WO2016163296A1 - Hydrogen sulfide separation material and hydrogen sulfide separation membrane - Google Patents
Hydrogen sulfide separation material and hydrogen sulfide separation membrane Download PDFInfo
- Publication number
- WO2016163296A1 WO2016163296A1 PCT/JP2016/060618 JP2016060618W WO2016163296A1 WO 2016163296 A1 WO2016163296 A1 WO 2016163296A1 JP 2016060618 W JP2016060618 W JP 2016060618W WO 2016163296 A1 WO2016163296 A1 WO 2016163296A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydrogen sulfide
- sulfide separation
- water
- separation membrane
- amine
- Prior art date
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- 239000003480 eluent Substances 0.000 description 1
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- 238000001704 evaporation Methods 0.000 description 1
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- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 description 1
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- JDDJZTXSCDRXRJ-UHFFFAOYSA-N n-[2-[2-(hydroxyamino)ethoxy]ethyl]hydroxylamine Chemical compound ONCCOCCNO JDDJZTXSCDRXRJ-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 239000001814 pectin Substances 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
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- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
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- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- 229940010747 sodium hyaluronate Drugs 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- YWIVKILSMZOHHF-QJZPQSOGSA-N sodium;(2s,3s,4s,5r,6r)-6-[(2s,3r,4r,5s,6r)-3-acetamido-2-[(2s,3s,4r,5r,6r)-6-[(2r,3r,4r,5s,6r)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2- Chemical compound [Na+].CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 YWIVKILSMZOHHF-QJZPQSOGSA-N 0.000 description 1
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Classifications
-
- 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
- B01D69/1213—Laminated layers
-
- 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
-
- 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
- B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
-
- 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
- B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
- B01D71/441—Polyvinylpyrrolidone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
Abstract
To provide a hydrogen sulfide separation material which is useful for the production of a hydrogen sulfide separation membrane that has excellent hydrogen sulfide permeation performance (permeance) and hydrogen sulfide separation performance (selectivity).
A hydrogen sulfide separation material which contains a water absorbent polymer and an amine-based carrier. In addition, this hydrogen sulfide separation material satisfies the condition expressed by formula (1)
(X1-X2) × Y × 100/Z ≤ 0.1 (1)
X1: the number of moles of an alkali metal contained in the water absorbent polymer
X2: the number of equivalents of an ion exchange group contained in the water absorbent polymer
Y: the average atomic weight of an alkali metal contained in the water absorbent polymer
Z: the mass of the water absorbent polymer
Description
本発明は、硫化水素を含むガスから硫化水素を分離するための硫化水素分離材および該硫化水素分離材から得られる硫化水素分離膜に関する。
The present invention relates to a hydrogen sulfide separation material for separating hydrogen sulfide from a gas containing hydrogen sulfide and a hydrogen sulfide separation membrane obtained from the hydrogen sulfide separation material.
硫化水素を含む原料ガスから硫化水素を分離するための分離膜として、特許文献１には硬化ポリサルファイドポリマーの選択透過性薄膜を用いた硫化水素分離膜が記載されている。
As a separation membrane for separating hydrogen sulfide from a raw material gas containing hydrogen sulfide, Patent Document 1 describes a hydrogen sulfide separation membrane using a selectively permeable thin film of a cured polysulfide polymer.
しかしながら、特許文献１に記載された硫化水素分離膜は、硫化水素透過性能（パーミアンス）および硫化水素分離性能（選択率）が必ずしも十分に満足できるものではなかった。そこで、本発明は、硫化水素透過性能（パーミアンス）および硫化水素分離性能（選択率）に優れた硫化水素分離膜の製造に有用な硫化水素分離材を提供することを目的とする。
However, the hydrogen sulfide separation membrane described in Patent Document 1 is not necessarily satisfactory in terms of hydrogen sulfide permeation performance (permeance) and hydrogen sulfide separation performance (selectivity). Therefore, an object of the present invention is to provide a hydrogen sulfide separation material useful for producing a hydrogen sulfide separation membrane having excellent hydrogen sulfide permeation performance (permeance) and hydrogen sulfide separation performance (selectivity).
本発明は、以下の〔１〕～〔７〕記載の発明を含む。
〔１〕吸水性ポリマーおよびアミン系キャリアを含む硫化水素分離材。
〔２〕下記式（１）で表される条件を満たす〔１〕記載の硫化水素分離材。
（Ｘ１－Ｘ２）×Ｙ×１００／Ｚ ≦ ０．１ （１）
Ｘ１：前記吸水性ポリマーに含まれるアルカリ金属のモル数
Ｘ２：前記吸水性ポリマーに含まれるイオン交換基の当量数
Ｙ：前記吸水性ポリマーに含まれるアルカリ金属の平均原子量
Ｚ：前記吸水性ポリマーの質量
〔３〕前記アミン系キャリアがヘテロ環式アミン化合物である〔１〕または〔２〕記載の硫化水素分離材。
〔４〕前記へテロ環式アミンがピペラジンである〔３〕記載の硫化水素分離材。
〔５〕〔１〕から〔４〕のいずれか一項記載の硫化水素分離材と、多孔膜とを有する硫化水素分離膜。
〔６〕〔５〕記載の硫化水素分離膜を含む硫化水素分離装置。
〔７〕〔１〕から〔４〕のいずれか一項記載の硫化水素分離材または〔５〕に記載の硫化水素分離膜に、硫化水素を含む混合ガスを接触させて、硫化水素を分離する方法。 The present invention includes the following inventions [1] to [7].
[1] A hydrogen sulfide separator comprising a water-absorbing polymer and an amine carrier.
[2] The hydrogen sulfide separation material according to [1], which satisfies a condition represented by the following formula (1).
(X 1 −X 2 ) × Y × 100 / Z ≦ 0.1 (1)
X 1 : Number of moles of alkali metal contained in the water-absorbing polymer X 2 : Equivalent number of ion-exchange groups contained in the water-absorbing polymer Y: Average atomic weight of alkali metal contained in the water-absorbing polymer Z: Water-absorbing property Polymer mass [3] The hydrogen sulfide separator according to [1] or [2], wherein the amine carrier is a heterocyclic amine compound.
[4] The hydrogen sulfide separating material according to [3], wherein the heterocyclic amine is piperazine.
[5] A hydrogen sulfide separation membrane comprising the hydrogen sulfide separator according to any one of [1] to [4] and a porous membrane.
[6] A hydrogen sulfide separator including the hydrogen sulfide separation membrane according to [5].
[7] Hydrogen sulfide is separated by bringing the hydrogen sulfide separation material according to any one of [1] to [4] or the hydrogen sulfide separation membrane according to [5] into contact with a mixed gas containing hydrogen sulfide. Method.
〔１〕吸水性ポリマーおよびアミン系キャリアを含む硫化水素分離材。
〔２〕下記式（１）で表される条件を満たす〔１〕記載の硫化水素分離材。
（Ｘ１－Ｘ２）×Ｙ×１００／Ｚ ≦ ０．１ （１）
Ｘ１：前記吸水性ポリマーに含まれるアルカリ金属のモル数
Ｘ２：前記吸水性ポリマーに含まれるイオン交換基の当量数
Ｙ：前記吸水性ポリマーに含まれるアルカリ金属の平均原子量
Ｚ：前記吸水性ポリマーの質量
〔３〕前記アミン系キャリアがヘテロ環式アミン化合物である〔１〕または〔２〕記載の硫化水素分離材。
〔４〕前記へテロ環式アミンがピペラジンである〔３〕記載の硫化水素分離材。
〔５〕〔１〕から〔４〕のいずれか一項記載の硫化水素分離材と、多孔膜とを有する硫化水素分離膜。
〔６〕〔５〕記載の硫化水素分離膜を含む硫化水素分離装置。
〔７〕〔１〕から〔４〕のいずれか一項記載の硫化水素分離材または〔５〕に記載の硫化水素分離膜に、硫化水素を含む混合ガスを接触させて、硫化水素を分離する方法。 The present invention includes the following inventions [1] to [7].
[1] A hydrogen sulfide separator comprising a water-absorbing polymer and an amine carrier.
[2] The hydrogen sulfide separation material according to [1], which satisfies a condition represented by the following formula (1).
(X 1 −X 2 ) × Y × 100 / Z ≦ 0.1 (1)
X 1 : Number of moles of alkali metal contained in the water-absorbing polymer X 2 : Equivalent number of ion-exchange groups contained in the water-absorbing polymer Y: Average atomic weight of alkali metal contained in the water-absorbing polymer Z: Water-absorbing property Polymer mass [3] The hydrogen sulfide separator according to [1] or [2], wherein the amine carrier is a heterocyclic amine compound.
[4] The hydrogen sulfide separating material according to [3], wherein the heterocyclic amine is piperazine.
[5] A hydrogen sulfide separation membrane comprising the hydrogen sulfide separator according to any one of [1] to [4] and a porous membrane.
[6] A hydrogen sulfide separator including the hydrogen sulfide separation membrane according to [5].
[7] Hydrogen sulfide is separated by bringing the hydrogen sulfide separation material according to any one of [1] to [4] or the hydrogen sulfide separation membrane according to [5] into contact with a mixed gas containing hydrogen sulfide. Method.
本発明の硫化水素分離材を使用すれば、硫化水素透過性能（パーミアンス）および硫化水素分離性能（選択率）に優れた硫化水素分離膜を製造できる。
If the hydrogen sulfide separation material of the present invention is used, a hydrogen sulfide separation membrane excellent in hydrogen sulfide permeation performance (permeance) and hydrogen sulfide separation performance (selectivity) can be produced.
以下、本発明について詳細に説明する。
Hereinafter, the present invention will be described in detail.
＜吸水性ポリマー＞
本発明の硫化水素分離材に含まれる吸水性ポリマーとは、親水基を有し、且つ、三次元網目構造を有するものであり、水を内包して膨潤体となるものを表す。吸水性ポリマーは、架橋構造を有する高分子、すなわち、架橋高分子であることが好ましい。該架橋高分子は、架橋剤を用いて化学反応により形成されたものでもよいし、物理的な相互作用によって形成されたものでもよい。 <Water-absorbing polymer>
The water-absorbing polymer contained in the hydrogen sulfide separating material of the present invention has a hydrophilic group and a three-dimensional network structure, and represents a swelled body containing water. The water-absorbing polymer is preferably a polymer having a crosslinked structure, that is, a crosslinked polymer. The crosslinked polymer may be formed by a chemical reaction using a crosslinking agent or may be formed by physical interaction.
本発明の硫化水素分離材に含まれる吸水性ポリマーとは、親水基を有し、且つ、三次元網目構造を有するものであり、水を内包して膨潤体となるものを表す。吸水性ポリマーは、架橋構造を有する高分子、すなわち、架橋高分子であることが好ましい。該架橋高分子は、架橋剤を用いて化学反応により形成されたものでもよいし、物理的な相互作用によって形成されたものでもよい。 <Water-absorbing polymer>
The water-absorbing polymer contained in the hydrogen sulfide separating material of the present invention has a hydrophilic group and a three-dimensional network structure, and represents a swelled body containing water. The water-absorbing polymer is preferably a polymer having a crosslinked structure, that is, a crosslinked polymer. The crosslinked polymer may be formed by a chemical reaction using a crosslinking agent or may be formed by physical interaction.
ここで言う親水基とは、水との相互作用を持つことができる極性基や解離基を含む原子団を表し、例えば、水酸基、カルボキシル基、ビニル基、アミノ基、シアノ基、オキシエチレン基、カルボニル基、スルホ基、ホスホノ基、スルホニルイミド基、フェノール性水酸基等があげられる。該親水基はイオン交換基であることが好ましく、イオン交換基としては、スルホ基、カルボキシル基、ホスホノ基、スルホニルイミド基、フェノール性水酸基があげられる。これらのイオン交換基が有するプロトンは、部分的にまたは全てが金属イオンや４級アンモニウムイオン等で交換されて塩を形成されていてもよい。
The hydrophilic group as used herein represents an atomic group containing a polar group or a dissociating group capable of interacting with water. For example, a hydroxyl group, a carboxyl group, a vinyl group, an amino group, a cyano group, an oxyethylene group, Examples include carbonyl group, sulfo group, phosphono group, sulfonylimide group, phenolic hydroxyl group and the like. The hydrophilic group is preferably an ion exchange group, and examples of the ion exchange group include a sulfo group, a carboxyl group, a phosphono group, a sulfonylimide group, and a phenolic hydroxyl group. Protons of these ion exchange groups may be partially or wholly exchanged with metal ions or quaternary ammonium ions to form salts.
吸水性ポリマーには、通常、アルカリ金属が含まれる。
The water-absorbing polymer usually contains an alkali metal.
吸水性ポリマーに含まれるアルカリ金属の量は、下記式（１）で表される条件を満たすことが好ましい。
（Ｘ１－Ｘ２）×Ｙ×１００／Ｚ ≦ ０．１ （１）
Ｘ１：前記吸水性ポリマーに含まれるアルカリ金属のモル数
Ｘ２：前記吸水性ポリマーに含まれるイオン交換基の当量数
Ｙ：前記吸水性ポリマーに含まれるアルカリ金属の平均原子量
Ｚ：前記吸水性ポリマーの質量 The amount of alkali metal contained in the water-absorbing polymer preferably satisfies the condition represented by the following formula (1).
(X 1 −X 2 ) × Y × 100 / Z ≦ 0.1 (1)
X 1 : Number of moles of alkali metal contained in the water-absorbing polymer X 2 : Equivalent number of ion-exchange groups contained in the water-absorbing polymer Y: Average atomic weight of alkali metal contained in the water-absorbing polymer Z: Water-absorbing property Polymer mass
（Ｘ１－Ｘ２）×Ｙ×１００／Ｚ ≦ ０．１ （１）
Ｘ１：前記吸水性ポリマーに含まれるアルカリ金属のモル数
Ｘ２：前記吸水性ポリマーに含まれるイオン交換基の当量数
Ｙ：前記吸水性ポリマーに含まれるアルカリ金属の平均原子量
Ｚ：前記吸水性ポリマーの質量 The amount of alkali metal contained in the water-absorbing polymer preferably satisfies the condition represented by the following formula (1).
(X 1 −X 2 ) × Y × 100 / Z ≦ 0.1 (1)
X 1 : Number of moles of alkali metal contained in the water-absorbing polymer X 2 : Equivalent number of ion-exchange groups contained in the water-absorbing polymer Y: Average atomic weight of alkali metal contained in the water-absorbing polymer Z: Water-absorbing property Polymer mass
ここで、Ｘ２で表される吸水性ポリマーに含まれるイオン交換基の当量数とは、吸水性ポリマーに含まれるイオン交換基のモル数に、イオン交換基の価数の絶対値を乗じたものである。例えば、吸水性ポリマーにＳＯ４
２－が１モル含まれている場合、吸水性ポリマーに含まれるイオン交換基の当量数は２モルとなり、吸水性ポリマーにＣＯＯ－が１モル含まれている場合、吸水性ポリマーに含まれるイオン交換基の当量数は１モルとなる。
Here, the number of equivalents of ion-exchange groups in the water-absorbing polymer represented by X 2, the number of moles of ion-exchange groups in the water-absorbing polymer, multiplied by the absolute value of the valence of the ion-exchange group Is. For example, when 1 mol of SO 4 2− is contained in the water-absorbing polymer, the number of equivalents of ion exchange groups contained in the water-absorbing polymer is 2 mol, and 1 mol of COO − is contained in the water-absorbing polymer. The equivalent number of ion exchange groups contained in the water-absorbing polymer is 1 mol.
上記式（１）の左辺は、吸水性ポリマーに含まれる、イオン交換基と結合可能なアルカリ金属を除いたアルカリ金属の質量割合（質量％）を表す。この値は、硫化水素分離性能を高く保つ観点から、０以下であることが好ましい。ここで、アルカリ金属とは、アルカリ金属化合物に含まれるアルカリ金属原子（アルカリ金属イオン）を含む。アルカリ金属イオンが結合したイオン交換基以外に、アルカリ金属炭酸塩、アルカリ金属炭酸水素塩、アルカリ金属水酸化物等を含まないことが好ましい。
The left side of the above formula (1) represents the mass ratio (mass%) of the alkali metal contained in the water-absorbing polymer, excluding the alkali metal that can bind to the ion exchange group. This value is preferably 0 or less from the viewpoint of maintaining high hydrogen sulfide separation performance. Here, the alkali metal includes an alkali metal atom (alkali metal ion) contained in the alkali metal compound. It is preferable not to contain an alkali metal carbonate, an alkali metal hydrogen carbonate, an alkali metal hydroxide or the like other than an ion exchange group to which an alkali metal ion is bonded.
本発明の硫化水素分離材に含まれる吸水性ポリマーは、天然高分子（多糖類系、微生物系、動物系）、半合成高分子（セルロース系、デンプン系、アルギン酸系）および合成高分子（ビニル系、アクリル系、その他）であり、以下に述べるポリビニルアルコールに代表される合成高分子や、植物由来のセルロース等を原料とする天然高分子または半合成高分子を適宜選択して使用することができる。
The water-absorbing polymer contained in the hydrogen sulfide separation material of the present invention includes natural polymers (polysaccharides, microorganisms, animals), semi-synthetic polymers (cellulose, starch, alginic acid) and synthetic polymers (vinyl). A synthetic polymer typified by polyvinyl alcohol described below, or a natural polymer or semi-synthetic polymer made from plant-derived cellulose or the like as appropriate. it can.
吸水性ポリマーのうち、天然高分子および半合成高分子について詳しく説明する。
植物多糖類系の天然高分子としては、アラビアガム、κ－カラギーナン、ι－カラギーナン、λ－カラギーナン、グアガム（Squalon製Supercolなど）、ローカストビーンガム、ペクチン、トラガント、トウモロコシデンプン（National Starch ＆ Chemical Co.製Purity-21など）、リン酸化デンプン（National Starch ＆ Chemical Co.製National 78-1898など）などがあげられる。微生物多糖類系の天然高分子としては、キサンタンガム（Kelco製Keltrol Tなど）、デキストリン（National Starch ＆ Chemical Co.製Nadex360など）などがあげられる。動物系の天然高分子としては、ゼラチン（Croda製Crodyne B419など）、カゼイン、コンドロイチン硫酸ナトリウム（Croda製Cromoist CSなど）などがあげられる。
セルロース系の半合成高分子としては、エチルセルロース（I.C.I.製Cellofas WLDなど）、カルボキシメチルセルロース(ダイセル製CMCなど)、ヒドロキシエチルセルロース(ダイセル製HECなど)、ヒドロキシプロピルセルロース（Aqualon製Klucelなど）、メチルセルロース（Henkel製Viscontranなど）、ニトロセルロース（Hercules製Isopropyl Wetなど）、カチオン化セルロース（Croda製Crodacel QMなど）などがあげられる。デンプン系の半合成高分子としては、リン酸化デンプン（National Starch ＆ Chemical製National 78-1898など）などがあげられる。アルギン酸系の半合成高分子としては、アルギン酸ナトリウム（Kelco製Keltoneなど）、アルギン酸プロピレングリコールなどがあげられる。
天然高分子または半合成高分子のその他の分類として、カチオン化グアガム（Alcolac製Hi-care1000など）、ヒアルロン酸ナトリウム（Lifecare Biomedial製Hyalureなど）があげられる。
これらの吸水性ポリマーはいずれも、市販品を使用することができ、例えば、それぞれの化合物名に添えて（ ）内に記載されるメーカーより提供される商品を使用することができる。 Of the water-absorbing polymers, natural polymers and semisynthetic polymers will be described in detail.
Plant polysaccharide-based natural polymers include gum arabic, κ-carrageenan, ι-carrageenan, λ-carrageenan, guar gum (Squalon Supercol, etc.), locust bean gum, pectin, tragacanth, corn starch (National Starch & Chemical Co Purity-21, etc.) and phosphorylated starch (National Starch & Chemical Co., National 78-1898, etc.). Examples of microbial polysaccharide-based natural polymers include xanthan gum (such as Keltrol T from Kelco) and dextrin (such as Nadex 360 from National Starch & Chemical Co.). Examples of animal-based natural polymers include gelatin (such as Crodyne B419 from Croda), casein, sodium chondroitin sulfate (such as Cromoist CS from Croda), and the like.
Cellulose semi-synthetic polymers include ethyl cellulose (ICI Cellofas WLD, etc.), carboxymethyl cellulose (Daicel CMC, etc.), hydroxyethyl cellulose (Daicel HEC, etc.), hydroxypropyl cellulose (Aqualon Klucel, etc.), methyl cellulose (Henkel Viscontran, etc.), nitrocellulose (Isopropyl Wet, etc. from Hercules), and cationized cellulose (Crodacel QM, etc. from Croda). Examples of the starch-based semi-synthetic polymer include phosphorylated starch (National Starch &Chemical's National 78-1898, etc.). Examples of the alginic acid-based semi-synthetic polymer include sodium alginate (such as Keltone manufactured by Kelco) and propylene glycol alginate.
Other classifications of natural or semi-synthetic polymers include cationized guar gum (such as Hi-care 1000 from Alcolac) and sodium hyaluronate (such as Hyalure from Lifecare Biomedial).
Any of these water-absorbing polymers may be a commercially available product, for example, a product provided by a manufacturer described in parentheses in addition to the name of each compound.
植物多糖類系の天然高分子としては、アラビアガム、κ－カラギーナン、ι－カラギーナン、λ－カラギーナン、グアガム（Squalon製Supercolなど）、ローカストビーンガム、ペクチン、トラガント、トウモロコシデンプン（National Starch ＆ Chemical Co.製Purity-21など）、リン酸化デンプン（National Starch ＆ Chemical Co.製National 78-1898など）などがあげられる。微生物多糖類系の天然高分子としては、キサンタンガム（Kelco製Keltrol Tなど）、デキストリン（National Starch ＆ Chemical Co.製Nadex360など）などがあげられる。動物系の天然高分子としては、ゼラチン（Croda製Crodyne B419など）、カゼイン、コンドロイチン硫酸ナトリウム（Croda製Cromoist CSなど）などがあげられる。
セルロース系の半合成高分子としては、エチルセルロース（I.C.I.製Cellofas WLDなど）、カルボキシメチルセルロース(ダイセル製CMCなど)、ヒドロキシエチルセルロース(ダイセル製HECなど)、ヒドロキシプロピルセルロース（Aqualon製Klucelなど）、メチルセルロース（Henkel製Viscontranなど）、ニトロセルロース（Hercules製Isopropyl Wetなど）、カチオン化セルロース（Croda製Crodacel QMなど）などがあげられる。デンプン系の半合成高分子としては、リン酸化デンプン（National Starch ＆ Chemical製National 78-1898など）などがあげられる。アルギン酸系の半合成高分子としては、アルギン酸ナトリウム（Kelco製Keltoneなど）、アルギン酸プロピレングリコールなどがあげられる。
天然高分子または半合成高分子のその他の分類として、カチオン化グアガム（Alcolac製Hi-care1000など）、ヒアルロン酸ナトリウム（Lifecare Biomedial製Hyalureなど）があげられる。
これらの吸水性ポリマーはいずれも、市販品を使用することができ、例えば、それぞれの化合物名に添えて（ ）内に記載されるメーカーより提供される商品を使用することができる。 Of the water-absorbing polymers, natural polymers and semisynthetic polymers will be described in detail.
Plant polysaccharide-based natural polymers include gum arabic, κ-carrageenan, ι-carrageenan, λ-carrageenan, guar gum (Squalon Supercol, etc.), locust bean gum, pectin, tragacanth, corn starch (National Starch & Chemical Co Purity-21, etc.) and phosphorylated starch (National Starch & Chemical Co., National 78-1898, etc.). Examples of microbial polysaccharide-based natural polymers include xanthan gum (such as Keltrol T from Kelco) and dextrin (such as Nadex 360 from National Starch & Chemical Co.). Examples of animal-based natural polymers include gelatin (such as Crodyne B419 from Croda), casein, sodium chondroitin sulfate (such as Cromoist CS from Croda), and the like.
Cellulose semi-synthetic polymers include ethyl cellulose (ICI Cellofas WLD, etc.), carboxymethyl cellulose (Daicel CMC, etc.), hydroxyethyl cellulose (Daicel HEC, etc.), hydroxypropyl cellulose (Aqualon Klucel, etc.), methyl cellulose (Henkel Viscontran, etc.), nitrocellulose (Isopropyl Wet, etc. from Hercules), and cationized cellulose (Crodacel QM, etc. from Croda). Examples of the starch-based semi-synthetic polymer include phosphorylated starch (National Starch &Chemical's National 78-1898, etc.). Examples of the alginic acid-based semi-synthetic polymer include sodium alginate (such as Keltone manufactured by Kelco) and propylene glycol alginate.
Other classifications of natural or semi-synthetic polymers include cationized guar gum (such as Hi-care 1000 from Alcolac) and sodium hyaluronate (such as Hyalure from Lifecare Biomedial).
Any of these water-absorbing polymers may be a commercially available product, for example, a product provided by a manufacturer described in parentheses in addition to the name of each compound.
吸水性ポリマーのうち、合成高分子について詳しく説明する。
アクリル系の合成高分子としては、ポリアクリル酸、ポリアクリル酸ナトリウム、ポリアクリル酸共重合体、ポリアクリルアミド、ポリアクリルアミド共重合体、ポリジエチルアミノエチル（メタ）アクリレート四級塩またはその共重合体などがあげられる。ビニル系の合成高分子としては、ポリビニルピロリドン、ポリビニルピロリドン共重合体、ポリビニルアルコールなどがあげられる。その他の合成高分子としては、ポリエチレングリコール、ポリプロピレングリコール、ポリイソプロピルアクリルアミド、ポリメチルビニルエーテル、ポリエチレンイミン、ポリアリルアミン、ポリビニルアミン、ナフィオン、ポリスチレンスルホン酸またはその共重合体、ナフタレンスルホン酸縮合物塩、ポリビニルスルホン酸またはその共重合体、ポリアクリル酸またはその共重合体、アクリル酸またはその共重合体等、マレイン酸共重合体、マレイン酸モノエステル共重合体、アクリロイルメチルプロパンスルホン酸またはその共重合体、など）、ポリジメチルジアリルアンモニウムクロライドまたはその共重合体、ポリアミジンまたはその共重合体、ポリイミダゾリン、ジシアンシアミド系縮合物、エピクロルヒドリン・ジメチルアミン縮合物、ポリアクリルアミドのホフマン分解物、水溶性ポリエステルなどがあげられる。
合成高分子としては、市販品を使用してもよく、例えば、水溶性ポリエステル（互応化学(株)製プラスコートＺ－２２１、Ｚ－４４６、Ｚ－５６１、Ｚ－４５０、Ｚ－５６５、Ｚ－８５０、Ｚ－３３０８、ＲＺ－１０５、ＲＺ－５７０、Ｚ－７３０、ＲＺ－１４２：いずれも商品名）などがあげられる。 Of the water-absorbing polymers, the synthetic polymer will be described in detail.
Examples of acrylic synthetic polymers include polyacrylic acid, sodium polyacrylate, polyacrylic acid copolymer, polyacrylamide, polyacrylamide copolymer, polydiethylaminoethyl (meth) acrylate quaternary salt or copolymer thereof, etc. Can be given. Examples of the vinyl-based synthetic polymer include polyvinyl pyrrolidone, a polyvinyl pyrrolidone copolymer, and polyvinyl alcohol. Other synthetic polymers include polyethylene glycol, polypropylene glycol, polyisopropylacrylamide, polymethyl vinyl ether, polyethylene imine, polyallylamine, polyvinyl amine, nafion, polystyrene sulfonic acid or copolymers thereof, naphthalene sulfonic acid condensate salt, polyvinyl Sulfonic acid or copolymer thereof, polyacrylic acid or copolymer thereof, acrylic acid or copolymer thereof, maleic acid copolymer, maleic acid monoester copolymer, acryloylmethylpropane sulfonic acid or copolymer thereof , Etc.), polydimethyldiallylammonium chloride or its copolymer, polyamidine or its copolymer, polyimidazoline, dicyanciamide condensate, epichlorohydrin-dimethyla Down condensates, Hofmann degradation product of polyacrylamide, such as water-soluble polyester are exemplified.
As the synthetic polymer, commercially available products may be used. For example, water-soluble polyesters (Plus Coat Z-221, Z-446, Z-561, Z-450, Z-565, Z, manufactured by Kyoyo Chemical Co., Ltd.) -850, Z-3308, RZ-105, RZ-570, Z-730, RZ-142: all are trade names).
アクリル系の合成高分子としては、ポリアクリル酸、ポリアクリル酸ナトリウム、ポリアクリル酸共重合体、ポリアクリルアミド、ポリアクリルアミド共重合体、ポリジエチルアミノエチル（メタ）アクリレート四級塩またはその共重合体などがあげられる。ビニル系の合成高分子としては、ポリビニルピロリドン、ポリビニルピロリドン共重合体、ポリビニルアルコールなどがあげられる。その他の合成高分子としては、ポリエチレングリコール、ポリプロピレングリコール、ポリイソプロピルアクリルアミド、ポリメチルビニルエーテル、ポリエチレンイミン、ポリアリルアミン、ポリビニルアミン、ナフィオン、ポリスチレンスルホン酸またはその共重合体、ナフタレンスルホン酸縮合物塩、ポリビニルスルホン酸またはその共重合体、ポリアクリル酸またはその共重合体、アクリル酸またはその共重合体等、マレイン酸共重合体、マレイン酸モノエステル共重合体、アクリロイルメチルプロパンスルホン酸またはその共重合体、など）、ポリジメチルジアリルアンモニウムクロライドまたはその共重合体、ポリアミジンまたはその共重合体、ポリイミダゾリン、ジシアンシアミド系縮合物、エピクロルヒドリン・ジメチルアミン縮合物、ポリアクリルアミドのホフマン分解物、水溶性ポリエステルなどがあげられる。
合成高分子としては、市販品を使用してもよく、例えば、水溶性ポリエステル（互応化学(株)製プラスコートＺ－２２１、Ｚ－４４６、Ｚ－５６１、Ｚ－４５０、Ｚ－５６５、Ｚ－８５０、Ｚ－３３０８、ＲＺ－１０５、ＲＺ－５７０、Ｚ－７３０、ＲＺ－１４２：いずれも商品名）などがあげられる。 Of the water-absorbing polymers, the synthetic polymer will be described in detail.
Examples of acrylic synthetic polymers include polyacrylic acid, sodium polyacrylate, polyacrylic acid copolymer, polyacrylamide, polyacrylamide copolymer, polydiethylaminoethyl (meth) acrylate quaternary salt or copolymer thereof, etc. Can be given. Examples of the vinyl-based synthetic polymer include polyvinyl pyrrolidone, a polyvinyl pyrrolidone copolymer, and polyvinyl alcohol. Other synthetic polymers include polyethylene glycol, polypropylene glycol, polyisopropylacrylamide, polymethyl vinyl ether, polyethylene imine, polyallylamine, polyvinyl amine, nafion, polystyrene sulfonic acid or copolymers thereof, naphthalene sulfonic acid condensate salt, polyvinyl Sulfonic acid or copolymer thereof, polyacrylic acid or copolymer thereof, acrylic acid or copolymer thereof, maleic acid copolymer, maleic acid monoester copolymer, acryloylmethylpropane sulfonic acid or copolymer thereof , Etc.), polydimethyldiallylammonium chloride or its copolymer, polyamidine or its copolymer, polyimidazoline, dicyanciamide condensate, epichlorohydrin-dimethyla Down condensates, Hofmann degradation product of polyacrylamide, such as water-soluble polyester are exemplified.
As the synthetic polymer, commercially available products may be used. For example, water-soluble polyesters (Plus Coat Z-221, Z-446, Z-561, Z-450, Z-565, Z, manufactured by Kyoyo Chemical Co., Ltd.) -850, Z-3308, RZ-105, RZ-570, Z-730, RZ-142: all are trade names).
硫化水素分離材に含まれる吸水性ポリマーとしては、ポリアクリル酸、ポリビニルアルコール、ビニルアルコール－ポリアクリル酸共重合体のケン化物が好ましく、ポリビニルアルコール、ビニルアルコール－ポリアクリル酸共重合体のケン化物がより好ましい。
The water-absorbing polymer contained in the hydrogen sulfide separator is preferably a saponified product of polyacrylic acid, polyvinyl alcohol, vinyl alcohol-polyacrylic acid copolymer, and a saponified product of polyvinyl alcohol, vinyl alcohol-polyacrylic acid copolymer. Is more preferable.
本発明の硫化水素分離材に含まれる吸水性ポリマーの含有量は、本発明の硫化水素分離材に含まれる吸水性ポリマーおよびアミン系キャリアの種類にもよるが、吸水性ポリマーおよびアミン系キャリアの合計含有量に対して、５質量％～９９質量％であることが好ましく、７．５質量％～９０質量％であることがより好ましく、１０質量％～８５質量％であることがさらに好ましい。また、本発明の硫化水素分離材に含まれる吸水性ポリマーは１種単独で用いてもよいし、２種以上を併用してもよい。
The content of the water-absorbing polymer contained in the hydrogen sulfide separating material of the present invention depends on the type of the water-absorbing polymer and amine-based carrier contained in the hydrogen sulfide separating material of the present invention. The content is preferably 5% by mass to 99% by mass, more preferably 7.5% by mass to 90% by mass, and still more preferably 10% by mass to 85% by mass with respect to the total content. Moreover, the water absorbing polymer contained in the hydrogen sulfide separating material of the present invention may be used alone or in combination of two or more.
ここで言う吸水性ポリマーの含有量とは、絶乾状態のポリマーの含有量を表す。ここで言う絶乾状態のポリマーとは、吸水性ポリマーを、水の沸点以上の温度に保持し、質量減少がほとんどなくなり質量の経時変化がほぼ一定値に収束したポリマーをいう。
The content of the water-absorbing polymer referred to here represents the content of the absolutely dry polymer. The completely dry polymer as used herein refers to a polymer in which the water-absorbing polymer is maintained at a temperature equal to or higher than the boiling point of water, and the mass change is almost eliminated and the change with time of the mass converges to a substantially constant value.
＜アミン系キャリア＞
キャリアとは、硫化水素と可逆的に反応する物質であり、本発明の硫化水素分離材に含まれるアミン系キャリアとは、硫化水素と可逆的に反応するアミン化合物である。硫化水素と、アミン系キャリアとの可逆的な反応としては、例えば、下記反応式（２）で表される反応および下記式（３）で表される反応からなる群より選ばれる１種以上の反応があげられる。 <Amine carrier>
The carrier is a substance that reacts reversibly with hydrogen sulfide, and the amine carrier contained in the hydrogen sulfide separation material of the present invention is an amine compound that reacts reversibly with hydrogen sulfide. Examples of the reversible reaction between hydrogen sulfide and an amine carrier include, for example, one or more selected from the group consisting of a reaction represented by the following reaction formula (2) and a reaction represented by the following formula (3): Reaction.
キャリアとは、硫化水素と可逆的に反応する物質であり、本発明の硫化水素分離材に含まれるアミン系キャリアとは、硫化水素と可逆的に反応するアミン化合物である。硫化水素と、アミン系キャリアとの可逆的な反応としては、例えば、下記反応式（２）で表される反応および下記式（３）で表される反応からなる群より選ばれる１種以上の反応があげられる。 <Amine carrier>
The carrier is a substance that reacts reversibly with hydrogen sulfide, and the amine carrier contained in the hydrogen sulfide separation material of the present invention is an amine compound that reacts reversibly with hydrogen sulfide. Examples of the reversible reaction between hydrogen sulfide and an amine carrier include, for example, one or more selected from the group consisting of a reaction represented by the following reaction formula (2) and a reaction represented by the following formula (3): Reaction.
アミン化合物は、キャリア数あたりの硫化水素吸収量が多いため、硫化水素分離キャリアとして優れていると考えられる。また、酸素混在環境下では、硫化水素からチオ硫酸イオン、硫酸イオン、亜硫酸イオンなどの硫黄酸化物イオンが生成し、キャリアと不可逆反応を起こすことによって、硫化水素と可逆的に反応するキャリア数が低下する恐れがあるが、アミン化合物をキャリアとして用いた場合、酸素混在環境下においても、硫化水素から生成する硫黄酸化物イオン量は少ない。
An amine compound is considered to be excellent as a hydrogen sulfide separation carrier because it absorbs a large amount of hydrogen sulfide per carrier. In an oxygen-mixed environment, sulfur oxide ions such as thiosulfate ions, sulfate ions, and sulfite ions are generated from hydrogen sulfide, causing an irreversible reaction with the carriers, thereby reducing the number of carriers that react reversibly with hydrogen sulfide. Although there is a risk of a decrease, when an amine compound is used as a carrier, the amount of sulfur oxide ions generated from hydrogen sulfide is small even in an oxygen-mixed environment.
アミン系キャリアとしては、例えば、グリシン、アラニン、セリン、プロリン、タウリン、ジアミノプロピオン酸、２－アミノプロピオン酸、２－アミノイソ酪酸、３,４－ジヒドロキシフェニルアラニンなどのアミノ酸類；アミノ酸類の酸基をアルカリ金属の化合物などを用いてケン化したアミノ酸ケン化物；ピリジン、ヒスタミン、ヒスチジン、ピペラジン、イミダゾール、トリアジン、キサントシン、２メチルピペラジン、ｃｉｓ－２,６－ジメチルピペラジン、アセトアルデヒドアンモニアトリマーなどのヘテロ環式アミン化合物（ヘテロ化合物類ともいう。）；モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ジイソプロパノールアミン、メチルジエタノールアミン、ジグリコールアミン、β，β－ヒドロキシアミノエチルエーテル、３－アミノ－１－プロパノール、Ｎ－（３－ヒドロキシプロピル）エチレンジアミン、ジプロパノールアミン、トリイソプロパノールアミン、２－ヒドロキシエチルトリメチルアンモニウムヒドロキシドなどのアルカノールアミン類；クリプタンド〔２．１〕、クリプタンド〔２．２〕などの環状ポリエーテルアミン類；クリプタンド〔２．２．１〕、クリプタンド〔２．２．２〕などの双環式ポリエーテルアミン類；ポルフィリン、フタロシアニン、エチレンジアミン四酢酸などがあげられる。
Examples of the amine carrier include amino acids such as glycine, alanine, serine, proline, taurine, diaminopropionic acid, 2-aminopropionic acid, 2-aminoisobutyric acid, and 3,4-dihydroxyphenylalanine; Saponified amino acids saponified using an alkali metal compound, etc .; heterocyclic compounds such as pyridine, histamine, histidine, piperazine, imidazole, triazine, xanthosine, 2-methylpiperazine, cis-2,6-dimethylpiperazine, acetaldehyde ammonia trimer Amine compounds (also called hetero compounds); monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine, methyldiethanolamine, diglycolamine, β, β-hydroxy Alkanolamines such as minoethyl ether, 3-amino-1-propanol, N- (3-hydroxypropyl) ethylenediamine, dipropanolamine, triisopropanolamine, 2-hydroxyethyltrimethylammonium hydroxide; cryptand [2.1] Cyclic polyetheramines such as cryptand [2.2]; bicyclic polyetheramines such as cryptand [2.2.1] and cryptand [2.2.2]; porphyrin, phthalocyanine, ethylenediaminetetraacetic acid, etc. Can be given.
好ましいアミン系キャリアとしては、グリシン、ヒスチジン、２－アミノイソ酪酸などの酸基を有するアミノ酸類；ヒスタミン、ヒスチジン、ピペラジン、キサントシンなどのヘテロ環式アミン化合物；モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ジイソプロパノールアミン、メチルジエタノールアミン、ジグリコールアミン、β，β－ヒドロキシアミノエチルエーテルなどのアルカノールアミン類があげられ、より好ましいアミン系キャリアとしては、ヘテロ環式アミン化合物があげられ、さらに好ましいアミン系キャリアとしては、ピペラジンがあげられる。
Preferred amine carriers include amino acids having acid groups such as glycine, histidine and 2-aminoisobutyric acid; heterocyclic amine compounds such as histamine, histidine, piperazine and xanthosine; monoethanolamine, diethanolamine, triethanolamine, diethanolamine Alkanolamines such as isopropanolamine, methyldiethanolamine, diglycolamine, β, β-hydroxyaminoethyl ether and the like, and more preferable amine carriers include heterocyclic amine compounds, and more preferable amine carriers. Is piperazine.
アミン系キャリアとしては、沸点が５０℃以上であるアミン系キャリアが好ましく、沸点が８０℃以上であるアミン系キャリアがより好ましい。このような沸点を有するアミン系キャリアであると、硫化水素分離材を使用して硫化水素分離膜を製造するとき、アミン系キャリアが揮発しにくくなる。
As the amine carrier, an amine carrier having a boiling point of 50 ° C. or higher is preferable, and an amine carrier having a boiling point of 80 ° C. or higher is more preferable. When the amine carrier has such a boiling point, when the hydrogen sulfide separation membrane is produced using the hydrogen sulfide separator, the amine carrier is less likely to volatilize.
本発明の硫化水素分離材に含まれるアミン系キャリアの含有量は、吸水性ポリマーおよびアミン系キャリアの種類にもよるが、吸水性ポリマーの含有量に対して、１５質量％～７５０質量％の範囲である。アミン系キャリアの含有量が吸水性ポリマーの含有量に対して、１５質量％以上であると硫化水素透過性（パーミアンス）の点で好ましく、７５０質量％以下であると、膜の取り扱い性の点で好ましい。また、本発明の硫化水素分離材に含まれるアミン系キャリアは１種単独で用いてもよいし、２種以上を併用してもよい。
The content of the amine carrier contained in the hydrogen sulfide separation material of the present invention depends on the type of the water absorbent polymer and the amine carrier, but is 15% by mass to 750% by mass with respect to the content of the water absorbent polymer. It is a range. From the viewpoint of hydrogen sulfide permeability (permeance), the content of the amine carrier is preferably 15% by mass or more with respect to the content of the water-absorbing polymer, and when the content is 750% by mass or less, the film is easy to handle. Is preferable. Moreover, the amine carrier contained in the hydrogen sulfide separator of the present invention may be used alone or in combination of two or more.
本発明の硫化水素分離材にはアミン系キャリアが含まれるが、アミン系キャリア以外のキャリアが更に含まれていてもよい。アミン系キャリア以外のキャリアとしては、公知のキャリアが挙げられるが、アルカリ金属化合物は、キャリア数あたりの硫化水素吸収数が少ないため、硫化水素分離キャリアとして優れていないと考えられる。また、酸素混在環境下では、硫化水素からチオ硫酸イオン、硫酸イオン、亜硫酸イオンなどの硫黄酸化物イオンが生成し、アルカリ金属化合物と不可逆反応を起こすことによって、硫化水素と可逆的に反応するアルカリ金属化合物のキャリア数が低下する恐れがある。そのため、本発明の硫化水素分離材は、アミン系キャリア以外のキャリアとして、アルカリ金属化合物を含まないことが好ましい。なお、アルカリ金属化合物を構成するアルカリ金属は、吸水性ポリマーに含まれるアルカリ金属とは異なるものである。
The hydrogen sulfide separating material of the present invention contains an amine carrier, but may further contain a carrier other than the amine carrier. Examples of carriers other than amine carriers include known carriers, but alkali metal compounds are considered not to be excellent as hydrogen sulfide separation carriers because the number of absorbed hydrogen sulfides per carrier number is small. In an oxygen-mixed environment, sulfur oxide ions such as thiosulfate ions, sulfate ions, and sulfite ions are generated from hydrogen sulfide, causing an irreversible reaction with the alkali metal compound, thereby causing an alkali that reacts reversibly with hydrogen sulfide. There is a possibility that the number of carriers of the metal compound may decrease. Therefore, it is preferable that the hydrogen sulfide separating material of the present invention does not contain an alkali metal compound as a carrier other than the amine carrier. Note that the alkali metal constituting the alkali metal compound is different from the alkali metal contained in the water-absorbing polymer.
＜硫化水素分離材およびその製造方法＞
本発明の硫化水素分離材は、例えば、下記工程Ａを含む製造方法により得られる。
Ａ：アミン系キャリアと、吸水性ポリマーと、溶媒とを混合する工程 <Hydrogen sulfide separator and method for producing the same>
The hydrogen sulfide separation material of the present invention can be obtained, for example, by a production method including the following step A.
A: A step of mixing an amine carrier, a water-absorbing polymer, and a solvent.
本発明の硫化水素分離材は、例えば、下記工程Ａを含む製造方法により得られる。
Ａ：アミン系キャリアと、吸水性ポリマーと、溶媒とを混合する工程 <Hydrogen sulfide separator and method for producing the same>
The hydrogen sulfide separation material of the present invention can be obtained, for example, by a production method including the following step A.
A: A step of mixing an amine carrier, a water-absorbing polymer, and a solvent.
溶媒としては、水や有機溶媒を用いることが可能であり、特に水を用いることが好ましい。溶媒の使用量は、得られる硫化水素分離材が後述する工程Ｂに供する際に均一溶液として存在し得る量であることが好ましい。工程Ａにおける混合順序は特に限定されず、混合温度は５℃～９０℃の範囲が好ましい。得られた硫化水素分離剤は、工程Ａの後に乾燥させてもよい。
As the solvent, water or an organic solvent can be used, and water is particularly preferable. The amount of the solvent used is preferably an amount that can be present as a homogeneous solution when the obtained hydrogen sulfide separator is subjected to Step B described later. The order of mixing in step A is not particularly limited, and the mixing temperature is preferably in the range of 5 ° C to 90 ° C. The obtained hydrogen sulfide separating agent may be dried after step A.
＜硫化水素分離膜およびその製造方法＞
本発明の硫化水素分離膜は、本発明の硫化水素分離材と、多孔膜とを有する。本発明の硫化水素分離膜は、通常、本発明の硫化水素分離材が多孔膜に担持されている。 <Hydrogen sulfide separation membrane and manufacturing method thereof>
The hydrogen sulfide separation membrane of the present invention has the hydrogen sulfide separation material of the present invention and a porous membrane. In the hydrogen sulfide separation membrane of the present invention, the hydrogen sulfide separation material of the present invention is usually carried on a porous membrane.
本発明の硫化水素分離膜は、本発明の硫化水素分離材と、多孔膜とを有する。本発明の硫化水素分離膜は、通常、本発明の硫化水素分離材が多孔膜に担持されている。 <Hydrogen sulfide separation membrane and manufacturing method thereof>
The hydrogen sulfide separation membrane of the present invention has the hydrogen sulfide separation material of the present invention and a porous membrane. In the hydrogen sulfide separation membrane of the present invention, the hydrogen sulfide separation material of the present invention is usually carried on a porous membrane.
多孔膜としては、フッ素樹脂製の多孔膜、ポリオレフィン製の多孔膜、ポリアミド系樹脂製の多孔膜、ポリスルホン系樹脂製の多孔膜、セラミックス製の多孔膜、金属製の多孔膜等があげられ、フッ素樹脂製の多孔膜が好ましい。フッ素樹脂製の多孔膜のなかでも、四フッ化エチレン共重合体（ＰＴＦＥ）多孔膜がより好ましい。
Examples of the porous film include a fluororesin porous film, a polyolefin porous film, a polyamide resin porous film, a polysulfone resin porous film, a ceramic porous film, a metal porous film, and the like. A porous film made of a fluororesin is preferred. Among the fluororesin porous membranes, a tetrafluoroethylene copolymer (PTFE) porous membrane is more preferable.
多孔膜は、１００℃以上の耐熱性、機械的強度、および、本発明の硫化水素分離材との密着性を有することが好ましい。また、空隙率が５０％以上であり、細孔径が０．０１μｍ以上１０μｍ以下の範囲である多孔膜が好ましく、空隙率が５５％以上であり、細孔径が０．１μｍ以上１μｍ以下の範囲である多孔膜がより好ましい。
The porous membrane preferably has heat resistance of 100 ° C. or higher, mechanical strength, and adhesion with the hydrogen sulfide separation material of the present invention. Further, a porous membrane having a porosity of 50% or more and a pore diameter in the range of 0.01 μm to 10 μm is preferable, and a porosity is 55% or more in a range of the pore diameter of 0.1 μm to 1 μm. Some porous membranes are more preferred.
多孔膜としては、親水性の多孔膜、疎水性の多孔膜のうちいずれも用いることができる。また、親水性の多孔膜と疎水性の多孔膜との積層体を用いることもできる。
As the porous membrane, either a hydrophilic porous membrane or a hydrophobic porous membrane can be used. A laminate of a hydrophilic porous membrane and a hydrophobic porous membrane can also be used.
本発明の硫化水素分離膜は、例えば、下記工程ＡおよびＢを含む製造方法により得られる。
Ａ：アミン系キャリアと、吸水性ポリマーと、溶媒とを混合して硫化水素分離材を得る工程
Ｂ：硫化水素分離材を多孔膜に塗布する工程 The hydrogen sulfide separation membrane of the present invention is obtained, for example, by a production method including the following steps A and B.
A: Step of obtaining a hydrogen sulfide separator by mixing an amine carrier, a water-absorbing polymer, and a solvent B: Step of applying a hydrogen sulfide separator to a porous membrane
Ａ：アミン系キャリアと、吸水性ポリマーと、溶媒とを混合して硫化水素分離材を得る工程
Ｂ：硫化水素分離材を多孔膜に塗布する工程 The hydrogen sulfide separation membrane of the present invention is obtained, for example, by a production method including the following steps A and B.
A: Step of obtaining a hydrogen sulfide separator by mixing an amine carrier, a water-absorbing polymer, and a solvent B: Step of applying a hydrogen sulfide separator to a porous membrane
工程Ａは、上述したとおりである。工程Ｂにおける塗布は、多孔膜の少なくとも一方の面に、本発明の硫化水素分離材を含む層（すなわち、アミン系キャリアと、吸水性ポリマーとを含む層）を形成するように行うことが好ましい。
Process A is as described above. The coating in the step B is preferably performed so as to form a layer containing the hydrogen sulfide separation material of the present invention (that is, a layer containing an amine carrier and a water-absorbing polymer) on at least one surface of the porous membrane. .
工程Ｂにおける塗布を容易にするために、工程Ａにおいて、溶媒として、水を混合することが好ましい。即ち、工程Ｂに供給される硫化水素分離材は、溶媒として、水を含むことが好ましく、水溶液であることがより好ましい。
In order to facilitate application in step B, it is preferable to mix water as a solvent in step A. That is, the hydrogen sulfide separating material supplied to Step B preferably contains water as a solvent, and more preferably an aqueous solution.
工程Ｂにおける塗布は、コーター（ドクターブレードともいう）による塗布、刷け塗りによる塗布等の工業的に通常行われる方法により行うことができる。硫化水素分離材層（硫化水素分離材を含む層）の厚さは、アミン系キャリアと吸水性ポリマーとの量および量比を調節することによって制御することができる。硫化水素分離材層の厚さは２５μｍ以上２００μｍ以下の範囲であると、硫化水素分離膜の硫化水素透過性能と、硫化水素分離膜の機械耐久性とのバランスが優れるため、好ましい。ここでいう硫化水素分離材層の厚さとは、後述する工程Ｄにおいて硫化水素分離膜に熱処理を施した後、作成された硫化水素分離膜を室温まで冷まし、測定した該硫化水素分離膜の厚さと、前述の工程Ｂで多孔膜に硫化水素分離材を塗布する前に測定した該多孔膜の厚さとの差を表す。
Application in the step B can be performed by an industrially usual method such as application by a coater (also referred to as a doctor blade) or application by brush coating. The thickness of the hydrogen sulfide separating material layer (the layer containing the hydrogen sulfide separating material) can be controlled by adjusting the amount and amount ratio of the amine carrier and the water-absorbing polymer. The thickness of the hydrogen sulfide separation material layer is preferably in the range of 25 μm or more and 200 μm or less because the hydrogen sulfide permeation performance of the hydrogen sulfide separation membrane and the mechanical durability of the hydrogen sulfide separation membrane are excellent. The thickness of the hydrogen sulfide separation material layer here refers to the thickness of the hydrogen sulfide separation membrane measured after the hydrogen sulfide separation membrane was cooled to room temperature after heat treatment was performed on the hydrogen sulfide separation membrane in Step D described later. And the difference between the thickness of the porous membrane measured before applying the hydrogen sulfide separator to the porous membrane in Step B described above.
多孔膜の少なくとも一方の面に、硫化水素分離材層（すなわち、アミン系キャリアと吸水性ポリマーとを含む層）を形成するために、本発明の硫化水素分離膜の製造方法は、さらに工程ＣおよびＤを含むことが好ましい。
Ｃ：塗布後の硫化水素分離材を乾燥させて硫化水素分離材層を形成する工程
Ｄ：硫化水素分離材層を熱処理する工程 In order to form a hydrogen sulfide separation material layer (that is, a layer containing an amine carrier and a water-absorbing polymer) on at least one surface of the porous membrane, the method for producing a hydrogen sulfide separation membrane of the present invention further includes a step C. And D are preferred.
C: Step of drying the hydrogen sulfide separator after coating to form a hydrogen sulfide separator layer D: Step of heat treating the hydrogen sulfide separator layer
Ｃ：塗布後の硫化水素分離材を乾燥させて硫化水素分離材層を形成する工程
Ｄ：硫化水素分離材層を熱処理する工程 In order to form a hydrogen sulfide separation material layer (that is, a layer containing an amine carrier and a water-absorbing polymer) on at least one surface of the porous membrane, the method for producing a hydrogen sulfide separation membrane of the present invention further includes a step C. And D are preferred.
C: Step of drying the hydrogen sulfide separator after coating to form a hydrogen sulfide separator layer D: Step of heat treating the hydrogen sulfide separator layer
工程Ｃにおける乾燥とは、塗布後の硫化水素分離材に含まれる溶媒を除去することを表す。ここで言う乾燥は、例えば、常温常圧下での自然乾燥手段、恒温槽やホットプレート等の加熱手段または減圧装置等の減圧手段により、或いは、これらの手段の組み合わせにより、該硫化水素分離材層から溶媒を蒸発させることにより行われる。加熱手段や減圧手段の条件は、多孔膜の透気度を低下させない範囲で適宜選択でき、例えば恒温槽やホットプレートを用いる場合、それらの温度設定を多孔膜の融点以下の範囲にすることが好ましい。また、減圧手段では、適当な減圧装置の中に、塗布物を封入した後、該減圧装置の内部圧力を１Ｐａ～１．０×１０５Ｐａ程度にすればよい。
Drying in the process C represents removing the solvent contained in the hydrogen sulfide separator after coating. The drying referred to here is, for example, a natural drying means under normal temperature and normal pressure, a heating means such as a thermostatic bath or a hot plate, a decompression means such as a decompression device, or a combination of these means, or the hydrogen sulfide separator layer. By evaporating the solvent. The conditions of the heating means and the decompression means can be appropriately selected within a range that does not lower the air permeability of the porous membrane. For example, when using a thermostatic bath or a hot plate, the temperature setting may be set to a range below the melting point of the porous membrane. preferable. Further, in the decompression means, after the coated material is sealed in a suitable decompression device, the internal pressure of the decompression device may be set to about 1 Pa to 1.0 × 10 5 Pa.
加熱手段における温度が、後述する工程Ｄの熱処理温度の範囲である場合には、工程Ｃと工程Ｄとを連続して行うことができる。例えば、工程Ｃで塗布後の硫化水素分離材を乾燥させ、そのままの条件で引き続き工程Ｄの熱処理を行うことができる。
When the temperature in the heating means is within the range of the heat treatment temperature in step D described later, step C and step D can be performed continuously. For example, the hydrogen sulfide separator after application in step C can be dried, and the heat treatment in step D can be continued under the same conditions.
工程Ｄにおける熱処理は、通常、恒温槽やホットプレート等の加熱手段により行われる。熱処理温度は、８０℃～１６０℃の範囲が好ましい。熱処理時間は、熱処理温度にもよるが、１０分間～４時間の範囲が好ましい。
The heat treatment in the process D is usually performed by a heating means such as a thermostatic bath or a hot plate. The heat treatment temperature is preferably in the range of 80 ° C to 160 ° C. The heat treatment time is preferably in the range of 10 minutes to 4 hours, although it depends on the heat treatment temperature.
＜硫化水素分離膜モジュールおよび硫化水素分離装置＞
本発明の硫化水素分離膜は硫化水素分離膜モジュールとすることができる。また、本発明の硫化水素分離装置は、硫化水素分離膜または硫化水素分離膜モジュールを含み、硫化水素を分離させるための手段を有する。 <Hydrogen sulfide separation membrane module and hydrogen sulfide separator>
The hydrogen sulfide separation membrane of the present invention can be a hydrogen sulfide separation membrane module. In addition, the hydrogen sulfide separation device of the present invention includes a hydrogen sulfide separation membrane or a hydrogen sulfide separation membrane module, and has means for separating hydrogen sulfide.
本発明の硫化水素分離膜は硫化水素分離膜モジュールとすることができる。また、本発明の硫化水素分離装置は、硫化水素分離膜または硫化水素分離膜モジュールを含み、硫化水素を分離させるための手段を有する。 <Hydrogen sulfide separation membrane module and hydrogen sulfide separator>
The hydrogen sulfide separation membrane of the present invention can be a hydrogen sulfide separation membrane module. In addition, the hydrogen sulfide separation device of the present invention includes a hydrogen sulfide separation membrane or a hydrogen sulfide separation membrane module, and has means for separating hydrogen sulfide.
本発明の硫化水素分離膜はモジュール化することでより好適に使用することができる。モジュールの型式の例としては、スパイラル型、中空糸型、プリーツ型、管状型、プレート＆フレーム型などがあげられる。また本発明の硫化水素分離膜は、例えば、特開２００７－２９７６０５号に記載の吸収液等と併用した膜・吸収ハイブリッド法としての気体分離回収装置に使用してもよい。
The hydrogen sulfide separation membrane of the present invention can be used more suitably by modularization. Examples of module types include spiral type, hollow fiber type, pleated type, tubular type, plate & frame type and the like. Further, the hydrogen sulfide separation membrane of the present invention may be used, for example, in a gas separation / recovery device as a membrane / absorption hybrid method used in combination with an absorbing solution described in JP-A-2007-297605.
＜硫化水素を分離する方法＞
本発明の硫化水素分離膜または本発明の硫化水素分離材に、硫化水素を含む混合ガスを接触させることにより、混合ガスから硫化水素を選択的に分離することができる。混合ガスに、その他酸性ガスおよび水が含まれる場合、その他酸性ガスおよび水も、硫化水素とともに選択的に分離される。ここで、その他酸性ガスとしては、例えば、硫化水素、二酸化炭素、硫化カルボニル、一酸化炭素、シアン化水素、二硫化炭素、二酸化硫黄等があげられる。 <Method for separating hydrogen sulfide>
By bringing the mixed gas containing hydrogen sulfide into contact with the hydrogen sulfide separation membrane of the present invention or the hydrogen sulfide separation material of the present invention, hydrogen sulfide can be selectively separated from the mixed gas. When the mixed gas contains other acidic gas and water, the other acidic gas and water are also selectively separated together with hydrogen sulfide. Here, examples of the other acidic gas include hydrogen sulfide, carbon dioxide, carbonyl sulfide, carbon monoxide, hydrogen cyanide, carbon disulfide, and sulfur dioxide.
本発明の硫化水素分離膜または本発明の硫化水素分離材に、硫化水素を含む混合ガスを接触させることにより、混合ガスから硫化水素を選択的に分離することができる。混合ガスに、その他酸性ガスおよび水が含まれる場合、その他酸性ガスおよび水も、硫化水素とともに選択的に分離される。ここで、その他酸性ガスとしては、例えば、硫化水素、二酸化炭素、硫化カルボニル、一酸化炭素、シアン化水素、二硫化炭素、二酸化硫黄等があげられる。 <Method for separating hydrogen sulfide>
By bringing the mixed gas containing hydrogen sulfide into contact with the hydrogen sulfide separation membrane of the present invention or the hydrogen sulfide separation material of the present invention, hydrogen sulfide can be selectively separated from the mixed gas. When the mixed gas contains other acidic gas and water, the other acidic gas and water are also selectively separated together with hydrogen sulfide. Here, examples of the other acidic gas include hydrogen sulfide, carbon dioxide, carbonyl sulfide, carbon monoxide, hydrogen cyanide, carbon disulfide, and sulfur dioxide.
硫化水素を含む混合ガスには、水が含まれることが好ましい。混合ガスの相対湿度は、３０％ＲＨ～１００％ＲＨであることが好ましく、５０％ＲＨ～１００％ＲＨであることがより好ましく、７０％ＲＨ～１００％ＲＨであることが更に好ましい。混合ガスが乾燥状態である場合、本発明の硫化水素分離材または本発明の硫化水素分離膜には、水が含まれていることが好ましい。
The mixed gas containing hydrogen sulfide preferably contains water. The relative humidity of the mixed gas is preferably 30% RH to 100% RH, more preferably 50% RH to 100% RH, and still more preferably 70% RH to 100% RH. When the mixed gas is in a dry state, the hydrogen sulfide separation material of the present invention or the hydrogen sulfide separation membrane of the present invention preferably contains water.
硫化水素を含む混合ガスには、硫化水素が５ｐｐｍ～５０％含まれることが好ましく、５ｐｐｍ～２０％含まれることがより好ましく、５ｐｐｍ～１％含まれることがさらに好ましい。本発明の硫化水素を分離する方法は、硫化水素を低濃度で含む混合ガスからでも、硫化水素を選択的に分離することができる。
The mixed gas containing hydrogen sulfide preferably contains 5 ppm to 50% of hydrogen sulfide, more preferably 5 ppm to 20%, and even more preferably 5 ppm to 1%. The method for separating hydrogen sulfide of the present invention can selectively separate hydrogen sulfide even from a mixed gas containing hydrogen sulfide at a low concentration.
本発明の硫化水素分離材または本発明の硫化水素分離膜に、硫化水素を含む混合ガスを接触させることにより、混合ガスから硫化水素を選択的に分離した後、既存の脱硫プロセスや化学吸収法などの酸性ガス分離プロセスと併用して硫化水素をさらに分離および／または除去してもよい。既存の脱硫プロセスや酸性ガス分離プロセスと併用することで、既存プロセスの負荷を減らすことができる。
After the hydrogen sulfide is selectively separated from the mixed gas by bringing the mixed gas containing hydrogen sulfide into contact with the hydrogen sulfide separation material of the present invention or the hydrogen sulfide separation membrane of the present invention, the existing desulfurization process or chemical absorption method is used. The hydrogen sulfide may be further separated and / or removed in combination with an acidic gas separation process such as By using it together with the existing desulfurization process and acid gas separation process, the load on the existing process can be reduced.
本発明の適用分野は特に制限されないが、例えば、嫌気性処理法で発生したバイオガスからの硫化水素を含む酸性ガスの分離；石油精製；石炭ガス化発電；各種化学プラントにおける乾式脱硫法、湿式脱硫法、生物脱硫法およびアミン吸収法；などの前処理用途や代替用途が想定される。
Although the field of application of the present invention is not particularly limited, for example, separation of acid gas containing hydrogen sulfide from biogas generated by anaerobic treatment method; petroleum refining; coal gasification power generation; dry desulfurization method, wet method in various chemical plants Pretreatment applications such as desulfurization, biodesulfurization, and amine absorption; and alternative applications are envisaged.
有機成分濃度の高い排水に対しては、通常、嫌気性微生物を用いた嫌気性処理法が利用されている。嫌気性微生物を用いた嫌気性処理法により、有機成分は分解され、メタンを主成分としたバイオガスが生成する。バイオガス中のメタンはエネルギー利用が可能であり、ガスエンジンの燃料ガスとしての利用が実用化されている。今後は、バイオガス中のメタンを固体酸化物型燃料電池の燃料ガスとして利用することが期待されている。
An anaerobic treatment method using anaerobic microorganisms is usually used for wastewater with a high concentration of organic components. By an anaerobic treatment method using anaerobic microorganisms, organic components are decomposed and biogas containing methane as a main component is generated. Methane in biogas can be used for energy, and its use as a fuel gas for gas engines has been put to practical use. In the future, it is expected that methane in biogas will be used as fuel gas for solid oxide fuel cells.
嫌気性微生物は、種類によって活性化しやすい温度が異なり、低温菌では４０℃前後に多くのバイオガスを生成し、高温菌では５５℃前後に多くバイオガスを生成する。バイオガスの組成は、排水条件によって異なるが、主成分としてメタンが６５体積％～８５体積％、二酸化炭素が１５体積％～３５体積％、硫化水素が１０００ｐｐｍ～６０００ｐｐｍ（体積百万分率）程度含まれる。
Anaerobic microorganisms have different temperatures that are likely to be activated depending on the type. Thermophilic bacteria produce a lot of biogas around 40 ° C, and thermophilic bacteria produce a lot of biogas around 55 ° C. The composition of biogas varies depending on drainage conditions, but the main components are 65% to 85% by volume of methane, 15% to 35% by volume of carbon dioxide, and 1000ppm to 6000ppm of hydrogen sulfide (parts per million by volume). included.
ガスエンジンや固体酸化物型燃料電池の燃料ガスとしてバイオガスを利用する場合、バイオガス中に含まれる硫化水素を分離・回収する必要がある。硫化水素の分離・回収手法は、処理排水に応じて、生物脱硫法、乾式脱硫法、これらの併用が使い分けられている。生物脱硫法は、ランニングコストは安いが、広大な面積を要することが難点である。乾式脱硫法は、高純度で脱硫することが可能であるが、定期的に脱硫剤の交換費が生じるため維持費が高いことが難点である。このような背景から、硫化水素の安価な分離・回収法が求められており、本発明の硫化水素分離材または硫化水素分離膜を用いた硫化水素の分離方法は有用である。
When using biogas as a fuel gas for gas engines and solid oxide fuel cells, it is necessary to separate and recover hydrogen sulfide contained in the biogas. For the separation and recovery of hydrogen sulfide, the biological desulfurization method, the dry desulfurization method, or a combination of these is properly used depending on the treated wastewater. The biodesulfurization method has a low running cost, but it is difficult to require a large area. In the dry desulfurization method, desulfurization with high purity can be performed. However, since a desulfurization agent replacement cost is periodically generated, a high maintenance cost is difficult. From such a background, an inexpensive method for separating and recovering hydrogen sulfide is required, and the method for separating hydrogen sulfide using the hydrogen sulfide separation material or the hydrogen sulfide separation membrane of the present invention is useful.
本発明の硫化水素分離材または硫化水素分離膜を用いた硫化水素の分離方法により、分離されたメタンガスは、硫化水素を含む酸性ガスを分離する前のバイオガスと比較して二酸化炭素および水分の含有量が小さくなるため、燃料ガスとして利用する際の効率向上が見込まれる。
According to the method for separating hydrogen sulfide using the hydrogen sulfide separator or hydrogen sulfide separation membrane of the present invention, the separated methane gas contains carbon dioxide and moisture as compared with the biogas before separating the acidic gas containing hydrogen sulfide. Since the content is small, an improvement in efficiency when used as fuel gas is expected.
本発明の硫化水素分離材または硫化水素分離膜を用いた硫化水素の分離方法により、バイオガスから分離された硫化水素は、公知の硫化水素の処理方法によって処理することができる。
The hydrogen sulfide separated from the biogas by the hydrogen sulfide separation method using the hydrogen sulfide separation material or the hydrogen sulfide separation membrane of the present invention can be treated by a known hydrogen sulfide treatment method.
本発明の硫化水素分離材または硫化水素分離膜を用いた硫化水素の分離方法により、バイオガスから分離された硫化水素を処理する手法の１つとして、好気性排水処理プロセスを活用する手法があげられる。分離された硫化水素を好気性排水処理槽に注入することで、活性汚泥中の硫黄酸化細菌の働きにより硫化水素は硫酸に変換される。
One of the methods for treating hydrogen sulfide separated from biogas by the hydrogen sulfide separation method using the hydrogen sulfide separation material or hydrogen sulfide separation membrane of the present invention is a method utilizing an aerobic waste water treatment process. It is done. By injecting the separated hydrogen sulfide into the aerobic wastewater treatment tank, the hydrogen sulfide is converted into sulfuric acid by the action of sulfur-oxidizing bacteria in the activated sludge.
本発明の硫化水素分離材または硫化水素分離膜を用いた硫化水素の分離方法は、分離する混合ガスの温度が、比較的低温、具体的には、１０℃～８０℃の範囲、好ましくは２０℃～７０℃の範囲、より好ましくは３５℃～６０℃の範囲でも使用可能なため、エネルギーの観点で工業的にも好ましい。
In the method for separating hydrogen sulfide using the hydrogen sulfide separation material or hydrogen sulfide separation membrane of the present invention, the temperature of the mixed gas to be separated is relatively low, specifically in the range of 10 ° C. to 80 ° C., preferably 20 Since it can be used in the range of from 70 ° C. to 70 ° C., more preferably in the range of from 35 ° C. to 60 ° C., it is industrially preferable from the viewpoint of energy.
以下に、実施例をあげて本発明を説明する。
Hereinafter, the present invention will be described with reference to examples.
＜硫化水素透過係数＞
硫化水素分離膜をセルに挟み、供給側には窒素／硫化水素混合ガス（窒素ガスおよび硫化水素ガスを含む混合ガス）を流し、透過側には窒素ガスを流した。供給側の硫化水素ガス濃度は条件によって所定の濃度に設定した。セルの温度は条件によって所定の温度に設定した。供給・透過側のそれぞれのガスは、条件によって所定の温度に加熱したバブラーを通して加湿した。硫化水素混合ガス、窒素ガスの流量はそれぞれ５０ｃｃ／ｍｉｎに設定した。背圧は供給側、透過側共に０ｋＰａＧとした。硫化水素透過係数［ｍｏｌ／ｍ２／ｓｅｃ／ｋＰａ］は透過側出口ガス中の硫化水素濃度を検知管（ガステック製検知管、硫化水素測定用、使用検知管名４Ｈ、測定範囲１０ｐｐｍ～４０００ｐｐｍ）を用いて測定することにより得た。 <Hydrogen sulfide permeability coefficient>
A hydrogen sulfide separation membrane was sandwiched between the cells, a nitrogen / hydrogen sulfide mixed gas (a mixed gas containing nitrogen gas and hydrogen sulfide gas) was allowed to flow on the supply side, and nitrogen gas was allowed to flow on the permeate side. The hydrogen sulfide gas concentration on the supply side was set to a predetermined concentration depending on conditions. The temperature of the cell was set to a predetermined temperature depending on conditions. Each gas on the supply / permeation side was humidified through a bubbler heated to a predetermined temperature depending on conditions. The flow rates of the hydrogen sulfide mixed gas and nitrogen gas were each set to 50 cc / min. The back pressure was 0 kPaG on both the supply side and the permeation side. Hydrogen sulfide permeation coefficient [mol / m 2 / sec / kPa] indicates the concentration of hydrogen sulfide in the permeate side outlet gas (Gasek detector tube, for hydrogen sulfide measurement, detector tube name 4H, measurement range 10 ppm to 4000 ppm) ) Was used to measure.
硫化水素分離膜をセルに挟み、供給側には窒素／硫化水素混合ガス（窒素ガスおよび硫化水素ガスを含む混合ガス）を流し、透過側には窒素ガスを流した。供給側の硫化水素ガス濃度は条件によって所定の濃度に設定した。セルの温度は条件によって所定の温度に設定した。供給・透過側のそれぞれのガスは、条件によって所定の温度に加熱したバブラーを通して加湿した。硫化水素混合ガス、窒素ガスの流量はそれぞれ５０ｃｃ／ｍｉｎに設定した。背圧は供給側、透過側共に０ｋＰａＧとした。硫化水素透過係数［ｍｏｌ／ｍ２／ｓｅｃ／ｋＰａ］は透過側出口ガス中の硫化水素濃度を検知管（ガステック製検知管、硫化水素測定用、使用検知管名４Ｈ、測定範囲１０ｐｐｍ～４０００ｐｐｍ）を用いて測定することにより得た。 <Hydrogen sulfide permeability coefficient>
A hydrogen sulfide separation membrane was sandwiched between the cells, a nitrogen / hydrogen sulfide mixed gas (a mixed gas containing nitrogen gas and hydrogen sulfide gas) was allowed to flow on the supply side, and nitrogen gas was allowed to flow on the permeate side. The hydrogen sulfide gas concentration on the supply side was set to a predetermined concentration depending on conditions. The temperature of the cell was set to a predetermined temperature depending on conditions. Each gas on the supply / permeation side was humidified through a bubbler heated to a predetermined temperature depending on conditions. The flow rates of the hydrogen sulfide mixed gas and nitrogen gas were each set to 50 cc / min. The back pressure was 0 kPaG on both the supply side and the permeation side. Hydrogen sulfide permeation coefficient [mol / m 2 / sec / kPa] indicates the concentration of hydrogen sulfide in the permeate side outlet gas (Gasek detector tube, for hydrogen sulfide measurement, detector tube name 4H, measurement range 10 ppm to 4000 ppm) ) Was used to measure.
＜窒素透過係数＞
ガス透過測定装置（ＧＴＲテック（株）製、型式：ＧＴＲ－３０ＸＡＦ３ＳＣ）を用いて、等圧法にて窒素透過係数［ｍｏｌ／ｍ２／ｓｅｃ／ｋＰａ］を測定した。硫化水素分離膜を挟むセルの温度は条件によって所定の温度に設定した。供給側には窒素ガスを流し、透過側にはアルゴンガスを流した。供給・透過側のそれぞれのガスは、条件によって所定の温度に加熱したバブラーを通して加湿した。窒素ガス、アルゴンガスの流量はそれぞれ５０ｃｃ／ｍｉｎに設定した。背圧は供給側、透過側共に０ｋＰａＧとした。 <Nitrogen permeability coefficient>
A nitrogen permeation coefficient [mol / m 2 / sec / kPa] was measured by an isobaric method using a gas permeation measuring apparatus (GTR Tech Co., Ltd., model: GTR-30XAF3SC). The temperature of the cell sandwiching the hydrogen sulfide separation membrane was set to a predetermined temperature depending on the conditions. Nitrogen gas was allowed to flow on the supply side, and argon gas was allowed to flow on the permeate side. Each gas on the supply / permeation side was humidified through a bubbler heated to a predetermined temperature depending on conditions. The flow rates of nitrogen gas and argon gas were each set to 50 cc / min. The back pressure was 0 kPaG on both the supply side and the permeation side.
ガス透過測定装置（ＧＴＲテック（株）製、型式：ＧＴＲ－３０ＸＡＦ３ＳＣ）を用いて、等圧法にて窒素透過係数［ｍｏｌ／ｍ２／ｓｅｃ／ｋＰａ］を測定した。硫化水素分離膜を挟むセルの温度は条件によって所定の温度に設定した。供給側には窒素ガスを流し、透過側にはアルゴンガスを流した。供給・透過側のそれぞれのガスは、条件によって所定の温度に加熱したバブラーを通して加湿した。窒素ガス、アルゴンガスの流量はそれぞれ５０ｃｃ／ｍｉｎに設定した。背圧は供給側、透過側共に０ｋＰａＧとした。 <Nitrogen permeability coefficient>
A nitrogen permeation coefficient [mol / m 2 / sec / kPa] was measured by an isobaric method using a gas permeation measuring apparatus (GTR Tech Co., Ltd., model: GTR-30XAF3SC). The temperature of the cell sandwiching the hydrogen sulfide separation membrane was set to a predetermined temperature depending on the conditions. Nitrogen gas was allowed to flow on the supply side, and argon gas was allowed to flow on the permeate side. Each gas on the supply / permeation side was humidified through a bubbler heated to a predetermined temperature depending on conditions. The flow rates of nitrogen gas and argon gas were each set to 50 cc / min. The back pressure was 0 kPaG on both the supply side and the permeation side.
＜選択率＞
該硫化水素透過係数と、該窒素透過係数とを用いて、下記式より選択率を得た。
（選択率［－］）＝（硫化水素透過係数［ｍｏｌ／ｍ２／ｓｅｃ／ｋＰａ］）／（窒素透過係数［ｍｏｌ／ｍ２／ｓｅｃ／ｋＰａ］） <Selectivity>
The selectivity was obtained from the following equation using the hydrogen sulfide permeability coefficient and the nitrogen permeability coefficient.
(Selectivity [−]) = (hydrogen sulfide permeability coefficient [mol / m 2 / sec / kPa]) / (nitrogen permeability coefficient [mol / m 2 / sec / kPa])
該硫化水素透過係数と、該窒素透過係数とを用いて、下記式より選択率を得た。
（選択率［－］）＝（硫化水素透過係数［ｍｏｌ／ｍ２／ｓｅｃ／ｋＰａ］）／（窒素透過係数［ｍｏｌ／ｍ２／ｓｅｃ／ｋＰａ］） <Selectivity>
The selectivity was obtained from the following equation using the hydrogen sulfide permeability coefficient and the nitrogen permeability coefficient.
(Selectivity [−]) = (hydrogen sulfide permeability coefficient [mol / m 2 / sec / kPa]) / (nitrogen permeability coefficient [mol / m 2 / sec / kPa])
＜硫化水素曝露手法＞
φ３２０ｍｍ×３００ｍｍのアクリル水槽に硫化水素ガスを６０ｍｌ／ｍｉｎで７２０秒通気することで作成した３．０体積％硫化水素ガス、９７体積％空気の環境下に各硫化水素キャリア水溶液を２４時間曝露した。 <Hydrogen sulfide exposure method>
Each hydrogen sulfide carrier aqueous solution was exposed for 24 hours in an environment of 3.0% by volume hydrogen sulfide gas and 97% by volume air prepared by aeration of hydrogen sulfide gas at 60 ml / min for 720 seconds in an acrylic water tank of φ320 mm × 300 mm. .
φ３２０ｍｍ×３００ｍｍのアクリル水槽に硫化水素ガスを６０ｍｌ／ｍｉｎで７２０秒通気することで作成した３．０体積％硫化水素ガス、９７体積％空気の環境下に各硫化水素キャリア水溶液を２４時間曝露した。 <Hydrogen sulfide exposure method>
Each hydrogen sulfide carrier aqueous solution was exposed for 24 hours in an environment of 3.0% by volume hydrogen sulfide gas and 97% by volume air prepared by aeration of hydrogen sulfide gas at 60 ml / min for 720 seconds in an acrylic water tank of φ320 mm × 300 mm. .
＜硫化水素吸収量定量＞
溶液中の吸収硫黄成分は系内の硫黄成分を過剰量の過酸化水素を加えることで完全に酸化させ、ＳＯ４ ２－とした後、ＩＣＰ発光分析法（ＩＣＰ－ＡＥＳ）（ＳＩＩ製 ＳＰＳ３０００）を用いて定量した。検量線にはＳＯ４ ２－検量線を用いた。 <Quantitative determination of hydrogen sulfide absorption>
Absorbed sulfur components in the solution are completely oxidized by adding an excessive amount of hydrogen peroxide to make SO 4 2- , then ICP emission analysis (ICP-AES) (SPS3000 manufactured by SII) Was quantified. An SO 4 2- calibration curve was used as the calibration curve.
溶液中の吸収硫黄成分は系内の硫黄成分を過剰量の過酸化水素を加えることで完全に酸化させ、ＳＯ４ ２－とした後、ＩＣＰ発光分析法（ＩＣＰ－ＡＥＳ）（ＳＩＩ製 ＳＰＳ３０００）を用いて定量した。検量線にはＳＯ４ ２－検量線を用いた。 <Quantitative determination of hydrogen sulfide absorption>
Absorbed sulfur components in the solution are completely oxidized by adding an excessive amount of hydrogen peroxide to make SO 4 2- , then ICP emission analysis (ICP-AES) (SPS3000 manufactured by SII) Was quantified. An SO 4 2- calibration curve was used as the calibration curve.
＜生成硫黄酸化物イオン量定量＞
生成硫黄酸化物イオン量はイオンクロマトグラフ（Ｄｉｏｎｅｘ製 ＩＸＳ－２０００）を用いて定量した。カラムは日本ダイオネクス株式会社製ＩｏｎＰａｃＡＳ１７を使用した。溶離液は水酸化カリウム１ｍｍｏｌ／ｌ（０－１．５ｍｉｎ）、１－２０ｍｍｏｌ／ｌ（１．５－５ｍｉｎ）、２０－４０ｍｍｏｌ／ｌ（５－７ｍｉｎ）を用い、流量１．０ｍｌ／ｍｉｎで測定した。検出器はサプレッサー付電気伝導度検出器を用いた。恒温槽温度は３０℃とした。 <Quantitative determination of the amount of generated sulfur oxide ions>
The amount of generated sulfur oxide ions was quantified using an ion chromatograph (IXS-2000 manufactured by Dionex). As the column, IonPacAS17 manufactured by Nippon Dionex Co., Ltd. was used. The eluent used was potassium hydroxide 1 mmol / l (0-1.5 min), 1-20 mmol / l (1.5-5 min), 20-40 mmol / l (5-7 min) at a flow rate of 1.0 ml / min. It was measured. An electric conductivity detector with a suppressor was used as a detector. The thermostat temperature was 30 ° C.
生成硫黄酸化物イオン量はイオンクロマトグラフ（Ｄｉｏｎｅｘ製 ＩＸＳ－２０００）を用いて定量した。カラムは日本ダイオネクス株式会社製ＩｏｎＰａｃＡＳ１７を使用した。溶離液は水酸化カリウム１ｍｍｏｌ／ｌ（０－１．５ｍｉｎ）、１－２０ｍｍｏｌ／ｌ（１．５－５ｍｉｎ）、２０－４０ｍｍｏｌ／ｌ（５－７ｍｉｎ）を用い、流量１．０ｍｌ／ｍｉｎで測定した。検出器はサプレッサー付電気伝導度検出器を用いた。恒温槽温度は３０℃とした。 <Quantitative determination of the amount of generated sulfur oxide ions>
The amount of generated sulfur oxide ions was quantified using an ion chromatograph (IXS-2000 manufactured by Dionex). As the column, IonPacAS17 manufactured by Nippon Dionex Co., Ltd. was used. The eluent used was potassium hydroxide 1 mmol / l (0-1.5 min), 1-20 mmol / l (1.5-5 min), 20-40 mmol / l (5-7 min) at a flow rate of 1.0 ml / min. It was measured. An electric conductivity detector with a suppressor was used as a detector. The thermostat temperature was 30 ° C.
（合成例１）酢酸ビニル－アクリル酸メチル共重合体の合成
撹拌機、温度計、Ｎ２ガス導入管、還流冷却機および滴下ロートを備えた容量２Ｌの反応槽に、水７６８ｇおよび無水硫酸ナトリウム１２ｇを加え、Ｎ２ガスで系内を置換した。その後、そこへ、部分鹸化ポリビニルアルコール（鹸化度８８％）１ｇおよびラウリルパーオキシド１ｇを加え、内温６０℃まで昇温した。その後、そこへ、アクリル酸メチル１０４ｇ（１．２０９ｍｏｌ）および酢酸ビニル１５５ｇ（１．８０２ｍｏｌ）を滴下ロートにより、それぞれ同時に４時間かけて滴下した。滴下中は、撹拌回転数６００ｒｐｍにて内温を６０℃に保持した。滴下終了後、内温６５℃で２時間攪拌し、得られた混合物を遠心分離により脱水することにより、酢酸ビニル－アクリル酸メチル共重合体２８８ｇ（１０．４質量％含水）を得た。 Synthesis Example 1 Synthesis of Vinyl Acetate-Methyl Acrylate Copolymer 768 g of water and anhydrous sodium sulfate were added to a 2 L reaction vessel equipped with a stirrer, thermometer, N 2 gas introduction tube, reflux condenser and dropping funnel. 12 g was added and the system was replaced with N 2 gas. Thereafter, 1 g of partially saponified polyvinyl alcohol (saponification degree 88%) and 1 g of lauryl peroxide were added thereto, and the temperature was raised to an internal temperature of 60 ° C. Thereafter, 104 g (1.209 mol) of methyl acrylate and 155 g (1.802 mol) of vinyl acetate were simultaneously added dropwise thereto over 4 hours. During the dropping, the internal temperature was kept at 60 ° C. at a stirring rotational speed of 600 rpm. After completion of the dropwise addition, the mixture was stirred at an internal temperature of 65 ° C. for 2 hours, and the resulting mixture was dehydrated by centrifugation to obtain 288 g of vinyl acetate-methyl acrylate copolymer (containing 10.4% by mass water).
撹拌機、温度計、Ｎ２ガス導入管、還流冷却機および滴下ロートを備えた容量２Ｌの反応槽に、水７６８ｇおよび無水硫酸ナトリウム１２ｇを加え、Ｎ２ガスで系内を置換した。その後、そこへ、部分鹸化ポリビニルアルコール（鹸化度８８％）１ｇおよびラウリルパーオキシド１ｇを加え、内温６０℃まで昇温した。その後、そこへ、アクリル酸メチル１０４ｇ（１．２０９ｍｏｌ）および酢酸ビニル１５５ｇ（１．８０２ｍｏｌ）を滴下ロートにより、それぞれ同時に４時間かけて滴下した。滴下中は、撹拌回転数６００ｒｐｍにて内温を６０℃に保持した。滴下終了後、内温６５℃で２時間攪拌し、得られた混合物を遠心分離により脱水することにより、酢酸ビニル－アクリル酸メチル共重合体２８８ｇ（１０．４質量％含水）を得た。 Synthesis Example 1 Synthesis of Vinyl Acetate-Methyl Acrylate Copolymer 768 g of water and anhydrous sodium sulfate were added to a 2 L reaction vessel equipped with a stirrer, thermometer, N 2 gas introduction tube, reflux condenser and dropping funnel. 12 g was added and the system was replaced with N 2 gas. Thereafter, 1 g of partially saponified polyvinyl alcohol (saponification degree 88%) and 1 g of lauryl peroxide were added thereto, and the temperature was raised to an internal temperature of 60 ° C. Thereafter, 104 g (1.209 mol) of methyl acrylate and 155 g (1.802 mol) of vinyl acetate were simultaneously added dropwise thereto over 4 hours. During the dropping, the internal temperature was kept at 60 ° C. at a stirring rotational speed of 600 rpm. After completion of the dropwise addition, the mixture was stirred at an internal temperature of 65 ° C. for 2 hours, and the resulting mixture was dehydrated by centrifugation to obtain 288 g of vinyl acetate-methyl acrylate copolymer (containing 10.4% by mass water).
（合成例２）ビニルアルコール－アクリル酸共重合体のセシウムケン化物の合成
撹拌機、温度計、Ｎ２ガス導入管、還流冷却機および滴下ロートを備えた容量２Ｌの反応槽に、メタノール５００ｇ、水４１０ｇ、水酸化セシウム一水和物５５４．２ｇ（３．３ｍｏｌ）および合成例１で得られた酢酸ビニル－アクリル酸メチル共重合体２８８ｇ（１０．４質量％含水）を加え、４００ｒｐｍの撹拌下で、３０℃で３時間鹸化反応を行った。鹸化反応終了後、得られた反応混合物を６００ｇのメタノールで３回洗浄し、濾過した後、７０℃で６時間乾燥させることにより、ビニルアルコール－アクリル酸共重合体のセシウムケン化物３０８ｇを得た。
該ビニルアルコール－アクリル酸共重合体のセシウムケン化物３０８ｇを、ジェットミル（日本ニューマチック工業社製ＬＪ）により粉砕し、微粉末状のビニルアルコール－アクリル酸共重合体のセシウムケン化物２８０ｇを得た。 (Synthesis Example 2) Synthesis of cesium saponification product of vinyl alcohol-acrylic acid copolymer 500 g of methanol and water in a 2 L reaction tank equipped with a stirrer, thermometer, N 2 gas introduction pipe, reflux condenser and dropping funnel 410 g, cesium hydroxide monohydrate 554.2 g (3.3 mol) and 288 g (containing 10.4% by mass water) of the vinyl acetate-methyl acrylate copolymer obtained in Synthesis Example 1 were added, and the mixture was stirred at 400 rpm. The saponification reaction was performed at 30 ° C. for 3 hours. After completion of the saponification reaction, the obtained reaction mixture was washed with 600 g of methanol three times, filtered, and dried at 70 ° C. for 6 hours to obtain 308 g of a cesium saponified product of a vinyl alcohol-acrylic acid copolymer.
308 g of the cesium saponified product of the vinyl alcohol-acrylic acid copolymer was pulverized by a jet mill (LJ manufactured by Nippon Pneumatic Industry Co., Ltd.) to obtain 280 g of a cesium saponified product of a vinyl alcohol-acrylic acid copolymer in a fine powder form.
撹拌機、温度計、Ｎ２ガス導入管、還流冷却機および滴下ロートを備えた容量２Ｌの反応槽に、メタノール５００ｇ、水４１０ｇ、水酸化セシウム一水和物５５４．２ｇ（３．３ｍｏｌ）および合成例１で得られた酢酸ビニル－アクリル酸メチル共重合体２８８ｇ（１０．４質量％含水）を加え、４００ｒｐｍの撹拌下で、３０℃で３時間鹸化反応を行った。鹸化反応終了後、得られた反応混合物を６００ｇのメタノールで３回洗浄し、濾過した後、７０℃で６時間乾燥させることにより、ビニルアルコール－アクリル酸共重合体のセシウムケン化物３０８ｇを得た。
該ビニルアルコール－アクリル酸共重合体のセシウムケン化物３０８ｇを、ジェットミル（日本ニューマチック工業社製ＬＪ）により粉砕し、微粉末状のビニルアルコール－アクリル酸共重合体のセシウムケン化物２８０ｇを得た。 (Synthesis Example 2) Synthesis of cesium saponification product of vinyl alcohol-acrylic acid copolymer 500 g of methanol and water in a 2 L reaction tank equipped with a stirrer, thermometer, N 2 gas introduction pipe, reflux condenser and dropping funnel 410 g, cesium hydroxide monohydrate 554.2 g (3.3 mol) and 288 g (containing 10.4% by mass water) of the vinyl acetate-methyl acrylate copolymer obtained in Synthesis Example 1 were added, and the mixture was stirred at 400 rpm. The saponification reaction was performed at 30 ° C. for 3 hours. After completion of the saponification reaction, the obtained reaction mixture was washed with 600 g of methanol three times, filtered, and dried at 70 ° C. for 6 hours to obtain 308 g of a cesium saponified product of a vinyl alcohol-acrylic acid copolymer.
308 g of the cesium saponified product of the vinyl alcohol-acrylic acid copolymer was pulverized by a jet mill (LJ manufactured by Nippon Pneumatic Industry Co., Ltd.) to obtain 280 g of a cesium saponified product of a vinyl alcohol-acrylic acid copolymer in a fine powder form.
（実施例１）硫化水素分離材の製造
合成例２で得られたビニルアルコール－アクリル酸共重合体のセシウムケン化物（ビニルアルコールに由来する構造単位：アクリル酸のセシウムケン化物に由来する構造単位＝６０ｍｏｌ％：４０ｍｏｌ％）１４．０１ｇに水２５０．０２ｇを加えて室温で攪拌した。その後、そこへ、ピペラジン７．８１ｇおよびイソプロピルアルコール６．４１ｇを加えて室温で一昼夜攪拌して硫化水素分離材を得た。 Example 1 Production of Hydrogen Sulfide Separating Material Cesium Saponified Vinyl Alcohol-Acrylic Acid Copolymer Obtained in Synthesis Example 2 (Structural Unit Derived from Vinyl Alcohol: Structural Unit Derived from Cesium Saponified Acrylic Acid = 60 mol) %: 40 mol%) 25.02 g of water was added to 14.01 g and stirred at room temperature. Thereafter, 7.81 g of piperazine and 6.41 g of isopropyl alcohol were added thereto, and the mixture was stirred overnight at room temperature to obtain a hydrogen sulfide separator.
合成例２で得られたビニルアルコール－アクリル酸共重合体のセシウムケン化物（ビニルアルコールに由来する構造単位：アクリル酸のセシウムケン化物に由来する構造単位＝６０ｍｏｌ％：４０ｍｏｌ％）１４．０１ｇに水２５０．０２ｇを加えて室温で攪拌した。その後、そこへ、ピペラジン７．８１ｇおよびイソプロピルアルコール６．４１ｇを加えて室温で一昼夜攪拌して硫化水素分離材を得た。 Example 1 Production of Hydrogen Sulfide Separating Material Cesium Saponified Vinyl Alcohol-Acrylic Acid Copolymer Obtained in Synthesis Example 2 (Structural Unit Derived from Vinyl Alcohol: Structural Unit Derived from Cesium Saponified Acrylic Acid = 60 mol) %: 40 mol%) 25.02 g of water was added to 14.01 g and stirred at room temperature. Thereafter, 7.81 g of piperazine and 6.41 g of isopropyl alcohol were added thereto, and the mixture was stirred overnight at room temperature to obtain a hydrogen sulfide separator.
（実施例２）硫化水素分離膜の製造
実施例１で得られた硫化水素分離材を、疎水性ＰＴＦＥ多孔膜（住友電工ファインポリマー製、ＨＰ－０１０－５０、膜厚５０μｍ、細孔径０．１μｍ）の面上に、塗布した。次に、硫化水素分離材塗布後の親水性ＰＴＦＥ多孔膜を９０℃で１時間乾燥させ、さらに１２０℃で２時間程度熱架橋させることにより、硫化水素分離膜を得た。乾燥後の硫化水素分離膜の厚みは２６μｍであった。 Example 2 Production of Hydrogen Sulfide Separation Membrane The hydrogen sulfide separation material obtained in Example 1 was prepared from a hydrophobic PTFE porous membrane (manufactured by Sumitomo Electric Fine Polymer, HP-010-50, film thickness 50 μm, pore diameter 0. It was applied on the surface of 1 μm). Next, the hydrophilic PTFE porous membrane after application of the hydrogen sulfide separator was dried at 90 ° C. for 1 hour and further thermally crosslinked at 120 ° C. for about 2 hours to obtain a hydrogen sulfide separation membrane. The thickness of the hydrogen sulfide separation membrane after drying was 26 μm.
実施例１で得られた硫化水素分離材を、疎水性ＰＴＦＥ多孔膜（住友電工ファインポリマー製、ＨＰ－０１０－５０、膜厚５０μｍ、細孔径０．１μｍ）の面上に、塗布した。次に、硫化水素分離材塗布後の親水性ＰＴＦＥ多孔膜を９０℃で１時間乾燥させ、さらに１２０℃で２時間程度熱架橋させることにより、硫化水素分離膜を得た。乾燥後の硫化水素分離膜の厚みは２６μｍであった。 Example 2 Production of Hydrogen Sulfide Separation Membrane The hydrogen sulfide separation material obtained in Example 1 was prepared from a hydrophobic PTFE porous membrane (manufactured by Sumitomo Electric Fine Polymer, HP-010-50, film thickness 50 μm, pore diameter 0. It was applied on the surface of 1 μm). Next, the hydrophilic PTFE porous membrane after application of the hydrogen sulfide separator was dried at 90 ° C. for 1 hour and further thermally crosslinked at 120 ° C. for about 2 hours to obtain a hydrogen sulfide separation membrane. The thickness of the hydrogen sulfide separation membrane after drying was 26 μm.
（実施例３）
実施例２で示した硫化水素分離膜の硫化水素透過係数［ｍｏｌ／ｍ２／ｓｅｃ／ｋＰａ］および選択率［－］を表１に表す。表中のセル温度は、硫化水素分離膜を挟むセルの温度の設定値を示す。相対湿度は、供給側、透過側ガスの相対湿度の設定値を示す。供給側硫化水素濃度は、供給側ガス中の硫化水素の実測濃度を示す。 (Example 3)
The hydrogen sulfide permeability coefficient [mol / m 2 / sec / kPa] and the selectivity [−] of the hydrogen sulfide separation membrane shown in Example 2 are shown in Table 1. The cell temperature in the table indicates a set value of the temperature of the cell sandwiching the hydrogen sulfide separation membrane. The relative humidity indicates a set value of the relative humidity of the supply side and permeation side gas. The supply-side hydrogen sulfide concentration indicates the measured concentration of hydrogen sulfide in the supply-side gas.
実施例２で示した硫化水素分離膜の硫化水素透過係数［ｍｏｌ／ｍ２／ｓｅｃ／ｋＰａ］および選択率［－］を表１に表す。表中のセル温度は、硫化水素分離膜を挟むセルの温度の設定値を示す。相対湿度は、供給側、透過側ガスの相対湿度の設定値を示す。供給側硫化水素濃度は、供給側ガス中の硫化水素の実測濃度を示す。 (Example 3)
The hydrogen sulfide permeability coefficient [mol / m 2 / sec / kPa] and the selectivity [−] of the hydrogen sulfide separation membrane shown in Example 2 are shown in Table 1. The cell temperature in the table indicates a set value of the temperature of the cell sandwiching the hydrogen sulfide separation membrane. The relative humidity indicates a set value of the relative humidity of the supply side and permeation side gas. The supply-side hydrogen sulfide concentration indicates the measured concentration of hydrogen sulfide in the supply-side gas.
（合成例３）ビニルアルコール－アクリル酸共重合体のナトリウムケン化物の合成
上記の合成例２において、水酸化セシウム一水和物に替えて、水酸化ナトリウムを用いる以外は合成例２と同様にして、ビニルアルコール－アクリル酸共重合体のナトリウムケン化物を得た。 (Synthesis Example 3) Synthesis of Sodium Saponification Product of Vinyl Alcohol-Acrylic Acid Copolymer Similar to Synthesis Example 2 except that sodium hydroxide is used in place of cesium hydroxide monohydrate in Synthesis Example 2 above. Thus, a sodium saponified product of vinyl alcohol-acrylic acid copolymer was obtained.
上記の合成例２において、水酸化セシウム一水和物に替えて、水酸化ナトリウムを用いる以外は合成例２と同様にして、ビニルアルコール－アクリル酸共重合体のナトリウムケン化物を得た。 (Synthesis Example 3) Synthesis of Sodium Saponification Product of Vinyl Alcohol-Acrylic Acid Copolymer Similar to Synthesis Example 2 except that sodium hydroxide is used in place of cesium hydroxide monohydrate in Synthesis Example 2 above. Thus, a sodium saponified product of vinyl alcohol-acrylic acid copolymer was obtained.
（実施例４）硫化水素分離材の製造
合成例３で得られたビニルアルコール－アクリル酸共重合体のナトリウムケン化物（ビニルアルコールに由来する構造単位：アクリル酸のナトリウムケン化物に由来する構造単位＝６０ｍｏｌ％：４０ｍｏｌ％）８．３０ｇに水２５０．０２ｇを加えて室温で攪拌した。その後、そこへ、ピペラジン７．８１ｇおよびイソプロピルアルコール６．４１ｇを加えて室温で一昼夜攪拌して硫化水素分離材を得た。 (Example 4) Production of hydrogen sulfide separating material Sodium saponified product of vinyl alcohol-acrylic acid copolymer obtained in Synthesis Example 3 (Structural unit derived from vinyl alcohol: Structural unit derived from sodium saponified product of acrylic acid) = 60 mol%: 40 mol%) 250.02 g of water was added to 8.30 g and stirred at room temperature. Thereafter, 7.81 g of piperazine and 6.41 g of isopropyl alcohol were added thereto, and the mixture was stirred overnight at room temperature to obtain a hydrogen sulfide separator.
合成例３で得られたビニルアルコール－アクリル酸共重合体のナトリウムケン化物（ビニルアルコールに由来する構造単位：アクリル酸のナトリウムケン化物に由来する構造単位＝６０ｍｏｌ％：４０ｍｏｌ％）８．３０ｇに水２５０．０２ｇを加えて室温で攪拌した。その後、そこへ、ピペラジン７．８１ｇおよびイソプロピルアルコール６．４１ｇを加えて室温で一昼夜攪拌して硫化水素分離材を得た。 (Example 4) Production of hydrogen sulfide separating material Sodium saponified product of vinyl alcohol-acrylic acid copolymer obtained in Synthesis Example 3 (Structural unit derived from vinyl alcohol: Structural unit derived from sodium saponified product of acrylic acid) = 60 mol%: 40 mol%) 250.02 g of water was added to 8.30 g and stirred at room temperature. Thereafter, 7.81 g of piperazine and 6.41 g of isopropyl alcohol were added thereto, and the mixture was stirred overnight at room temperature to obtain a hydrogen sulfide separator.
（実施例５）硫化水素分離膜の製造
実施例４で得られた硫化水素分離材を、疎水性ＰＴＦＥ多孔膜（住友電工ファインポリマー製、ＨＰ－０１０－５０、膜厚５０μｍ、細孔径０．１μｍ）の面上に、塗布した。次に、硫化水素分離材塗布後の親水性ＰＴＦＥ多孔膜を９０℃で１時間乾燥させ、さらに１２０℃で２時間程度熱架橋させることにより、硫化水素分離膜を得た。乾燥後の硫化水素分離膜の厚みは２９μｍであった。 Example 5 Production of Hydrogen Sulfide Separation Membrane The hydrogen sulfide separation material obtained in Example 4 was prepared from a hydrophobic PTFE porous membrane (manufactured by Sumitomo Electric Fine Polymer, HP-010-50, film thickness 50 μm, pore diameter 0. It was applied on the surface of 1 μm). Next, the hydrophilic PTFE porous membrane after application of the hydrogen sulfide separator was dried at 90 ° C. for 1 hour and further thermally crosslinked at 120 ° C. for about 2 hours to obtain a hydrogen sulfide separation membrane. The thickness of the hydrogen sulfide separation membrane after drying was 29 μm.
実施例４で得られた硫化水素分離材を、疎水性ＰＴＦＥ多孔膜（住友電工ファインポリマー製、ＨＰ－０１０－５０、膜厚５０μｍ、細孔径０．１μｍ）の面上に、塗布した。次に、硫化水素分離材塗布後の親水性ＰＴＦＥ多孔膜を９０℃で１時間乾燥させ、さらに１２０℃で２時間程度熱架橋させることにより、硫化水素分離膜を得た。乾燥後の硫化水素分離膜の厚みは２９μｍであった。 Example 5 Production of Hydrogen Sulfide Separation Membrane The hydrogen sulfide separation material obtained in Example 4 was prepared from a hydrophobic PTFE porous membrane (manufactured by Sumitomo Electric Fine Polymer, HP-010-50, film thickness 50 μm, pore diameter 0. It was applied on the surface of 1 μm). Next, the hydrophilic PTFE porous membrane after application of the hydrogen sulfide separator was dried at 90 ° C. for 1 hour and further thermally crosslinked at 120 ° C. for about 2 hours to obtain a hydrogen sulfide separation membrane. The thickness of the hydrogen sulfide separation membrane after drying was 29 μm.
（実施例６）
実施例５で示した硫化水素分離膜の硫化水素透過係数［ｍｏｌ／ｍ２／ｓｅｃ／ｋＰａ］および選択率［－］を表２に表す。表中のセル温度は、硫化水素分離膜を挟むセルの温度の設定値を示す。相対湿度は、供給側、透過側ガスの相対湿度の設定値を示す。供給側硫化水素濃度は、供給側ガス中の硫化水素の実測濃度を示す。 (Example 6)
The hydrogen sulfide permeability coefficient [mol / m 2 / sec / kPa] and the selectivity [−] of the hydrogen sulfide separation membrane shown in Example 5 are shown in Table 2. The cell temperature in the table indicates a set value of the temperature of the cell sandwiching the hydrogen sulfide separation membrane. The relative humidity indicates a set value of the relative humidity of the supply side and permeation side gas. The supply-side hydrogen sulfide concentration indicates the measured concentration of hydrogen sulfide in the supply-side gas.
実施例５で示した硫化水素分離膜の硫化水素透過係数［ｍｏｌ／ｍ２／ｓｅｃ／ｋＰａ］および選択率［－］を表２に表す。表中のセル温度は、硫化水素分離膜を挟むセルの温度の設定値を示す。相対湿度は、供給側、透過側ガスの相対湿度の設定値を示す。供給側硫化水素濃度は、供給側ガス中の硫化水素の実測濃度を示す。 (Example 6)
The hydrogen sulfide permeability coefficient [mol / m 2 / sec / kPa] and the selectivity [−] of the hydrogen sulfide separation membrane shown in Example 5 are shown in Table 2. The cell temperature in the table indicates a set value of the temperature of the cell sandwiching the hydrogen sulfide separation membrane. The relative humidity indicates a set value of the relative humidity of the supply side and permeation side gas. The supply-side hydrogen sulfide concentration indicates the measured concentration of hydrogen sulfide in the supply-side gas.
（実施例７）硫化水素分離材の製造
合成例３で得られたビニルアルコール－アクリル酸共重合体のナトリウムケン化物（ビニルアルコールに由来する構造単位：アクリル酸のナトリウムケン化物に由来する構造単位＝６０ｍｏｌ％：４０ｍｏｌ％）８．３１ｇに水２５０．０２ｇを加えて室温で攪拌した。その後、そこへ、ピペラジン７．０３ｇ、Ｌ－ヒスチジン１．４１ｇおよびイソプロピルアルコール６．４１ｇを加えて室温で一昼夜攪拌して硫化水素分離材を得た。 (Example 7) Production of hydrogen sulfide separating material Sodium saponified product of vinyl alcohol-acrylic acid copolymer obtained in Synthesis Example 3 (Structural unit derived from vinyl alcohol: Structural unit derived from sodium saponified product of acrylic acid) = 60 mol%: 40 mol%) 250.02 g of water was added to 8.31 g and stirred at room temperature. Thereafter, 7.03 g of piperazine, 1.41 g of L-histidine and 6.41 g of isopropyl alcohol were added thereto, and the mixture was stirred overnight at room temperature to obtain a hydrogen sulfide separator.
合成例３で得られたビニルアルコール－アクリル酸共重合体のナトリウムケン化物（ビニルアルコールに由来する構造単位：アクリル酸のナトリウムケン化物に由来する構造単位＝６０ｍｏｌ％：４０ｍｏｌ％）８．３１ｇに水２５０．０２ｇを加えて室温で攪拌した。その後、そこへ、ピペラジン７．０３ｇ、Ｌ－ヒスチジン１．４１ｇおよびイソプロピルアルコール６．４１ｇを加えて室温で一昼夜攪拌して硫化水素分離材を得た。 (Example 7) Production of hydrogen sulfide separating material Sodium saponified product of vinyl alcohol-acrylic acid copolymer obtained in Synthesis Example 3 (Structural unit derived from vinyl alcohol: Structural unit derived from sodium saponified product of acrylic acid) = 60 mol%: 40 mol%) 250.02 g of water was added to 8.31 g and stirred at room temperature. Thereafter, 7.03 g of piperazine, 1.41 g of L-histidine and 6.41 g of isopropyl alcohol were added thereto, and the mixture was stirred overnight at room temperature to obtain a hydrogen sulfide separator.
（実施例８）硫化水素分離膜の製造
実施例７で得られた硫化水素分離材を、疎水性ＰＴＦＥ多孔膜（住友電工ファインポリマー製、ＨＰ－０１０－５０、膜厚５０μｍ、細孔径０．１μｍ）の面上に、塗布した。次に、硫化水素分離材塗布後の親水性ＰＴＦＥ多孔膜を９０℃で１時間乾燥させた後、さらに１２０℃で２時間程度熱架橋させて硫化水素分離膜を得た。乾燥後の硫化水素分離材の厚みは３３μｍであった。 Example 8 Production of Hydrogen Sulfide Separation Membrane The hydrogen sulfide separation material obtained in Example 7 was treated with a hydrophobic PTFE porous membrane (manufactured by Sumitomo Electric Fine Polymer, HP-010-50, film thickness 50 μm, pore diameter 0. It was applied on the surface of 1 μm). Next, after drying the hydrophilic PTFE porous membrane after application of the hydrogen sulfide separator at 90 ° C. for 1 hour, it was further thermally crosslinked at 120 ° C. for about 2 hours to obtain a hydrogen sulfide separation membrane. The thickness of the hydrogen sulfide separator after drying was 33 μm.
実施例７で得られた硫化水素分離材を、疎水性ＰＴＦＥ多孔膜（住友電工ファインポリマー製、ＨＰ－０１０－５０、膜厚５０μｍ、細孔径０．１μｍ）の面上に、塗布した。次に、硫化水素分離材塗布後の親水性ＰＴＦＥ多孔膜を９０℃で１時間乾燥させた後、さらに１２０℃で２時間程度熱架橋させて硫化水素分離膜を得た。乾燥後の硫化水素分離材の厚みは３３μｍであった。 Example 8 Production of Hydrogen Sulfide Separation Membrane The hydrogen sulfide separation material obtained in Example 7 was treated with a hydrophobic PTFE porous membrane (manufactured by Sumitomo Electric Fine Polymer, HP-010-50, film thickness 50 μm, pore diameter 0. It was applied on the surface of 1 μm). Next, after drying the hydrophilic PTFE porous membrane after application of the hydrogen sulfide separator at 90 ° C. for 1 hour, it was further thermally crosslinked at 120 ° C. for about 2 hours to obtain a hydrogen sulfide separation membrane. The thickness of the hydrogen sulfide separator after drying was 33 μm.
（実施例９）
実施例８で示した硫化水素分離膜の硫化水素透過係数［ｍｏｌ／ｍ２／ｓｅｃ／ｋＰａ］および選択率［－］を表３に表す。表中のセル温度は、硫化水素分離膜を挟むセルの温度の設定値を示す。相対湿度は、供給側、透過側ガスの相対湿度の設定値を示す。供給側硫化水素濃度は、供給側ガス中の硫化水素の実測濃度を示す。 Example 9
Table 3 shows the hydrogen sulfide permeability coefficient [mol / m 2 / sec / kPa] and the selectivity [−] of the hydrogen sulfide separation membrane shown in Example 8. The cell temperature in the table indicates a set value of the temperature of the cell sandwiching the hydrogen sulfide separation membrane. The relative humidity indicates a set value of the relative humidity of the supply side and permeation side gas. The supply-side hydrogen sulfide concentration indicates the measured concentration of hydrogen sulfide in the supply-side gas.
実施例８で示した硫化水素分離膜の硫化水素透過係数［ｍｏｌ／ｍ２／ｓｅｃ／ｋＰａ］および選択率［－］を表３に表す。表中のセル温度は、硫化水素分離膜を挟むセルの温度の設定値を示す。相対湿度は、供給側、透過側ガスの相対湿度の設定値を示す。供給側硫化水素濃度は、供給側ガス中の硫化水素の実測濃度を示す。 Example 9
Table 3 shows the hydrogen sulfide permeability coefficient [mol / m 2 / sec / kPa] and the selectivity [−] of the hydrogen sulfide separation membrane shown in Example 8. The cell temperature in the table indicates a set value of the temperature of the cell sandwiching the hydrogen sulfide separation membrane. The relative humidity indicates a set value of the relative humidity of the supply side and permeation side gas. The supply-side hydrogen sulfide concentration indicates the measured concentration of hydrogen sulfide in the supply-side gas.
（参考例１）ピペラジン水溶液の硫化水素吸収量測定
ピペラジンを水に溶かし１．０ｍｏｌ／ｌとした水溶液を前記硫化水素曝露手法を用いて硫化水素ガス／空気の混合条件下（すなわち、酸素ガスも含まれる混合条件下）に曝露した。得られたサンプル中の硫黄成分量を前記硫化水素吸収量定量手法を用いて定量した。ピペラジン水溶液の硫化水素吸収量を表４に表す。 (Reference Example 1) Measurement of hydrogen sulfide absorption of piperazine aqueous solution An aqueous solution in which piperazine was dissolved in water to make 1.0 mol / l was mixed with hydrogen sulfide gas / air under the hydrogen sulfide exposure technique (that is, oxygen gas also Exposed to the mixing conditions involved). The amount of sulfur component in the obtained sample was quantified using the hydrogen sulfide absorption quantification method. Table 4 shows the amount of hydrogen sulfide absorbed by the piperazine aqueous solution.
ピペラジンを水に溶かし１．０ｍｏｌ／ｌとした水溶液を前記硫化水素曝露手法を用いて硫化水素ガス／空気の混合条件下（すなわち、酸素ガスも含まれる混合条件下）に曝露した。得られたサンプル中の硫黄成分量を前記硫化水素吸収量定量手法を用いて定量した。ピペラジン水溶液の硫化水素吸収量を表４に表す。 (Reference Example 1) Measurement of hydrogen sulfide absorption of piperazine aqueous solution An aqueous solution in which piperazine was dissolved in water to make 1.0 mol / l was mixed with hydrogen sulfide gas / air under the hydrogen sulfide exposure technique (that is, oxygen gas also Exposed to the mixing conditions involved). The amount of sulfur component in the obtained sample was quantified using the hydrogen sulfide absorption quantification method. Table 4 shows the amount of hydrogen sulfide absorbed by the piperazine aqueous solution.
（参考例２）ピペラジン水溶液中の生成硫黄酸化物濃度測定
ピペラジンを水に溶かし０．００２ｍｏｌ／ｌとした水溶液を前記硫化水素曝露手法を用いて硫化水素ガス／空気の混合条件下（すなわち、酸素ガスも含まれる混合条件下）に曝露した。得られたサンプル中の硫黄酸化物イオン量を前記生成硫黄酸化物量定量手法を用いて定量した。ピペラジン水溶液の生成硫黄酸化物量を表５に表す。 Reference Example 2 Measurement of Concentration of Sulfur Oxide in Piperazine Aqueous Solution An aqueous solution in which piperazine was dissolved in water to make 0.002 mol / l was mixed with hydrogen sulfide gas / air under the hydrogen sulfide exposure technique (that is, oxygen Exposure to gas). The amount of sulfur oxide ions in the obtained sample was quantified using the method for determining the amount of generated sulfur oxide. Table 5 shows the amount of sulfur oxide formed in the piperazine aqueous solution.
ピペラジンを水に溶かし０．００２ｍｏｌ／ｌとした水溶液を前記硫化水素曝露手法を用いて硫化水素ガス／空気の混合条件下（すなわち、酸素ガスも含まれる混合条件下）に曝露した。得られたサンプル中の硫黄酸化物イオン量を前記生成硫黄酸化物量定量手法を用いて定量した。ピペラジン水溶液の生成硫黄酸化物量を表５に表す。 Reference Example 2 Measurement of Concentration of Sulfur Oxide in Piperazine Aqueous Solution An aqueous solution in which piperazine was dissolved in water to make 0.002 mol / l was mixed with hydrogen sulfide gas / air under the hydrogen sulfide exposure technique (that is, oxygen Exposure to gas). The amount of sulfur oxide ions in the obtained sample was quantified using the method for determining the amount of generated sulfur oxide. Table 5 shows the amount of sulfur oxide formed in the piperazine aqueous solution.
本発明の硫化水素分離材を使用すれば、硫化水素透過性能（パーミアンス）および硫化水素分離性能（選択率）に優れた硫化水素分離膜を製造できる。
If the hydrogen sulfide separation material of the present invention is used, a hydrogen sulfide separation membrane excellent in hydrogen sulfide permeation performance (permeance) and hydrogen sulfide separation performance (selectivity) can be produced.
Claims (7)
- 吸水性ポリマーおよびアミン系キャリアを含む硫化水素分離材。 Hydrogen sulfide separator containing water-absorbing polymer and amine carrier.
- 下記式（１）で表される条件を満たす請求項１記載の硫化水素分離材。
（Ｘ１－Ｘ２）×Ｙ×１００／Ｚ ≦ ０．１ （１）
Ｘ１：前記吸水性ポリマーに含まれるアルカリ金属のモル数
Ｘ２：前記吸水性ポリマーに含まれるイオン交換基の当量数
Ｙ：前記吸水性ポリマーに含まれるアルカリ金属の平均原子量
Ｚ：前記吸水性ポリマーの質量 The hydrogen sulfide separation material according to claim 1, wherein a condition represented by the following formula (1) is satisfied.
(X 1 −X 2 ) × Y × 100 / Z ≦ 0.1 (1)
X 1 : Number of moles of alkali metal contained in the water-absorbing polymer X 2 : Equivalent number of ion-exchange groups contained in the water-absorbing polymer Y: Average atomic weight of alkali metal contained in the water-absorbing polymer Z: Water-absorbing property Polymer mass - 前記アミン系キャリアがヘテロ環式アミンである請求項１または２記載の硫化水素分離材。 The hydrogen sulfide separation material according to claim 1 or 2, wherein the amine carrier is a heterocyclic amine.
- 前記へテロ環式アミンがピペラジンである請求項３記載の硫化水素分離材。 The hydrogen sulfide separation material according to claim 3, wherein the heterocyclic amine is piperazine.
- 請求項１から４のいずれか一項記載の硫化水素分離材と、多孔膜とを有する硫化水素分離膜。 A hydrogen sulfide separation membrane comprising the hydrogen sulfide separation material according to any one of claims 1 to 4 and a porous membrane.
- 請求項５記載の硫化水素分離膜を含む硫化水素分離装置。 A hydrogen sulfide separation apparatus comprising the hydrogen sulfide separation membrane according to claim 5.
- 請求項１から４のいずれか一項記載の硫化水素分離材または請求項５に記載の硫化水素分離膜に、硫化水素を含む混合ガスを接触させて、硫化水素を分離する方法。 A method for separating hydrogen sulfide by bringing a mixed gas containing hydrogen sulfide into contact with the hydrogen sulfide separation material according to any one of claims 1 to 4 or the hydrogen sulfide separation membrane according to claim 5.
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| WO2018147421A1 (en) * | 2017-02-09 | 2018-08-16 | 独立行政法人石油天然ガス・金属鉱物資源機構 | System for removing hydrogen sulfide and method for removing hydrogen sulfide |
| WO2018179531A1 (en) | 2017-03-31 | 2018-10-04 | 住友化学株式会社 | Gel including condensation product of organic silicon compound |
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| JP2001293340A (en) * | 2000-04-17 | 2001-10-23 | Tosoh Corp | Permeable separating membrane for acid gas |
| JP2011183379A (en) * | 2010-02-10 | 2011-09-22 | Fujifilm Corp | Gas separation membrane, manufacturing method therefor, gas separation method using the same, module, and separator |
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| JP2001293340A (en) * | 2000-04-17 | 2001-10-23 | Tosoh Corp | Permeable separating membrane for acid gas |
| JP2011183379A (en) * | 2010-02-10 | 2011-09-22 | Fujifilm Corp | Gas separation membrane, manufacturing method therefor, gas separation method using the same, module, and separator |
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| WO2018147421A1 (en) * | 2017-02-09 | 2018-08-16 | 独立行政法人石油天然ガス・金属鉱物資源機構 | System for removing hydrogen sulfide and method for removing hydrogen sulfide |
| WO2018179531A1 (en) | 2017-03-31 | 2018-10-04 | 住友化学株式会社 | Gel including condensation product of organic silicon compound |
| KR20190129959A (en) | 2017-03-31 | 2019-11-20 | 스미또모 가가꾸 가부시키가이샤 | Gels Condensate of Organosilicon Compounds |
| US10765993B2 (en) | 2017-03-31 | 2020-09-08 | Sumitomo Chemical Company, Limited | Gel including condensation product of organic silicon compound |
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