JP2014213219A - Method of manufacturing gas separation membrane - Google Patents

Method of manufacturing gas separation membrane Download PDF

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JP2014213219A
JP2014213219A JP2013089814A JP2013089814A JP2014213219A JP 2014213219 A JP2014213219 A JP 2014213219A JP 2013089814 A JP2013089814 A JP 2013089814A JP 2013089814 A JP2013089814 A JP 2013089814A JP 2014213219 A JP2014213219 A JP 2014213219A
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laminate
peeling
manufacturing
polymer layer
gas
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隼人 杉山
Hayato Sugiyama
隼人 杉山
敦暢 小山
Atsunobu Koyama
敦暢 小山
雄大 太田
Yudai Ota
雄大 太田
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Sumitomo Chemical Co Ltd
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    • 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
    • B01D69/06—Flat membranes
    • 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
    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • 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
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • 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
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a gas separation membrane, which can stably convey a laminate having a porous membrane by suppressing elongation of the porous membrane, where the gas separation membrane includes at least one layer of a polymer layer having a substance reversibly reacting with acid gas and laminated on a porous membrane.SOLUTION: A method includes: a first process of obtaining a first laminate 13 by laminating a porous membrane 11 and a support body 12 for peeling; a second process of obtaining a second laminate 14 by applying a coating liquid 41 including a hydrophilic polymer, a substance reversibly reacting with acid gas, and at least one medium selected from a group of water, methanol, ethanol, 1-propanol, and 2-propanol on a porous membrane side of the first laminate 13, and then laminating and forming a polymer layer on the porous membrane 11 by evaporating and removing the medium from a coated membrane; and a third process of obtaining a gas separation membrane 15 by peeling the support body 12 for peeling from the second laminate 14.

Description

本発明はガス分離膜の製造方法に関し、より詳細には、多孔膜を有するガス分離膜の製造方法に関するものである。   The present invention relates to a method for producing a gas separation membrane, and more particularly to a method for producing a gas separation membrane having a porous membrane.

例えば、水素製造や尿素製造等の大規模プラントで合成される合成ガスや、天然ガス、排ガスから二酸化炭素ガス等の酸性ガスを分離する場合などに、省エネルギー化を実現するプロセスであるガス膜分離プロセスが用いられる。該ガス膜分離プロセスにかかるガス分離膜の基材には、機械的強度を高めるため多孔膜が用いられている。   For example, gas membrane separation, which is a process that realizes energy saving when separating acidic gas such as carbon dioxide gas from natural gas or exhaust gas that is synthesized in large-scale plants such as hydrogen production or urea production A process is used. A porous membrane is used as a base material for the gas separation membrane in the gas membrane separation process in order to increase mechanical strength.

ところが、張力により塑性変形しやすい多孔膜は塗布後の高温乾燥時に伸びてしまうため、低温で長時間乾燥させる必要があり、ガス分離膜の生産性を上げることが容易ではなかった。このため、高温乾燥時における多孔膜の伸びを抑制できる製造方法の開発が望まれていた。   However, since a porous membrane that is easily plastically deformed by tension stretches during high-temperature drying after application, it is necessary to dry at a low temperature for a long time, and it is not easy to increase the productivity of the gas separation membrane. For this reason, development of the manufacturing method which can suppress the elongation of the porous film at the time of high temperature drying was desired.

特許第1904315号公報Japanese Patent No. 1904315 特開2009-195900号公報JP 2009-195900

そこで本発明の目的は、多孔膜を有するガス分離膜の製造方法において、高温乾燥時における多孔膜の伸びを抑制し、多孔膜を有する積層体の安定な搬送が可能となるようにすることにある。   Accordingly, an object of the present invention is to suppress the elongation of the porous membrane during high-temperature drying in a method for producing a gas separation membrane having a porous membrane so that a laminate having the porous membrane can be stably conveyed. is there.

前記目的を達成する本発明に係るガス分離膜の製造方法は、少なくとも酸性ガスを選択透過するガス分離膜の製造方法であって、多孔膜の一方面側に剥離用支持体を積層する第１工程と、第１工程で得られた積層体の多孔膜側に、酸性ガスと可逆的に反応する物質を有するポリマー層を少なくとも１層積層する第２工程と、第２工程で得られた積層体から前記剥離用支持体を剥離する第３工程とを有することを特徴とする。   The method for producing a gas separation membrane according to the present invention that achieves the above object is a method for producing a gas separation membrane that selectively permeates at least an acidic gas, and is a first method in which a peeling support is laminated on one side of a porous membrane. A step, a second step of laminating at least one polymer layer having a substance that reacts reversibly with an acidic gas, on the porous membrane side of the laminate obtained in the first step, and a laminate obtained in the second step And a third step of peeling the peeling support from the body.

また本発明によれば、多孔膜の一方面側に剥離用支持体を積層する第１工程と、第１工程で得られた積層体の多孔膜側に、酸性ガスと可逆的に反応する物質を有するポリマー層を少なくとも１層積層する第２工程とを有することを特徴とするガス分離膜製造用積層体の製造方法が提供される。   Moreover, according to this invention, the substance which reversibly reacts with acidic gas on the porous film side of the 1st process which laminate | stacks the peeling support body in the one surface side of a porous film, and the laminated body obtained at the 1st process And a second step of laminating at least one polymer layer having a gas layer. A method for producing a laminate for producing a gas separation membrane is provided.

前記ポリマー層は、親水性ポリマーと、酸性ガスと可逆的に反応する物質とを有するものであるのが好ましい。前記親水性ポリマーとしてはポリビニルアルコール−ポリアクリル酸共重合体が好ましい。   The polymer layer preferably has a hydrophilic polymer and a substance that reacts reversibly with an acidic gas. The hydrophilic polymer is preferably a polyvinyl alcohol-polyacrylic acid copolymer.

前記剥離用支持体は、非多孔質フィルムであるのが好ましい。非多孔質フィルムとしてはポリエチレンテレフタレートフィルムが好ましい。   The peeling support is preferably a non-porous film. A polyethylene terephthalate film is preferable as the non-porous film.

そしてまた、第２工程は、親水性ポリマーと、酸性ガスと可逆的に反応する物質と、水、メタノール、エタノール、１−プロパノール及び２−プロパノールからなる群から選択される少なくとも１つの媒質とを含む塗工液を、前記多孔膜側に塗布した後、塗工膜から媒質を除去する操作を少なくとも１回行い、前記ポリマー層を少なくとも１層積層する工程であるのが好ましい。   The second step includes a hydrophilic polymer, a substance that reacts reversibly with an acidic gas, and at least one medium selected from the group consisting of water, methanol, ethanol, 1-propanol, and 2-propanol. It is preferable that after the coating liquid containing the coating liquid is applied to the porous film side, an operation of removing the medium from the coating film is performed at least once to laminate at least one polymer layer.

また、前記媒質の除去は、温度８０℃〜１５０℃の範囲での媒質の蒸発によって行うのが好ましい。   The medium is preferably removed by evaporation of the medium at a temperature in the range of 80 ° C to 150 ° C.

第１工程と第２工程とは連続的に実施するのが好ましい。   The first step and the second step are preferably performed continuously.

また、第１工程で得られる積層体を一旦ロール状に巻き取り、該ロール状の積層体を巻き出して第２工程に供するようにしてもよい。   Alternatively, the laminate obtained in the first step may be temporarily wound into a roll, and the roll-like laminate may be unwound and used for the second step.

そしてまた、第２工程で得られる積層体を一旦ロール状に巻き取り、巻き取られた積層体を巻き出して第３工程に供するようにしてもよい。   And the laminated body obtained at the 2nd process may be once wound up in roll shape, and the wound laminated body may be unwound and used for the 3rd process.

第１工程は連続搬送により行われるのが好ましく、第２工程も連続搬送により行われるのが好ましい。   The first step is preferably performed by continuous conveyance, and the second step is also preferably performed by continuous conveyance.

本発明の製造方法では、多孔膜の一方面側に剥離用支持体を積層した後、得られた積層体の多孔膜側に、酸性ガスと可逆的に反応する物質を有するポリマー層を少なくとも１層積層し、その後、前記多孔膜から前記剥離用支持体を剥離するので、例えば、ポリマー層の積層形成する際に乾燥操作を高温で行う場合でも、多孔膜の伸びが抑制され、多孔膜を有する積層体の安定な搬送が可能となり、ガス分離膜の生産性を上げることができる。   In the production method of the present invention, after a peeling support is laminated on one side of the porous film, at least one polymer layer having a substance that reacts reversibly with an acidic gas is formed on the porous film side of the obtained laminated body. Since the peeling support is peeled off from the porous film, the elongation of the porous film is suppressed even when the drying operation is performed at a high temperature when the polymer layer is laminated, for example. Stable transportation of the laminated body having it becomes possible, and the productivity of the gas separation membrane can be increased.

さらに、本発明の製造方法に付随する効果として、多孔膜を裏抜けすることによる塗工液のロスを防ぎ、剥離用支持体の多孔膜と接していない面を表面処理することで、「ポリマー層／多孔膜／剥離用支持体」の積層体をロール状に巻き付ける際にポリマー層を保護する合紙の役割を果たすことも可能となる。   Furthermore, as an effect accompanying the production method of the present invention, the loss of the coating liquid due to the penetration of the porous film is prevented, and the surface of the support for peeling that is not in contact with the porous film is surface-treated, whereby “polymer” When the laminate of “layer / porous membrane / peeling support” is wound into a roll, it can also serve as an interleaf to protect the polymer layer.

第１工程と第２工程とを連続的に実施し、両工程がいずれも連続搬送で行い、第２工程で得られる積層体を一旦ロール状に巻き取る本発明に係る製造方法を実施する製造装置の一例を示す概略図である。Manufacturing that carries out the manufacturing method according to the present invention in which the first step and the second step are carried out continuously, both steps are carried out by continuous conveyance, and the laminate obtained in the second step is wound up into a roll. It is the schematic which shows an example of an apparatus. 第２工程で巻き取られた積層体を巻き出して第３工程を連続搬送で行う本発明に係る製造方法を実施する製造装置の一例を示す概略図である。It is the schematic which shows an example of the manufacturing apparatus which implements the manufacturing method based on this invention which unwinds the laminated body wound up at the 2nd process, and performs a 3rd process by continuous conveyance.

以下、本発明に係る製造方法について詳述するが、本発明はこれらの実施形態に限定されるものではなく、請求項に示した範囲で種々の変更が可能であり、異なる実施形態にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態についても本発明の技術的範囲に含まれる。   Hereinafter, the production method according to the present invention will be described in detail, but the present invention is not limited to these embodiments, and various modifications are possible within the scope shown in the claims, and each is disclosed in different embodiments. Embodiments obtained by appropriately combining the technical means provided are also included in the technical scope of the present invention.

本発明に係るガス分離膜の製造方法について各工程ごとに説明する。まず。第１工程として、多孔膜の一方面側に剥離用支持体を積層し第１積層体を作製する。剥離用支持体によって、多孔膜の乾燥時における伸びが抑制され、多孔膜を有する積層体の安定な搬送が可能となる。   The method for producing a gas separation membrane according to the present invention will be described for each step. First. As a 1st process, the support body for peeling is laminated | stacked on the one surface side of a porous film, and a 1st laminated body is produced. The exfoliation support suppresses the elongation of the porous film during drying, and enables stable conveyance of the laminate having the porous film.

本発明で使用する多孔膜としては、高分子多孔膜が好ましく、その材質としては、従来公知の高分子、例えばポリエチレン、ポリプロピレン等のポリオレフィン系樹脂等、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリフッ化ビニル、ポリフッ化ビニリデン等の含フッ素樹脂等、ポリスチレン、酢酸セルロース、ポリウレタン、ポリアクリロニトリル、ポリスルホン、ポリエーテルスルホン、ポリイミド、ポリアラミド等の各種樹脂を挙げられ、好ましくはＰＴＦＥ、ポリスルホン、ポリエーテルスルホン、ポリアクリロニトリル、酢酸セルロース、ポリイミドなどが好ましく使用される。これらの中でも、ＰＴＦＥは、微小孔径を得やすいこと、気孔率を高くできるために分離のエネルギー効率が良いこと等の理由から特に好適である。   The porous membrane used in the present invention is preferably a polymer porous membrane, and the material thereof is a conventionally known polymer, for example, a polyolefin resin such as polyethylene or polypropylene, polytetrafluoroethylene (PTFE), polyvinyl fluoride. And various resins such as polystyrene, cellulose acetate, polyurethane, polyacrylonitrile, polysulfone, polyethersulfone, polyimide, polyaramid, etc., preferably PTFE, polysulfone, polyethersulfone, polyacrylonitrile. , Cellulose acetate, polyimide and the like are preferably used. Among these, PTFE is particularly suitable for the reasons that it is easy to obtain a micropore diameter and that the porosity can be increased, so that the energy efficiency of separation is good.

多孔膜の厚さに特に限定はないが、機械的強度の観点からは、通常、１０μｍ〜３０００μｍの範囲が好ましく、より好ましくは１０μｍ〜５００μｍの範囲であり、更に好ましくは１５μｍ〜１５０μｍの範囲である。   The thickness of the porous membrane is not particularly limited, but from the viewpoint of mechanical strength, it is usually preferably in the range of 10 μm to 3000 μm, more preferably in the range of 10 μm to 500 μm, and still more preferably in the range of 15 μm to 150 μm. is there.

多孔膜の細孔の平均孔径に特に限定はないが、１０μｍ以下が好ましく、より好ましくは０．１μｍ以下である。また多孔膜の空孔率は５％〜９９％の範囲が好ましく、より好ましくは３０％〜９０％の範囲である。   The average pore diameter of the pores of the porous membrane is not particularly limited, but is preferably 10 μm or less, more preferably 0.1 μm or less. The porosity of the porous film is preferably in the range of 5% to 99%, more preferably in the range of 30% to 90%.

本発明で使用する剥離用支持体に特に限定はないが、耐熱性を有する従来公知のものが使用でき、例えば、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）等のポリエステル、ポリカーボネート、ポリイミド、ポリエーテルエーテルケトン、ポリエーテルイミド、ポリアミド、アラミド、ポリフェニレンサルファイド、ガラス、フッ素樹脂、ポリ塩化ビニル、ポリ塩化ビニリデン、セルロース系樹脂、シリコーン樹脂等からなる群から選択される少なくとも１つが含まれるフィルムが挙げられる。中でも、表面処理性などの観点からＰＥＴが特に好適に使用される。   The release support used in the present invention is not particularly limited, but conventionally known ones having heat resistance can be used. For example, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polycarbonate, polyimide, A film containing at least one selected from the group consisting of polyetheretherketone, polyetherimide, polyamide, aramid, polyphenylene sulfide, glass, fluororesin, polyvinyl chloride, polyvinylidene chloride, cellulose resin, silicone resin, etc. Can be mentioned. Among these, PET is particularly preferably used from the viewpoint of surface treatment properties.

多孔膜と剥離用支持体との積層は、例えば、フィルム同士を粘着剤などを用いて貼り合わせればよく、連続搬送で実施することが好ましい。   The lamination of the porous film and the peeling support may be performed by continuous conveyance, for example, by bonding the films together using an adhesive or the like.

次に、第２工程として、第１積層体の多孔膜側に、酸性ガスと可逆的に反応する物質を有するポリマー層を少なくとも１層積層し第２積層体を作製する。ここで使用するポリマー層としては、親水性ポリマーと、酸性ガスと可逆的に反応する物質とを有するものであることが好ましい。親水性ポリマーとしては、例えば、ポリビニルアルコール（ＰＶＡ）、ポリエチレングリコール、ポリエチレンオキサイド、ポリアクリル酸（ＰＡＡ）、ポリスルホン酸、ポリアクリルアミド、ポリアリルアミン、ポリエチレンイミン、ＰＶＡ−ＰＡＡ共重合体、メタクリル酸−ビニルベンゼン共重合体、スルホン酸−ＰＡＡ共重合体等を挙げられる。これらの中でもＰＶＡ−ＰＡＡ共重合体が好適に使用される。   Next, as a second step, at least one polymer layer having a substance that reacts reversibly with acid gas is laminated on the porous film side of the first laminate to produce a second laminate. The polymer layer used here preferably has a hydrophilic polymer and a substance that reversibly reacts with an acidic gas. Examples of the hydrophilic polymer include polyvinyl alcohol (PVA), polyethylene glycol, polyethylene oxide, polyacrylic acid (PAA), polysulfonic acid, polyacrylamide, polyallylamine, polyethyleneimine, PVA-PAA copolymer, methacrylic acid-vinyl. A benzene copolymer, a sulfonic acid-PAA copolymer, etc. are mentioned. Among these, a PVA-PAA copolymer is preferably used.

酸性ガスと可逆的に反応する物質としては、例えば、酸性ガスが二酸化炭素ガスである場合、炭酸セシウム、重炭酸セシウム、水酸化セシウム、炭酸ルビジウム、重炭酸ルビジウム、水酸化ルビジウム、アルカリ金属イオンなどが挙げられる。   As a substance that reacts reversibly with acid gas, for example, when the acid gas is carbon dioxide gas, cesium carbonate, cesium bicarbonate, cesium hydroxide, rubidium carbonate, rubidium bicarbonate, rubidium hydroxide, alkali metal ions, etc. Is mentioned.

第１積層体にポリマー層を積層する方法に特に限定はないが、ポリマー層を構成する溶液を第１積層体に塗布した後、塗工膜から媒質を除去してポリマー層を第１積層体上に積層形成する方法が好ましい。もちろん、ポリマー層を別途作製した後、第１積層体に積層しても良いし、その際、粘着剤などで貼り合わせてもよい。   The method for laminating the polymer layer on the first laminate is not particularly limited, but after the solution constituting the polymer layer is applied to the first laminate, the medium is removed from the coating film and the polymer layer is removed from the first laminate. A method of forming a laminate on top is preferred. Of course, the polymer layer may be separately prepared and then laminated on the first laminate, and at that time, the polymer layer may be bonded with an adhesive or the like.

なお、第１積層体を一旦ロール状に巻き取り、必要なときに第１積層体を巻き出し、第１積層体の多孔膜側に、酸性ガスと可逆的に反応する物質を有するポリマー層を少なくとも１層積層し、第２積層体を作製してもよい。   In addition, the first laminated body is once wound up in a roll shape, the first laminated body is unwound when necessary, and a polymer layer having a substance that reacts reversibly with an acidic gas is formed on the porous film side of the first laminated body. At least one layer may be laminated to produce a second laminate.

ポリマー層を構成する塗工液を第１積層体に塗布する方法についてさらに説明する。ポリマー層を構成する塗工液は、ＰＶＡ−ＰＡＡ共重合体などの親水性ポリマーと、酸性ガスと可逆的に反応する物質とを、メタノール、エタノール、１−プロパノール及び２−プロパノール等のアルコール類と水とからなる群から選択される少なくとも１つの媒質と混合して塗工液としたものが好ましい。   The method for applying the coating liquid constituting the polymer layer to the first laminate will be further described. The coating liquid constituting the polymer layer comprises a hydrophilic polymer such as a PVA-PAA copolymer and a substance that reversibly reacts with an acidic gas, and alcohols such as methanol, ethanol, 1-propanol, and 2-propanol. A coating liquid is preferably mixed with at least one medium selected from the group consisting of water and water.

酸性ガスと可逆的に反応する物質と親水性ポリマーとの総重量に対する、酸性ガスと可逆的に反応する物質の重量割合としては、２０重量％〜９０重量％の範囲が好ましい。   The weight ratio of the substance reversibly reacting with the acid gas to the total weight of the substance reversibly reacting with the acid gas and the hydrophilic polymer is preferably in the range of 20% by weight to 90% by weight.

塗工液を第１積層体に塗布する方法としては、とくに制限はなく、目的に応じて適宜選択することができ、例えばスピンコート法、バー塗布、ダイコート塗布、ブレード塗布、エアナイフ塗布、グラビアコート、ロールコーティング塗布、スプレー塗布、ディップ塗布、コンマロール法、キスコート法、スクリーン印刷、インクジェット印刷などが挙げられる。塗工液の塗工膜厚は１０μｍ〜１０００μｍであることが好ましく、５０μｍ〜１０００μｍであることがより好ましく、更に好ましくは１００μｍ〜５００μｍである。塗工膜厚の調整は、塗工膜の形成速度（例えば、第１工程で得られた積層体の搬送速度）や塗工液の濃度、塗工液の吐出量などで制御できる。   There is no restriction | limiting in particular as a method of apply | coating a coating liquid to a 1st laminated body, According to the objective, it can select suitably, For example, spin coating method, bar coating, die coating coating, blade coating, air knife coating, gravure coating , Roll coating application, spray application, dip application, comma roll method, kiss coating method, screen printing, inkjet printing and the like. The coating film thickness of the coating solution is preferably 10 μm to 1000 μm, more preferably 50 μm to 1000 μm, and still more preferably 100 μm to 500 μm. The adjustment of the coating film thickness can be controlled by the coating film formation speed (for example, the transport speed of the laminate obtained in the first step), the concentration of the coating liquid, the discharge amount of the coating liquid, and the like.

次に、塗工液から媒質を除去し、ポリマー層を作製する。媒質の除去方法に特に限定はなく従来公知の方法を用いることができるが、加熱された空気等を通風させることにより塗工膜を乾燥させて媒質を蒸発除去する方法が好ましい。例えば、所定温度及び所定湿度に調整された通風乾燥炉に積層体を搬入して、塗工膜から媒質を蒸発除去する。これにより、第１積層体上にポリマー層が積層された第２積層体が作製される。なお、加熱乾燥時における多孔膜の伸びは、積層された剥離用支持体によって抑制され、積層体の安定な搬送が可能となる。   Next, the medium is removed from the coating liquid to produce a polymer layer. A method for removing the medium is not particularly limited, and a conventionally known method can be used, but a method of evaporating and removing the medium by drying the coating film by ventilating heated air or the like is preferable. For example, the laminate is carried into a ventilation drying furnace adjusted to a predetermined temperature and a predetermined humidity, and the medium is evaporated and removed from the coating film. Thereby, the 2nd laminated body by which the polymer layer was laminated | stacked on the 1st laminated body is produced. In addition, the elongation of the porous film at the time of heat drying is suppressed by the laminated support for peeling, and the laminate can be stably conveyed.

乾燥温度は、塗工液の媒質と多孔膜及び剥離用支持体の種類により適宜決定すればよい。通常、媒質の凝固点よりも高く且つ多孔膜及び剥離用支持体の融点よりも低い温度とするのが好ましく、一般に、８０℃〜１５０℃の範囲が好適である。   What is necessary is just to determine a drying temperature suitably with the kind of the medium of a coating liquid, a porous film, and the support body for peeling. Usually, the temperature is preferably higher than the freezing point of the medium and lower than the melting point of the porous membrane and the support for peeling, and generally in the range of 80 ° C to 150 ° C.

また、第２工程を複数回繰り返すことが好ましい。例えば、１層のポリマー層にピンホールがあった場合、複数回塗ることでピンホール同士が重なる確率は極めて低くなるため、ポリマー層のピンホールの発生を防止できる。   Moreover, it is preferable to repeat a 2nd process in multiple times. For example, when there is a pinhole in one polymer layer, the probability that the pinholes are overlapped with each other by applying a plurality of times becomes extremely low, so that the occurrence of pinholes in the polymer layer can be prevented.

次に、第１積層体にポリマー層が積層された第２積層体を、必要により所定温度まで冷却した後、第２積層体から剥離用支持体を剥離して、多孔膜とポリマー層とが積層されたガス分離膜を得る。   Next, after cooling the 2nd laminated body by which the polymer layer was laminated | stacked on the 1st laminated body to predetermined temperature if necessary, the support body for peeling was peeled from the 2nd laminated body, and a porous film and a polymer layer became A laminated gas separation membrane is obtained.

なお、第２積層体を一旦ロール状に巻き取り、必要なときに第２積層体を巻き出し第２積層体から剥離用支持体を剥離して分離膜を得るようにしてもよい。この場合、剥離用支持体の多孔膜と接していない面を表面処理しておけば、第２積層体をロール状に巻き取った際に、剥離用支持体が、多孔膜を保護する合紙の役割を果たす。   Alternatively, the second laminated body may be wound into a roll once, and the second laminated body may be unwound when necessary to peel the peeling support from the second laminated body to obtain a separation membrane. In this case, if the surface of the peeling support that is not in contact with the porous film is surface-treated, the peeling support protects the porous film when the second laminate is wound into a roll. To play a role.

第２積層体から剥離用支持体を剥離する方法に特に限定はなく従来公知の方法を用いることができる。例えば、剥離ローラ対を用いて、剥離ローラ対のニップ部を通過後に、多孔膜とポリマー層とが積層されたガス分離膜と剥離用支持体とをそれぞれ異なる方向に搬送することによって第２積層体から剥離用支持体を剥離する。   There is no limitation in particular in the method of peeling a peeling support body from a 2nd laminated body, A conventionally well-known method can be used. For example, using the pair of peeling rollers, after passing through the nip portion of the pair of peeling rollers, the gas separation membrane in which the porous film and the polymer layer are laminated and the peeling support are conveyed in different directions, respectively. The support for peeling is peeled from the body.

第２積層体から剥離用支持体を剥離する際、ガス分離膜に剥離痕や皺などが生じないようにする観点からは、ガス分離膜と剥離用支持体とのそれぞれに張力をかけるのが好ましい。また、剥離ローラ対のニップ部を通過した後の、ガス分離膜の搬送方向と剥離用支持体の搬送方向とのなす角度θ（図２に図示）は、３０°〜１８０°であることが好ましく、９０°〜１８０°であることがより好ましく、更に好ましくは１２０°〜１８０°である。   When peeling the peeling support from the second laminate, it is necessary to apply tension to each of the gas separation membrane and the peeling support from the viewpoint of preventing peeling marks and wrinkles from occurring in the gas separation membrane. preferable. In addition, the angle θ (shown in FIG. 2) between the transport direction of the gas separation membrane and the transport direction of the peeling support after passing through the nip portion of the peeling roller pair is 30 ° to 180 °. Preferably, it is 90 ° to 180 °, more preferably 120 ° to 180 °.

なお、１本の剥離ローラを用いてガス分離膜と剥離用支持体との搬送方向を変え、第２積層体から剥離用支持体を剥離させるようにしてももちろん構わない。   Of course, the peeling support may be peeled from the second laminate by changing the transport direction of the gas separation membrane and the peeling support using a single peeling roller.

本発明の製造方法で製造されたガス分離膜は、様々な分野での利用が期待され、例えば、水素製造や尿素製造等の大規模プラントで合成される合成ガスや、天然ガス、排ガスから二酸化炭素ガス等の酸性ガスを分離する場合などに好適に用いられる。   The gas separation membrane produced by the production method of the present invention is expected to be used in various fields. For example, synthesis gas synthesized in large-scale plants such as hydrogen production and urea production, natural gas, and exhaust gas from exhaust gas. It is suitably used for separating acidic gases such as carbon gas.

図１に、本発明に係る製造方法を実施する製造装置の一例を示す概説図を示す。図１に示す製造装置は、ロール状に巻き付けられた多孔膜１１及び剥離用支持体１２を連続してそれぞれ巻き出す第１供給部１及び第２供給部２と、圧着ローラ対３と、ポリマー層を構成する塗工液４１を塗布する塗布部４と、乾燥装置５と、第２積層体１４をロール状に巻き取る巻取部６とを備える。   FIG. 1 is a schematic diagram showing an example of a manufacturing apparatus that performs the manufacturing method according to the present invention. The manufacturing apparatus shown in FIG. 1 includes a first supply unit 1 and a second supply unit 2 that continuously unwind a porous film 11 and a peeling support 12 wound in a roll shape, a pressure roller pair 3, and a polymer. The coating part 4 which apply | coats the coating liquid 41 which comprises a layer, the drying apparatus 5, and the winding-up part 6 which winds up the 2nd laminated body 14 in roll shape are provided.

このような構成の製造装置において、多孔膜１１と剥離用支持体１２とが第１供給部１と第２供給部２とからそれぞれ巻き出される。そして、圧着ローラ対３によって、多孔膜１１と剥離用支持体１２とは圧着され第１積層体１３とされる。次いで、塗布部４において、第１積層体１３上に、ポリマー層を構成する塗工液４１が塗布される。そして、塗工液４１が塗布された第１積層体１３は乾燥装置５に搬送され乾燥される。これによって塗工液４１の塗工膜から媒質が蒸発除去されて、多孔膜１１上にポリマー層（不図示）が積層形成されて第２積層体１４とされる。その後、第２積層体１４は巻取部６にロール状に巻き取られる。   In the manufacturing apparatus having such a configuration, the porous film 11 and the peeling support 12 are unwound from the first supply unit 1 and the second supply unit 2, respectively. Then, the porous film 11 and the peeling support 12 are pressure-bonded by the pressure-bonding roller pair 3 to form the first laminated body 13. Next, in the application unit 4, a coating liquid 41 constituting a polymer layer is applied on the first laminate 13. And the 1st laminated body 13 with which the coating liquid 41 was apply | coated is conveyed to the drying apparatus 5, and is dried. As a result, the medium is evaporated and removed from the coating film of the coating liquid 41, and a polymer layer (not shown) is laminated on the porous film 11 to form the second laminate 14. Then, the 2nd laminated body 14 is wound up by the winding part 6 in roll shape.

多孔膜１１及び剥離用支持体１２は、圧着ローラ対３の回転及び巻取部６の巻芯の回転によって供給部から巻取部まで連続搬送される。この間、ガイドローラを回転駆動可能なものとし、多孔膜１１及び剥離用支持体１２の走行を補助するようにしてもよい。   The porous film 11 and the peeling support 12 are continuously conveyed from the supply unit to the winding unit by the rotation of the pressure roller pair 3 and the winding core of the winding unit 6. During this time, the guide roller may be driven to rotate, and the traveling of the porous film 11 and the peeling support 12 may be assisted.

また、図２に、本発明に係る製造方法を実施する製造装置における第２積層体から剥離用支持体を剥離する工程の一例を示す概説図を示す。図２に示す製造装置は、ロール状に巻き付けられた第２積層体１４を連続して巻き出す供給部７と、剥離ローラ対８と、ガス分離膜１５と剥離用支持体１２とをそれぞれロール状に巻き取る第一巻取部９及び第２巻取部１０とを備える。   FIG. 2 is a schematic view showing an example of a process of peeling the peeling support from the second laminate in the production apparatus for carrying out the production method according to the present invention. The manufacturing apparatus shown in FIG. 2 rolls the supply unit 7 for continuously unwinding the second laminate 14 wound in a roll shape, the separation roller pair 8, the gas separation membrane 15, and the separation support 12. A first winding unit 9 and a second winding unit 10 that are wound in a shape.

このような構成の製造装置において、第２積層体１４が供給部７から巻き出される。そして、剥離ローラ対８によって、第２積層体１４から剥離用支持体１２が剥離され、ガス分離膜１５と剥離用支持体１２とは第１巻取部９と第２巻取部１０とにそれぞれロール状に巻き取られる。また、図２に示す製造装置では、ニップ部Ｎを通過した後の、ガス分離膜１５の搬送方向と剥離用支持体１２の搬送方向とのなす角度θは固定されているが、角度θを可変としても構わない。   In the manufacturing apparatus having such a configuration, the second stacked body 14 is unwound from the supply unit 7. Then, the peeling support 12 is peeled from the second laminate 14 by the peeling roller pair 8, and the gas separation film 15 and the peeling support 12 are separated into the first winding unit 9 and the second winding unit 10. Each is wound into a roll. In the manufacturing apparatus shown in FIG. 2, the angle θ between the transport direction of the gas separation membrane 15 and the transport direction of the peeling support 12 after passing through the nip portion N is fixed. It may be variable.

実施例１
ＰＴＦＥ多孔膜（住友電工社製「WPW-045-80」）と、ＰＥＴ剥離用支持体（サンエー化研社製「ＳＡＴ１０６Ｔ」、厚み６６μｍ）とを貼り合わせて第１積層体を作製した。一方、ＰＶＡ−ＰＡＡ共重合体（住友精化社製「ＳＳゲル」）４．３重量部と、炭酸セシウム１０．０重量部とを水に混合し塗工液を作製した。そして、作製した塗工液を第１積層体のＰＴＦＥ多孔膜側に塗布した後、温度１２０℃で乾燥させて塗工膜から媒質を蒸発除去し、ポリマー層を第１積層体上に積層した第２積層体を得た。
得られた第２積層体におけるＰＴＦＥ多孔膜の伸びを下記方法によって測定した。測定結果を表１に示す。 Example 1
A PTFE porous film (“WPW-045-80” manufactured by Sumitomo Electric Industries) and a support for peeling PET (“SAT106T” manufactured by Sanei Kaken Co., Ltd., thickness: 66 μm) were bonded together to prepare a first laminate. On the other hand, 4.3 parts by weight of PVA-PAA copolymer (“SS gel” manufactured by Sumitomo Seika Co., Ltd.) and 10.0 parts by weight of cesium carbonate were mixed in water to prepare a coating solution. And after apply | coating the produced coating liquid to the PTFE porous membrane side of a 1st laminated body, it dried at the temperature of 120 degreeC, the medium was evaporated and removed from the coated film, and the polymer layer was laminated | stacked on the 1st laminated body. A second laminate was obtained.
The elongation of the PTFE porous membrane in the obtained second laminate was measured by the following method. The measurement results are shown in Table 1.

（フィルムの伸び測定）
第２積層体を幅１０ｃｍにカットしたものを測定サンプルとし、そのサンプルの長手方向の端部の一方を固定し、もう一方の端部に６８Ｎ／ｍの張力をかけながら、１２０℃で１０分間乾燥させた。乾燥前後の伸びの変化を測定した。 (Elongation measurement of film)
A sample obtained by cutting the second laminate to a width of 10 cm is used as a measurement sample, one end in the longitudinal direction of the sample is fixed, and a tension of 68 N / m is applied to the other end, at 120 ° C. for 10 minutes. Dried. The change in elongation before and after drying was measured.

実施例２
ＰＥＴ剥離用支持体としてサンエー化研社製「ＳＡＴ３０７Ｔ」（厚み５７μｍ）を用いた以外は実施例１と同様にして第２積層体を得た。そして、得られた第２積層体におけるＰＴＦＥ多孔膜の伸びを実施例１と同じ方法によって測定した。測定結果を表１に示す。 Example 2
A second laminate was obtained in the same manner as in Example 1 except that “SAT307T” (57 μm thickness) manufactured by Sanei Kaken Co., Ltd. was used as the PET peeling support. And the elongation of the PTFE porous membrane in the obtained 2nd laminated body was measured by the same method as Example 1. FIG. The measurement results are shown in Table 1.

比較例１
剥離用支持体を用いず、ＰＴＦＥ多孔膜に塗工液を塗布した後、温度１２０℃で乾燥させて塗工膜から媒質を蒸発除去し、ポリマー層をＰＴＦＥ多孔膜上に積層した積層体を得た。
得られた積層体におけるＰＴＦＥ多孔膜の伸びを実施例１と同じ方法によって測定した。測定結果を表１に示す。 Comparative Example 1
After applying the coating liquid to the PTFE porous membrane without using the peeling support, the medium was evaporated and removed from the coating membrane by drying at a temperature of 120 ° C., and a laminate in which the polymer layer was laminated on the PTFE porous membrane was obtained. Obtained.
The elongation of the PTFE porous membrane in the obtained laminate was measured by the same method as in Example 1. The measurement results are shown in Table 1.

ガス分離膜の製膜性試験
前記実施例１〜２に記載の第２積層体から剥離用支持体を剥離したガス分離膜と比較例１のガス分離膜のヘリウムガスの透過度を測定し、ヘリウムガス透過度が１．０×１０−８ｍｏｌ／（ｍ２・ｓｅｃ・ｋＰａ）を超えたガス分離膜をピンホール有りの膜として、製膜性試験を実施した。試験結果を表１に示す。 Film separation test of gas separation membrane Measured the helium gas permeability of the gas separation membrane obtained by peeling the support for peeling from the second laminate described in Examples 1 and 2 and the gas separation membrane of Comparative Example 1. A film-forming test was conducted using a gas separation membrane having a helium gas permeability exceeding 1.0 × 10 −8 mol / (m 2 · sec · kPa) as a membrane with pinholes. The test results are shown in Table 1.

本発明の製造方法によれば、ポリマー層の積層形成する際に乾燥操作を行う場合であっても、多孔膜の伸びが抑制され、多孔膜を有する積層体の安定な搬送が可能となり有用である。   According to the production method of the present invention, even when a drying operation is performed when a polymer layer is laminated, the elongation of the porous film is suppressed, and the laminate having the porous film can be stably conveyed, which is useful. is there.

１ 第１供給部
２ 第２供給部
３ 圧着ローラ対
４ 塗布部
５ 乾燥装置
６ 巻取部
７ 供給部
８ 剥離ローラ対
９ 第１巻取部
１０ 第２巻取部
１１ 多孔膜
１２ 剥離用支持体
１３ 第１積層体
１４ 第２積層体
１５ ガス分離膜
４１ 塗工液 DESCRIPTION OF SYMBOLS 1 1st supply part 2 2nd supply part 3 Pressing roller pair 4 Application | coating part 5 Drying device 6 Winding part 7 Supply part 8 Peeling roller pair 9 1st winding part 10 2nd winding part 11 Porous film 12 Support for peeling Body 13 First laminated body 14 Second laminated body 15 Gas separation membrane 41 Coating liquid

Claims (13)

少なくとも酸性ガスを選択透過するガス分離膜の製造方法であって、
多孔膜の一方面側に剥離用支持体を積層する第１工程と、
第１工程で得られた積層体の多孔膜側に、酸性ガスと可逆的に反応する物質を有するポリマー層を少なくとも１層積層する第２工程と、
第２工程で得られた積層体から前記剥離用支持体を剥離する第３工程と
を有することを特徴とするガス分離膜の製造方法。 A method for producing a gas separation membrane that selectively permeates at least acid gas,
A first step of laminating a peeling support on one side of the porous membrane;
A second step of laminating at least one polymer layer having a substance that reacts reversibly with acid gas on the porous membrane side of the laminate obtained in the first step;
And a third step of peeling the peeling support from the laminate obtained in the second step. 第２工程で得られる積層体を一旦ロール状に巻き取り、巻き取られた積層体を巻き出して第３工程に供することを特徴とする請求項１記載の製造方法。   The manufacturing method according to claim 1, wherein the laminate obtained in the second step is once wound up in a roll shape, and the wound laminate is unwound and used in the third step. 多孔膜の一方面側に剥離用支持体を積層する第１工程と、
第１工程で得られた積層体の多孔膜側に、酸性ガスと可逆的に反応する物質を有するポリマー層を少なくとも１層積層する第２工程と
を有することを特徴とするガス分離膜製造用積層体の製造方法。 A first step of laminating a peeling support on one side of the porous membrane;
For the production of a gas separation membrane, comprising a second step of laminating at least one polymer layer having a substance that reacts reversibly with an acid gas on the porous membrane side of the laminate obtained in the first step A manufacturing method of a layered product. 前記ポリマー層が、親水性ポリマーと、酸性ガスと可逆的に反応する物質とを有するものであることを特徴とする請求項１〜３のいずれか記載の製造方法。   The manufacturing method according to claim 1, wherein the polymer layer has a hydrophilic polymer and a substance that reacts reversibly with an acidic gas. 前記親水性ポリマーがポリビニルアルコール−ポリアクリル酸共重合体であることを特徴とする請求項４記載の製造方法。   The method according to claim 4, wherein the hydrophilic polymer is a polyvinyl alcohol-polyacrylic acid copolymer. 前記剥離用支持体が非多孔質フィルムであることを特徴とする請求項１〜５のいずれか記載の製造方法。   The manufacturing method according to claim 1, wherein the peeling support is a non-porous film. 前記非多孔質フィルムがポリエチレンテレフタレートフィルムであることを特徴とする請求項６記載の製造方法。   The manufacturing method according to claim 6, wherein the non-porous film is a polyethylene terephthalate film. 第２工程が、親水性ポリマーと、酸性ガスと可逆的に反応する物質と、水、メタノール、エタノール、１−プロパノール及び２−プロパノールからなる群から選択される少なくとも１つの媒質とを含む塗工液を、前記多孔膜側に塗布した後、塗工膜から媒質を除去する操作を少なくとも１回行い、前記ポリマー層を少なくとも１層積層する工程であることを特徴とする請求項１〜７のいずれか記載の製造方法。   The second step is a coating comprising a hydrophilic polymer, a substance that reacts reversibly with an acid gas, and at least one medium selected from the group consisting of water, methanol, ethanol, 1-propanol, and 2-propanol. The liquid is applied to the porous film side, and then the operation of removing the medium from the coating film is performed at least once, and the polymer layer is a step of laminating at least one layer. Any manufacturing method. 前記媒質の除去は、温度８０℃〜１５０℃の範囲での媒質の蒸発によって行う請求項８記載の製造方法。   The method according to claim 8, wherein the removal of the medium is performed by evaporation of the medium at a temperature in the range of 80C to 150C. 第１工程と第２工程とを連続的に実施することを特徴とする請求項１〜９のいずれか記載の製造方法。   The manufacturing method according to claim 1, wherein the first step and the second step are continuously performed. 第１工程で得られる積層体を一旦ロール状に巻き取り、該ロール状の積層体を巻き出して第２工程に供することを特徴とする請求項１〜１０のいずれか記載の製造方法。   The manufacturing method according to any one of claims 1 to 10, wherein the laminate obtained in the first step is once wound into a roll, and the roll-like laminate is unwound and used in the second step. 第１工程が連続搬送により行われることを特徴とする請求項１〜１１のいずれか記載の製造方法。   The manufacturing method according to claim 1, wherein the first step is performed by continuous conveyance. 第２工程が連続搬送により行われることを特徴とする請求項１〜１２のいずれか記載の製造方法。   The manufacturing method according to claim 1, wherein the second step is performed by continuous conveyance.
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