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By: M.Wadah Jawich
Gas Separation Membranes
1. Types of Membranes
I. II. III.
Microporous Membranes Nonporous, Dense Membranes Electrically Charged Membranes
Anisotropic Membranes Ceramic, Metal and Liquid Membranes
2. Membrane Processes
I. II. III.
Developed membrane separation industrial technologies
Microfiltration and Ultrafiltration Reverse osmosis Electrodialysis
Developing industrial membrane separation technologies
Gas separation Pervaporation
I. II. III.
To-be-developed membrane separation technologies
Carrier facilitated transport Membrane contactors Piezodialysis membrane
III. Natural Gas Separations Dehydration H2 Separation . II. IV.3. II. Metal Membranes Polymeric Membranes Ceramic and Zeolite Membranes Mixed-matrix Membranes Applications of Gas Separation Membranes I. III. Gas Separation Membrane Membrane Materials and Structure I.
V. IV. VI. VII.4. Slip Casting Tape Casting Pressing Extrusion Sol-Gel Process Dip Coating Chemical Vapor Deposition (CVD) Zeolite membranes Silica membranes Carbon membranes Industrial Ceramic Membranes A. Summary and Conclusion . C. III. II. B. Ceramic Membranes for Gas Separation Preparation of Ceramic Membranes I. 5.
y For a porous ceramic membrane. they are typically governed by : Thickness y Pore size y Surface porosity of the membrane.Introduction y In general. y Permeability and separation factor of a ceramic membrane are the two most important performance indicators . y . a membrane can be described as a permselective barrier or a fine sieve.
What Does A Ceramic Membrane Consist Of?
y Ceramic membranes are usually composite ones consisting of several layers of one or
more different ceramic materials.
y They generally have:
y A macroporous support y One or two mesoporous intermediate layers y And a microporous (or a dense) top layer.
y The bottom layer provides mechanical support, while the middle layers bridge the
pore size differences between the support layer and the top layer where the actual separation takes place.
Commonly used materials for ceramic membranes are Al2O3, TiO2, ZrO2, SiO2 etc. or a combination of these materials
y Most commercial ceramic membranes are in disc, plate or tubular configuration in
order to increase the surface area to volume ratio , which gives more separation area per unit volume of membrane element
SEM micrograph of a layered ceramic membrane for oxygen permeation
and plate-and-frame modules were also developed y . y Through the nineteenth and early twentieth centuries. hollow-fine-fiber. capillary.1 m or less . y Building on the original Loeb Sourirajan technique. were developed for making high performance membranes with selective layers as thin as 0. Methods of packaging membranes into large-membrane-area spiral-wound. including interfacial polymerization and multilayer composite casting and coating.A Brief Overview On The Development of Artificial Membranes y Systematic studies of membrane phenomena can be traced to the eighteenth century philosopher scientists. y The period from 1960 to 1980 produced a significant change in the status of membrane technology. but were used as laboratory tools to develop physical/chemical theories. Other membrane formation processes. membranes had no industrial or commercial uses.
y The principal development in the 1980s was the emergence of industrial membrane gas separation processes. microfiltration.y By 1980. The first major development was the Monsanto Prism membrane for hydrogen separation. a small German engineering company. introduced in 1980. y Gas separation technology is evolving and expanding rapidly. of the first commercial pervaporation systems for dehydration of alcohol. y Within a few years. further substantial growth will be seen in the coming years . y The final development of the 1980s was the introduction by GFT. ultrafiltration. reverse osmosis and electrodialysis were all established processes with large plants installed worldwide. and Cynara and Separex were producing systems to separate carbon dioxide from natural gas. Dow was producing systems to separate nitrogen from air.
Ceramic.Nonporous.Microporous Membranes 2. Metal and Liquid Membranes .Isotropic Membranes 1.A. Dense Membranes 3.Electrically Charged Membranes B-Anisotropic Membranes C.
Isotropic Membranes.01 to 10 m in diameter. on the order of 0. It has a rigid. highly voided structure with randomly distributed. these pores differ from those in a conventional filter by being extremely small. 1. interconnected pores. However. . Separation of solutes by microporous membranes is mainly a function of molecular size and pore size distribution.A. All particles larger than the largest pores are completely rejected by the membrane.Microporous Membranes A microporous membrane is very similar in structure and function to a conventional filter.
. The separation of various components of a mixture is related directly to their relative transport rate within the membrane. Nonporous. concentration. dense membranes consist of a dense film through which permeants are transported by diffusion under the driving force of a pressure. which is determined by their diffusivity and solubility in the membrane material.2. Dense Membranes. or electrical potential gradient.Nonporous.
and to a much lesser extent by the pore size. The separation is affected by the charge and concentration of the ions in solution. A membrane with fixed positively charged ions is referred to as an anionexchange membrane because it binds anions in the surrounding fluid.Electrically Charged Membranes. with the pore walls carrying fixed positively or negatively charged ions. Similarly. . a membrane containing fixed negatively charged ions is called a cation-exchange membrane. but are most commonly very finely microporous. Electrically charged membranes can be dense or microporous. Separation with charged membranes is achieved mainly by exclusion of ions of the same charge as the fixed ions of the membrane structure.3.
the substructure functions as a mechanical support. the membrane should be as thin as possible. The advantages of the anisotropic membranes is higher fluxes. therefore.B. . Anisotropic Membranes The transport rate of a species through a membrane is inversely proportional to the membrane thickness. High transport rates are desirable in membrane separation processes for economic reasons. The separation properties and permeation rates of the membrane are determined exclusively by the surface layer.
The surface layer and its substructure may be formed in a single operation or separately . porous substructure.Anisotropic membranes consist of an extremely thin surface layer supported on a much thicker.
and supported liquid films are being developed for carrier-facilitated transport processes . Dense metal membranes. a special class of microporous membranes. Metal and Liquid Membranes Ceramic membranes. are being used in ultrafiltration and microfiltration applications for which solvent resistance and thermal stability are required . Ceramic. are being considered for the separation of hydrogen from gas mixtures. particularly palladium membranes.C.
A- l 1.l ctr i l sis r s r ti i stri l t c l i s ltr filtr ti 12- l ss r i r ti r ti i stri l r s r ti t c l i s - - - l r rt s r ti t c l i s 1.i i l sis r .icr filtr ti 2rs s sis 3.rri r f cilit t tr s 2r c t ct rs 3.
separation is .A.Reverse osmosis. such proteins.Developed Membrane Separation Industrial Technologies 1.Microfiltration membranes filter colloidal particles and bacteria -Ultrafiltration membranes can filter dissolved macromolecules.Microfiltration and Ultrafiltration In ultrafiltration and microfiltration the mode of molecular sieving through increasingly fine pores. In osmosis membranes the membrane pores are so small and are within the range of thermal motion of the polymer chains that form the membrane. from solutions as 2. . The accepted mechanism of transport through these membranes is called the solution-diffusion model.
each formed by a pair of anion and cation exchange membranes.3.Electrodialysis A charged membranes are used to separate ions from aqueous solutions under the driving force of an electrical potential difference. built on the filter-press principle and containing several hundred individual cells. The process utilizes an electrodialysis stack. .
Gas separation In gas separation.Developing Membrane Separation Industrial Technologies 1.B. Major current applications of gas separation membranes are the separation of hydrogen from nitrogen. the membrane permeate is enriched in this species. the production of nitrogen from air. and the separation of carbon dioxide from methane in natural gas operations . a gas mixture at an elevated pressure is passed across the surface of a membrane that is selectively permeable to one component of the feed mixture. argon and methane in ammonia plants.
Pervaporation In pervaporation. Pervaporation offers the possibility of separating closely boiling mixtures or azeotropes that are difficult to separate by distillation or other means (the dehydration of 90 95% ethanol solutions) .2. a liquid mixture contacts one side of a membrane. and the permeate is removed as a vapor from the other. The driving force for the process is the low vapor pressure on the permeate side of the membrane generated by cooling and condensing the permeate vapor.
Membrane Contactors Membrane contactors are devices that allow a gaseous phase and a liquid phase to come into direct contact with each other. A typical use for these devices is the removal or dissolution of gases in water.To-Be. for the purpose of mass transfer between the phases.Developed Membrane Separation Technologies 1. . without dispersing one phase into the other. The carrier agent reacts with one component of a mixture on the feed side of the membrane and then diffuses across the membrane to release the permeant on the product side of the membrane.Carrier Facilitated Transport It employs liquid membranes containing a complexing or carrier agent. 2.C.
Piezodialysis Membrane If fixed-ions of both anion and cation species are attach to a polymeric membrane. A zeolite-based piezodialysis membranes are being developed for desalination processes and some medical applications in urology and cardiology . leaving a diluted aqueous stream on the pressurized side.3. pressure can be used as the driving force to transport both ions of a salt across a single membrane.
III. Natural Gas Separations Dehydration H2 Separation . III. II. IV. II. Metal Membranes Polymeric Membranes Ceramic and Zeolite Membranes Mixed-matrix Membranes Applications of Gas Separation Membranes I.Membrane Materials and Structure I.
y If the pores are < 0. and no separation occurs.1 to 10 m : => Gases permeate the membrane by convective flow. and the transport rate of any gas is inversely proportional to the square root of its molecular weight. Three types of porous membranes.1 m: => The pore diameter is the mean free path of the gas molecules : => Diffusion through such pores is governed by Knudsen diffusion. are shown in the figure below.Theoretical Background Both porous and dense membranes can be used as selective gas separation barriers. y If the pores size = 0. . differing in pore size.
. => Transport includes both diffusion in the gas phase and diffusion of adsorbed species on the surface of the pores (surface diffusion).y If the pores are extremely small. of the order 5 20 A => gases are separated by molecular sieving.
the metal membrane must be operated at high temperatures (>300 C) to obtain useful permeation rates and to prevent embrittlement and cracking of the metal by adsorbed hydrogen. . iron. copper. being extremely permeable to hydrogen but essentially impermeable to all other gases.Hydrogen permeates a number of metals including palladium. nickel. cobalt and platinum. vanadium.Membrane Materials and Structure 1. tantalum. *.Metal Membranes *. *.In most cases. niobium. *-Hydrogen-permeable metal membranes are extraordinarily selective.The study of gas permeation through metals began with Graham s observation of hydrogen permeation through palladium.
Hydrogen permeation through a metal membrane is believed to follow the multistep process illustrated in the figure .
=> The capillary forces generated as the liquid evaporates cause collapse of the finely microporous substrate of the cellulose acetate membrane. then for hexane. destroying its usefulness.Early gas separation membranes were adapted from the cellulose acetate membranes produced for reverse osmosis. *.Polymeric Membranes *. *.This problem has been overcome by a solvent exchange process in which the water is first exchanged for an alcohol.These membranes are produced by precipitation in water.Experience has shown that gas separation membranes are far more sensitive to minor defects. such as pinholes in the selective membrane layer.2. the water must be removed before the membranes can be used to separate gases. than membranes used in reverse osmosis or ultrafiltration . *.
These membranes are all multilayer composite structures formed by coating a thin selective ceramic or zeolite layer onto a microporous ceramic support.Ceramic and Zeolite Membranes *. in which the thin zeolite layer is crystallized at high pressure and temperature directly onto the microporous support.Ceramic membranes are prepared by the sol gel process .Zeolite membranes are prepared by direct crystallization. *-This stability makes ceramic microfiltration/ultrafiltration membranes particularly suitable for food.3.These microporous membranes are made from aluminum. *. biotechnology and pharmaceutical applications. .Ceramic membranes have the advantages of being chemically inert and stable at high temperatures. conditions under which polymer membranes fail. . *. titanium or silica oxides.
The ceramic and zeolite membranes have exceptional selectivities for a number of important separations. *. However. *.Mixed-Matrix Membranes *. the membranes are not easy to make and expensive for many separations. Such membranes are called mixed-matrix membranes.4. .One solution to this problem is to prepare membranes from materials consisting of zeolite particles dispersed in a polymer matrix.These membranes are expected to combine the selectivity of zeolite membranes with the low cost and ease of manufacture of polymer membranes.
Propane and other hydrocarbons. because of their condensability. some propane and butane. *-Carbon dioxide is best separated by glassy membranes (utilizing size selectivity) *. .The major component of raw natural gas is methane. and other hydrocarbons in the high-pressure residue gas. carbon dioxide. the gas contains undesirable impurities: water. nitrogen and hydrogen sulfide. Natural gas also contains significant amounts of ethane. typically 75 90% of the total.Natural Gas Separations *. impurities must be removed from the gas. ethane. *.To minimize recompression costs at gas processing plants. is best separated by rubbery membranes (utilizing sorption selectivity).Applications of Ceramic Membranes 1. which is larger and more condensable than carbon dioxide.Hydrogen sulfide. leaving the methane. *. are best separated from methane with rubbery sorption-selective membranes. and 1 3% of other higher hydrocarbons. In addition.
The relative size and condensability (boiling point) of the principal components of natural gas. Glassy membranes generally separate by differences in size. rubbery membranes separate by differences in condensability .
However. low-pressure permeate gas is recompressed and cooled. the wet. but the capital cost of the system approximately doubles . a small one-stage system removes 90% of the water in the feed gas.Dehydration *. The natural gas that permeates the membrane is then recovered.Currently glycol dehydrators are widely used. *. increasingly common sources of natural gas *.2. In the first design. so the water vapor condenses and is removed as liquid water.Membrane processes offer an alternative approach to natural gas dehydration. Two possible process designs are available. This gas contains the removed water In the second design. glycol dehydrators are not well suited for use on small gas streams or on offshore platforms.All natural gas must be dried before entering the national distribution pipeline to control corrosion of the pipeline and to prevent formation of solid hydrocarbon/water hydrates that can choke valves. producing a low-pressure permeate gas representing 5 6% of the initial gas flow.
.Dehydration of natural gas is easily performed by membranes but high cost may limit its scope to niche applications.
Post-treat existing zeolite membranes to systematically reduce the pore size and/or the number of defects. CO2. CO). . because they either have zeolite pores too big for separating H2 from other light gases or have many non-zeolite pores bigger than the zeolite pores.3-0. *-To accomplish this sieving we need to: A.4 nm in size and 0. CH4). the zeolite membrane will have to discriminate between molecules that are approximately 0.H2 Separation *-It is desirable to develop inorganic zeolite membranes that are capable of highly selective H2 separation from other light gases (CO2.3.Synthesize zeolite membranes with small pore in this size range B. so called defects.1 nm or less in size difference. *-To selectively separate H2 from other light gases (CO. CH4. *-Currently used zeolite membranes have not been successful for H2 separation.
V. B. Slip Casting Tape Casting Pressing Extrusion Sol-Gel Process Dip Coating Chemical Vapor Deposition (CVD) Indusrtial Ceramic Membranes A. Zeolite membranes Silica membranes Carbon membranes . C. III.Preparation of Ceramic Membranes I. VII. VI. IV. II.
In most cases. *. *. giving extremely high selectivity towards oxygen or hydrogen.Ceramic Membranes For Gas Separation y There are two types of ceramic membranes suitable for gas separations: (1) dense and (2) porous. y Dense Ceramic Membranes are made from crystalline ceramic materials such as fluorites.They are usually prepared as a thin film supported on a macroporous ceramic support. they are mostly impermeable to all other gases. membranes. . some intermediate layers are required between the macroporous support and the top separation layer to bridge the gap between the large pores of the support and the small pores of the top separation layer.They are mainly composed of amorphous silica or zeolites. which provides mechanical strength. which allow permeation of only oxygen or hydrogen through the crystal lattice. y Microporous Ceramic Membranes with pore sizes less than 2 nm. *. but offers minimal gas transfer resistances. Therefore. especially microporous.
monolith or tube (3) Consolidation of the membrane precursor by a heat treatment at high temperatures. . preparation of ceramic membranes involves several steps: (1) Formation of particle suspensions.Preparation of Ceramic Membranes y In general. (2) Packing of the particles in the suspensions into a membrane precursor with a certain shape such as flat sheet.
A generalized flow sheet for preparation of ceramic membranes using various conventional methods .
solvent of suspension is extracted into the pores of the mould via the capillary driving force or capillary suction.Slip Casting *.When a well mixed powder suspension (slurry) is poured into a porous mould. consolidated on the surface of the mould to form a layer of particles or a gel layer. .1. therefore. The slip particles are.
2. a moving carrier and a drying zone. a reservoir for powder suspensions. *-The wet cast layer passes into a drying chamber. and the solvent is evaporated from surface. speed of carrier and viscosity of the powder suspension. Other variables which are important include reservoir depth.The process consists of a stationary casting knife. the powder suspension is poured into a reservoir behind the casting knife. . *-The casting knife gap between the knife blade and carrier determines the thickness of the cast layer. In preparing flat sheet ceramic membranes.Tape Casting *. leaving a dry membrane precursor on the carrier surface. and the carrier to be cast upon is set in motion.
*. the thickness is often around 0. .5 mm and the disc is dense after firing.The particle consolidation into a dense layer occurs by an applied force.Pressing *. The diameter of the disc is usually a few of cm. This easily handled pressure press method has been frequently employed in screening new ionic and mixed conducting materials for development of oxygen or hydrogen permeable ceramic membranes.3.A special press machine is used to apply more than 100 MPa pressure to press powders into a compacted disc.
y In extrusion: a stiff paste is compacted and shaped by forcing it through a nozzle. A requirement is that the precursor should exhibit plastic behavior. . y In spinning: a viscous solution or suspension is transformed into a stable shape in a coagulation bath through a spinneret.The extrusion process is similar to fibre spinning processes. that is at lower stresses behave like a rigid solid and deform only when the stress reaches a certain value called the yield stress. the precursor made by extrusion possesses a homogeneous structure over the cross section. but there are a few differences between extrusion and spinning. while it shows an asymmetric structure if prepared through the spinning process.4.Extrusion *. y In addition.
where it forms a colloidal gel. in which metal organic precursors are mixed with organic solvent to form a sol. which is then coated on a membrane support.There are two main routes through which the sol-gel membrane is prepared: (1) The colloidal route.The advantage of the sol-gel technique is that the pore size of the membrane can be desirably controlled.5. especially for small pores. (2) The polymer route. . in which a metal salt is mixed with water to form a sol.Sol-Gel Process *. *. where it forms a polymer gel. The sol is coated on a membrane support.
Sol-Gel Process *. => In this case.The Colloidal sols are the colloidal solutions of dense oxide particles such as Al2O3. the pore size of the membrane prepared is determined by the degree of branching of the inorganic polymer. TiO2 or ZrO2. *. => The partial charges of the metal in the alkoxides and hydrolyses speed influence the hydrolysis behavior . the membrane can be prepared through the polymer sol route using the -alumina membrane as a support. SiO2. ceramic membranes with pore sizes less than 1 nm must be employed.It should be noted that in the polymer sol route.Sols of very small particles are prepared through hydrolysis and condensation of their corresponding alkoxides. *. *.For gas separation based on molecular sieving effects.5.
The drying process starts simultaneously with the dip coating.Dip Coating *. after calcinations of the first layer. .In a multiple step process. drying and calcination is repeated. when the substrate is in contact with a atmosphere that has a relative humidity below 100 %. *. the complete cycle of dipping. *.6.The critical factors in dip coating are the viscosity of the particle suspension and the coating speed or time.
*.CVD system which includes a system of metering a mixture of reactive and carrier gases. a heated reaction chamber. and reactive gases such as metal halides and hydrocarbons) is carried into a reaction chamber that is heated to the desired temperature. oxidation and hydrolysis .7.Chemical Vapor Deposition (CVD) *. and a system for the treatment and disposal of exhaust gases.The deposition of coatings by CVD can be achieved in a number of ways such as thermal decomposition. nitrogen or argon.The gas mixture (which typically consists of hydrogen.Chemical vapor deposition is a technique which modifies the properties of membrane surfaces by depositing a layer of the same or a different compound through chemical reactions in a gaseous medium surrounding the component at an elevated temperature. *. *.
etc. The practically useful crystalline microporous membranes have polycrystalline structures. namely crystalline zeolite membranes and XRD amorphous membranes such as silica. consisting of many crystallites packed together without any crystallite (grain) boundary gap in the ideal case. .Industrial Ceramic Membranes In According to the IUPAC definition: Microporous membranes are referred to as those with a pore diameter smaller than 2 nm There are two main types of microporous membranes used in gas separations. carbon.
(2) their thermal and chemical stabilities.In order to perform the molecular sieving function. *.1. . the membranes must have negligible amounts of defects and pinholes of larger than 2 nm. which are also the general of ceramic membranes. which is relatively stable at high temperatures.Zeolites are crystalline microporous aluminosilicate materials with a regular three dimensional pore structure.Due to their molecular sieve function.The unique properties of zeolite membranes are: (1) their size and shape selective separation behavior. advantages *. *. *.They are currently used as catalysts or catalyst supports for a number of high temperature reactions.Zeolite Membranes *. zeolite membranes can principally discriminate the components of gaseous or liquid mixtures dependent on their molecular size.
Silica Membranes *.2. *.Chemical vapor deposition (CVD) is another method used in preparation of microporous silica membranes. .Microporous silica (SiO2) membranes are prominent representatives of amorphous membranes.The acid catalyst reduces hydrolysis but enhances polycondenstion rates during the sol preparation process resulting in a polymeric sol containing silica particles of fractal structure. *.The first successful silica membranes for gas permeation/separation with good quality and high flux were prepared in 1989 using a sol-gel method where SiO2 polymer sols were firstly prepared by acid catalysed hydrolysis of tetraethoxysilane (TEOS) in alcoholic solution. *.
*. carbon membranes were prepared by ultrasonic deposition of polyfurfuryl alcohol on a porous inorganic support. y One approach is to make the membranes on mesoporous substrates. It is expected that carbonized materials are stable at high temperatures and resist chemical attack. followed by pyrolysis at 473 873 K to convert the polymer layer to microporous carbon film. . y For example. y Another approach is using asymmetric hollow fiber membrane precursors. highly selective due to their pores of molecular dimensions.Carbon Membranes *.3. *-The challenge for carbon membranes is how to increase the gas permeation rate.Carbon membranes are inexpensive.They are prepared basically by carbonizing organic polymers as starting materials at high temperatures under controlled conditions.
ceramic and zeolite membranes . dehydration. To-be-developed membrane separation technologies (Carrier facilitated transport . membrane contactors. a membrane can be described as a permselective barrier or a fine sieve. polymeric membranes. Developed membrane separation industrial technologies (microfiltration and ultrafiltration.y In general. Developing industrial membrane separation technologies (Gas separation and pervaporation) C. y . and electrodialysis) B. and piezodialysis membrane) y There are a lot of applications of gas separation membranes ( natural gas separations. and mixed-matrix membrane. and H2 separation) Membrane materials include metal membranes. y There are several fields on which membrane technologies are used: A. reverse osmosis .
membranes. Gas separation technology is evolving and expanding rapidly. y There are two types of ceramic membranes suitable for gas separations: (1) dense and (2) porous. y Ceramic membranes. y Dense ceramic membranes are made from crystalline ceramic materials y Microporous ceramic membranes are mainly composed of amorphous silica or zeolites . are being used in ultrafiltration and microfiltration applications for which solvent resistance and thermal stability are required. further substantial growth will be seen in the coming years. a special class of microporous membranes.y Gas separation has become a major industrial application of membrane technology only during the past 20 years. especially microporous. y Ceramic membranes are usually composite ones consisting of several layers of one or more different ceramic materials.
y Several researches are being held for the manufacturing of ceramic membranes for gas separation out of zeolite.y Dense metal membranes. namely crystalline zeolite membranes and XRD amorphous membranes such as silica. carbon. particularly palladium membranes. and there are several other medical and military applications that will find its way to the market in the coming years . are being considered for the separation of hydrogen from gas mixtures. the specifications that zeolite have makes it a promising material for investigation. and supported liquid films are being developed for carrier-facilitated transport processes. etc y Zeolite membrane synthesis is an important new field for development of ceramic membrane. y On the industrial level: There are two main types of microporous membranes used in gas separations.
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