JPS6393326A - Preparation of gas separating membrane - Google Patents
Preparation of gas separating membraneInfo
- Publication number
- JPS6393326A JPS6393326A JP61240285A JP24028586A JPS6393326A JP S6393326 A JPS6393326 A JP S6393326A JP 61240285 A JP61240285 A JP 61240285A JP 24028586 A JP24028586 A JP 24028586A JP S6393326 A JPS6393326 A JP S6393326A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- gas
- membrane
- gas separation
- separating membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title description 2
- 229920001721 polyimide Polymers 0.000 claims abstract description 41
- 239000004642 Polyimide Substances 0.000 claims abstract description 40
- 239000000178 monomer Substances 0.000 claims abstract description 36
- 125000003118 aryl group Chemical group 0.000 claims abstract description 29
- 238000000926 separation method Methods 0.000 claims description 52
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000007654 immersion Methods 0.000 claims description 8
- 239000003505 polymerization initiator Substances 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 11
- 230000035699 permeability Effects 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 3
- ORGHESHFQPYLAO-UHFFFAOYSA-N vinyl radical Chemical compound C=[CH] ORGHESHFQPYLAO-UHFFFAOYSA-N 0.000 abstract 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 abstract 1
- 229920002554 vinyl polymer Polymers 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 63
- 239000012510 hollow fiber Substances 0.000 description 34
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 25
- 239000000243 solution Substances 0.000 description 22
- 238000005406 washing Methods 0.000 description 16
- 239000007788 liquid Substances 0.000 description 15
- 239000010410 layer Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000001569 carbon dioxide Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 8
- -1 aromatic tetracarboxylic acids Chemical class 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- 230000001112 coagulating effect Effects 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 150000004984 aromatic diamines Chemical group 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 229940090668 parachlorophenol Drugs 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NBAUUNCGSMAPFM-UHFFFAOYSA-N 3-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=C1C(O)=O NBAUUNCGSMAPFM-UHFFFAOYSA-N 0.000 description 1
- ULPWATNJVBJKGM-UHFFFAOYSA-N 3-[2-(3-amino-2-phenoxyphenyl)propan-2-yl]-2-phenoxyaniline Chemical compound C=1C=CC(N)=C(OC=2C=CC=CC=2)C=1C(C)(C)C1=CC=CC(N)=C1OC1=CC=CC=C1 ULPWATNJVBJKGM-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- 241001669573 Galeorhinus galeus Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【発明の詳細な説明】 [発明の技術的分野] 本発明は、気体分離膜の製造方法に関するものである。[Detailed description of the invention] [Technical field of invention] The present invention relates to a method for manufacturing a gas separation membrane.
更に詳しくは、本発明は、水素分jll膜、炭醜ガス分
離膜、水蒸気分R1膜あるいは酸素富化膜などとして有
用な芳香族ポリイミドからなる均質層を有する気体分1
lll膜の改良された製造方法に関するものである。More specifically, the present invention provides a gas component R1 membrane having a homogeneous layer made of aromatic polyimide useful as a hydrogen component membrane, a carbon gas separation membrane, a water vapor component R1 membrane, an oxygen enrichment membrane, and the like.
The present invention relates to an improved method of manufacturing a llll film.
[発明の背景]
気体分l11膜は、各種の気体の分離、eLlilなど
の目的で利用されており、その代表的な構成としては、
全体が均質な層からなる均質膜、均質層と多孔質層とか
らなる非対称性膜、そして全体か多孔質の層からなる多
孔質膜などが知られている。非対称性膜は、多孔質膜の
片面に塗布により均質層を形成して得た一体膜と多孔質
膜の片面に別に調製した均質膜を付設して得た複合膜と
に分けることがてきる。[Background of the Invention] Gas fraction l11 membranes are used for purposes such as separation of various gases and eLlil, and their typical configurations are as follows:
Homogeneous membranes consisting of entirely homogeneous layers, asymmetric membranes consisting of a homogeneous layer and a porous layer, and porous membranes consisting entirely of porous layers are known. Asymmetric membranes can be divided into integral membranes obtained by forming a homogeneous layer on one side of a porous membrane by coating, and composite membranes obtained by attaching a separately prepared homogeneous membrane to one side of a porous membrane. .
複合膜の例としては、特公昭59−51321号公報に
開示されている。多孔質膜にポリマーを被覆した支持体
ポリマー固有の分離性能を利用した気体分離膜を挙げる
ことができる。An example of a composite membrane is disclosed in Japanese Patent Publication No. 59-51321. Examples include gas separation membranes in which a porous membrane is coated with a polymer and utilizes the separation performance inherent to a support polymer.
一体膜の例としては、特公昭4B−17589号公報に
開示されている、多孔質膜にポリマ一層を重層して得た
気体分離膜を挙げることができる。この分離膜では、分
離性能は塗布により形成したポリマ一層に委ねられてい
る。An example of an integral membrane is a gas separation membrane obtained by laminating a single layer of polymer on a porous membrane, as disclosed in Japanese Patent Publication No. 4B-17589. In this separation membrane, the separation performance is dependent on the single layer of polymer formed by coating.
これらの気体分離膜のうち、均質層を有する気体分11
1114、すなわち、均j!III!fJおよび非対称
性膜は高い気体分離性能を有するところから、熱心な研
究か進められている。なかでも、均質膜の材料として芳
香族ポリイミド樹脂を用いたものは、その材ネ1の高い
耐熱性および耐候性が有効に作用するため、厳しい条件
における使用に適しているとされ、注目を集めている。Among these gas separation membranes, gas fraction 11 having a homogeneous layer
1114, that is, average j! III! fJ and asymmetric membranes are being actively researched because they have high gas separation performance. Among these, those using aromatic polyimide resin as the homogeneous membrane material are attracting attention as they are said to be suitable for use under harsh conditions due to their high heat resistance and weather resistance. ing.
ところか、気体分gl膜を実際に使用して気体分子Ia
操作を行なうと時間の経過に伴ってガスの透過性の小さ
くなることかしばしばみられる。この現象は、耐熱性ポ
リマーである芳香族ポリイミドな均質膜材料として用い
た気体分離膜であつても発生するため、その改良が必要
である。すなわち、耐熱性の高い芳香族ポリイミドを均
質膜材料として用いた気体分離膜は、その高い耐熱性を
有効に生かすためにも、継続使用条件における気体分離
性ス距の低下をできるだけ少なくすることが必要である
。However, when a gas component GL membrane is actually used, gas molecules Ia
It is often observed that gas permeability decreases over time during operation. This phenomenon occurs even in gas separation membranes made of aromatic polyimide, which is a heat-resistant polymer, used as a homogeneous membrane material, so it is necessary to improve it. In other words, in order to effectively utilize the high heat resistance of gas separation membranes using aromatic polyimide, which has high heat resistance, as a homogeneous membrane material, it is necessary to minimize the decrease in gas separation distance under continuous use conditions. is necessary.
[発明の目的]
本発明は、気体透過性能が改良された芳香族ポリイミド
からなる均質層を有する気体分離膜の製造方法を提供す
ることを目的とする。[Object of the Invention] An object of the present invention is to provide a method for manufacturing a gas separation membrane having a homogeneous layer made of aromatic polyimide with improved gas permeability.
本発明は、特に継続使用条件における気体分離性能の低
下が少なくなった芳香族ポリイミドからなる均質層を有
する気体分aSの製造方法を提供することを目的とする
。An object of the present invention is to provide a method for producing a gaseous component aS having a homogeneous layer made of aromatic polyimide, which exhibits less deterioration in gas separation performance especially under conditions of continued use.
[発明の構成]
本発明は、芳香族ポリイミドからなる均質層を有する気
体分離膜を、ビニル基を有するモノマーの溶液中で浸漬
処理して該気体分離膜上ツマ−を付着させ、次いで該モ
ノマーが付着した該気体分gl膜を加熱処理することを
特徴とする気体分離膜の製造方法にある。[Structure of the Invention] The present invention involves immersing a gas separation membrane having a homogeneous layer made of aromatic polyimide in a solution of a monomer having a vinyl group to attach a layer on the gas separation membrane, and then soaking the monomer in a solution of a monomer having a vinyl group. The present invention provides a method for producing a gas separation membrane, which comprises heat-treating the gas-separated GL membrane to which is adhered.
本発明における処理対象の気体分離膜の代表的な例とし
ては、炭酸ガスの透過度(P’C02)が1 x l
O−’ c c / c rrr’ ・秒・cmHg以
上であって、炭酸ガスとメタンの透過度の比(分離度:
p’ [CO2]/P’ [CHal)が15以上
のものを挙げることかできる。A typical example of a gas separation membrane to be treated in the present invention has a carbon dioxide permeability (P'C02) of 1 x l
O-' c c / c rrr' ・sec・cmHg or more, and the ratio of permeability of carbon dioxide to methane (separation degree:
Examples include those in which p'[CO2]/P' [CHal) is 15 or more.
本発明によって′I!A潰される気体分離膜は、均質膜
であっても、あるいは非対称性膜であってもよい、また
、本発明の気体分gl膜は中空糸状、シート状などのい
ずれの形状にあってもよい。By the present invention 'I! A The gas separation membrane to be crushed may be a homogeneous membrane or an asymmetric membrane, and the gas separation membrane of the present invention may be in any shape such as a hollow fiber shape or a sheet shape. .
本発明の気体分a膜は、芳香族ポリイミドからなる均質
層を有する気体分離膜を前記規定の芳香族基含有ポリマ
ーで処理したものである。The gas separation membrane of the present invention is obtained by treating a gas separation membrane having a homogeneous layer made of aromatic polyimide with the aromatic group-containing polymer specified above.
芳香族ポリイミドからなる均質層を有する気体分離膜(
以下、tnに「ポリイミド気体分離膜」ともいう)とし
ては、これまでに各種の芳香族ポリイミドから得られた
ものが知られており、本発明の処理対象のポリイミド気
体分子a膜はそのような任意の芳香族ポリイミドから得
た気体分離膜であってよい。Gas separation membrane with a homogeneous layer made of aromatic polyimide (
As ``polyimide gas separation membrane'' (hereinafter also referred to as ``polyimide gas separation membrane''), those obtained from various aromatic polyimides have been known, and the polyimide gas molecule a membrane to be treated in the present invention is made of such a membrane. The gas separation membrane may be made from any aromatic polyimide.
芳香族ポリイミドは一般に芳香族テトラカルボン酸骨格
と芳香族ジアミン骨格とから構成されており、それぞれ
について各種の化学構造を有するものを選ぶことにより
各種の物理的・化学的特性を有する芳香族ポリイミドが
得られることが知られている。Aromatic polyimides are generally composed of an aromatic tetracarboxylic acid skeleton and an aromatic diamine skeleton, and by selecting compounds with various chemical structures for each, aromatic polyimides with various physical and chemical properties can be created. known to be obtained.
すなわち芳香族ポリイミドの芳香族テトラカルボン酸骨
格としては、3.3’ 、4.4’−ベンゾフェノンテ
トラカルボン酸、2,3.3’ 。That is, the aromatic tetracarboxylic acid skeleton of the aromatic polyimide includes 3.3', 4.4'-benzophenonetetracarboxylic acid, and 2,3.3'.
4′−ベンゾフェノンテトラカルボン醜、ピロメリット
酸、3,3°、4.4°−ビフェニルテトラカルボン酸
、および2,3.3’ 、4’−ビフェニルテトラカル
ボン酸、そして、これらの芳香族テトラカルボン酸の酸
二無水物、エステル、塩などから誘導されたカルボン酸
骨格を挙げることかできる。これらのうち、3.3’
、4゜4″−ビフェニルテトラカルボン酸の酸二無水物
と2.3.3”、4°−ビフェニルテトラカルボン酸の
酸二無水物などにより代表されるビフェニルテトラカル
ボン酸二無水物から誘導された酸骨格な土酸骨格とする
芳香族ポリイミド気体分aSを利用した場合に1本発明
は特に有用である。4'-benzophenonetetracarboxylic acid, pyromellitic acid, 3,3°,4.4°-biphenyltetracarboxylic acid, and 2,3,3',4'-biphenyltetracarboxylic acid, and these aromatic tetracarboxylic acids. Examples include carboxylic acid skeletons derived from acid dianhydrides, esters, salts, etc. of carboxylic acids. Of these, 3.3'
, 4°, 4″-biphenyltetracarboxylic acid dianhydride, and 2.3.3″, 4°-biphenyltetracarboxylic acid dianhydride, etc. The present invention is particularly useful when an aromatic polyimide gas component aS having an earth acid skeleton is used.
芳香族ポリイミドの芳香族ジアミン骨格としては、パラ
フェニレンジアミン、メタフェニレンジアミン、2.4
−ジアミノトルエン、4.4’ −ジアミノジフェニル
エーテル、4.4′−ジアミノジフェニルメタン、0−
)−リジン、1.4−ビスく4−アミノフェノキシ)ベ
ンゼン、2,8−ジメチル−3,7−ジアミツジベンゾ
チオフエンー5,5−ジオキシド、ビス(アミノフェノ
キシ−フェニル)プロパンおよびビス(アミノフェノキ
シ−フェニル)スルホンなどを挙げることができる。The aromatic diamine skeleton of aromatic polyimide includes para-phenylene diamine, meta-phenylene diamine, 2.4
-diaminotoluene, 4.4'-diaminodiphenyl ether, 4.4'-diaminodiphenylmethane, 0-
)-lysine, 1,4-bis(4-aminophenoxy)benzene, 2,8-dimethyl-3,7-diamitudibenzothiophene-5,5-dioxide, bis(aminophenoxy-phenyl)propane and bis( Examples include aminophenoxy-phenyl) sulfone.
上記のような芳香族カルボン酸成分と芳香族ジアミン成
分とを用いてポリイミドを製造する方法も各種知られて
いる。たとえば、上記の芳香族カルボン酸成分と芳香族
ジアミン成分とを有機極性溶媒に溶解した状態で加熱し
て一段階反応にて重合とイミド化とを行ないポリイミド
を得る方法。Various methods for producing polyimide using the above aromatic carboxylic acid component and aromatic diamine component are also known. For example, a method of obtaining polyimide by heating the above-mentioned aromatic carboxylic acid component and aromatic diamine component dissolved in an organic polar solvent to perform polymerization and imidization in a one-step reaction.
および芳香族カルボン酸成分と芳香族ジアミン成分とを
有機極性溶媒に溶解した状態にて室温付近の低温で重合
反応を起させて、一旦ポリアミック酸としたのち、この
アミック酸からポリイミド均質層を得る方法などが知ら
れている。and an aromatic carboxylic acid component and an aromatic diamine component dissolved in an organic polar solvent, a polymerization reaction is caused at a low temperature near room temperature to once form a polyamic acid, and then a polyimide homogeneous layer is obtained from this amic acid. Methods are known.
本発明において使用する芳香族ポリイミドは、いずれの
方法によって得られたものであってもよい。The aromatic polyimide used in the present invention may be obtained by any method.
本発明において処理の対象とすることのできる芳香族ポ
リイミド気体分離膜の製造方法の例を、中空糸膜の形態
にある気体分離膜の製造方法を例にして以下に説明する
。An example of a method for manufacturing an aromatic polyimide gas separation membrane that can be treated in the present invention will be described below using a method for manufacturing a gas separation membrane in the form of a hollow fiber membrane as an example.
まず、芳香族ポリイミド溶液を中空糸の紡糸用ノズルか
ら、一旦大気中を経て、または直接に凝固液中へ中空糸
状に押し出す。押し出された中空糸状体を、必要であれ
ば緊張状態で僅かに伸張させながら、好ましくは約−1
0〜60’Cの凝固液中で直ちに凝固させて、湿潤状態
の中空糸(凝固または固化して自己支持性を有する中空
糸)を連続的に形成し、この湿潤状態の中空糸を充分洗
浄して芳香族ポリイミド中空糸膜な得る。First, an aromatic polyimide solution is extruded from a hollow fiber spinning nozzle into the air or directly into a coagulating liquid in the form of a hollow fiber. The extruded hollow filament is preferably stretched by about -1, while being slightly stretched under tension if necessary.
Immediately coagulate in a coagulation solution at 0 to 60'C to continuously form wet hollow fibers (hollow fibers that are self-supporting after coagulating or solidifying), and thoroughly wash the wet hollow fibers. Then, an aromatic polyimide hollow fiber membrane is obtained.
これを更に詳しく述べれば、ノズルヘッドへ、濾過およ
び脱泡されたドープ液を供給し、そして、そのノズルヘ
ットの底部のオリフィスの開口部の内周面と芯管の外周
面との間の空隙部(ドーナツ状空隙または環状空隙部)
からドープ液を適当な背圧下に押し出し、同時に前記芯
管の内部孔から気体(窒素ガスなど)または液体(芯液
ともいう)を供給しながら、トープ液の中空糸状体を形
成し、その中空糸状体を凝固液に接触させて凝固させる
ことにより中空糸を形成する。To describe this in more detail, the filtered and defoamed dope liquid is supplied to the nozzle head, and the gap between the inner peripheral surface of the opening of the orifice at the bottom of the nozzle head and the outer peripheral surface of the core tube is supplied to the nozzle head. (doughnut-shaped cavity or annular cavity)
While extruding the dope liquid under appropriate back pressure from the core tube and simultaneously supplying gas (nitrogen gas, etc.) or liquid (also called core liquid) from the internal hole of the core tube, a hollow filament of the dope liquid is formed, and the hollow fibers of the dope liquid are Hollow fibers are formed by bringing the filamentous body into contact with a coagulating liquid and coagulating it.
前述の凝固液は、前述の芳香族ポリイミドを実質的に溶
解せず、しかもトープ液に使用されたフェノール系化合
物と相溶性が優れている低い粘度(回転粘度)の有機極
性溶媒でなければならないことは言うまでもなく、例え
ば、メタノール、エタノール、n−プロピルアルコール
、イソプロピルアルコール、n−ブチルアルコール、イ
ソブチルアルコール、n−ペンチルアルコールなどの炭
素数1〜5の低級アルキルアルコールと水との混合溶媒
などのような、低級アルコールまたは水を主として含有
する混合溶媒が好ましく、特に低級アルコールの濃度が
約40〜9o容量%、さらに好ましくは45〜b
水溶液が最適である。The coagulating liquid mentioned above must be an organic polar solvent with a low viscosity (rotational viscosity) that does not substantially dissolve the aromatic polyimide mentioned above and has excellent compatibility with the phenolic compound used in the tope liquid. Needless to say, for example, a mixed solvent of water and a lower alkyl alcohol having 1 to 5 carbon atoms such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, n-pentyl alcohol, etc. A mixed solvent mainly containing a lower alcohol or water is preferable, and an aqueous solution in which the concentration of the lower alcohol is about 40 to 9% by volume, more preferably 45 to 90% by volume is most suitable.
洗浄工程は第一洗浄と第二洗浄の二回に分けて行なうこ
とが望ましい、第一洗浄は、上記の凝固液と同一もしく
は類似の低級アルコールを用いて行なうことか望ましい
。It is preferable that the washing step is carried out in two parts, a first washing and a second washing. The first washing is preferably carried out using a lower alcohol that is the same as or similar to the above-mentioned coagulating liquid.
第−洗浄を行なった後の、第一洗浄液で湿潤している中
空糸について、炭化水素溶媒が主として(約70容量%
以上)含有されている第二洗浄液で、その第二洗浄液が
洗浄中の中空糸に接触した後に、中空糸の低級アルコー
ル含有量かを1重量%以下、好ましくは0.5重量%以
下になる迄、第二洗浄を行なうことが望ましい。After the first washing, the hollow fibers wetted with the first washing liquid are mainly composed of hydrocarbon solvent (approximately 70% by volume).
(above) The lower alcohol content of the hollow fibers is reduced to 1% by weight or less, preferably 0.5% by weight or less after the second cleaning liquid comes into contact with the hollow fibers being cleaned. It is desirable to carry out a second cleaning until then.
第二洗浄液に用いる炭化水素溶媒としては、炭素数が5
〜20.特に5〜15It1度であり、沸点が約25〜
300℃、特に25〜200 ’C程度である脂肪族ま
たは脂環式炭素水素化合物が望ましい、脂肪族炭化水素
化合物の例としては、ペンタン、ヘキサン、ヘプタン、
オクタン、ノナン、デカン、ドデカンなどを挙げること
ができる。脂環式炭化水素化合物の例としては、シクロ
ヘキサン、シクロペンタン、シクロオクタン、シクロド
デカン、メチルシクロヘキサンなどを挙げることができ
る。The hydrocarbon solvent used for the second cleaning liquid has a carbon number of 5.
~20. In particular, it is 5 to 15It1 degree, and the boiling point is about 25 to 15 degrees.
Desirable are aliphatic or alicyclic hydrocarbon compounds having a temperature of about 300°C, especially about 25 to 200'C. Examples of aliphatic hydrocarbon compounds include pentane, hexane, heptane,
Examples include octane, nonane, decane, and dodecane. Examples of alicyclic hydrocarbon compounds include cyclohexane, cyclopentane, cyclooctane, cyclododecane, methylcyclohexane, and the like.
前記の第一洗浄は、前記低級アルコールの沸点までの温
度で、特に0℃以上であって前記低級アルコールの沸点
より5℃以上低い温度までの温度で行なうことか好まし
く、また、前記の第二洗浄は、約o ’c以上てあって
前記炭化水素化合物の沸点より低い温度までの範囲内の
温度で行なうことか好ましく、第二洗浄の温度は30〜
100℃、特に40〜80℃程度の温度で行なうことが
好適である。The first washing is preferably carried out at a temperature up to the boiling point of the lower alcohol, particularly at a temperature of 0°C or higher and 5°C or more lower than the boiling point of the lower alcohol; The washing is preferably carried out at a temperature in the range of about 0'C or more and lower than the boiling point of the hydrocarbon compound, and the temperature of the second washing is from 30 to 30 °C.
It is preferable to carry out the reaction at a temperature of about 100°C, particularly about 40 to 80°C.
洗浄工程か終了した後は、中空糸に乾燥熱処理を行なう
か又は、乾燥熱処理を行なうことなく、第二洗節液に湿
潤状態のままで本発明の特徴的要件であるビニル基含有
上ツマー溶液中の浸漬処理を行なう。After the washing process is completed, the hollow fibers are subjected to a dry heat treatment, or without being subjected to a dry heat treatment, the hollow fibers are left wet in the second washing solution, which is a characteristic requirement of the present invention, and the vinyl group-containing supernatant solution is applied. Perform the soaking process.
本発明においては、ポリイミド気体分子!1膜を、まず
、ビニル基を有するモノマーの溶液中で浸漬処理して、
ポリイミド気体分lll&膜に上記モノマーを付着させ
る。In the present invention, polyimide gas molecules! 1 membrane is first immersed in a solution of a monomer having a vinyl group,
The above monomer is attached to the polyimide gas mixture & membrane.
上記モノマーとしては、スチレン、α−メチルスチレン
、ビニルトルエンの如きスチレン系モノマー、アクリル
醜またはメタクリル酸のメチル、エチル、プロピル、ブ
チルの如き低級アルキルエステルのような一個のビニル
基を有するモノマー、ジビニルベンゼンの如き二個のビ
ニル基を有するモノマーを例示することができる。特に
、−個のビニル基を有するモノマーと二個のビニル基を
有するモノマーとの混合物か好ましい。The above monomers include styrene monomers such as styrene, α-methylstyrene, and vinyltoluene, monomers having one vinyl group such as acrylic acid or lower alkyl esters such as methyl, ethyl, propyl, and butyl methacrylate, and divinyl monomers. Examples include monomers having two vinyl groups such as benzene. Particularly preferred is a mixture of a monomer having - vinyl groups and a monomer having two vinyl groups.
モノマー溶液の溶媒としては、上記モノマーを溶解し、
上記モノマーの重合を阻害しないものてあれば特に限定
はなく、たとえば、ベンゼン、トルエン、キシレンの如
き芳香族炭化水素、ペンタン、ヘキサン、ヘプタン、オ
クタン、ノナン、デカンなどの如き脂肪族炭化水素、シ
クロペンタン、シクロヘキサン、メチルシクロヘキサン
などの如き脂環式炭化水素、クロロホルム、クロルベン
ゼンの如きハロゲン化炭化水素を挙げることができる。As a solvent for the monomer solution, the above monomer is dissolved,
There are no particular limitations on the substance as long as it does not inhibit the polymerization of the above monomers. Mention may be made of alicyclic hydrocarbons such as pentane, cyclohexane, methylcyclohexane, etc., and halogenated hydrocarbons such as chloroform, chlorobenzene.
なお、に記モノマー溶液の溶媒が芳香族炭化水素、ハロ
ゲン化炭化水素などのような、飽和炭化水素以外の溶媒
であった場合には、千ツマー溶液の溶媒は上記分離膜な
浸漬処理したのちに上記飽和炭化水素溶媒で洗浄して、
モノマーの溶媒を飽和炭化水素で置き換えることが望ま
しい。In addition, if the solvent of the monomer solution mentioned above is a solvent other than a saturated hydrocarbon, such as an aromatic hydrocarbon or a halogenated hydrocarbon, the solvent of the monomer solution should be used after the above-mentioned separation membrane immersion treatment. washed with the above saturated hydrocarbon solvent,
It is desirable to replace the monomer solvent with a saturated hydrocarbon.
上記浸漬処理は、−上記モノマー濃度が001〜10重
量%、好ましくは1〜5重量%であり、溶液温度が10
〜100℃、好ましくは40〜80℃である上記七ツマ
ー溶液中にポリイミド気体分i1膜を浸清し、ポリイミ
ド気体分離膜に上記モノマーか0.01〜5重量%付着
するように行なうことにより実施することが好ましい、
また、上記浸漬処理は、常圧下、または必要により加圧
下で行なうことができる。The above-mentioned immersion treatment includes: - the above-mentioned monomer concentration is 0.001 to 10% by weight, preferably 1 to 5% by weight, and the solution temperature is 10% by weight.
By immersing the polyimide gas separation membrane in the above-mentioned seven-mer solution at ~100°C, preferably 40-80°C, so that 0.01-5% by weight of the above monomer adheres to the polyimide gas separation membrane. It is preferable to carry out
Further, the above-mentioned immersion treatment can be carried out under normal pressure or, if necessary, under increased pressure.
さらに、上記モノマー溶液中に、一般にビニル基含有上
ツマ−の重合に使用される重合開始剤、例えば、過酸化
ベンゾイルの如き有機過酸化物、アゾビスイソブチロニ
トリルの如きアゾ化合物を通常使用される量存在させる
ことが好ましい。Furthermore, in the monomer solution, a polymerization initiator generally used for the polymerization of vinyl group-containing polymers, such as an organic peroxide such as benzoyl peroxide, or an azo compound such as azobisisobutyronitrile, is usually used. Preferably, the amount is present.
本発明においては、上記浸漬処理したポリイミド気体分
離膜を、続いて通常は、100〜300℃、好ましくは
150〜250℃の温度で空気または不活性ガス中で、
30〜200分間加熱処理する。この加熱処理は、該ポ
リイミド気体分離膜に付着または含浸されている溶剤お
よび揮発性のモノマーが除去されるまで行なう。In the present invention, the above-mentioned immersion-treated polyimide gas separation membrane is then usually heated in air or an inert gas at a temperature of 100 to 300°C, preferably 150 to 250°C.
Heat treatment for 30-200 minutes. This heat treatment is continued until the solvent and volatile monomer attached to or impregnated in the polyimide gas separation membrane are removed.
なお、これまで中空糸状の気体分離膜な例に挙げて説明
したか、ベース膜として用いる気体分離膜は平膜やチュ
ーブラ−タイプの形状であってもよいことはいうまても
ない。It should be noted that although the explanation has been given using a hollow fiber gas separation membrane as an example, it goes without saying that the gas separation membrane used as the base membrane may have a flat membrane or tubular type shape.
[発明の効果]
本発明に従って処理されたポリイミド気体分離膜の気体
分難速度は、初期速度については未処理のものに劣る場
合もあるが、長期に使用した場合の性能低下が未処理の
ものに比較して顕著に少なくなるため、初期を過ぎた時
点以降については、未処理のものに比較して顕著に高い
気体分離速度を示す。[Effects of the invention] Although the gas separation rate of the polyimide gas separation membrane treated according to the present invention may be inferior to that of the untreated membrane in terms of initial rate, the performance deterioration when used for a long period of time is greater than that of the untreated membrane. As a result, after the initial stage, the gas separation rate is significantly higher than that of untreated gas.
このような優れた効果を奏する作用機構については必ず
しも明らかではないが、前記浸漬処理および加熱処理の
間に上記モノマーが重合してポリマーを形成し、これが
ポリイミド気体分l!1膜に付着しているか、あるいは
吸着されているためと推定される。Although the mechanism of action that produces such excellent effects is not necessarily clear, the monomers polymerize during the immersion treatment and heat treatment to form a polymer, which forms a polyimide gas component l! It is presumed that this is because it is attached to one film or is adsorbed.
以下に参考例および本発明の実施例を示す。Reference examples and examples of the present invention are shown below.
[参考例]
芳香族ポリイミド溶液の調製
3.3’ 、4.4“−ビフェニルテトラカルボン醜二
無水物(s−BPDA)500ミリモル、2.8−ジメ
チル−3,7−ジアミツジベンゾチオフエンー5.5−
ジオキシド450ミリモル、4.4′−ジアミノジフェ
ニルエーテル50ミリモルおよびパラクロルフェノール
1470gを、攪拌機と窒素ガス導入管及び冷却管とが
付設されたセパラブルフラスコに入れ、窒素ガスを流し
ながら室温から180’Cまて約1時間で加熱昇温した
のち、180℃で10時間の重合を行ない、芳香族ポリ
イミド溶液(重合反応液)を得た。[Reference Example] Preparation of aromatic polyimide solution 3.3',4.4''-biphenyltetracarboxylic dianhydride (s-BPDA) 500 mmol, 2.8-dimethyl-3,7-diamitudibenzothiophene -5.5-
450 mmol of dioxide, 50 mmol of 4,4'-diaminodiphenyl ether, and 1,470 g of parachlorophenol were placed in a separable flask equipped with a stirrer, a nitrogen gas introduction tube, and a cooling tube, and heated from room temperature to 180'C while flowing nitrogen gas. After heating and raising the temperature for about 1 hour, polymerization was carried out at 180°C for 10 hours to obtain an aromatic polyimide solution (polymerization reaction liquid).
体 )離 中 糸 の ゛
上記の重合反応液をそのままドープ液として用い、紡糸
装置のチューブ・イン・オリフィス型の中空糸紡糸用ノ
ズル(開口部の内径が1.0mmであるオリフィスの開
口部中央から外径が0.6mmであり、内径が0.3m
mである芯管が同軸状にセットされている)に、70℃
に加熱されたドープ液を加圧して供給し、前記芯管から
窒素ガスを少量供給しながら、前記ドープ液を紡糸用ノ
ズルのオリフィスの開口部内周と芯管の外周との間の環
状空間から押し出して、中空糸状体を形成し、続いて、
その中空糸状体を約70重量%のエタノール水溶液から
なる凝固液(約O″C)に充分に浸漬し凝固させて、湿
潤状態で凝固(固化)している中空糸(パラクロルフェ
ノールの含有率:5重量%)を形成した。この中空糸は
湿潤状態のままカセに巻き取り、さらに、その中空糸の
糸巻体を約50℃のエタノール(第−洗浄液)の流れの
中に浸漬し、次いで第一洗浄の終った湿潤状態の糸巻体
を50℃のn−ヘキサン(第二洗浄液)の流れの中に浸
漬して、第二洗浄を行なった。最後に、第二洗浄の終了
した中空糸を、150℃で1時間、熱風乾燥・熱処理し
て、芳香族ポリイミド製の気体分離用中空糸膜な得た。Body) Separation of the medium yarn ゛Use the above polymerization reaction solution as it is as a dope solution, and insert it into the tube-in-orifice type hollow fiber spinning nozzle of the spinning device (the center of the opening of the orifice with an inner diameter of 1.0 mm). The outer diameter is 0.6mm and the inner diameter is 0.3m.
70°C
A dope solution heated to 100% is supplied under pressure, and while a small amount of nitrogen gas is supplied from the core tube, the dope solution is supplied from the annular space between the inner periphery of the opening of the orifice of the spinning nozzle and the outer periphery of the core tube. extrusion to form a hollow filament, followed by
The hollow fibers are sufficiently immersed in a coagulation solution (approximately O''C) consisting of an aqueous solution of approximately 70% ethanol, and the hollow fibers are coagulated (solidified) in a wet state (parachlorophenol content: :5% by weight).The hollow fibers were wound up in a skein in a wet state, and the wound body of the hollow fibers was further immersed in a flow of ethanol (first cleaning solution) at about 50°C. After the first washing, the wet thread wound body was immersed in a flow of n-hexane (second washing liquid) at 50°C to perform a second washing.Finally, the hollow fibers after the second washing were washed. was dried with hot air and heat treated at 150° C. for 1 hour to obtain a hollow fiber membrane for gas separation made of aromatic polyimide.
[実施例1]
参考例の気体分離用中空糸膜の製造工程において、第二
洗浄の終了した中空糸を、スチレン:ジビニルベンゼン
:過酸化ベンゾイルの重量比が85:10:5であるス
チレン、ジビニルベンゼンおよび過酸化ベンゾイルを、
合計量で5rfL量%含有するシクロヘキサン溶液中に
浸清し、60’Cて5時間処理した。次いで、浸漬処理
した中空糸を50℃のn−ヘキサン中に浸清し、中空糸
に付着していたシクロヘキサンをn−ヘキサンで置換し
た。以上の方法によりモノマー(スチレンとジビニルベ
ンゼン)が1重量%付着した中空糸を製造した。その後
、該中空糸を熱風乾燥器中で150℃で1時間加熱処理
して気体分離用中空糸膜を製造した。[Example 1] In the manufacturing process of the hollow fiber membrane for gas separation of the reference example, the hollow fibers after the second washing were treated with styrene, which has a weight ratio of styrene:divinylbenzene:benzoyl peroxide of 85:10:5. divinylbenzene and benzoyl peroxide,
It was immersed in a cyclohexane solution containing a total amount of 5 rfL and treated at 60'C for 5 hours. Next, the immersed hollow fibers were immersed in n-hexane at 50° C. to replace cyclohexane adhering to the hollow fibers with n-hexane. Hollow fibers to which 1% by weight of monomers (styrene and divinylbenzene) were attached were manufactured by the above method. Thereafter, the hollow fibers were heat-treated at 150° C. for 1 hour in a hot air dryer to produce a hollow fiber membrane for gas separation.
上記中空糸についてガス透過試験用モジュールを作成し
、そのモジュールを使用し、炭酸ガスとメタンガスにつ
いて2.3kg/cm”G (炭酸ガス:0.6kg/
crn’G、メタン: 1.7kg/cm″G)、常温
でのガス透過速度(初期性t@>をそれぞれ測定した。A gas permeation test module was created for the above hollow fibers, and the module was used to test 2.3 kg/cm"G for carbon dioxide and methane gas (carbon dioxide: 0.6 kg/
crn'G, methane: 1.7 kg/cm''G), and gas permeation rate at room temperature (initiality t@>) were measured.
さらにこのモジュール内に窒素を常圧下でみかけの線速
度3.5m/秒の流速で20時間流した後のガス透過速
度(窒素流通後の性能)をそれぞれ測定した。Further, the gas permeation rate (performance after nitrogen flow) was measured after nitrogen was flowed into this module for 20 hours at an apparent linear velocity of 3.5 m/sec under normal pressure.
測定された炭酸ガスの透過速度、および炭酸ガスの透過
速度の測定値とメタンガスの透過速度の測定値に基づい
て算出された選択透過性を第1表に示す。なお、各数値
の表示は下記による。Table 1 shows the measured permeation rate of carbon dioxide and the selective permselectivity calculated based on the measured value of the permeation rate of carbon dioxide and the measured value of the permeation rate of methane gas. In addition, the display of each numerical value is as follows.
炭酸ガス透過速度(P’ Co□):
X I O−’crn”/ crn’−秒・cmHg選
択透過性α(炭酸ガスとメタンガスとの透過速度比):
α= P ’ CO2/ P ’ COa結果を第1表
に示す。Carbon dioxide gas permeation rate (P'Co□):
α=P'CO2/P'COa The results are shown in Table 1.
第1表
p’co2(α) p’co、 (α)実施例1
24 (27) 22 (27)参考例 2
4 (22) 16 (19)[実施例2.3]
スチレン、ジビニルベンゼンおよび過酸化ベンゾイルの
合計量の濃度を0.5重量%に変え、溶媒をベンゼン(
実施例2)またはシクロヘキサン(実施例3)にした溶
液を使用して浸漬処理したほかは、実施例1におけると
同様にして処理して気体分離用中空糸膜を製造した。そ
れらの性能試験結果(ただし、窒素流通時間は70時間
)を第2表に示す。Table 1 p'co2(α) p'co, (α) Example 1
24 (27) 22 (27) Reference example 2
4 (22) 16 (19) [Example 2.3] The total concentration of styrene, divinylbenzene and benzoyl peroxide was changed to 0.5% by weight, and the solvent was changed to benzene (
Hollow fiber membranes for gas separation were produced in the same manner as in Example 1, except for the immersion treatment using a solution of Example 2) or cyclohexane (Example 3). The performance test results (however, the nitrogen flow time was 70 hours) are shown in Table 2.
第2表
P”CO2(a ) P”CO2(a )実施
例2 28 (20) 24 (21)実施例3
29 (21) 25 (22)参考例 2
4 (22) 12 (16)ffS1表と第2
表の結果から明らかなように、無処理の参考例の気体分
離用中空糸膜は、長期使用後に炭酸ガス透過速度の顕著
な低下が見られる。Table 2 P”CO2 (a) P”CO2 (a) Example 2 28 (20) 24 (21) Example 3
29 (21) 25 (22) Reference example 2
4 (22) 12 (16) ffS1 table and 2nd
As is clear from the results in the table, the untreated reference example hollow fiber membrane for gas separation shows a significant decrease in carbon dioxide gas permeation rate after long-term use.
一方、本発明に従って処理した気体分離用中空糸膜は長
期使用後の炭酸ガス透過速度の低下が少なくなっている
。On the other hand, the hollow fiber membrane for gas separation treated according to the present invention shows less decrease in carbon dioxide gas permeation rate after long-term use.
Claims (1)
膜を、ビニル基を有するモノマーの溶液中で浸漬処理し
て該気体分離膜に該モノマーを付着させ、次いで、該モ
ノマーが付着した該気体分離膜を加熱処理することを特
徴とする気体分離膜の製造方法。 2、該モノマーの付着量が、付着前の該気体分離膜に対
し、0.01〜5重量%になるように浸漬処理すること
を特徴とする特許請求の範囲第1項記載の製造方法。 3、該モノマーの溶液中に該モノマーの重合開始剤を共
存させることを特徴とする特許請求の範囲第1項記載の
製造方法。 4、該浸漬処理を10〜100℃の温度で行ない、該加
熱処理を100〜300℃の温度で行なうことを特徴と
する特許請求の範囲第1項記載の製造方法。[Claims] 1. A gas separation membrane having a homogeneous layer made of aromatic polyimide is immersed in a solution of a monomer having a vinyl group to adhere the monomer to the gas separation membrane, and then the monomer is 1. A method for producing a gas separation membrane, which comprises heat-treating the gas separation membrane to which is adhered. 2. The manufacturing method according to claim 1, characterized in that the immersion treatment is carried out so that the amount of the monomer deposited on the gas separation membrane before deposition is 0.01 to 5% by weight. 3. The manufacturing method according to claim 1, characterized in that a polymerization initiator for the monomer is present in the solution of the monomer. 4. The manufacturing method according to claim 1, wherein the immersion treatment is performed at a temperature of 10 to 100°C, and the heat treatment is performed at a temperature of 100 to 300°C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61240285A JPS6393326A (en) | 1986-10-09 | 1986-10-09 | Preparation of gas separating membrane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61240285A JPS6393326A (en) | 1986-10-09 | 1986-10-09 | Preparation of gas separating membrane |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS6393326A true JPS6393326A (en) | 1988-04-23 |
Family
ID=17057208
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61240285A Pending JPS6393326A (en) | 1986-10-09 | 1986-10-09 | Preparation of gas separating membrane |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6393326A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02293030A (en) * | 1989-05-09 | 1990-12-04 | Ube Ind Ltd | Separation of aqueous solution of inorganic substance by permeation and vaporization |
JP2014113550A (en) * | 2012-12-10 | 2014-06-26 | Fujifilm Corp | Gas separation composite membrane and manufacturing method thereof |
WO2015122312A1 (en) * | 2014-02-12 | 2015-08-20 | 富士フイルム株式会社 | Composite gas separation membrane, gas separation module, gas separation apparatus, gas separation method and method for producing composite gas separation membrane |
-
1986
- 1986-10-09 JP JP61240285A patent/JPS6393326A/en active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02293030A (en) * | 1989-05-09 | 1990-12-04 | Ube Ind Ltd | Separation of aqueous solution of inorganic substance by permeation and vaporization |
JP2014113550A (en) * | 2012-12-10 | 2014-06-26 | Fujifilm Corp | Gas separation composite membrane and manufacturing method thereof |
US9687777B2 (en) | 2012-12-10 | 2017-06-27 | Fujifilm Corporation | Gas separation composite membrane, gas separation module, gas separation apparatus, gas separation method, and method of producing gas separation composite membrane |
WO2015122312A1 (en) * | 2014-02-12 | 2015-08-20 | 富士フイルム株式会社 | Composite gas separation membrane, gas separation module, gas separation apparatus, gas separation method and method for producing composite gas separation membrane |
JP2015150474A (en) * | 2014-02-12 | 2015-08-24 | 富士フイルム株式会社 | Gas separation composite membrane, gas separation module, gas separator, gas separation method and production method of gas separation composite membrane |
US10226743B2 (en) | 2014-02-12 | 2019-03-12 | Fujifilm Corporation | Gas separation composite membrane, gas separation module, gas separation device, gas separation method, and method of producing gas separation composite membrane |
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