JP2014014803A - Method of producing complex for carbon dioxide separation, complex for carbon dioxide separation, module for carbon dioxide separation, carbon dioxide separation apparatus, and carbon dioxide separation method - Google Patents
Method of producing complex for carbon dioxide separation, complex for carbon dioxide separation, module for carbon dioxide separation, carbon dioxide separation apparatus, and carbon dioxide separation method Download PDFInfo
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- JP2014014803A JP2014014803A JP2012155771A JP2012155771A JP2014014803A JP 2014014803 A JP2014014803 A JP 2014014803A JP 2012155771 A JP2012155771 A JP 2012155771A JP 2012155771 A JP2012155771 A JP 2012155771A JP 2014014803 A JP2014014803 A JP 2014014803A
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- Prior art keywords
- carbon dioxide
- dioxide separation
- composite
- coating
- separation layer
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- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 300
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 299
- 238000000926 separation method Methods 0.000 title claims abstract description 218
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 96
- 238000005259 measurement Methods 0.000 claims abstract description 40
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- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
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- 238000000576 coating method Methods 0.000 claims description 171
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- 238000004519 manufacturing process Methods 0.000 claims description 42
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Classifications
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- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B01D71/06—Organic material
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
- B01D71/381—Polyvinylalcohol
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D71/06—Organic material
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- B01D71/401—Polymers based on the polymerisation of acrylic acid, e.g. polyacrylate
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- C—CHEMISTRY; METALLURGY
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D71/06—Organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
Description
本発明は、二酸化炭素分離用複合体の製造方法、二酸化炭素分離用複合体、二酸化炭素分離モジュール、二酸化炭素分離装置、及び二酸化炭素分離方法に関する。 The present invention relates to a method for producing a carbon dioxide separation complex, a carbon dioxide separation complex, a carbon dioxide separation module, a carbon dioxide separation device, and a carbon dioxide separation method.
近年、二酸化炭素とそれ以外の分離対象ガスとを含む混合ガスから、二酸化炭素を選択的に分離する技術の開発が進んでいる。例えば、地球温暖化対策として排ガス中の二酸化炭素を回収して濃縮する技術や、水蒸気改質により炭化水素を水素と一酸化炭素（ＣＯ）に改質し、さらに一酸化炭素と水蒸気を反応させて二酸化炭素と水素を生成させ、二酸化炭素を選択的に透過する膜によって二酸化炭素を排除することで水素を主成分とする燃料電池用等のガスを得る技術が開発されている。
一方、二酸化炭素の分離はアミン類による吸着及び放散を繰り返すアミン吸収法が一般的で広く用いられてきている。しかしながらこの方法は広大な設備設置面積を必要とする上に吸着／放散時に昇圧／降圧、及び降温／昇温を繰り返す必要があり、多大なエネルギーを必要とする欠点を有している。またシステムの能力は設計時に決定してしまい、一旦作られたシステムの能力の拡縮は容易でない。これに対して、膜分離法は分離膜で区画された２つの領域の二酸化炭素分圧により自然に分離を行うものでエネルギー消費が少なく、かつ設置面積がコンパクトな利点を有する。またシステムの能力の拡縮もフィルターユニットの増減で対応出来るためにスケーラビリティーに優れたシステムが可能であり、近年注目を浴びている。
二酸化炭素分離用複合体は大別すると、支持体上の二酸化炭素分離層中に、二酸化炭素キャリアを含有し、このキャリアによって二酸化炭素が膜の反対側に輸送される、いわゆる促進輸送膜と、二酸化炭素分離層に対する二酸化炭素と二酸化炭素以外の分離対象ガス（以下、単に「分離対象物質」という。）との間での溶解性、及び膜中の拡散性の差を利用して分離を行う、いわゆる溶解拡散膜とに大別される。
溶解拡散膜は、二酸化炭素と分離対象物質との間での当該膜への溶解性及び当該膜中の拡散性の差に基づいて分離を行うため、膜の材質及び物性が決まればその分離度合いは一義的に決定され、かつ、膜厚が薄いほど混合ガスの透過速度が大きくなる。そのため、溶解拡散膜は、一般的に層分離法、界面重合法などの製造方法を用いて、膜厚が１μｍ以下の薄膜として製造される。
これに対して、促進輸送膜は二酸化炭素キャリアを膜中に添加することで二酸化炭素の溶解度を飛躍的に増大させ、膜中での二酸化炭素の輸送が高濃度で行われるため、一般的に溶解拡散膜に比べ分離対象物質に対する二酸化炭素の分離度合いが高く、また二酸化炭素の透過速度が速いという特長を有する。また膜中の二酸化炭素濃度が高濃度であることから、膜中の二酸化炭素の拡散速度が律速になることは希であり、むしろ分離対象物質との分離度合いを上げる意味からは１０μｍ以上の厚膜とする方が好ましい。
In recent years, development of a technique for selectively separating carbon dioxide from a mixed gas containing carbon dioxide and other gas to be separated has been advanced. For example, as a global warming countermeasure, carbon dioxide in exhaust gas is collected and concentrated, or by steam reforming, hydrocarbons are reformed to hydrogen and carbon monoxide (CO), and carbon monoxide and steam are reacted. In order to produce carbon dioxide and hydrogen, a technology for obtaining a gas for fuel cells, etc., mainly containing hydrogen by eliminating carbon dioxide with a membrane that selectively permeates carbon dioxide has been developed.
On the other hand, for the separation of carbon dioxide, an amine absorption method that repeats adsorption and emission by amines is common and widely used. However, this method requires a large facility installation area and needs to repeatedly increase / decrease pressure and decrease / temperature increase during adsorption / dissipation, and thus has a drawback of requiring a large amount of energy. In addition, the capacity of the system is determined at the time of design, and it is not easy to expand or reduce the capacity of the system once made. On the other hand, the membrane separation method performs the separation naturally by the partial pressure of carbon dioxide in two regions partitioned by the separation membrane, and has the advantages of low energy consumption and a compact installation area. In addition, since the capacity of the system can be increased or decreased by increasing or decreasing the filter unit, a highly scalable system is possible, and has attracted attention in recent years.
The carbon dioxide separation composite is roughly classified as follows: a so-called facilitated transport membrane in which a carbon dioxide carrier is contained in a carbon dioxide separation layer on a support and carbon dioxide is transported to the opposite side of the membrane by the carrier; Separation is performed by utilizing the difference in solubility between the carbon dioxide and the gas to be separated other than carbon dioxide (hereinafter simply referred to as “substance to be separated”) and the diffusivity in the membrane. The so-called dissolution diffusion film is roughly classified.
Dissolving diffusion membrane performs separation based on the difference in solubility in the membrane and the diffusivity in the membrane between carbon dioxide and the substance to be separated, so if the material and physical properties of the membrane are determined, the degree of separation Is uniquely determined, and the permeation rate of the mixed gas increases as the film thickness decreases. Therefore, the dissolution diffusion film is generally manufactured as a thin film having a thickness of 1 μm or less by using a manufacturing method such as a layer separation method or an interfacial polymerization method.
In contrast, the facilitated transport membrane dramatically increases the solubility of carbon dioxide by adding a carbon dioxide carrier into the membrane, and the transport of carbon dioxide in the membrane is performed at a high concentration. Compared with the dissolution diffusion membrane, the carbon dioxide is separated to a substance to be separated, and the carbon dioxide has a high permeation rate. Further, since the concentration of carbon dioxide in the membrane is high, it is rare that the diffusion rate of carbon dioxide in the membrane becomes rate limiting. Rather, it has a thickness of 10 μm or more in order to increase the degree of separation from the substance to be separated. A film is preferred.
例えば、特許文献１には、未架橋のビニルアルコール−アクリル酸塩共重合体水溶液を二酸化炭素透過性支持体上へ膜状に塗布して、当該支持体上に未架橋のビニルアルコール−アクリル酸塩共重合体水溶液の液膜を形成した後、この液膜を加熱して架橋させることにより水不溶化膜とし、この水不溶化膜に、二酸化炭素キャリア（二酸化炭素と親和性を有する物質）を含む水溶液を吸収させてハイドロゲル膜とした二酸化炭素分離用複合体の製造方法が記載されている。 For example, in Patent Document 1, an uncrosslinked vinyl alcohol-acrylate copolymer aqueous solution is applied in a film form onto a carbon dioxide permeable support, and the uncrosslinked vinyl alcohol-acrylic acid is applied onto the support. After forming a liquid film of the salt copolymer aqueous solution, the liquid film is heated and cross-linked to form a water-insoluble film, and the water-insoluble film contains a carbon dioxide carrier (a substance having an affinity for carbon dioxide). A method for producing a composite for separating carbon dioxide by absorbing an aqueous solution into a hydrogel membrane is described.
また、特許文献２には、ポリビニルアルコール−ポリアクリル酸共重合体水溶液に、架橋剤としてのグルタルアルデヒド又はホルムアルデヒドを添加し、更に炭酸セシウム若しくは重炭酸セシウム若しくは水酸化セシウムからなる添加剤を添加して調製したＣＯ２促進輸送膜用塗布液を調製し、これを支持体としての親水性の多孔膜上に塗布してＣＯ２促進輸送膜用塗布液の液膜を担持させ、これを室温で一昼夜乾燥させることによりＣＯ２促進輸送膜（二酸化炭素分離層）を形成する二酸化炭素分離用複合体の製造方法が記載されている。そして、所定の主成分ガスに少なくとも二酸化炭素と水蒸気が含まれる混合ガスを上記二酸化炭素分離用複合体の一方の表面（原料側面）に１００℃以上の供給温度で供給して、ＣＯ２促進輸送膜を透過した二酸化炭素を二酸化炭素分離用複合体の他方の表面（透過側面）から取り出す二酸化炭素分離装置が記載されている。 In Patent Document 2, glutaraldehyde or formaldehyde as a crosslinking agent is added to an aqueous polyvinyl alcohol-polyacrylic acid copolymer solution, and an additive composed of cesium carbonate, cesium bicarbonate, or cesium hydroxide is added. The coating liquid for the CO 2 facilitated transport film prepared above was prepared, and this was coated on a hydrophilic porous film as a support to carry the liquid film of the coating liquid for the CO 2 facilitated transport film. A method for producing a composite for carbon dioxide separation that forms a CO 2 facilitated transport membrane (carbon dioxide separation layer) by drying all day and night is described. Then, a mixed gas containing at least carbon dioxide and water vapor in a predetermined main component gas is supplied to one surface (side surface of the raw material) of the carbon dioxide separation composite at a supply temperature of 100 ° C. or more to facilitate CO 2 transport. A carbon dioxide separator that takes out carbon dioxide that has permeated through a membrane from the other surface (permeation side surface) of the composite for carbon dioxide separation is described.
特許文献１に記載されている二酸化炭素分離用複合体の製造方法においては、二酸化炭素透過性支持体上に、二酸化炭素キャリアを含まないビニルアルコール−アクリル酸塩共重合体水溶液を塗布する工程、加熱して架橋して水不溶化膜を形成する工程、及び当該水不溶化膜に二酸化炭素キャリアを含む水溶液を吸収させる工程の少なくとも三つの工程が必要である。そのため、生産効率が悪く、生産コストが高価となり、しかも各工程のばらつきが重ね合わさって、二酸化炭素分離用複合体としての性能の変動が大きくならざるを得ないという課題がある。
また、特許文献２に記載されているＣＯ２促進輸送膜を有する二酸化炭素分離用複合体の製造方法においては、ＣＯ２促進輸送膜用塗布液中で、炭酸セシウムのような二酸化炭素キャリアが溶解せずに沈降してしまうことがないように、当該塗布液の固形分濃度を一定以下に抑える必要がある。
他方で、ＣＯ２促進輸送膜の膜厚を１０μｍ以上とする必要があることから、所望の膜厚のＣＯ２促進輸送膜を得るために、ＣＯ２促進輸送膜用塗布液の塗布と乾燥のサイクルを複数回繰り返す必要があり、生産効率が悪く、生産コストが高価となり、しかも各サイクルにより形成されるＣＯ２促進輸送膜のばらつきが重ね合わさって、二酸化炭素分離用複合体としての性能の変動が大きくならざるを得ないという課題がある。
In the method for producing a composite for carbon dioxide separation described in Patent Document 1, a step of applying a vinyl alcohol-acrylate copolymer aqueous solution not containing a carbon dioxide carrier on a carbon dioxide permeable support, At least three steps of forming a water-insolubilized film by heating and crosslinking and absorbing the aqueous solution containing carbon dioxide carrier in the water-insolubilized film are required. Therefore, there is a problem that production efficiency is low, production cost is expensive, and variations in each process are overlapped, so that variation in performance as a composite for carbon dioxide separation has to be large.
In addition, in the method for producing a composite for separating carbon dioxide having a CO 2 facilitated transport film described in Patent Document 2, a carbon dioxide carrier such as cesium carbonate is dissolved in the coating liquid for the CO 2 facilitated transport film. Therefore, it is necessary to suppress the solid content concentration of the coating liquid to a certain level or less so that the liquid does not settle.
On the other hand, the thickness of the CO 2 -facilitated transport membrane because it is necessary to be more than 10 [mu] m, in order to obtain a desired film thickness of the CO 2 -facilitated transport membrane, and drying the coating of the CO 2 -facilitated transport membrane coating liquid Cycles need to be repeated multiple times, resulting in poor production efficiency, high production costs, and variations in CO 2 facilitated transport membranes formed by each cycle, resulting in fluctuations in performance as a composite for carbon dioxide separation There is a problem that must be large.
従って、本発明の課題は、所望の厚さ（例えば、１０μｍ以上）を有し、二酸化炭素の分離度合が高い二酸化炭素分離層を有する二酸化炭素分離用複合体が、少ない工程数で、二酸化炭素分離用複合体としての性能の変動が少なく、且つ、効率よく製造される二酸化炭素分離用複合体の製造方法、並びに、前記製造方法により製造された二酸化炭素分離用複合体、前記複合体を含む二酸化炭素分離モジュール、前記モジュールを含む二酸化炭素分離装置、及び前記二酸化炭素分離用複合体を用いる二酸化炭素分離方法を提供することを課題とする。 Accordingly, an object of the present invention is to provide a carbon dioxide separation complex having a carbon dioxide separation layer having a desired thickness (for example, 10 μm or more) and a high degree of carbon dioxide separation. A method for producing a complex for carbon dioxide separation that is produced with little variation in performance as a separation complex and is efficiently produced, a complex for carbon dioxide separation produced by the production method, and the complex It is an object to provide a carbon dioxide separation module, a carbon dioxide separation device including the module, and a carbon dioxide separation method using the carbon dioxide separation composite.
上記課題を達成する本発明は、以下のとおりである。
＜１＞ 吸水性ポリマー、二酸化炭素キャリア、及び水を含み、前記吸水性ポリマーと前記二酸化炭素キャリアとの質量比が１：９以上２：３以下の二酸化炭素分離層形成用塗布液を調製する塗布液調製工程と、
前記二酸化炭素分離層形成用塗布液を、１５℃以上３５℃以下の温度、かつＢ型粘度測定において回転数６０ｒｐｍにおける粘度測定値が０．５Ｐａ・ｓ以上１０Ｐａ・ｓ以下の粘度で支持体上に塗布して、前記二酸化炭素分離層形成用塗布液の液膜を前記支持体上に形成する塗布工程と、
前記支持体上の二酸化炭素分離層形成用塗布液の液膜を乾燥して二酸化炭素分離層とする乾燥工程と、
を含む二酸化炭素分離用複合体の製造方法。
＜２＞ 前記塗布工程は、前記支持体上の二酸化炭素分離層形成用塗布液の液膜を厚さ０．５ｍｍ以上２．５ｍｍ以下の範囲にて形成する＜１＞に記載の二酸化炭素分離用複合体の製造方法。
＜３＞ 前記塗布工程は、前記二酸化炭素分離層形成用塗布液をロールコート法又はブレードコート法で前記支持体上に塗布する＜１＞又は＜２＞に記載の二酸化炭素分離用複合体の製造方法。
＜４＞ 前記塗布液調製工程における前記二酸化炭素分離層形成用塗布液が、更に増粘剤を含む＜１＞〜＜３＞のいずれか一項に記載の二酸化炭素分離用複合体の製造方法。
＜５＞ 前記増粘剤が、カルボキシメチルセルロースである＜４＞に記載の二酸化炭素分離用複合体の製造方法。
＜６＞ 前記吸水性ポリマーが、ポリビニルアルコール−ポリアクリル酸共重合体である＜１＞〜＜５＞のいずれか一項に記載の二酸化炭素分離用複合体の製造方法。
＜７＞ 前記二酸化炭素キャリアが、アルカリ金属炭酸塩から選ばれる少なくとも１つである＜１＞〜＜６＞のいずれか一項に記載の二酸化炭素分離用複合体の製造方法。
＜８＞ 前記二酸化炭素キャリアが、セシウム、ルビジウム、及びカリウムからなる群から選ばれる少なくとも１つを含む化合物を含有する＜１＞〜＜７＞のいずれか一項に記載の二酸化炭素分離用複合体の製造方法。
＜９＞ ＜１＞〜＜８＞のいずれか一項に記載の二酸化炭素分離用複合体の製造方法により製造された二酸化炭素分離用複合体。
＜１０＞ ＜９＞に記載の二酸化炭素分離用複合体を含む二酸化炭素分離モジュール。
＜１１＞ ＜１０＞に記載の二酸化炭素分離モジュールを含む二酸化炭素分離装置。
＜１２＞ ＜９＞に記載の二酸化炭素分離用複合体の一方の表面側に、二酸化炭素を含む混合ガスを供給し、前記混合ガス中の二酸化炭素の少なくとも一部を前記二酸化炭素分離用複合体に吸収させる二酸化炭素分離方法。
The present invention for achieving the above object is as follows.
<1> A coating solution for forming a carbon dioxide separation layer is prepared, comprising a water-absorbing polymer, a carbon dioxide carrier, and water, wherein a mass ratio of the water-absorbing polymer and the carbon dioxide carrier is 1: 9 or more and 2: 3 or less. Coating liquid preparation process;
The coating solution for forming a carbon dioxide separation layer is formed on the support at a temperature of 15 ° C. or more and 35 ° C. or less and a viscosity measurement value at a rotation speed of 60 rpm in the B-type viscosity measurement is 0.5 Pa · s or more and 10 Pa · s or less. An application step of forming a liquid film of the coating solution for forming a carbon dioxide separation layer on the support;
A drying step of drying the liquid film of the coating liquid for forming a carbon dioxide separation layer on the support to form a carbon dioxide separation layer;
The manufacturing method of the composite_body | complex for carbon dioxide separation containing this.
<2> The carbon dioxide separation according to <1>, wherein the coating step forms a liquid film of a coating solution for forming a carbon dioxide separation layer on the support in a thickness range of 0.5 mm to 2.5 mm. For producing a composite for use.
<3> The carbon dioxide separation layer-forming composite according to <1> or <2>, wherein the carbon dioxide separation layer forming coating solution is applied on the support by a roll coating method or a blade coating method. Production method.
<4> The method for producing a composite for carbon dioxide separation according to any one of <1> to <3>, wherein the coating liquid for forming a carbon dioxide separation layer in the coating liquid preparation step further includes a thickener. .
<5> The method for producing a composite for separating carbon dioxide according to <4>, wherein the thickener is carboxymethylcellulose.
<6> The method for producing a composite for carbon dioxide separation according to any one of <1> to <5>, wherein the water-absorbing polymer is a polyvinyl alcohol-polyacrylic acid copolymer.
<7> The method for producing a composite for carbon dioxide separation according to any one of <1> to <6>, wherein the carbon dioxide carrier is at least one selected from alkali metal carbonates.
<8> The composite for carbon dioxide separation according to any one of <1> to <7>, wherein the carbon dioxide carrier contains a compound containing at least one selected from the group consisting of cesium, rubidium, and potassium. Body manufacturing method.
<9> A composite for carbon dioxide separation produced by the method for producing a composite for carbon dioxide separation according to any one of <1> to <8>.
<10> A carbon dioxide separation module comprising the complex for carbon dioxide separation according to <9>.
<11> A carbon dioxide separator including the carbon dioxide separation module according to <10>.
<12> A mixed gas containing carbon dioxide is supplied to one surface side of the composite for carbon dioxide separation according to <9>, and at least a part of carbon dioxide in the mixed gas is used for the composite for carbon dioxide separation. A carbon dioxide separation method that is absorbed by the body.
本発明によれば、二酸化炭素の分離度合が高い二酸化炭素分離層を有する二酸化炭素分離用複合体が、少ない工程数で、二酸化炭素分離用複合体としての性能の変動が少なく、且つ、効率よく製造される二酸化炭素分離用複合体の製造方法、並びに、前記製造方法により製造された二酸化炭素分離用複合体、前記分離用複合体を含む二酸化炭素分離モジュール、前記モジュールを含む二酸化炭素分離装置、及び前記二酸化炭素分離用複合体を用いる二酸化炭素分離方法が提供される。 According to the present invention, the composite for carbon dioxide separation having a carbon dioxide separation layer having a high degree of carbon dioxide separation has few variations in performance as a composite for carbon dioxide separation with a small number of steps, and efficiently. Method for producing carbon dioxide separation complex to be produced, carbon dioxide separation complex produced by the production method, carbon dioxide separation module comprising the separation complex, carbon dioxide separation apparatus comprising the module, And a carbon dioxide separation method using the composite for carbon dioxide separation.
本発明に係る二酸化炭素分離用複合体の製造方法は、吸水性ポリマー、二酸化炭素キャリア、及び水を含み、前記吸水性ポリマーと前記二酸化炭素キャリアとの質量比が１：９以上２：３以下の二酸化炭素分離層形成用塗布液を調製する塗布液調製工程と、前記二酸化炭素分離層形成用塗布液を、１５℃以上３５℃以下の温度、かつＢ型粘度測定において回転数６０ｒｐｍにおける粘度測定値が０．５Ｐａ・ｓ以上１０Ｐａ・ｓ以下の粘度で支持体上に塗布して、前記二酸化炭素分離層形成用塗布液の液膜を前記支持体上に形成する塗布工程と、前記支持体上の二酸化炭素分離層形成用塗布液の液膜を乾燥して二酸化炭素分離層とする乾燥工程と、を含む。 The method for producing a composite for carbon dioxide separation according to the present invention includes a water-absorbing polymer, a carbon dioxide carrier, and water, and a mass ratio of the water-absorbing polymer to the carbon dioxide carrier is from 1: 9 to 2: 3. A coating liquid preparation step of preparing a coating liquid for forming a carbon dioxide separation layer, and measuring the viscosity of the coating liquid for forming a carbon dioxide separation layer at a temperature of 15 ° C. or more and 35 ° C. or less and at a rotational speed of 60 rpm in B-type viscosity measurement. A coating step of coating the support with a viscosity of 0.5 Pa · s to 10 Pa · s and forming a liquid film of the carbon dioxide separation layer forming coating solution on the support; and the support. And a drying step of drying the liquid film of the coating liquid for forming the carbon dioxide separation layer to form a carbon dioxide separation layer.
本発明に係る塗布液調製工程においては、吸水性ポリマー、二酸化炭素キャリア、及び水を含み、前記吸水性ポリマーと前記二酸化炭素キャリアとの質量比が１：９以上２：３以下の二酸化炭素分離層形成用塗布液を調製する。
二酸化炭素分離層形成用塗布液おいて、吸水性ポリマーと二酸化炭素キャリアとの質量比が１：９以上２：３以下であることは、当該塗布液を１５℃以上３５℃以下の温度条件下において、Ｂ型粘度測定において回転数６０ｒｐｍにおける粘度測定値０．５Ｐａ・ｓ以上１０Ｐａ・ｓ以下の粘度で支持体上に塗布して、前記二酸化炭素分離層形成用塗布液の液膜を前記支持体上に形成する塗布工程を可能とする上で必須である。吸水性ポリマーと二酸化炭素キャリアとの質量比が１：９より小さくなると、１５℃以上３５℃以下の温度範囲で、Ｂ型粘度測定において回転数６０ｒｐｍにおける粘度測定値が０．５Ｐａ・ｓ以上の粘度を示す塗布液を得ることが困難である。他方、吸水性ポリマーと二酸化炭素キャリアとの質量比が２：３より大きくなると、塗布液（水溶液）に含まれる固形分が均一に混合せずに白濁し、場合によっては、塗布に適する流動性が不足してしまう。更に、塗布液を１５℃以上３５℃以下の温度条件下で、Ｂ型粘度測定において回転数６０ｒｐｍにおける粘度測定値が０．５Ｐａ・ｓより低い粘度で塗布を行うと、所望の厚さの二酸化炭素分離層の形成が困難であり、結果として、分離効率の優れる二酸化炭素分離層をえることができない上、塗布工程において、塗布液が漏れ出したり、所望の厚みを有する分離層が形成し難いという問題が生じ易くなる。また、塗布液を１５℃以上３５℃以下の温度で、Ｂ型粘度測定において回転数６０ｒｐｍにおける粘度測定値１０Ｐａ・ｓより高い粘度で塗布を行うと、塗布工程において、膜厚の均一な二酸化炭素分離層を形成することが困難となり、二酸化炭素の分離効率が高く、また二酸化炭素の透過速度が速い、優れた性能を有する二酸化炭素分離層が得難い。
更に、吸水性ポリマーと二酸化炭素キャリアとの質量比が１：９以上２：３以下であることにより、分離対象物質に対する二酸化炭素の分離度合いが高く、また二酸化炭素の透過速度が速い、優れた性能を有する二酸化炭素分離層が得られる。
In the coating liquid preparation step according to the present invention, carbon dioxide separation comprising a water-absorbing polymer, a carbon dioxide carrier, and water, wherein the mass ratio of the water-absorbing polymer and the carbon dioxide carrier is 1: 9 or more and 2: 3 or less. A layer forming coating solution is prepared.
In the coating solution for forming a carbon dioxide separation layer, the mass ratio of the water-absorbing polymer and the carbon dioxide carrier is 1: 9 or more and 2: 3 or less. In the B-type viscosity measurement, the measured viscosity value at a rotational speed of 60 rpm is applied on a support with a viscosity of 0.5 Pa · s to 10 Pa · s, and the liquid film of the coating liquid for forming a carbon dioxide separation layer is supported on the support. It is essential for enabling the coating process to be formed on the body. When the mass ratio of the water-absorbing polymer and the carbon dioxide carrier is smaller than 1: 9, the viscosity measurement value at a rotation speed of 60 rpm is 0.5 Pa · s or more in the B-type viscosity measurement in a temperature range of 15 ° C. or more and 35 ° C. or less. It is difficult to obtain a coating solution exhibiting viscosity. On the other hand, when the mass ratio of the water-absorbing polymer to the carbon dioxide carrier is larger than 2: 3, the solid content contained in the coating solution (aqueous solution) becomes cloudy without being uniformly mixed, and in some cases, the fluidity suitable for coating. Will run out. Furthermore, when the coating solution is applied at a temperature of 15 ° C. or more and 35 ° C. or less and the viscosity measurement value at a rotation speed of 60 rpm is less than 0.5 Pa · s in the B-type viscosity measurement, a desired thickness of dioxide dioxide is obtained. It is difficult to form a carbon separation layer, and as a result, a carbon dioxide separation layer with excellent separation efficiency cannot be obtained. In addition, in the coating process, it is difficult to form a separation layer having a desired thickness or the coating liquid leaks out. The problem is likely to occur. Further, when the coating solution is applied at a temperature of 15 ° C. or more and 35 ° C. or less at a viscosity higher than the measured viscosity value of 10 Pa · s at a rotational speed of 60 rpm in B-type viscosity measurement, carbon dioxide having a uniform film thickness is applied in the coating process. It is difficult to form a separation layer, and it is difficult to obtain a carbon dioxide separation layer having excellent performance with high carbon dioxide separation efficiency and high carbon dioxide permeation rate.
Furthermore, since the mass ratio of the water-absorbing polymer and the carbon dioxide carrier is 1: 9 or more and 2: 3 or less, the degree of separation of carbon dioxide from the substance to be separated is high and the permeation rate of carbon dioxide is high. A carbon dioxide separation layer having performance is obtained.
本発明の好ましい態様においては、本発明に係る塗布工程が、二酸化炭素分離層形成用塗布液を、１５℃以上３５℃以下の範囲、かつＢ型粘度測定において回転数６０ｒｐｍにおける粘度測定値が０．７Ｐａ・ｓ以上９Ｐａ・ｓ以下の粘度で支持体上に塗布され、特に好ましい態様においては、１５℃以上３５℃以下の範囲、かつＢ型粘度測定において回転数６０ｒｐｍにおける粘度測定値が１Ｐａ・ｓ以上５Ｐａ・ｓ以下の粘度で支持体上に塗布される。これにより、気泡の混入等の欠陥のない、均一な膜厚を有する二酸化炭素分離層が一段と容易かつ安定に得られる。このような範囲とすることにより、塗布工程における塗布液の温度が上下に５℃の範囲で変動しても、Ｂ型粘度測定において回転数６０ｒｐｍにおける粘度測定値が０．５Ｐａ・ｓ以上１０Ｐａ・ｓ以下の粘度の塗布液を塗布することが容易となる。 In a preferred embodiment of the present invention, the coating step according to the present invention is such that the carbon dioxide separation layer forming coating solution has a viscosity measurement value of 0 in the range of 15 ° C. or more and 35 ° C. or less and B-type viscosity measurement at a rotation speed of 60 rpm. In a particularly preferred embodiment, the viscosity measured at a rotation speed of 60 rpm in the range of 15 ° C. or more and 35 ° C. or less is 1 Pa · s. It is applied on the support with a viscosity of s to 5 Pa · s. As a result, a carbon dioxide separation layer having a uniform film thickness and free from defects such as bubbles can be obtained more easily and stably. By setting it as such a range, even if the temperature of the coating liquid in the coating process fluctuates up and down within a range of 5 ° C., the viscosity measurement value at a rotational speed of 60 rpm in the B-type viscosity measurement is 0.5 Pa · s or more and 10 Pa · It becomes easy to apply a coating solution having a viscosity of s or less.
上記のようにして支持体上に形成された前記二酸化炭素分離層形成用塗布液の液膜の厚さは、好ましくは０．５ｍｍ以上２．５ｍｍ以下の範囲である。これにより、次の工程である乾燥工程において、厚みムラが生ずることが少なく、従って、均質な二酸化炭素分離層を安定して支持体上に形成することが容易となる。上記液膜の厚さは、１．０ｍｍ以上２．５ｍｍ以下の範囲が更に好ましく、１．０ｍｍ以上２．０ｍｍ以下の範囲が特に好ましい。 The thickness of the liquid film of the coating solution for forming a carbon dioxide separation layer formed on the support as described above is preferably in the range of 0.5 mm to 2.5 mm. Thereby, in the subsequent drying process, thickness unevenness is less likely to occur, and therefore it becomes easy to stably form a homogeneous carbon dioxide separation layer on the support. The thickness of the liquid film is more preferably in the range of 1.0 mm to 2.5 mm, and particularly preferably in the range of 1.0 mm to 2.0 mm.
本発明に係る乾燥工程においては、前記塗布工程において支持体上に形成された二酸化炭素分離層形成用塗布液の液膜が乾燥される。
ここで、「乾燥」とは、前記塗布工程で支持体上に形成された二酸化炭素分離層形成用塗布液の液膜に含まれる水の少なくとも一部を除去することを意味する。
本発明に係る乾燥工程においては、乾燥後の二酸化炭素分離層に含まれる水の含有量が、１２０℃の環境下に２時間放置した場合を基準として、２質量％以上１０質量％以下の範囲となるように乾燥することが好ましい。このような範囲とすることで、分離対象物質に対する二酸化炭素の分離度合いが高く、また二酸化炭素の透過速度が速い二酸化炭素分離用複合体が得られる。
In the drying step according to the present invention, the liquid film of the coating liquid for forming a carbon dioxide separation layer formed on the support in the coating step is dried.
Here, “drying” means removing at least a part of water contained in the liquid film of the coating solution for forming a carbon dioxide separation layer formed on the support in the coating step.
In the drying step according to the present invention, the content of water contained in the carbon dioxide separation layer after drying is in the range of 2% by mass or more and 10% by mass or less based on the case where it is left in an environment of 120 ° C. for 2 hours. It is preferable to dry so that it becomes. By setting it as such a range, the composite_body | complex for carbon dioxide separation with the high isolation | separation degree of the carbon dioxide with respect to the isolation | separation target substance and a quick permeation | transmission rate of a carbon dioxide is obtained.
本発明に係る製造方法によれば、帯状（ウェブ状）の支持体を用いるロール・トゥー・ロール（Ｒｏｌｌ−ｔｏ−Ｒｏｌｌ）方式の製造装置により、二酸化炭素分離用複合体としての性能の変動が少ない二酸化炭素分離用複合体を、高い生産効率で、かつ生産コストが低い方法で製造することができる。
以下、上記製造装置の一実施態様について、図１を用いて説明する。
According to the production method of the present invention, the roll-to-roll production apparatus using a belt-like (web-like) support allows fluctuations in performance as a composite for carbon dioxide separation. A complex for separating carbon dioxide can be produced with a high production efficiency and a low production cost.
Hereinafter, an embodiment of the manufacturing apparatus will be described with reference to FIG.
図１は、本発明に係る二酸化炭素分離用複合体の製造工程で用いる装置構成の一例を概略的に示している。この装置１００は、帯状の支持体１２を送り出す送り出しロール１０と、支持体１２上に二酸化炭素分離層形成用塗布液３０を塗布するコーター２０（図１では、図中の矢印の方向に回転するアプリケーターロール２１と、メータリングロール２２と、帯状の支持体１２の搬送を兼ねるバックアップロール６２とかなる３本ロールコーター）と、支持体１２上に形成された前記塗布液３０の液膜（図示せず）を乾燥させる乾燥部４０、得られた二酸化炭素分離用複合体５２を巻き取る巻取りロール５０と、を備えている。また、各部２０、４０、５０に支持体１２を搬送するための搬送ロール６２（図１では、ロールコーターのバックアップロールとしても機能している。）、６４、６６、６８が配置されている。 FIG. 1 schematically shows an example of an apparatus configuration used in the production process of the composite for carbon dioxide separation according to the present invention. The apparatus 100 is provided with a feed roll 10 for feeding a belt-like support 12 and a coater 20 for applying a coating solution 30 for forming a carbon dioxide separation layer on the support 12 (in FIG. 1, it rotates in the direction of the arrow in the figure). The applicator roll 21, the metering roll 22, and a three-roll coater serving as a backup roll 62 that also serves to convey the belt-like support 12, and a liquid film (not shown) of the coating liquid 30 formed on the support 12. And a winding roll 50 for winding up the obtained carbon dioxide separating composite 52. Moreover, the conveyance roll 62 (it functions also as a backup roll of a roll coater in FIG. 1), 64, 66, and 68 for conveying the support body 12 to each part 20, 40, 50 is arrange | positioned.
このような構成を有する装置１００を用いることで、Ｒｏｌｌ−ｔｏ−Ｒｏｌｌ、すなわち、送り出しロール１０から支持体１２を送り出し、該支持体１２を搬送しながら塗布工程、及び乾燥工程を順次行い、得られた二酸化炭素分離用複合体５２を巻取りロール５０に巻き取ることができ、さらに必要に応じて架橋工程を行うことで優れたガス分離特性を有する二酸化炭素分離用複合体５２を連続的に効率良く製造することができる。なお、架橋工程は、乾燥工程後に得られた膜を巻取りロール５０に巻き取る前に行ってもよいし、巻き取った後に行ってもよい。
以下、本発明に係る二酸化炭素分離層形成用塗布液、及びに二酸化炭素分離用複合体の製造工程ついて具体的に説明する。
By using the apparatus 100 having such a configuration, roll-to-roll, that is, the support 12 is sent out from the feed roll 10 and the coating process and the drying process are sequentially performed while the support 12 is being transported. The obtained carbon dioxide separation complex 52 can be wound on the take-up roll 50, and the carbon dioxide separation complex 52 having excellent gas separation characteristics can be continuously obtained by performing a crosslinking step as necessary. It can be manufactured efficiently. In addition, a bridge | crosslinking process may be performed before winding up the film | membrane obtained after the drying process on the winding roll 50, and may be performed after winding up.
Hereinafter, the manufacturing process of the coating liquid for forming a carbon dioxide separation layer and the composite for carbon dioxide separation according to the present invention will be specifically described.
−二酸化炭素分離層用塗布液の調製工程−
まず、吸水性ポリマーと、二酸化炭素キャリアと、水とを含有する二酸化炭素分離層形成用塗布液（以下、略して「塗布液」ともいう。）を調製する。本発明に係る二酸化炭素分離層形成用塗布液の調製工程では、吸水性ポリマーと、二酸化炭素キャリアとが、それぞれ適量水に添加される。
-Preparation process of coating solution for carbon dioxide separation layer-
First, a coating solution for forming a carbon dioxide separation layer (hereinafter also referred to as “coating solution” for short) containing a water-absorbing polymer, a carbon dioxide carrier, and water is prepared. In the step of preparing the coating liquid for forming a carbon dioxide separation layer according to the present invention, an appropriate amount of water-absorbing polymer and carbon dioxide carrier are added to water.
（吸水性ポリマー）
本発明に係る塗布液に含まれる吸水性ポリマーはバインダーとして機能するものであり、二酸化炭素分離用複合体として使用するときに、二酸化炭素分離層に水分を保持して二酸化炭素キャリアによる二酸化炭素の分離機能を発揮させる。吸水性ポリマーは、水に溶けて塗布液を形成することができるとともに、二酸化炭素分離層が高い吸水性（保湿性）を有する観点から、吸水性が高いものが好ましく、生理食塩液の吸水量が０．５ｇ／g以上の吸水性を有することが好ましく、さらには１ｇ／ｇ以上の吸水性を有することがより好ましく、さらには５ｇ／ｇ以上の吸水性を有することが好ましく、さらには１０ｇ／ｇ以上の吸水性を有することが特に好ましく、さらには２０ｇ／ｇ以上の吸水性を有することが最も好ましい。
(Water-absorbing polymer)
The water-absorbing polymer contained in the coating liquid according to the present invention functions as a binder, and when used as a composite for carbon dioxide separation, water is retained in the carbon dioxide separation layer and carbon dioxide by the carbon dioxide carrier is retained. Demonstrate the separation function. The water-absorbing polymer can be dissolved in water to form a coating solution, and the carbon dioxide separation layer preferably has high water absorption from the viewpoint of high water absorption (moisturizing property). Preferably has a water absorption of 0.5 g / g or more, more preferably 1 g / g or more, more preferably 5 g / g or more, and more preferably 10 g. It is particularly preferable to have a water absorption of at least 20 g / g, and most preferable to have a water absorption of at least 20 g / g.
本発明に係る塗布液に含まれる吸水性ポリマーとしては、従来公知の親水性高分子を用いることができるが、吸水性、製膜性、強度などの観点から、例えば、ポリビニルアルコール類、ポリアクリル酸類、ポリエチレンオキサイド類、水溶性セルロース類、デンプン類、アルギン酸類、キチン類、ポリスルホン酸類、ポリヒドロキシメタクリレート類、ポリビニルピロリドン類、ポリＮビニルアセトアミド類、ポリアクリルアミド類、ポリエチレンイミン類、ポリアリルアミン類、ポリビニルアミン類などが好ましく、またこれらの共重合体も好ましく用いることができる。
特にポリビニルアルコール−ポリアクリル酸塩共重合体が好ましい。ポリビニルアルコール−ポリアクリル酸塩共重合体は、吸水能が高い上に、高吸水時においてもハイドロゲルの強度が大きい。ポリビニルアルコール−ポリアクリル酸塩共重合体におけるポリアクリル酸塩の含有率は、例えば１〜９５モル％、好ましくは２〜７０モル％、より好ましくは３〜６０モル％、特に好ましくは５〜５０モル％である。ポリアクリル酸塩としては、ナトリウム塩、カリウム塩等のアルカリ金属塩の他、アンモニウム塩や有機アンモニウム塩等が挙げられる。
市販されているポリビニルアルコール−ポリアクリル酸塩共重合体（ナトリウム塩）として、例えば、クラストマーＡＰ２０（クラレ社製）が挙げられる。
また吸水性ポリマーは２種以上を混合して使用してもかまわない。
As the water-absorbing polymer contained in the coating liquid according to the present invention, conventionally known hydrophilic polymers can be used. From the viewpoint of water absorption, film-forming property, strength, etc., for example, polyvinyl alcohols, polyacrylic Acids, polyethylene oxides, water-soluble celluloses, starches, alginic acids, chitins, polysulfonic acids, polyhydroxymethacrylates, polyvinylpyrrolidones, polyNvinylacetamides, polyacrylamides, polyethyleneimines, polyallylamines, Polyvinylamines and the like are preferable, and these copolymers can also be preferably used.
In particular, a polyvinyl alcohol-polyacrylate copolymer is preferable. The polyvinyl alcohol-polyacrylate copolymer has a high water absorption capacity and a high hydrogel strength even at high water absorption. The content of polyacrylate in the polyvinyl alcohol-polyacrylate copolymer is, for example, 1 to 95 mol%, preferably 2 to 70 mol%, more preferably 3 to 60 mol%, and particularly preferably 5 to 50 mol%. Mol%. Examples of polyacrylic acid salts include alkali metal salts such as sodium salt and potassium salt, as well as ammonium salts and organic ammonium salts.
As a commercially available polyvinyl alcohol-polyacrylate copolymer (sodium salt), for example, Crustomer AP20 (manufactured by Kuraray Co., Ltd.) can be mentioned.
Two or more water-absorbing polymers may be mixed and used.
塗布液中の吸水性ポリマーの含有量としては、その種類にもよるが、バインダーとして膜を形成し、二酸化炭素分離層が水分を十分保持できるようにする観点から、０．５質量％以上５０質量％以下であることが好ましく、さらには１質量％以上３０質量％以下であることがより好ましく、さらには２質量％以上１５質量％以下であることが特に好ましい。 The content of the water-absorbing polymer in the coating solution depends on the type, but from the viewpoint of forming a film as a binder and allowing the carbon dioxide separation layer to sufficiently retain moisture, 0.5% by mass or more 50 It is preferably no greater than 1% by mass, more preferably no less than 1% by mass and no greater than 30% by mass, and even more preferably no less than 2% by mass and no greater than 15% by mass.
（二酸化炭素キャリア）
本発明に係る塗布液に含まれる二酸化炭素キャリアは、二酸化炭素と親和性を有し、かつ水溶性を示すものであればよく、公知のものを用いることができる。この場合の二酸化炭素キャリアは、二酸化炭素と親和性を有する物質であり、塩基性を示す各種の水溶性の無機及び有機物質が用いられる。例えば、アルカリ金属炭酸塩及び／又はアルカリ金属重炭酸塩及び／又はアルカリ金属水酸化物、アルカリ金属炭酸塩及び／又はアルカリ金属重炭酸塩及び／又はアルカリ金属水酸化物を含む水溶液にアルカリ金属イオンと錯体を形成する多座配位子を添加した水溶液、アンモニア、アンモニウム塩、各種直鎖状、及び環状のアミン、アミン塩、アンモニウム塩等が挙げられる。またこれら水溶性誘導体も好ましく用いることができる。
分離層中に長期間保持できるキャリアが有用であるから、アミノ酸やベタインなどの蒸発しづらいアミン含有化合物が特に好ましい。
(Carbon dioxide carrier)
The carbon dioxide carrier contained in the coating solution according to the present invention is not particularly limited as long as it has an affinity for carbon dioxide and exhibits water solubility. The carbon dioxide carrier in this case is a substance having an affinity for carbon dioxide, and various water-soluble inorganic and organic substances showing basicity are used. For example, alkali metal ions in an aqueous solution containing alkali metal carbonate and / or alkali metal bicarbonate and / or alkali metal hydroxide, alkali metal carbonate and / or alkali metal bicarbonate and / or alkali metal hydroxide. An aqueous solution to which a polydentate ligand that forms a complex with ammonia, ammonia, ammonium salts, various linear and cyclic amines, amine salts, ammonium salts, and the like are included. These water-soluble derivatives can also be preferably used.
Since a carrier that can be retained in the separation layer for a long period of time is useful, amine-containing compounds that are difficult to evaporate, such as amino acids and betaines, are particularly preferable.
アルカリ金属炭酸塩としては、例えば、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、炭酸ルビジウム、炭酸セシウムを挙げられる。
アルカリ金属重炭酸塩としては、例えば、炭酸水素リチウム、炭酸水素ナトリウム、炭酸水素カリウム、炭酸水素ルビジウム、炭酸水素セシウムを挙げられる。
アルカリ金属水酸化物としては、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化セシウム、水酸化ルビジウムなどが挙げられる。
これらの中でもアルカリ金属炭酸塩が好ましく、溶解度の高いセシウム、ルビジウム、カリウムを含む化合物が好ましい。
アルカノールアミンとしては、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、モノプロパノールアミン、ジプロパノールアミン、トリプロパノールアミン等の水溶性を有する各種のものを挙げることができる。二酸化炭素キャリアは、前記したものに限られるものではなく、二酸化炭素と親和性を有し、かつ水溶性を示すものであればよく、有機酸のアルカリ金属塩等各種のものを用いることができる。
アルカリ金属イオンと錯体を形成する多座配位子としては、従来公知のもの、例えば：１２−クラウン−４、１５−クラウン−５、１８−クラウン−６、ベンゾ−１２−クラウン−４、ベンゾ−１５−クラウン−５、ベンゾ−１８−クラウン−６、ジベンゾ−１２−クラウン−４、ジベンゾ−１５−クラウン−５、ジベンゾ−１８−クラウン−６、ジシクロヘキシル−１２−クラウン−４、ジシクロヘキシル−１５−クラウン−５、ジシクロヘキシル−１８−クラウン−６、ｎ−オクチル−１２−クラウン−４、ｎ−オクチル−１５−クラウン−５、ｎ−オクチル−１８−クラウン−６等の環状ポリエーテル；クリプタンド〔２．１〕、クリプタンド〔２．２〕等の環状ポリエーテルアミン；クリプタンド〔２．２．１〕、クリプタンド〔２．２．２〕、等の双環式ポリエーテルアミンの他、ポルフィリン、フタロシアニン、ポリエチレングリコール、エチレンジアミン四酢酸等を用いることができる。
Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate.
Examples of the alkali metal bicarbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, and cesium hydrogen carbonate.
Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, and rubidium hydroxide.
Among these, alkali metal carbonates are preferable, and compounds containing cesium, rubidium, and potassium having high solubility are preferable.
Examples of the alkanolamine include various water-soluble substances such as monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, and tripropanolamine. The carbon dioxide carrier is not limited to those described above, and any carbon dioxide carrier may be used as long as it has an affinity for carbon dioxide and exhibits water solubility, and various kinds of organic acid alkali metal salts can be used. .
As the polydentate ligand that forms a complex with an alkali metal ion, conventionally known ones such as: 12-crown-4, 15-crown-5, 18-crown-6, benzo-12-crown-4, benzo -15-crown-5, benzo-18-crown-6, dibenzo-12-crown-4, dibenzo-15-crown-5, dibenzo-18-crown-6, dicyclohexyl-12-crown-4, dicyclohexyl-15 -Cyclic polyethers such as crown-5, dicyclohexyl-18-crown-6, n-octyl-12-crown-4, n-octyl-15-crown-5, n-octyl-18-crown-6; 2.1], cyclic polyether amines such as cryptand [2.2]; cryptand [2.2.1], cryptand [2] 2.2], other bicyclic polyether amines etc. can be used porphyrins, phthalocyanines, polyethylene glycol, ethylene diamine tetraacetic acid and the like.
アミノ酸としてはグリシン、アラニン、セリン、プロリン、ヒスチジン、システイン、タウリン、ジアミノプロピオン酸、ホスホセリン、サルコシン、ジメチルグリシン、βアラニン、２−アミノイソ酪酸など天然、非天然に限らず用いることができ、またいくつかのアミノ酸が連なったペプチドでもよい。なお、疎水性のアミノ酸の場合、親水性のゲル膜と相分離を起こして二酸化炭素以外のガスの透過度も上昇するが、親水性のアミノ酸は溶解度が高く、吸水性ポリマー及び多糖類との親和性も高いので特に好ましい。具体的には、アミノ酸の親疎水性を示す指標であるＬｏｇＰ値（Ｐ：オクタノール−水系への分配係数）が、−１．５以下であることが好ましく、−２．０以下がより好ましく、−２．５以下が特に好ましい。ＬｏｇＰ値が−２．５以下のアミノ酸としては、アルギニン、リシン、アスパラギン酸、グルタミン酸、グルタミン、ヒスチジン、プロリン、セリン、トレオニン、グリシン、アラニン、ジアミノプロピオン酸、タウリン等が挙げられる。
なお、アミノ酸のＬｏｇＰ値は、計算化学的手法あるいは経験的方法により見積もられる。計算方法としては、Ｃｒｉｐｐｅｎ’ｓ ｆｒａｇｍｅｎｔａｔｉｏｎ法（Ｊ．Ｃｈｅｍ．Ｉｎｆ．Ｃｏｍｐｕｔ．Ｓｃｉ．，２７，２１（１９８７）．）、Ｖｉｓｗａｎａｄｈａｎ’ｓ ｆｒａｇｍｅｎｔａｔｉｏｎ法（Ｊ．Ｃｈｅｍ．Ｉｎｆ．Ｃｏｍｐｕｔ．Ｓｃｉ．，２９，１６３（１９８９）．）、Ｂｒｏｔｏ’ｓ ｆｒａｇｍｅｎｔａｔｉｏｎ法（Ｅｕｒ．Ｊ．Ｍｅｄ．Ｃｈｅｍ．− Ｃｈｉｍ．Ｔｈｅｏｒ．，１９，７１（１９８４）．）などがあるが、ある化合物のｌｏｇＰの値が測定方法あるいは計算方法により異なる場合には、本発明では、Ｃｒｉｐｐｅｎ’ｓ ｆｒａｇｍｅｎｔａｔｉｏｎ法により判断する。
具体的に好ましいアミノ酸は、アルギニン、リシン、アスパラギン酸、グルタミン酸、グルタミン、ヒスチジン、プロリン、セリン、トレオニン、グリシン、アラニン、ジアミノプロピオン酸、タウリンであり、より好ましくはグリシン、セリン、アラニン、ジアミノプロピオン酸、タウリンであり、特に好ましくはグリシン、セリンである。
アミノ酸の添加量は、多いほうが二酸化炭素の透過速度が上昇するため好ましいが、添加しすぎるとゲル膜が脆くなり二酸化炭素以外のガスの透過度も上昇する観点から、ゲル膜に対して３質量％以上９０質量％以下であることが好ましく、より好ましくは５質量％以上６０質量％以下、特に好ましくは１０質量％以上５０質量％以下である。
As amino acids, glycine, alanine, serine, proline, histidine, cysteine, taurine, diaminopropionic acid, phosphoserine, sarcosine, dimethylglycine, β-alanine, 2-aminoisobutyric acid and the like can be used. A peptide in which such amino acids are linked may be used. In the case of hydrophobic amino acids, phase separation with a hydrophilic gel membrane occurs, and the permeability of gases other than carbon dioxide increases, but hydrophilic amino acids have a high solubility, and have a high solubility between the water-absorbing polymer and polysaccharide. It is particularly preferred because of its high affinity. Specifically, the Log P value (P: octanol-water partition coefficient), which is an index indicating the hydrophilicity / hydrophobicity of amino acids, is preferably −1.5 or less, more preferably −2.0 or less, − 2.5 or less is particularly preferable. Examples of amino acids having a Log P value of −2.5 or less include arginine, lysine, aspartic acid, glutamic acid, glutamine, histidine, proline, serine, threonine, glycine, alanine, diaminopropionic acid, taurine and the like.
In addition, the LogP value of an amino acid is estimated by a computational chemical method or an empirical method. As a calculation method, Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)), Viswanadhan's fragmentation method (J. Chem. Inf. Comput. Sci., 29,). 163 (1989).), Broto's fragmentation method (Eur. J. Med. Chem.-Chim. Theor., 19, 71 (1984).), Etc. In the case of different calculation methods, in the present invention, the determination is made by the Crippen's fragmentation method.
Specific preferred amino acids are arginine, lysine, aspartic acid, glutamic acid, glutamine, histidine, proline, serine, threonine, glycine, alanine, diaminopropionic acid, taurine, more preferably glycine, serine, alanine, diaminopropionic acid. Taurine, particularly preferably glycine and serine.
A larger amount of amino acid is preferred because the permeation rate of carbon dioxide increases, but if added too much, the gel film becomes brittle and the permeability of gases other than carbon dioxide also increases, so that 3 mass relative to the gel film. % To 90% by mass, more preferably 5% to 60% by mass, and particularly preferably 10% to 50% by mass.
また、二酸化炭素キャリアは２種以上を混合して使用してもかまわない。
特にアルカリ金属炭酸塩とアミノ酸を併用することは二酸化炭素透過速度、分離係数の向上の点から好ましい。特に炭酸セシウム、炭酸ルビジウム、及び炭酸カリウムの１種以上に親水性のアミノ酸を添加することが好ましく、特にグリシン及び／又はセリンを用いることが好ましい。二酸化炭素キャリアとして、アルカリ金属炭酸塩のほかにアミノ酸が添加されることで、アミノ酸による二酸化炭素の吸収、放散の経路も形成され、二酸化炭素の透過が促進されると考えられる。
Two or more carbon dioxide carriers may be used as a mixture.
In particular, it is preferable to use an alkali metal carbonate and an amino acid in combination from the viewpoint of improving the carbon dioxide permeation rate and separation factor. In particular, it is preferable to add a hydrophilic amino acid to at least one of cesium carbonate, rubidium carbonate, and potassium carbonate, and it is particularly preferable to use glycine and / or serine. By adding an amino acid in addition to an alkali metal carbonate as a carbon dioxide carrier, it is considered that a path for absorption and emission of carbon dioxide by the amino acid is formed, and the permeation of carbon dioxide is promoted.
二酸化炭素キャリアとして好ましいベタインとしては、カルニチン、トリメチルグリシンが挙げられ、特にトリメチルグリシンが好ましい。 Preferred betaines for the carbon dioxide carrier include carnitine and trimethylglycine, with trimethylglycine being particularly preferred.
塗布液中の二酸化炭素キャリアの含有量としては、その種類にもよるが、塗布前の塩析を防ぐとともに、二酸化炭素の分離機能を確実に発揮させるため、０．３〜３０質量％であることが好ましく、さらに０．５〜２５質量％であることがより好ましく、さらに１〜２０質量％であることが特に好ましい。 The content of the carbon dioxide carrier in the coating liquid is 0.3 to 30% by mass in order to prevent salting out before coating and to surely exhibit the carbon dioxide separation function, depending on the type. It is more preferable, it is more preferable that it is 0.5-25 mass%, and it is especially preferable that it is 1-20 mass% further.
本発明に係る塗布液においては、吸水性ポリマーと二酸化炭素キャリアとの質量比が１：９以上２：３以下で含有する。より好ましくは１：４以上２：３以下、更に好ましくは３：７以上２：３以下の範囲とされる。 In the coating liquid which concerns on this invention, the mass ratio of a water absorbing polymer and a carbon dioxide carrier contains 1: 9 or more and 2: 3 or less. More preferably, it is 1: 4 or more and 2: 3 or less, More preferably, it is the range of 3: 7 or more and 2: 3 or less.
（増粘剤）
吸水性ポリマーと、二酸化炭素キャリアと、水とからなり、吸水性ポリマーと二酸化炭素キャリアとの質量比が１：９以上２：３以下で含有する二酸化炭素分離層形成用塗布液組成物の１５℃以上３５℃以下の温度範囲内における粘度を調整する目的で、該塗布液組成物に、さらに増粘剤を用いてもよい。
本発明に使用しうる増粘剤としては、１５℃以上３５℃以下の温度範囲内において塗布液組成物の粘度を上昇させうる化合物であればいずれのものを用いてもよく、例えば、寒天、カルボキシメチルセルロース、カラギナン、キタンサンガム、グァーガム、ペクチン等の増粘多糖類が好ましく、製膜性、入手の容易性、コストの点から、カルボキシメチルセルロースが好ましい。
本発明に好適に使用しうるカルボキシメチルセルロースは、エーテル化度が０．６以上１．５以下の範囲にあり、１質量％の水溶液としたときのＢ型粘度測定において回転数６０ｒｐｍにおける粘度測定値が１Ｐａ・ｓ以上１０Ｐａ・ｓ以下の範囲にあるものである。このようなカルボキシメチルセルロースを使用すると、少量の含有量で、所望の粘度を示す二酸化炭素分離層形成用塗布液組成物が容易に得られるうえ、塗布液に含まれる溶媒以外の成分の少なくとも一部が塗布液中で溶解できずに析出してしまう恐れも少ない。このようなカルボキシメチルセルロースは市販品から入手することができ、好ましいものには、ダイセルファインケム株式会社製のＣＭＣ２２８０が挙げられる。
(Thickener)
15 of the coating liquid composition for forming a carbon dioxide separation layer, comprising a water-absorbing polymer, a carbon dioxide carrier, and water, and having a mass ratio of the water-absorbing polymer and the carbon dioxide carrier of 1: 9 or more and 2: 3 or less. A thickener may be further used in the coating liquid composition for the purpose of adjusting the viscosity within a temperature range of from ° C to 35 ° C.
As the thickener that can be used in the present invention, any compound that can increase the viscosity of the coating solution composition within a temperature range of 15 ° C. or more and 35 ° C. or less may be used. Thickening polysaccharides such as carboxymethylcellulose, carrageenan, chitansan gum, guar gum, pectin and the like are preferred, and carboxymethylcellulose is preferred from the viewpoint of film forming property, availability and cost.
Carboxymethylcellulose that can be suitably used in the present invention has a degree of etherification in the range of 0.6 to 1.5, and a viscosity measurement value at a rotation speed of 60 rpm in B-type viscosity measurement when a 1% by mass aqueous solution is obtained. Is in the range of 1 Pa · s to 10 Pa · s. When such a carboxymethyl cellulose is used, a coating solution composition for forming a carbon dioxide separation layer having a desired viscosity can be easily obtained with a small amount of content, and at least a part of components other than the solvent contained in the coating solution. Is less likely to precipitate without being dissolved in the coating solution. Such carboxymethylcellulose can be obtained from commercial products, and preferred examples include CMC2280 manufactured by Daicel Finechem Co., Ltd.
調製された二酸化炭素分離層形成用塗布液が、１５℃以上３５℃以下の範囲内のいずれかの温度において、Ｂ型粘度測定において回転数６０ｒｐｍにおける粘度測定値が０．５Ｐａ・ｓ以上１０Ｐａ・ｓ以下の範囲内のいずれかの粘度を示すか否かは、次のようにして確認することができる。
即ち、調製された二酸化炭素分離層形成用塗布液をステンレス製の容器（例えば、内径４ｃｍ、高さ１２ｃｍ）内に投入し、粘度計円筒（ローター）が十分塗布液に浸るようにする。上記ステンレス容器を温度調整の可能な水槽に浸漬し、投入された塗布液の温度を１５℃から３５℃の範囲に調整しつつ、Ｂ型粘度計（テックジャム社製、ＢＬ２ １〜１００，０００ｍＰａ・ｓ ／ ＫＮ３３１２４８１）を動作させ、回転数６０ｒｐｍにおける各温度ごとの値を読み取り、ＪＩＳ Ｚ８８０３に準じて塗布液の粘度を測定する。
The prepared coating liquid for forming a carbon dioxide separation layer has a viscosity measurement value of 0.5 Pa · s or more and 10 Pa · 10 at a rotation speed of 60 rpm in B-type viscosity measurement at any temperature within a range of 15 ° C. or more and 35 ° C. or less. Whether or not any viscosity in the range of s or less is exhibited can be confirmed as follows.
That is, the prepared coating liquid for forming a carbon dioxide separation layer is put into a stainless steel container (for example, an inner diameter of 4 cm and a height of 12 cm) so that the viscometer cylinder (rotor) is sufficiently immersed in the coating liquid. The stainless steel container is immersed in a temperature-adjustable water tank, and while adjusting the temperature of the applied coating solution in the range of 15 ° C. to 35 ° C., a B-type viscometer (manufactured by Techjam, BL2 1 to 100,000 mPa S / KN3312481) is operated, the value for each temperature at a rotational speed of 60 rpm is read, and the viscosity of the coating solution is measured according to JIS Z8803.
組成物（塗布液）中の増粘剤の含有量は、１５℃以上３５℃以下の範囲内のいずれかの温度において、Ｂ型粘度測定において回転数６０ｒｐｍにおける粘度測定値が０．５Ｐａ・ｓ以上１０Ｐａ・ｓ以下の範囲内のいずれかの粘度を示すように調整することが可能であれば、できるだけ少ないほうが好ましい。一般的な指標としては、１０質量％以下が好ましく、０．１質量％以上５質量％以下がより好ましく、さらには０．１質量％以上２質量％以下が最も好ましい。 The content of the thickener in the composition (coating liquid) is 0.5 Pa · s at a rotation speed of 60 rpm in the B-type viscosity measurement at any temperature within the range of 15 ° C. to 35 ° C. If it can be adjusted to show any viscosity within the range of 10 Pa · s or less, it is preferably as small as possible. As a general index, it is preferably 10% by mass or less, more preferably 0.1% by mass or more and 5% by mass or less, and most preferably 0.1% by mass or more and 2% by mass or less.
（架橋剤）
吸水性ポリマーの架橋は熱架橋、紫外線架橋、電子線架橋、放射線架橋など従来公知の手法が実施することができる。本発明の組成物は、架橋剤を含むことが好ましい。特に、ポリビニルアルコール−ポリアクリル酸塩共重合体と反応し熱架橋し得る官能基を２以上有する架橋剤を含むことが好ましく、多価グリシジルエーテル、多価アルコール、多価イソシアネート、多価アジリジン、ハロエポキシ化合物、多価アルデヒド、多価アミン等が挙げられる。
ここで、上記多価グリシジルエーテルとしては、例えば、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセロールポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ソルビトールポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、プロピレングリコールグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル等が挙げられる。
また、上記多価アルコールとしては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ポリエチレングリコール、グリセリン、ポリグリセリン、プロピレングリコール、ジエタノールアミン、トリエタノールアミン、ポリオキシプロピル、オキシエチエンオキシプロピレンブロック共重合体、ペンタエリスリトール、ソビトール等が挙げられる。
また、上記多価イソシアネートとしては、例えば、２，４−トルイレンジイソシアネート、ヘキサメチレンジイソシアネート等が挙げられる。また、上記多価アジリジンとしては、例えば、２，２−ビスヒドロキシメチルブタノール−トリス〔３−（１−アシリジニル）プロピオネート〕、１，６−ヘキサメチレンジエチレンウレア、ジフェニルメタン−ビス−４，４’−Ｎ，Ｎ’−ジエチレンウレア等が挙げられる。
また、上記ハロエポキシ化合物としては、例えば、エピクロルヒドリン、α−メチルクロルヒドリン等が挙げられる。
また、上記多価アルデヒドとしては、例えば、グルタルアルデヒド、グリオキサール等が挙げられる。
また、上記多価アミンとしては、例えば、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、ポリエチレンイミン等が挙げられる。
上記架橋剤のうち、ポリビニルアルコール−ポリアクリル酸塩共重合体の熱架橋剤とし
てはグルタルアルデヒドが特に好ましい。
(Crosslinking agent)
Crosslinking of the water-absorbing polymer can be carried out by a conventionally known method such as thermal crosslinking, ultraviolet crosslinking, electron beam crosslinking, or radiation crosslinking. It is preferable that the composition of this invention contains a crosslinking agent. In particular, it preferably contains a cross-linking agent having two or more functional groups capable of reacting with a polyvinyl alcohol-polyacrylate copolymer and thermally cross-linking, polyvalent glycidyl ether, polyhydric alcohol, polyvalent isocyanate, polyvalent aziridine, Examples include haloepoxy compounds, polyhydric aldehydes, polyhydric amines, and the like.
Here, as the polyvalent glycidyl ether, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol poly Examples thereof include glycidyl ether, propylene glycol glycidyl ether, and polypropylene glycol diglycidyl ether.
Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, polyglycerin, propylene glycol, diethanolamine, triethanolamine, polyoxypropyl, and oxyethyleneoxypropylene. Examples include block copolymers, pentaerythritol, and sobitol.
Examples of the polyvalent isocyanate include 2,4-toluylene diisocyanate and hexamethylene diisocyanate. Examples of the polyvalent aziridine include 2,2-bishydroxymethylbutanol-tris [3- (1-acylidinyl) propionate], 1,6-hexamethylenediethyleneurea, diphenylmethane-bis-4,4′-. N, N′-diethylene urea and the like can be mentioned.
Examples of the haloepoxy compound include epichlorohydrin and α-methylchlorohydrin.
Examples of the polyvalent aldehyde include glutaraldehyde and glyoxal.
Examples of the polyvalent amine include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and polyethyleneimine.
Of the crosslinking agents, glutaraldehyde is particularly preferable as the thermal crosslinking agent for the polyvinyl alcohol-polyacrylate copolymer.
（その他の成分）
本発明に係る塗布液は、塗布性やガス分離特性に悪影響しない範囲で、吸水性ポリマー、二酸化炭素キャリア、及び増粘剤以外の、１以上の他の成分（添加剤）を含むことができる。
他の成分の例としては、前記架橋剤のほか、例えば、界面活性剤、触媒、保湿（吸水）剤、補助溶剤、膜強度調整剤、欠陥検出剤が挙げられる。
(Other ingredients)
The coating liquid according to the present invention can contain one or more other components (additives) other than the water-absorbing polymer, the carbon dioxide carrier, and the thickener as long as the coating properties and gas separation characteristics are not adversely affected. .
Examples of other components include, in addition to the crosslinking agent, a surfactant, a catalyst, a moisturizing (water absorbing) agent, an auxiliary solvent, a film strength adjusting agent, and a defect detecting agent.
本発明に係る塗布液の調製は、前記した吸水性ポリマー及び、二酸化炭素キャリア、さらに必要に応じて増粘剤、架橋剤を含む他の添加剤を、それぞれ適量で水（常温水又は加温水）に添加して十分攪拌して行い、必要に応じて攪拌しながら加熱することで溶解を促進させる。なお、吸水性ポリマー、及び二酸化炭素キャリアを別々に水に添加してもよいし、予め混ぜ合わせたものを添加してもよい。例えば、増粘剤を含有させる場合には、増粘剤を水に加えて溶解させた後、これに吸水性ポリマー、二酸化炭素キャリアを徐々に加えて攪拌することで吸水性ポリマーや増粘剤の析出（塩析）を効果的に防ぐことができる。 The coating liquid according to the present invention is prepared by adding water (normal temperature water or warm water) in an appropriate amount to each of the above-described water-absorbing polymer, carbon dioxide carrier, and, if necessary, other additives including a thickener and a crosslinking agent. ) And stirring sufficiently, and if necessary, heating is performed with stirring to promote dissolution. In addition, you may add a water absorbing polymer and a carbon dioxide carrier separately to water, and you may add what was mixed beforehand. For example, in the case of containing a thickener, after adding the thickener to water and dissolving it, the water-absorbent polymer and the carbon dioxide carrier are gradually added to this and stirred to absorb the water-absorbent polymer and the thickener. Precipitation (salting out) can be effectively prevented.
−塗布工程−
二酸化炭素分離層形成用塗布液は、送り出しロール１０から帯状の支持体１２を送り出して、塗布部２０に搬送し、上記塗布液を１５℃以上３５℃以下の温度、かつＢ型粘度測定において回転数６０ｒｐｍにおける粘度測定値が０．５Ｐａ・ｓ以上１０Ｐａ・ｓ以下の粘度で支持体１２上に塗布して上記塗布液の液膜を支持体１２上に設ける。
塗布工程における塗布液の温度、及び粘度の少なくとも一方が上記の範囲を外れると、上記塗布液の液膜に沈降が発生するか、又は塗布装置のコーター２０の塗布液３０が流れ出してしまったり、吸水性ポリマーが析出（塩析）して支持体への塗布が困難となったり、膜厚のバラツキが大きくなるおそれがある。
-Application process-
The coating liquid for forming a carbon dioxide separation layer is fed out from the feed roll 10 to the belt-like support 12 and conveyed to the coating unit 20, and the coating liquid is rotated at a temperature of 15 ° C. or more and 35 ° C. or less and B-type viscosity measurement. A viscosity measured value at several 60 rpm is applied on the support 12 with a viscosity of 0.5 Pa · s or more and 10 Pa · s or less, and a liquid film of the coating solution is provided on the support 12.
When at least one of the temperature and viscosity of the coating liquid in the coating process is out of the above range, sedimentation occurs in the liquid film of the coating liquid, or the coating liquid 30 of the coater 20 of the coating apparatus flows out. There is a possibility that the water-absorbing polymer is precipitated (salting out) and it becomes difficult to apply to the support or the film thickness varies greatly.
支持体１２は、二酸化炭素分離層１４を支持するものであり、二酸化炭素透過性を有し、本発明に係る二酸化炭素分離層形成用組成物（塗布液）を塗布して二酸化炭素分離層１４を形成することができ、さらにこの膜を支持することができるものであれば特に限定されない。
支持体１２の材質としては、紙、上質紙、コート紙、キャストコート紙、合成紙、さらに、セルロース、ポリエステル、ポリオレフィン、ポリアミド、ポリイミド、ポリスルフォンアラミド、ポリカーボネート、金属、ガラス、セラミックスなどが好適に使用できる。より具体的にはポリプロピレン、ポリエチレン、ポリスチレン、ポリフェニルサルファイド、ポリエーテルイミド、ポリエーテルエーテルケトン、ポリスルフォン、ポリエーテルサルフォン、ポリエチレンテレフタレート、ポリテトラフルオロエチレン、ポリフッ化ビニリデンなどの樹脂材料が好適に使用できる。これら中でもポリオレフィン及びそのフッ化物が、経時安定性の観点から特に好ましく使用できる。
支持体１２の形態としては織布、不織布、多孔質膜等を採用することができる。一般的には自己支持性が高く、空隙率が高い支持体が好適に使用できる。ポリスルフォン、セルロースのメンブレンフィルター膜、ポリアミド、ポリイミドの界面重合薄膜、ポリテトラフルオロエチレン、高分子量ポリエチレンの延伸多孔膜は空隙率が高く、二酸化炭素の拡散阻害が小さく、強度、製造適性などの観点から好ましい。この中でも特にポリテトラフルオロエチレン（ＰＴＦＥ）の延伸膜が好ましい。
これらの支持体を単独に用いる事も出来るが、補強用の支持体と一体化した複合膜も好適に使用できる。
The support 12 supports the carbon dioxide separation layer 14 and has carbon dioxide permeability. The carbon dioxide separation layer 14 is formed by applying the carbon dioxide separation layer forming composition (coating liquid) according to the present invention. There is no particular limitation as long as the film can be formed and the film can be supported.
As the material of the support 12, paper, fine paper, coated paper, cast coated paper, synthetic paper, and further, cellulose, polyester, polyolefin, polyamide, polyimide, polysulfone aramid, polycarbonate, metal, glass, ceramics and the like are preferable. Can be used. More specifically, resin materials such as polypropylene, polyethylene, polystyrene, polyphenyl sulfide, polyether imide, polyether ether ketone, polysulfone, polyether sulfone, polyethylene terephthalate, polytetrafluoroethylene, and polyvinylidene fluoride are preferable. Can be used. Among these, polyolefins and fluorides thereof can be particularly preferably used from the viewpoint of stability over time.
As the form of the support 12, a woven fabric, a non-woven fabric, a porous membrane or the like can be adopted. In general, a support having a high self-supporting property and a high porosity can be suitably used. Polysulfone, cellulose membrane filter membrane, polyamide, polyimide interfacially polymerized thin film, polytetrafluoroethylene, high-molecular-weight polyethylene stretched porous membrane has high porosity, low carbon dioxide diffusion inhibition, strength, manufacturing suitability, etc. To preferred. Among these, a stretched film of polytetrafluoroethylene (PTFE) is particularly preferable.
These supports can be used alone, but a composite membrane integrated with a support for reinforcement can also be suitably used.
支持体１２は厚すぎるとガス透過性が低下し、薄すぎると強度に難がある。そこで支持体の厚さは３０〜５００μｍが好ましく、さらには５０〜３００μｍがより好ましく、さらには５０〜２００μｍが特に好ましい。また、Ｒｏｌｌ−ｔｏ−Ｒｏｌｌ製造において支持体の歪みや断裂が発生することのないよう、例えば支持体のヤング率は０．４ＧＰａ以上であることが好ましい。 If the support 12 is too thick, the gas permeability decreases, and if it is too thin, the strength is difficult. Therefore, the thickness of the support is preferably 30 to 500 μm, more preferably 50 to 300 μm, and even more preferably 50 to 200 μm. Further, for example, the Young's modulus of the support is preferably 0.4 GPa or more so that the support is not distorted or broken in the production of Roll-to-Roll.
支持体１２の搬送速度は、支持体１２の種類や組成物（塗布液）の粘度などにもよるが、支持体の搬送速度が高すぎると塗布工程における塗布膜の膜厚均一性が低下するおそれがあり、遅過ぎると生産性が低下するほか、冷却工程の前に組成物の粘度が上昇して塗布膜の均一性が低下するおそれもある。支持体１２の搬送速度は、上記の点も考慮して支持体１２の種類や組成物の粘度などに応じて決めればよいが、１ｍ／分以上が好ましく、さらには１０ｍ／分以上２００ｍ／分以下がより好ましく、さらには２０ｍ／分以上２００ｍ／分以下が特に好ましい。 The transport speed of the support 12 depends on the type of the support 12 and the viscosity of the composition (coating liquid), but if the transport speed of the support is too high, the film thickness uniformity of the coating film in the coating process is reduced. If it is too slow, the productivity may be lowered, and the viscosity of the composition may be increased before the cooling step to reduce the uniformity of the coating film. The conveyance speed of the support 12 may be determined according to the type of the support 12 and the viscosity of the composition in consideration of the above points, but is preferably 1 m / min or more, and more preferably 10 m / min or more and 200 m / min. The following is more preferable, and 20 m / min or more and 200 m / min or less is particularly preferable.
本発明に係る塗布液を支持体に塗布するコーターとしては、特に、ロールコーター又はブレードコーターが好ましい。
ロールコーターは、単数又は複数のロールを組み合わせて、支持体に最も近い位置に配置されているロール（アプリケターロール）表面に保持される塗布液の量を制御し、（アプリケターロール）上の塗布液の一定割合量を支持体表面に転移させるコーターである。好適なロールコーターは、ダイレクトグラビアコーター、オフセットグラビアコーター、一本ロールキスコーター、３本リバースロールコーター、正回転ロールコーターなどが含まれるが、Ｂ型粘度測定において回転数６０ｒｐｍにおける粘度測定値が０．３Ｐａ・ｓ以上２０Ｐａ・ｓ以下の中粘度から高粘度な塗布液の塗布に適した３本リバースロールコーターが好ましい。
ブレードコーターは、支持体上に過剰量の塗布液を塗布した後、支持体上の過剰分の塗布液をブレードで掻き落とすコーターである。
As the coater for applying the coating solution according to the present invention to the support, a roll coater or a blade coater is particularly preferable.
A roll coater controls the amount of coating liquid held on the surface of a roll (applicator roll) arranged in the position closest to the support by combining one or a plurality of rolls on the (applicator roll). It is a coater that transfers a certain proportion of the coating solution to the surface of the support. Suitable roll coaters include a direct gravure coater, an offset gravure coater, a single roll kiss coater, a three reverse roll coater, a forward rotation roll coater, etc., but the viscosity measurement value at a rotational speed of 60 rpm is 0 in B-type viscosity measurement. A three reverse roll coater suitable for application of a coating solution having a medium viscosity to a high viscosity of 3 Pa · s or more and 20 Pa · s or less is preferable.
The blade coater is a coater that, after applying an excessive amount of coating solution on a support, scrapes off the excess amount of the coating solution on the support with a blade.
（乾燥工程）
本発明に係る乾燥工程においては、前記塗布工程において支持体上に形成された二酸化炭素分離層形成用塗布液の塗膜に含まれる溶媒としての水の少なくとも一部が除去される。このような乾燥工程は、塗膜が保持された支持体を加熱するか、塗膜に乾燥風を吹き付けるか、又はこれらの両者により行われる。
支持体上の塗布液の塗膜は、１５℃以上３５℃以下の範囲内のいずれかの温度で、Ｂ型粘度測定において回転数６０ｒｐｍにおける粘度測定値が０．５Ｐａ・ｓ以上１０Ｐａ・ｓ以下の範囲内のいずれかの粘度を有するので、乾燥用の風が当たっても液膜の厚みむらが生ずることなく、溶媒の少なくとも一部が除去される。
乾燥風の風速は、支持体上の塗布液の液膜との早退速度が、例えば１ｍ／分以上８０ｍ／分以下の範囲が好ましく、さらには２ｍ／分以上７０ｍ／分以下の範囲がより好ましく、さらには３ｍ／分以上４０ｍ／分以下の範囲が特に好ましい。
風の温度は、支持体の変形などが生じず、かつ、塗布液の液膜を迅速に乾燥させることができるように膜面温度１５℃以上８０℃以下の範囲が好ましく、さらには３０℃以上７０℃以下がより好ましく、さらには４０℃以上６０℃以下が特に好ましい。
(Drying process)
In the drying step according to the present invention, at least a part of water as a solvent contained in the coating film of the carbon dioxide separation layer forming coating solution formed on the support in the coating step is removed. Such a drying step is performed by heating the support on which the coating film is held, blowing dry air on the coating film, or both.
The coating film of the coating solution on the support has a viscosity measurement value of 0.5 Pa · s or more and 10 Pa · s or less at a rotation speed of 60 rpm in B-type viscosity measurement at any temperature within the range of 15 ° C. or more and 35 ° C. or less. Thus, at least a part of the solvent is removed without causing unevenness of the thickness of the liquid film even when the drying wind hits it.
The wind speed of the drying air is preferably such that the rapid retreat speed of the coating liquid film on the support is, for example, in the range of 1 m / min to 80 m / min, and more preferably in the range of 2 m / min to 70 m / min. Furthermore, the range of 3 m / min or more and 40 m / min or less is particularly preferable.
The temperature of the wind is preferably in the range of a film surface temperature of 15 ° C. or more and 80 ° C. or less, and more preferably 30 ° C. or more so that deformation of the support does not occur and the liquid film of the coating solution can be dried quickly. 70 ° C. or lower is more preferable, and 40 ° C. or higher and 60 ° C. or lower is particularly preferable.
（架橋工程）
架橋工程は乾燥工程と同時に行ってもよいし、別々に行ってもよい。また、架橋手法は公知の架橋手法を用いることができる。例えば、上記の乾燥工程後に二酸化炭素分離層を赤外線ヒータなどの加熱手段によって加熱して架橋させてもよいし、乾燥工程の温風によって乾燥とともに架橋させてもよい。熱架橋は例えば１００〜１５０℃程度に加熱することによって行うことができる。塗布工程において、支持体上に形成された塗布液の液膜にＵＶ又は電子線架橋を施し、その後乾燥させてもかまわない。なお、乾燥工程により得られた乾燥膜を巻取りロール５０に巻き取った後に架橋させる、いわゆるバルク処理により架橋させてもよい。
(Crosslinking process)
The crosslinking step may be performed simultaneously with the drying step or may be performed separately. Moreover, a well-known crosslinking method can be used for the crosslinking method. For example, the carbon dioxide separation layer may be heated and cross-linked by a heating means such as an infrared heater after the drying step, or may be cross-linked with drying by warm air in the drying step. Thermal crosslinking can be performed by heating to about 100 to 150 ° C., for example. In the coating step, UV or electron beam crosslinking may be applied to the liquid film of the coating solution formed on the support and then dried. In addition, you may bridge | crosslink by what is called bulk processing which is made to bridge | crosslink after winding the dry film | membrane obtained by the drying process on the winding roll 50. FIG.
上記工程を経て本発明に係る二酸化炭素分離用複合体が得られる。
得られた二酸化炭素分離用複合体の二酸化炭素分離層は、吸水性ポリマーと、二酸化炭素キャリアとを含み、場合により、更に増粘剤を含む。二酸化炭素分離層での各成分の組成比は、塗布液の配合比が反映される。
乾燥状態での二酸化炭素分離層中の各成分の含有量は以下の範囲であることが好ましい。吸水性ポリマーは、５質量％以上９０質量％以下が好ましく、１０質量％以上８５質量％以下がより好ましく、１５質量％以上８０質量％以下が特に好ましい。二酸化炭素キャリアは、５質量％以上９０質量％以下が好ましく、１０質量％以上８５質量％以下が特に好ましく、２０質量％以上８０質量％以下がさらに好ましい。場合により含まれる増粘剤は、０．１質量％以上１０質量％以下が好ましく、０．１質量％以上５質量％以下がより好ましく、０．１質量％以上２質量％以下が特に好ましい。
例えば二酸化炭素キャリアとしてセシウムを含む化合物を用いる場合は、二酸化炭素の分離特性を向上させる観点から、乾燥状態での二酸化炭素分離層中の含有量は５０質量％以上であることが好ましく、５５質量％以上であることがより好ましく、６０質量％以上であることが特に好ましい。また、二酸化炭素キャリアとして、例えばカリウムを含む化合物を用いる場合は、乾燥状態での二酸化炭素分離層中の含有量は１０質量％以上であることが好ましく、１５質量％以上で用いることがより好ましく、２０質量％以上であることが特に好ましい。
また、二酸化炭素キャリアとして、例えばセシウム又はカリウムを含む化合物とアミノ酸を用いる場合は、アミノ酸は、乾燥状態での膜に対して１０質量％以上であることが好ましく、１５質量％以上で用いることがより好ましく、２０質量％以上であることが特に好ましい。
なお、二酸化炭素分離層を形成した後、必要に応じて、二酸化炭素キャリアの溶出を防ぐために二酸化炭素分離層上にキャリア溶出防止層を設けてもよい。キャリア溶出防止層は二酸化炭素、水蒸気などの気体は透過するが水などは透過しない性質を持つことが好ましく、疎水性の多孔質膜であることが好ましい。
この様な性質の膜を膜面上に塗布しても良いし、別に作成した膜をラミネートしても良い。
The composite for carbon dioxide separation which concerns on this invention is obtained through the said process.
The carbon dioxide separation layer of the obtained composite for carbon dioxide separation contains a water-absorbing polymer and a carbon dioxide carrier, and optionally further contains a thickener. The composition ratio of each component in the carbon dioxide separation layer reflects the blending ratio of the coating solution.
The content of each component in the carbon dioxide separation layer in the dry state is preferably in the following range. 5 mass% or more and 90 mass% or less are preferable, as for a water absorbing polymer, 10 mass% or more and 85 mass% or less are more preferable, and 15 mass% or more and 80 mass% or less are especially preferable. The carbon dioxide carrier is preferably 5% by mass to 90% by mass, particularly preferably 10% by mass to 85% by mass, and further preferably 20% by mass to 80% by mass. The thickener contained in some cases is preferably from 0.1% by weight to 10% by weight, more preferably from 0.1% by weight to 5% by weight, and particularly preferably from 0.1% by weight to 2% by weight.
For example, when a compound containing cesium is used as the carbon dioxide carrier, the content in the carbon dioxide separation layer in the dry state is preferably 50% by mass or more from the viewpoint of improving the carbon dioxide separation characteristics, and 55% by mass. % Or more is more preferable, and 60% by mass or more is particularly preferable. Further, when a compound containing potassium, for example, is used as the carbon dioxide carrier, the content in the carbon dioxide separation layer in a dry state is preferably 10% by mass or more, and more preferably 15% by mass or more. 20% by mass or more is particularly preferable.
In addition, when a compound containing cesium or potassium and an amino acid are used as the carbon dioxide carrier, for example, the amino acid is preferably 10% by mass or more, and 15% by mass or more based on the film in a dry state. More preferably, it is particularly preferably 20% by mass or more.
In addition, after forming a carbon dioxide separation layer, you may provide a carrier elution prevention layer on a carbon dioxide separation layer in order to prevent the elution of a carbon dioxide carrier as needed. The carrier elution prevention layer preferably has a property of allowing gas such as carbon dioxide and water vapor to pass therethrough but not passing water or the like, and is preferably a hydrophobic porous film.
A film having such properties may be applied on the film surface, or a film prepared separately may be laminated.
（二酸化炭素分離モジュール）
図２は、本発明に係る二酸化炭素分離用複合体をスパイラル状に組み込んだ二酸化炭素分離モジュール２００の一実施形態を示す、一部切り欠きを設けてなる概略構成図であり、図３は、図２に示す二酸化炭素分離モジュールの要部の断面を示す斜視図である。
(CO2 separation module)
FIG. 2 is a schematic configuration diagram showing one embodiment of a carbon dioxide separation module 200 in which the composite for carbon dioxide separation according to the present invention is incorporated in a spiral shape. It is a perspective view which shows the cross section of the principal part of the carbon dioxide separation module shown in FIG.
図２に示すように、二酸化炭素分離モジュール２００は、その基本構造として、透過ガス集合管８２の周りに、二酸化炭素分離用複合体８４を単数あるいは複数が巻き付けられた状態で二酸化炭素分離用複合体５４の最外周が被覆層５８で覆われ、これらユニットの両端にそれぞれテレスコープ防止板８８Ａ、８８Ｂが取り付けられて構成される。
このような構成の二酸化炭素分離モジュール２００は、その一端部８０Ａ側から二酸化炭素分離用複合体５４に二酸化炭素を含む混合ガス９０が供給されると、後述する二酸化炭素分離用積層体８４の構成により、混合ガス９０を二酸化炭素９２と残余のガス９４に分離して他端部８０Ｂ側に別々に排出するものである。
As shown in FIG. 2, the carbon dioxide separation module 200 has, as its basic structure, a carbon dioxide separation composite with one or more carbon dioxide separation complexes 84 wound around a permeate gas collecting pipe 82. The outermost periphery of the body 54 is covered with a coating layer 58, and telescope prevention plates 88A and 88B are attached to both ends of these units, respectively.
When the mixed gas 90 containing carbon dioxide is supplied to the carbon dioxide separation composite 54 from the one end 80A side of the carbon dioxide separation module 200 having such a configuration, the structure of the carbon dioxide separation laminate 84 described later is provided. Thus, the mixed gas 90 is separated into carbon dioxide 92 and the remaining gas 94 and separately discharged to the other end 80B side.
透過ガス集合管８２は、その管壁に複数の貫通孔８２Ａが形成された円筒状の管である。透過ガス集合管８２の管一端部側（一端部８０Ａ側）は閉じられており、管他端部側（他端部８０Ｂ側）は開口し二酸化炭素分離用複合体５４を透過して貫通孔８２Ａから集合した二酸化炭素等の二酸化炭素９２が排出される排出口９６となっている。 The permeate gas collecting pipe 82 is a cylindrical pipe having a plurality of through holes 82A formed in the pipe wall. One end side (one end 80A side) of the permeate gas collecting pipe 82 is closed, and the other end side (the other end 80B side) of the permeate gas collecting pipe 82 is opened and passes through the carbon dioxide separation complex 54 and passes through. A discharge port 96 from which carbon dioxide 92 such as carbon dioxide gathered from 82A is discharged.
被覆層５８は、二酸化炭素分離モジュール２００内を通過する混合ガス９０を遮断しうる遮断材料で形成されている。この遮断材料は、さらに耐熱湿性を有していることが好ましい。なお、本実施形態において特に他の言及がない限り「耐熱湿性」のうち「耐熱性」とは、８０℃以上の耐熱性を有していることを意味する。具体的に、８０℃以上の耐熱性とは、８０℃以上の温度条件下に２時間保存した後も保存前の形態が維持され、熱収縮或いは熱溶融による目視で確認しうるカールが生じないことを意味する。また、本実施形態において「耐熱湿性」のうち「耐湿性」とは、４０℃の温度かつ８０％ＲＨの条件下に２時間保存した後も保存前の形態が維持され、熱収縮或いは熱溶融による目視で確認しうるカールが生じないことを意味する。
テレスコープ防止板８８Ａ、８８Ｂは、それぞれ耐熱湿性の材料で形成されていることが好ましい。
The coating layer 58 is formed of a blocking material that can block the mixed gas 90 passing through the carbon dioxide separation module 200. This barrier material preferably further has heat and humidity resistance. In the present embodiment, unless otherwise specified, “heat resistance” in “heat resistance and humidity” means that the film has heat resistance of 80 ° C. or higher. Specifically, the heat resistance of 80 ° C. or higher means that the shape before storage is maintained even after being stored for 2 hours under a temperature condition of 80 ° C. or higher, and there is no curling that can be visually confirmed by heat shrinkage or heat melting. Means that. Further, in the present embodiment, “moisture resistance” of “heat resistance and humidity resistance” means that the form before storage is maintained even after storage for 2 hours at a temperature of 40 ° C. and 80% RH, and heat shrinkage or heat melting. This means that no curl that can be visually confirmed by is generated.
The telescope prevention plates 88A and 88B are each preferably formed of a heat and moisture resistant material.
本発明に係る二酸化炭素分離用複合体５４は、透過ガス集合管８２の回りに、二酸化炭素分離用複合体８４とこれに隣接して設けられた流路材５６とからなる積層体８４を単数あるいは複数を巻き回して構成される。二酸化炭素分離用複合体５４と流路材５６とにより形成された二酸化炭素を分離する領域の周辺は、モジュール内を通過する気体などの流体を遮断しうる材料で形成された被覆層５８で被覆されている。
ここで、二酸化炭素分離用複合体５４は、支持体上に二酸化炭素分離層を有する複合体である、前記本発明の二酸化炭素分離用複合体である。
二酸化炭素分離積層体８４に使用される流路材５６は、供給される流体の乱流（膜面の表面更新）を促進して供給流体中の二酸化炭素の膜透過速度を増加させる機能と、供給側の圧損をできるだけ小さくする機能とが備わっていることが好ましい。
流路材５６としては、スペーサーとしての機能を有し、且つ、流体に乱流を生じさせることが好ましいことから、ネット状の部材が好ましく用いられる。ネットの形状により流体の流路が変わることから、ネットの単位格子の形状は、目的に応じて、例えば、菱形、平行四辺形などの形状から選択して用いられる。流路材５６の材質としては、何ら限定されるものではないが、１００℃以上の温度条件下で使用されることから、耐熱性の材料が好ましい。具体的には、紙、上質紙、コート紙、キャストコート紙、合成紙、セルロース、ポリエステル、ポリオレフィン、ポリアミド、ポリイミド、ポリスルホン、アラミド、ポリカーボネートなどの樹脂材料、金属、ガラス、セラミックスなどの無機材料等が挙げられる。樹脂材料としては、ポリエチレン、ポリスチレン、ポリエチレンテレフタレート、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリエーテルスルホン（ＰＥＳ）、ポリフェニレンサルファイド（ＰＰＳ）、ポリスルホン（ＰＳＦ）、ポリプロピレン（ＰＰ）、ポリイミド、ポリエーテルイミド、ポリエーテルエーテルケトン及びポリフッ化ビニリデン等が好適なものとして挙げられる。
The carbon dioxide separation complex 54 according to the present invention includes a single layered body 84 including a carbon dioxide separation complex 84 and a flow path member 56 provided adjacent thereto around the permeate gas collecting pipe 82. Alternatively, it is configured by winding a plurality. The area around the carbon dioxide separation region formed by the carbon dioxide separation complex 54 and the flow path material 56 is covered with a coating layer 58 formed of a material capable of blocking a fluid such as a gas passing through the module. Has been.
Here, the carbon dioxide separation complex 54 is the carbon dioxide separation complex of the present invention, which is a complex having a carbon dioxide separation layer on a support.
The channel material 56 used for the carbon dioxide separation laminate 84 promotes turbulent flow of the supplied fluid (renewing the surface of the membrane surface) and increases the membrane permeation rate of carbon dioxide in the supplied fluid; It is preferable to have a function of minimizing the pressure loss on the supply side.
As the flow path member 56, a net-like member is preferably used because it has a function as a spacer and preferably causes turbulence in the fluid. Since the flow path of the fluid changes depending on the shape of the net, the shape of the unit cell of the net is selected from shapes such as a rhombus and a parallelogram according to the purpose. The material of the flow path material 56 is not limited at all, but a heat resistant material is preferable because it is used under a temperature condition of 100 ° C. or higher. Specifically, paper, high-quality paper, coated paper, cast coated paper, synthetic paper, cellulose, polyester, polyolefin, polyamide, polyimide, polysulfone, aramid, polycarbonate and other inorganic materials, metals, glass, ceramics and other inorganic materials, etc. Is mentioned. The resin materials include polyethylene, polystyrene, polyethylene terephthalate, polytetrafluoroethylene (PTFE), polyethersulfone (PES), polyphenylene sulfide (PPS), polysulfone (PSF), polypropylene (PP), polyimide, polyetherimide, poly Suitable examples include ether ether ketone and polyvinylidene fluoride.
また、耐湿熱性の観点から好ましい材質としては、セラミック、ガラス、金属などの無機材料、１００℃以上の耐熱性を有した有機樹脂材料などが挙げられ、高分子量ポリエステル、ポリオレフィン、耐熱性ポリアミド、ポリイミド、ポリスルホン、アラミド、ポリカーボネート、金属、ガラス、セラミックスなどが好適に使用できる。より具体的には、セラミックス、ポリテトラフルオロエチレン、ポリフッ化ビニリデン、ポリエーテルスルホン、ポリフェニレンサルファイド、ポリスルホン、ポリイミド、ポリプロピレン、ポリエーテルイミド、及び、ポリエーテルエーテルケトンからなる群より選ばれた少なくとも１種の材料を含んで構成されることが好ましい。 In addition, preferable materials from the viewpoint of heat and humidity resistance include inorganic materials such as ceramics, glass, and metals, organic resin materials having heat resistance of 100 ° C. or higher, high molecular weight polyester, polyolefin, heat resistant polyamide, polyimide, and the like. Polysulfone, aramid, polycarbonate, metal, glass, ceramics and the like can be suitably used. More specifically, at least one selected from the group consisting of ceramics, polytetrafluoroethylene, polyvinylidene fluoride, polyethersulfone, polyphenylene sulfide, polysulfone, polyimide, polypropylene, polyetherimide, and polyetheretherketone. It is preferable that it is comprised including these materials.
流路材５６の厚みは、特に限定されないが、１００μｍ以上１０００μｍ以下が好ましく、より好ましくは１５０μｍ以上９５０μｍ以下、さらに好ましくは２００μｍ以上９００μｍ以下である。
。
The thickness of the channel material 56 is not particularly limited, but is preferably 100 μm or more and 1000 μm or less, more preferably 150 μm or more and 950 μm or less, and further preferably 200 μm or more and 900 μm or less.
.
二酸化炭素分離モジュールは、前記二酸化炭素分離用複合体を平膜として設置してもよいし、逆浸透膜モジュールとして知られるスパイラル型や、例えば特開２０１０−２７９８８５公報に記載される如き形状を有するプリーツ型などに加工して利用することもできる。
更に、本発明に係る二酸化炭素分離モジュールは、二酸化炭素分離装置にセットして使用することができる。
The carbon dioxide separation module may be installed with the carbon dioxide separation complex as a flat membrane, or has a spiral type known as a reverse osmosis membrane module, or a shape as described in, for example, Japanese Patent Application Laid-Open No. 2010-279885. It can also be used after processing into a pleated shape.
Furthermore, the carbon dioxide separation module according to the present invention can be used by being set in a carbon dioxide separator.
以下、本発明を実施例により更に具体的に説明するが、本発明はその主旨を越えない限り、以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof.
＜二酸化炭素分離層用塗布液の調液＞
（１）下記のようにして塗布液１〜４、及び塗布液Ｃ１〜Ｃ３を調製した。
ポリビニルアルコール−ポリアクリル酸共重合体（クラレ社製）、炭酸セシウム水溶液を加え、さらに各固形分濃度になるように純水を追加し、常温で強力マグネチックスターラーを用いて、よく攪拌した。ポリビニルアルコール−ポリアクリル酸共重合体と炭酸セシウムとの質量比は１：２となるようにして、塗布液の固形分濃度を下記の表１に記載したように変えて調液した各二酸化炭素分離層用塗布液をステンレス製の円筒容器に入れ、２５℃でＢ型粘度計（東京計器製造所製、型式ＢＬ）を用いて、回転数６０ｒｐｍにおける粘度測定を行った。下記表１に、各調液内容と粘度測定結果を示す。また調液物の状態を目視にて確認し、沈降物の無い状態を良好な塗工液、炭酸セシウムの塩析による沈降物が確認された場合は均一な塗工液でないため、不良な塗工液と判断した。なお、表１中の質量比は、ポリビニルアルコール−ポリアクリル酸共重合体と炭酸セシウムとの質量比を示した。
<Preparation of coating solution for carbon dioxide separation layer>
(1) Coating solutions 1 to 4 and coating solutions C1 to C3 were prepared as follows.
A polyvinyl alcohol-polyacrylic acid copolymer (manufactured by Kuraray Co., Ltd.) and an aqueous cesium carbonate solution were added, and pure water was further added so as to obtain each solid content concentration, followed by thorough stirring at room temperature using a strong magnetic stirrer. Each carbon dioxide prepared by changing the solid content concentration of the coating solution as described in Table 1 below so that the mass ratio of the polyvinyl alcohol-polyacrylic acid copolymer and cesium carbonate is 1: 2. The separation layer coating solution was placed in a stainless steel cylindrical container, and the viscosity was measured at 25 ° C. using a B-type viscometer (manufactured by Tokyo Keiki Seisakusho, model BL) at a rotation speed of 60 rpm. Table 1 below shows the contents of each preparation and the viscosity measurement results. Also, check the condition of the liquid preparation visually, and if there is no sediment, a good coating solution, or a sediment due to salting out of cesium carbonate, is not a uniform coating solution. Judged as a working solution. In addition, mass ratio in Table 1 showed mass ratio of polyvinyl alcohol-polyacrylic acid copolymer and cesium carbonate.
（２）塗布液１の場合と同様にして、但し、ポリビニルアルコール−ポリアクリル酸共重合体と炭酸セシウムとの質量比は１：１９となるようにして、塗布液５、及び塗布液Ｃ４〜Ｃ７を調製した。
塗布液の固形分濃度を下記の表２〜表４に記載したように変えて調液した各二酸化炭素分離層用塗布液について、塗布液１の場合と同様にして粘度測定を行った。下記表２〜表４に、各調液内容と粘度測定結果を示す。また調液物の状態を目視にて確認し、沈降物の無い状態を良好な塗工液、炭酸セシウムの塩析による沈降物が確認された場合は均一な塗工液でないため、不良な塗工液と判断した。
(2) In the same manner as in the coating liquid 1, except that the mass ratio of the polyvinyl alcohol-polyacrylic acid copolymer and cesium carbonate is 1:19, the coating liquid 5 and the coating liquids C4 to C4 C7 was prepared.
Viscosity measurement was performed in the same manner as in the coating liquid 1 for each coating liquid for carbon dioxide separation layer prepared by changing the solid content concentration of the coating liquid as described in Tables 2 to 4 below. Tables 2 to 4 below show the contents of each preparation and the viscosity measurement results. Also, check the condition of the liquid preparation visually, and if there is no sediment, a good coating solution, or a sediment due to salting out of cesium carbonate, is not a uniform coating solution. Judged as a working solution.
表１から表５の結果から、ポリビニルアルコール−ポリアクリル酸共重合体と炭酸セシウムとの質量比が、１：９、１：２、及び２：３の場合には、温度２５℃で、Ｂ型粘度測定において回転数６０ｒｐｍにおける粘度測定値が０．５Ｐａ・ｓ以上１０Ｐａ・ｓ以下の範囲の粘度を有し、かつ沈降物のない水溶液が得られることが分かる。
しかし、ポリビニルアルコール−ポリアクリル酸共重合体と炭酸セシウムとの質量比が、０．５：９．５の場合には、沈降物のない溶液においてはＢ型粘度測定において回転数６０ｒｐｍにおける粘度測定値が０．００１Ｐａ・ｓの粘度しか示さず、それより高粘度の水溶液を得ようとすると沈降物が生じてしまい、結局のところ、粘度が０．５Ｐａ・ｓ以上１０Ｐａ・ｓ以下の範囲の水溶液が得られないことが分かる。更に、ポリビニルアルコール−ポリアクリル酸共重合体と炭酸セシウムとの質量比が１：１の場合は、固形分濃度が５質量％という低濃度において、２５℃における粘度が０．５８Ｐａ・ｓを示し、固形分が水に溶解しきれずに白濁したものしか得られず、固形分濃度をそれよりも高くすると、流動性のない水溶液となってしまい、塗布液としての適正を有していないことが分かる。
From the results of Table 1 to Table 5, when the mass ratio of the polyvinyl alcohol-polyacrylic acid copolymer to cesium carbonate is 1: 9, 1: 2, and 2: 3, the temperature is 25 ° C. In the mold viscosity measurement, it can be seen that an aqueous solution having a viscosity in the range of 0.5 Pa · s to 10 Pa · s at a rotational speed of 60 rpm and having no precipitate is obtained.
However, when the mass ratio of the polyvinyl alcohol-polyacrylic acid copolymer and cesium carbonate is 0.5: 9.5, the viscosity measurement at a rotational speed of 60 rpm is performed in the B-type viscosity measurement in a solution without a precipitate. The value shows only a viscosity of 0.001 Pa · s, and when an aqueous solution having a higher viscosity than that is obtained, a precipitate is formed. As a result, the viscosity is in a range of 0.5 Pa · s to 10 Pa · s. It can be seen that an aqueous solution cannot be obtained. Furthermore, when the mass ratio of the polyvinyl alcohol-polyacrylic acid copolymer and cesium carbonate is 1: 1, the viscosity at 25 ° C. is 0.58 Pa · s at a low solid content concentration of 5 mass%. If the solid content cannot be completely dissolved in water and only white turbidity can be obtained, and if the solid content concentration is higher than that, it becomes a non-flowable aqueous solution and does not have suitability as a coating solution. I understand.
上記の塗布液については、温度２５℃でのＢ型粘度測定による回転数６０ｒｐｍにおける粘度測定値を示したが、ポリビニルアルコール−ポリアクリル酸共重合体と炭酸セシウムとの質量比の異なり、温度２５℃でのＢ型粘度測定による回転数６０ｒｐｍにおける粘度測定値が略同等の値を示す塗布液１、５及び６について、温度１５℃及び３５℃でのＢ型粘度測定による回転数６０ｒｐｍにおける粘度測定値を下記表６に示した。下記表６の結果から、温度が１５℃以上３５℃以下の範囲における粘度の変動幅は高々０．０７Ｐａ・ｓであり、僅かな変動幅しかないことが分かる。このことから、温度２５℃でのＢ型粘度測定による回転数６０ｒｐｍにおける粘度測定値が０．５Ｐａ・ｓ以上１０Ｐａ・ｓ以下の範囲を示せば、温度１５℃又は３５℃においても、同等の結果が得られるものと推定することができる。 For the above coating solution, the viscosity measurement value at a rotation speed of 60 rpm by B-type viscosity measurement at a temperature of 25 ° C. was shown, but the mass ratio of the polyvinyl alcohol-polyacrylic acid copolymer and cesium carbonate was different, and the temperature was 25 Viscosity measurement at a rotational speed of 60 rpm by B-type viscosity measurement at temperatures of 15 ° C. and 35 ° C. with respect to coating solutions 1, 5 and 6 in which the viscosity measurement values at a rotational speed of 60 rpm by a B-type viscosity measurement at 0 ° C. are substantially equal. The values are shown in Table 6 below. From the results of Table 6 below, it can be seen that the fluctuation range of the viscosity in the range of the temperature of 15 ° C. or more and 35 ° C. or less is 0.07 Pa · s at most, and there is only a slight fluctuation range. From this, if the viscosity measured value at a rotational speed of 60 rpm by B-type viscosity measurement at a temperature of 25 ° C. shows a range of 0.5 Pa · s to 10 Pa · s, the same result even at a temperature of 15 ° C. or 35 ° C. Can be estimated to be obtained.
＜二酸化炭素分離用複合体の製造＞
上記で調液された二酸化炭素分離層用塗布液のうち、塗布液Ｃ１及びＣ２、並びに塗布液１から４を用いて、ＰＥＴフィルム（東レ社製Ｔ６０、１００μｍ厚）とサポーテッドＰＴＦＥ（中尾フィルター社製、テトラトックス７００８、２００μｍ厚）上に塗工時の膜厚を０．２ｍｍ／１．０ｍｍ／２．０ｍｍ／３．０ｍｍに変化させて、２５℃で塗工を行った。また塗工方法は２．０ｍ／ｍｉｎでロールコーターにより行い、８０℃で乾燥を行った。
下記の表７に塗工適性を示し、下記の表８（ＰＥＴフィルムを使用した場合）及び表９（ＰＴＦＥを使用した場合）に、得られた二酸化炭素分離層の膜面状態の目視観察結果を示した。ここで塗工適性の判断は、塗工中にロールコーターにおける液ダメとクリアランスの隙間から塗工液が流れ落ちた場合を、塗工適性無し（表中に×として記入。）とし、そのような液ダレと塗工液の流れ落ちのなかった場合を塗工適正あり（表中に○として記入。）とした。また、同じ塗布液について、ブレードコーターにて塗布した場合についても、塗工適性を判断し、表７に示した。
<Manufacture of composite for carbon dioxide separation>
Of the coating liquids for carbon dioxide separation layer prepared as described above, coating films C1 and C2 and coating liquids 1 to 4 were used, and PET film (T60 manufactured by Toray Industries, Inc., 100 μm thickness) and supported PTFE (Nakao Filter Co., Ltd.) The film thickness at the time of coating was changed to 0.2 mm / 1.0 mm / 2.0 mm / 3.0 mm, and coating was performed at 25 ° C. The coating method was 2.0 m / min using a roll coater, and drying was performed at 80 ° C.
Table 7 below shows the coating suitability, and the following Table 8 (when PET film is used) and Table 9 (when PTFE is used) are the results of visual observation of the membrane surface state of the carbon dioxide separation layer obtained. showed that. Here, the judgment of coating suitability is defined as “no coating suitability” (indicated as “X” in the table) when the coating liquid flows down from the gap between the liquid coater and the clearance in the roll coater during coating. The case where there was no dripping of the liquid and the flow of the coating liquid was deemed appropriate for coating (filled in the table as ◯). Also, the same coating solution was applied with a blade coater, and the suitability for coating was determined and shown in Table 7.
表７の結果から、塗布液１〜４の場合には、ロールコーター及びブレードコーターの何れにおいても塗工適正を有していることが分かる。 From the results of Table 7, it can be seen that in the case of the coating liquids 1 to 4, both the roll coater and the blade coater have coating suitability.
表８及び表９の結果から、塗布液１〜４の場合には、塗布液の液膜の厚さが０．２ｍｍ以上２．５ｍｍの範囲で、ムラのない良好な塗膜が得られることが分かる。 From the results of Tables 8 and 9, in the case of the coating liquids 1 to 4, a good coating film without unevenness is obtained when the thickness of the liquid film of the coating liquid is in the range of 0.2 mm to 2.5 mm. I understand.
＜増粘剤を含有する二酸化炭素分離層用塗布液の調液＞
増粘剤としてカルボキシメチルセルロースＣＭＣ２２８０（ダイセル化学製）を選定し、前記塗布液Ｃ１の水溶液に粉末の状態で増粘剤を表９に記載した量を添加し、強力マグネチックスターラーにて充分に攪拌を行った。ここで、表９に記載した増粘剤の量を表す数値は、増粘剤を加える前の塗布液に含まれる全固形分量を１００質量部としたときの増粘剤の添加量を質量部で表した値を意味する。ＰＶＡ−ＰＡＡ（ポリビニルアルコール−ポリアクリル酸共重合体）追添加量の数値も同じ意味である。粘度測定は、２５℃で粘度計（コーンプレート型）を用いて測定を行った。また、それぞれの塗布液の塗工適性とＰＴＦＥへ塗布液の液膜の厚さが０．５ｍｍとなるようにロールコーターで塗布し、乾燥した塗膜の状態を、上記と同様の方法で評価した。結果を表１０に示した。
<Preparation of coating solution for carbon dioxide separation layer containing thickener>
Select carboxymethyl cellulose CMC2280 (manufactured by Daicel Chemical) as the thickener, add the amount of thickener listed in Table 9 to the aqueous solution of the coating solution C1, and stir well with a strong magnetic stirrer. Went. Here, the numerical value representing the amount of thickener described in Table 9 is the amount of thickener added when the total solid content contained in the coating liquid before adding the thickener is 100 parts by weight. Means the value The numerical value of the additional amount of PVA-PAA (polyvinyl alcohol-polyacrylic acid copolymer) has the same meaning. The viscosity was measured at 25 ° C. using a viscometer (cone plate type). In addition, the coating suitability of each coating solution and the coating film applied to PTFE with a roll coater so that the thickness of the coating solution is 0.5 mm, and the state of the dried coating film were evaluated in the same manner as described above. did. The results are shown in Table 10.
表１０の結果から、増粘剤を含有させることによって、２５℃の温度における塗布液の粘度を回転数６０ｒｐｍにおける粘度測定値が０．５Ｐａ・ｓ以上１０Ｐａ・ｓ以下の範囲とすることができれば、塗工適正を有し、かつムラのない均質な二酸化炭素分離層が得られることが分かる。 From the results of Table 10, if the viscosity of the coating solution at a temperature of 25 ° C. can be measured within a range of 0.5 Pa · s to 10 Pa · s in terms of the viscosity measured at a rotation speed of 60 rpm by including a thickener. It can be seen that a homogeneous carbon dioxide separation layer having coating suitability and no unevenness can be obtained.
−ガス分離評価−
実施例１〜３で製造した二酸化炭素分離用複合体を用いて二酸化炭素ガスの分離性能について、以下のように評価した。
実施例１及び実施例３では、上記ＰＥＴフィルム上に製膜した二酸化炭素分離層（直径４７ｍｍ）をＰＥＴフィルムから丁寧にはがし、ＰＴＦＥメンブレンフィルター（孔径０．１０μｍ、ＡＤＶＡＮＴＥＣ社製）を２枚用いて膜両面から挟んで透過試験サンプルを作製した。
実施例２では、支持体ごと直径４７ｍｍに切り取り、同様にＰＴＦＥメンブレンフィルターで挟んで透過試験サンプルを作製した。
テストガスとしてＣＯ２／Ｈ２：１０／９０（容積比）の混合ガスを相対湿度７０％、流量１００ｍｌ／分、温度１３０℃、全圧３ａｔｍで、前記の各サンプル（有効面積２．４０ｃｍ２）に供給し、透過側にＡｒガス（流量９０ｍｌ／分）をフローさせた。透過してきたガスをガスクロマトグラフで分析し、ＣＯ２透過速度と分離係数を算出した。その結果を表１０に示す。
-Gas separation evaluation-
Using the carbon dioxide separation composites produced in Examples 1 to 3, the carbon dioxide gas separation performance was evaluated as follows.
In Example 1 and Example 3, the carbon dioxide separation layer (diameter 47 mm) formed on the PET film was carefully peeled off from the PET film, and two PTFE membrane filters (pore diameter 0.10 μm, manufactured by ADVANTEC) were used. A transmission test sample was prepared by sandwiching the film from both sides.
In Example 2, the entire support was cut to a diameter of 47 mm and similarly sandwiched between PTFE membrane filters to produce a transmission test sample.
As a test gas, a mixed gas of CO 2 / H 2 : 10/90 (volume ratio) was used with each sample (effective area 2.40 cm 2 ) at a relative humidity of 70%, a flow rate of 100 ml / min, a temperature of 130 ° C., and a total pressure of 3 atm. ) And Ar gas (flow rate 90 ml / min) was allowed to flow on the permeate side. The permeated gas was analyzed with a gas chromatograph, and the CO 2 permeation rate and the separation factor were calculated. The results are shown in Table 10.
表１１に示すように、本発明に係る二酸化炭素分離用複合体は、二酸化炭素の透過速度、分離係数とも優れた性能を示すことが分かる。 As shown in Table 11, it can be seen that the composite for carbon dioxide separation according to the present invention exhibits excellent performance in both the permeation rate of carbon dioxide and the separation factor.
１０ 送り出しロール
１２ 支持体
２０ コーター
３０ 二酸化炭素分離層形成用塗布液
４０ 乾燥部
５０ 巻取りロール
５２ 二酸化炭素分離用複合体
６２，６４，６６，６８ 搬送ロール
DESCRIPTION OF SYMBOLS 10 Sending roll 12 Support body 20 Coater 30 Coating solution 40 for carbon dioxide separation layer formation Drying part 50 Winding roll 52 Composite body 62, 64, 66, 68 for carbon dioxide separation
Claims (12)
前記二酸化炭素分離層形成用塗布液を、１５℃以上３５℃以下の温度、かつＢ型粘度測定において回転数６０ｒｐｍにおける粘度測定値が０．５Ｐａ・ｓ以上１０Ｐａ・ｓ以下の粘度で支持体上に塗布して、前記二酸化炭素分離層形成用塗布液の液膜を前記支持体上に形成する塗布工程と、
前記支持体上の二酸化炭素分離層形成用塗布液の液膜を乾燥して二酸化炭素分離層とする乾燥工程と、
を含む二酸化炭素分離用複合体の製造方法。 Preparation of coating solution comprising a water-absorbing polymer, a carbon dioxide carrier, and water, and preparing a coating solution for forming a carbon dioxide separation layer having a mass ratio of the water-absorbing polymer to the carbon dioxide carrier of 1: 9 or more and 2: 3 or less. Process,
The coating solution for forming a carbon dioxide separation layer is formed on the support at a temperature of 15 ° C. or more and 35 ° C. or less and a viscosity measurement value at a rotation speed of 60 rpm in the B-type viscosity measurement is 0.5 Pa · s or more and 10 Pa · s or less. An application step of forming a liquid film of the coating solution for forming a carbon dioxide separation layer on the support;
A drying step of drying the liquid film of the coating liquid for forming a carbon dioxide separation layer on the support to form a carbon dioxide separation layer;
The manufacturing method of the composite_body | complex for carbon dioxide separation containing this.
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| JP2012155771A JP2014014803A (en) | 2012-07-11 | 2012-07-11 | Method of producing complex for carbon dioxide separation, complex for carbon dioxide separation, module for carbon dioxide separation, carbon dioxide separation apparatus, and carbon dioxide separation method |
| PCT/JP2013/066757 WO2014010377A1 (en) | 2012-07-11 | 2013-06-18 | Production method of complex for carbon dioxide separation, complex for carbon dioxide separation, carbon dioxide separation module, carbon dioxide separation device and carbon dioxide separation method |
| TW102123406A TW201406448A (en) | 2012-07-11 | 2013-07-01 | Method for producing composition for separating carbon dioxide, composition for separating carbon dioxide, carbon dioxide separation module, carbon dioxide separation apparatus, and method for separating carbon dioxide |
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| JP2015188866A (en) * | 2014-03-28 | 2015-11-02 | 次世代型膜モジュール技術研究組合 | gas separation membrane |
| JP2015188867A (en) * | 2014-03-28 | 2015-11-02 | 次世代型膜モジュール技術研究組合 | gas separation membrane |
| JP2015188865A (en) * | 2014-03-28 | 2015-11-02 | 次世代型膜モジュール技術研究組合 | gas separation membrane |
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| JP2016117045A (en) * | 2014-12-23 | 2016-06-30 | 住友化学株式会社 | Method for producing carbon dioxide separation membrane, resin composition for carbon dioxide separation membrane, carbon dioxide separation membrane module, and apparatus for separating carbon dioxide |
| JP7204392B2 (en) | 2018-09-18 | 2023-01-16 | 株式会社東芝 | Acid gas absorbent, method for removing acid gas, and apparatus for removing acid gas |
| CN112793264A (en) * | 2019-11-14 | 2021-05-14 | Csir公司 | Food packaging film |
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| AU2009207025B2 (en) * | 2008-01-24 | 2012-05-17 | Renaissance Energy Research Corporation | CO2-facilitated transport membrane and manufacturing method for same |
| US8747521B2 (en) * | 2010-02-10 | 2014-06-10 | Fujifilm Corporation | Gas separation membrane and method for producing the same, and gas separating method, module and separation apparatus using the same |
| JP2011161387A (en) * | 2010-02-10 | 2011-08-25 | Fujifilm Corp | Gas separation membrane, method for manufacturing the same, method for separating gas mixture using the same, gas separation membrane module and gas separator |
| US8992668B2 (en) * | 2010-03-29 | 2015-03-31 | Fujifilm Corporation | Gas separation membrane and method for producing the same, and method for separating gas mixture, gas separation membrane module and gas separation apparatus using the same |
| JP5484361B2 (en) * | 2011-01-12 | 2014-05-07 | 富士フイルム株式会社 | Method and apparatus for producing composite for carbon dioxide separation |
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|---|---|---|---|---|
| JP2015188866A (en) * | 2014-03-28 | 2015-11-02 | 次世代型膜モジュール技術研究組合 | gas separation membrane |
| JP2015188867A (en) * | 2014-03-28 | 2015-11-02 | 次世代型膜モジュール技術研究組合 | gas separation membrane |
| JP2015188865A (en) * | 2014-03-28 | 2015-11-02 | 次世代型膜モジュール技術研究組合 | gas separation membrane |
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