Chapter 6 : Isothermal Reactor Design, Molar

Flow Rates
6.1 Molar Flow Rates Balance Algorithm

There are many instances when it is much

more convenient to work in terms of
number of moles (NA , NB) or molar flow
rates (FA, FB , etc.) rather than conversion.
Membrane reactors & multiple reactions
taking place in gas phase are two such cases
where molar flow rates are preferred rather
than conversion. 1
We now modify our
algorithm by using
concentrations for liquids
& molar flow rates for
gases as our dependent
variables.
2
The main difference between
conversion algorithm & molar flow
rate/concentration algorithm is that,

in conversion algorithm, write a mole

balance on only one species,

whereas in molar flow rate &

concentration algorithm, write a mole
balance on each & every species. 3
This algorithm is shown in Figure 6-11.

First we write mole balances on all

species present as shown in Step (1).

Next write rate law, Step (2),

& then relate mole balances to one
another through relative rates of
reaction as shown in Step (3).
4
5
6

6
Steps (4) & (5) are used to
relate concentrations in rate
law to molar flow rates.

In Step (6), all steps are

combined by ODE solver
(e.g., Polymath).
7
6.2 Mole Balances on CSTRs, PFRs, PBRs, & Batch Reactors

6.2.1 Liquid Phase

For liquid-phase reactions in which there is no
volume change, concentration is preferred
variable. The mole balances for generic
reaction are shown in Table 6-1 in terms of
concentration for four reactor types we have
been discussing.

8
From Table 6-1, we have only to
specify parameter values for system
(CA0, 0, etc.) & for rate law
parameter. (e.g., kA , , ) to solve
coupled ordinary differential
equations for either PFR, PBR, or
batch reactors or to solve coupled
algebraic equations for CSTR.

9
(6-1)

10
6.2.2 Gas Phase
The mole balances for gas-phase
reactions are given in Table 6-2 in
terms of number moles (batch) or
molar flow rates for generic rate
law for generic reaction Equation
(2-1).
11
The molar flow rates for
each species Fj are
obtained from a mole
balance on each species, as
given in Table 6-2. For
example, for a plug-flow
reactor. 12
 (3-3)

(4-17)

5
5

13
6-2

14
6-2

15
16
6.3 Applications of Molar Flow Rate Algorithm to Microreactors

Microreactors are emerging as a

new technology in CRE.
Microreactors are characterized
by their high surface area-to-
volume ratios in their
microstructured regions that
contain tubes or channels. 17
A typical channel width might be
for the 100 m with a length of
20,000 m (2 cm).
The resulting high surface area-
to volume ratio reduces or even
eliminates heat & mass transfer
resistances often found in larger
reactors.
18
Consequently, surface catalyzed
reactions can be greatly
facilitated, hot spots in highly
exothermic reactions can be
eliminated, & in many cases
highly exothermic reactions can
be carried out isothermally.
19
 Microreactors are also used for
production of specialty chemicals,
combinatorial chemical screening,
lab-on-a-chip, & chemical sensors.
In modeling microreactors, assume
they are in plug flow for which mole
balance is

For the plug-flow case, the algorithm is

described in Figure 6-1. 20
Example 6-1 Gas-Phase Reaction in a Microreactor-Molar Flow Rates

21
22
Although this particular
problem could be solved
using conversion, we shall
illustrate how it can also be
solved using molar flow
rates as variable in mole
balance. 23
First write reaction in
symbolic form & then
divide by stoichiometric
coefficient of limiting
reactant, NOCl.
24
 (6-1.1)

(6-1.2)

(6-1.3)

(6-1.4)

25
(4-17)

(6-1.5)

26
(6-1.6)

(6-1.7)

(6-1.8)

27
 6-1.1
6-1.1
6-1.1

6-1.1
28
9-4-2009
29
6-4 Membrane Reactors
Membrane reactors can be used to
increase conversion when the
reaction is thermodynamically
limited as well as to increase the
selectivity when multiple
reactions are occurring.
30
Thermodynamically limited reactions
are reactions where the equilibrium lies
far to the left (i.e., reactant side) & there
is little conversion.
If the reaction is exothermic, increasing
the temperature will only drive reaction
further to left, & decreasing
temperature will result in a reaction rate
so slow that there is very little
conversion.
31
The term membrane
reactor describes a
number of different
types of reactor
configurations that
contain a membrane. 32
The membrane can either
provide a barrier to certain
components while being
permeable to others, prevent
certain components such as
particulates from contacting the
catalyst, or contain reactive sites
& be a catalyst in itself.
33
 Like reactive distillation, the
membrane reactor is another
technique for driving
reversible reactions to the
right toward completion in
order to achieve very high
conversions.
34
These high conversions
can be achieved by having
one of the reaction
products diffuse out of a
semipermeable membrane
surrounding the reacting
mixture. 35
As a result, the reverse
reaction will not be able
to take place, & the
reaction will continue to
proceed to the right
toward completion.
36
Two of the main types of
catalytic membrane reactors
are shown in Figure 6-3.
The reactor in Figure 6-3(b) is
called an inert membrane
reactor with catalyst pellets on
the feed side (IMRCF).
37
Here membrane is inert &
serves as a barrier to
reactants & some of
products. The reactor in
Figure 6-3(c) is a catalytic
membrane reactor (CMR).
38
39
6-3

40
The catalyst is deposited directly
on membrane, & only specific
reaction products are able to exit
permeate side.
For example, in reversible
reaction

41
Hydrogen molecule is small
enough to diffuse through small
pores of membrane while C6H12
& C6H6 cannot.
Consequently, reaction continues
to proceed to right even for a
small value of equilibrium
constant. 42
43
Hydrogen, species B, flows
out through sides of
reactor as it flows down
reactor with other products,
which cannot leave until
they exit the reactor.
44
In analyzing membrane reactors,
we only need to make a small
change to algorithm shown in
Figure 6-1.
Choose reactor volume rather
than catalyst weight as our
independent variable for this
example.
45
The mole balances on chemical species
that stay within reactor, namely A & C,
are shown in Figure 6-3 (d).

The mole balance on C is carried out in an

identical manner to A, & resulting equation is
(6-1)

46
However, mole balance
on B (H2) must be
modified because
hydrogen leaves through
both sides of reactor &
at end of reactor. 47
First we shall perform mole balances
on volume element V shown in
Figure 6-3(d). The mole balance on
hydrogen (B) is over a differential
volume V shown in Figure 6-3(d)
& it yields
Balance on B in catalytic bed:

(6-2)
48
where RB is molar rate of B leaving
through the sides of reactor per unit
volume of reactor (mol/dm3.s).
Dividing by V & taking the limit as
V 0 gives (6-3)

The rate of transport B out through

membrane RB is product of molar flux of B,
WB, & a, surface area, per unit volume of
reactor. 49
The molar flux of B, WB in (mol/m2. s) out of
reactor is a mass transfer coefficient times
concentration driving force across membrane.

(6-4)

Where kC is overall mass transfer coefficient

in m/s & CBS is concentration of B in sweep
gas channel (mol/dm3). 50
The overall mass transfer
coefficient accounts for all
resistances to transport:
-tube side resistance of
membrane,
-membrane itself, &
-on shell (sweep gas) side
resistance. 51
In general, this coefficient
can be a function of
-membrane &
-fluid properties,
-fluid velocity, &
-tube diameters.
52
To obtain rate of removal
of B, need to multiply
flux through membrane
by surface area of
membrane in reactor.
53
The rate at which B is
removed per unit volume
of reactor, RB , is just flux
WB times surface area
membrane per volume of
reactor, a (m / m ); that is,
2 3

54
(6-5)

(6-5)

55
6-2

56
57
 6-3(d)

6-2

(6-3)
6-2

6-2
58
 6-2

6-5

6-2.8

4-17

59
 6-2.9

6-2.10

6-2.11

6-2.12

E6-2.5

6-2.6
E6-2.7

60
E6-2.1 E6-2.11

61
E6-2.1
E6-2.1

E6-2.1

62
 E6-2.1

E6-2.1

63
Use of Membrane Reactors to Enhance Selectivity

In addition to species leaving

through the sides of membrane
reactor, species can also be fed to
reactor through the sides of
membrane. For example, for
reaction
64
8

(6-7)

65
6.5 Unsteady-State Operation of Stirred Reactors

In this section, we discuss two other

aspects of unsteady operation: startup
of a CSTR & semibatch reactors. First,
startup of a CSTR is examined to
determine time necessary to reach
steady-state operation [see Figure 6-
4(a)], & then semibatch reactors are
discussed. 66
6-4

67
In each of these cases, we are interested
in predicting concentration &
conversion as a function of time.
Closed-form analytical solutions to
differential equations arising from mole
balance of these reaction types can be
obtained only for zero-& first-order
reactions. ODE solvers must be used
for other reaction orders.
68
There are two basic types of semibatch
operations. In one type, one of reactants in
reaction

(e.g., B) is slowly fed to a reactor

containing other reactant (e.g., A),
which has already been charged to a
reactor such as that shown in Figure
6-4(b).
69
This type of reactor is
generally used when
unwanted side reactions
occur at high
concentrations of B or
when reaction is highly
exothermic. 70
The other type of semibatch
reactor is reactive distillation &
is shown schematically in
Figure 6-4(c).
Here reactants A & B are
charged simultaneously & one
of products is vaporized &
withdrawn continuously. 71
Removal of one of products in
this manner (e.g., C) shifts
equilibrium toward right,
increasing final conversion
above that which would be
achieved had C not been
removed.
72
In addition, removal of one of
products further concentrates
reactant, thereby producing an
increased rate of reaction &
decreased processing time.
This type of reaction operation
is called reactive distillation.
73
6.6 Semibatch Reactors
One of best reasons to use
semibatch reactors is to enhance
selectivity in liquid-phase
reactions. For example, consider
the following two simultaneous
reactions. One reaction produces
desired product D. 74
6-8

75
& guides us how to produce most of our
desired product & least of our undesired
product (see Section 8.1). From
instantaneous selectivity that we can
increase formation of D & decrease
formation of U by keeping concentration of
A high & concentration of B low.
This result can be achieved through use of
semibatch reactor, which is charged with
Pure A & to which B is fed slowly to A in
vat.
76
6.6.2 Semibatch Reactor Mole Balances
Of the two types of semibatch
reactors, focus attention primarily on
one with constant molar feed. A
schematic diagram of this semibatch
reactor is shown in Figure 6-5.
consider elementary liquid-phase
reaction.
A+BC
77
78
reactant B is slowly added to a well-
mixed vat containing reactant A.
A mole balance on species A yields

Three variables can be used to formulate

& solve semibatch reactor problems:
concentrations, number of moles, &
conversion, X.
79
use concentration as our variable, (NA = CA V) rewrite Equation (6-9) as

reactor volume at any time t can be found

from an overall mass balance

constant-density system, 0 = ,

80
V = V0 at t = 0, integrating with constant volumetric
flow rate 0 yields

Substituting Equation (6-12) into right-hand

side of Equation (6-10) & rearranging

balance on A [Equation (6-10)] can be rewritten as

81
mole balance on B fed to reactor at a rate FB0

82
83
At time t = 0, initial concentrations of B,
C, & D in vat are zero, CBi = 0. The
concentration of B in feed is CB0 If
reaction order is other than zero or 1st-
order, or if reaction is nonisothermal, must
use numerical techniques to determine
conversion as a function of time.
Equations (6-14), (6-16), (6-19), & (6-20)
are easily solved with an ODE solver.
84
85
86
87
88
89
90