Membrane Reactor

What is a membrane reactor?
A membrane reactor is really just a plug-flow reactor that contains an additional cylinder of some
porous material within it, kind of like the tube within the shell of a shell-and-tube heat
exchanger. This porous inner cylinder is the membrane that gives the membrane reactor its name.
The membrane is a barrier that only allows certain components to pass through it. The selectivity
of the membrane is controlled by its pore diameter, which can be on the order of Angstroms, for
microporous layers, or on the order of microns for macroporous layers.
Why use a membrane reactor?

Membrane reactors combine reaction with separation to increase conversion. One of the
products of a given reaction is removed from the reactor through the membrane, forcing the
equilibrium of the reaction "to the right" (according to Le Chatelier's Principle), so that more of
that product is produced.
Membrane reactors are commonly used in dehydrogenation reactions (e.g., dehydrogenation of

ethane), where only one of the products (molecular hydrogen) is small enough to pass through
the membrane. This raises the conversion for the reaction, making the process more economical.
What kinds of membrane reactors are available?

Membrane reactors are most commonly used when a reaction involves some form of catalyst,
and there are two main types of these membrane reactors: the inert membrance reactor and the
catalytic membrane reactor.
The inert membrane reactor allows catalyst pellets to flow with the reactants on the feed side
(usually the inside of the membrane). It is known as an IMRCF, which stands for Inert
Membrane Reactor with Catalyst on the Feed side. In this kind of membrane reactor, the
membrane does not participate in the reaction directly; it simply acts as a barrier to the reactants
and some products.
A catalytic membrane reactor (CMR) has a membrane that has either been coated with or is
made of a material that contains catalyst, which means that the membrane itself participates in
the reaction. Some of the reaction products (those that are small enough) pass through the
membrane and exit the reactor on the permeate side.
Algorithm:
The basic algorithm for solving reaction engineering problems is described below. This
algorithm is a useful tool, and it can be applied to a wide variety of reactor problems, not just
membrane reactor problems.
For demonstration purposes, we'll examine a membrane reactor in which the following gas phase
reaction occurs:
Product B diffuses through the membrane, but reactant A and product C do not.
1. Mole Balance:
For a differential mole balance on A in the catalytic bed at steady state:
IN (by flow) - OUT (by flow) + Generation = Accumulation
Dividing by
and taking the limit as
gives:
Similarly, a differential mole balance on C in the catalytic bed at steady state will give:
IN (by flow) - OUT (by flow) + Generation = Accumulation
Dividing by
gives:
The steady state, differential mole balance on B looks slightly different, since B is the only
species that passes through the membrane:
IN (by flow) - OUT (by flow) + Generation - OUT (by diffusion) = Accumulation
where RB is the molar flowrate of B through the membrane per unit volume of the reactor.
Dividing by
gives:
2. Rate Law:
The rate of disappearance of reactant A follows the rate law:
where k is the specific reaction rate constant, and KC is the equilibrium constant. Products B and
C obey the following rate laws:
3. Transport Law:
The transport or flux of species B through the membrane follows the transport law:
where km is a mass transport coefficient for the flow of product B through the membrane.
4. Stoichiometry:
For gas-phase reactions:
The subscript o indicates initial conditions and v is the volumetric flow rate.
The concentrations, in terms of molar flow rates, are:
Substituting for the volumetric flow rate, we get:
If we make use of the fact that:
we can get our concentrations in terms of the total initial concentration:
Quite often we can make the assumption that the reactor operates isothermally and isobarically:
5. Combine:
Substituting the concentration terms into the rate law yields:
where the total molar flow rate is:

and:
Sample Membrane Reactor Problem

A membrane reactor is used for the reaction
, where the membrane is
permeable to product B, but not to reactant A or product C.
Additional Information:
P0
T0
k
KC
km
FA0
FB0 = FC0
6.0 atm
373 K
0.7 min-1
0.05 mol/dm3
0.2 min-1
15 mol/min
0 mol/min
Consider the following questions:

1. What volume is required for the base case membrane reactor?
Base Case
List of Equations:
Summary Table
FA, FB, and FC versus Volume
Conversion versus Volume
2. What if the membrane transfer coefficient, km , were 0.002 min-1?

Compare plots of molar flowrates versus volume and conversion
versus volume for this case with your base case.
Base Case
List of Equations:
Question 2
Summary Table
FA, FB, and FC versus Volume
3. What if the membrane transfer coefficient, km , were 20.0 min-1?

Compare plots of molar flowrates versus volume and conversion
versus volume for this case with your base case.
4. Base Case
5. List of Equations:
6.
7.
8. Question 3
9. Summary Table
10.
11.
12. FA, FB, and FC versus Volume
13.
14.
15. Isolating FB versus Volume
16.
17.
18. Conversion versus Volume
19.
4. What if the base case flowrate were changed from 15 mol/min to 5

mol/min?
How would this affect the behavior of the membrane reactor?
5. List of Equations:
6.
7.
8. Question 4
9. Summary Table
10.
11.
13.
14.
16.
5. What if the base case flowrate were changed from 15 mol/min to 25

mol/min?
How would this affect the behavior of the membrane reactor?
6.
7.
8. Question 5
9. Summary Table
10.
11.
13.
14.
16.
Break It Down for Me:
List of Equations
Summary Tables
o Membrane Reactor
o PFR
Flowrates versus Volume
o Membrane Reactor
o PFR
o Membrane Reactor
o PFR
List of Equations The same equations are used by both membrane reactors and PFRs
(note that km will be set to zero for a PFR).
Summary Table -- Membrane Reactor
Summary Table -- PFR
FA, FB, and FC versus Volume -- Membrane Reactor
FA, FB, and FC versus Volume -- PFR
Conversion versus Volume -- Membrane Reactor
Conversion versus Volume -- PFR
Comparing Membrane Reactors with PFRs, Part

2
Changing FA0
Let's take a look at the effects of changing the inlet flowrate, F A0, and how it affects
our individual flowrates and the conversion:
As expected, our flowrates increase as FA0 increases. Interestingly though, conversion

actually decreases as FA0 increases. Why? Even though more of reactant A enters the
reactor as the flowrate increases, it spends less time in the reactor, which causes the
decrease in conversion.
Changing km
Now let's see what happens when we vary k m:
The transport coefficient, km, is a measure of how easily a species will pass through a
given substance (i.e., the membrane). The lower the value of k m, the more difficult it
will be for species B to pass through the membrane, so it makes sense that our highest
conversion occurs when km is highest. (See the page on flux for more information.)
The resulting effect on our flowrates is also no surprise, since the removal of species
B through the membrane will drive our reaction equilibrium to the right. In our
extreme case of large km, species B is removed as quickly as it is produced.

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What is a membrane reactor?

Why use a membrane reactor?

Membrane reactors are commonly used in dehydrogenation reactions (e.g., dehydrogenation of

What kinds of membrane reactors are available?

and taking the limit as

and taking the limit as

Substituting for the volumetric flow rate, we get:

If we make use of the fact that:

we can get our concentrations in terms of the total initial concentration:

where the total molar flow rate is:

Sample Membrane Reactor Problem

Consider the following questions:

FA, FB, and FC versus Volume

Conversion versus Volume

2. What if the membrane transfer coefficient, km , were 0.002 min-1?

FA, FB, and FC versus Volume

Conversion versus Volume

3. What if the membrane transfer coefficient, km , were 20.0 min-1?

4. What if the base case flowrate were changed from 15 mol/min to 5

5. What if the base case flowrate were changed from 15 mol/min to 25

Break It Down for Me:

Summary Table -- Membrane Reactor

Summary Table -- PFR

FA, FB, and FC versus Volume -- Membrane Reactor

FA, FB, and FC versus Volume -- PFR

Conversion versus Volume -- Membrane Reactor

Conversion versus Volume -- PFR

Comparing Membrane Reactors with PFRs, Part

As expected, our flowrates increase as FA0 increases. Interestingly though, conversion

Now let's see what happens when we vary k m:

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