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WO2017098916A1 - Membrane de séparation permettant de traiter un gaz contenant un gaz acide, et procédé de production de membrane de séparation permettant de traiter un gaz contenant un gaz acide - Google Patents

Membrane de séparation permettant de traiter un gaz contenant un gaz acide, et procédé de production de membrane de séparation permettant de traiter un gaz contenant un gaz acide Download PDF

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Publication number
WO2017098916A1
WO2017098916A1 PCT/JP2016/084556 JP2016084556W WO2017098916A1 WO 2017098916 A1 WO2017098916 A1 WO 2017098916A1 JP 2016084556 W JP2016084556 W JP 2016084556W WO 2017098916 A1 WO2017098916 A1 WO 2017098916A1
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Prior art keywords
gas
separation membrane
separation
intermediate layer
hydrocarbon group
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English (en)
Japanese (ja)
Inventor
智彦 倉橋
蔵岡　孝治
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Toyo Tire Corp
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Toyo Tire and Rubber Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/05—Cermet materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/108—Inorganic support material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/52—Polyethers
    • B01D71/521—Aliphatic polyethers
    • B01D71/5211—Polyethylene glycol or polyethyleneoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
    • B01D71/702—Polysilsesquioxanes or combination of silica with bridging organosilane groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention relates to a separation membrane for treating an acid gas-containing gas that treats a mixed gas containing an acid gas and another gas and separates the gas into respective gas components, and a method for producing the same.
  • methane gas has been studied as an energy resource to replace petroleum.
  • Methane gas is mainly obtained as natural gas, but in recent years, methane gas has been used to produce methane hydrate, deep-sea methane hydrate, digestion gas generated when biological waste is processed biologically, off-gas generated as a by-product in petroleum refining It is considered to be a source.
  • these methane gas sources may contain acidic gas (carbon dioxide, hydrogen sulfide, etc.) in addition to methane gas.
  • exhaust gas discharged from factories and power plants contains nitrogen gas and acid gas. If the mixed gas containing the nitrogen gas and the acid gas is also appropriately treated and separated into the respective gas components, the utility value of the gas is increased.
  • carbon dioxide which is an acidic gas
  • it can be commercialized as liquefied carbon dioxide gas.
  • CCS Carbon Dioxide Capture and Storage
  • a gas separation membrane has been studied as one of the techniques for separating a specific gas from a mixed gas containing plural kinds of gases.
  • a conventional gas separation membrane for separating carbon dioxide from a mixed gas containing carbon dioxide and methane gas there is a separation membrane made of an amorphous oxide having a plurality of pores formed by cyclic siloxane bonds ( For example, see Patent Document 1).
  • Patent Document 1 describes a gas separation filter in which a functional group containing basic nitrogen (N) and silicon (Si) is bonded to a side chain of Si. According to Patent Document 1, this gas separation filter is considered to have high separation performance because an acidic gas such as carbon dioxide efficiently passes through narrow pores.
  • the gas separation filter of Patent Document 1 promotes separation of carbon dioxide by introducing a functional group containing basic nitrogen (N) and silicon (Si) on the surface of the separation membrane.
  • a functional group containing basic nitrogen (N) and silicon (Si) on the surface of the separation membrane.
  • N basic nitrogen
  • Si silicon
  • the gas separation filter of Patent Document 1 forms a separation membrane by applying a liquid (sol-like) separation membrane forming material to a support and heat-treating it. If it is uniform, defects such as pinholes may be generated in the separation membrane. If there is a defect in the separation membrane, the carbon dioxide separation performance cannot be fully exhibited.
  • the present invention has been made in view of the above problems, and includes an acid gas-containing gas treatment separation membrane having a defect-free, uniform and dense separation layer, and the acid gas-containing gas treatment separation membrane.
  • An object is to provide a manufacturing method.
  • the characteristic structure of the separation membrane for acid gas-containing gas treatment according to the present invention for solving the above problems is as follows: An inorganic porous support; An intermediate layer comprising a polysiloxane network or a hydrocarbon group-containing polysiloxane network formed on the surface of the inorganic porous support; A separation layer comprising polyethylene glycol and a hydrocarbon group-containing polysiloxane network formed on the intermediate layer; It is in having.
  • the separation layer containing the polysiloxane network structure or the hydrocarbon group-containing polysiloxane network structure on the intermediate layer containing the hydrocarbon group-containing polysiloxane network structure
  • the separation layer contains polyethylene glycol.
  • Polyethylene glycol is a component that contributes to improving film formability. Therefore, when polyethylene glycol is contained in the separation layer, a uniform and dense membrane structure without defects can be obtained. As a result, the gas separation performance (acid gas selectivity) of the separation membrane for acid gas containing gas treatment can be sufficiently exhibited.
  • the basis weight of the intermediate layer is preferably 0.1 to 4.0 mg / cm 2
  • the basis weight of the separation layer is preferably 0.1 to 3.0 mg / cm 2 .
  • the basis weight of the intermediate layer and the separation layer is set in the above appropriate range, so that the stability by the intermediate layer is improved and the separation layer is excellent. Both gas separation performance and gas permeability can be achieved.
  • the content of the polyethylene glycol in the separation layer is preferably 0.1 to 5.0% by weight.
  • the separation membrane for acid gas-containing gas treatment of this configuration since the content of polyethylene glycol in the separation layer is set in the above-described appropriate range, the separation layer is improved while improving the film formability of the separation layer. It is possible to achieve both excellent gas separation performance and gas permeability.
  • the molecular weight of the polyethylene glycol is preferably 600 to 5000000.
  • the raw material liquid of the separation layer has an appropriate viscosity, and as a result, the membrane It is possible to form a separation layer with little variation in thickness.
  • the polyethylene glycol is preferably linear polyethylene glycol.
  • the film formability of the separation layer can be further improved by using linear polyethylene glycol as the polyethylene glycol.
  • the intermediate layer and / or the separation layer may be at least one metal acetate, nitrate, carbonate, boron selected from the group consisting of Li, Na, K, Cs, Mg, Ca, Ni, Fe, and Al. It is preferable that an acid salt or a phosphate is included.
  • the above-mentioned significant metal salt is selected as the metal salt having an affinity for the acidic gas, so that the gas separation performance can be further enhanced.
  • the characteristic configuration of the method for producing a separation membrane for acid gas-containing gas treatment according to the present invention is (A) a first mixed liquid obtained by mixing tetraalkoxysilane and / or hydrocarbon group-containing trialkoxysilane, an acid catalyst, water, and an organic solvent, tetraalkoxysilane, hydrocarbon group-containing trialkoxysilane, A preparatory step of preparing a second mixed liquid in which polyethylene glycol, an acid catalyst, water, and an organic solvent are mixed; (B) a first coating step of coating the first mixed liquid on the surface of the inorganic porous support; (C) an intermediate layer forming step of heat-treating the inorganic porous support after the first coating step is completed, and forming an intermediate layer including a polysiloxane network structure on the surface of the inorganic porous support; (D) a second coating step of coating the second mixed solution on the intermediate layer; (E) a separation layer forming step
  • the same excellent effects as the above-described separation membrane for acid gas-containing gas treatment are exhibited.
  • polyethylene glycol is a component that contributes to improving film formability
  • by adding polyethylene glycol to the second mixed solution a uniform and dense film structure is realized without causing defects in the formed separation layer. It can be.
  • the gas separation performance (acid gas selectivity) of the separation membrane for acid gas containing gas treatment can be sufficiently exhibited.
  • the polyethylene glycol is added to a mixture of the tetraalkoxysilane, the hydrocarbon group-containing trialkoxysilane, the acid catalyst, the water, and the organic solvent. It is preferable.
  • polyethylene glycol is added last, so that the viscosity of the second mixed solution is low. Tetraalkoxysilane and hydrocarbon group-containing trialkoxysilane are uniformly mixed, and the sol-gel reaction between them can be surely advanced. Further, by adding polyethylene glycol at the end, the hydrolysis reaction of alkoxysilane is not greatly affected, and as a result, a uniform separation layer can be formed.
  • the second coating step includes an immersing step of immersing the inorganic porous support having the intermediate layer formed therein in the second mixed solution, and the inorganic porous support from the second mixed solution is 0.5 to 50 mm / It is preferable to include a pulling-up step of pulling up in seconds.
  • the second mixed liquid is applied to the inorganic porous support by a so-called dipping method (dipping method), and the inorganic porous support at that time Since the body lifting speed is set in an appropriate range, a separation layer having an appropriate film thickness can be formed.
  • the separation membrane for treatment of acid gas-containing gas of the present invention uses a mixed gas containing acid gas and methane gas and / or nitrogen gas (hereinafter sometimes referred to as “acid gas-containing gas”) as a treatment target.
  • a mixed gas of acid gas and methane gas will be described as an example.
  • the acidic gas is a gas that shows acidity when dissolved in water, and examples thereof include carbon dioxide and hydrogen sulfide.
  • carbon dioxide is assumed as the acidic gas, and the following description will be given.
  • the acidic gas-containing gas treatment separation membrane of the present invention will be described as a carbon dioxide separation membrane for separating carbon dioxide, but a methane gas separation membrane for separating methane gas, a nitrogen gas separation membrane for separating nitrogen gas, or carbon dioxide It is also possible to configure as a carbon dioxide / (methane gas and / or nitrogen gas) separation membrane capable of simultaneously separating methane gas and / or nitrogen gas.
  • the separation membrane for treatment of acid gas-containing gas may be simply referred to as “separation membrane”.
  • the acidic gas-containing gas treatment separation membrane is formed by forming an intermediate layer on a base inorganic porous support and further forming a separation layer thereon.
  • a separation layer thereon.
  • the inorganic porous support is made of, for example, a material such as silica-based ceramics, silica-based glass, alumina-based ceramics, stainless steel, titanium, or silver.
  • the inorganic porous support is provided with an inflow portion into which gas flows and an outflow portion from which gas flows out.
  • the gas inflow portion is an opening provided in the inorganic porous support
  • the gas outflow portion is the outer surface of the inorganic porous support. It is also possible to use the outer surface of the inorganic porous support as a gas inflow portion and the opening provided in the inorganic porous support as a gas outflow portion.
  • innumerable micropores are formed on the outer surface of the inorganic porous support, gas can flow from the entire outer surface.
  • the configuration of the inorganic porous support include a cylindrical structure with a gas flow path inside, a circular pipe structure, a tubular structure, a spiral structure, and a large number of flow paths such as lotus holes in one element.
  • an inorganic porous support may be configured by preparing a solid flat plate or a bulk body made of an inorganic porous material and forming a gas flow path by hollowing out a part thereof.
  • the size of the fine pores of the inorganic porous support can be selected from the order of nm to the order of ⁇ m depending on the application, but is preferably 4 to 200 nm.
  • middle layer An intermediate
  • middle layer is provided in order to stabilize the surface of an inorganic porous support body, and to make it easy to form the below-mentioned separated layer.
  • a liquid mixture (sol) containing a material for forming a separation layer which will be described later
  • the liquid mixture penetrates excessively into the micropores.
  • the surface of the inorganic porous support is equalized by the intermediate layer, separation and cracking of the separation layer can be suppressed.
  • the intermediate layer is configured to contain a silane compound.
  • the intermediate layer of the present embodiment includes a polysiloxane network structure or a hydrocarbon group-containing polysiloxane network structure.
  • the polysiloxane network structure or the hydrocarbon group-containing polysiloxane network structure is a reaction product obtained by a sol-gel reaction of alkoxysilane containing tetraalkoxysilane and / or hydrocarbon group-containing trialkoxysilane. Therefore, tetraalkoxysilane and hydrocarbon group-containing trialkoxysilane are precursors of a polysiloxane network structure or a hydrocarbon group-containing polysiloxane network structure.
  • Tetraalkoxysilane is a tetrafunctional alkoxysilane represented by the following formula (1).
  • a preferred tetraalkoxysilane in the formula (1) is tetramethoxysilane (TMOS) in which R 1 to R 4 are the same methyl group or tetraethoxysilane (TEOS) in which the same ethyl group is used.
  • TMOS tetramethoxysilane
  • TEOS tetraethoxysilane
  • the alkoxysilane that is the raw material of the intermediate layer is only tetraalkoxysilane
  • the polysiloxane in which the siloxane bond (Si—O bond) is three-dimensionally linked by the sol-gel reaction of the tetraalkoxysilane of the formula (1) A network structure is obtained.
  • hydrocarbon group-containing trialkoxysilane containing a hydrocarbon group is a trifunctional alkoxysilane represented by the following formula (2).
  • a preferred hydrocarbon group-containing trialkoxysilane is a trimethoxysilane in which R 6 to R 8 in the formula (2) are the same methyl group or a triethoxysilane in which the same ethyl group is a Si atom of 1 to 6 carbon atoms. In which an alkyl group or a phenyl group is bonded.
  • Examples include silane, hexyltrimethoxysilane, hexyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.
  • the alkoxysilane that is the raw material of the intermediate layer is a tetraalkoxysilane and a hydrocarbon group-containing trialkoxysilane
  • a tetraalkoxysilane of the formula (1) and a hydrocarbon group-containing trialkoxysilane of the formula (2) are sol-
  • the gel reaction for example, a hydrocarbon group-containing polysiloxane network structure having a molecular structure represented by the following formula (3) is obtained.
  • the hydrocarbon group R 5 is present in the polysiloxane network structure and forms a certain organic-inorganic composite.
  • the hydrocarbon group-containing trialkoxysilane of the formula (2) is subjected to a sol-gel reaction so that the hydrocarbon of the formula (3) In the group-containing polysiloxane network structure, the density of the hydrocarbon group R 5 increases.
  • the hydrocarbon group-containing trialkoxysilane of formula (2) which is one of the raw materials of the hydrocarbon group-containing polysiloxane network structure of formula (3), has different characteristics depending on the difference in R 5 .
  • methyltrimethoxysilane or methyltriethoxysilane (having a hydrocarbon group with 1 carbon atom) has an affinity mainly for carbon dioxide, and the number of carbon atoms in the Si atom of trimethoxysilane or triethoxysilane Those having 2 to 6 alkyl groups or phenyl groups bonded thereto (hydrocarbon groups having 2 to 6 carbon atoms) have an affinity mainly for methane gas.
  • the tetraalkoxy is synthesized.
  • A1 silane
  • B1 hydrocarbon group-containing trialkoxysilane
  • the blending ratio (A1 / B1) of the tetraalkoxysilane (A1) to the hydrocarbon group-containing trialkoxysilane (B1) is 30/70 to 99.9 / 0.1 by weight ratio
  • the tetraalkoxysilane of the formula (1) and the hydrocarbon group-containing trialkoxysilane of the formula (2) are blended so that the ratio is preferably 60/40 to 99.9 / 0.1.
  • the intermediate layer contains a hydrocarbon group derived from a hydrocarbon group-containing trialkoxysilane, the intermediate layer is more flexible than a general network structure, and a certain degree of rigidity is maintained by the tetraalkoxysilane.
  • the hydrocarbon group-containing polysiloxane network structure of the formula (3) is a kind of organic-inorganic composite in which a hydrocarbon group R 5 is present in the polysiloxane network structure, and has a dense polysiloxane network structure. An amorphous inorganic porous body is formed.
  • the separation layer has a function of selectively attracting and separating carbon dioxide from a mixed gas containing carbon dioxide and methane gas.
  • the separation layer is required to achieve both gas separation performance and gas permeability at a high level. Therefore, in forming the separation layer, it is desirable to finish the film as uniform and dense as possible while reducing the film thickness as much as possible. Therefore, the present inventors diligently studied the formation conditions of the separation layer. When an appropriate amount of polyethylene glycol was added to the raw material mixture (sol) of the separation layer, the film formability of the separation layer was improved and the film thickness was increased. It has been found that a uniform and dense film structure without defects can be obtained even when the thickness is reduced.
  • a separated layer shall contain polyethyleneglycol with a hydrocarbon group containing polysiloxane network structure.
  • polyethylene glycol is mainly classified into linear polyethylene glycol and branched polyethylene glycol, it is preferable to use linear polyethylene glycol in terms of improving the film forming property of the separation layer.
  • the content of polyethylene glycol in the separation layer is 0.1 to 5.0% by weight, preferably 0.5 to 3.0% by weight.
  • the content of polyethylene glycol is less than 0.1% by weight, the effect of improving the film formability is small, and it is difficult to make the separation layer sufficiently thin.
  • the content of polyethylene glycol exceeds 5.0% by weight, alkoxysilane and polyethylene glycol are easily phase-separated, making it difficult to obtain a flat film.
  • the molecular weight of polyethylene glycol is 600 to 5000000, preferably 15000 to 2200000, and more preferably 600000 to 2200000.
  • polyethylene glycol When the molecular weight of polyethylene glycol is less than 600, since polyethylene glycol is easily decomposed, polyethylene glycol may disappear when heat treatment is performed. When the molecular weight of the polyethylene glycol exceeds 5000000, the polyethylene glycol is not uniformly mixed with the raw material mixture (sol) of the separation layer, and the viscosity of the raw material mixture increases, so that the film forming operation becomes difficult.
  • a polyethylene glycol having a molecular weight of about 500,000 or more may be referred to as polyethylene oxide.
  • the hydrocarbon group-containing polysiloxane network structure contained in the separation layer is a reaction product obtained by a sol-gel reaction of tetraalkoxysilane and hydrocarbon group-containing trialkoxysilane. Therefore, tetraalkoxysilane and hydrocarbon group-containing trialkoxysilane are precursors of a hydrocarbon group-containing polysiloxane network structure.
  • tetraalkoxysilane imparts rigidity to the separation layer, and hydrocarbon group-containing trialkoxysilane improves carbon dioxide affinity (that is, carbon dioxide separation performance) in the separation layer.
  • the tetraalkoxysilane and the hydrocarbon group-containing trialkoxysilane are the tetraalkoxysilane represented by the above formula (1) and the hydrocarbon group-containing trialkoxysilane represented by the formula (2) used for forming the intermediate layer. Can be used.
  • a preferred tetraalkoxysilane is the same as that in the intermediate layer, and in formula (1), R 1 to R 4 are tetramethoxysilane (TMOS) having the same methyl group or tetraethoxysilane (TEOS) having the same ethyl group. It is.
  • R 6 to R 8 are trimethoxysilane having the same methyl group or triethoxysilane having the same ethyl group.
  • An alkyl group having 1 to 6 carbon atoms or a phenyl group is bonded to a Si atom.
  • the molecular structure represented by the above formula (3) is obtained by sol-gel reaction of the tetraalkoxysilane of the formula (1) and the hydrocarbon group-containing trialkoxysilane of the formula (2).
  • a hydrocarbon group-containing polysiloxane network structure is obtained.
  • the blending ratio (A2 / B2) of the tetraalkoxysilane (A2) to the hydrocarbon group-containing trialkoxysilane (B2) is 0/100 to 70/30, preferably 40 / A tetraalkoxysilane of the formula (1) and a hydrocarbon group-containing trialkoxysilane of the formula (2) are blended so as to be 60 to 70/30.
  • tetraalkoxysilane and carbonization are performed so that the blending ratio (A1 / B1) at the time of forming the intermediate layer is larger than the blending ratio (A2 / B2) at the time of forming the separation layer.
  • a hydrogen group-containing trialkoxysilane is blended.
  • the separation layer contains more hydrocarbon groups derived from the hydrocarbon group-containing trialkoxysilane than the intermediate layer, the carbon dioxide in the mixed gas is selectively attracted to the separation layer, The carbon dioxide can be efficiently separated.
  • a metal salt having an affinity for carbon dioxide is added (dope) to the hydrocarbon group-containing polysiloxane network structure of the above formula (3), and the metal salt is added to the separation membrane.
  • a metal salt include at least one metal acetate, nitrate, carbonate, borate selected from the group consisting of Li, Na, K, Cs, Mg, Ca, Ni, Fe, and Al. Or phosphate.
  • magnesium nitrate or magnesium acetate is used as a preferred metal salt. Since the above metal salts including magnesium nitrate have good affinity with carbon dioxide, they are effective in improving the separation efficiency of carbon dioxide.
  • the metal salt can be easily added by adding a metal salt to the raw material of the hydrocarbon group-containing polysiloxane network structure in advance.
  • the generated hydrocarbon group-containing polysiloxane network structure can be obtained by adding the metal salt to the metal salt. It is also possible to carry out by an impregnation method in which a metal salt is impregnated alone or together with other substances inside the hydrocarbon group-containing polysiloxane network structure.
  • the acid gas-containing gas separation membrane of the present invention is produced by the following steps (a) to (e). Hereinafter, each step will be described in detail.
  • Each compounding amount of alkoxysilane (tetraalkoxysilane and / or hydrocarbon group-containing trialkoxysilane), acid catalyst, water, and organic solvent is the total amount of tetraalkoxysilane and / or hydrocarbon group-containing trialkoxysilane 1 It is preferable to adjust the acid catalyst to 0.001 to 0.1 mol, water 0.5 to 60 mol, and organic solvent 5 to 80 mol with respect to mol.
  • the compounding amount of the acid catalyst is less than 0.001 mol, the hydrolysis rate becomes low and the time required for producing the separation membrane becomes long.
  • the compounding amount of the acid catalyst is more than 0.1 mol, the hydrolysis rate becomes excessive, and it becomes difficult to obtain a uniform separation membrane.
  • the amount of water When the amount of water is less than 0.5 mol, a sol-gel reaction product accompanied by a hydrolysis reaction does not grow sufficiently. When the amount of water is more than 60 mol, the film formability is deteriorated.
  • the blending amount of the organic solvent When the blending amount of the organic solvent is less than 5 mol, the concentration of the first mixed solution becomes high and it becomes difficult to obtain a dense and uniform separation membrane.
  • the blending amount of the organic solvent When the blending amount of the organic solvent is more than 80 mol, the concentration of the first mixed solution is lowered, the number of coating times (number of steps) of the mixed solution is increased, and the production efficiency is lowered.
  • the acid catalyst for example, nitric acid, hydrochloric acid, sulfuric acid and the like are used.
  • nitric acid or hydrochloric acid is preferred.
  • organic solvent for example, methanol, ethanol, propanol, butanol, acetonitrile, benzene, toluene and the like are used. Of these, methanol or ethanol is preferred.
  • the sol-gel reaction in which both the tetraalkoxysilane and the hydrocarbon group-containing trialkoxysilane are included as the alkoxysilane contained in the first mixed solution will be described as an example.
  • a sol-gel reaction in which tetraalkoxysilane repeats hydrolysis and polycondensation starts As the tetraalkoxysilane, those described in the above-mentioned item “Separation membrane for treatment of acid gas-containing gas” can be used.
  • TEOS tetraethoxysilane
  • the sol-gel reaction is considered to proceed as shown in Scheme 1 below. Note that Scheme 1 is a model representing the progress of the sol-gel reaction and does not necessarily reflect the actual molecular structure as it is.
  • first hydrolysis reaction a part of ethoxy groups of tetraethoxysilane are hydrolyzed and dealcoholized to produce silanol groups.
  • first hydrolysis reaction Some ethoxy groups of tetraethoxysilane are not hydrolyzed and can remain as they are.
  • silanol groups associate with neighboring silanol groups and are polycondensed by dehydration. As a result, a siloxane skeleton in which silanol groups or ethoxy groups remain is formed.
  • the silanol group or ethoxy group exists in a substantially uniformly dispersed state in the siloxane skeleton.
  • the molecular weight of the siloxane is not very high and is in an oligomer rather than a polymer. Therefore, the silanol group or ethoxy group-containing siloxane oligomer is in a state of being dissolved in the first mixed liquid containing the organic solvent.
  • reaction between the siloxane oligomer and the hydrocarbon group-containing trialkoxysilane starts.
  • hydrocarbon group-containing trialkoxysilane those described in the item “Separation membrane for gas treatment containing acid gas” described above can be used.
  • methyltriethoxysilane is used as an example of a hydrocarbon group-containing trialkoxysilane
  • the reaction is considered to proceed as shown in Scheme 2 below. Note that Scheme 2 is a model representing the progress of the reaction, and does not necessarily reflect the actual molecular structure as it is.
  • the silanol group or ethoxy group of the siloxane oligomer reacts with the ethoxy group of methyltriethoxysilane, and the dealcoholization is performed to form a polysiloxane bond.
  • the silanol group or ethoxy group of the siloxane oligomer is dispersed substantially uniformly in the siloxane skeleton as described above, the reaction between the silanol group or ethoxy group of the siloxane oligomer and the ethoxy group of methyltriethoxysilane ( (Dealcoholization) is also considered to proceed substantially evenly.
  • a second mixed solution in which tetraalkoxysilane, hydrocarbon group-containing trialkoxysilane, polyethylene glycol, acid catalyst, water, and organic solvent are mixed is further prepared.
  • a 2nd liquid mixture is used in the below-mentioned "2nd application
  • the compounding amounts of tetraalkoxysilane, hydrocarbon group-containing trialkoxysilane, acid catalyst, water, and organic solvent are each 0% for the total amount of tetraalkoxysilane and hydrocarbon group-containing trialkoxysilane in 1 mol. It is preferable to adjust to 0.005 to 0.1 mol, water 0.017 to 3 mol, and organic solvent 5 to 60 mol.
  • the hydrolysis rate becomes low and the time required for producing the separation membrane becomes long.
  • the hydrolysis rate becomes excessive, and it becomes difficult to obtain a uniform separation membrane.
  • the blending amount of water is set to be smaller than that of the first mixed solution. However, when the blending amount of water is less than 0.017 mol, the hydrolysis rate decreases and the sol-gel reaction described later does not proceed sufficiently. When the amount of water is more than 3 mol, it becomes difficult to obtain a dense and uniform separation membrane.
  • the concentration of the second mixed solution becomes high, and it becomes difficult to obtain a dense and uniform separation membrane.
  • the concentration of the second mixed solution is lowered, the number of coating times (number of steps) of the mixed solution is increased, and the production efficiency is lowered.
  • the acid catalyst the same one as in the first mixed solution can be used.
  • methanol, ethanol, propanol, butanol, acetonitrile, benzene, toluene or the like is used as the organic solvent. Of these, methanol, ethanol, or acetonitrile is preferred.
  • the blending amount of polyethylene glycol is preferably adjusted to 0.05 to 2.0% of the total weight of tetraalkoxysilane and hydrocarbon group-containing trialkoxysilane.
  • the blending amount of polyethylene glycol is less than 0.05%, the effect of improving the film forming property is small, and it is difficult to sufficiently reduce the separation layer.
  • the blending amount of polyethylene glycol exceeds 2.0%, the alkoxysilane and the polyethylene glycol are easily phase-separated, making it difficult to obtain a flat film. Moreover, since the viscosity of the raw material mixture of the separation layer increases, it becomes difficult to handle.
  • the content of polyethylene glycol in the separation layer becomes 0.1 to 5.0% by weight.
  • the hydrolysis reaction of alkoxysilane is not greatly affected, and as a result, a uniform separation layer can be formed.
  • blend the metal salt which has an affinity with a carbon dioxide it is also possible to mix
  • the compounding amount of the metal salt is adjusted to 0.01 to 0.3 mol in the above compounding conditions.
  • the metal salt having an affinity for carbon dioxide those described in the above item “Separation membrane for treatment of acid gas-containing gas” can be used.
  • a metal salt is added, it is considered that the metal salt taken into the polysiloxane during the sol-gel reaction is dispersed substantially evenly in the polysiloxane bond.
  • the reaction of the second mixed solution is the same as in the above scheme 1 and scheme 2.
  • the hydrolysis reaction that proceeds in the second mixed solution is referred to as “second hydrolysis reaction”.
  • the amount of water contained in the first mixed solution is set to be greater than the amount of water contained in the second mixed solution.
  • the hydrolysis reaction has a higher hydrolysis rate than the second hydrolysis reaction. When the hydrolysis rate is increased, the polysiloxane network structure obtained by the sol-gel reaction is polymerized, and the surface of the inorganic porous support described later can be stabilized.
  • the preparation step is performed as described above, in the preparation of the first mixed solution, it is preferable to mix water in a plurality of times. In this case, since the first hydrolysis reaction can surely proceed, the surface of the inorganic porous support can be further stabilized.
  • the acid catalyst should be mixed in a plurality of times, or the hydrocarbon group-containing trialkoxysilane which is easily hydrolyzed is mixed at the end. Is preferred.
  • the composition is prepared so that the pH of the mixed solution always falls within the range of 0.8 to 2.5.
  • the pH of the mixed solution does not vary greatly, hydrolysis of the hydrocarbon group-containing trialkoxysilane does not proceed rapidly, and the sol-gel reaction can proceed in a stable state.
  • the ratio (W1 / W2) between them is 10 in terms of mole. It is preferably set to .about.20.
  • the intermediate layer described later is further stabilized, and the gas selectivity and gas permeability of the separation layer formed on the intermediate layer can be improved.
  • miniaturized polysiloxane network structure) obtained at the preparation process is apply
  • the method for applying the first mixed liquid to the inorganic porous support include a dipping method, a spray method, and a spin method.
  • the dipping method is a preferable coating method because the mixed solution can be uniformly and easily applied to the surface of the inorganic porous support. A specific procedure of the dipping method will be described. First, the inorganic porous support is immersed in the first mixed solution.
  • the dipping time is preferably 5 seconds to 10 minutes so that the first mixed solution is sufficiently adhered to the inorganic porous support. If the immersion time is shorter than 5 seconds, the film thickness is not sufficient, and if it exceeds 10 minutes, the film thickness becomes too large.
  • the inorganic porous support is pulled up from the first mixed solution.
  • the pulling speed is preferably 0.1 to 2 mm / second. If the pulling rate is in the above range, an intermediate layer having an appropriate film thickness can be formed.
  • the pulled up inorganic porous support is dried.
  • the drying conditions are preferably 15 to 40 ° C. and 0.5 to 3 hours. If the drying time is less than 0.5 hours, sufficient drying cannot be performed, and the drying state hardly changes even if the drying time exceeds 3 hours.
  • the drying is finished, a fine polysiloxane network structure adhered to the surface of the inorganic porous support (including the inner surfaces of some fine pores) is obtained.
  • miniaturized polysiloxane network structure to an inorganic porous support body can be increased by repeating a series of procedures of immersion of an inorganic porous support body, pulling up, and drying several times.
  • the first mixed liquid can be uniformly applied to the inorganic porous support by repeating a series of procedures, the finally obtained separation membrane for treatment of acid gas-containing gas can be further stabilized. .
  • (C) Intermediate layer forming step As the intermediate layer forming step, the inorganic porous support that has been subjected to the first coating step is heat-treated, and the refined polysiloxane network structure is fixed to the surface of the inorganic porous support.
  • An intermediate layer mainly composed of a polysiloxane network structure is formed by fusing.
  • a heating means such as a calciner is used. A specific procedure for the heat treatment will be described. First, the inorganic porous support is heated up to a heat treatment temperature described later. The temperature raising time is preferably 1 to 24 hours.
  • the temperature rising time is shorter than 1 hour, it is difficult to obtain a uniform film due to a rapid temperature change, and if it is longer than 24 hours, the film may be deteriorated by heating for a long time.
  • heat treatment (firing) is performed for a certain time.
  • the heat treatment temperature is preferably 30 to 300 ° C, more preferably 50 to 200 ° C. If the heat treatment temperature is lower than 30 ° C., sufficient heat treatment cannot be performed, so that a dense film cannot be obtained. If the heat treatment temperature is higher than 300 ° C., the film may be deteriorated by heating at a high temperature.
  • the heat treatment time is preferably 0.5 to 6 hours.
  • the heat treatment time is shorter than 0.5 hours, sufficient heat treatment cannot be performed, so that a dense film cannot be obtained. If the heat treatment time is longer than 6 hours, the film may be deteriorated by heating for a long time. After the heat treatment is finished, the inorganic porous support is cooled to room temperature. The cooling time is preferably 5 to 10 hours. If the cooling time is shorter than 5 hours, the film may be cracked or peeled off due to a rapid temperature change, and if it is longer than 10 hours, the film may be deteriorated. An intermediate layer is formed on the surface of the inorganic porous support after cooling (including the inner surfaces of some of the micropores).
  • the intermediate layer has a basis weight adjusted to 0.1 to 4.0 mg / cm 2 , preferably 0.5 to 2.0 mg / cm 2 .
  • the process returns to the “first applying step” described above, and the first applying step and the intermediate layer forming step are repeated as a set.
  • an intermediate layer having a denser and uniform film quality can be formed.
  • (D) Second coating step As the second coating step, a second mixed liquid (suspension of the refined polysiloxane network structure) is applied to the inorganic porous support on which the intermediate layer has been formed by the intermediate layer forming step. Apply. Since the second mixed liquid applied in the second application step is applied to the inorganic porous support through the intermediate layer, the amount of penetration of the second mixed liquid into the inorganic porous support (inorganic porous The distance that the tetraalkoxysilane or hydrocarbon group-containing trialkoxysilane soaks in the depth direction from the surface of the support can be suppressed to 50 ⁇ m or less.
  • the method for applying the second mixed solution is the same as in the first application step.
  • the conditions for applying the second mixed liquid are preferably 0.5 to 50 mm / second for the pulling speed for pulling up the inorganic porous support from the second mixed liquid.
  • a separation layer having an appropriate film thickness can be formed.
  • Other conditions are the same as in the first application step.
  • a series of steps of immersing, pulling up, and drying the inorganic porous support in the second mixed solution is repeated a plurality of times, thereby refining the polysiloxane network structure on the inorganic porous support.
  • the amount of body adhesion can be increased.
  • the second mixed liquid can be uniformly applied to the inorganic porous support by repeating a series of procedures, the separation performance of the finally obtained separation membrane for treatment of acid gas-containing gas is further improved. be able to.
  • (E) Separation layer formation step As the separation layer formation step, the inorganic porous support having been subjected to the second coating step is heat-treated, and the refined polysiloxane network structure is fixed to the surface of the inorganic porous support. By fusing, a separation layer mainly comprising a polysiloxane network structure is formed.
  • the heat treatment method and conditions are the same as those in the intermediate layer forming step.
  • a separation layer is formed on the intermediate layer by the separation layer forming step.
  • the separation layer has a basis weight adjusted to 0.1 to 3.0 mg / cm 2 , preferably 0.3 to 1.5 mg / cm 2 .
  • the process returns to the “second application step” described above, and when the second coating step and the separation layer forming step are repeated as a set, the surface of the inorganic porous support is obtained.
  • the separation membrane for gas treatment with acid gas of the present invention is completed.
  • a separation layer having a site (methyl group) that attracts a specific gas (carbon dioxide in this embodiment) is formed on an inorganic porous support as a base.
  • the separation layer is formed on the intermediate layer, but polyethylene glycol contained in the separation layer has the effect of improving the film formability of the separation layer. A uniform and dense film structure without any defects can be obtained.
  • the polysiloxane network structure contained in the intermediate layer contains a hydrocarbon group derived from a hydrocarbon group-containing trialkoxysilane, the polysiloxane network structure has more flexibility than a general network structure.
  • the intermediate layer is improved in overall flexibility and flexibility while maintaining a certain degree of rigidity by the tetraalkoxysilane.
  • the film formability of the intermediate layer is also improved.
  • a more uniform and dense separation membrane can be formed by a synergistic effect with the improvement of the film formability of the separation layer, thereby preventing the intermediate layer from being cracked or peeled off, and to an inorganic porous support.
  • the amount of the raw material liquid infiltrated in the separation layer is reduced. There is no problem as long as the amount of the raw material liquid permeated (the distance to permeate) is 50 ⁇ m or less, but preferably 20 ⁇ m or less. In this case, an increase in the thickness of the separation layer can be suppressed, and an acidic gas-containing gas treatment separation membrane excellent in gas permeability can be obtained.
  • the acid gas in the mixed gas is selectively attracted to the separation layer, and the separation membrane is used as it is. Transparent.
  • the concentrated methane gas can be used as a raw material for city gas and a raw material for hydrogen used in fuel cells.
  • the separation layer has a site that attracts methane gas (hydrocarbon group having an ethyl group or more carbon number)
  • methane gas is selectively contained in the separation layer. Attracted, methane gas passes through the pores as they are. Therefore, in this case, methane gas that has permeated through the separation membrane can be recovered and used as a raw material for city gas or a raw material for hydrogen used in a fuel cell.
  • a separation membrane for treatment was prepared.
  • the unit of the blending amount of each raw material is “g”, but the present invention can be scaled up at an arbitrary magnification. That is, the unit of the blending amount of each raw material can be read as “parts by weight”.
  • the blending amount of each raw material is 0.003 mol of nitric acid, 60 mol of ethanol, 2 mol of water (first stage), 2 mol of water when the total number of moles of tetraethoxysilane and methyltriethoxysilane is 1 mol. (Second stage) is 8 moles.
  • Glycols (Examples 1 to 9) were added at the blending amounts shown in Table 1 and stirred appropriately to prepare a separation layer forming alkoxide liquid (second mixed liquid).
  • polyethylene oxide or polyethylene glycol was not added.
  • the blending amount of each raw material is 0.01 mol of nitric acid, 20 mol of acetonitrile or ethanol, 2 mol of water, and magnesium nitrate hexahydrate when the total number of moles of tetraethoxysilane and methyltriethoxysilane is 1 mol. Japanese product becomes 0.05 mol.
  • the first mixed liquid was applied to the surface of an alumina ceramic tubular body having a tubular structure by a dipping method.
  • the lifting speed of the dipping method was 5 mm / s, and after the lifting, the film was dried at room temperature for 1 hour.
  • heat treatment was performed in a calciner. The heat treatment was performed by heating from room temperature (25 ° C.) to 150 ° C. over 5 hours, holding at 150 ° C. for 2 hours, and cooling to 25 ° C. over 5 hours.
  • the above operation (coating) was repeated three times to form an intermediate layer on the surface of the tubular body.
  • the 2nd liquid mixture was apply
  • the lifting speed of the dipping method was 5 mm / s, and after the lifting, the film was dried at room temperature for 1 hour.
  • heat treatment was performed in a calciner. The heat treatment was performed by heating from room temperature (25 ° C.) to 150 ° C. over 5 hours, holding at 150 ° C. for 2 hours, and cooling to 25 ° C. over 5 hours.
  • the above operation (coating) was repeated twice to form a separation layer on the intermediate layer.
  • the intermediate layer and the separation layer in Examples 1 to 9 had no problem in film formability.
  • FIG. 1 is a schematic configuration diagram of a gas permeation rate measuring apparatus 10 used in a separation performance confirmation test.
  • the gas transmission rate measuring device 10 includes a gas cylinder 1, a pressure gauge 2, a chamber 3, and a mass flow meter 4.
  • the separation membrane 5 is installed inside the chamber 3.
  • Carbon dioxide or nitrogen which is a measurement gas, is filled in the gas cylinder 1 in advance.
  • the pressure of the carbon dioxide discharged from the gas cylinder 1 is adjusted by the pressure gauge 2 and supplied to the chamber 3 on the downstream side.
  • the supply pressure of carbon dioxide was adjusted to 0.1 MPa at room temperature.
  • the separation membrane 5, which is a tubular body, has one end (front end side) 5 a sealed and the other end (base end side) 5 b connected to the heat resistant glass tube 6.
  • a Pyrex (registered trademark) tube an outer diameter of 8 mm, an inner diameter of 6 mm, and a length of 10 mm manufactured by Corning was used.
  • one end side of the heat-resistant glass tube 6 is reduced in diameter so that the outer diameter is 7 mm or less so that it can be inserted into the separation membrane 5 (inner diameter 7 mm).
  • the connection between the separation membrane 5 and the heat-resistant glass tube 6 is bonded with an adhesive (adhesive “Cemedine (registered trademark) C” manufactured by Cemedine Co., Ltd.), and further an epoxy resin (two liquid manufactured by Nagase ChemteX Corporation). Adhesive epoxy adhesives “AV138” and “HV998”).
  • mass flow meter 4 As the mass flow meter 4, a thermal mass flow meter (mass flow meter “5410”) manufactured by Cofrock was used. The measurement conditions were a flow rate range of 10 mL / min and an accuracy with respect to the full scale (FS) maximum flow rate of ⁇ 1% (20 ° C.). From the flow rate [mL / min] of carbon dioxide measured with the mass flow meter 4, the gas permeation rate of carbon dioxide [P (CO 2 )] (m 3 / (m 2 ⁇ s (seconds) ⁇ Pa)) was calculated. . For nitrogen, the gas permeation rate [P (N 2 )] (m 3 / (m 2 ⁇ s (seconds) ⁇ Pa)) was calculated by the same procedure as described above.
  • FS full scale
  • the permeation rate ratio [ ⁇ (CO 2 / N 2 )] of carbon dioxide and nitrogen is larger than that of the separation membrane of Comparative Example 1.
  • the separation performance of carbon dioxide was excellent.
  • the permeation rate ratio [ ⁇ (CO 2 / N 2 )] tends to increase as the blending amount of polyethylene oxide increases. It was.
  • the separation membrane for treatment of acid gas-containing gas and the production method thereof of the present invention can be used in city gas production facilities, hydrogen supply facilities for fuel cells, factory exhaust gas purification facilities, liquefied carbon dioxide production facilities, and the like. . It can also be used in CCS, which is being studied as a countermeasure against global warming.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne une membrane de séparation permettant de traiter un gaz contenant un gaz acide, qui comprend une couche de séparation dense et uniforme qui est exempte de défauts. Une membrane de séparation permettant de traiter un gaz contenant un gaz acide comprend : un corps de support poreux inorganique; une couche intermédiaire qui est formée sur la surface du corps de support poreux inorganique et contient une structure de réseau polysiloxane ou une structure de réseau polysiloxane contenant un groupe hydrocarboné; et une couche de séparation qui est formée sur la couche intermédiaire et contient un polyéthylène glycol et une structure de réseau polysiloxane contenant un groupe hydrocarboné. Le poids par mètre carré de la couche intermédiaire est de 0,1 à 4,0 mg/cm2; et le poids par mètre carré de la couche de séparation est de 0,1 à 3,0 mg/cm2.
PCT/JP2016/084556 2015-12-07 2016-11-22 Membrane de séparation permettant de traiter un gaz contenant un gaz acide, et procédé de production de membrane de séparation permettant de traiter un gaz contenant un gaz acide Ceased WO2017098916A1 (fr)

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WO2024232367A1 (fr) * 2023-05-08 2024-11-14 国立大学法人 鹿児島大学 Membrane composite de séparation de co2 et son procédé de production

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JP2005074317A (ja) * 2003-09-01 2005-03-24 Daiso Co Ltd 気体分離膜
JP2013111507A (ja) * 2011-11-25 2013-06-10 Fujifilm Corp ガス分離膜、その製造方法、それを用いたガス分離膜モジュール
JP2015503667A (ja) * 2011-12-27 2015-02-02 ダウ コーニング コーポレーションＤｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐｏｒａｔｉｏｎ 膜として有用な高自由体積シロキサン組成物
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WO2024232367A1 (fr) * 2023-05-08 2024-11-14 国立大学法人 鹿児島大学 Membrane composite de séparation de co2 et son procédé de production

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