Membrane Reactors 487

X-t
Figure 12-5 Concentration profiles of a reactant that migrates into one phase through a membrane and into a second phase
for reaction.

Membrane reactor configurations

It is important to attain as high an area as possible for a membrane reactor. Configurations with
multilayer planar membranes, coiled membranes, or as multiple tubes also can be used for
similar processes with potentially very high surface areas, as sketched in Figure 12-6. Fuel
cells and batteries are examples of membrane reactors in which a conducting membrane separates
the anode and cathode compartments, which supply fuel and oxidant,
respectively. With fuel cells we have the added complexity that we need an ion-conducting
electrode, which is also a catalyst at each electrode so that we can extract electrical power
from the energy of the reaction. A battery is similar to a fuel cell except that now the fuel
and oxidant are stored and supplied within the cell rather than being supplied externally. A
fuel cell is usually operated as a continuous-flow reactor, while a battery is a rechargeable
batch reactor.
Crucial factors in designing membrane reactors are (1) high area for high mass transfer,
(2) membranes that have a high permeability to only one species, (3) membranes that are
catalytic, and (4) membranes that have no holes that leak reactants from one compartment
to the other. With any process the reactor will not function properly if all these criteria are
not met, and for oxidation reactions any leaks between compartments can be disastrous.
It should be evident, therefore, that the design of membrane reactors is largely
concerned with finding membranes that have sufficient area, catalytic activity, mechanical
strength, and freedom from cracks, holes, and clogging.

Figure 12-6 Sketches of membrane re-

actors to attain high areas for transfer of a
species.
488 Multiphase Reactors

FALLING FILM REACTOR

In the membrane reactor a wall of area separates the phases, and this area is generally
fixed by the geometry of the reactor using planar or cylindrical membranes. However,
most multiphase reactors do not have fixed boundaries separating phases, but rather allow
the boundary between phases to be the interfacial area between insoluble phases. This is
commonly a variable-area boundary whose area will depend on flow conditions of the
phases, as shown in Figure 12-7.
Before we deal with these situations, it is instructive to consider a fixed-area version
of a membraneless reactor, the falling film reactor. We cannot think of many applications of
this reactor type because one usually benefits considerably by using configurations where
the surface area is as large as possible, but the falling film reactor leads naturally to the
description of many variable-area multiphase reactors.
We consider a vertical cylindrical tube of length and diameter (radius with
liquid admitted at the top such that it forms a that coats the walls of the tube.
We also add a gas into the top of the tube or into the bottom (countercurrent).
This is a standard unit in extraction processes called a wetted-wall column.
In analysis of the wetted-wall column one finds the velocity profile in the film u(R)
and then places a solute A in one of the phases and calculates its extraction to the other phase
by first integrating across the liquid film to find and the average concentration, and
then integrating along the column to find and then When used as a chemical
reactor, we assume that species A is a reactant that reacts with another solute in the liquid
or with a catalyst in the liquid or on the walls of the column.
Since we do not want to consider the fluid mechanics of this reactor in detail, we will
assume that the liquid falls with a constant average velocity and forms a liquid film of
thickness with the radius in the tube at the surface of the liquid film. If these
assumptions hold, then and are independent of the position in the tube of
length (actually the height, since the tube must be vertical). Similarly, if the liquid film
thickness is constant, then the cross section occupied by the gas is constant, and the velocity
of the gas is also independent of if the density of the gas is constant. These distances
are sketched in Figure 12-8.
The interface between the gas and liquid is at and its area is

Figure 12-7 Sketches of four types of gas-liquid

multiphase reactors.

bubble catalytic wall trickle

column falling film bed
 Falling Film Reactor 489

Figure 12-8 Sketch of a falling film re-

actor with positions and indicated.
At the right are sketched possible concen-
tration profiles of a reactant A, which is
supplied in the gas but reacts in the liquid.

Since the phases are gas and liquid in this section, we use g and rather than and to
designate phases. The cross section of the tube is the gas will occupy a cross-sectional
area and the liquid will occupy a cross-sectional area The volumes
occupied by the phases are

=
=
so that the residence times are
L

Thus we have defined all the parameters for the reactor mass balances in gas and liquid
phases in terms of the inputs to the tube. In all this analysis we make the assumption that
all parameters are independent of height in the column.
Next we add solute A to the gas phase and solute B to the liquid phase and allow the
reaction

+ + De
to occur to form products C and D. We assume that the reactions are irreversible, and we
usually assume that the products can easily escape from this phase so the specific products
are not important. We further assume that reaction occurs only in the liquid phase with a rate

so that = 0.
Multiphase Reactors

The reactant A must be transferred from the gas phase into the liquid phase in order
to react with B. The rate of mass transfer per unit of area is

where is the equilibrium distribution of A between gas and liquid phases, as discussed
previously. The area of this interface is
We can now write the mass-balance equations for the phases as

We included the term = 0 to indicate that there is no reaction in the gas phase. The mass
transfer rates obviously have opposite signs, and we have to multiply the mass transfer
flux by [area/volume], where the volume is that occupied by that phase. Note that the mass
transfer term after dividing out becomes proportional to Since the reactor volume is
proportional to while the surface area for mass transfer is proportional to R, the falling film
column obviously becomes less efficient for larger reactor sizes. This is a fundamental problem
with the falling film reactor in that small tubes give high mass transfer rates but low total
production of product.
The mass transfer coefficient is usually much lower in the liquid phase, and therefore
is a function of R, the distance from the wall to the interface. One would have to
solve for the steady-state profile and find its average CA(Z) to insert into the
mass-balance equations simultaneously to find in each phase.

Example 12-1 An aqueous solution containing IO ppm by weight of an organic

of molecular weight 120 is to be removed by air oxidation in a l-cm-diameter falling
film reactor at 25°C. The liquid flows at an average velocity of 10 and forms a film 1
mm thick on the wall, while the air at 1 atm flows at an average velocity of 2
The reaction in the liquid phase has the stoichiometry A + products with a rate
=
(a) What are the compositions when the reaction has gone to completion?

We assume that both phases are in nearly plug flow, and we need first to calculate
the flow rates of each reactant.

= = x = 2.83
= = x x 2 = 1.005
The feed concentrations are

8.33 x moles/cm3
assuming the density of water is 1 g/cm3 and

= 8.58 x moles/cm3
 Falling Film Reactor 491

Therefore, the molar flow rates are

= = 2.83 x 8.33 x 2.36 x

= 1.005 x 8.58 x 8.62 x
Thus we see that there is an excess of so all A will be consumed at complete
conversion. This gives

(there are 2 moles of consumed per mole of A reacted), so that if the reaction goes
to completion, we have

= 0
6
= 8.14 x moles/cm3
which we will assume to be a negligible change in

(b) Write the equation(s) that must be solved to find the reactor length required for a given
organic removal.

At these flow rates the in the air is not depleted, and we do not need to worry about
the mass balance of the air in the gas phase. We only need to solve the equation for
the organic in the liquid phase, which is
e

(c) How many tubes in parallel are required to process 100 of water? What will
be the diameter of the tube bundle if the tubes are packed in a square array and the tube
wall thickness is neglected?

One tube processes 2.83 so to process 100 liters/mm we will need

100 x
590 tubes
2.83 x 60
If these are packed in a square configuration with a negligible tube wall thickness,
each tube occupies an area 1 in the tube bundle. The cross-sectional area of
the tube bundle is 590 so the diameter of the column is

= 27.4 cm 1 ft

(d) Estimate the reactor length needed to reduce the organic concentration to 1 ppm if the
reaction rate in the liquid is infinite and the reaction is limited by the mass transfer of in
the gas. Assume 0.1 sec.

This doesn’t seem to be a good approximation because mass transfer in gases is

almost always much faster than in liquids. If it were true, the Sherwood number
492 Multiphase Reactors

would be for laminar flow of the air flowing in the 0.8-cm-diameter tube. Thus
we have

=
We have to solve for A in the liquid phase,
A
=
The interfacial area per volume of reactor is
A
V =
and the equation becomes
Co,
dz =
The right-hand side is constant because Co, does not change significantly, so this
equation can be simply integrated to yield

0.031 cm
Co,
This answer is clearly nonsense because we would need a reactor length of less
than 1 millimeter!

(e) Estimate the reactor length needed to reduce the organic concentration to 1 ppm if
mass transfer is sufficiently fast that the liquid solution remains saturated with and the
rate coefficient is 1 x liter/mole sec. The Henry’s Law constant for in water is
1x atm.

Now mass transfer of is assumed to be fast so that the liquid remains saturated with
and the process is assumed to be limited by the reaction in the liquid phase.
Therefore, we have to solve the equation

We need the concentration in the liquid phase. We assume Henry’s Law

=
so that
0.2 x 32

which gives = 5.56 x moles/liter.

Recall that Co, nearly constant so this equation can be rearranged to yield

10
10 = 415 cm = = 16ft
x 5.56 x
 Bubble Column Reactors 493

a reasonable column height.

Estimate the reactor length needed to reduce the organic concentration to 1 ppm if the
reaction actually occurs on a catalyst on the wall of the reactor tube. Assume that the reaction
rate on the wall is infinite and the process is limited by the diffusion of through the liquid,
with = and that the concentration profile is linear.

Now we assume that reaction occurs on the exterior surface of the tube. The
equation to be solved is
Al
= --
v2

= -3.47 x moles/liter
The area for mass transfer per unit volume of reactor in the liquid is given by
A
11.1
V
We now solve the preceding differential equation, noting that all terms on the right-
hand side are constants to obtain the reactor length needed,

L= = 2160 cm = 22 meters = 70 ft
3.47 x
This is a very tall column.

(g) How would the answers to (c), (d), and (e) change if the pressure of air were increased
from 1 to 2 atm?

Doubling Co, will double the rate of the reaction and the rate of mass transfer
to the wall of the reactor. Therefore, the reactor length needed will be half of those
calculated in each of the previous situations.

BUBBLE COLUMN REACTORS

We just noted that the falling film reactor has the problem that the surface area increases as
the perimeter between gas and liquid while the volume increases as the cross section
area 2 1
volume gas volume D
In order to design an efficient reactor using a falling film reactor, we would need to have
many small tubes in parallel so that the interfacial area can be large. This is difficult
to accomplish with flow down tubes, but it is easy to accomplish with rising bubbles
or falling drops. The interfacial area is not now the area of between gas