FI61636B - FLASH COMPONENT FOER GASSEPARATIONER OR FOER FARANDE FOER DESS ANVAENDNING - Google Patents

Description

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PltMt- och regirterttyrelaen AiMttkM utlagd och utl.tkrift · »publicerid (32) (33) (31) Pyydatty« cuotkoui — Bogftrd priority 15-11.76 13.09.77 USA (US) 7 ^ 2159, 832U81 (71) Monsanto Company, 800 North Lindbergh Boulevard, St. Louis, Missouri 63166, USA (72) Jay Myls Stuart Henis, Creve Coeur, Missouri, Mary Kathryn Tripodi,

Creve Coeur, Missouri, USA (US!) (7! +) 0y Kolster Ah (5I *) Multicomponent membrane for gas separations and method of using it

The invention relates to a multicomponent membrane for separating at least one gas from gas mixtures and to a method for selectively separating at least one gas from gas mixtures using such a multicomponent membrane.

Separation, which involves increasing the concentration of at least one selected gas in the gas mixture, is a particularly important step in terms of the requirements for the supply of chemical feedstocks to be fed. Often, these requirements are met by separating one or more desired gases from gas mixtures and utilizing these gas products for processing. It has been proposed to use separation films to selectively separate one or more gases from gas mixtures. To achieve selective separation, the film has less resistance to the migration of one or more gases than at least one of the other gases in the mixture. Thus, selective separation may provide a privileged depletion or concentration of one or more gases in the mixture over at least one other gas and therefore provide a product in which the ratio of one or more desired gases to at least one other gas is different from this ratio in the mixture. However, for the selective separation of one or more gases using a separation membrane to be economically attractive, the membranes must not only be able to withstand the conditions to which they are exposed during the separation step, but must also allow a sufficiently selective separation of one or more desired gases at a sufficiently high flow rate. the rate of transmission per unit area, so that the use of the separation method is on an economically attractive basis. Thus, separation films which are capable of sufficiently good selective separation but which have undesirably low flows require such large areas of separation film that the use of these films is not economically feasible. Likewise, separation films with high flow but low selective resolution are also not economically attractive. Thus, work has continued to develop separation membranes that can provide a sufficiently selective separation of one or more desired gases as well as a sufficiently large flow so that the use of these separation membranes on a commercial basis is economically feasible.

In general, the passage of gas through the membrane can proceed through the pores, i.e., for continuous flow along continuous channels that communicate with both the inlet and outlet surfaces of the membrane (where the pores may or may not be suitable for Knudsen flow or diffusion separation); in another mechanism, according to the general understanding of membrane theory, the passage of gas through the membrane may occur by the interaction of the gas and the membrane substance. In this latter required mechanism, gas permeation through the membrane is believed to involve gas dissolution in the membrane material and gas diffusion through the membrane. The permeability constant for an individual gas is now considered to be the product of the solubility and diffusion capacity of this gas in the membrane. The given film material 3 61636 has an explicit permeability constant for the flow of a given gas due to the interaction of the gas with the film material. The permeation rate of the gas, i.e. the flow through the membrane, is proportional to the permeability constant, but is also influenced by various variables such as membrane thickness, physical nature of the membrane, partial pressure differential pressure of the permeable gas across the membrane, temperature, etc.

Until now, various modifications to the membranes used for liquid separation have been proposed in attempts to solve specific problems related to the separation process. The following presentation illustrates specific modifications made to membranes used for liquid separation to solve specific problems and provides a basis on which the invention can be fully evaluated. For example, cellulose films were first developed and used to desalt water, and these films could be generally described as "dill" or "dense" films. "Dense" or "tight" films are films that are substantially free of pores, i.e., fluid flow channels that communicate with the film surfaces, and are substantially free of cavities, i.e., areas in the film thickness that do not contain film material. In the case of dense films, each surface is suitable as a feed contact surface, since the properties of the dense film are the same from the direction of both surfaces, i.e. the film is symmetrical. Because the membrane is essentially similar in size throughout, it falls within the definition of isotropic membranes. Although some of these dense films are quite selective, their main disadvantage is the low permeation flow due to the relatively large thickness of these films. Therefore, it has been uneconomical to build equipment installations that are necessary to remove salt from substantial amounts of water using tight membranes. Attempts to increase the flow of membranes for liquid separations have included, for example, the addition of fillers to the membrane to change the porosity and to make the membranes as thin as possible to increase the flow rates. Although improved permeation rates have been achieved to a limited extent, these improved rates have generally been obtained at the expense of the selectivity of specific films.

In another attempt to improve film performance, Loeb and his co-workers disclose, for example, in U.S. Patent No. 3,133,132 a method of making a modified cellulose acetate film for desalting from water by first casting the cellulose acetate solution into a thin layer and forming] , a dense membrane film on this thin layer by various methods, such as evaporation of the solvent, followed by quenching in cold water. The formation of these dense membranes was usually accompanied by a final heat treatment in hot water. Membranes made by the Loeb method consist of two distinct regions made of the same cellulose acetate wave, a thin dense semipermeable film, and a less dense, cavity-containing, non-selective support region. Because membranes are not substantially uniform in density throughout their entire structure, they are considered to belong to the membranes defined as anisotropic. Due to these two distinct regions and the differences in membrane properties that can be observed depending on which surface of the membrane is towards the saline to be fed, Loeb-type membranes can be described as asymmetric.

For example, in practical desalination experiments, asymmetric dense membranes have been shown to have better permeation flow compared to older types of dense membranes. The improvement in the permeation rate of Loeb-type membranes has been attributed to an increase in the thickness of the dense selective region. A less dense area in such a membrane provides sufficient structural support to prevent membrane rupture at operating pressures, but provides little resistance to flow-through. Because of this, the dense film mainly performs the separation and the primary function of the less dense support area is to physically support the dense film. However, in such Loeb-type membranes, this less dense support region is often compressed by the pressures desired for desalination of water, and under such conditions the less dense support region loses some of its void volume. As a result, the free flow of the flow-through substance away from the outflow side of the dense film is prevented, as a result of which the permeation rate is reduced. In addition, Loeb et al. cellulose acetate membranes are also subject to clogging and various chemical degradations. Therefore, attention has been directed to the development of Loeb-type membranes from materials other than cellulose acetate, which can provide stronger structural properties and increased chemical resistance. "Loeb» processing "of polymeric materials to obtain individual component films with good selectivity and good permeation rate has been found to be very difficult. Most attempts result in membranes that are either porous, i.e., have flow channels through the dense membrane and do not separate, or have a dense membrane that is too thick to provide usable permeation rates. Thus, often these asymmetric membranes do not function acceptably in liquid separation processes such as reverse osmosis. As further described below, it is even more difficult to produce Loeb-type membranes with good selectivity and good permeation rates for gas separation processes.

Further developments to provide preferred separation films for desalination and other liquid / liquid separations, such as for the separation of organic matter from liquids, have resulted in composite membranes comprising a porous substrate that can easily penetrate and be strong enough to withstand operating conditions. supported by a semipermeable membrane. The proposed composite membranes belong to the so-called to "dynamically formed" membranes formed by continuously precipitating a polymeric film material from a feed solution on a porous substrate. This continuous blending is necessary because the polymeric film material is subject to migration into and through the porous substrate and therefore needs replenishment. In addition, the polymeric film material is often sufficiently soluble in the liquid mixture that is introduced for separation, so that it is usually also subject to unilateral wear, i.e., it is washed away from the substrate.

It has been proposed to prepare composite desalting membranes by providing a substantially solid diffusion or separation membrane on a porous substrate. See. for example, Sachs, et al., U.S. Patent No. 3,676,203, which discloses a polyacrylic acid separation film on a porous substrate such as cellulose acetate, polysulfone, etc. The thickness of the separation film is relatively large, e.g.

Up to 60 microns so that the separating film is strong enough that it does not tend to run into or rupture in the pores of the porous substrate. Other proposals have involved the use of an anisotropic substrate with a denser area on the surface, e.g., a film, as an immediate support surface for the separation film. See. for example, Cabasso et al., Research and Development of NS-1 and Related Polysulfone Hollow Fibers for Reverse Osmosis Desalination of Seawater, Gulf South Research Institute, July, 1975, distributed by the National Technical Information Service, U.S. Pat. Department of Commerce, Publication PB 248 666. Cabasso et al. disclose composite membranes for desalination of water consisting of hollow anitropic polysulfone fibers coated with, e.g., polyethyleneimine crosslinked in situ or furfuryl alcohol polymerized in situ to provide an overlapping separation membrane. Another way to make counter-osmosis membranes is disclosed by Shorr in U.S. Patent 3,556,305. Shorr discloses three-part separation membranes for counter-osmosis and these comprise an anisotropic porous substrate, an extremely thin binder layer on a porous substrate and a thin semipermeable membrane having a thin semipermeable membrane. Often, these extremely thin semipermeable films in combination with porous substrates are made by separately preparing an extremely thin film and a porous substrate, followed by contacting the two against the surface.

Other types of membranes that have been used to handle liquids are the so-called "Ultrafiltration M membranes with pores of the desired diameter. Sufficiently small molecules can pass through the pores, while larger, more bulky molecules are retained on the membrane feed surface. An example of ultrafiltration membrane types is provided by Massucco in U.S. Patent No. 3,556,997. is an anisotropic medium and a gel irreversibly compressed into a medium to give membranes of suitable pore sizes for the separation of basic hydroxides from hemicellulose and ultrafiltration through the gel.

The foregoing description of the background of the present invention has been directed to membranes for separating a liquid from a liquid mixture, such as desalting water. Today, more emphasis has been placed on the development of separation films suitable for the separation of gas from a gas mixture. Gas penetration through separation membranes has been the subject of many different studies; however, gas separation films with both high throughput and usable selective resolution are unlikely to be manufactured, at least not commercially. The following description illustrates the specific modifications made to the membranes used for the gas separations and provides a basis on which the present invention can be fully evaluated.

Attempts have been made to approach the information developed for liquid / liquid separation membranes. However, there are many different important considerations in developing a suitable separation film for gas systems compared to developing a suitable film for liquid systems. For example, the presence of small pores in the film does not unduly adversely affect the performance of the film for liquid separations, such as desalting, due to absorption and swelling of the membrane and high viscosity and good cohesiveness properties of the liquids. Because the gases have extremely low absorption, viscosity, and cohesive properties, there is no barrier to preventing the gases from easily passing through the pores in such a film, resulting in very little, if any, gas separation. One extremely important difference between liquids and gases that can affect selective separation by penetration through membranes is the generally lower solubility of gases in membranes compared to the solubility of liquids in such membranes, resulting in lower permeation constants for gases compared to liquid permeation constants. Other differences between liquids and gases that could affect selective separation by penetration through the membranes include density and internal pressure, effect of temperature on viscosity, surface tension, and degree of readiness.

It has been found that substances with good gas resolution often have lower permeability constants compared to the corresponding constants for substances with low gas resolution. In general, efforts are directed to produce the gas separation film material in as thin a form as possible with low permeabilities, to provide sufficient flow to still make the film as free of pores as possible so that gases pass through the film from mutual interaction with the film material. One attempt to develop separation membranes suitable for gas systems has involved the production of composite membranes with an overlapping membrane supported on an anisotropic porous substrate, whereby the overlapping membrane provides the desired separation, i.e. the overlapping membrane is semipermeable. The overlap membranes are preferably thin enough, i.e., ultra thin, to provide reasonable flows. The essential function of a porous substrate is to support and protect the overlapping membrane without damaging the delicate, thin overlapping membrane. Suitable substrates provide low resistance to passage after the overlapping membrane has completed its function of selectively separating the permeable material from the feed mixture. Thus, these substrates are preferably porous to provide low resistance to permeation and are still sufficiently profitable, i.e., their pore sizes are small enough to prevent overlapping membrane rupture under separation conditions. Klass et al., U.S. Patent No. 3,616,607, Stancell et al., U.S. Patent No. 3,657,113, and Yasuda, U.S. Patent No. 3,775,303 provide examples of overlapping gas separation membranes. membranes on a porous substrate.

Such composite membranes for gas separations have not been without problems. For example, Browall discloses in U.S. Pat. -ti copolymer. In the manufacture of membranes, Browall has found it impractical or impossible to exclude extremely small particulate impurities, i.e. particles smaller than about 3,000 Angstroms. These fine particles can settle under or between the preformed ultra-thin membrane layers, and due to their large size compared to ultra-thin membranes, these burst. Such fractures reduce the efficiency of the membrane. The Bro-wall patent discloses the use of a preformed organopolysiloxane / polycarbonate copolymer as a sealing compound with an ultra-thin membrane to cover fractures caused by fine particles. Browall also discloses the use of a preformed layer of an organopolysiloxane / polycarbonate copolymer between an ultra-thin membrane and a porous polycarbonate substrate as a binder. Thus, Browall composite membranes are complex in their structural materials and methods.

In summary, apparently, suitable anisotropic membranes have not been prepared for gas separations with sufficient flow and separation selectivity for general commercial processes in the absence of overlapping membrane, selective separation. In addition, composite membranes for gas separation with an overlapping membrane to provide selective separation appear to have achieved only a slight or modest improvement in membrane performance, and these gas separation membranes do not appear to have successful large-scale commercial use. In addition, the overlay membrane, although as ultra-thin as possible to provide the desired selective separation, can significantly reduce the flow of permeable gas through the composite membrane compared to the permeation of a porous substrate without an overlapping membrane.

The present invention relates to specific multicomponent or composite membranes for gas separation and comprises a coating in contact with a porous separation membrane, wherein the separation properties of multicomponent membranes are primarily determined by the multicomponent -komponenttikalvoja. These multicomponent films for separating at least one gas from the gas mixture may have the desired selectivity and still usable flow. The present invention provides multicomponent membranes for gas separation and can be made from a wide variety of different gas separation membrane materials and thus allow for a greater scope than has hitherto been the case in selecting such a membrane material which is preferred for a particular gas separation. The present invention provides multicomponent films in which the desired combinations of flow and selective separation can be achieved by configuration and manufacturing methods as well as by combining the components. Thus, a material having a high separation selectivity but a relatively low permeability constant can be used to make multicomponent films with the desired permeation rates and the desired separation selectivity. In addition, the films of the present invention may be relatively insensitive to the effects of contamination, i.e., fine particles during manufacture, which previously caused difficulties in making composite membranes from a preformed ultra-thin separating film placed on a substrate. Preferably, the use of binders in the preparation of the multicomponent films of this invention is not necessary. Therefore, the multicomponent films of the present invention need not be complicated in their structural technique. The multicomponent films of this invention can be made to provide high structural strength, toughness, and resistance to abrasion and chemicals while still having commercially advantageous flow and selective resolution. These multicomponent films may also have desirable handling properties, such as low sensitivity to static electrical forces, low adhesion to adjacent multicomponent films, and so on.

Definitions According to the present invention, multicomponent films for gas separation comprise a porous separation film having feed and discharge surfaces and a coating agent in contact with the porous separation film. The porous separating film has essentially the same composition, i.e. the substance throughout its entire structure, i.e. the porous separating film is essentially chemically homogeneous. The porous separation film material selectively permeates at least one gas from the gas mixture with at least one gas remaining in the gas mixture, and therefore the porous separation film is defined as a "separation" film. When describing a separation film as "porous", it is meant that the film has continuous channels for gas flow, i.e., pores that communicate with the inlet surface and the outlet surface. These continuous channels, if of sufficient number and cross-section, can allow substantially the entire gas mixture to flow through the porous separation membrane, with little or no separation due to the interaction with the porous separation membrane material. The present invention preferably provides multicomponent films in which the separation of at least one gas from the gas mixture due to the interaction of the porous separation film substance is improved compared to the porous separation film alone. The multicomponent films of this invention comprise porous separation films and coatings having special ratios. Some of these ratios can be conveniently expressed as relative separation factors for a gas pair of porous separation films, coatings and multicomponent films. The difference factor (α 2) for the gas pair a and b applied to the film is defined as the ratio of the permeability constant (P) of the film, for gas α, to the permeability constant (P 2) of the film, for gas b. The separation factor is also equal to the ratio of the permeability (P / X) of the film of thickness ji to the permeability of the gas mixture to gas a, 3 to the permeability of the same membrane to gas b (P ^ / X), where the permeability to a given gas is the volume of gas (NTP), which passes through the membrane per square centimeter of surface per second, for a decrease in the partial pressure of 1 centimeter of mercury across the membrane per unit thickness, and is expressed by the expression 2 in 2 languages P = cm / cm -s-cmHg / X.

In practice, the difference factor for a given gas pair can be determined using a number of methods that provide sufficient information to calculate permeability constants or permeabilities for each gas pair. Several of the many methods available for determining permeability constants, permeabilities, and resolution factors have been reported by Hwang, et al., Techniques of Chemistry, Volume VII, Membranes in Separations, John Wiley & Sons, 1975, Chapter 12, pages 296-322.

The specific separation factor, as referred to herein, is the separation factor for a substance that does not have channels for gas flow across the substance, and is the largest achievable separation factor for that substance. Such a substance can be said to be continuous or non-porous. The specific separation factor of a substance can be estimated by measuring the separation factor of the tight film of the substance. However, there may be numerous difficulties in determining the characteristic separation factor, such as imperfections in the production of a dense film, such as the presence of pores, the presence of fine particles in a dense film, an undefined molecular order due to variations in film production, etc. as a characteristic differentiator. Thus, "determined specific separation factor", as used herein, means the separation factor of a dry tight film made of this material.

The multicomponent film of the present invention for gas separation has a separation factor for at least one gas pair that is significantly greater than the specific separation factor determined for the coating material in closed contact with the porous separation film. By "significantly greater" when describing the relationship between the separation factor of a multicomponent film and the determined specific separation factor of the coating material, it is meant that the difference in separation factors is important, i.e., it is generally at least about 10% greater. By "closed contact" is meant that the coating is in contact with the porous separating film so that in a multi-component film, the ratio of gases passing through the porous separating film material to the gases passing through the pores increases relative to this ratio in the porous separating film alone. Thus, the contact is such that in a multicomponent film, an increased contribution of the porous separating film material to the separation factor of the multicomponent film for at least one gas pair is obtained compared to the contribution in the porous separating film alone. Thus, for at least this one gas pair, the separation factor of the multicomponent membrane is higher than the separation factor of the porous separation membrane. In addition, for at least one gas pair, the determined specific separation factor of the porous separating film material is greater than the determined specific separation factor of the coating material. Also, for at least one gas pair, the separation factor of the multicomponent film is often equal to or less than the determined specific separation factor of the porous separation film material. Often, despite the intended gas separation use of the multicomponent membrane, separation factor ratios can be assigned for at least one gas pair comprising some hydrogen, helium, ammonia, and carbon dioxide, and some carbon monoxide, nitrogen, argon, sulfur hexafluoride, methane, or ethane. Also, in some of the multicomponent films of this invention, the ratios of the separation factors may be assigned to a pair of gases comprising carbon dioxide and some of hydrogen, helium and ammonia, or ammonia and some of carbon dioxide, hydrogen and helium.

It is desirable that the multicomponent film of the invention have a separation factor for at least one gas pair that is at least about 35% greater, and preferably at least about 50% greater and sometimes at least about 100% greater than the defined intrinsic separation factor of the coating material. Often, for at least one gas pair, the separation factor of the multicomponent film is at least about 5, often at least about 10% greater, and sometimes at least about 50 or about 100% greater than the separation factor of the porous separation film.

This invention encompasses many different aspects. One section relates to multicomponent membranes for gas separations, another section relates to methods for gas separations using these multicomponent membranes, and the third section is an apparatus for performing gas separations, wherein the apparatus includes these multicomponent membranes.

One aspect of the present invention relating to multicomponent films comprises multicomponent films comprising a coating in closed contact with a porous separating film made of a material that selectively permeates at least one gas from a gas mixture with at least one or more gases remaining in the gas mixture, the porous separating wherein the multicomponent film has a significantly higher separation factor for at least one gas pair than the determined specific separation factor of the coating material. The cavities are areas in the porous separation membrane that are free of porous separation membrane material. Thus, when present from the cavity, the density of the porous separating film is lower than the density of the porous separating film mass material. By describing a cavity volume as "substantial" is meant that sufficient cavities, e.g., at least about 5% by volume of the cavity by the thickness of the porous separating film, are present to provide a feasible increase in permeation through the film compared to detectable permeability through a dense film of the same thickness. Preferably, the cavity volume is about.

Up to 90%, such as between about 10-80, and sometimes about 20 or 30-70% based on the external volume, i.e. the volume formed by the volume according to the external dimensions of the porous separating film. One method of determining the void volume of a porous separation film involves comparing the density with a volume of bulk material in the porous separation film corresponding to a film having the same physical external dimensions and shapes as the porous separation film. Therefore, the void space of the ont-staple porous separating film would not affect the density of the porous separating film.

The density of the porous separating film may be substantially the same throughout its thickness, i.e. isotropically or the porous separating film may be characterized by having at least one relatively denser region of its thickness as a barrier to the gas flow across the porous separating film, i.e. the porous separating film is anisopic. The coating is preferably in closed contact with a relatively dense region of the anisotropic porous separation film. Because the relatively dense area can be porous, it can be more easily made quite thin compared to making a dense film of the same thickness. The use of porous separating films with relatively dense areas that are thin provides improved flow through the multicomponent film.

In one aspect of the multicomponent films section of the invention, the multicomponent films comprise a coating in closed contact with a porous separating film made of a material that selectively permeates at least one gas in a gas mixture to leave one or more other gases wherein, for at least one gas pair, the multicomponent film has a separation factor that is significantly greater than the specific separation factor determined by the coating material. The substance applied to the porous separating film is mainly a liquid, in that it is unable to retain its shape in the absence of external support. The coating agent may be a liquid or may be dissolved or suspended as a finely divided solid (e.g., in a colloidal size) in a liquid solvent to provide a substantially liquid agent for application to a porous separating film. Preferably, the coating agent or coating agent in the liquid solvent moistens the porous separating film material, i.e. tends to adhere to it. Thus, contact of the coating with the porous separating film is often facilitated. The use of a substantially liquid substance to provide a coating for a porous separating film makes it possible to use simpler methods than those used in the manufacture of composite films from separately formed solids. In addition, a wide variety of materials can be used for coating, and the application methods can be easily adapted to use porous separating films of various shapes.

In a further aspect of the multicomponent film section of the present invention, the multicomponent film comprises a coating in closed contact with a porous separating film of polysulfone, wherein for at least one gas pair the multicomponent film has a significantly higher distinguishing factor than the specified characteristic. In another aspect of this paragraph, the multicomponent films comprise a coating in closed contact with a hollow fiber porous separation film made of a material that selectively permeates at least one gas in a gas mixture over one or more remaining gases in that gas mixture. specified characteristic factor. In hollow micelles (i.e., hollow fibers), the outer surface may be the feed or discharge surface of the porous separating film and the inner surface may be the discharge or feed surface, respectively. The hollow fibers preferably facilitate the provision of a gas separation device with large available areas for separation in the given volumes of the device. Hollow fibers are known to be able to withstand greater pressure differences than unsupported films with essentially the same thickness and morphology.

Another aspect of the present invention relates to methods for separating gas using multicomponent membranes. In this aspect of the invention, at least one gas in the gas mixture is separated from the at least one other gas by selective permeation to give a permeable product containing at least one permeable gas. The method comprises: contacting a gas mixture with the surface (feed surface) of a multicomponent well, wherein in a gas mixture of at least one gas pair, the multicomponent membrane selectively passes one gas from the gas pair leaving the gas pair with another gas; holding the opposite surface (outlet surface) of the multi-component film at a lower chemical potential for at least one permeable gas than the chemical potential on said second surface; allowing at least one permeable gas to penetrate and permeate the multicomponent membrane; and removing from the vicinity of the opposite surface the permeable product, wherein the ratio of the first gas in the gas mixture to the at least one other gas in the gas mixture is different from the ratio of the at least one gas to the at least one other gas in the gas mixture. The separation processes of the present invention comprise concentrating this at least one gas on the feed side of the multicomponent film to obtain a concentrated product and comprising penetrating this at least one gas to obtain a permeated product through the multicomponent film, wherein said ratio is a higher ratio.

In one aspect of this section, the multicomponent film comprises a coating in closed contact with a porous separating film having a substantial cavity volume. In another aspect of this aspect of the invention, hydrogen is selectively separated from a gas mixture that also contains at least one of carbon monoxide, carbon dioxide, helium, nitrogen, oxygen, argon, hydrogen sulfide, nitric oxide, ammonia, and a hydrocarbon having from 1 to about 5 carbon atoms. In a further aspect of this aspect of the invention, the at least one gas in the gas mixture is separated from the at least one other gas by contacting the gas mixture with a multicomponent film comprising a coating in closed contact with a porous separation film which is polysulfone.

A further aspect of the invention relates to an apparatus for gas separations utilizing the multicomponent films of this invention. The apparatus comprises a frame having at least one multicomponent film according to the present invention having a feed surface and an outlet surface opposite it, and the frame has means for feeding and removing a gas mixture to and from the supply surface of the multicomponent film and means for removing permeable product from the multicomponent film.

17 61 636

Surprisingly, it has been found that an agent for a coating which may have a low determined specific separation factor can be provided on a porous separating film which may have a low separation factor to produce a multicomponent film having a separation factor greater than both the coating and the porous separation. This result is quite surprising in contrast to previous proposals for gas separation composite films with an overlay film supported on a porous substrate, which proposals have primarily required that the superimposed film have a high separation factor to achieve selective separation on the film. The finding that low separation factor coatings can be used in conjunction with porous separation films to provide multicomponent films with a higher separation factor than either coating or porous separation film results in highly preferred multicomponent films for gas separation. For example, materials having the desired characteristic resolution factors but difficult to utilize as overlapping membranes can be used as the porous separation film material of the present invention, with the selectivity of the porous separation film material resolution significantly contributing to the multicomponent film separation factor.

It can be clearly seen that the porous separation film of multicomponent films can be anisotropic, with the separation area being thin but relatively dense. Thus, a porous separating film can take advantage of the low permeation resistance provided by anisotropic films and provide multicomponent films with the desired separation factors. In addition, the presence of flow channels, which can make one-component (non-combination) anisotropic films unacceptable for gas separations, may be acceptable and even desirable in the porous separation films used in the multicomponent films of this invention. The coating may advantageously provide a low permeation resistance and the coating material may have a low determined intrinsic separation factor. In some multicomponent films, the coating may tend to selectively repel the desired permeable gas, but the resulting multicomponent film using this coating may have a higher separation factor than the porous separating film.

This invention relates to multicomponent films formed by combining a preformed porous separating film, i.e., a porous separating film prepared prior to application of a coating, and a coating. In particular, the invention relates to multicomponent gas separation films in which the selectivity of the resolution of the porous separation film material contributes significantly to the relative permeation rates and selectivity of the gases passing through the multicomponent film. The multicomponent films of the invention can generally have higher penetration rates than the composite films described prior to the present invention, which utilize overlapping membranes with high separation factors. In addition, the multicomponent films of the present invention provide a separation factor that is superior to that of the coating and the porous separation film. The multicomponent films of the invention may be in some way similar, but not only superficial, to the gas separation films described prior to the present invention and having overlapping membranes with a high separation factor on a porous substrate. These composite films, which were described prior to the present invention, do not use a support or substrate that provides a substantial portion of the separation.

The multicomponent films of this invention allow high flexibility to make specific separations because both the coating and the porous separating film contribute to the overall separation performance. The result is an increased ability to adapt these membranes to specific separation requirements, e.g., to separate the desired gas or gases from different gas mixtures in commercially acceptable combinations of speed and separation selectivity. Multicomponent films can be made from a wide variety of gas separation agents and thus have a wider range of motion than has hitherto existed in selecting a preferred film agent for a given gas separation. In addition, these multicomponent films are capable of imparting good physical properties such as toughness, abrasion resistance, strength and longevity, and good chemical resistance.

19 61 6 3 6

The invention relates to special multicomponent films for gas separations and these comprise a coating in contact with a porous separating film, the separating properties of the multicomponent film being determined mainly by the porous separating film as opposed to a coating using these methods for gas separation.

Multicomponent membranes are widely used in gas separation processes. Gas mixtures suitable for feeding in accordance with this invention include gaseous substances, or substances which are normally liquid or solid but are vapors at the temperature at which the separation is carried out. The invention, as described in detail below, relates mainly to, for example, the separation of oxygen from nitrogen; separating hydrogen from at least one of carbon monoxide, carbon dioxide, helium, nitrogen, oxygen, argon, hydrogen sulfide, nitric oxide, ammonia and hydrocarbons having from 1 to about 5 carbon atoms, especially methane, ethane and ethylene; to separate ammonia from at least one of hydrogen, nitrogen, argon and a hydrocarbon having from 1 to about 5 carbon atoms, e.g. methane; to separate carbon dioxide from at least one of carbon monoxide and a hydrocarbon having from 1 to about 5 carbon atoms, e.g., methane; to separate helium from a hydrocarbon having from 1 to about 5 carbon atoms, e.g. from methane; to separate hydrogen sulfide from a hydrocarbon having 1 to about 5 carbon atoms, for example, methane, ethane or ethylene; and to separate carbon monoxide from at least one of hydrogen, helium, nitrogen, and a hydrocarbon having from 1 to about 5 carbon atoms. It should be emphasized that the invention is not limited to these specific separation applications or gases, nor to the specific multicomponent films shown in the examples.

The multicomponent films for the gas separation according to the invention can be films or hollow micelles or fibers with a porous separation film or a substrate and a coating in closed contact with the porous separation film. Some factors that affect the behavior of multicomponent films are the permeability constants of the coating and the porous separating film materials, the total cross-sectional area of the holes (i.e., pores or flow channels) relative to the thickness of the porous separating film, and the total area of the porous separating film. , the morphology of the porous separating film and, most importantly, the relative resistance to the flow of both the coating and the porous separating film in the multicomponent film. In general, the degree of separation of a multicomponent film is affected by the relative resistance to the gas flow of each gas in the gas mixture in the coating and the porous separation film, which may be specifically selected based on their gas flow resistance properties.

The material used for the porous separation film may be a solid natural or synthetic material having useful gas separation properties. In the case of polymers, both addition and condensation polymers can be used, which can be molded, extruded, or otherwise treated to give porous separation films. Porous separating films can be prepared in a porous form, for example, by casting a solution comprising a solvent for a polymeric substance in a solvent which dissolves the substance weakly or not at all. Spinning and / or casting conditions and / or treated after initial formation, etc. may affect the porosity and gas flow resistance of the porous separating film.

Generally, organic polymers or organic polymers mixed with inorganic filters are used to make a porous separation film. Typical polymers suitable for the porous separation film of the invention may be substituted or unsubstituted polymers and may be selected from the group consisting of polysulfones; polystyrenes which are styrene-containing copolymers such as acrylonitrile / styrene copolymers, styrene / butadiene copolymers and styrene / vinylbenzyl halide copolymers; polycarbonate it; cellulose polymers such as cellulose acetate butyrate, cellulose propionate, ethylcellulose, methylcellulose, nitrocellulose, etc .; polyamides and polyimides such as aryl polyamides and aryl polyimides; polyethers; polyarylene oxides such as polyphenylene oxide and polyxylylene oxide; polyesteramide-diisocyanate; polyurethanes; polyesters such as polyethylene terephthalate, polyalkyl methacrylates, polyalkyl acrylates, polyphenylene terephthalate, etc .; polysulfides; polymers of monomers with alpha-olefinic unsaturation other than those mentioned above, such as polyethylene, polypropylene, poly (butene-1), polyO + -methylpentene-1), polyvinyls, e.g. polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride , polyvinylidene fluoride, polyvinyl alcohol, polyvinyl esters such as polyvinyl acetate and polyvinyylipro-propionate, polyvinylpyridine, polyvinylpyrrolidone, poly-vinyl ethers, polyvinyl ketones, polyvinyylialdohydit, such as polyvinyl and polyvinyl butyral, polyvinyyliamidit, acid-lyvinyyliamiinit, polyvinyyliuretaanit, polyvinyyliureat, polyvinyl nyylifosfaatit and polyvinyl; polyallyl; polybentso-benzimide; polyhydratsidit; polyoxadiazole i.t .; polytriatso-lit; polybentsimidiatsoli; polycarbodiimides; polyphosphazines; etc., and copolymers such as block copolymers containing continuous units of the foregoing, such as sodium salt terpolymers of acrylonitrile / vinyl bromide / para-sulfophenylmethyl ethers; as well as graft copolymers and blends containing some of the foregoing. Typical substituents that give substituted polymers include halogens such as fluorine, chlorine and bromine; The hydroxyl groups; lower alkyl groups; lower alkoxy groups; monocyclic aryl; lower acyl groups, etc.

The selection of a porous separating film for this multicomponent film for gas separations can be made on the basis of the heat resistance, solvent resistance and mechanical strength of the porous separating film as well as other factors determined by the operating conditions for at least . The porous separating film is preferably at least partially self-supporting, and may in some cases be substantially self-supporting. The porous separation membrane may provide substantially all of the structural support to the membrane, or the multicomponent membrane may include a structural support member with very little, if any, resistance to gas flow.

One of the preferred porous separation films used to form multicomponent films is polysulfone. Useful polysulfones are those having a polymer backbone consisting of a repeating structural unit: 22 61 636 ~ o 11 - -R — s — r »-

Tl o wherein R and R * may be the same or different and are aliphatic or aromatic hydrocarbyl-containing moieties having 1 -n. 40 carbon atoms, wherein the sulfur in the sulfonyl group is attached to aliphatic or aromatic carbon atoms, and the average molecular weight of the polysulfone is suitable for film or fiber formation, often at least about 10,000. When the polysulfone is not crosslinked, the polysulfone generally has a molecular weight of less than n.

500,000 and often less than about 100,000. The repeating units may be linked, i.e., R and R 'may be linked by carbon-carbon bonds or various linking groups such as 0 0 0 -O-, -S-, - C-, -CN-, -NCN-, -O-C-, etc.

* »T

H H H

Particularly preferred polysulfones are those in which at least one of R and R 'is an aromatic hydrocarbyl-containing moiety and the sulfonyl moiety is attached to at least one aromatic carbon atom. Common aromatic hydrocarbyl-containing moieties include phenylene and substituted phenylene moieties; bisphenyl and substituted bisphenyl moieties, bisphenylmethane and substituted besphenylmethane moieties having rings R ~ R7 Rq Rr R4 R8 R10 R6 substituted and unsubstituted bisphenyl ethers of formula 23, s -7 s 616 3 6 R3 R7 R9 Rs R 8 R 10 R 6 wherein X is oxygen or sulfur; etc. In the bisphenylmethane and bisphenyl ether moieties described, R 1 to g represent substituents which may be the same or different and have the structure z

t-L-L

X 2 wherein and X 2 are the same or different and are hydrogen or halogen (e.g. fluorine, chlorine and bromine); p is 0 or an integer, for example from 1 to about 6; and Z is hydrogen, halogen, (e.g. fluorine, chlorine and bromine) - (- Y -) - R 11 (wherein q is 0 or 1, Y is -O-, -S-,

0 0 q M

If ft is -SS-, -OC- or -C-, and R 1 is hydrogen, substituted or unsubstituted alkyl having 1 to about 8 carbon atoms, or substituted or unsubstituted aryl, monocyclic or bicyclic having n.

6-15 carbon atoms), a heterocyclic compound in which the heteroatom is at least one of nitrogen, oxygen and sulfur and which is monocyclic or bicyclic and has about 5-15 ring atoms, sulphate or sulphone, especially lower alkyl or monocyclic or bicyclic aryl sulfate or sulfone, phosphorus-containing moiety such as phosphine and phosphate, and phosphone, especially lower alkyl or monocyclic or bicyclic aryl-containing phosphate or phosphone, amine such as primary, secondary, tertiary, and quaternary amines, with secondary quaternary and tertiary contain lower alkyl or monocyclic or bicyclic aryl moieties, isothiourea, thioureyl, guanidyl, trialkylsilyl, trialkylstannyl, trialkylpumumbyl, dialkyltibinyl, etc. Often the substituents on the bisphenylmethane and bisphenyl ether moieties of position, i.e. R? - g are hydrogen. Polysulfones with aromatic hydrocarbyl-containing moieties generally have good heat resistance, are resistant to chemical action, and have an excellent combined toughness and flexibility. Useful polysulfones are sold under the tradenames “P — 1700” and “P-3500” by Union Carbide, and both of these commercial products have a straight chain of the general formula - <oV - (0) -0- / 0 h -yyy-0 - \ - 'I' - '' - 'o' - CH «υ 3 τι where n, which represents the degree of polymerization, is about 50-80.

Polyarylene ether sulfones are also preferred. Also useful are polyether sulfones having the structure _ 0 _ and supplied by ICI, Ltd, England. Still other useful polysulfones could be prepared by polymeric variants, for example, by crosslinking, grafting, quaternization, etc.

A wide variety of spinning conditions can be used to make hollow fiber porous separation films. One method of making hollow polysulfone fibers has been proposed by Cabasso, et al., Research and Development of NS-1 and Related Polysulfone Hollow Fibers for Reverse Osmosis Desalination of Seawater, as described above. Particularly preferred hollow fibers of polysulfones, e.g., polysulfone P-3500 produced by the polyether sulfones of Union Carbide and ICI, Ltd., can be prepared by spinning a polysulfone in a solution comprising a solvent for that polysulfone. Typical solvents are dimethylformamide, dimethylacetamide and N-methylpyrrolidone. The weight percentage of polymer in the solution can vary widely, but is sufficient to give a hollow fiber under drip conditions. Often the weight percentage of polymer in the solution is about 15-50, for example about 20-35. If the polysulfone and / or solvent contain contaminants such as water, particles, etc., the amount of these contaminants should be low enough to allow spinning. If necessary, contaminants can be removed from the polysulfone and / or solvent. The size of the spinning nozzle varies depending on the inside and outside diameters of the hollow product fiber. In one class of spinning nozzles, the orifice diameters may be about 15 to 35 mils (0.38 to 0.88 mm) and the needle diameters may be about 8 to 15 mils (0.2 to 0.38 mm), with the needle having an injection capillary. . The diameter of the injection capillary may vary within the limits prescribed by the needle. The spinning solution is often maintained in a predominantly inert atmosphere to prevent contamination and / or coagulation of the polysulfone prior to spinning and to avoid excessive fire hazard with volatile and flammable solvents. A suitable atmosphere is dry nitrogen. The presence of excessive amounts of gas in the spinning solution may lead to the formation of large cavities.

Spinning can be performed using the wet nozzle or dry nozzle method, i.e. the nozzle can be in or separate from the coagulation bath. The wet nozzle method is often used for convenience. Preferably, the spinning conditions are not such that the fiber stretches excessively. Often spinning speeds are in the range of about 5-100 m / min, although higher spinning speeds may be used, provided that the fiber is not excessively stretched and sufficient residence time is provided in the coagulation bath. For the coagulation bath, a solvent in which the polysulfone is substantially insoluble can be used. Preferably, water is used as the main ingredient in the coagulation bath. Usually a liquid is injected into the fiber. The liquid may be, for example, air, isopropanol, water, etc. The residence time of the spun fiber in the coagulation bath is at least sufficient to ensure solidification of the fiber. The temperature of the coagulation bath can also vary widely, e.g. from -15 ° C to 90 ° or more, and is most often about.

26 61 636 between 1-35 ° C, about 2 ° to 8 or 10 °. The coagulated hollow fiber is preferably washed with water to remove the solvent and can be stored in a water bath for at least about two hours. The fibers are usually dried before the coating is applied and assembled in a device for gas separation. Drying can be performed at a temperature of about 0-90 ° C, suitably at about room temperature, e.g. about 15-38 ° C, and about 5-95%, preferably about 40-60%. at relative humidity.

The foregoing description of methods for making hollow fiber porous separation films from polysulfone is provided solely to illustrate methods available for making porous separation films and does not limit the invention.

The coating may be in the form of a substantially continuous film, i.e., a substantially non-porous film, in contact with the porous separating film, or the coating may be discontinuous or discontinuous. When the coating is suspended, it is sometimes called a barrier because it can block the channels from the gas flow, i.e. the pores. Preferably, the coating is not so thick as to adversely affect the performance of the multicomponent film, e.g., by causing an excessive reduction in flow or by causing a resistance in the gas flow such that the separation factor of the multicomponent film is substantially the same as that of the coating. Often the average thickness of the coating can be up to about 50 microns. Once the coating is suspended, there are, of course, areas where there is no coating at all. The average thickness of the coating is often between about 0.0001 and 50 microns. In some cases, the average thickness of the coating is less than about 1 micron and may even be less than about 0.5 microns. The coating may comprise a single layer or at least two separate layers, which may or may not be the same material. When the porous separating film is anisotropic, i.e. has a relatively dense region along its thickness in the gas flow barrier ratio, the coating is preferably applied to be in closed contact in a relatively dense region. The relatively dense region may be on one or both surfaces of the porous separation film, or it may be in the middle of the thickness of the porous separation film. The coating is suitably applied to at least one of the outlet and feed surfaces of the porous separation film, and when the multicomponent film is a hollow fiber, the coating may be applied to the outer surface to protect and / or facilitate handling of the multicomponent film.

While any suitable method can be used, the method by which the coating is applied can also have some effect on the overall performance of the multicomponent films. The multicomponent films of the invention can be prepared, for example, by coating the porous separating film with a material containing a coating material, so that in the multicomponent film, the resistance of the coating; for gas flow is low compared to the total resistance of the multicomponent. The coating may be applied in any suitable manner, e.g. by spraying, brushing, immersing in a substantially liquid substance containing a coating agent or the like. As stated above, the coating material is preferably in a substantially liquid material, when applied and may be in solution, using a solvent for the coating material, which solvent is essentially a non-solvent for the porous separation film material. Preferably, the material containing the coating agent is applied to the surface of the porous separating film and the other side of the porous separating film is brought to a lower absolute pressure. If the substantially liquid substance is a polymerizable substance and the polymerizable substance polymerizes after application to the porous separating film to provide a coating, the second surface of the porous separating film is preferably brought to a lower absolute pressure during or before polymerization. However, the invention itself is not limited by the specific method by which the coating material is applied.

Particularly preferred materials for the coating have relatively high permeability constants for the gases, so that the presence of the coating does not unduly reduce the permeation rate of the multicomponent films. The resistance of the coating to the gas flow is preferably relatively small compared to the resistance of the multicomponent film. As noted above, the choice of materials depends on the determined specific separation factor of the coating material relative to the determined separation factor of the porous separating film material to obtain a multicomponent value having the desired separation factor. The coating material should be able to make closed contact with the porous separating film. For example, when applied, it should be sufficiently moist and adhere to the separating film of 60 616 3 6 that closed contact can occur. The wetting properties of the coating material can be readily determined by contacting the coating material, either alone or in a solvent, with the porous separating film material. In addition, based on the evaluation of the average pore diameter of the porous separation film, substances with a suitable molecular size can be selected for the coating. If the molecular size of the coating material is too large to fit in the pores of the porous separating film, the material is not useful for making a closed contact. On the other hand, if the molecular size of the coating material is too small, it may flow through the pores of the porous separating film during the coating and / or separation steps. Thus, porous separating films with larger pores may have the advantage of using materials with a larger molecular size for coating than smaller pores. When the pore sizes vary widely, it may be advantageous to use as a coating material a polymerizable material which is polymerized after application to a porous separating film, or to use two or more coating materials of different molecular sizes, e.g.

The coating materials may be natural or artificial, and are often polymers and preferably have suitable properties to provide closed contact with the porous separating film. The active ingredients comprise both addition and condensation polymers. Typical useful materials that can form a coating include polymers, which may be substituted or unsubstituted, and which are solid or liquid under gas separation conditions, and include synthetic rubbers; natural rubbers; relatively high molecular weight and / or high boiling liquids; organic prepolymers; polysiloxanes (silicone polymers); poly silazanes; polyurethanes; polyepichlorohydrin; polyamines; polyimines; polyamides; copolymers containing acrylonitrile, such as poly (n-chloroacrylonitrile) copolymers; polyesters (such as polylactams), e.g., polyalkyl acrylates and polyalkyl methacrylates having from 1 to about 8 carbon atoms in the alkyl groups, polysebasates, polysuccinates, and alkyd resins; terpinoid resins such as linseed oil; cellulosic polymers; polysulfones, 29 61 6 3 6 especially polysulfones containing aliphatic compounds; polyalkylene glycols such as polyethylene glycol, polypropylene glycol, etc .; polyalkeenipolysulfaatit; polypyrrolidonit; polymers of monomers with α-olefinic unsaturation, such as polyolefins, e.g., polyethylene, polypropylene, polybutadiene, poly (2,3-dichlorobutadiene), polyisoprene, polychloroprene, polystyrene, poly-styrene copolymers, e.g. -butadi.ee -ni copolymer, polyvinyls such as polyvinyl alcohol, polyvinyl aldehydes (e.g. polyvinyl formal and polyvinyl butyral), polyvinyl ketones (e.g. polymethyl vinyl halide), polyvinyl esters, polyvinyl esters polyvinylidene carbonate, poly (N-vinylmaleimide), etc., poly (1,5-cyclooctadiene), polymethylisopropenyl ketone, fluorinated ethylene copolymer; polyarylene oxides, e.g. polyxylylene oxide; polycarbonates; polyphosphates, e.g. polyethylene methyl phosphate; etc. as well as some copolymers such as block copolymers containing repeating units of the foregoing and graft polymers and blends containing some of the above. The polymers may or may not be polymerized after application to the porous separating film.

Particularly useful materials for coatings are polysiloxanes. Typical polysiloxanes may comprise aliphatic and aromatic moieties and often have repeating units containing from 1 to about 20 carbon atoms. The molecular weight of polysiloxanes can vary widely, but is generally at least about 1,000. Often, the molecular weight of polysiloxanes is between about 1,000 and 300,000 when applied to a porous separating film. Common aliphatic and aromatic polysiloxanes include polymonosubstituted and di-substituted siloxanes, e.g., wherein the substituents are lower aliphatic groups, for example lower alkyl such as cycloalkyl, especially methyl, ethyl and propyl, lower alkoxy; aryl such as mono- or bicyclic aryl such as biphenylene, naphthalene, etc .; lower mono- and bicyclic aryloxy; acyl such as lower aliphatic and lower aromatic acyl, etc. Aliphatic and aromatic substituents may be substituted, e.g. by halogens such as fluorine, chlorine and bromine, hydroxyl groups, lower alkyl groups, lower alkoxy groups, lower acyl groups, etc. The polysiloxane may be crosslinked in the presence of a crosslinking agent to give a silicone rubber, and the polysiloxane may be a copolymer with a crosslinkable comonomer such as α-methylstyrene to facilitate crosslinking. Typical catalysts to promote crosslinking are organic and inorganic peroxides. Crosslinking may occur prior to application of the polysiloxane to the porous separation film, but preferably the polysiloxane is crosslinked after application to the porous separation film. Often, the molecular weight of the polysiloxane is between about 1,000 and 100,000 before crosslinking. Particularly preferred polysiloxanes are polydimethylsiloxane, polyphenylmethylsiloxane, polytrifluoropropylmethylsiloxane, a copolymer of α-methylstyrene and dimethylsiloxane. Some polysiloxanes do not sufficiently wet the porous polysulfone separation film to provide as much closed contact as desired. However, dissolving or dispersing the polysiloxane in a solvent that does not substantially affect the polysulfone can facilitate closed contact. Suitable solvents are normally liquid alkanes, e.g. pentane, cyclohexane, etc .; aliphatic alcohols, e.g. methanol-li; some halogenated alkanes; and dialkyl ether, etc .; as well as mixtures thereof.

The following agents for porous separation films and coatings are representative of useful agents and combinations thereof to provide the multicomponent films and gas separations of this invention for which they may be used. However, these agents, combinations, and applications are only representative of the broad group of agents useful in the invention and are not intended to limit the invention, but are intended solely to illustrate the broad use of their advantages. Typical agents for porous separation membranes to separate oxygen from nitrogen include cellulose acetate, e.g., cellulose acetate having a degree of substitution of about 2.5; polysulfone; a styrene / acrylonitrile copolymer in which 31 61636 contains e.g. about 20-70% by weight of styrene and about 30-80% by weight of acrylonitrile, mixtures of styrene / acrylonitrile copolymers, etc. Suitable coating materials are polysiloxanes polydimethylsiloxane, polyphenylmethylsiloxane, polytrifluoropropylmethylsiloxane, pre-vulcanized and post-vulcanized silicone rubbers, etc .; polystyrene, e.g., polystyrene having a degree of polycrystallization of about 2-20; polyisopropylene, e.g. isopropylene prepolymer and poly (cis-1,4-isoprene); aliphatic hydrocarbyl-containing compounds having about 14 to 30 carbon atoms, e.g. hexadecane, linseed oil, especially crude linseed oil, etc.

Typical agents for porous separation films for separating hydrogen from hydrogen-containing gas mixtures include cellulose acetate, e.g., cellulose acetate having a degree of substitution of about 2.5; polysulfone; a styrene / acrylonitrile copolymer having e.g. about 20-70% by weight styrene and about 30-80% by weight acrylonitrile, blends of styrene / acrylonitrile copolymers, etc .; polycarbonates; polyarylene oxides such as polyphenylene oxide, polyxylylene oxide, brominated polyxylylene oxide, brominated polyxylylene oxide post-treated with trimethylamine, thiourea, etc. Suitable coating materials include polysiloxanes (polysilicones); e.g. polydimethylsiloxane, pre-vulcanized and post-vulcanized silicone rubber, etc .; polyisoprene; methylstyrene / di-methyl siloxane-möhkälesekapolymeeri; aliphatic hydrocarbyl-containing compounds having about 14 to 30 carbon atoms, etc.

Preferably, the porous separating films used in this invention are not too porous and thus provide a sufficient surface area of the porous separating film material to perform the separation on a commercially attractive base. The porous separating films have a significant effect on the resolving power of the multicomponent films of the present invention, and thus it is desirable to provide a high ratio of total surface area to total pore cross-sectional area in the porous separating film. This result is clearly the opposite of the prior art objectives in the production of composite films in which the overlapping membrane mainly performs separation and the substrates are preferably made porous as well as their main function, i.e. to support the overlapping membrane, and preferably the substrate does not interact with permeable gas; slow or block gas flow from the overlapping membrane.

The amount of gas passing through the porous separation film material and its effect on the performance of the multicomponent films of the invention are clearly influenced by the ratio of the total surface area of the porous separation film to the total pore cross-sectional area and / or the average particle diameter. Often with porous separating films, the ratios of the total surface area to the total cross-sectional area of the pores are at least n.

3 8 10: 1, preferably at least 10: 1 to 10: 1 and some porous 3 8 separation films may have ratios between about 10: 1 to 10: 1 or 12 -. . .

10: 1. The average pore cross-sectional diameter can vary widely and can often be from about 5 to 20,000 Ang-stroms, and in some porous separating films, especially some porous polysulfone separating films, the average porous cross-sectional diameter may be from about 5,000 to 1,000 or up to about 5-200 Angstroms.

The coating is preferably in closed contact with the porous separation film, so that, compared to the designs developed based on the performance observations of the multicomponent films of this invention, increased resistance to gas passage through the separation film pores and gases passing through the porous separation film through the pores is improved compared to the ratio when using a non-coated porous separating film.

One useful feature of gas separation films is the effective separation thickness. The effective separation thickness, as used herein, is the dense film thickness of a continuous (non-porous) and porous separation film material having the same permeation rate for a given gas as a multicomponent film, i.e., the effective separation thickness is a quotient obtained by dividing the porous separation film material by the permeability of the multicomponent membrane to this gas. By providing lower effective separation thicknesses, the permeation rate for a particular gas is increased. Often, the effective separation thickness of multicomponent films is substantially less than the total film thickness, especially when 33 61 636 multicomponent films are anisotropic. Often, the effective separation thickness of multicomponent films for a gas, which may be at least one of the following, carbon monoxide, carbon dioxide, nitrogen, argon, sulfur hexafluoride, methane, and ethane, is less than about 100,000, preferably less than about 15,000, and is between about 100 -15,000 Angstroms. In multicomponent films comprising, for example, porous polysulfone separation films, the effective separation thickness of the multicomponent film for at least one of said gases is preferably less than about 5,000 Angstroms. In some multicomponent films, the effective separation thickness, in particular with respect to at least one of said gases, is less than about 50, preferably less than about 20% of the thickness of the multicomponent film.

Prior to the present invention, in one method of making films for gas separations from pore-containing films, at least one surface of the pore-containing film was treated to seal the surface and thus reduce the presence of pores, which pores reduce the film separation selectivity. This densification has taken place, for example, by chemical treatment with solvents or swelling agents for the film material or by heat treatment, which can be carried out either with or without the film in contact with the liquid. Such sealing processes usually result in a substantial reduction in flow through the membrane. Some particularly preferred multicomponent films of this invention have greater permeability than a film that is substantially the same as the porous separating film used in the multicomponent film, except that at least one of the film surfaces is sufficiently treated to seal the film or sufficiently heat treated with or without , which is equal to or greater than the multicomponent film separation factor. Another method for improving the selectivity of film separation is to vary its manufacturing conditions so that it is less porous than a film made under the same unmodified conditions. In general, the addition of the selective ivisyter, due to the manufacturing conditions, is performed at a substantially lower flow through the membrane. Some particularly preferred multicomponent films of the present invention, for example those in which the porous separating film is an anisotropic hollow fiber, have a higher permeability than an anisotropic hollow fibrous film consisting of at least a porous separating film material capable of retaining the gas. At absolute pressure differences of 10 kg / cm, and wherein the separation factor of the anisotropic hollow fibrous film, for at least one gas pair, is equal to or greater than the separation factor of the multicomponent film.

Preferably, the porous separating film is thick enough that no special equipment is required to handle it. Often the thickness of the porous separating film is about 20-500, between about 50-200 or 300 microns. When the multicomponent film is in the form of a hollow fiber, the outer diameter of the fiber can often be about 200 to 1,000, between about 200 and 800 microns, and the wall thicknesses are about 50 to 200 or 300 microns.

When performing gas separations involving concentrations using the multicomponent membranes of this invention, the multicomponent membrane discharge side is maintained at a lower chemical potential for at least one permeable gas than the chemical potential on the feed side. The driving force for the desired permeation through the multicomponent membrane is the difference in chemical potentials across the multicomponent membrane, as described by Olaf A. Hougen and K.M. In Watson's Chemical Process Principles, Part II, John Wiley, New York (1974), for example, provided by the difference in partial pressure. The permeable gas passes to and through the monikomponenttikalvoon and can be removed from the multi-component film side of the vicinity of the outlet in order to maintain the desired driving force for the gas-permeable. The performance of a multicomponent membrane does not depend on the direction of the gas flow or the surface of the membrane that first comes into contact with the feed gas mixture.

In addition to providing a method for separating at least one gas from gas mixtures, which method does not require expensive cooling and / or other expensive energy inputs, the present invention offers numerous advantages that are very flexible in selective permeation processes. Multicomponent gas separation membranes, whether in the form of a sheet or hollow fiber, are useful in separating industrial gases, enriching oxygen for medical use, in pollution control devices, and for all needs where it is desired to separate at least one gas from gas mixtures. Relatively rarely, a one-component membrane has both a reasonably high degree of separation selectivity and good permeation rate properties, and even then these one-component membranes are only suitable for the separation of very few specific gases. The multicomponent gas separation films of this invention can use a wide variety of materials for porous separation films that have not previously been desired as one-component films for gas separation due to undesirable combinations of permeation rates and separation factor. Because the choice of porous separating film material can be based on its selectivity and permeability constants for the given gases rather than its ability to form thin and substantially pore-free films, the multicomponent films of this invention can be advantageously adapted to separate a large number of gases from gas mixtures.

Mathematical model

The cross-sectional diameter of the pores in the porous separating film can be of the order of Angstroms, and thus the pores of the porous separating film and the interface between the coating and the porous separating film are not directly detectable using currently available optical microscopes. Currently available methods that provide higher magnification of the sample, such as using a beam electron microscope and a transmission electron microscope, involve special sample preparations that limit their viability when describing the exact features of the sample, especially the organic sample. For example, when using a beam electron microscope, an organic sample is coated, e.g., with a gold layer at least 40-50 Angstroms thick to provide a reflection that gives a observed image. Even the manner in which the coating is applied can affect the observed image. In addition, the mere presence of the coating required to use a beam electron microscope can obscure or ostensibly alter the characteristics of the sample. In addition, when using both a beam electron microscope and a transmission electron microscope, the methods used to obtain sufficiently small portions of the sample can substantially alter the characteristics of the sample. Thus, the complete structure of a multicomponent membrane cannot be visibly detected by even the best available microscopic methods.

The multicomponent films of the present invention operate in a unique manner and mathematical models can be developed which, as demonstrated by various methods, generally correspond to the observed performance of the multicomponent film of the present invention. However, these mathematical models do not limit the invention, but rather serve to further illustrate the advantages and benefits of the invention.

For a better understanding of the following mathematical model of the multicomponent films of the present invention, reference is made to the outlined models given in Figures 1, 2, 3, 4, 6 and 7 of these drawings. structures. In addition, in order to help understand the concepts of the mathematical model, the models outlined present the presence of features related to the mathematical model; however, these outlined models are greatly magnified with respect to proportional relationships among these features to facilitate feature detection. Figure 5 is shown to help show the correspondence between the flow-through of the mathematical model of the resistance concept and the resistance to electric current.

Figures 1, 2 and 4 are outlined models for understanding the mathematical model and illustrate the interface between the coating and the porous separating film, i.e., the enlarged area shown in Figure 6 as the area between lines A-A and B-B, but not necessarily on the same scale. Figure 3 is an enlarged outlined model of the area shown in Figure 7 between lines C-C and D-D. In these outlined models, the same markings mean the same items.

Figure 1 is an enlarged cross-sectional view of one outlined model illustrating a substantially continuous and uninterrupted cover 1 of a coating material X in contact with a porous separating film material Y having fixed portions 2 having pores 3, which are filled or partially filled with substance X;

Figure 2 is an enlarged view of another outlined model in which the porous separating film material Y is in the form of a curved surface, the partition areas being cavity or partially filled with the coating material X in uniform contact, i.e. in a continuous manner;

Figure 3 is an enlarged view of an outlined model in which substance X is present in the pores 3 but no continuous cover 1 is present.

Figure H is another outlined model for facilitating the description of concepts in accordance with the mathematical model of the present invention. Figure 4 in conjunction with Figure 5 shows a correspondence with the well-known electric current resistance circuit shown in Figure 5;

Fig. 6 is another cross-sectional view of an outlined model in which the coating material X is molded as a pore-sealing film on a denser surface of a porous separating film, which porous separating film is characterized by a correspondingly gradual density and porous structure throughout the film thickness; and

Figure 7 is a cross-sectional view of an outlined model showing a closed anisotropic separation film that does not necessarily require a continuous or uninterrupted cover 1.

The following equations illustrate a mathematical model developed to explain the observed performances of the multicomponent films of this invention. By appropriately using this mathematical model, porous separating films and materials for coatings can be selected that provide the preferred multi-component films of this invention.

As will be shown below, the flow Q_, for the gas i, a a through the multicomponent membrane, can be represented as a function of the flow resistance of the gas a through each part of the multicomponent membrane (see, for example, the model outlined in Figure 4) mathematically equivalent.

38 61 6 36 1) Q = Δρ it R1, a (R2, a * R3, a) R2, a * R3, a T'a PT'a [_ R2, aR3, a J [R2, aR3, a ΔΡΤ is the pressure difference for the gas across the multicomponent membrane and R 1, * · 1, a R 2 a and R 3 Represent the resistance to the gas flow in the coating 1 in the fixed portions 2 of the porous separating film and in the pores 3 of the porous separating film, respectively. The flow Q, p of another gas b through the same multicomponent membrane can be expressed in the same way, but in the most suitable terms for the pressure differences of the gas b and the flow resistances of the gas b through the coating 1, the porous separation membrane solid parts 2 and the pores 3. Each of these resistors for gas b may be different from each of the resistors for gas a. Thus, selective permeation can be achieved with a monocomponent film. Preferred multicomponent films can be formed by exchanging R 1, R 2 and R 1 relative to each gas a and b to obtain the desired calculated flows for each of the gases a and b and varying the resistors for gas a relative to the resistors for gas b to obtain the calculated selective transmission for gas a for gas b.

Other equations that are useful for understanding this mathematical model are listed below.

For a given release agent, the separation factor for the two gases a and b, ot ^ »is defined by Equation 2 for a film n of a given material with a given thickness ε and an area A

2) <*; = new = Qa Δ pb

Pn, b «b * Pa where a ^ n b ova * the corresponding permeation constants of the substance n for the gases a and b, and Q and Q. are the respective flow rates of the gases a and b.

a D

set through the membrane when Δρ3 and Δρ. are the driving forces, ie the partial

CL O

reductions for gases a and b across the membrane. The flow Q through the membrane of substance n ci to the gas a can be expressed by the equation: 39 61636 o) n - ^ Pa? N »a An - ΔΡ ^ fn, an where An is the surface area of the membrane of substance n, i is the thickness of the membrane of substance n and R defined for the purposes of the model from the substance nn 5a.

in response to the flow of gas a.

It can be seen from Equation 3 that the resistor R is represented by ma * n, a thematically by the equation M: *> Rn, a = Γ ^ ΊΓ n, a n This resistor is mathematically analogous to the electrical resistance of matter to an electric current.

For the purpose of illustrating this mathematical model, reference may be made, for example, to the model outlined in Figure 4. The porous separation film is shown to contain the solid portions 2 of the substance Y and the pores or holes 3. Substance X is present in the model outlined in Figure 4 as a coating 1 and as a substance entering the pores 3 of the porous separating film. the total multi-component film can be compared to a similar electrical circuit as shown in Fig. 5, in which the resistor R1 is in series with two resistors R2 and Rg which are parallel.

If the substance X is in the form of a continuous, dense coating 1, then its resistance R 1 to the flow of the given gas can be represented by Equation 4 and is a function of the coating thickness, the coating surface area A 1 and the permeability constant of the substance X.

The porous separating film of the multicomponent film of the present invention is represented by the model as two parallel resistors. According to Equation 4, the resistance R2 of the solid portions 2 of the porous separation film, which are of substance Y, is a function of the thickness A2 of these solid portions> the total area A2 of the solid portions 2 and the permeability resistance Py of the substance Y. The resistance Rg of the pores 3 in the porous separation film is parallel to R2. The pore resistance R 1 is represented, as in Equation 4, by the thickness 40 61 6 3 6 μl divided by the permeability constant and the total pore cross-sectional area A3. For the purposes of the mathematical model, it is assumed that <? 3 is represented by the average penetration depth of substance X into the pores 3, as described in the model outlined in Figure 4, and the permeability constant is represented by the permeability constant P of substance X present in the pores.

A

The permeability constants P ^ and Ργ are measurable properties of substances. The area A1 can be determined from the shape and size of the multicomponent curve, and the areas A 1 and Ag can be determined or bounded using a conventional beam electron microscope in conjunction with methods based on porous separation membrane gas flow measurements. The thicknesses 6, and a 2 can be determined in the same way. Thus, Q_ for the multicomponent film ^ 1 j ci can be calculated from Equations 1 and 4 using the values Δρ ^ Ile ^ 1 '^ 2 * Ρχ: 11β »for Fy, A ^ r, Aki and A3, which can be observed. The difference factor (<Χ ^) can also be determined in the same way from Equations 1 and 2.

A mathematical model may be helpful in developing the preferred multicomponent films of this invention. For example, since the separation of at least one gas in the gas mixture from the at least one remaining gas occurs primarily in a porous separation film in particularly preferred multicomponent films, a substance for a porous separation film can be selected based on its determined specificity for these gases and its physical, chemical and chemical properties. toughness, longevity, chemical resistance, etc. The substance can then be made into a porous film form using a suitable method. The porous separation membrane can be characterized, as noted above, using a beam electron microscope, preferably in conjunction with gas flow measurement methods, as described by H. Yasuda et al., Journal of Applied Science, Volume 18, pp. 805-819 (1974).

For the purposes of the model, the porous separation membrane can be presented as two parallel resistances to the gas flow, solid parts 2 and pores 3. The pore resistance depends on the average pore size, which determines whether the gas flow through the pores is a laminar flow or a Knudsen diffusion flow (as described above, 41 616 3 6 for example, Hwang, et al., as above on page 50-) and the number of pores. Because the diffusion rates of the gases through the open pores are much higher than through the solids, the calculated resistance to pore gas flow is generally substantially less than the calculated resistance R2 of the solids in the porous separation membrane, even when the total pore cross-sectional area is much smaller than the total solids . In order to obtain an increase in the proportion of gas flow passed through the solids 2 with respect to the flow through the pores 3, the pore resistance R 1 must be increased relative to the solids resistance R 1.

After obtaining an evaluation of the resistance to gas flow through the pores and knowing the gas flow resistance of the porous separating film material, the desired increase in resistance to gas flow through the pores required to provide a multicomponent film having the desired separation factor can be evaluated. Conveniently, but not necessarily, it can be assumed that the depth of the coating material in the pores (^) and the minimum gas permeation distance through the porous separating film material are the same. Then, based on the permeability constants of the coating materials being known, a material can be selected for the coating to obtain the desired resistance. The agent for the coating can also be selected for other properties in addition to the addition of R3, as described below. If the coating material also forms a cover on the porous separating film, as shown in Figure 4, it can reduce the flow. Such a situation is described according to the mathematical model by Equation 1. In such a case, the properties of the coating material should also be such that the flow does not decrease too much.

The choice of material for a coating depends on its determined specific separation factor relative to the specified specific separation factor of the porous separating film material and its ability to provide the desired resistance to the multicomponent film. The coating material should be able to be in closed contact with the porous separating film. Based on the average pore size of the porous separating film, coatings with a suitable molecular size can be selected. If the molecular size of the coating is too large, or if the coating material joins the pores on the surface, the model requires that the pore resistance Rg does not increase relative to the resistance R2 of the portions of the porous separating film, and in this case the gas portion permeable to the portions 2 relative to the gases , which diffuse through the pores, would not increase relative to the portion in the porous separation membrane alone. On the other hand, if the molecular size of the coating material is too small, it will be absorbed through the pores during coating and / or separation operations.

Often the coating is made in the form of a cover 1 (see the model outlined in Figure · +) in addition to the coating material that goes into the pores. In these cases, the cover 1 represents a resistor R 1 for the gas flow, which is in series with the combined resistors of the porous separation film. When such a situation occurs, the coating material should preferably be selected so that the coating layer in the multicomponent film does not provide too much resistance to gas flow (while the coating still provides sufficient resistance in the pores) so that the porous separation film essentially causes at least one gas to separate in the gas mixture. This could be accomplished, for example, by coating a material with high permeability constants for gases and low selectivity.

The thickness of the cover, as shown in the model, can also have some effect on the flow and selectivity of the multicomponent film, since the resistance (R 1) of the cover 1 is a function of its thickness.

If a suitable substance X and substance Y are selected, different configurations of multicomponent films containing these substances can be formed using Equations 1, 2 and 4. Information on, for example, the more desired ratios of the total pore area (Ag) to the total surface area (A ^ + Ag) for the porous separating film and more desired thicknesses for the separating layer j of the porous separating film can be obtained from this mathematically formed. This information can be useful, for example, in determining procedures for making porous separating films having the desired surface area ratios Ag / (A2 + Ag) as well as the desired separation thicknesses ^ 2 as well as the desired coating layer thicknesses. In the case of anisotropic '61636 hollow, porous fiber separation films, this can be accomplished by appropriately selecting spinning conditions and / or post-treatment conditions. The above study describes the way in which configurations of multicomponent films can be mathematically formed. Several methods have been proposed for varying the relative resistances of the coating layers 1, the portions of the porous separation film solids 2 and the pores 3 with respect to at least one gas pair to give preferred multicomponent films with high flow and high selectivity for at least one gas pair.

The following is a mathematical derivation that, together with Equations 3 and 4, gives Equation 1.

From the well-known law of Ohm's electrical resistors, a mathematical expression can be obtained for the total resistance R, p of the electric circuit shown in Fig. 5.

5) RT = R1 + R23 = R1 + R2 + R3 where R22 is the combined resistance of R2 and R2 and is equal to the latter term in Equation 5.

Analogously, the mathematical model described above utilizes the same mathematical equation to express the total flow resistance of a given gas for a multicomponent membrane, as illustrated in an enlarged manner in the model outlined in Figure 4. Resistor R23 represents the combined resistance of each part of the porous separating film, the solid parts 2 and the pores 3 filled with substance X. If the coating is not arranged as a substantially uniform cover 1, but only as a substance X entering the pores 3, the situation described in the model outlined in Figure 3, then the resistance of the coating layer R1 is 0 and this term falls out of Equations 5 and all subsequent equations .

The total flow of a given gas through the multicomponent membrane is equal to the flow in the electric current and is given at steady state by Equation 6.

^ 61636 6> ^ T, a = Va = ^ 23, a where Q. is the gas flow through the surface layer 1 and Q9q is the combined gas flow through both the portions 2 and the pores 3 of the porous separation film (which are filled with the substance). X).

75 Q23, a = Q2, a + Q3, a

The total partial pressure drop for the gas a across the multicomponent membrane is the partial pressure drop through the coating 1, Äp. and the partial pressure drop across the solid parts 2 and the filled pores 3 of the porous separation membrane, the sum of Λρ00

L O 9 CL

85 * PT, a = «> 1.3 + ** 23, a

The flow of gas a through each part of the multicomponent membrane can be expressed by Equation 3 using resistances and partial pressure decreases specific to each part.

a 9) Qi a "1, a R1, a

10) Q0. = 4p23, a _ Ap23, a (R2, a + R3, aJ

Toya. · = - p “-s K2 3, a 2, a 3, a

From equations 6, 8, 9 and 10, the expression for the total decrease in resistances and partial pressure can be derived for poa: R1 a ^ R2 a + R3 a ^ 11) Δρ23, a = * pT, a 1 + * R2 a * R3 a 2

Equation 11 together with Equations 6 and 10 gives Equation 1.

According to the present invention, the coating is in closed contact with the porous separating film to obtain a multicomponent film. This mathematical model, developed to explain the phenomena occurring in the multicomponent films of the present invention, requires that the pores 3 in the porous separating film contain the substance X. The resistance of the pores containing substance X to the gas flow X, resistance to gas flow, because the permeability of any substance to gases is much lower than the permeability of an open flow channel. Thus, it grows in a multicomponent membrane and, referring to Equation 10, R e becomes more significant in its effect on R e. Because Rg increases relative to R1 in the multicomponent membrane, a larger portion of the gas passes through the solid portions of the porous separation membrane compared to the pores 3 filled with the gas X than the portion of the gas in the porous separation membrane alone. Thus, the separation factor of at least one gas pair is improved in the multicomponent membrane by the interaction with the substance Y, compared to the separation factor in the porous separation membrane alone.

The following examples illustrate the invention but do not limit it. All parts and percentages of gases are by volume and all parts and percentages of liquids and solids are by weight unless otherwise indicated.

Examples 1-3

Examples 1-3 in Table I represent multicomponent films consisting of porous cellulose acetate separating films and a coating. Examples 2 and 3 show the same combined hollow fibrous films separating the two different gas mixtures. These two examples show that the porous substrate film separates the two gas mixtures to some degree even in the absence of a coating, but in both cases the separation factor is much lower than the determined specific separation factor of cellulose acetate. In such porous separation films, most of the gas passes through the pores and relatively little permeable flow occurs through the cellulose acetate.

After coating, the separation factor for the gases in the multicomponent films of Examples 2 and 3 is greater than both the determined specific separation factor of the coating material and the separation factor of the porous separation film. Thus, in a multicomponent membrane, more of the gas flow occurs through cellulose acetate than through pores; as a result, the separation factor of the multicomponent film is much closer to the determined specific separation factor of cellulose acetate.

46 61 6 3 6

Example 1 shows a different sample of a hollow cellulose acetate fiber having somewhat different properties when coated and uncoated, which can be compared to Example 2. Although the porous separation film has a higher permeability to C 1 and a lower separation factor, with a porous separating film substance separately.

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Examples 4-10 616 3 6

Examples 4-10 illustrate various liquid coatings with porous hollow polysulfone fiber separation films for the selective separation of oxygen from air and are shown in Table II. Porous separation membranes do not separate oxygen from nitrogen. The coating materials used are representative high molecular weight organic and silicone fluids with sufficiently low vapor pressures so that they do not easily evaporate from the coated surface and generally have oxygen-nitrogen separation factors of less than about 2.5. The molecular sizes of the coatings are small enough to make closed contact with the porous separation film, but are not too small so that the coating material can pass through the pores under coating and / or separation conditions. The observed separation factors for multicomponent films are greater than both the porous separation film separation factor (1.0 in all examples) and the coating agent separation factor (2.5 or less for the coating materials of the examples).

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Examples 11-15 616 3 6 52

Examples 11-15 illustrate various coatings that are either applied to porous separating films as liquids and reacted in place to form solid polymer coatings (post-vulcanization) or applied, as is usually the case with solid polymers dissolved in a solvent. The results are shown in Table III. In the examples, oxygen is enriched from the air supply with a multicomponent film and a variety of treated hollow fibrous, porous polysulfone separation films are used.

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Examples 16-18

Examples 16, 17 and 18 show that multicomponent films using hollow, fibrous porous polysulfone separation films can also be efficiently separated from CO / t 2 mixtures in accordance with the invention. The separation factor of the porous separation film was not measured before coating with Examples 16 and 18, but numerous experiments with similar porous separation films show that the separation factors can be expected to be between about 1.3 and about 2.5. This expectation is confirmed in Example 17, where the separation factor of the porous separation film for H 2 with respect to CO was measured to be 1.3. These porous separation films thus have some resolution between H 2 and CO due to Knudsen diffusion. These examples describe various coatings, coating methods, permeabilities, and separation factors for multicomponent and porous separation films in the preparation of the multicomponent films of the invention. Examples 14 and 17 and Examples 15 and 18 are performed simultaneously on a multicomponent membrane, and a comparison of these examples shows that the use of a multicomponent membrane for one separation or with one gas mixture does not prevent its subsequent operation with another gas combination. Examples are shown in Table IV.

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Examples 19-21 56 6 1 6 3 6

Examples 19, 20 and 21 (Table V) show the permeation properties for air and CO 2 H2 of multicomponent films consisting of different coating materials with porous, hollow fibrous copoly (styrene-acrylonitrile) separation films. In each example, the multicomponent film has a higher separation factor than any of the coatings and porous separation films alone. Example 21 shows a porous separating film having a separation factor of H 2 O '- He CO of 15 before application of the coating, i.e. the porous separating film has relatively few pores and a small average pore diameter. A comparison of Examples 20 and 21 shows that the multicomponent film of Example 20 has a higher penetration rate and a higher separation factor than the porous separation film of Example 21, even though this film has a higher separation factor than the separation factor of the porous separation film of Example 20. Thus, the multicomponent films of the present invention may have a higher penetration rate than a film having an equal or greater separation factor and consisting essentially of a porous separation film material.

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Example 22

A gas stream having five components is used as a feed to the multicomponent membrane of Examples 15 and 18. The gas stream contains hydrogen, carbon dioxide, carbon monoxide, nitrogen and methane, and amounts of water and methanol up to saturation values. The feed stream is directed at a pressure of 4.5 kg / cm 2 and a temperature of 40 ° C to the coating side of the multicomponent film. Cavity pressure is one atmosphere. The following gas permeabilities and separation factors in relation to hydrogen are observed: Permeability: Separation factor for H 2 H2 (8.5 x 10 0-5): CO 2 (3.7 x 10-5): CO 2 2.3 CCKO, 27 for x 10 "5) CO 31.0 N 2 (0.68 x 10-5) for N? 12.4 CH 2 (0.23 x 10 5) CH 4 36.9 * In cm 3 ( NPT) / cm2-s-cm Hg.

It will be appreciated that in this example, the separation of hydrogen from gas mixtures containing at least one of CO, N 2 and CH 2 can be readily performed. The presence of one or more other gases in the gas mixture, such as the presence of saturated water and methanol vapor, does not appear to interfere with the separation performance of the multicomponent film. It will also be appreciated that other different gases in the mixture may be separated from each other, for example the separation factor for CO2 with respect to CO2 would be the permeability ratio, i.e. about 14. Example 22 also illustrates the effect of a porous separation film to provide relative permeation rates through a multicomponent membrane. Thus, the determined specific separation factor of the coating material (Sylgard 184) is about 0.3 to 0.4 for H2 with respect to CO2 (i.e., CO2 is faster than H2), but the separation factor of the multicomponent film for H2 with respect to CO2 * is 2. , 3. This value is essentially equal, within the limits of the experimental errors, to the determined specific separation factor of polysulfone for H2 with respect to CO2.

Example 23

Example 23 (Table VI) shows the permeabilities (P / ii) for a number of gases through a multicomponent film using a hollow, porous polysulfone fiber separation film. Example 23 also shows the same values for the same gases through a continuous 60 6 1 6 3 6 dense film made of polysulfonic material. The ratio of any two values of P or Ρ / ί?: Η determines the approximate difference factor for these gases through a dense membrane or a multicomponent membrane, respectively. The example illustrates the clear tendency for permeabilities for multicomponent curves to generally vary from gas to gas in the same order as permeabilities for a dense polysulfone film. This tendency indicates that the porous separating film material provides a significant portion of the multicomponent film separation. This example also shows that a multicomponent membrane can be used to separate any of a number of gases from each other. For example, it can be seen from the table that voitaisiin 2 could be easily separated from H 2 or N 2, He 2 CH 2, N 2 O, N 2, O 2 N 2 or H 2 S CH 2 using this multicomponent film. The advantage of the permeation rates of multicomponent films is demonstrated by the values shown in Table VI.

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Comparative Examples 2 * 1-26 (not according to the invention)

Examples 24-26 are shown in Table VII and are so i. I; i find that not all composite films are within the scope of the invention, i.e. , (tin multicomponent film having a separation factor significantly greater than the determined specific separation factor of the coating material, even if they consist of porous separating films and coating l-sheets, each of which can be used with other coating compositions or porous separating films according to the invention.

Example 24 provides a multicomponent film having a pre-vulcanized silicone rubber coating with a porous polysulfone separation film. Since the pre-vulcanized silicone rubber may have too large molecular dimensions to be expected to close the pores according to the pattern, for example, the molecules can only connect the pores, the coating does not change the resistance of the pores to air flow. In Example 24, the coating compound is a pre-vulcanized polymer having the same major polymer backbone as Sylgard 184, described, for example, in Examples 11, 14 and 15 in Table III. However, the pre-vulcanized silicone rubber has a much higher molecular weight and size than Sylgard 184 due to the pre-vulcanization and thus apparently cannot fill the pores and thus the composite film separation factor is as high (within test errors) as the coating separation factor.

Example 25 illustrates a multicomponent film in which Sylgard 184 has been used as a coating material and porous polyacrylonitrile as a separating film. The permeability of polyacrylonitrile to gases is very low when it is in a continuous, non-porous form. Referring to the model, such a porous separating film has a very high resistance to flow through its solid parts, so that when a high permeability coating material such as Sylgard 184 is in closed contact with it, gas flow predominantly through the coating and the clogged pores, and thus the multicomponent large or smaller than the cover-membrane separation factor.

The difference between the multicomponent 1 described in Example 26 and 64 616 3 6 is less than the determined specific separation of the topcoat. This situation is similar to that shown in Example 4 in that the polyvinyl butyral] 1a used as a coating material has a high molecular weight. In addition, it does not wet polysulfone as well as many silicones and other inexpensive coatings. EdelTeen polyvinyl libutyral has a relatively low permeability. The finding that this multi-component film has a lower separation factor than that expected from the coating material is reminiscent of the shortcomings of the coating itself.

Table VII (not according to the invention)

Example 24 Coating General Electric 4164 pre-vulcanized silicone rubber

Porous hollow fiber film Polysulfone P-3600 Union Carbide

Gas supply Air

Enriched gas (passed 0 ^ gas)

Coating Method E

The coefficient determined for Olille with respect to N 2 was 1, the characteristic difference was * 3 -4

Permeability of the porous separation membrane to air HB x l] e

The difference between the porosity of the porous separating film and the ol is n

The difference factor of 1.61 for the multicomponent membrane is 3 *

The swellability of the multicomponent film is C ^ Hle 4> 1 x ^ c

Example 25 65 61 6 3 6 Coating Dow Corning Sylgard 184 post-vulcanized silicone rubber

Porous, hollow fibrous film Polyacrylonitrile

Gas supply Air

Enriched gas (passed 0 ^ gas)

Coating method F

Coating agent assigned to O ^. N ^ n GU ^ te 7, 8 characteristic resolution factor ^ -3

Through the porous separating membrane? x 10 c swelling

The difference in porosity of the porous separation film with respect to N9 is 1.0. . ,. . „B tusteki] a

The difference in the multicomponent membrane with respect to N 2 is 1.9

Transparency of the multicomponent membrane 1.7 x 10

Example 26 Coating Polyvinyl buffer

Porous, hollow fiber film Polysulfone P-3800 Union Curhide

Gas supply Air

Enriched gas (passed 0 ^ gas)

Coating method C

The coating material was determined to have a specific resolution factor of 4.7 for Olille N? -4

The porosity of the porous separating film is 1.8 x 10 c

The difference between the porosity of the porous separating film with respect to N is 1.0 e + V · · -b

The difference between the multicomponent membrane and N with respect to N is 4.0 4- +. i · · -b 1 7 t u s t e k i j a

The multicomponent membrane is 1.4 x 1 ^

O

swelling “66 _ - 6 '1 6 3 6

(a) as footnote (d) in Table I.

(b) as in footnote (e) to Table I.

(c) as footnote (a) in Table I.

Examples 27-34

Examples 27-34 are shown in Table VIII and describe a series of porous separation film treatments after spinning and the manner in which these treatments affect the separation properties of multicomponent ages made from such post-treated porous separation films. In Table VIII, the coating material and the application method are essentially the same to emphasize that changes in the permeability rate and separation factor of the multicomponent film (both air and CO / H 2 gas mixture feed) are apparently due to changes in the relatively dense pores of the porous separation film. The treatments are believed to affect the available pore cross-sectional area (Ag) relative to the total area of the porous separating film (A £ + A 2). The increase in N 1 relative to the total area causes an increase in the relative resistance to flow through the pores in the porous separation and multi-component film. This, in turn, forces more permeable gas to flow through the porous separation film material, and the separation factor of the multicomponent membrane becomes closer to the specific separation factor of the porous separation film material.

The porous separating film used in all the examples in Table VIII is a porous, hollow polysulfone fibrous film (Union Carbide, P-3500) on the same side that was wet-spun from a solution of 25% solids in dimethylformamide solvent to a water coagulant at about 3 ° C. through a tubular orifice in which water was sprayed into the hole and the fibers were spooled at a speed of 21.4 m / min. The porous separating film used in each example is stored in deionized water at room temperature after spinning until they enter the post-treatment process.

Table VIII

Examples 27-34

Post-treatment of hollow fibrous film

The multicomponent films of Examples 27-34 are used as a headstock for Dow Corning Sylgard 184 post-vulcanized silicone fibers, following the coating method shown in Table XVI. The treatment was performed on the hollow fiber film after spinning but before coating.

Example 27 Post-treatment Evaporation of water

Gas supply Air

Enriched gas (passed 0 ^ gas)

1.5 x 10 a swelling for the multicomponent film

Difference in the multicomponent membrane with respect to Oj 4.7 N-factor ^ -4 Post-treated porous difference- Air permeability 3.7 x 10 Transparency of the post-treated porous film

Example 28 Post-treatment Evaporation of water

Gas supply CO, H2

Enriched gas (passed Hj gas) r - 5

7.6 x 10 a · a permeability of the multicomponent film

The difference H of the multicomponent film with respect to CO is 23.1. . . . ... b tust factor -4 After-treated porous difference- For them about 2.0 x 10. membrane permeability for post-treated porous difference H_ with respect to CO approx. 2.6 membrane separation factor 68 61 63 6

Example 29 Post-treatment Evaporation of water; followed by exposure to acetone vapor at 1 ° C at 5 ° C; followed by alternation of water immersion and methanol immersion with a cavity vacuum (3 times); followed by alternation of immersion in water and isopropyl immersion (2 times)

Gas supply Air

Enriched gas (passed 0 ^ gas)

7.7 x 10 ~ G for the multicomponent film

permeability

The difference of the multicomponent film with respect to NO0 is 5.3. . b il tust factor. -5 Permeability of the post-treated porous membrane to 3.5 x 10 • 3. ^ permeability of the post-treated porous membrane to N0 1.0 v cc membrane separation factor D Example 30 Post-treatment Evaporation of water; followed by exposure to acetone vapor at 25 ° C under vacuum; followed by alternation of immersion in water and immersion in methanol with a cavity vacuum (3 times); followed by alternation of immersion in water and immersion in isopropyl alcohol (2 times)

Gas supply CO, H2

Enriched gas (gas passed)

For the multicomponent membrane k, 5 x 10 S

.. · a swelling

Permeability of the multicomponent film with respect to C0 30.4 tact factor ^ -4 Permeability of the post-treated porous diffuser

Example 31 69 61636 Post-treatment Evaporation of water; followed by heating in a hot air oven at 80-9 ° C for about 3 hours

Gas supply Air

Enriched gas (passed 0 ^ gas)

. . - C

The permeability of the multicomponent film is 1.6 x 10 ... a ^

The difference of the multicomponent film with respect to N is 5.0. . b ^ ^ transduction factor Permeability of post-treated porous air to air permeability 3.7 x 10 ~ 4 Transparency of post-treated porous difference- 1.0 L C. C.

membrane separation factor D Example 32 Post-treatment Evaporation of water; followed by heating in a hot air oven at 80-95 ° C for about 3 hours

Gas supply CO, H2

Enriched gas (gas passed)

The permeability of the multicomponent film to 9.8 x 10 5 permeability3

Permeability of the multicomponent film to H 2 with respect to CO 23 permeability of the post-treated porous difference to H 2, 2.5 x 10

For the post-treated porous difference H_ with respect to CO, a separation factor D of about 1.3

Example 33 70 61 636 Post-treatment Dry by exchanging water for isopropyl alcohol; followed by exchange of isopropyl for pantane, followed by evaporation of pentane

Gas supply Air

Enriched gas (passed 0 ^ gas)

The multicomponent film has a thickness of 2.0 x 10-5 ... a ^

The difference factor of the multicomponent membrane with respect to N 2 is 4.2 ^ 2 2

. . . _ O

Permeability of the post-treated porous membrane to air 1.5 x 10 Permeability of the post-treated porous membrane to the · · · · to N0 of the post-treated porous membrane Example 2 Post-treatment Dry by exchanging water for isopropyl alcohol; followed by conversion of isopropyl alcohol to pentane, followed by evaporation of the pentane

Gas supply CO, H2

Enriched gas (passed H2 gas)

1.2 x 10-'4 u · a 1 permeability of the multicomponent film

The difference of the multicomponent membrane for H0 with respect to CO is 15.9

tustekijäD

. , · - il Permeability of the post-treated porous difference H 2 to about 2.5 x 10 Tissue membrane3 Post-treated porous difference H 2 to CO about 1.3 Tissue separation factor ^

(a) as footnote (a) in Table I.

(b) as in footnote (e) to Table I.

71 61636

Examples 35-39

Examples 35-39 in Table IX illustrate the effect that additives in the coating material have on the multicomponent film separation factor for the feed streams of the bi-gas mixtures (air and CO / H 2). These additives are combined with the coating material in small amounts before the coating is applied to the porous separating film. Such additives can alter the separating properties of multicomponent films, for example, by altering the wetting properties of the coating material and thus affecting its ability to be in closed contact with the porous separating film. If the additive improves sealed contact, the multicomponent film separation factor with such an additive is expected to be closer to the specific separation factor of the porous separation film material than that of a similar multicomponent film without such an additive.

The porous, hollow separation fiber films used in Examples 35-39 were all from the same spool and were made of polysulfone (P-3500) in a highly porous form (see footnote a) by spinning according to the same method as the hollow fibers of Examples 27-3 <4. . The determined specific separation factor of polysulfone for Olille N2 from the air supply is about 6.0 and for Heille CO for the CO / H 2 mixture is about 40.

17 61636

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Examples 40-43 74 616 3 6

Examples 40-43 in Table X illustrate multicomponent films in which porous separation films are prepared under different spinning conditions. The multicomponent films of Examples 40-43 use Dow Corning Sylgard 184 post-vulcanized silicone rubber coating (coating method F, Table XVI) with porous polysulfone (Union Carbide P-3500) release films. The porous hollow polysulfone fibrous substrate films are spun from the solutions shown by the wet nozzle method into the water coagulant at the indicated temperature and at the indicated spinning speed by means of a hollow fiber spinning nozzle having an opening for injecting the coagulant into the fiber hole. The permeabilities (0 ^ and) and separation factors (0 ^) of the multicomponent films shown in Examples 40-43

With respect to Ng and with respect to CO) for either the air supply or the CO / H 2 mixture supply may be proportional to the variability of the relative resistances of the pores of the porous separation membranes and the substance to the gas flow. The conditions under which the porous substrate material is spun will largely determine the porosity properties and the effective separation thickness that the substrate will have. In addition, these properties can be modified by post-spinning treatments of the porous substrate (see Examples 27-34).

Table X

Spinning conditions for hollow, porous P-3500 polysulfone separating fiber films

Example 40

Solvent Dimethylformamide

Coagulation temperature ° C 3 °

Spinning speed, m / min 21.4 m / min

Spinning liquid concentration% by weight polymer 25%

Multicomponent membrane resolution factor, 4.5 for O 2 relative to N 2 ^ Permeability to Ol 3 3 7.7 x 10 ^

Multicomponent film separation factor, 16.7 for H 2 with respect to C 0 * 5 Permeability to H 2 5.0 x 10 2

Air permeability of the porous separating film 6x10 616 3 6 75

Example 41

Solvent Dimethyl formamide

Coagulation temperature ° C 5 °

Spinning speed, m / min 21.4 m / min

Spinning solution concentration% by weight polymer 25%

Multicomponent membrane separation factor, 5.09 C ^ He ratio15 Permeability O ^ tlle3 6.2 x 10 6

Multicomponent membrane separation factor, 25 for H 2 with respect to CO 15

^ o _ C

Permeability to H? 4.9 x 10 * a -4

Air permeability of the porous separating film 9x10

Example 42

Solvent Dimethylformamide

Coagulation temperature ° C 4 °

Spinning speed, m / min 33 m / min

Spinning liquid concentration% by weight polymer 28%

Multicomponent membrane separation factor, 5.9

Olille ^ in relation to15

Permeability Olille 8.0 x 10 G

Multicomponent film separation factor 30 for H9 with respect to CO15 ^ a -5 Permeability to H9 5.9 x 10 cl 4

Air permeability of the porous separating film 2x10 76 61 636

Example 4 3

Solvent Dimethylacetamide

Coagulation temperature ° C 5 °

Spinning speed, m / min 33 m / min

Spinning liquid concentration% by weight polymer 27%

Multicomponent membrane separation factor, 5.6 02 = 116 for N2 = n ** Permeability to ditches 6.0 x 10 ~ 6

Multicomponent membrane separation factor, 27

For CO with respect to CO * 5 Permeability3 to H2 3.8 x 10 ~ 5

Permeability of the porous separating film3 to air 4.5 x 1 O-4

(a) as in Table I.

(b) as in footnote (e) to Table I.

Examples 44-51

Examples 44-47 in Table XI illustrate multicomponent films in which the porous separation film is in the form of an anisotropic film which is an acrylonitrile / styrene copolymer having a determined specific separation factor Η2 = 11β for CO 76. The films were cast from solvents and dimethylform solvents, as shown in the table, on a plate, the solvent was removed in air for 5-45 seconds, coagulated as follows and immersed in water at 25 ° C for washing, removed therefrom and dried. Examples 48-51 illustrate multicomponent films in the form of dense films. These examples illustrate the multicomponent films of the invention which are in the form of films and may include porous release films coated on each surface.

77 61 636

Table XI

Multicomponent films in film form Example 44 Coating Dow Corning Sylgard 184 post-cured silicone rubber

Poroly separating film Kopoly (acrylonitrile / sLyrene), 32% / 68% by weight

Gas supply CO., LTD

Coating method B

Coating agent determined 1.9 specific separation factor * 3, For them with respect to CO

Porous separation film separation factor * 3, for H2 with respect to CO

Multicomponent Membrane Separation Factor 34.8 for H2 Example 45 Coating Dow Corning 200 Polydimethylsiloxane

Poroly separating film Kopoly (acrylonitrile / styrene), 32% / 68% by weight

Gas supply H2, CO

Coating method B

Specified resolution factor 1.9 for the coating material * 3, Η2: 1ΐ6 for CO

12.2 separation factor of the porous separation membrane * 3 for H2 with respect to CO Multiplication factor of the multicomponent membrane with respect to CO 2 78 616 3 6

Example 46 Coating Dow Corning Sylgard 184 Vulcanized Silicone Rubber

Poroly separating film Kopoly (acrylonitrile / styrene), 32% / 68% by weight

Gas supply, CO

Coating method B

Coating agent determined 1.9 specific separation factor * 5, for H 2 with respect to CO

A separation factor of 4.0 for the porous separation film for H 2 with respect to CO

Multicomponent membrane separation factor for H 2 with respect to CO

Example 47 Coating Dow Corning 200 polydimethylsiloxane

Poroly separating film Kopoly (acrylonitrile / styrene), 32% / 68% by weight Coating Dow Corning 200 polydimethylsiloxane

Gas supply H-, CO

Coating method B

Coating agent determined for the specific separation factor b, 1, 9, H2 with respect to CO

Particulate Separation Film Separation Factor 3.4 for CO

Multicomponent film, coating 7.6 on one side, differentiation factor for H0 with respect to CO

Continued 79 61 636

Multicomponent film, coating on each side, separation factor for H 2 with respect to CO (a) as described in Table XVI

(b) as in footnote (e) to Table I.

(c) coagulated ethylene glycol / in aqueous mixture (50/50, v / v) 30 minutes at 25 ° C (d) coagulated isopropyl alcohol / in aqueous mixture (90/10, v / v) 30 minutes at 25 ° C (e) coagulated isopropyl alcohol / in aqueous mixture (10/90, v / v) for 30 minutes at 25 ° C (f) coagulated in water at 25 ° C

Example 48 Coating Dow Corning Sylgard 184 post-cured silicone rubber

Poroly porous separating film (acrylonitrile / styrene), 25% / 75% by weight

Gas supply Air

Enriched gas (passed 02 gas)

Coating Method E

A specific separation factor of 2.3 determined for the coating material

Difference factor 3.6 for Civile N2 in the porous separation membrane * 5

Factor 5.4 for multicomponent membrane difference 02 relative to N2 ^ 80 61 6 3 6

Example 49 Coating Dow Corning 200 polydimethylsiloxane

Porous Separation Film Poly Acrylonitrile / Styrene Copolymer Polymer Blend

Gas supply Air

Enriched gas (passed 0 ^ gas)

Coating method A

The determined 2.3 specific separation factor of the coating material is

The difference in porosity of the porous separating membrane with respect to N2 is 4.9.

The difference in the multicomponent membrane with respect to N

Example 50 Coating Dow Corning 200 polydimethyl.i siloxane

Poroly separating film Kopoly (acrylonitrile / styrene), 32% / 68% by weight, suspension polymerized

Gas supply Air

Enriched gas (passed 02 gas)

Coating method3 A

The specific separation factor of 2.3 determined for the coating material ^

The difference between the porosity of the porous separation film and the

The difference in the multicomponent film with respect to N »is 6.3 t)

tustekijäD

81 61 636

Example 51 Coating Dow Corning 200 polydiinethyl jS3 ·} 0) <_ sane

Poroly separating film Kopoly (acrylonitrile / styrene), 32% / 68% by weight, bulk polymerized + n

Gas supply Air

Enriched gas (passed 0 ^ gas)

Coating method A

The specific separation factor of 2.3 determined for the coating material ^

The difference in porosity of the porous separation film from C2 to N2 is 3.6

The difference of the multicomponent membrane with respect to N „is 4.9 V. t t

tustekijäD

(a) as explained in Table XVI

(b) as in footnote (e) to Table I.

Examples 52-57

Examples 52-57 illustrate several multicomponent films in hollow fiber form. Porous hollow films can be prepared by wet spinning, as generally described above. The polycarbonate fiber of Examples 52 and 53 was spin-wetted from a spinning liquid containing 27.5% by weight of polycarbonate in N-methylpyrrolidone into a water coagulant at 25 ° C at a speed of 21.4 m / min. The hollow polysulfone fiber of Example 54 was spun from a spinning liquid containing 27.5% by weight of polysulfone (P-3500) in a mixed 80/20 dimethylacetamide / acetone solvent to a water coagulant at 2 ° C at a rate of 21.4 m / min. The acrylonitrile / styrene copolymer fiber of Example 55 was spun from a spinning fluid containing 27.5% by weight of the copolymer in a mixed solvent 80/20-dimethylformamide / formamide in a water coagulant at 3 ° C at a rate of 21.4 m / min. The acrylonitrile / styrene copolymer fiber of Examples 56-57 was spun from a spinning liquid containing 25% by weight of the copolymer in the same mixed solvent as in Example 55 to a water coagulant at about 20 ° C at a rate of 21.4 m / min. The results of the tests on hollow multicomponent fibers separated from the hydrogen / carbon monoxide gas mixture are shown in Table XII below: 83 61 6 3 6

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Example 58 84 616 36 The present invention describes a multicomponent film having multiple coatings to obtain a desired resolution factor. A porous hollow separation fiber film consisting of a copolymer of 63% acrylonitrile and 37% styrene was wet-spun from a solution of 27.5% by weight copolymer in a 93/7-dimethylformamide / formamide copolymer at 2 ° C in water at a rate of 21 m / min. This fiber was first treated by dipping in methanol while vacuuming the hole, drying, and repeating the methanol treatment and drying. The dried substrate fiber was then coated using Method D in poly (cis-isoprene) pentane solvent, cured for 30 minutes at 85 ° C, and then coated with a 10% solution of Sylgard 184 in pentane by Method F. The coated substrate was recoated with poly (cis-isoprene). isoprene), dried and recoated with Sylgard 184 solution and then cured for 30 minutes at 90 ° C, 30 minutes at 100 ° C and finally for 30 minutes at 105 ° C. The results obtained when testing an uncoated porous and multi-coated multicomponent film are shown in Table XIII.

Table XIII

Characteristic specificity of the coating - Cis-isoprene 3.5 factor for H2 with respect to C0 Sylgard 184 1.9

Porous separation film separation factor 5.09

For them in terms of CO

Multicomponent membrane separation factor 82 for H_ with respect to CO 1. -7

The permeability of the multicomponent film to H? 6.5 x 10 1 -5

Permeability of the porous separation membrane For them 2.65 x 10 Determined specific separation factor for H ^ ^ for 320 CO for the porous separation membrane material

Examples 59 and 60 85 6 '! 6 36

Examples 59 and 60 illustrate a multicomponent using a porous brominated polyxylylene oxide separation film coated in a hollow fiber form. A hollow fiber from a spinning solution of wet spinning containing 30% by weight of polymer in N-methylpyrrolidone to a water coagulant at 85 ° C at a rate of 14.8 m / min. In Example 59, brominated polyxylylene oxide in which the bromination is predominantly in methyl groups is coated without post-spinning treatment. In Example 60, the brominated polyxylylene oxide is post-treated by impregnation for 20 hours in a 10% aqueous solution of trimethylamine. In all cases, the coating was Dow Corning Sylgard 184 silicone rubber applied by Method B (see Table XVI). The results are shown in Table XIV below.

Table XIV

59 60

Dow Corning Dow Corning

Sylgard 184 Sylgard 184 post-vulcanised post-vulcanised silicone rubber silicone rubber Brominated poly- Brominated poly-xylyleneoxy-xylylene oxide, di post-treated with (CH3) 3N Coating material determined 1.9 1.9 specific separation factor, For them for CO

Porous separation membrane separation factor 1.48 2.85, for them for CO

Multicomponent membrane separation factor 11.1 9.59 for H9 with respect to CO 1 -5 -5

Multi-component membrane permeability 9.58 x 10 1.27 x 10 for H9. 1. -3 -5

Permeability of the porous separation film to 1.25 x 10 3.83x10 for H 2 Determined specific separation factor 15 34

They're CO with respect to the porous separation membrane material

Example 61 86 61 636 This example illustrates a multicomponent film using a different modified porous brominated polyxylylene oxide separation film in hollow fiber form. The hollow brominated polyxylylene oxide fiber of Example 59 was post-treated by soaking for about 70 hours at 50 ° C in a 5% w / w solution of thiourea dissolved in 95/5, v / v, water / methanol. After drying, the hollow fibrous film was coated with a 5% solution of Dow Corning Sylgard 184 in pentane using Method F (see Table XVI). Testing of the post-treated hollow, porous fiber separation film and the coated multicomponent film gave the following results: The determined specific separation factor of the coating material for 1.9 P ^ for CO

Particle separation film separation factor for H2 with respect to C0 5.6

Multicomponent membrane separation factor for H2 with respect to CO 46.1

_ C

The permeability of the multicomponent membrane to H 2 is 7.2 x 10

Permeability of the porous separation membrane to H2 3.9 x 10 Determined specific separation factor for H2 with respect to CO for about 150 porous separation membrane substances

Examples 62 and 63 The purpose of these examples is to illustrate the flexibility of the invention when the coating may be present on the inner surface of the hollow, fibrous porous separating film and on both the inner and outer surfaces. They also illustrate the invention in a process in which a gaseous feed stream is brought into contact with the surface of a multicomponent film opposite the coating. In Example 62, a porous, hollow polysulfone fiber separating film was coated on its inner surface with a 3% solution of Sylgard 184 post-vulcanized silicone rubber in pentane by slowly pumping such a solution through a hole in the hollow fibrous substrate and allowing the fiber to air dry. The permeability was determined by causing the H 2 / CO 2 mixture to penetrate the resulting composite film from the outer surface to the inner cavity. In Example 63, the fiber coated from the inner cavity of Example 62 was further coated with the same Sylgard 184 solution using Method F. The results of testing these multicomponent films are shown in Table XV below.

Table XV

62 63

Dow Corning Dow Corning

Sylgard 184 Sylgard 184 post-vulcanized post-vulcanized silicone rubber tsu silicone rubber

Polysulfoni a Polysulfoni. d (only hole (inner hole and hand coated) outer surface coated) Determined specific characteristic of the coating material 2,3 2,3 female separation factor for H2 with respect to CO

Porous separation membrane separation factor 3.23 3.23 for H2 with respect to CO

Multicomponent membrane separation 22.0 21.2 factor for H2 with respect to CO

3.6 x 10-5 2.31 x 10 5 permeability of the multicomponent membrane H »: lie ^ - U -Li

Permeability of the porous separating film to 2.06 x 10 2.06 x 10 permeability to H2 (a) Polysulfone, Union Carbide, P-3500, wet-spun from a 30% by weight spinning solution in a 50/50 dimethylformamide / N-methyl-pyrrolidone solvent mixture in water at 2 ° C at a speed of 21.4 m / min and spun after washing and stretching at a speed of 33 m / min

Example 64 This example illustrates a process for preparing a multicomponent film in a hollow fiber form using a porous polysulfone separation film and a Sylgard 184 coating. The polysulfone polymer (P-3500 produced by Union Carbide) is dried at 100 ° C at 125 mm Hg for about 25 hours. The dried polysulfone is mixed with dimethylacetamide (moisture content less than about 0.1% by weight) at a temperature of about 65-70 ° C to give a solution containing 27.5% by weight of polysulfone. The solution is transferred to a holding tank with a nitrogen atmosphere of 2 88 61 636 at a pressure of about 1.4 kg / cm. The solution is not heated while in the holding tank and is thus allowed to cool to ambient temperature.

The polymer solution is pumped from the retention tank into a hollow fiber-spinning nozzle immersed in a water bath at about 4 ° C. The diameter of the outer opening of the spinning nozzle is 0.0559 cm and the diameter of the inner needle is 0.0229 cm and the diameter of the injection opening in the needle is 0.0127 cm. The polymer solution is pumped and measured into the spinneret at a rate of about 7.2 ml / min and removed from the nozzle at a rate of about 33 m / min. The polymer solution coagulates into a hollow fiber upon contact with a water bath. through the nozzle injection port is passed distilled water to coagulate the hollow fiber interior. The fiber passes through a water bath for a distance of about 1 m. A certain amount of water bath is continuously emptied to keep the dimethylacetamide content below about 4% by weight in the bath.

The fiber is then immersed in another water bath maintained at a temperature of about 4 ° C for a length of about 5 m. Leaving the second water bath, the fiber contains some dimethylacetamide.

The fiber from the second water bath is immersed in two father-water baths at room temperature, each about 5 m in length, and the fiber is spun only with sufficient tension to perform the spooling. The fiber is kept wet with water during spooling and after spooling the spool is immersed in a water tank and stored at room temperature. The fiber is then dried at ambient conditions, preferably at about 20 ° C and 50% relative humidity. The dried fiber is then coated with a solution of a silicone rubber prepolymer containing about 5% dimethylsiloxane (Sylgard 184, manufactured by Dow Corning) and a curing agent in n-pentane. The application of the coating is carried out by immersing the fiber in the prepolymer solution while keeping the solution under positive pressure. The fiber is allowed to air dry and crosslink to provide a silicone rubber coating.

Table XVI - Coating Methods A. The porous, hollow fibrous film was dipped in undiluted liquid coating material. Excess liquid was allowed to drip off.

89 6 1 6 3 6 B. The porous, hollow fibrous film was immersed in an uncoated liquid coating material while the inner cavity of the porous, hollow fiber was evacuated. After the fiber was removed, the vacuum was released and the excess liquid was allowed to drip off.

C. The porous, hollow fibrous film was dipped in a liquid finishing agent diluted with a hydrocarbon solvent. The solvent was allowed to evaporate.

D. The porous, hollow fibrous film was dipped in a liquid coating material having a hydrocarbon solvent while vacuuming the inner cavity of the hollow fiber. After the fiber was removed, the vacuum was released and the solvent was allowed to evaporate.

E. The porous, hollow fibrous film was dipped in a solution containing a coating material in the form of a polymerizable prepolymer, a suitable hardener, and a hydrocarbon solvent. The solvent was allowed to evaporate and the film prepolymer cured in place.

F. The procedure described in E was used, except that a vacuum was applied to the inner cavity of the hollow fiber while immersing it in the coating solution.

Claims (39)

A multi-component membrane for gas separation consisting of a coating material in contact with a porous substrate, characterized in that the porous substrate is a porous separation membrane which has a substantial pore volume and consists of a material which selectively emits at least one gas. of a gas mixture at least relative to one or more residual gases and the coating material is in closed contact with the porous separation membrane, the material of the porous separation membrane having at least a couple of gases having a definite own separation factor greater than the determined own separator. The tensile factor of the coating material and the multicomponent membrane exhibits a separation factor significantly greater than the determined own separation factor of the coating material and greater than the porous separation membrane's own separation factor. 2. A multi-component membrane according to claim 1, characterized in that at least a couple of gases consist of hydrogen, helium, ammonia and carbon dioxide as well as carbon monoxide, nitrogen, argon, sulfur hexafluoride, methane and ethane and the membrane's pore volume is about 10-80%. . Multicomponent membrane according to claim 1 or 2, characterized in that the separability factor of the multicomponent membrane is at least about 35% larger than the determined own separation factor of the coating material, the coating being in contact with the at least one surface of the membrane and the separation of the porous separating membrane. anisotropic and having a relatively dense region, Multicomponent membrane according to any one of claims 1-3, characterized in that the porous separation membrane consists of at least some of the following substances: polysylphone, copolymer of styrene and acrylonitrile, polyarylene oxide, polycarbonate or cellulose acetate. Multicomponent membrane according to claim 4, characterized in that the polysulfone has a repetitive unit represented by the structure OM --R - SR * - MO 97 61 636 where both R and R 'are aliphatic or aromatic hydrocarbyl containing parts having 1 - about 40 carbon atoms. The multi-component membrane of claim 5, wherein the repetitive unit of the polysulfone represented by the formula _______ where n is about 50-80. The multicomponent membrane of claim 5, characterized in that the polysulfone is poly (arylene ether) sulfone. Multicomponent membrane according to any of claims 5-7, characterized in that the effective separation thickness of the multicomponent membrane is at least a gas selected from the group comprising carbon monoxide, nitrogen, argon, sulfur-hexafluoride, methane, ethane and carbon dioxide. is less than about 5,000 Angstroms units calculated on the permeability constant of the polysulfone for this gas; the ratio of the total area of the porous separation membrane 3 to the total cross-sectional area of the pores of at least.ca 10: 1; The average pore diameter of the porous separation membrane is less than about 20,000 Angstrom units and the molecular weight of the polysulfone is at least about 10,000. Multicomponent membrane according to claim 4, characterized in that the poly (arylene oxide) is a poly (xylene oxide). Multicomponent membrane according to claim 9, characterized in that the poly (xylene oxide) is a brominated poly (xylene oxide), Multicomponent membrane according to claim 4, characterized in that the porous separation membrane consists of a copolymer of styrene and acrylonitrile containing about 20-70% by weight styrene and about 30-80% by weight acrylonitrile. Multicomponent membrane according to any of claims 1-11, characterized in that the coating consists of at least one of the following: polysiloxane, polyisoprene, copolymer of cX-methylstyrene and polysiloxane, polystyrene having a degree of polymerization of about 2 -20, and aliphatic hydrocarbyl containing organic compounds of about 14-30 carbon atoms. Multicomponent membrane according to any one of claims 1-12, characterized in that the coating is applied using a substantially liquid substance suitable for forming the coating, and the coating thickness of the surface of the porous separation membrane to which it is applied is up to approx. 50 microns. Multicomponent membrane according to claim 13, characterized in that the substantially liquid substance is applied to one surface of the porous separation membrane and the other surface is subjected to a lower absolute pressure during application. A multicomponent membrane according to claim 13 or 14, characterized in that a mainly liquid substance consisting of a polymerizable material is applied to the porous separation membrane and the polymerizable material is polymerized after application to the porous separation membrane to give the coating. Multicomponent membrane according to any of claims 12-15, characterized in that the coating consists of a polysiloxane and the coating is substantially uninterrupted. Multicomponent membrane according to any one of claims 1-16, characterized in that the coating consists of At least at least one aliphatic and aromatic polysiloxane having repetitive units containing 1 to about 20 carbon atoms. A multicomponent membrane according to claim 16 or 17, characterized in that the polysiloxane is crosslinked to produce silicone rubber while having a molecular weight of about 1,000 - 100,000 before the crosslinking. Multicomponent membrane according to any one of claims 1-7 and 9-18, characterized in that with respect to At least one gas selected from the group comprising carbon monoxide, nitrogen, argon, sulfur hexafluoride, methane, ethane and carbon dioxide the multicomponent membrane is effective separation thickness. less than about 15,000 Angstrom units based on the permeability constant of the porous separation membrane material for this gas and the ratio of the total area of the porous separation membrane to the total cross-sectional area of the pores is at least about 103: 1. 99 61 636 Multicomponent membrane according to any of claims 1-19, characterized in that the coating material having at least one gas of the gas pair has a higher permeability constant than the material of the porous separation membrane. Multicomponent membrane according to any of claims 1-20, characterized in that the permeability of the multicomponent membrane is greater than that of a membrane which is substantially the same as the porous separation membrane, except that at least one surface of the membrane has been sufficiently heat treated, a liquid, to give a pair of gases a separation factor equal to or greater than the separation factor of the multi-component membrane, in view of this ethereal tone. Multicomponent membrane according to any of claims 1-20, characterized in that the permeability of the multicomponent membrane is greater than that of a membrane which is substantially the same as the porous separation membrane, except that at least one surface of the membrane has been treated to sufficiently compress the membrane. with respect to this, at least a few gases give a separation factor equal to or greater than the separation factor of the multicomponent membrane. Multicomponent membrane according to any one of claims 1-20, characterized in that the porous separation membrane is an anisotropic hollow fiber capable of maintaining the configuration of a hollow fiber under the gas separation conditions and a larger component component has a multi-component membrane. fiber membrane, consisting of the material of the porous separation membrane and which membrane is capable of maintaining the configuration of the hollow fiber under gas separation conditions, and with respect to at least one gas pair, this membrane exhibits a separation factor equal to or greater than the component component. Multicomponent membrane according to any one of claims 1-23, characterized in that both the separation factor and the permeability of the multicomponent membrane are affected by the ratio of the total area of the porous separation membrane to the average cross-sectional area of the pores and / or to the pore cross-sectional area. 100 61636 Multicomponent membrane according to any of claims 1-24, characterized in that both the separation factor and the permeability of the multicomponent membrane are affected by the relative resistance of gas flow through the pores of the porous separation membrane and through the porous separation membrane. Multicomponent membrane according to any one of claims 1-25, characterized in that the multicomponent membrane comprises a hollow fiber. Multicomponent membrane according to claim 26, characterized in that the coating is in contact with at least the outer surface of the hollow fiber. Multicomponent membrane according to any one of claims 1-27, characterized in that the coating is in contact with the at least one feeding surface of the porous separation membrane. Multicomponent membrane according to any of claims 1-28, characterized in that the coating is in contact with the porous separating membrane's bath surfaces and the coating in contact with the bed surfaces has an average thickness of up to about 50 microns. Multicomponent membrane according to any one of claims 1-29, characterized in that the coating comprises at least two layers. Multicomponent membrane according to any one of claims 1-30, characterized in that the coating material has a sufficiently large molecular size, so that the coating material does not pass through the pores of the porous separation membrane during the gas separation. A method of using a multi-component membrane for separating the at least one gas in a gas mixture from the at least another gas in this gas mixture, wherein a product penetrated through the membrane is provided containing the at least one permeated gas, characterized in that the gas mixture is contacted with the at least one gas. a surface of a multicomponent membrane defined in claims 1-31, which multicomponent membrane selectively transmits at least one pair of gases of the gas mixture to one gas of this gas pair relative to the other gas of this gas pair; the opposite surface of the multicomponent membrane is poured at a lower chemical potential for this at least one penetrating gas than the chemical potential at this surface; this at least one permeable gas was allowed to penetrate into and through the multicomponent membrane; and penetrated