Permeation gasification membrane

Abstract

The permeation gasification film 10A of the present application has a separation function layer 1. The separation function layer 1 contains a silicone resin. The silicone resin has a crosslinked structure, and the molecular weight between crosslinking points is 2000 g / mol or more and 10000 g / mol or less. The permeation gasification film 10A is used, for example, for separating an organic compound from an aqueous solution containing the volatile organic compound.

Description

Technical Field

[0001] This invention relates to pervaporation membranes. Background Technology

[0002] As a method for obtaining valuable substances derived from non-petroleum sources, methods utilizing microbial fermentation are known. For example, a method has been developed to produce volatile organic compounds (fermented products) such as alcohols by fermenting carbon sources like glucose using microorganisms. The fermentation of the carbon source is carried out, for example, in an aqueous solution. In this method, if the content of the fermented product in the aqueous solution increases, the microbial fermentation sometimes stops. To continuously produce microbial fermented products, it is necessary to separate the fermented product from the aqueous solution.

[0003] As an example of a method for separating an organic compound from an aqueous solution containing a volatile organic compound, the pervaporation (PV) method using a pervaporation membrane can be cited. The pervaporation method is suitable for separating volatile organic compounds from aqueous solutions containing various substances. Compared to distillation, the pervaporation method tends to suppress energy consumption and carbon dioxide emissions. Patent Document 1 discloses an example of a pervaporation membrane used in the pervaporation method.

[0004] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 10-147546 Summary of the Invention

[0005] The problem that the invention aims to solve When using a pervaporation membrane to separate an organic compound from an aqueous solution containing volatile organic compounds, improvements in separation performance are sought.

[0006] Methods for solving problems This invention provides a pervaporation membrane, which is a pervaporation membrane having a separation functional layer comprising an organosilicon resin. The aforementioned organosilicon resin has a cross-linked structure, and the molecular weight between the cross-linking points is between 2000 g / mol and 10000 g / mol.

[0007] Invention Effects According to the present invention, a pervaporation membrane suitable for improving separation performance can be provided when separating an organic compound from an aqueous solution containing a volatile organic compound. Attached Figure Description

[0008] [ Figure 1 [Illustrated] is a cross-sectional view schematically showing a pervaporation membrane according to one embodiment of the present invention.

[0009] [ Figure 2[ ] is a cross-sectional view schematically showing a modified example of a pervaporation membrane.

[0010] [ Figure 3 [This is a schematic cross-sectional view of a membrane separation device equipped with a pervaporation membrane.]

[0011] [ Figure 4 [This is a perspective view schematically showing a modified example of a membrane separation device.]

[0012] [ Figure 5 [Illustration] is a schematic diagram showing an example of a membrane separation system. Detailed Implementation

[0013] The pervaporation membrane according to the first aspect of the present invention is a pervaporation membrane having a separation functional layer comprising an organosilicon resin. The aforementioned organosilicon resin has a cross-linked structure, and the molecular weight between the cross-linking points is between 2000 g / mol and 10000 g / mol.

[0014] In the second aspect of the present invention, for example, in the pervaporation membrane involved in the first aspect, the molecular weight between the aforementioned crosslinking points is 3000 g / mol or more.

[0015] In the third aspect of the present invention, for example, in the permeation vaporization membrane involved in the first or second aspect, the aforementioned organosilicon resin is formed from an organosilicon resin composition having a solvent content of 5 wt% or less.

[0016] In the fourth aspect of the present invention, for example, in the permeation vaporization membrane involved in any of the first to third aspects, the aforementioned organosilicon resin is formed from an addition-type organosilicon resin composition.

[0017] In the fifth aspect of the present invention, for example, in the permeation vaporization membrane involved in the fourth aspect, the aforementioned addition-type silicone resin composition comprises a silicone base agent and a curing agent. The aforementioned organosilicon main agent has a weight-average molecular weight of more than 10,000 and less than 200,000.

[0018] In the sixth aspect of the present invention, for example, in the permeation vaporization membrane involved in any of the first to fifth aspects, the thickness of the aforementioned separation functional layer is more than 1 μm and less than 50 μm.

[0019] In the seventh aspect of the present invention, for example, in the pervaporation membrane involved in any of the first to sixth aspects, the aforementioned separation functional layer further includes a packing material.

[0020] In the eighth aspect of the present invention, for example, in the pervaporation membrane involved in the seventh aspect, the aforementioned filler comprises silica.

[0021] In a ninth aspect of the present invention, for example, in the pervaporation membrane involved in the seventh or eighth aspect, the aforementioned filler has a surface modified by a modifying group containing a hydrocarbon group.

[0022] In the tenth aspect of the present invention, for example, the permeation vaporization membrane involved in any of the first to ninth aspects further comprises a porous support body supporting the aforementioned separation functional layer.

[0023] In the eleventh aspect of the present invention, for example, in the permeation vaporization membrane involved in the tenth aspect, the aforementioned porous support comprises an organic material.

[0024] In the 12th aspect of the present invention, for example, in the pervaporation membrane involved in the 10th or 11th aspects, the aforementioned porous support has a main body portion and a microporous layer disposed on the aforementioned main body portion. The aforementioned microporous layer contains polysulfone.

[0025] In the 13th aspect of the present invention, for example, any one of the 1st to 12th aspects involves a pervaporation membrane used to separate the aforementioned organic compound from an aqueous solution containing a volatile organic compound.

[0026] In the 14th aspect of the present invention, for example, in the pervaporation membrane involved in the 13th aspect, the aforementioned organic compound is an alcohol.

[0027] The present invention will now be described in detail, but this description is not intended to limit the invention to specific embodiments.

[0028] <Implementation Methods of Pervaporation Membranes> Figure 1 This is a schematic cross-sectional view illustrating a pervaporation membrane according to one embodiment of the present invention. The pervaporation membrane 10A of this embodiment includes a separation functional layer 1 comprising an organosilicon resin. This organosilicon resin has a cross-linked structure, and the molecular weight between the cross-linking points is between 2000 g / mol and 10000 g / mol. The pervaporation membrane 10A may also include a porous support 5 supporting the separation functional layer 1. The separation functional layer 1, for example, has a surface directly in contact with the porous support 5 and a surface exposed on the outside of the pervaporation membrane 10A. The pervaporation membrane 10A, for example, is composed only of the separation functional layer 1 and the porous support 5.

[0029] The pervaporation membrane 10A is typically a membrane (separation membrane) that preferentially allows organic compound C to permeate from an aqueous solution S containing volatile organic compound C. The pervaporation membrane 10A is suitable for improving the separation performance of organic compound C from aqueous solution S, especially for increasing the flux of the permeate fluid passing through the pervaporation membrane 10A under low temperature and low pressure conditions.

[0030] (Separate functional layers) The separation functional layer 1 is, for example, a layer that allows organic compound C to preferentially permeate from the aqueous solution S described above. The separation functional layer 1 is typically a dense layer (non-porous layer) whose pores cannot be identified when observed using a scanning electron microscope (SEM) at a magnification of 5000x.

[0031] The separation functional layer 1 comprises a silicone resin with a cross-linked structure. The molecular weight between the cross-linking points of the silicone resin is between 2000 g / mol and 10000 g / mol. According to the inventors' research, the separation functional layer 1 comprising a silicone resin with a molecular weight between the cross-linking points of 2000 g / mol and 10000 g / mol can increase the flux of the permeate fluid passing through the pervaporation membrane 10A. The mechanism of this effect is as follows. Since the molecular weight between the cross-linking points of the silicone resin is not too small, the cross-linking does not become too dense, and the network structure is not constrained to a dense state. In addition, since the molecular weight between the cross-linking points of the silicone resin is not too large, the cross-linking does not become too sparse, and the network structure has appropriate flexibility. In this way, the size of the gaps in the network structure suitable for the permeate fluid can be ensured, thereby increasing the flux. If the molecular weight between the cross-linking points is too small, the gaps in the network structure become smaller, and the flux decreases. Furthermore, it is speculated that water with a molecular size smaller than that of organic compound C will preferentially permeate, and the separation coefficient will also decrease. If the molecular weight between crosslinking points is too large, i.e., the flexibility of the network structure is too high, large gaps will be generated, as well as gaps so small that the permeable fluid cannot pass through. It is speculated that the presence of such impermeable portions leads to a decrease in flux. The molecular weight between crosslinking points of the silicone resin can be adjusted by the structure, number of branches, number of reaction sites, and molecular weight of the polyorganosiloxanes (typically, polyorganosiloxanes P1 and P2, described later) contained in the silicone main agent and curing agent in the silicone resin composition forming the silicone resin.

[0032] From the viewpoint of further improving the separation performance of the pervaporation membrane 10A, the molecular weight between the crosslinking points of the organosilicon resin is preferably 3000 g / mol or more and 10000 g / mol or less, more preferably 4000 g / mol or more and 9000 g / mol or less.

[0033] The molecular weight Mc [g / mol] between the crosslinking points of silicone resin can be determined based on the density ρ [g / m] of the silicone resin. 3 The elastic modulus E[Pa] of the silicone resin is calculated using the following formula (1).

[0034] Mc=2(1+μ)ρRT / E (1) In equation (1), μ is Poisson's ratio, set to 0.5. Density ρ is the value at 25℃. R is the gas constant (8.314 J / mol·K). T is the measurement temperature (298.15 K).

[0035] The elastic modulus E of silicone resin is Young's modulus. The Young's modulus of silicone resin can be determined using the following method. First, a monolayer film of silicone resin (400 μm thick) is prepared. Next, strips of the monolayer film measuring 10 mm × 60 mm are cut as test pieces. The test pieces are placed in a commercially available tensile testing machine, and tensile tests are performed under the following conditions.

[0036] (Measurement conditions) Temperature: 25℃ Tensile direction: along the length of the test piece Initial chuck spacing: 20mm Stretching speed: 300mm / minute Next, based on the results of the tensile test, a stress-strain curve (SS curve) is generated. A tangent line can be drawn at the origin of the SS curve, and the Young's modulus can be calculated based on the slope of the tangent line.

[0037] The Young's modulus (elastic modulus E) of the silicone resin is, for example, below 4.4 MPa, but can be below 4.0 MPa, below 3.0 MPa, or below 2.0 MPa. The Young's modulus of the silicone resin is, for example, above 0.56 MPa, but can be above 0.60 MPa, above 0.70 MPa, or above 0.80 MPa.

[0038] As described above, the separation functional layer 1 comprises a silicone resin. The silicone resin is, for example, formed from a silicone resin composition. The silicone resin composition comprises, for example, a silicone base agent and a curing agent. The silicone base agent is, for example, a mixture of polyorganosiloxanes. The curing agent comprises, for example, a curing catalyst. The curing agent may also contain polyorganosiloxanes, depending on the situation.

[0039] The weight-average molecular weight of the silicone base agent can be between 10,000 and 200,000. The weight-average molecular weight of the curing agent can also be between 10,000 and 200,000.

[0040] The silicone resin is not particularly limited; for example, it can be formed from a condensation-type silicone resin composition, an addition-type silicone resin composition, or a UV-curable silicone resin composition, but it is preferred to be formed from an addition-type silicone resin composition. Addition-type silicone resin compositions can be cured with almost no use of metals (especially tin) that promote the hydrolysis of silicone resins. Therefore, the separation functional layer 1 containing silicone resin formed from an addition-type silicone resin composition contains almost no metals that promote the hydrolysis of silicone resins, and tends to have high durability against the aforementioned aqueous solution S. The silicone resin is preferably formed from a silicone resin composition containing 5 wt% or less of a solvent such as an organic solvent, and more preferably from a solvent-free silicone resin composition that substantially does not contain any solvents such as organic solvents.

[0041] [Addition-type silicone resin composition] Addition-type silicone resin compositions are silicone resin compositions that are cured by an addition reaction. For example, addition-type silicone resin compositions may contain polyorganosiloxane P1 having an alkenyl group and polyorganosiloxane P2 having a hydrosilane (SiH) group. Preferably, the addition-type silicone resin composition further contains a curing catalyst (hydrosilaneization catalyst). It should be noted that addition-type silicone resin compositions may also be formed by adding a curing catalyst to a commercially available silicone resin composition. However, addition-type silicone resin compositions may also be free of a curing catalyst.

[0042] In the case of addition-type silicone resin compositions, for example, a reaction (hydrosilaneation reaction) can be carried out between the alkenyl group of polyorganosiloxane P1 and the hydrosilyl group of polyorganosiloxane P2 by heat treatment to form a silicone resin. In this hydrosilaneation reaction, polyorganosiloxane P2 functions as a crosslinking agent.

[0043] Examples of alkenyl groups in polyorganosiloxane P1 include vinyl and hexenyl groups. The number of alkenyl groups in polyorganosiloxane P1 is, for example, two or more. The alkenyl groups are, for example, located at the end of the polyorganosiloxane P1.

[0044] Polyorganosiloxane P1 is, for example, a polyalkylalkylsiloxane such as polydimethylsiloxane (PDMS), polydiethylsiloxane, polymethylethylsiloxane, etc.; polyalkylarylsiloxane; poly(dimethylsiloxane-diethylsiloxane), etc., in which an alkenyl group has been introduced. PDMS is preferred as the polyorganosiloxane P1.

[0045] The weight-average molecular weight of polyorganosiloxane P1 can be above 1000, but can also be above 10,000, 15,000, 100,000, 200,000, 300,000, or even above 400,000. There is a tendency for a higher weight-average molecular weight of polyorganosiloxane P1 to improve the separation characteristics of the pervaporation membrane 10A. There is no specific upper limit to the weight-average molecular weight of polyorganosiloxane P1; for example, it can be 1 million, but can also be below 500,000, 200,000, 100,000, or even below 35,000. The weight-average molecular weight of polyorganosiloxane P1 can be above 10,000 and below 500,000, above 10,000 and below 200,000, or above 15,000 and below 35,000.

[0046] The number of hydrosilyl groups in polyorganosiloxane P2 is, for example, 2 or more. The hydrosilyl groups can be located at the end of polyorganosiloxane P2 or contained in the main chain of polyorganosiloxane P2.

[0047] Examples of polyorganosiloxanes P2 include polymethylhydrosiloxane, poly(dimethylsiloxane-methylhydrosiloxane), and hydrosilyl-terminated polydimethylsiloxane.

[0048] The weight-average molecular weight of polyorganosiloxane P2 can be above 100, but can also be above 1000, above 10,000, above 15,000, above 100,000, above 200,000, above 300,000, or even above 400,000. There is no specific upper limit to the weight-average molecular weight of polyorganosiloxane P2; for example, it can be below 1 million, but can also be below 500,000, below 200,000, below 100,000, or even below 35,000. The weight-average molecular weight of polyorganosiloxane P2 can also be above 10,000 and below 500,000, above 10,000 and below 200,000, or above 15,000 and below 35,000.

[0049] The addition-type silicone resin composition comprises polyorganosiloxane P1 and polyorganosiloxane P2, wherein the weight-average molecular weight of at least one of the polyorganosiloxane P1 and polyorganosiloxane P2 can be above 10,000 and below 200,000.

[0050] The weight ratio of polyorganosiloxane P2 to polyorganosiloxane P1, P2 / P1, is, for example, 500 wt% or less, or it can be 100 wt% or less, 50 wt% or less, 20 wt% or less, 10 wt% or less, or even 5 wt% or less. The lower limit of the weight ratio P2 / P1 is, for example, 0.01 wt% or more.

[0051] Platinum-based catalysts can be cited as examples of curing catalysts. In other words, addition-type silicone resin compositions can contain a platinum-based curing catalyst. Specific examples of platinum-based catalysts include chloroplatinic acid, platinum olefin complexes, and chloroplatinic acid olefin complexes. As mentioned above, addition-type silicone resin compositions may also be free of curing catalysts.

[0052] Addition-type silicone resin compositions may contain compounds that are catalytically active species that produce a catalytic addition reaction when irradiated with active energy rays such as ultraviolet (UV). According to an addition-type silicone resin composition containing such a compound, an addition reaction can be carried out, for example, by UV irradiation.

[0053] In addition to the components mentioned above, addition-type silicone resin compositions may also contain organic solvents. Examples of organic solvents include hydrocarbon solvents such as cyclohexane, n-hexane, and n-heptane; aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate and methyl acetate; ketone solvents such as acetone and methyl ethyl ketone; and alcohol solvents such as methanol, ethanol, and butanol. One organic solvent may be used alone, or two or more may be used in combination. The content of organic solvents and other solvents in the addition-type silicone resin composition may be less than 5 wt%, or it may be a solvent-free type that substantially does not contain organic solvents and other solvents.

[0054] [Condensation-type silicone resin composition] Condensation-type silicone resin compositions are silicone resin compositions that are cured through a condensation reaction. Examples of condensation-type silicone resin compositions include polyorganosiloxanes P3 having silanol (SiOH) groups and silane compounds P4 having functional groups such as alkoxy, alkenoxy, acyloxy, amino, ketoxime, and amide groups. Condensation-type silicone resin compositions may or may not contain a curing catalyst. It should be noted that condensation-type silicone resin compositions can also be formed by adding a curing catalyst to commercially available silicone resin compositions.

[0055] In the case of condensation-type silicone resin compositions, for example, a condensation reaction (reaction) can be carried out between the silanol groups of polyorganosiloxane P3 and the aforementioned functional groups of silane compound P4 by heat treatment to form a silicone resin. In this condensation reaction, silane compound P4 functions as a crosslinking agent.

[0056] The number of silanol groups in polyorganosiloxane P3 is, for example, two or more. The silanol groups are, for example, located at the end of the polyorganosiloxane P3. In polyorganosiloxane P3, alkyl groups such as methyl and ethyl, phenyl, etc., can be introduced as substituents in the side chains.

[0057] Polyorganosiloxane P3 is, for example, a substance obtained by introducing silanol groups into polyorganosiloxanes described above, specifically polyorganosiloxane P1.

[0058] The weight-average molecular weight of polyorganosiloxane P3 can be above 1000, but can also be above 10,000, 15,000, 100,000, 200,000, 300,000, or even above 400,000. The upper limit of the weight-average molecular weight of polyorganosiloxane P1 is not specifically limited; for example, it can be 1 million, but can also be below 500,000, 200,000, 100,000, or even below 35,000. The weight-average molecular weight of polyorganosiloxane P3 can be above 10,000 and below 500,000, above 10,000 and below 200,000, or above 15,000 and below 35,000.

[0059] As described above, silane compound P4 has functional groups such as alkoxy, alkenoxy, acyloxy, amino, ketoxime, and amide. Examples of alkoxy groups include methoxy and ethoxy. Examples of alkenoxy groups include isopropenoxy. Examples of acyloxy groups include acetoxy. Examples of amino groups include dimethylamino, diethylamino, and ethylmethylamino. Examples of ketoxime groups include acetyloxime and methylethylketoxime. Examples of amide groups include acetamido, N-methylacetamido, and N-ethylacetamido. The number of functional groups in silane compound P4 is, for example, two or more. Specifically, silane compound P4 preferably contains an alkoxysilyl group as its alkoxy group.

[0060] Silane compound P4 can be a low molecular weight compound with a molecular weight of around 1000 or less, or a high molecular weight compound with a polysiloxane backbone.

[0061] Examples of solidification catalysts include tin-based catalysts. Examples of organotin catalysts include dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin dioctanoate.

[0062] In addition to the components described above, condensation-type silicone resin compositions may also contain organic solvents. Examples of organic solvents include those described above for addition-type silicone resin compositions. Condensation-type silicone resin compositions may also be solvent-free, containing no organic solvents or other solvents.

[0063] [UV-curable silicone resin composition] UV-curable silicone resin compositions are silicone resin compositions that are cured by ultraviolet (UV) irradiation. UV-curable silicone resin compositions are cured by, for example, free radical polymerization, free radical addition, ionic polymerization, etc. UV-curable silicone resin compositions cured by free radical polymerization include, for example, a polyorganosiloxane P5 having double bonds (specifically, carbon-carbon double bonds) derived from alkenyl, acryloyl, etc. UV-curable silicone resin compositions cured by free radical addition include, for example, a polyorganosiloxane P5 having double bonds (specifically, carbon-carbon double bonds) derived from alkenyl, acryloyl, etc., and a compound P6 having functional groups such as thiol groups capable of free radical addition. UV-curable silicone resin compositions cured by ionic polymerization include, for example, a polyorganosiloxane P7 having functional groups capable of ionic polymerization such as epoxy groups, and a compound that generates catalytically active species for ionic polymerization upon UV irradiation.

[0064] According to a UV-curable silicone resin composition that undergoes a curing reaction via free radical polymerization, for example, by UV irradiation, the double bonds contained in the alkenyl, acryloyl, etc. of polyorganosiloxane P5 undergo a free radical polymerization reaction with each other, thereby forming a silicone resin.

[0065] Examples of alkenyl groups in polyorganosiloxane P5 include vinyl and hexenyl groups. The number of alkenyl groups in polyorganosiloxane P5 is, for example, two or more. The alkenyl group is, for example, located at the end of the polyorganosiloxane P5. As substituents in the side chain of polyorganosiloxane P5, alkyl groups such as methyl and ethyl, phenyl groups, etc., can be introduced.

[0066] Polyorganosiloxane P5, for example, is a substance obtained by introducing substituents such as alkenyl or acryloyl groups with double bonds into polyorganosiloxane P1, which is described above.

[0067] The weight-average molecular weight of polyorganosiloxane P5 can be above 1000, but can also be above 10,000, 15,000, 100,000, 200,000, 300,000, or even above 400,000. There is no specific upper limit to the weight-average molecular weight of polyorganosiloxane P5; for example, it can be below 1,000,000, but can also be below 500,000, 200,000, 100,000, or even below 35,000. The weight-average molecular weight of polyorganosiloxane P5 can be above 10,000 and below 500,000, above 10,000 and below 200,000, or above 15,000 and below 35,000.

[0068] According to a UV-curable silicone resin composition that undergoes a curing reaction via free radical addition, for example, by UV irradiation, the functional groups in compound P6 capable of free radical addition undergo free radical addition to the double bonds contained in the alkenyl, acryloyl, etc., groups of polyorganosiloxane P5. This allows the free radical addition reaction to proceed, forming a silicone resin.

[0069] In compound P6, the functional groups capable of free radical addition are, for example, thiol groups and alkylthiol groups. Examples of alkylthiol groups include mercaptomethyl and mercaptoethyl groups. The number of functional groups capable of free radical addition in compound P6 is, for example, two or more.

[0070] Compound P6 can be a polyorganosiloxane containing a functional group capable of radical addition. This functional group is, for example, located at the end of the polyorganosiloxane. Substituents such as alkyl groups (e.g., methyl), ethyl groups, and phenyl groups can be introduced as substituents in the side chain of the polyorganosiloxane.

[0071] Compound P6 is, for example, a substance obtained by introducing functional groups such as thiol groups into the polyorganosiloxanes described above, which are polyorganosiloxanes.

[0072] The weight-average molecular weight of compound P6 can be above 1000, but can also be above 10,000, above 15,000, above 100,000, above 200,000, above 300,000, or even above 400,000. There is no specific upper limit to the weight-average molecular weight of compound P6; for example, it can be below 1,000,000, but can also be below 500,000, below 200,000, below 100,000, or even below 35,000. The weight-average molecular weight of compound P6 can be above 10,000 and below 500,000, above 10,000 and below 200,000, or above 15,000 and below 35,000.

[0073] According to a UV-curable silicone resin composition that undergoes a curing reaction via ion polymerization, for example, by UV irradiation, catalytically active species that catalyze ion polymerization are generated, and ion polymerization reactions occur between the functional groups contained in polyorganosiloxane P7 that are capable of ion polymerization. Thus, a silicone resin can be formed.

[0074] In polyorganosiloxane P7, the functional group capable of ion polymerization is, for example, an epoxy group. Examples of substituents containing the epoxy group include the epoxy group itself, glycidyl group, glycidyloxypropyl group, etc. The number of ion-polymerizable functional groups in polyorganosiloxane P7 is, for example, two or more. The ion-polymerizable functional group is, for example, located at the end of the polyorganosiloxane P7. As substituents in the side chain of polyorganosiloxane P7, alkyl groups such as methyl and ethyl, phenyl, etc., can be introduced.

[0075] Polyorganosiloxane P7 is, for example, a substance obtained by introducing functional groups such as epoxy groups into the polyorganosiloxanes described above for polymerization.

[0076] The weight-average molecular weight of polyorganosiloxane P7 can be above 1000, but can also be above 10,000, 15,000, 100,000, 200,000, 300,000, or even above 400,000. There is no specific upper limit to the weight-average molecular weight of polyorganosiloxane P7; for example, it can be 1 million, but can also be below 500,000, 200,000, 100,000, or even below 35,000. The weight-average molecular weight of polyorganosiloxane P7 can be above 10,000 and below 500,000, above 10,000 and below 200,000, or above 15,000 and below 35,000.

[0077] In addition to the components mentioned above, UV-curable silicone resin compositions may also contain organic solvents. Examples of organic solvents include hydrocarbon solvents such as cyclohexane, n-hexane, and n-heptane; aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate and methyl acetate; ketone solvents such as acetone and methyl ethyl ketone; and alcohol solvents such as methanol, ethanol, and butanol. One organic solvent may be used alone, or two or more may be used in combination. UV-curable silicone resin compositions can be solvent-free, meaning they are substantially free of organic solvents or other solvents.

[0078] The separation functional layer 1 may contain silicone resin as the main component, or it may be composed of silicone resin in essence. "Main component" refers to the component that is present in the separation functional layer 1 by weight.

[0079] The thickness of the separation functional layer 1 can be, for example, less than 200 μm, less than 100 μm, less than 50 μm, or less than 20 μm. The thickness of the separation functional layer 1 can be greater than 0.05 μm, greater than 0.1 μm, greater than 0.5 μm, or greater than 1 μm. The thickness of the separation functional layer 1 can be greater than 1 μm and less than 50 μm.

[0080] (Porous support) The porous support 5 supports the separation functional layer 1. The porous support 5 preferably contains organic material, more preferably is formed substantially from organic material, and even more preferably is formed solely from organic material.

[0081] The porous support 5, for example, includes a main body 6 and a microporous layer 7 disposed on the main body 6. In the pervaporation membrane 10A, the microporous layer 7 is located between the main body 6 and the separation functional layer 1, and is directly contacted with both the main body 6 and the separation functional layer 1. The porous support 5 is typically an ultrafiltration membrane.

[0082] The main body 6 is preferably a fibrous structure. Examples of fibrous structures include woven fabrics, nonwoven fabrics, and stretched porous membranes containing fibrils. Typically, the fibrous structure is a nonwoven fabric or a stretched porous membrane. According to the above, the flux of the permeate fluid passing through the pervaporation membrane 10A can be increased.

[0083] When the fiber structure is a woven fabric or a nonwoven fabric, the fibers contained in the fiber structure can be, for example, natural fibers such as wood pulp, cotton, and hemp (e.g., Manila hemp); or chemical fibers (synthetic fibers) such as polyester fibers, rayon, vinylon, acetate fibers, polyvinyl alcohol (PVA) fibers, polyamide fibers, polyolefin fibers, and polyurethane fibers. The main body 6 is, for example, a nonwoven fabric made of polyester fibers. The nonwoven fabric is preferably a polyethylene terephthalate (PET) nonwoven fabric.

[0084] When the fibrous structure is a stretched porous membrane, the fibrous structure preferably contains a fluoropolymer. Examples of fluoropolymers include polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), perfluoroalkoxy fluoropolymer (PFA), and tetrafluoroethylene-hexafluoropropylene copolymer (FEP), with PTFE being the most preferred.

[0085] As an example, PTFE stretched porous membranes are formed by stretching a paste extruder or cast film containing PTFE particles. PTFE stretched porous membranes are composed of fine PTFE fibrils, and compared to the fibrils, they also have nodes in a state of PTFE aggregation.

[0086] The main body 6 has an average pore size of, for example, 1 μm to 50 μm.

[0087] Examples of materials for the microporous layer 7 include fluoropolymers such as polyvinylidene fluoride and polytetrafluoroethylene; polyaryl ether sulfones such as polysulfone and polyether sulfone; and polyimide. The microporous layer 7 preferably comprises polysulfone. The microporous layer 7 has an average pore size of, for example, 0.01 μm to 0.4 μm.

[0088] The thickness of the porous support 5 is not particularly limited; for example, it can be 10 μm or more, 50 μm or more, or 100 μm or more. The thickness of the porous support 5 can be, for example, 300 μm or less, or 200 μm or less.

[0089] The average diameter of the openings in the surface of the porous support 5 on the side of the separation functional layer 1 (the surface of the porous support 5 in contact with the separation functional layer 1) is, for example, 1 nm or more and 100 nm or less, preferably 5 nm or more and 20 nm or less.

[0090] The porosity of the porous support 5 is, for example, 30% or more and 80% or less, preferably 50% or more and 70% or less.

[0091] Depending on the circumstances, the porous support 5 may be formed only from the main body 6 without having a microporous layer 7.

[0092] The surface of the porous support 5, which is in contact with the separation functional layer 1, can be treated for easy adhesion. Examples of easy adhesion treatments include surface treatments such as corona discharge treatment and plasma treatment.

[0093] Alternatively, the easy-bonding treatment can be a coating treatment based on a molecular bonding agent. The molecular bonding agent comprises a molecular bonding compound (hereinafter referred to as "Compound C1") and a solvent such as an organic solvent or water, used as needed. Compound C1 has a reactive group F1 that can react with the surface of the porous support 5 and a reactive group F2 that can react with the resin (especially silicone resin) contained in the separation functional layer 1. The reactive group F2 can react not only with the silicone resin but also with the surface of the porous support 5.

[0094] The reactive group F1 is, for example, at least one selected from the group consisting of amino, azide, mercapto, isocyanate, urea, and epoxy groups, typically azide. The reactive group F2 is, for example, at least one selected from the group consisting of silanol and a group G that can be hydrolyzed to form a silanol. A specific example of group G is alkoxysilyl.

[0095] Compound C1 is represented, for example, by the following formula (2).

[0096] R A -ZR B (2) In equation (2), R A R represents a reactive group F1 or a monovalent substituent having one or more reactive groups F1. B F2 represents the reactive group, and Z represents a divalent organic group.

[0097] In formula (2), Z can be represented by alkylene groups with 1 to 20 carbon atoms that may have substituents, alkenyl groups with 2 to 20 carbon atoms that may have substituents, ynylene groups with 2 to 20 carbon atoms that may have substituents, arylene groups with 6 to 20 carbon atoms that may have substituents, etc.

[0098] Examples of alkylene groups having 1 to 20 carbon atoms include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene, with methylene, ethylene, and propylene being preferred, and propylene being more preferred. Examples of alkenylene groups having 2 to 20 carbon atoms include vinylene, propenylene, butenylene, and pentenylene. Examples of yntynylene groups having 2 to 20 carbon atoms include ethynylene and propynylene. Examples of arylene groups having 6 to 20 carbon atoms include o-phenylene, m-phenylene, p-phenylene, 2,6-naphthylene, and 1,5-naphthylene.

[0099] Substituents that may be present in the aforementioned alkylene, alkenylene, and alkyne groups include, for example, halogen atoms such as fluorine and chlorine atoms; alkoxy groups such as methoxy and ethoxy; alkylthio groups such as methylthio and ethylthio; and alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl.

[0100] Examples of substituents that may be present in the aforementioned arylene group include cyano; nitro; halogen atoms such as fluorine, chlorine, and bromine atoms; alkyl groups such as methyl and ethyl; alkoxy groups such as methoxy and ethoxy; and alkyl thio groups such as methylthio and ethylthio.

[0101] The aforementioned substituents can be bonded to any position in alkylene, alkenylene, ynylene, and aryl groups, and multiple substituents can be bonded to the same element or different elements.

[0102] As R A Examples of such groups can be found in formulas (3) to (5) below.

[0103] [Chemical Formula 1] In equations (3) to (5), R represents the connection bond with Z in equation (2). 1 R represents a divalent hydrocarbon group with 1 to 10 carbon atoms. 2 and R 3 Each can independently represent a hydrocarbon group with 1 to 20 hydrogen or carbon atoms. R 4 and R 5 Each can independently represent the reactive group F1 or the group represented by formula (3) above. It should be noted that R... 4 and R 5 In the case where the group is represented by formula (3), in formula (3), R represents the bond connecting the carbon atom that forms the triazine ring in equation (5). 6 Indicates a single bond or -N (R) 7 )- represents a divalent group. R 7 A hydrocarbon group representing 1 to 20 hydrogen or carbon atoms.

[0104] In equation (3), R is used as 1 Preferably, it is a divalent hydrocarbon group with 2 to 6 carbon atoms. As R 1 Examples of alkylene or arylenes with 1 to 10 carbon atoms include, specifically, alkylenes such as ethylene and trimethylene; and arylenes such as o-phenylene, m-phenylene, and p-phenylene.

[0105] In equation (3), R 2 and R 3 Each is preferably a hydrocarbon group having 1 to 10 hydrogen atoms or carbon atoms. As R 2 and R 3 Examples of alkyl, alkynyl, or aryl groups with 1 to 20 carbon atoms include, specifically, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; alkenyl groups such as vinyl, 1-propenyl, 2-propenyl, isopropenyl, 3-butenyl, 4-pentenyl, and 5-hexenyl; alkynyl groups such as ethynyl, propynyl, and butynyl; and aryl groups such as phenyl, 1-naphthyl, and 2-naphthyl.

[0106] In equation (5), R 4 and R 5 Preferably, the reactive groups F1 are the same as each other.

[0107] In equation (5), R 6 Indicates a single bond or -N (R) 7 )- represents a divalent group. As R 7 Hydrocarbon groups, such as those used as R in the above example, can be cited. 2 and R 3 The same group as the hydrocarbon group described above. R 6 The preferred expression is -NH-.

[0108] In the groups represented by formulas (3) to (5) above, R A Preferably, it is a group represented by formula (5), more preferably a group represented by formula (5), and R 4 or R 5 It is an azide group or a group represented by the above formula (3).

[0109] As R A Examples of such groups can be found in formula (6) below.

[0110] [Chemical Formula 2] In equation (6), R represents the connection bond with Z in equation (2). 1 ~R 3 and R 6Each is identical to the groups described above for formulas (3) and (5). R 1 ~R 3 They can be the same or different.

[0111] In equation (2), R B It can be a group represented by the following formula (7).

[0112] -Si(X) a (Y) 3-a (7) In formula (7), X represents a hydroxyl group or an alkoxy group with 1 to 10 carbon atoms, and Y represents a hydrocarbon group with 1 to 20 carbon atoms. a represents an integer from 1 to 3.

[0113] In formula (7), X can be, for example, methoxy, ethoxy, n-propoxy, isopropoxy, etc., with ethoxy being preferred. Y can be, for example, R in formula (3). 2 and R 3 The hydrocarbon group is one of the groups described above.

[0114] R B Preferably, X represents a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms, and a is a group of 3. More preferably, X represents a hydroxyl group or an ethoxy group, and a is a group of 3.

[0115] As R A Compounds with an amino group at C1 include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, [3-(N,N-dimethylamino)propyl]trimethoxysilane, [3-(phenylamino)propyl]trimethoxysilane, trimethyl[3-(triethoxysilyl)propyl]ammonium chloride, and trimethyl[3-(trimethoxysilyl)propyl]ammonium chloride.

[0116] As R A Compounds with an azide group (C1) include (11-azidoundecyl)trimethoxysilane and (11-azidoundecyl)triethoxysilane.

[0117] As R A Examples of compounds with a thiol group (C1) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropyldimethoxymethylsilane.

[0118] As R A Compounds with an isocyanate group (C1) include 3-(trimethoxysilyl)propyl isocyanate and 3-(triethoxysilyl)propyl isocyanate.

[0119] As R ACompounds with a urea group at C1 include 3-ureopropyltrimethoxysilane and 3-ureopropyltriethoxysilane.

[0120] As R A Compounds with an epoxy group at C1 include 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropyltriethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, and 3-epoxypropoxypropylmethyldiethoxysilane.

[0121] As R A Examples of compounds C1 that are monovalent substituents having one or more reactive groups F1 include 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and compounds represented by formulas (2-1) to (2-9) below.

[0122] [Chemical Formula 3] [Chemical Formula 4] (2-1): N,N'-bis(2-aminoethyl)-6-(3-trihydroxysilylpropyl)amino-1,3,5-triazine-2,4-diamine (2-2): N,N'-bis(2-aminoethyl)-6-(3-trimethoxysilylpropyl)amino-1,3,5-triazine-2,4-diamine (2-3): N,N'-bis(2-aminoethyl)-6-(3-triethoxysilylpropyl)amino-1,3,5-triazine-2,4-diamine (2-4): N,N'-bis(2-aminomethyl)-6-(3-trihydroxysilylpropyl)amino-1,3,5-triazine-2,4-diamine (2-5): N,N'-bis(2-aminomethyl)-6-(3-trimethoxysilylpropyl)amino-1,3,5-triazine-2,4-diamine (2-6): N,N'-bis(2-aminomethyl)-6-(3-triethoxysilylpropyl)amino-1,3,5-triazine-2,4-diamine (2-7): 6-(3-trihydroxysilylpropyl)amino-1,3,5-triazine-2,4-diazidide (2-8): 6-(3-trimethoxysilylpropyl)amino-1,3,5-triazine-2,4-diazidide (2-9): 6-(3-triethoxysilylpropyl)amino-1,3,5-triazine-2,4-diazidide Compound C1 is preferably a compound represented by formulas (2-1) to (2-9) above, and more preferably a compound represented by formula (2-1) or a compound represented by formula (2-9).

[0123] The pervaporation membrane 10A may also include an intermediate layer disposed between the separation functional layer 1 and the porous support 5. The intermediate layer is typically formed from an adhesive composition. The adhesive composition may be a composition containing a silicone-based polymer (silicone adhesive).

[0124] The permeation vaporization membrane involved in this embodiment may also not have a porous support 5.

[0125] (Manufacturing method of pervaporation membrane) The pervaporation membrane 10A can be fabricated, for example, by forming a separation functional layer 1 on a microporous layer 7 of a porous support 5. Specifically, firstly, a coating liquid containing the separation functional layer 1 is prepared. The coating liquid can be, for example, an organosilicon resin composition (addition-type organosilicon resin composition, condensation-type organosilicon resin composition, or UV-curable organosilicon resin composition). Next, a coated membrane is obtained by coating the coating liquid onto the porous support 5. The separation functional layer 1 is formed by curing the coated membrane. Curing of the coated membrane can be carried out at room temperature or under heating conditions. Curing of the coated membrane can also be carried out by irradiation with active energy rays such as UV.

[0126] When curing a coated film by heating, the heating conditions are not particularly limited. For example, the heating temperature can be above 80°C, 90°C, 100°C, or 120°C. The higher the heating temperature of the coated film, the more complete the curing reaction of the components in the silicone resin composition. There is no particular upper limit to the heating temperature of the coated film, for example, 200°C. The heating time of the coated film can be appropriately adjusted according to the composition of the silicone resin composition used.

[0127] (Applications of pervaporation membranes) The pervaporation membrane 10A of this embodiment is suitable for applications such as separating organic compound C from an aqueous solution S containing a volatile organic compound C. The organic compound C is not particularly limited as long as it is volatile. In this specification, "volatile organic compound" refers to, for example, an organic compound with a boiling point of 20°C to 260°C at atmospheric pressure (101.325 kPa). It should be noted that, for example, when the concentration of organic compound C in the aqueous solution is high, an aqueous phase containing water as the main component and an organic phase in which the content of organic compound C is higher than that of the aqueous phase are produced. However, organic compound C may also not produce an aqueous phase or an organic phase.

[0128] There is no particular limitation on the number of carbon atoms in organic compound C; for example, it can be less than 10, less than 8, less than 6, or even less than 4. The lower limit for the number of carbon atoms in organic compound C can be 1 or 2. Organic compound C may have functional groups containing oxygen atoms, such as hydroxyl, carbonyl, ether, or ester groups. Typically, organic compound C contains only one oxygen-containing functional group.

[0129] Examples of organic compound C include alcohols, ketones, and esters, with alcohols being typical. Alcohols can be alkyl alcohols consisting only of alkyl groups and hydroxyl groups, or aryl alcohols containing aryl groups and hydroxyl groups. Alkyl alcohols can be linear, branched, or cyclic. Examples of alkyl alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, tert-butanol, and n-pentanol, with n-butanol, 2-butanol, isopropanol, and ethanol being preferred, and n-butanol and isopropanol being more preferred. Examples of aryl alcohols include phenol.

[0130] Ketones can be dialkyl ketones consisting only of alkyl and carbonyl groups. Examples of dialkyl ketones include methyl ethyl ketone (MEK) and acetone.

[0131] Esters can be fatty acid alkyl esters consisting only of alkyl groups and ester groups. Examples of fatty acid alkyl esters include ethyl acetate.

[0132] It should be noted that organic compound C is not limited to the compounds mentioned above. Organic compound C can be aromatic hydrocarbons such as benzene, toluene, and xylene, or amide solvents such as N,N-dimethylformamide (DMF) and N-methyl-2-pyrrolidone (NMP).

[0133] The aqueous solution S may contain one or more organic compounds C. The content of organic compound C in the aqueous solution S may be, for example, 0.5 wt% or more, 1 wt% or more, 2 wt% or more, or 5 wt% or more. There is no particular upper limit to the content of organic compound C, for example, 50 wt%.

[0134] Organic compound C can be a fermentation product produced by microorganisms fermenting a carbon source, or it can be an alcohol (bio-alcohol) produced by microorganisms. That is, the aqueous solution S can be a fermentation broth containing organic compound C as a fermentation product. However, the aqueous solution S is not limited to fermentation broth, and can also be waste liquid or wastewater discharged from chemical equipment, etc.

[0135] Besides water and organic compounds C, the aqueous solution S may also contain other components such as microorganisms that produce fermentation products, carbon sources, nitrogen sources, and inorganic ions. The microorganisms that produce fermentation products are typically bacteria. Examples of carbon sources include polysaccharides such as starch and monosaccharides such as glucose.

[0136] (Characteristics of pervaporation membrane) In the pervaporation membrane 10A, the separation coefficient of organic compound C relative to water is not particularly limited. As an example, the separation coefficient α of n-butanol (BuOH) relative to water in the pervaporation membrane 10A is... BuOH For example, it can be 8 or higher, or it can be 10 or higher, 13 or higher, 15 or higher, or even 17 or higher. Separation coefficient α BuOH The upper limit is, for example, 100.

[0137] Separation coefficient α BuOH The following method can be used to determine the separation coefficient α. With a mixed liquid containing BuOH and water in contact with one side of the pervaporation membrane 10A (e.g., the main surface of the separation functional layer 1 side of the pervaporation membrane 10A), the space adjacent to the other side of the pervaporation membrane 10A (e.g., the main surface of the porous support 5 side of the pervaporation membrane 10A) is depressurized. This yields the permeate fluid that passes through the pervaporation membrane 10A. The weight ratio of water and the weight ratio of BuOH in the permeate fluid are measured. In the above operation, the BuOH content in the mixed liquid is 0.8 wt%. The temperature of the mixed liquid in contact with the pervaporation membrane 10A is 30°C. The space adjacent to the other side of the pervaporation membrane 10A is depressurized to 1.5 kPa. BuOH It can be calculated using the following formula. Where, in the following formula, X... A and X B These represent the weight ratios of BuOH and water in the mixed liquid, respectively. A and Y B These represent the weight ratios of BuOH and water in the permeate fluid passing through the pervaporation membrane 10A, respectively.

[0138] Separation coefficient α BuOH =(Y A / Y B ) / (X A / X B ) The above separation coefficient α BuOHIn the measurement conditions, the flux of BuOH permeating through the pervaporation membrane 10A is not particularly limited; for example, it can be 0.001 kg / m³. 2 Above / hr, it can also be 0.010kg / m 2 / hr or more, 0.020kg / m 2 / hr or more, I thought it was 0.025kg / m 2 / hr or more. The flux of BuOH permeating from the 10A permeation membrane can be 1.0 kg / m³. 2 Below / hr, it can also be 0.8kg / m 2 Below / hr, I thought it was 0.6kg / m 2 / hr or less.

[0139] Furthermore, the separation coefficient α of isopropanol (IPA) relative to water in the pervaporation membrane 10A is... IPA For example, it could be 5 or higher, 6 or higher, or even 7 or higher. Separation coefficient α IPA The upper limit is, for example, 100.

[0140] Besides using a mixed liquid with an IPA content of 10 wt% and a mixed liquid temperature of 40°C, the separation coefficient α can be utilized. BuOH The separation coefficient α was determined using the same method. IPA .

[0141] The above separation coefficient α IPA In the measurement conditions, the flux of IPA permeating through the 10A pervaporation membrane is not particularly limited; for example, it can be 0.05 kg / m³. 2 Above / hr, it can also be 0.10kg / m 2 / hr or more, 0.20kg / m 2 / hr or more, 0.25kg / m 2 Above / hr, it can also be 0.28kg / m 2 / hr or more. The flux of IPA permeating from the 10A permeation membrane can be 1.0 kg / m³. 2 Below / hr, it can also be 0.9kg / m 2 Below / hr, it can also be 0.8kg / m 2 / hr or less.

[0142] In the pervaporation membrane 10A of this embodiment, by making the separation functional layer 1 contain an organosilicon resin with a molecular weight between crosslinking points of 2000 g / mol and 10000 g / mol, there is a tendency for good separation performance (especially the flux of the permeate fluid (organic compound C) passing through the pervaporation membrane) in separating organic compound C from the aqueous solution S.

[0143] <Examples of modified pervaporation membranes> Figure 2 A cross-sectional view illustrating a modified example of the pervaporation membrane. (e.g.) Figure 2 As shown, in the pervaporation membrane 10B, the separation functional layer 1 has a matrix 2 containing silicone resin and a filler 3 dispersed in the matrix 2. Except as described above, the structure of the pervaporation membrane 10B is the same as that of the pervaporation membrane 10A. Therefore, sometimes the same reference numerals are used to denote common elements between the pervaporation membrane 10A and the modified pervaporation membrane 10B, and their descriptions are omitted. That is, the descriptions of each embodiment are applicable to each other as long as they do not contradict each other technically. Furthermore, the embodiments can be combined with each other as long as they do not contradict each other technically.

[0144] As described above, in the pervaporation membrane 10B, the separation functional layer 1 also includes packing material 3. All or part of the packing material 3 is embedded within the substrate 2. Within the substrate 2, all of the packing material 3 can be separated from each other or partially aggregated.

[0145] As an example of the organosilicon resin contained in the matrix 2, the substances described above for the pervaporation membrane 10A can be cited.

[0146] The filler 3 comprises inorganic materials such as zeolite, silica, and bentonite. The filler 3 comprises at least one material selected from the group consisting of zeolite and silica, preferably silica. Compared to fillers containing zeolite, fillers containing silica tend to have superior hydrolysis resistance. Furthermore, using a filler containing silica tends to increase the free volume of the resin (especially silicone resin) contained in the matrix 2. If the free volume of the resin increases, the separation characteristics of the pervaporation membrane 10B tend to improve, particularly the flux of the permeate fluid (organic compound C) passing through the pervaporation membrane. Using the filler 3, the viscosity of the resin composition can be appropriately adjusted, thereby facilitating the preparation of resin compositions suitable for coating.

[0147] Silica typically refers to silicon dioxide. Filler 3 can be a silica filler containing silicon dioxide as its main component. Silica fillers, for example, do not have a crystalline structure. Silica fillers can be produced, for example, by reacting metallic silicon with oxygen. Silica fillers can be produced using methods such as sol-gel processes, sedimentation processes, and aqueous wet processes. Filler 3 can be substantially composed solely of silicon dioxide.

[0148] The filler 3 may also contain zeolite. Examples of zeolite contained in the filler 3 include high-silica zeolite with a high silica-to-alumina ratio and silica zeolite that does not contain alumina. As filler 3 containing high-silica zeolite, HSZ (registered trademark) manufactured by Tosoh Corporation, HiSiv (registered trademark) manufactured by UNION Showa Corporation, USKY manufactured by UNION Showa Corporation, and Zeoal (registered trademark) manufactured by Nakamura Superhard Corporation can be used.

[0149] Filler 3, particularly silica fillers, does not have micropores with a diameter of less than 2 nm. On the other hand, filler 3 can have mesopores with a diameter of 2 nm to 50 nm and macropores with a diameter of more than 50 nm.

[0150] The filler 3, particularly the silica filler, preferably has a surface modified with a modifying group containing a hydrocarbon group. In other words, the filler 3 preferably undergoes surface modification based on the modifying group. The surface-modified filler 3 has high dispersibility in the resin, which is suitable for suppressing the generation of cracks during the fabrication of the separation functional layer 1 and other conditions.

[0151] The number of carbon atoms in the hydrocarbon group contained in the modifying group is not particularly limited, for example, it can be 1 to 25. The number of carbon atoms in the hydrocarbon group can be 5 or less. The hydrocarbon group can be any of the following: straight-chain, branched, or cyclic. Examples of hydrocarbon groups include alkyl groups such as methyl and ethyl.

[0152] The modifying group may also contain a silicon atom, to which a hydrocarbon group may be bonded. The modifying group may contain at least one selected from the group consisting of organosilicon alkyl groups and polyorganosiloxane alkyl groups. Examples of organosilicon alkyl groups include trimethylsilyl alkyl groups such as trimethylsilyl alkyl and dimethylsilyl alkyl groups such as dimethylsilyl alkyl. Examples of polyorganosiloxane alkyl groups include dimethylpolysiloxane alkyl.

[0153] Surface modification based on modifying groups can be carried out, for example, by reacting the hydroxyl groups present on the surface of filler 3 with a known silane coupling agent.

[0154] Specific examples of surface-modified silica fillers include the "AEROSIL (registered trademark) RX series" (RX50, RX200, RX300, etc.), "AEROSIL (registered trademark) RY series" (RY50, RY200, RY200S, etc.), "AEROSIL (registered trademark) NY series" (NY50, NY50L, etc.), "AEROSIL (registered trademark) NAX series" (NAX50, etc.), and "AEROSIL (registered trademark) R series" (R972, R974, R976, etc.) manufactured by Aerosil Corporation of Japan.

[0155] From the viewpoint of dispersibility in the resin, filler 3 is preferably sufficiently surface-modified by the modified groups. In other words, it is preferable to have a small number of hydroxyl groups present on the surface of filler 3. Whether filler 3 is sufficiently surface-modified by the modified groups can be determined, for example, based on the pH of the dispersion of filler 3 and the Hansen solubility parameter (HSP value) of filler 3. It should be noted that the Hansen solubility parameter is obtained by dividing the solubility parameter introduced by Hildebrand into three components: dispersion term δD, polar term δP, and hydrogen bonding term δH. Details of the Hansen solubility parameter are disclosed in "Hansen Solubility Parameters; A Users Handbook" (CRC Press, 2007), etc.

[0156] In this embodiment, the pH of the dispersion of filler 3, as determined by the following tests, is, for example, 4.0 to 9.0, and can be 6.0 to 8.0. The pH of the dispersion is preferably neutral (around pH 7.0). When the pH of the dispersion is neutral, it can be considered that the filler 3 has been sufficiently surface-modified by the modifying groups, and the number of hydroxyl groups present on the surface is low.

[0157] Experiment: A dispersion was prepared by mixing water, methanol, and filler, and the pH of the dispersion was measured. Here, the filler content in the dispersion was 4 wt%, the weight ratio of water to methanol was 1:1, and the temperature of the dispersion was 25°C.

[0158] The shape of the filler 3 is, for example, granular. In this specification, "granular" includes spherical, ellipsoidal, scaly, and fibrous shapes. The filler 3 can be in powder form. The average particle size of the filler 3 is not particularly limited; for example, it can be 50 μm or less, or 20 μm or less, 10 μm or less, 1 μm or less, 500 nm or less, 100 nm or less, 50 nm or less, 30 nm or less, or even 20 nm or less. With the above configuration, the filler 3 is less likely to detach from the separation functional layer 1. Furthermore, with respect to the separation functional layer 1 containing the filler 3 with a small average particle size, the stress applied to the separation functional layer 1 is easily dispersed, tending to have, for example, high adhesion to the porous support 5. The lower limit of the average particle size of the filler 3 is not particularly limited; for example, it is 1 nm. The average particle size of the filler 3 can be 5 nm or more, 10 nm or more, or 100 nm or more. In this specification, average particle size refers to primary particle size.

[0159] The average particle size of filler 3 can be determined, for example, by the following method. First, the cross-section of the separated functional layer 1 is observed using a transmission electron microscope. In the obtained electron microscope image, the area of ​​a specific filler is calculated by image processing. The diameter of a circle with the same area as the calculated area is taken as the particle size (particle diameter) of that specific filler. The particle sizes of any number (at least 50) of fillers are calculated, and the average of the calculated values ​​is taken as the average particle size of filler 3.

[0160] The content of packing material 3 in the separation functional layer 1 can be, for example, 1 wt% or more, or 5 wt% or more, 10 wt% or more, 20 wt% or more, 30 wt% or more, or even 40 wt% or more. There is no particular upper limit to the content of packing material 3 in the separation functional layer 1; for example, it can be 50 wt% or less, or even 20 wt% or less. If the content of packing material 3 is 50 wt% or less, it can prevent a decrease in the flux of the permeate fluid passing through the pervaporation membrane 10B. Furthermore, during the fabrication of the separation functional layer 1, there is a tendency to sufficiently suppress the generation of defects such as cracks. The content of packing material 3 in the separation functional layer 1 can be 1 wt% or more and 50 wt% or less, or 5 wt% or more and 20 wt% or less.

[0161] The content of matrix 2 in the separation functional layer 1 is not particularly limited, for example, it can be 30wt%~99wt%, or it can be 30wt%~90wt%.

[0162] The surface area D1 of the filler 3 per unit weight of matrix 2 is not particularly limited, for example, it is 5m². 2 / g or more, can be 10m 2 / g or more, 20m 2 / g or more, 30m 2 / g or more, 40m 2 / g or more, and can also be 50m 2 / g or more. There is no specific upper limit for the surface area D1, for example, 100m². 2 / g or less. Surface area D1 can be based on the BET specific surface area D2 (m²) obtained by nitrogen adsorption using filler 3. 2 The weights W1 (g) of the matrix 2 contained in the separation functional layer 1 and W2 (g) of the filler 3 contained in the separation functional layer 1 are calculated using the following formula.

[0163] D1(m) 2 / g)=D2(m 2 / g)×W2(g) / W1(g) The pervaporation membrane 10B can be manufactured by further including filler 3 in a coating liquid containing the material of the separation functional layer 1, in the same manner as the pervaporation membrane 10A described above.

[0164] <Implementation Methods of Membrane Separation Devices> like Figure 3 As shown, the membrane separation apparatus 100 of this embodiment includes a pervaporation membrane 10A and a tank 23. In the membrane separation apparatus 100, the pervaporation membrane 10A can also be used instead. Figure 2 The pervaporation membrane 10B is described herein. The tank 23 has a first chamber 21 and a second chamber 22. The first chamber 21 functions as a supply space for the supply fluid (specifically, the aforementioned aqueous solution S). The second chamber 22 functions as a permeation space for the supply of the permeate fluid S1. The permeate fluid S1 can be obtained by permeating the aqueous solution S through the pervaporation membrane 10A.

[0165] A pervaporation membrane 10A is disposed inside the tank 23. Inside the tank 23, the pervaporation membrane 10A separates the first chamber 21 and the second chamber 22. The pervaporation membrane 10A extends from one of a pair of walls of the tank 23 to the other.

[0166] Chamber 1 21 has an inlet 21a and an outlet 21b. Chamber 22 has an outlet 22a. Inlet 21a is an opening for supplying aqueous solution S to the supply space (chamber 1 21). Outlet 22a is an opening for discharging permeate fluid S1 from the permeate space (chamber 2 22). Outlet 21b is an opening for discharging aqueous solution S (non-permeate fluid S2) that has not permeated through the pervaporation membrane 10A from the supply space (chamber 1 21). Inlet 21a, outlet 21b, and outlet 22a are each formed, for example, on the wall of tank 23.

[0167] The membrane separation device 100 is suitable for flow-through (continuous) membrane separation methods. However, the membrane separation device 100 can also be used for intermittent membrane separation methods.

[0168] (Operation method of membrane separation device) The membrane separation device 100 is operated as follows. First, an aqueous solution S is supplied to the first chamber 21 of the membrane separation device 100 through inlet 21a. This allows the aqueous solution S to come into contact with one side of the pervaporation membrane 10A (e.g., the main surface on the side of the separation functional layer 1).

[0169] Next, with the aqueous solution S in contact with one side of the pervaporation membrane 10A, the space adjacent to the other side of the pervaporation membrane 10A (e.g., the main surface of the porous support 5) is depressurized. Specifically, depressurization is performed in the second chamber 22 through outlet 22a. Depressurization in the second chamber 22 can be performed, for example, by a depressurization device such as a vacuum pump. The pressure in the second chamber 22 can be, for example, 50 kPa or less, but can be 20 kPa or less, 10 kPa or less, 5 kPa or less, 3 kPa or less, or even 2 kPa or less. It should be noted that, unless otherwise specified, "pressure" in this specification refers to absolute pressure.

[0170] By depressurizing the second chamber 22, a permeate fluid S1 with a high content of organic compound C can be obtained on the other side of the pervaporation membrane 10A. In other words, the permeate fluid S1 is supplied to the second chamber 22. Inside the second chamber 22, the permeate fluid S1 is typically a gas. The permeate fluid S1 is discharged to the outside of the membrane separation device 100 through the outlet 22a.

[0171] On the other hand, the content of organic compound C in the aqueous solution S decreases slowly from the inlet 21a of the first chamber 21 to the outlet 21b. The aqueous solution S (non-permeable fluid S2) treated in the first chamber 21 is discharged to the outside of the membrane separation device 100 through the outlet 21b. The non-permeable fluid S2 is typically a liquid.

[0172] As described above, the pervaporation membrane 10A preferentially allows organic compounds C contained in the aqueous solution S to permeate. Therefore, the permeate fluid S1 obtained through the operation of the membrane separation device 100 has a higher content of organic compounds C than the aqueous solution S supplied to the membrane separation device 100.

[0173] <Modifications of Membrane Separation Devices> The membrane separation device 100 can be a spiral membrane element, a hollow fiber membrane element, a coil-type membrane element with multiple pervaporation membranes stacked, a plate and frame type membrane element, etc. Figure 4 A spiral-shaped membrane element is shown. Figure 4 The membrane separation device 110 includes a central tube 26 and a laminate 27. The laminate 27 includes a pervaporation membrane 10A (or a pervaporation membrane 10B).

[0174] The central tube 26 has a cylindrical shape. Multiple holes or slits are formed on the surface of the central tube 26 to allow the permeable fluid S1 to flow into the interior of the central tube 26. Examples of materials for the central tube 26 include resins such as acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polyphenylene ether resin (PPE resin), and polysulfone resin (PSF resin); and metals such as stainless steel and titanium. The inner diameter of the central tube 26 is, for example, in the range of 20 to 100 mm.

[0175] In addition to the pervaporation membrane 10A, the laminate 27 also includes a supply-side flow path material 28 and a permeation-side flow path material 29. The laminate 27 is wound around the central tube 26. The membrane separation device 110 may also include an external material (not shown).

[0176] As the supply-side flow path material 28 and the through-side flow path material 29, nets, woven fabrics or knitted fabrics made of resins such as polyethylene, polypropylene, polyethylene terephthalate (PET), polyphenylene sulfide (PPS) or ethylene-chlorotrifluoroethylene copolymer (ECTFE) can be used.

[0177] The membrane separation device 110 can be operated, for example, by the following method: First, an aqueous solution S is supplied to one end of the wound laminate 27. The internal space of the central tube 26 is depressurized. As a result, the permeate fluid S1 that has permeated through the pervaporation membrane 10A of the laminate 27 moves into the interior of the central tube 26. The permeate fluid S1 passes through the central tube 26 and is discharged to the outside. The aqueous solution S (non-permeate fluid S2) treated in the membrane separation device 110 is discharged to the outside from the other end of the wound laminate 27.

[0178] <Implementation Methods of Membrane Separation Systems> like Figure 5 As shown, the membrane separation system 200 of this embodiment includes the membrane separation apparatus 100 described above. It should be noted that the membrane separation system 200 may also include... Figure 4 The membrane separation device 110 described herein is used instead of the membrane separation device 100.

[0179] The membrane separation system 200 includes a membrane separation unit 100 and a tank 30. The tank 30 stores an aqueous solution S to be supplied to the membrane separation unit 100. The tank 30 may also be a fermentation tank used to generate organic compound C by fermentation using a microbial-based carbon source.

[0180] The membrane separation system 200 also includes an aqueous solution supply path 70, a non-permeable fluid discharge path 71, and a permeable fluid discharge path 72. The aqueous solution supply path 70 is used to supply aqueous solution S from tank 30 to membrane separation unit 100 during operation, and is connected to the outlet 31 of tank 30 and the inlet 21a of membrane separation unit 100. For example, a pump 50 for controlling the flow rate of aqueous solution S is installed in the aqueous solution supply path 70.

[0181] The non-permeable fluid discharge path 71 is a path for discharging the non-permeable fluid S2 from the membrane separation unit 100 during operation, and is connected to the outlet 21b of the membrane separation unit 100. For example, a pump 51 for controlling the flow rate of the non-permeable fluid S2 is installed in the non-permeable fluid discharge path 71. It should be noted that the pump 51 may not be installed in the non-permeable fluid discharge path 71. The non-permeable fluid discharge path 71 may also be connected to the inlet 32 ​​of the tank 30 and configured to supply the non-permeable fluid S2 to the tank 30 during operation. That is, it may also be configured such that the non-permeable fluid S2 is mixed with the aqueous solution S in the tank 30 during operation and circulates in the aqueous solution supply path 70 and the non-permeable fluid discharge path 71. When the non-permeable fluid S2 is supplied to the tank 30, the aqueous solution S and the non-permeable fluid S2 are mixed within the tank 30, and the content of organic compound C in the aqueous solution S decreases. When tank 30 is a fermentation tank, the cessation of microbial-based fermentation can be inhibited by reducing the content of organic compound C in aqueous solution S, thereby enabling continuous production of fermented products.

[0182] The permeate discharge path 72 is a path for discharging the permeate fluid S1 from the membrane separation unit 100 during operation, and is connected to the outlet 22a of the membrane separation unit 100. A pressure reducing device 52 is provided in the permeate discharge path 72, for example. The pressure reducing device 52 can reduce the pressure within the permeate space of the membrane separation unit 100. The pressure reducing device 52 is preferably a vacuum device such as a vacuum pump. The vacuum pump is typically a gas-transporting vacuum pump, and examples include reciprocating vacuum pumps and rotary vacuum pumps. Examples of reciprocating vacuum pumps include diaphragm type and oscillating piston type vacuum pumps. Examples of rotary vacuum pumps include: liquid-sealed pumps; oil rotary pumps (rotary pumps); mechanical booster pumps; and various dry pumps such as Roots type, claw type, screw type, turbine type, and scroll type. The pump serving as the pressure reducing device 52 may also have a variable speed mechanism for changing the rotational speed, etc. An example of a variable speed mechanism is an inverter that drives the pump's motor. By using a variable speed mechanism to control the pump speed, the pressure of the permeation space of the membrane separation device 100 can be appropriately adjusted.

[0183] A heat exchanger for cooling the permeate fluid S1 can also be configured in the permeate discharge path 72. The heat exchanger allows the gaseous permeate fluid S1 to condense. The heat exchanger is, for example, a gas-liquid heat exchanger that generates heat exchange between a cooling medium such as antifreeze and the gaseous permeate fluid S1. The heat exchanger can be located between the membrane separation unit 100 and the pressure reducing unit 52 (upstream of the pressure reducing unit 52), or between the pressure reducing unit 52 and the recovery unit 40 (described later) (downstream of the pressure reducing unit 52).

[0184] The membrane separation system 200 also includes a recovery unit 40. The recovery unit 40 recovers the permeate fluid S1 from the membrane separation unit 100, and can, for example, store the permeate fluid S1. The recovery unit 40 is, for example, a tank for storing the permeate fluid S1. A permeate fluid discharge path 72 is connected to the inlet 41 of the recovery unit 40.

[0185] The membrane separation system 200 may also include a controller 60 for controlling the various components of the membrane separation system 200. The controller 60 may be, for example, a DSP (Digital Signal Processor) including an A / D conversion circuit, input / output circuit, arithmetic circuit, and storage device. The controller 60 stores a program for properly operating the membrane separation system 200.

[0186] Unless otherwise specified, the various paths of the membrane separation system 200 are, for example, made of metal or resin piping.

[0187] Example The present invention will now be described in more detail through examples and comparative examples, but the present invention is not limited thereto.

[0188] <Preparation of the pervaporation membrane> (Example 1) A silicone resin composition (coating liquid) was prepared by adding 2 parts by weight of a curing agent (SRX212 containing a platinum catalyst, manufactured by Dow Toray Co., Ltd.) containing polyorganosiloxane P1 to 100 parts by weight of the silicone base agent (BY24-489, manufactured by Dow Toray Co., Ltd.) as a polyorganosiloxane mixture. A coated film (10 μm thick) was obtained by coating the coating liquid onto a porous support. As the porous support, CF30-C (a laminate of polysulfone microporous layer and PET nonwoven fabric) manufactured by Nitto Denko Corporation was used. The coated film was formed on the polysulfone microporous layer of CF30-C. BY24-489 contains polyorganosiloxane P1 and polyorganosiloxane P2.

[0189] Next, the coated membrane was cured by heating it at 150°C for 10 minutes, thereby creating a separation functional layer with a thickness of 3 μm. Following the above procedure, the pervaporation membrane of Example 1 was fabricated.

[0190] (Example 2) 100 parts by weight of the organosilicon base agent (BY24-489, manufactured by Dow Toray Co., Ltd.) containing polyorganosiloxane P1, 1.8 parts by weight of the curing agent (SRX212 containing platinum catalyst, manufactured by Dow Toray Co., Ltd.) and 10 parts by weight of the silica filler (AEROSIL RX50, manufactured by Aerosil Corporation of Japan) were added as the coating liquid. Except as described above, the pervaporation membrane of Example 2 was prepared in the same manner as in Example 1.

[0191] (Example 3) The organosilicon main agent was modified as shown in Table 1. Otherwise, the same procedure as in Example 1 was followed to prepare the permeation vaporization membrane of Example 3.

[0192] (Example 4) The organosilicon main agent was modified as shown in Table 1. Otherwise, the same procedure as in Example 2 was followed to prepare the permeation vaporization membrane of Example 4.

[0193] (Comparative Example 1) The organosilicon main agent was modified as shown in Table 1. Otherwise, the same procedure as in Example 1 was followed to prepare the permeation vaporization membrane of Comparative Example 1.

[0194] (Comparative Example 2) The organosilicon main agent was modified as shown in Table 1. Otherwise, the same procedure as in Example 2 was followed to prepare the permeation vaporization membrane of Comparative Example 2.

[0195] (Comparative Example 3) 90 parts by weight of the silicone base agent (ELASTOSIL (registered trademark) RT604A, manufactured by Wacker Asahikasei Silicone Co., Ltd.) were mixed with 10 parts by weight of the curing agent (ELASTOSIL (registered trademark) RT604B, manufactured by Wacker Asahikasei Silicone Co., Ltd.) to form a coating liquid. Except as described above, the permeation vaporization membrane of Comparative Example 3 was prepared by operating in the same manner as in Example 1.

[0196] (Comparative Example 4) To 90 parts by weight of a silicone base agent (ELASTOSIL (registered trademark) RT604A, manufactured by Wacker Asahikasei Silicone Co., Ltd.), 10 parts by weight of a curing agent (ELASTOSIL (registered trademark) RT604B, manufactured by Wacker Asahikasei Silicone Co., Ltd.) is added, and further 10 parts by weight of a silica filler (AEROSIL RX50, manufactured by Nippon Aerosil Co., Ltd.) is added to prepare a coating liquid. A pervaporation membrane of Comparative Example 4 is produced in the same manner as in Example 1 except for the above operations.

[0197] <Molecular weight between crosslinking points of silicone resin> First, a layer having the same composition as the matrix (silicone resin) of the separation functional layer provided in the pervaporation membranes of Examples 1 to 4 and Comparative Examples 1 to 4 and having a thickness of 400 μm is formed on a release liner. As the release liner, a release-treated polyethylene terephthalate (PET) film (manufactured by Mitsubishi Chemical Corporation, MRE38) is used. The above layer is formed on the release surface of the release liner. Next, the release liner is removed to produce a single-layer film of the silicone resin. The Young's modulus of this self-supporting film is measured by the method described above. Further, based on the Young's modulus, the molecular weight between crosslinking points is calculated using the above formula (1). In the measurement of the Young's modulus, Autograph AGS-50NX manufactured by Shimadzu Corporation is used as a tensile tester.

[0198] <Observation of structure of separation functional layer> A cross section of the separation functional layer is observed using a scanning electron microscope (SU-3800, manufactured by Hitachi High-Tech Corporation), and the thickness of the separation functional layer is measured. The measurement results are shown in Table 1.

[0199] <PV Performance> (BuOH Separation Performance) For the produced pervaporation membranes of Examples 1 to 4 and Comparative Examples 1 to 4, the separation coefficient α of n-butanol (BuOH) relative to water is measured by the following method BuOH . First, the pervaporation membrane is cut into a size with a diameter of 74 mm to obtain a flat membrane-shaped test piece. This test piece is set in a batch-type membrane separation apparatus (cell). A mixed liquid containing BuOH and water is supplied to the supply space of the cell. The content of BuOH in the mixed liquid is 0.8 wt%.

[0200] Next, the unit was immersed in a water bath to adjust the temperature of the mixed liquid to 30°C. Then, using a stirrer located within the unit, the pressure in the permeation space was reduced to 1.5 kPa while stirring the mixed liquid. The mixed liquid then permeated through the pervaporation membrane to obtain the gas permeate. The gas permeate was cooled using a liquid nitrogen cooling trap, causing it to condense. The composition of the liquid permeate was analyzed using gas chromatography, and the separation coefficient α was calculated based on the results. BuOH and the flux of BuOH permeating through the pervaporation membrane [kg / m] 2 The evaluation results are shown in Table 1.

[0201] (IPA separation performance) For the pervaporation membranes of Examples 2 and 4 and Comparative Examples 2 and 4, the separation coefficient α of isopropanol (IPA) relative to water was determined using the following method. IPA First, a flat membrane-like test piece is obtained in the same manner as described above, and the test piece is placed in an intermittent membrane separation device (unit). A mixed liquid containing IPA and water is supplied to the supply space of this unit. The IPA content in the mixed liquid is 10 wt%.

[0202] Next, the unit was immersed in a water bath, and the temperature of the mixed liquid was adjusted to 40°C. Then, using a stirrer located within the unit, the pressure in the permeation space was reduced to 1.5 kPa while stirring the mixed liquid. The mixed liquid then permeated through the pervaporation membrane to obtain the gas permeate. The gas permeate was cooled using a liquid nitrogen cooling trap, causing it to condense. The composition of the liquid permeate was analyzed using gas chromatography, and the separation coefficient α was calculated based on the results. IPA and the flux of IPA permeating through the pervaporation membrane [kg / m] 2 The evaluation results are shown in Table 1.

[0203] [Table 1] Compared to the pervaporation membranes of Comparative Examples 1-4, the pervaporation membranes of Examples 1-4 exhibited increased BuOH flux permeating through them and possessed a practically harmless separation coefficient α. BuOH Furthermore, compared to the pervaporation membranes of Comparative Examples 2 and 4, the pervaporation membranes of Examples 2 and 4 exhibit increased IPA flux permeating through them and possess a practically harmless separation coefficient α. IPA In summary, the pervaporation membranes of Examples 1-4 are suitable for improving separation performance.

[0204] Industrial availability The pervaporation membrane of this embodiment is suitable for separating organic compounds from aqueous solutions containing volatile organic compounds.

Claims

1. A pervaporation membrane, which is a pervaporation membrane having a separation functional layer containing an organosilicon resin. The organosilicon resin has a cross-linked structure, and the molecular weight between the cross-linking points is between 2000 g / mol and 10000 g / mol.

2. The pervaporation membrane as described in claim 1, wherein, The molecular weight between the cross-linking points is above 3000 g / mol.

3. The pervaporation membrane as described in claim 1, wherein, The silicone resin is formed from a silicone resin composition containing less than 5 wt% solvent.

4. The pervaporation membrane as described in claim 1, wherein, The silicone resin is formed from an addition-type silicone resin composition.

5. The pervaporation membrane as described in claim 4, wherein, The addition-type silicone resin composition comprises a silicone base agent and a curing agent. The weight-average molecular weight of the organosilicon main agent is between 10,000 and 200,000.

6. The pervaporation membrane as described in claim 1, wherein, The thickness of the separation functional layer is between 1 μm and 50 μm.

7. The pervaporation membrane as described in claim 1, wherein, The separation functional layer also includes filler.

8. The pervaporation membrane as described in claim 7, wherein, The filler contains silica.

9. The pervaporation membrane as described in claim 7, wherein, The filler has a surface modified by a modifying group containing a hydrocarbon group.

10. The permeation vaporization membrane as claimed in claim 1, further comprising a porous support body supporting the separation functional layer.

11. The pervaporation membrane as described in claim 10, wherein, The porous support contains organic materials.

12. The pervaporation membrane as described in claim 10, wherein, The porous support has a main body and a microporous layer disposed on the main body. The microporous layer contains polysulfone.

13. The pervaporation membrane of claim 1, used for separating said organic compound from an aqueous solution containing a volatile organic compound.

14. The pervaporation membrane as described in claim 13, wherein, The organic compound is an alcohol.

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