1/4/2021 Membrane technology - Wikipedia
Membrane technology
Membrane technology covers all engineering approaches for the transport of substances between two
fractions with the help of permeable membranes. In general, mechanical separation processes for
separating gaseous or liquid streams use membrane technology.
Contents
Applications
Mass transfer
Solution-diffusion model
Hydrodynamic model
Membrane operations
Membrane shapes and flow geometries
Membrane performance and governing equations
Membrane separation processes
Pore size and selectivity
See also
Notes
References
Applications
Membrane separation processes operate without heating and
therefore use less energy than conventional thermal separation
processes such as distillation, sublimation or crystallization. The
separation process is purely physical and both fractions (permeate
and retentate) can be used. Cold separation using membrane
technology is widely used in the food technology, biotechnology and
pharmaceutical industries. Furthermore, using membranes enables
separations to take place that would be impossible using thermal
separation methods. For example, it is impossible to separate the
constituents of azeotropic liquids or solutes which form isomorphic Ultrafiltration for a swimming pool
crystals by distillation or recrystallization but such separations can
be achieved using membrane technology. Depending on the type of
membrane, the selective separation of certain individual substances or substance mixtures is possible.
Important technical applications include the production of drinking water by reverse osmosis
(worldwide approximately 7 million cubic metres annually), filtrations in the food industry, the recovery
of organic vapours such as petro-chemical vapour recovery and the electrolysis for chlorine production.
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In waste water treatment, membrane technology is becoming
increasingly important. With the help of ultra/microfiltration it is
possible to remove particles, colloids and macromolecules, so that
waste-water can be disinfected in this way. This is needed if waste-
water is discharged into sensitive waters especially those designated
for contact water-sports and recreation.
About half of the market is in medical applications such as use in
artificial kidneys to remove toxic substances by hemodialysis and as
artificial lung for bubble-free supply of oxygen in the blood. Venous-arterial extracorporeal
membrane oxygenation scheme
The importance of membrane technology is growing in the field of
environmental protection (NanoMemPro IPPC Database). Even in
modern energy recovery techniques membranes are increasingly
used, for example in fuel cells and in osmotic power plants.
Mass transfer
Two basic models can be distinguished for mass transfer through the membrane:
the solution-diffusion model and
the hydrodynamic model.
In real membranes, these two transport mechanisms certainly occur side by side, especially during ultra-
filtration.
Solution-diffusion model
In the solution-diffusion model, transport occurs only by diffusion. The component that needs to be
transported must first be dissolved in the membrane. The general approach of the solution-diffusion
model is to assume that the chemical potential of the feed and permeate fluids are in equilibrium with
the adjacent membrane surfaces such that appropriate expressions for the chemical potential in the fluid
and membrane phases can be equated at the solution-membrane interface. This principle is more
important for dense membranes without natural pores such as those used for reverse osmosis and in fuel
cells. During the filtration process a boundary layer forms on the membrane. This concentration
gradient is created by molecules which cannot pass through the membrane. The effect is referred as
concentration polarization and, occurring during the filtration, leads to a reduced trans-membrane flow
(flux). Concentration polarization is, in principle, reversible by cleaning the membrane which results in
the initial flux being almost totally restored. Using a tangential flow to the membrane (cross-flow
filtration) can also minimize concentration polarization.
Hydrodynamic model
Transport through pores – in the simplest case – is done convectively. This requires the size of the pores
to be smaller than the diameter of the two separate components. Membranes which function according
to this principle are used mainly in micro- and ultrafiltration. They are used to separate macromolecules
from solutions, colloids from a dispersion or remove bacteria. During this process the retained particles
or molecules form a pulpy mass (filter cake) on the membrane, and this blockage of the membrane
hampers the filtration. This blockage can be reduced by the use of the cross-flow method (cross-flow
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filtration). Here, the liquid to be filtered flows along the front of the membrane and is separated by the
pressure difference between the front and back of the membrane into retentate (the flowing concentrate)
on the front and permeate (filtrate) on the back. The tangential flow on the front creates a shear stress
that cracks the filter cake and reduces the fouling.
Membrane operations
According to the driving force of the operation it is possible to distinguish:
Pressure driven operations
microfiltration
ultrafiltration
nanofiltration
reverse osmosis
gas separation
Concentration driven operations
dialysis
pervaporation
forward osmosis
artificial lung
Operations in an electric potential gradient
electrodialysis
membrane electrolysis e.g. chloralkali process
electrodeionization
electrofiltration
fuel cell
Operations in a temperature gradient
membrane distillation
Membrane shapes and flow geometries
There are two main flow configurations of membrane
processes: cross-flow (or) tangential flow and dead-end
filtrations. In cross-flow filtration the feed flow is
tangential to the surface of membrane, retentate is
removed from the same side further downstream,
whereas the permeate flow is tracked on the other side.
In dead-end filtration the direction of the fluid flow is
normal to the membrane surface. Both flow geometries Cross-flow geometry
offer some advantages and disadvantages. Generally,
dead-end filtration is used for feasibility studies on a
laboratory scale. The dead-end membranes are relatively easy to fabricate which reduces the cost of the
separation process. The dead-end membrane separation process is easy to implement and the process is
usually cheaper than cross-flow membrane filtration. The dead-end filtration process is usually a batch-
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type process, where the filtering solution is loaded (or
slowly fed) into the membrane device, which then allows
passage of some particles subject to the driving force.
The main disadvantage of a dead end filtration is the
extensive membrane fouling and concentration
polarization. The fouling is usually induced faster at
higher driving forces. Membrane fouling and particle
retention in a feed solution also builds up a
concentration gradients and particle back flow
(concentration polarization). The tangential flow devices
are more cost and labor-intensive, but they are less
susceptible to fouling due to the sweeping effects and
high shear rates of the passing flow. The most commonly
used synthetic membrane devices (modules) are flat
sheets/plates, spiral wounds, and hollow fibers. Dead-end geometry
Flat plates are usually constructed as circular thin flat
membrane surfaces to be used in dead-end geometry modules. Spiral wounds are constructed from
similar flat membranes but in the form of a "pocket" containing two membrane sheets separated by a
highly porous support plate.[1] Several such pockets are then wound around a tube to create a tangential
flow geometry and to reduce membrane fouling. hollow fiber modules consist of an assembly of self-
supporting fibers with dense skin separation layers, and a more open matrix helping to withstand
pressure gradients and maintain structural integrity.[1] The hollow fiber modules can contain up to
10,000 fibers ranging from 200 to 2500 μm in diameter; The main advantage of hollow fiber modules is
very large surface area within an enclosed volume, increasing the efficiency of the separation process.
Hollow fiber Separation of air
Spiral wound membrane module
membrane module into oxygen and
nitrogen through a
membrane
Disc tube module is using a cross-flow geometry, and consists of a pressure tube and hydraulic discs,
which are held by a central tension rod, and membrane cushions that lie between two discs.[2]
Membrane performance and governing equations
The selection of synthetic membranes for a targeted separation process is usually based on few
requirements. Membranes have to provide enough mass transfer area to process large amounts of feed
stream. The selected membrane has to have high selectivity (rejection) properties for certain particles; it
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has to resist fouling and to have high mechanical stability. It also needs to be reproducible and to have
low manufacturing costs. The main modeling equation for the dead-end filtration at constant pressure
drop is represented by Darcy's law:[1]
where Vp and Q are the volume of the permeate and its volumetric flow rate respectively (proportional to
same characteristics of the feed flow), μ is dynamic viscosity of permeating fluid, A is membrane area,
Rm and R are the respective resistances of membrane and growing deposit of the foulants. Rm can be
interpreted as a membrane resistance to the solvent (water) permeation. This resistance is a membrane
intrinsic property and is expected to be fairly constant and independent of the driving force, Δp. R is
related to the type of membrane foulant, its concentration in the filtering solution, and the nature of
foulant-membrane interactions. Darcy's law allows for calculation of the membrane area for a targeted
separation at given conditions. The solute sieving coefficient is defined by the equation:[1]
where Cf and Cp are the solute concentrations in feed and permeate respectively. Hydraulic permeability
is defined as the inverse of resistance and is represented by the equation:[1]
where J is the permeate flux which is the volumetric flow rate per unit of membrane area. The solute
sieving coefficient and hydraulic permeability allow the quick assessment of the synthetic membrane
performance.
Membrane separation processes
Membrane separation processes have a very important role in the separation industry. Nevertheless,
they were not considered technically important until the mid-1970s. Membrane separation processes
differ based on separation mechanisms and size of the separated particles. The widely used membrane
processes include microfiltration, ultrafiltration, nanofiltration, reverse osmosis, electrolysis, dialysis,
electrodialysis, gas separation, vapor permeation, pervaporation, membrane distillation, and membrane
contactors.[3] All processes except for pervaporation involve no phase change. All processes except
(electro)dialysis are pressure driven. Microfiltration and ultrafiltration is widely used in food and
beverage processing (beer microfiltration, apple juice ultrafiltration), biotechnological applications and
pharmaceutical industry (antibiotic production, protein purification), water purification and wastewater
treatment, the microelectronics industry, and others. Nanofiltration and reverse osmosis membranes are
mainly used for water purification purposes. Dense membranes are utilized for gas separations (removal
of CO2 from natural gas, separating N2 from air, organic vapor removal from air or a nitrogen stream)
and sometimes in membrane distillation. The later process helps in the separation of azeotropic
compositions reducing the costs of distillation processes.
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Ranges of membrane based separations
Pore size and selectivity
The pore sizes of technical membranes are specified differently
depending on the manufacturer. One common distinction is by
nominal pore size. It describes the maximum pore size
distribution[4] and gives only vague information about the retention
capacity of a membrane. The exclusion limit or "cut-off" of the
membrane is usually specified in the form of NMWC (nominal
molecular weight cut-off, or MWCO, molecular weight cut off, with
units in Dalton). It is defined as the minimum molecular weight of a
globular molecule that is retained to 90% by the membrane. The cut-
off, depending on the method, can by converted to so-called D90, The pore distribution of a fictitious
which is then expressed in a metric unit. In practice the MWCO of ultrafiltration membrane with the
nominal pore size and the D90
the membrane should be at least 20% lower than the molecular
weight of the molecule that is to be separated.
Using track etched mica membranes[5] Beck and Schultz[6] demonstrated that hindered diffusion of
molecules in pores can be described by the Renkin[7] equation.
Filter membranes are divided into four classes according to pore size:
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Pore size Molecular mass Process Filtration Removal of
> 10 "Classic" filter
> 0.1 μm > 5000 kDa microfiltration < 2 bar larger bacteria, yeast, particles
100-2 nm 5-5000 kDa ultrafiltration 1-10 bar bacteria, macromolecules, proteins, larger viruses
2-1 nm 0.1-5 kDa nanofiltration 3-20 bar viruses, 2- valent ions[8]
< 1 nm < 100 Da reverse osmosis 10-80 bar salts, small organic molecules
The form and shape of the membrane pores are highly dependent on the manufacturing process and are
often difficult to specify. Therefore, for characterization, test filtrations are carried out and the pore
diameter refers to the diameter of the smallest particles which could not pass through the membrane.
The rejection can be determined in various ways and provides an indirect measurement of the pore size.
One possibility is the filtration of macromolecules (often dextran, polyethylene glycol or albumin),
another is measurement of the cut-off by gel permeation chromatography. These methods are used
mainly to measure membranes for ultrafiltration applications. Another testing method is the filtration of
particles with defined size and their measurement with a particle sizer or by laser induced breakdown
spectroscopy (LIBS). A vivid characterization is to measure the rejection of dextran blue or other colored
molecules. The retention of bacteriophage and bacteria, the so-called "bacteriachallenge test", can also
provide information about the pore size.
Nominal pore size micro-organism ATCC root number
0.1 μm Acholeplasma laidlawii 23206
0.3 μm Bacillus subtilis spores 82
0.5 μm Pseudomonas diminuta 19146
0.45 μm Serratia marcescens 14756
0.65 μm Lactobacillus brevis
To determine the pore diameter, physical methods such as porosimetry (mercury, liquid-liquid
porosimetry and Bubble Point Test) are also used, but a certain form of the pores (such as cylindrical or
concatenated spherical holes) is assumed. Such methods are used for membranes whose pore geometry
does not match the ideal, and we get "nominal" pore diameter, which characterizes the membrane, but
does not necessarily reflect its actual filtration behavior and selectivity.
The selectivity is highly dependent on the separation process, the composition of the membrane and its
electrochemical properties in addition to the pore size. With high selectivity, isotopes can be enriched
(uranium enrichment) in nuclear engineering or industrial gases like nitrogen can be recovered (gas
separation). Ideally, even racemics can be enriched with a suitable membrane.
When choosing membranes selectivity has priority over a high permeability, as low flows can easily be
offset by increasing the filter surface with a modular structure. In gas phase filtration different
deposition mechanisms are operative, so that particles having sizes below the pore size of the membrane
can be retained as well.
See also
Artificial membrane
Particle deposition
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Notes
1. Osada, Y., Nakagawa, T., Membrane Science and Technology, New York: Marcel Dekker, Inc,1992.
2. "RCDT Module - Radial Channel Disc Tube (RCDT) Module" (http://rcdt-module.com/rcdt-module/).
Radial Channel Disc Tube (RCDT) Module. Retrieved 2016-05-11.
3. Pinnau, I., Freeman, B.D., Membrane Formation and Modification, ACS, 1999.
4. TU Berlin script - 2 Principles of Membrane Processes ("Archived copy" (https://web.archive.org/we
b/20140416210417/http://www.verfahrenstechnik.tu-berlin.de/fileadmin/fg158/Dokumente/Skripte_Lo
esungen/MembranVL/K02_Grundlagen.pdf) (PDF). Archived from the original (http://www.verfahrens
technik.tu-berlin.de/fileadmin/fg158/Dokumente/Skripte_Loesungen/MembranVL/K02_Grundlagen.p
df) (PDF) on 2014-04-16. Retrieved 2013-09-06.; PDF-Datei; 6,85 MB) Page 6 (German)
5. Fleischer, R. L.; Price, P. B.; Walker, R. M. (May 1963). "Method of Forming Fine Holes of Near
Atomic Dimensions". Review of Scientific Instruments. 34 (5): 510–512.
Bibcode:1963RScI...34..510F (https://ui.adsabs.harvard.edu/abs/1963RScI...34..510F).
doi:10.1063/1.1718419 (https://doi.org/10.1063%2F1.1718419). ISSN 0034-6748 (https://www.world
cat.org/issn/0034-6748).
6. Beck, R. E.; Schultz, J. S. (1970-12-18). "Hindered Diffusion in Microporous Membranes with Known
Pore Geometry". Science. 170 (3964): 1302–1305. Bibcode:1970Sci...170.1302B (https://ui.adsabs.
harvard.edu/abs/1970Sci...170.1302B). doi:10.1126/science.170.3964.1302 (https://doi.org/10.112
6%2Fscience.170.3964.1302). ISSN 0036-8075 (https://www.worldcat.org/issn/0036-8075).
PMID 17829429 (https://pubmed.ncbi.nlm.nih.gov/17829429).
7. Renkin, Eugene M. (1954-11-20). "Filtration, diffusion, and molecular sieving through porous
cellulose membranes" (https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2147404). The Journal of
General Physiology. 38 (2): 225–243. ISSN 0022-1295 (https://www.worldcat.org/issn/0022-1295).
PMC 2147404 (https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2147404). PMID 13211998 (https://pu
bmed.ncbi.nlm.nih.gov/13211998).
8. Experience and potential application of nanofiltration - University of Linz (German) (PDF (http://www.i
vt.uni-linz.ac.at/Forschung/Publikationen/pdf/Membrantechnik%20in%20der%20Prozessindustrie.pd
f) Archived (https://web.archive.org/web/20130405101223/http://www.ivt.uni-linz.ac.at/Forschung/Pu
blikationen/pdf/Membrantechnik%20in%20der%20Prozessindustrie.pdf) 2013-04-05 at the Wayback
Machine)
References
Osada, Y., Nakagawa, T., Membrane Science and Technology, New York: Marcel Dekker, Inc,1992.
Zeman, Leos J., Zydney, Andrew L., Microfiltration and Ultrafitration, Principles and Applications.,
New York: Marcel Dekker, Inc,1996.
Mulder M., Basic Principles of Membrane Technology, Kluwer Academic Publishers, Netherlands,
1996.
Jornitz, Maik W., Sterile Filtration, Springer, Germany, 2006
Van Reis R., Zydney A. Bioprocess membrane technology. J Mem Sci. 297(2007): 16-50.
Templin T., Johnston D., Singh V., Tumbleson M.E., Belyea R.L. Rausch K.D. Membrane separation
of solids from corn processing streams. Biores Tech. 97(2006): 1536-1545.
Ripperger S., Schulz G. Microporous membranes in biotechnical applications. Bioprocess Eng.
1(1986): 43-49.
Thomas Melin, Robert Rautenbach, Membranverfahren, Springer, Germany, 2007, ISBN 3-540-
00071-2.
Munir Cheryan, Handbuch Ultrafiltration, Behr, 1990, ISBN 3-925673-87-3.
Eberhard Staude, Membranen und Membranprozesse, VCH, 1992, ISBN 3-527-28041-3.
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