Addis Ababa Science and Technology University

College Of Biological and Chemical Engineering

Department Of Chemical Engineering

Structured Reactive Systems ( Membrane Reactor )

By Melkamu Zeryihun

Submitted To Dr. Aman Kassaye

 Presentation Outline
Introduction
Membrane reactors
Membrane reactor design parameters
Types of Membrane and Membrane module
Membrane reactors technology in process intensification
Application
Introduction
• The concept of membrane processes is relatively simple but nevertheless often
unknown. Membranes (lat.: membrane = thin skin) might be described as
conventional filters (like a coffee filter) but with much finer mesh or much smaller
pores to enable the separation of tiny particles, even molecules (Z.F.Cui and H.S.
Muralidhara 2010).
• According to a definition given by the European Membrane Society, the
membrane is an intervening phase separating two phases and/or acting as
an active or passive barrier to the transport of matter between phases.
Basically, it is a thin layer that can separate materials depending on their
physical and chemical properties when a driving force, a gradient of
either chemical potential (concentration or pressure gradient) or
electrical potential, is applied across the membrane (Lawrence K. Wang,
et.al.2011).
 Membrane reactors
Membrane Reactor: A reactor equipped with a membrane that can serve
either as an extractor to remove products to shift equilibrium, as a distributor
to control the addition of reactants, or as an active contactor to control
diffusion of reactants (ravanchi, m. T., Kaghazchi, t., & Kargari, a. (2009).
Generally, MRs are classified into extractor, distributor, and contactor types.
1. In the extractor type, the membrane removes one or more products from the
reactor, thus promoting the reaction and shifting thermodynamic equilibrium;
2. In the distributor configuration, the membrane’s role is to distribute one or
more reactants along the reaction environment to ensure more uniform
reactions and avoid cold and hot spots;
3. In the contactor MR, a catalytic membrane is installed in order to improve
contact of reactants, thus increasing catalyst activity.
 Cont.
 Concerning the extractor‐type, which is the most diffused and interesting configuration
for industrial applications, Two different layouts have been proposed (Angelo Basile, et.al
2016). :-
 The Integrated Membrane Reactor (IMR), where the selective membrane is directly
assembled in the reaction environment, thus allowing the reaction and products
separation in one single compact device, and
 The Staged Membrane Reactor (SMR) composed of a series of reactor and separation
module steps.

Extractor, distributor, and contactor membrane reactor types for the general reaction
A + B ↔C + D Adapted from ( Angelo Basile, et.al 2016)
 Types of Membrane

1. Symmetric membranes and asymmetric membranes are two basic types of membrane
based on their structure. Symmetric membranes include non-porous (dense) symmetric
membranes and porous symmetric membranes, while asymmetric membranes include
integrally skinned asymmetric membranes, coated asymmetric membranes and
composite membranes.
• Microporous membranes are characterized by the membrane pores throughout the
membrane bodies. The pores are of uniform size (isotropic) or non-uniform size
(anisotropic-pic). Microporous membranes are designed to reject all the species
above their ratings. However, they tend to be blocked by the species that are of
similar sizes as the pores.
• The asymmetric membrane has a selective skin layer on the top of its membrane
body. The membrane body is usually void, only giving mechanical support to the
selective skin layer. Compared to the microporous membranes, the asymmetric
membranes rarely get blocked
 Cont.

Microporous Membrane
Asymmetry membrane
https
https
://ars.els-cdn.com/content/image/1-s2.0-S2211339815000301-fx1.jpg
://ars.els-cdn.com/content/image/1-s2.0-S0360319918341867-fx1.j
pg
Cont.
2. Membranes can be organic (polymeric) or inorganic (ceramic or metallic), according
to its composition, and their morphology is dependent on the nature of the material. A
membrane separation system separates an influent stream into two effluent streams:
the permeate and the retentate or concentrate. The permeate is the portion of the fluid,
which has passed through the membrane. The retentate (concentrate) contains the
constituents that have been rejected by the membrane (Lawrence K. Wang, et.al.2011)
 Polymeric or organic Membrane
Organic membranes are usually made up of various polymers, among which the
typical ones are cellulose acetate (CA), polyamide (PA), polysulfone (PS),
polyethersulfone (PES), poly-vinylidene fluoride (PVDF), polypropylene (PP), etc.
Polymeric membranes are relatively cheap, easy to manufacture, available in a wide
range of pore sizes, and they have been widely used in various industries (Z.F.Cui and
H.S. Muralidhara 2010).
Nevertheless, most of the polymeric membranes have limitations on one or more
operating conditions (either pH, or temperature, or pressure, or chlorine tolerance,
etc.), which hinder their wider applications.
Cont.
Inorganic Membrane
• Inorganic membranes (such as γ-alumina/α-alumina, borosilicate glass,
pyro-lyzed carbon, zirconia/stainless steel, or zirconia/carbon) have strong
tolerance to even extreme operating conditions.
• Due to their obvious advantages of high mechanical strength, and
chemical and thermal stability over the conventional polymeric
membranes, they have extended the application of membrane technology
into many new areas. They have wide limits of temperature, pH, and
pressure, and have extended lifetime. (Z.F.Cui and H.S. Muralidhara 2010).

Adapted from (Lawrence K. Wang, et.al.2011)

 Membrane reactor design parameters
The parameters that need to be determined or calculated for a design included are as
follows (Z.F.Cui and H.S. Muralidhara 2010). :
1. Related to the mass balance of the target separation: permeate and concentrate flow rates,
which, together with the membrane rejection, allow computing the amount of relevant
substances in both streams (and yield).
2.Related to the operation variables: feed pressure, temperature, membrane permeation rate
(averaged), and rejection (as a function of pressure, temperature, and feed concentration or
recovery).
3. Related to the system design: mode of operation, total number of elements, housings and
skids, arrangement of the elements inside housings, configuration, and staging.
The large surface areas are required for industrial applications of membrane processes. A
practical solution for providing this large surface area is packing the membranes into a
small unit called module. The module is the base for membrane installation and process
design.
 Membrane Module
Membrane module is the way the membrane is arranged into devices and
hardware to separate the feed stream into permeate and retentate streams.
During the process, a stream of feed enters the module with a specific
content at a specific flow rate. By passing through the membrane module,
the feed stream is separated into two streams: a retentate stream and a
permeate stream. There are four kinds of membrane modules that have been
widely used in industry (Z.F.Cui and H.S. Muralidhara 2010).They are
(1) Tubular modules,
(2) Hollow fiber modules,
(3) Flat sheet modules, and
(4) Spiral-wound modules.
 Membrane Module
1. Tubuluar Module
Tubular modules are composed of a number of membrane tubes assembled in a shell-
and-tube arrangement. The membrane tubes are usually made up of porous fabric or
plastic support with selective membranes on the inside. The internal diameters of the
tubes generally range from 5 to 25 mm, and the tube lengths are in the range of 0.6 to 6
m (Z.F.Cui and H.S. Muralidhara 2010).

https://synderfiltration.com/2014/wp-content/uploads/2014/07/LC24-Tubular-Module.jpg
 Membrane Module
2. Hollow fiber modules
Hollow fiber modules are actually the “thin” tubular membranes in compact modules, but in
the form of self-support that enables them to withstand high backpressure. Normally, hollow
fiber modules are composed of 50-3000 individual hollow fibers, bundled and sealed together
on each end with epoxy in a hydraulically symmetric housing. The fiber diameters typically
range from 0.2 to 3 mm (except those used in RO, which may be as thin as 0.04 mm and can
withstand much higher pressure) (Z.F.Cui and H.S. Muralidhara 2010).

https://www.researchgate.net/publicati
on/255766706/figure/fig2/AS:2979695
43860228@1448052883697/Sketch-of-
a-hollow-fibre-membrane-bioreactor-Th
e-hollow-fibre-membrane-acts-as-the-bl
ood.png
 Membrane module
3. Flat sheet modules
Flat sheet modules comprise a selective flat sheet membrane on the top and a flat plate at the
bottom, between which a net-like material is placed to provide space for the permeate
removal, and on the other side of the flat plate, another sheet membrane and another net-like
material are placed in mirror to form a sandwich-like module. With regard to packing
density, energy consumption, and cost, flat sheet modules lie in between tubular modules
and spiral-wound modules (Z.F.Cui and H.S. Muralidhara 2010).

https://www.researchgate.net/profile/Ping
 Membrane Module

4. Spiral-wound modules
Spiral-wound modules are constructed from a number of membrane envelopes. Two
membrane sheets are glued together on three sides to form an envelope. The fourth edge is
attached to a central collecting tube, around which one or more envelopes are wound. The
feed flows parallel to the central tube outside the membrane envelopes (axially). Material
permeates into the interior of the membrane envelopes and flows along the spiral, towards
the central tube. The modules are almost always operated with a cross-current flow pattern
(James Ingram Marriott, February 2001).

https://vertassets.blob.core.windows.net/image/fa
34f1c8/fa34f1c8-a37f-4c50-bdc4-
341ca2991446/375_250-spiralmembrane.jpg
Schematics classification of the Membrane . Adapted from (Angelo Basile, et.al 2016).
 Membrane Reactors Technology in process intensification

• A Membrane Reactor (MR) combines a chemical reaction with the separation

process of a reactant or a product. MR technology perfectly fits the Process
Intensive (PI) strategy focused on :
The reduction in the unit number in the chemical processes,
 Boosting efficiency and
Reducing environmental impact and installation costs
 Coupling a reaction with the separation step allows the development of more
compact units, replacing the conventional energy‐intensive separation techniques.
 Compared to the traditional reactors coupled with a separation step, a MR requires
a lower amount of energy, leading to an increased productivity and easier
downstream processing.
 Application Area
Membrane separation processes can be used for a wide range of applications and
can often offer significant advantages over conventional separation such as
distillation and adsorption since the separation is based on a physical mechanism.
Compared to conventional processes, therefore, no chemical, biological, or
thermal change of the component is involved for most mem-brane processes.
Membrane technology can be applied to particle – liquid separation, liquid -
liquid separation as well as gas separation (James Ingram Marriott, February
2001).
Solid - Liquid Separation (Reverse osmosis, Ultrafiltration, Microfiltration
Dialysis, Electro dialysis),
Liquid-Mixture Separation (Pervaporation, Perstraction)
Gas Mixture Separation (Gas separation).
 Membranes are applied to fluid treatment and they can be involved in different
processes such as Microfiltration (MF), Ultrafiltration (UF), Nano filtration (NF),
Pervaporation (PV), Gas Permeation (GP), Vapor Permeation (VP), and Reverse
Osmosis (RO) processes.
1. MF is related to the filtration of micron and submicron size particulates from liquid
and gases.
2. UF refers to the removal of macromolecules and colloids from liquids containing ionic
species.
3. PV refers to the separation of miscible liquids
4. The selective separation of mixtures of gases and vapor and gas mixtures are called GP
and VP, respectively.
5. RO refers to the (virtual) complete removal of all material, suspended and dissolved,
from water or other solvents.
Table Characterizations and applications of industrial membrane technology (James
Ingram Marriott, February 2001).
Steam reforming is an endothermic process for producing
hydrogen and carbon oxides from methane or syngas; it requires a
multistep process to overcome the thermodynamic equilibrium
limitations. Alternatively, removing the hydrogen produced by
using an MR means that, on the one hand it does not suffer from
thermodynamic limitations, but on the other hand, it allows
reduction of the seven steps needed to just the one (Angelo Basile,
et.al 2016).
The main industrial processes in which the catalytic membrane
may be used (steam reforming, water‐gas shift, auto‐thermal
reforming, dehydrogenation, and fuel cell) is provided.
Stem reforming process Adapted from (Angelo Basile, et.al 2016).
 Obstacles In Membrane reactor technology
 There are several key obstacles to move into an industrial/commercial
phase of membrane reactors ((Angelo Basile, et.al 2016):
1. Membrane stability under the process conditions and during accelerated aging
test for membrane life. The operating test of membranes is still reduced to less
than 5000 h, which is quite a limited time frame for commercial application.
2. Current lack of an emerging technology for membrane manufacturing to which
high fabrication costs and no commercial‐scale production unit are associated.
 Conclusion
 For the better use of resource and energy efficiency as well as to reduce the
environmental impact in the future production require development of new
process architectures and technologies that reduce process stages ,unit
operations, recycling in equilibrium driven reaction ,and energy intensity in
product recovery. Implementing membrane reactors technology within
process schemes is a necessary direction to proceed along.
 Reference
1. Angelo Basile,et.al. 2016. Membrane Reactor Engineering Applications for a Greener Process
Industry. John Wiley & sons, ltd, the Atrium, southern Gate, chichester, West sussex, Po19 8sq,
united Kingdom
2. James Ingram Marriott, February 2001.Detailed Modelling and Optimal Design Of Membrane
Separation Systems. Department of Chemical Engineering University College London
3. Lawrence K. Wang, et.al.2011. Membrane and Desalination Technologies. Handbook Of
Environmental engineering. Volume 13 .Human press
4. Ravanchi, m. T., Kaghazchi, t., & Kargari, a. 2009. Application of membrane separation processes
in petrochemical industry: a review. Desalination, 235(1), 199-244.)
5. Z.F.Cui and H.S. Muralidhara 2010. Membrane Technology A Practical Guide to Membrane
Technology and Applications in Food and Bioprocessing.Elsever .