
tB tP þ tf þ tU
where Q is the rate of raw materials coming into the facility, V is the volume of the raw mate-
rials can be loaded for each batch, which is the effective reactor volume, and tB is the batch
time or the total time required to complete one batch operation. The batch time required
includes the preparation time, tP, for loading the reactor with reaction mixture and raising
the temperature to reaction temperature; the reaction time, tf, to achieve the desired
156 4. BATCH REACTOR

tf

V
Q Q
V

tP
tU

FIGURE 4.2 An illustration of material flow in a bioprocess plant.

conversion fAf ; and the unloading time, tU, for unloading the reaction mixture and returning
the reactor to working conditions.
The reactor volume can be obtained from Eqn (4.21) as

V ¼ t B Q ¼ tP þ t f þ tU Q (4.22)

Example 4-4. Our winery takes grain in and put the wine on the market. The bottleneck of the
operation is the fermenter operation. The fermenter is loaded with 10% sugar (assuming
a density of 1000 kg/m3) and yeast before fermentation. This leads to a 5-h delay before
fermentation starts. The fermentation takes 5 days to complete to obtain a 4% alcohol
mixture. Finally, to unload the fermenter contents and clean the fermenter requires another
3 h. Assume that the final product wine (4% alcohol) also has a density of 1000 kg/m3. Deter-
mine the fermenter size needed if a daily production of 240 L of wine is needed.
Solution. tP ¼ 5 h; tf ¼ 5 days ¼ 120 h; tU ¼ 3 h. Thus, the total time for each batch of fermen-
tation will take tB ¼ 5 þ 120 þ 3 h ¼ 128 h.
The fermenter size can be determined as V ¼ (240/24)  128 L ¼ 1280 L.
Example 4-5. Consider the reaction:
A ! B; k ¼ 0:15 min
1
in a batch reactor. The loading, preparation, unloading, and cleaning of the reactor requires
10 h for each batch of production. A costs $2/mole, and B sells for $5/mole. The cost of oper-
ating the reactor (including the preparation time) is $0.03 per liter per hour. We need to
produce 100 moles of B per hour using CA0 ¼ 2 mol/L. Assume no value or cost of disposal
of unreacted A (i.e. separation or recovery cost to A is identical to the fresh A cost).
a. Perform a mole balance on the reactor to relate the conversion with reactor size.
b. What is the optimum conversion and reactor size?
c. What is the cash flow (or profit per mole of A feed to the reactor) from the process?
d. At what operating cost do we break even? What is the corresponding conversion?
 4.2. BATCH REACTOR SIZING 157
Solution. Let the reaction time be t and the total preparation time (reactor loading, prepara-
tion, unloading, and cleaning) be tL. The total time required for each batch is then tB ¼ t þ tL.
a. Mole balance of A in the reactor leads to

dnA
0
0 þ rA V ¼ (E4-5.1)
dt
The rate law gives
rA ¼ vA r ¼
k CA (E4-5.2)
It is understood that the reaction mixture density is not changing. We have
 
nA nA0 1
fA
CA ¼ ¼ ¼ CA0 ð1
fA Þ (E4-5.3)
V V
Substituting Eqns (E4-5.2) and (E4-5.3) into Eqn (E4-5.1) and integrating with the initial
point of fA ¼ 0 at t ¼ 0, we obtain
 
ln 1
fA
t ¼
(E4-5.4)
k
We know the production rate of B, FB0 ¼ 100 mol/h. From stoichiometry,
FB
FA0 ¼ (E4-5.5)
fA
Therefore, the reactor volume can be obtained from Eqn (4.22) as

  
FB ln 1
fA FB
V ¼ tB Q ¼ ðtL þ tÞ ¼ tL
(E4-5.6)
CA0 fA k CA0 fA

b. Based on the economic information at hand, we can estimate the gross profit for the
reaction process as

GP$ ¼ $B FB
$A FA0
$V V (E4-5.7)

where $B, $A, and $V are the molar value of product B, molar cost of reactant A, and the unit
operating cost of reactor based on the reactor volume and time, respectively.
Substituting Eqns (E4-5.5) and (E4-5.6) into Eqn (E5-4.7), we obtain
  
FB ln 1
fA FB
GP$ ¼ $B FB
$A
$V tL
(E4-5.8)
fA k CA0 fA

To find the optimum conversion, we maximize the gross profit. That is starting by
setting
dGP$
¼ 0 (E4-5.9)
dfA
158 4. BATCH REACTOR

Since the flow rate of product B is fixed, not a function of the conversion fA, we have
  
dGP$ FB $V F B ln 1
fA FB
0 ¼ ¼ 0 þ $A 2
  þ $V t L
(E4-5.10)
dfA fA kCA0 fA 1
fA k CA0 fA2
which can be reduced to,
$A kCA0 fA
0 ¼
þ ktL
lnð1
fA Þ (E4-5.11)
$V 1
fA
Since
$A kCA0 2ð$=molÞ  0:15=min  2ðmol=lÞ
þ ktL ¼ þ 0:15=min  10 h
$V 0:03$=ðL$hÞ
¼ 1290
Equation (E-5.11) is reduced to
fA
1290 ¼ þ lnð1
fA Þ (E4-5.12)
1
fA
This nonlinear equation can be solved to give
fA ¼ 0:9992297
Thus, the optimum conversion is fA ¼ 0.9992297. The reactor size can be computed from
Eqn (E4-5.6)
    
ln 1
fA FB lnð1
0:9992297Þ 100
V ¼ tL
¼ 10
L
k CA0 fA 0:15  60 2  0:9992297
¼ 540:24 L

c. The cash flow based on the optimum conversion:

  
GP$ $B FB FB ln 1
fA FB
¼
$A
$V tL

FA0 FA0 FA0 fA k FA0 CA0 fA
  
ln 1
fA $V
¼ $ B f A
$A
t L

k CA0
 
lnð1
0:99922297Þ 0:03
¼ 5  0:9992297
2
10
$=mol
A
0:15  60 2
¼ $2:8342 =mol
A

d. At breaking even point, the net profit (or in this case the gross profit) is zero. Therefore, at
the break-even point, operating cost and the value of product are equal.
The value of product is,
$B FB ¼ 5  100 $=h ¼ 500 $=h
which is also the operating cost at break even.
 4.3. NON-ISOTHERMAL BATCH REACTORS 159
The operating conditions for the break-even point can be obtained by setting the gross
profit to zero.
  
FB ln 1
fA FB
0 ¼ GP$ ¼ $B FB
$A
$V tL
(E4-5.13)
fA k CA0 fA
which can be rearranged to
  
$A $V ln 1
fA 1
fA

tL
¼ 0 (E4-5.14)
$B $B k CA0
or
0:001
fA
0:43 þ lnð1
fA Þ ¼ 0 (E4-5.15)
3
Solving Eqn (E4-5.15), we obtain
fA ¼ 0:430187

4.3. NON-ISOTHERMAL BATCH REACTORS

The solution of a batch reactor problem involves the solution of sets of ordinary differen-
tial equations from the species mole balance in the reactor as we have noted above. Mole
balance leads to,
dnj
rj V ¼ (4.2)
dt
or
dnj
¼ rj V (4.23)
dt
with initial conditions set in the reactor as t ¼ 0, nj ¼ nj0, or Cj ¼ Cj0. If the reactor is not oper-
ated isothermally, an energy balance equation is needed as well, Eqn (3.134), or
X
NS
dT dðpVÞ X
NR
CPj nj
_
W
¼ Q _ s
V ri DHRi (4.24)
j¼1
dt dt i¼1

dðpVÞ
with t ¼ 0, T ¼ T0. For liquids, z0, which further simplifies Eqn (4.24).
dt
The reaction rates rj’s given as functions of the concentrations (and temperature):

dnj X
NR
¼ rj V ¼ V nij ri (4.25)
dt i¼1

ri ¼ fðCk ; TÞ i ¼ 1; 2; 3; .:; NR (4.26)

160 4. BATCH REACTOR

In some cases (for example elementary reactions), the power-law rates can be applied,
that is
Ei Y
NS
OR
ri ¼ ki0 e
RT Cj j (4.27)
j¼1

as discussed in Chapter 3. In other cases, the reaction rates are more complicated functions of
the concentration and temperature. The concentration and number of moles are related by
definition:
nj
Cj ¼ (4.28)
V
For liquid phase reactions,
r0
V ¼ V0 (4.29)
r
And for gas phase reactions, the ideal gas law may be used to approximate the volume
change:
RT XNS
V ¼ nj (4.30)
P j¼1

Therefore, the solution to a non-isothermal batch reactor problem is similar to that to an

isothermal batch reactor problem. However, the temperature in the reactor needs to be solved
(considered) simultaneously with the reacting species.
The temperature is normally controlled via a heat jacket where thermal energy can be
supplied to the reactor or removed from the reactor (Fig. 4.3). When the reactor is insulated,
the reactor becomes adiabatic where temperature rise (for exothermic reaction) or decrease
(endothermic reaction) depending on the nature of the reaction taking place in the reactor.
 
Q_ ¼ UAH T
Tc (4.31)
where U is the overall heat transfer coefficient, AH is the total heat transfer area, and Tc
is the temperature of the fluid in the heat-exchanging jacket. In case of noninsulated
Heat transfer area is the surface area
between the jacket and reactor
Heat exchanging jacket
Reactor volume
Heat exchanging fluid in

T Tc

Heat exchanging fluid out

FIGURE 4.3 Schematic diagram of a batch reactor with a heat exchanger jacket.
 4.3. NON-ISOTHERMAL BATCH REACTORS 161
reactor, Tc is the temperature of the environment (surroundings). For an adiabatic
reactor, Q_ ¼ 0.
Example 4-6 H-Factor. A reaction with one single temperature-dependent reaction rate
constant,

vA A þ ð
vB Þ B ! products r ¼ kðTÞCO
A CB
RA ORB
(E4-6.1)
is carried out in a constant volume batch reactor. Each time when the reactor is loaded and
discharged, the temperature profile, i.e. temperature change with time during the intended
reaction period
T ¼ fðtÞ (E4-6.2)
is different. For comparison purposes, we would like to develop a method to quantify the
effect so that operators can control the reaction effectively. A concept of H-factor was devel-
oped, which is the effective reaction time equivalent to that at a constant temperature TR.
Figure E4-6.1 illustrates this concept. Derive a formula for the H-factor.
Solution. For reaction occurring in a batch reactor, mole balance of reactant A leads to
0 0

In – Out + Generation = Accumulation

dnA
nA rV ¼ (E4-6.3)
dt

At T K for t hours

At TR K for a period of time tR

or H hours

t=?

t=0

FIGURE E4-6.1 The concept of H-factors as applied to pulping and reactions involving woodchips.
162 4. BATCH REACTOR

Since the volume is constant (constant volume batch reactor), we further obtain
ORB dCA
nA kCO
A CB
RA
¼ (E4-6.4)
dt
Based on stoichiometry, we have
nA
nA;0 nB
nB;0
¼ (E4-6.5)
nA nB
For constant volume reactor, Eqn (E4-6.5) is reduced to
nB
CB ¼ CB0 þ ðCA
CA0 Þ (E4-6.6)
nA
Therefore, CB and CA are related. As the rate constant k is only a function of temperature
(Arrhenius relationship), separation of variables for Eqn (E4.3-4) leads to
 
dCA E
¼ n A kdt ¼ n k
A 0 exp
dt (E4-6.7)
CORA CORB
A B
RT

For a desired reaction end condition or conversion, the reaction time can be obtained by
integrating Eqn (E4-6.7).
ZCA Zt  
dCA E
¼ nA k0 exp
dt (E4-6.8)
CO
A CB
RA ORB RT
CA0 0

where CB is related to CA via Eqn (E4-6.6). Equation (E4.3-8) is applicable to reaction occur-
ring isothermally at a constant temperature, TR as well:
ZCA ZtR    
dCA E E
¼ nA k0 exp
dt ¼ nA k0 exp
tR (E4-6.9)
CO
A CB
RA ORB RTR RTR
CA0 0

where tR is the time required to reach the reaction end condition (concentration CA from CA0)
isothermally at a reaction temperature of TR. Substituting Eqn (E4-6.9) into Eqn (E4-6.8), we
obtain
  ZCA Zt  
E dCA E
nA k0 exp
tR ¼ ¼ n k
A 0 exp
dt (E4-6.10)
RTR CO
A CB
RA ORB RT
CA0 0

which can be reduced to

Zt  
E=R E=R
tR ¼ exp
dt (E4-6.11)
TR T
0

Thus, we have obtained a timescale that would give rise to the same conversion for
different temperatures and/or different temperature progressions. Integration for tR can be
achieved numerically (Liu, S. 2010, J. Biotech. Adv., 28: 563e582.)
 4.3. NON-ISOTHERMAL BATCH REACTORS 163
In chemical pulping, this temperature TR is usually taken as 100  C (or 373.15 K) and the
resulting tR is called H-factor. Once the activation energy is known, the effect of temperature
and time can be easily lumped together with this single parameter, tR, or H-factor. This
turned out to be smart idea as operators can control the reaction effectively even the temper-
ature varied during the process. Frequently quoted values of the constants are of those of
Vroom (1957) for kraft pulping of woodchips as shown below.
Zt  
16115 K
HF ¼ exp 43:2
dt (E4-6.12)
T
0

As temperature rises, more solvent evaporates to the vapor phase. As pressure increases,
more solvent returns to the liquid phase. Therefore for liquid or liquidesolid reactions at
high temperature, the effective reaction volume V changes with temperature and pressure
if not with concentration or composition. The constant volume assumption is only
approximate. The complexity further arises as the reaction kinetics is not the same when
temperature is increased causing different components in the plant biomass to be susceptible
to reaction. Thus, the H-factor treatment is only an approximation of the reaction system. One
variant of the H-factor is the severity factor. Equation (E4-6.11) can also be written as
Zt  
T
TR
tR ¼ exp dt (E4-6.13)
RTR T=E
0

If one approximates
RTR T
z TE (E4-6.14)
E
as a constant, then Eqn (E4-2.13) can be written as
Zt
T
TR T
TR
tR z exp dt ¼ t exp (E4-6.15)
TE TE
0

The severity factor is defined as the log of tR, that is

 
T
TR T
TR
SF ¼ log t exp ¼ log t þ (E4-6.16)
TE TE ln10

For hot water extraction of woody biomass, the frequently used TE is 14.75  C or 14.75 K to be
precise (Overend & Chornet 1987; Montane et al. 1994; Kabel et al. 2006). This is equivalent
E
to ¼ 10800 K for hot water extraction of woody biomass or hemicellulose reaction.
R
Example 4-7. Hot water extraction of woodchips. Hot water extraction is an excellent tech-
nique to remove hemicelluloses from wood. Hemicellulose extracted this way can be con-
verted to valuable products at low cost. Kate carefully prepared a batch of woodchips to
conduct hot water extraction experiment. She loaded 500 g of sugar maple chips and
164 4. BATCH REACTOR

2 L water into an M/K digester, quickly ramped up the temperature to 160  C. After 2 h at
160  C, she then quenched the reaction mixture down to room temperature. After thoroughly
washing the woodchips that were collected from the hot water extraction experiments, Kate
found that the woodchips are weighing 385 g.
a. How much mass loss (in %) for the woodchips occurred in the hot water extraction
experiment?
b. If Kate were to carry out the experiment at 180  C, what is the extraction time she should
keep in order to obtain roughly the same level of extraction?
Solution
a. Initially, the woodchips weigh 500 g and after extraction they weigh 385 g. Therefore,
500
385 g ¼ 115 g of wood was extracted or removed to the liquid phase. The mass loss is
thus 115/500 ¼ 23%.
b. Let us assume that the extraction reaction can be approximated by a single temperature
varying reaction rate constant. That is the rate of mass removal may be approximated
by

r ¼ kðTÞfðCÞ (E4-7.1)

where C is the concentration of components inside the wood.

For reaction occurring in a batch reactor, mole balance of reactant A leads to

0 0

In – Out + Generation = Accumulation

dnA
nA rV ¼ (E4-7.2)
dt

Since the volume is constant (constant volume batch reactor), we further obtain
dCA
nA kfðCÞ ¼ (E4-7.3)
dt

Since the rate constant k is only a function of temperature, separation of variables for Eqn
(E4.4-6) leads to
 
dCA E
¼ nA kdt ¼ nA k0 exp
dt (E4-7.4)
fðCÞ RT
For a desired reaction end condition or conversion, the reaction time can be obtained by
integrating Eqn (E4-7.4).
ZCA Zt    
dCA E E
¼ nA k0 exp
dt ¼ nA k0 exp
t (E4-7.5)
fðCÞ RT RT
CA0 0
 4.4. NUMERICAL SOLUTIONS OF BATCH REACTOR PROBLEMS 165
if the temperature is constant. For the reaction to take place at two different temperatures to
have the same conversion (or concentration change), we obtain from Eqn (E4-7.5)
   
E E
nA k0 exp
t1 ¼ nA k0 exp
t2 (E4-7.6)
RT1 RT2
which can be reduced to
 
E=R E=R
t2 ¼ exp
t1 (E4-7.7)
T2 T1
We can now estimate the time needed at a different temperature. Let us assume that
E
¼ 10800 K, substitute into Eqn (E4-7.7) to yield
R
 
10800 K 10800 K
t2 ¼ exp
t1
T2 T1
  (E4-7.8)
10800 K 10800 K
¼ exp
 2 h ¼ 0:6654 h ¼ 39:93 min
ð180 þ 273:15Þ ð160 þ 273:15ÞK

That is, at 180  C, an extraction time of 39.93 min is expected to yield the same level of
extraction as 2 h at 160  C.

4.4. NUMERICAL SOLUTIONS OF BATCH REACTOR PROBLEMS

In summary, a batch reactor problem as described by Eqns (4.2) and (4.23)e(4.31), can be
generalized mathematically as
dyj
¼ fj ðt; yÞ (4.32)
dt
with t ¼ 0, yj ¼ yj0. Here y ¼ {y1, y2, .}.
When you open the ODExLims visual basic code, you will see

Option Base 1
Option Explicit
’The following subroutine defines the ordinary differential equations y’ ¼ f(x,y,c)
’You may change the lines within Sub Func and Sub Jacobian
’Report bugs to Dr. Shijie Liu

Sub Func(f, ByVal x As Double, ByVal y, Optional c)

fð1Þ ¼ cð1Þ  yð1Þ
fð2Þ ¼ cð2Þ   þcð3Þ  yð2Þ ^ cð4Þ
0:1  yð1Þ
End Sub
166 4. BATCH REACTOR

by default, you only need to change the lines between

“Sub Func(f, ByVal x As Double, ByVal y, Optional c)” and “End Sub.”
In between these lines, you are to input the differential equations. You will need to write
each equation separately on a different line. In the example shown in the code, there are two
differential equations:

dy1
fð1Þ ¼ cð1Þ  yð1Þ 0 ¼ f 1 ¼ c 1 y1
dx
       ^     dy2
f 2 ¼ c 2   þc 3  y 2 c 4
0:1  y 1 0 ¼ f2 ¼ c2 x þ c3 yc24
0:1y1
dx

where cj’s are reserved as parameters (i.e. true constants) that one can pass from excel work-
sheet to the visual basic program at run time. This gives us freedom to make each code to be
more general and thus capable of solving a class of problems. When you change the values of
cj’s, the solution to the set of equations changes. You will not need to change the visual basic
code just for the different values of cj’s.
Example 4-8. Concentration profile for a series reaction with feedback regulation. A liquid
reaction system is carried out in a batch reactor:
A ! B ! C (E4-8.1)
with
k1 C A
r1 ¼ (E4-8.2)
K1 þ CA þ KC CC
k2 C B
r2 ¼ (E4-8.3)
K 2 þ CB
where k1 ¼ 1 mol$ L
1$ h
1, k2 ¼ 0.5 mol$ L
1$ h
1, K1 ¼ 0.1 mol$ L
1, K2 ¼ 0.2 mol$ L
1, and
KC ¼ 100.
Find the change of concentrations of A, B, and C as a function of time between 0 and 100 h
in a constant volume isothermal batch reactor starting with
a. pure A initially at CA0 ¼ 10 mol$ L
1; CB0 ¼ CC0 ¼ 0 mol$ L
1
b. CA0 ¼ 10 mol$ L
1, CB0 ¼ 0 mol$ L
1, CC0 ¼ 10 mol$ L
1
Solution. This is a set of two reactions occurring in series. Mole balance for species j leads to
dnj
¼ rj V (E4-8.4)
dt
Since the volume is constant, we have
dCj
¼ rj (E4-8.5)
dt
We next find the rates of reaction (Fig. E4.8-1). Applying Eqn (3.66), we obtain
rA ¼ n1A r1 þ n2A r2
k1 CA (E4-8.6)
¼
r1 ¼

K 1 þ CA þ K C CC
 4.4. NUMERICAL SOLUTIONS OF BATCH REACTOR PROBLEMS 167
t = 0, CA = CA0,
CB = 0,
CC = 0
A B C

A,
B, t = t, CA,
C CB,
CC

FIGURE E4-8.1 A schematic diagram of the batch reactor.

k1 C A k2 C B
rB ¼ n1B r1 þ n2B r2 ¼ r1
r2 ¼
(E4-8.7)
K1 þ CA þ KC CC K2 þ CB
k2 C B
rC ¼ n1C r1 þ n2C r2 ¼ r2 ¼ (E4-8.8)
K 2 þ CB
Substituting Eqn (E4-8.6) through (E4-8.8) into Eqn (E4-8.5), we obtain the differential
equations for the system:

dCA k1 C A
¼ rA ¼
(E4-8.9)
dt K1 þ CA þ KC CC
dCB k1 C A k2 C B
¼ rB ¼
(E4-8.10)
dt K1 þ CA þ KC CC K2 þ CB
dCC k2 CB
¼ rC ¼ (E4-8.11)
dt K2 þ CB
Now we are ready to solve the problem with an automatic integrator.
Open the excel file: odexlims.xls. If prompted, enable the macro. If not prompted, make sure
the macros are allowed to run from this file. You will see
168 4. BATCH REACTOR

Now save the file as Example 4-7. Delete the contents on the sheet shown.
On row 1, enter:
“k1” in cell A, “k2” in cell B, “K1” in cell C, “K2” in cell D, and “Kc” in cell E.
On row 2, enter:
“1” in cell A, “0.5” in cell B, “0.1” in cell C, “0.2” in cell D, and “100” in cell E.
On row 3, enter:
“t” in cell A, “CA” in cell B, “CB” in cell C, “CC” in cell D.
On row 4, enter:
“0” in cell A, “10” in cell B, “0” in cell C, and “0” in cell D.
In column 1 after row 4, enter:
0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.4, 1.6, 1.8, 2, 3, 4, 5, 6, 7, 8, 9, 10, .
It reads on screen now as

We next open the visual basic editor (from macro). Replace the two equations [“f(1) ¼ .” and
“f(2) ¼ .” ] with those of Eqns (E4.5-9) through (E4.5-11). In our case, we have three equations,
so another line needs to be inserted. Noting from the sequence of parameters we had input on
the Excel worksheet earlier: k1, k2, K1, K2, KC, which are now available as c(1), c(2), c(3), c(4), and
c(5). After entering the equations in the visual basic code, it reads on the screen:
 4.4. NUMERICAL SOLUTIONS OF BATCH REACTOR PROBLEMS 169

Make sure the equations you entered are correct (as you desired). We next go to the excel
worksheet. Select the region below the row of initial values (“0,” “10,” “0,” “0”) until the
last row you have time entered, between columns for CA and CC. Insert function, from
“User Defined”, find “ODExLIMS.” Here is how it reads

Click on “OK” and the dialog for the ODExLIMs shows up. On the row of “X,” enter the
locations of the values of t to be solved including the starting point (from t ¼ 0 to the last t
value you have entered). On the row of “Yintial,” enter the location of the initial values
(CA0, CB0, CC0), and on the row of “C,” enter the location of the parameters needed to be
passed into the program, which are the k’s values. Make sure the sequence of the “C” values
is correct. When this is done, the screen reads,
170 4. BATCH REACTOR

Hold on both “Ctrl” and “Shift” keys on your keyboard and click on “OK” in the same time.
When this is done, the screen reads as shown in Fig. E4-8.2a). One can now plot the solution
in Excel. This concludes part (a). You can save the file now.

(a) (b)
FIGURE E4-8.2 The excel solution.
 4.4. NUMERICAL SOLUTIONS OF BATCH REACTOR PROBLEMS 171
To perform part (b), you will only need to type 10 into the cell for CC0, which is currently 0.
The numbers (solution) should change automatically. If not, press “F9” key. You will see the
difference immediately. The screen is shown above on the right (Fig. E4-8.2b). Comparing the
solutions for part (a) and for part (b), one can observe that an increase in concentration C
decreases the rate of conversion for A significantly.
Figure E4-8.3 shows the final solutions as plotted out for the concentrations of A and C
(Fig. E4-8.3a) and B (Fig. E4-8.3b) as functions of time. One can observe that as the final

(a) 12
CC, b)
10 CA0
CA, b)
8

CA, a)
Cj

4 CC, a)

0
0 20 40 60 80 100
k1t

(b) C A andCC
0.30

0.25

0.20
CB

0.15

0.10

CB, a)
0.05

CB, b)
0.00
0 1 2 3 4 5 10 100
k1t
CB
FIGURE E4-8.3 The concentrations of A, B, and C in the reactor as functions of time.
172 4. BATCH REACTOR

product concentration is high in the reaction mixture, the reaction is slowed significantly due
to the feedback regulation. The intermediate product B formed is very low when the final
product concentration is high in the reactor.

4.5. SUMMARY
Batch reactor is widely used in industry and is the preferred reactor in laboratories and in
pharmaceutical industries. The performance of a batch reactor can be analyzed via mole
balance. For each species in the reactor, there is one mole balance equation that yields a differ-
ential equation:
dnj
¼ rj V (4.23)
dt
with initial conditions set in the reactor as t ¼ 0, nj ¼ nj0, or Cj ¼ Cj0. If the reactor is not oper-
ated isothermally, an energy balance equation is needed as well,

X
NS
dT dðpVÞ X
NR
CPj nj
_
W
¼ Q _ s
V ri DHRi (4.24)
j¼1
dt dt i¼1

with t ¼ 0, T ¼ T0.
The reaction rates are needed before the batch reactor problems can be solved. The concen-
tration and number of moles are related by definition:
nj
Cj ¼ (4.28)
V
For liquid phase reactions,
r0
V ¼ V0 (4.29)
r
And for gas phase reactions, the ideal gas law may be used to approximate the volume
change:

RT XNS
V ¼ n (4.30)
P j¼1 j

The solutions to the differential equations can be obtained either analytically (for simple
kinetics) or numerically with an automatic integrator.
The reactor preparation time (loading, unloading, etc.) affects the overall batch reactor
operation performance. The reactor volume can be obtained from Eqn (4.22)
 
V ¼ tB Q ¼ tP þ tf þ tU Q (4.22)
where tB is the batch time or the total time required for one batch operation that includes the
time for pre-reactor starting time tP, the reaction time tf and the reactor unloading and clean-
ing time tU, and Q is the volumetric rate that is treated with the batch reactor.
 PROBLEMS 173

Further Reading
Kabel, M.A., Bos, G., Zeevalking, J., Voragen, A.G.J., Schols, H.A., 2006. Effect of pretreatment severity on xylan solubility
and enzymatic breakdown of the remaining cellulose from wheat straw. Bioresource Technology, 98, 2034e2042.
Liu, S., 2010. Woody biomass: Niche position as a source of sustainable renewable chemicals and energy and
kinetics of hot-water extraction/hydrolysis. J. Biotech. Adv. 28, 563e582.
Montané, D., Salvadó, J., Farriol, X., Jollez, P., Chornet, E., 1994. Phenomenological kinetics of wood delignification:
application of a time-dependent rate constant and a generalized severity parameter to pulping and correlation of
pulp properties. Wood Science and Technology, 28, 387e402.
Overend, R., Chornet, E., 1986. Fractionation of lignocellulosics by steam-aqueous pretreatment. The Philosophical
Transactions of the Royal Society London, 321, 523e536.
Vroom, K.E., 1957. The “H” factor: a means of expressing cooking times and temperatures as a single variable. Pulp
Paper Mag. Can. 58(3), 228e231.

PROBLEMS
4.1. Our winery has discovered that all of last year’s crop now being stored for aging
contained 200 ppm of a chemical that gives it garlic flavor. However, we find that the
concentration of this chemical is 50 ppm 1 year after it was put in storage. Taste tests in
which this chemical was added to good wine shows that it can be detected only if its
concentration is greater than 10 ppm. How long will we have to age this wine before we
can sell it?
4.2. Our winery chemist has just found that the reaction by which the garlic-flavored
compound of the previous problem disappears is by a reaction that produces a tasteless
dimer of the chemical.
(a) With this mechanism, how long must we age our wine before we can sell it?
(b) Since we do not entirely trust his judgment (why would a competent chemist work
for a winery?), we decide to test his results by analyzing the wine after the second
year of aging. What percentages should we find if the reaction is first or second
order?
4.3. The carton of milk in your refrigerator contains 20 cells per glass of a strain of
Escherichia coli which makes people sick. This strain doubles every 2 days, and your
immune system can destroy up to 1000 cells per glass without noticeable effects.
(a) When should the carton of milk be poured down the drain?
(b) At room temperature, this strain doubles every 8 h. For how long is the milk
drinkable if left on the counter?
4.4. Your neighbor just sneezed on your desk, and the drop contains 200 virus particles.
Half of the virus particles are destroyed every 10 min by air oxidation. Can the person
who sits at your desk next hour catch his cold?
4.5. Yogurt is produced by adding a small amount of finished yogurt to fresh milk in
a process whose kinetics can be described approximately as
A ! 2A; r ¼ kCA
It is found that with a certain culture, the concentration of product in fresh milk doubles
in 8 h. If the process is started by adding 5% of finished yogurt to milk, how long is
required to prepare a batch of yogurt?
174 4. BATCH REACTOR

4.6. A certain drug is metabolized such that its concentration in the bloodstream halves
every 4 h. If the drug loses its effectiveness when the concentration falls to 10% of its
initial concentration, how frequently should the drug be taken?
4.7. An aqueous ester hydrolysis reaction A / B þ C has k ¼ 0.02/min and an equilibrium
constant of 10 with all concentrations in mol/L.
(a) Starting with CA0 ¼ 1 mol/L, and CB0 ¼ CC0 ¼ 0, what is the equilibrium
composition?
(b) What is the reverse rate constant in the above reaction?
(c) Find CA(t), CB(t), and CC(t) in a batch reactor for these initial conditions.
4.8. A gaseous reaction
A ! B þ C r ¼ kC2A ; with k ¼ 0:1 mol$L
1 $s
1
is occurring in an isothermal constant pressure batch reactor. The reactor is at 373 K
charged initially with 1 bar of A and 0.2 bar of N2 (not A, B, or C), that is not reacting.
Determine the time required for the reaction volume to expand by 50%, i.e. V/V0 ¼ 1.5.
4.9. Sterilization is a batch process by which bacteria and molds in food are killed by heat
treatment. A can of vegetables that originally contained 10,000 viable spores has 100
spores remaining after heating for 10 min at 250  F. Assuming first-order kinetics, how
long must this can be heated at this temperature to reduce the probability of having
a single spore to an average of 1 in 1 million cans?
4.10. In ethanol production by fermentation of corn, hydrolyzed ground corn in a water
suspension containing 50% corn by weight is mixed with sufficient enzyme to produce
ethanol by the approximate reaction
C6 H12 O6 ! 2C2 H5 OH þ 2CO2
When the solution reaches 12% ethanol, the yeast dies and the reaction stops.
(a) How many bushels of corn are required to produce 500 tons of pure ethanol per
day? Assume 1 bushel of corn weighs 56 lb.
(b) The process requires 72 h to go to completion. What size batch reactor tank or tanks
are required for this process?
4.11. Consider the reaction
A ! B; r ¼ 0:15=min CA
in a batch reactor. The total preparation time for each batch operation is 8 h. A costs
$2/mole, and B sells for $4/mole. The cost for operating the reactor is $0.04 per liter
hour. We need to produce 100 moles of B per hour using CA0 ¼ 2 mol/L. Assume no
value or cost of disposal of unreacted A.
(a) What is the optimum conversion and reactor size?
(b) What is the cash flow from the process?
(c) What is the cash flow ignoring operating cost?
(d) At what operating cost do we break even?
4.12. One hundred moles of A per hour are available in concentration of 0.1 mol/L by
a previous process. This stream is to be reacted with B to produce C and D. The reaction
proceeds by the aqueous-phase reaction,
A þ B ! C þ D; k ¼ 5 mol
1 $ L $ h
1
 PROBLEMS 175
The amount of C required is 95 mol/h. In extracting C from the reacted mixture, A and
B are destroyed; hence, recycling of unused reactants is not possible. Calculate the
optimum reactor size as well as feed composition for this process if the total prepara-
tion time for each batch operation is 10 h.
Data: B costs $1.25/mol in crystalline form. It is highly soluble in the aqueous solu-
tion and even when present in large amounts does not change the concentration of A in
solution. Capital and operating costs are $0.015 h
1$L
1.
4.13. One hundred fifty moles of B are to be produced hourly from a feed consisting of
a saturated solution of A (CA0 ¼ 0.1 mol/L) in a batch reactor. The reaction is

A ! B; r ¼ 0:2=hCA
The cost of reactant at CA0 ¼ 0.1 mol/l is $A ¼ $0.50/mol A. The cost of reactor including
installation, auxiliary equipment, instrumentation, overhead, labor, depreciation, etc.,
is $m ¼ $0.01 h
1$L
1. The total preparation time for each batch of operation is 9 h.
What reactor size, reactant rate, and conversion should be used for optimum opera-
tions? What is the unit cost of B for these conditions if unreacted A is discarded?
4.14. You wish to design a plant to produce 100 tons/day of ethylene glycol from ethane, air,
and water. The plant has three reactor stages, ethane dehydrogenation, ethylene
oxidation, and ethylene oxide hydration.
(a) What are the reactions?
(b) Both dehydrogenation and hydration have nearly 100% selectivity (with recycle of
unreacted reactants), but ethylene to ethylene oxide has only 70% selectivity with
an old catalyst and 90% selectivity with a new and expensive catalyst. How many
tons/day of ethane do we need to supply to this plant with each of these
catalysts?
4.15. We want to hydrolyze 500 lb/day of an ester at an initial concentration of 5 molar (the
ester has a molecular weight of 120) in aqueous basic solution in a batch process, and
we need product that is 99% hydrolyzed. In bench top experiments in a flask, we find
that 50% of the ester hydrolyzes in 15 min for initial ester concentrations of either 1 or
5 molar. We also find that, when we react for 8 h, all the ester has hydrolyzed. It takes
1 h to empty the reactor and refill and heat it to start another batch.
(a) What size reactor will we need?
(b) What size reactor will we need if we can tolerate 90% conversion?
(c) This process was found to have an activation energy of 12 kcal/mol, and we had
been operating at 40  C. What reactor volumes would we need if we can operate at
80  C?
(d) This hydrolysis reaction is exothermic with DHR ¼
8 kcal/mol. What must be the
average rate of cooling (in watts) during the reaction to maintain the reaction
isothermal?
(e) If we started the batch reactor at 40  C but forgot to turn on the cooling, what would
be the final temperature if the reactor were adiabatic (and the vessel would
withstand the pressure)? Assume the heat capacity of the solution to be that of
water, 1 cal/(cm3 K).
(f) What cautions do you recommend regarding operation at 80  C?
176 4. BATCH REACTOR

4.16. A pulp mill utilizing the saw dust from nearby lumber mills to produce a market pulp
for paper production. A recent development had the company thinking of increasing
the pulp production by 50% for entering the nonwoven market. A close examination at
the pulp mill has the engineers to conclude that the digesters were the bottleneck.
Currently, the woodchips were steamed, mixed with a pulping liquor, and underwent
delignification at 150  C for 3 h. For each load of woodchips, a minimum of 2 h is
needed for loading, heating the digester up, explosive decompression unloading, and
cleaning up the digester for the next load. Your task is to find a way to ease the
bottleneck quickly at a low cost. State your assumptions clearly and your solution to the
problem as stated.