JPH02268819A - Separation of aqueous solution of organic matter by permeation and vaporization - Google Patents
Separation of aqueous solution of organic matter by permeation and vaporizationInfo
- Publication number
- JPH02268819A JPH02268819A JP1087079A JP8707989A JPH02268819A JP H02268819 A JPH02268819 A JP H02268819A JP 1087079 A JP1087079 A JP 1087079A JP 8707989 A JP8707989 A JP 8707989A JP H02268819 A JPH02268819 A JP H02268819A
- Authority
- JP
- Japan
- Prior art keywords
- separation
- aqueous solution
- separation membrane
- asymmetric
- 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.)
- Granted
Links
- 238000000926 separation method Methods 0.000 title claims description 88
- 239000007864 aqueous solution Substances 0.000 title claims description 38
- 239000005416 organic matter Substances 0.000 title claims description 22
- 230000008016 vaporization Effects 0.000 title abstract 2
- 238000009834 vaporization Methods 0.000 title abstract 2
- 239000012528 membrane Substances 0.000 claims abstract description 82
- 239000004642 Polyimide Substances 0.000 claims abstract description 35
- 229920001721 polyimide Polymers 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 15
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical class OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims description 31
- 238000005373 pervaporation Methods 0.000 claims description 28
- -1 aromatic diamine compound Chemical class 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 18
- 150000004984 aromatic diamines Chemical class 0.000 claims description 10
- 239000012510 hollow fiber Substances 0.000 abstract description 20
- 150000004985 diamines Chemical class 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000012141 concentrate Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 235000013849 propane Nutrition 0.000 description 9
- 239000010408 film Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000012466 permeate Substances 0.000 description 6
- 239000001294 propane Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 230000003204 osmotic effect Effects 0.000 description 4
- 229940090668 parachlorophenol Drugs 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000002152 aqueous-organic solution Substances 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 2
- 239000004472 Lysine Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NKNIZOPLGAJLRV-UHFFFAOYSA-N 2,2-diphenylpropane-1,1-diamine Chemical compound C=1C=CC=CC=1C(C(N)N)(C)C1=CC=CC=C1 NKNIZOPLGAJLRV-UHFFFAOYSA-N 0.000 description 1
- KKTUQAYCCLMNOA-UHFFFAOYSA-N 2,3-diaminobenzoic acid Chemical class NC1=CC=CC(C(O)=O)=C1N KKTUQAYCCLMNOA-UHFFFAOYSA-N 0.000 description 1
- QHXGQHLKDODBGD-UHFFFAOYSA-N 2-[2-[2-(2-aminophenoxy)phenoxy]phenoxy]aniline Chemical class NC1=CC=CC=C1OC1=CC=CC=C1OC1=CC=CC=C1OC1=CC=CC=C1N QHXGQHLKDODBGD-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-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
- GEYAGBVEAJGCFB-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)propan-2-yl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1C(C)(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 GEYAGBVEAJGCFB-UHFFFAOYSA-N 0.000 description 1
- HCJSCAOEKCHDQO-UHFFFAOYSA-N 4-[3-[3-(4-aminophenoxy)phenoxy]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=C(OC=3C=CC(N)=CC=3)C=CC=2)=C1 HCJSCAOEKCHDQO-UHFFFAOYSA-N 0.000 description 1
- LDFYRFKAYFZVNH-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenoxy]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 LDFYRFKAYFZVNH-UHFFFAOYSA-N 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- MHDWQCSVXCLPGW-UHFFFAOYSA-N dibenzothiophene-1,2-diamine Chemical class C1=CC=C2C3=C(N)C(N)=CC=C3SC2=C1 MHDWQCSVXCLPGW-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical class C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- ZIYVHBGGAOATLY-UHFFFAOYSA-L methylmalonate(2-) Chemical compound [O-]C(=O)C(C)C([O-])=O ZIYVHBGGAOATLY-UHFFFAOYSA-L 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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】
〔産業上の利用分野〕
この発明は、ビフェニルテトラカルボン酸類を主成分と
するテトラカルボン酸成分と、ジ〔（アミノフェノキシ
）フェニル〕プロパン類を主として含有する芳香族ジア
ミン成分とから得られた可溶性の芳香族ポリイミドで形
成されている非対称性分離膜（例えば、平膜、又は中空
糸膜なと）を使用して、有機物水溶液を前記非対称性分
離膜に直接接触させて水分を選択的に浸透気化させる浸
透気化分離方法（パーベーパレーション法）で、有機水
溶液から水分を除去して、有機物を濃縮したり、分離し
たりする分離方法に係わる。Detailed Description of the Invention [Industrial Application Field] The present invention relates to an aromatic diamine mainly containing a tetracarboxylic acid component mainly containing biphenyltetracarboxylic acids and di[(aminophenoxy)phenyl]propanes. Using an asymmetric separation membrane (for example, a flat membrane or a hollow fiber membrane) formed of a soluble aromatic polyimide obtained from a component, an aqueous organic substance solution is brought into direct contact with the asymmetric separation membrane. The pervaporation separation method (pervaporation method) involves selectively pervaporating water using water, and is related to a separation method in which water is removed from an organic aqueous solution to concentrate or separate organic substances.
Ｃ従来技術の説明〕
従来、有機物水溶液を有機物と水分とに分離する方法と
して、蒸留法が知られている。しかし、蒸留法では、共
沸混合物、あるいは近沸点混合物、熱で化学変化を起こ
し易い有機化合物を分離することは、極めて困難であっ
た。C Description of Prior Art] Distillation is conventionally known as a method for separating an aqueous solution of organic matter into organic matter and water. However, with the distillation method, it is extremely difficult to separate azeotropic mixtures, near-boiling point mixtures, and organic compounds that are susceptible to chemical changes due to heat.
これらの問題点を解決するために、分離膜を用いて分離
する方法が研究されている。分離膜を用いて有機物水溶
液を濃縮、分離する方法において、一部の低濃度の有機
物水溶液の濃縮に対しては、有機物水溶液を分離膜と接
触させて特定の液状成分を浸透圧の差で選択的に透過さ
せる逆浸透法が用いられてきた。しかしながら、逆浸透
法は分離液の浸透圧以上の圧力を加える必要があるため
に、浸透圧が高くなる高濃度の有機物水溶液について適
用できないのであり、従って分離可能な有機物水溶液の
濃度範囲に限界がある。In order to solve these problems, separation methods using separation membranes are being researched. In the method of concentrating and separating organic substance aqueous solutions using a separation membrane, for concentrating some low-concentration organic substance aqueous solutions, the organic substance aqueous solution is brought into contact with the separation membrane and specific liquid components are selected by the difference in osmotic pressure. Reverse osmosis has been used to penetrate the membrane. However, the reverse osmosis method cannot be applied to high-concentration aqueous organic matter solutions where the osmotic pressure is high because it is necessary to apply a pressure higher than the osmotic pressure of the separation liquid.Therefore, there is a limit to the concentration range of organic matter aqueous solutions that can be separated. be.
これに対して、浸透圧の影響を受けない分離法ととして
、浸透気化分離法（パーベーパレーション法）が、新し
い分離膜使用の分離法として、注目されつつある。この
浸透気化分離法は、選択透過性を有する分離膜の一方の
側（供給側）に、分離されるべき有機物水溶液を液状の
ままで供給し、分離膜の供給側と直接に接触させ、分離
膜の他方の側（透過側）を真空又は減圧状態となし、そ
の結果、分離膜の供給側から透過側へ選択的に透過する
物質（水分など）を気体状で取り出し、有機物水溶液を
濃縮したり、有機物と水分などとを分離する方法である
。In contrast, a pervaporation separation method that is not affected by osmotic pressure is attracting attention as a new separation method that uses a separation membrane. In this pervaporation separation method, the aqueous organic matter solution to be separated is supplied in liquid form to one side (feed side) of a separation membrane that has selective permselectivity, and is brought into direct contact with the feed side of the separation membrane to separate it. The other side of the membrane (permeation side) is placed in a vacuum or reduced pressure state, and as a result, substances (such as water) that selectively permeate from the supply side of the separation membrane to the permeation side are extracted in gaseous form, and the organic aqueous solution is concentrated. It is a method of separating organic matter from moisture.
一方、芳香族ポリイミドは、ポリアミド膜、セルロース
膜、酢酸セルロース膜などよりも耐熱性、耐薬品性など
に極めて優れているので、分離膜の素材として最近注目
されてきており、芳香族ポリイミド製の非対称性分離膜
が、有機物水溶液の蒸気の水分離用にも提案されつつあ
る。しかし、従来の公知の芳香族ポリイミド膜は、高温
下、有機物水溶液又は水と長時間接触していると、芳香
族ポリイミドの加水分解作用により、ポリマーの劣化が
開始し、次第にその劣化が進行するので、非対称性分離
膜の透過性能や機械的強度などの著しい低下を招くとい
うことがあり、耐久性において問題があり、有機物水溶
液の膜分離法においては、必ずしも充分に満足できるも
のではなかった。また、公知の芳香族ポリイミド膜は、
有機物水溶液の浸透気化分離法に使用した場合に、水な
どの透過速度、有機物と水との選択的な分離性能などに
おいても必ずしも満足すべきものではないという問題点
もあった。On the other hand, aromatic polyimide has recently attracted attention as a material for separation membranes because it has extremely superior heat resistance and chemical resistance compared to polyamide membranes, cellulose membranes, cellulose acetate membranes, etc. Asymmetric separation membranes are also being proposed for water separation of vapors from organic aqueous solutions. However, when conventional aromatic polyimide membranes are in contact with an organic aqueous solution or water at high temperatures for a long time, the polymer begins to deteriorate due to the hydrolytic action of the aromatic polyimide, and the deterioration gradually progresses. As a result, the permeation performance and mechanical strength of the asymmetric separation membrane may be significantly reduced, leading to problems in durability, and membrane separation methods for aqueous organic solutions have not always been fully satisfactory. In addition, known aromatic polyimide membranes are
When used in a pervaporation separation method for an aqueous solution of organic matter, there is also the problem that the permeation rate of water, selective separation performance between organic matter and water, etc. are not necessarily satisfactory.
この発明の目的は、芳香族ポリイミド製の非対称性分離
膜を使用する有機物水溶液の浸透気化分離方法において
、公知の浸透気化法における欠点もなく、有機物水溶液
から水分を効率的および選択的に浸透気化法で分離する
ことができ、しかも、工業的に長期間浸透気化分離法を
実施できる？芳香族ポリイミド膜を用いる浸透気化分離
方法」を提供することである。An object of the present invention is to provide a pervaporative separation method for an organic substance aqueous solution using an asymmetric separation membrane made of aromatic polyimide, to efficiently and selectively pervaporate water from an organic substance aqueous solution without the drawbacks of known pervaporation methods. Is it possible to carry out the pervaporation separation method industrially for a long period of time? An object of the present invention is to provide a "pervaporation separation method using an aromatic polyimide membrane."
この発明は、有機物水溶液を、耐熱性重合体からなる非
対称性分離膜と接触させて、有機物水溶液から主として
水分を選択的に浸透気化させる浸透気化分離方法におい
て、
前記の耐熱性重合体が、
で示される反復単位を６０〜１００モル含有し、そして
、残部の反復単位がビフェニルテトラカルボン酸類とヘ
ンゼン環を２〜５個有する他の芳香族ジアミン化合物で
ある芳香族ジアミン成分とから形成された反復単位であ
る可溶性の芳香族ポリイミドであることを特徴とする有
機物水溶液の浸透気化分離方法に関する。This invention provides a pervaporation separation method for selectively pervaporating mainly water from the organic matter aqueous solution by contacting the organic matter aqueous solution with an asymmetric separation membrane made of a heat-resistant polymer, wherein the heat-resistant polymer is A repeating unit containing 60 to 100 moles of the indicated repeating unit, and the remaining repeating unit is formed from a biphenyltetracarboxylic acid and an aromatic diamine component that is another aromatic diamine compound having 2 to 5 Hensen rings. The present invention relates to a method for pervaporative separation of an aqueous solution of organic matter, characterized in that the unit is a soluble aromatic polyimide.
以下、この各発明の各要件についてさらに詳しく説明す
る。Each requirement of each invention will be explained in more detail below.
本発明の浸透気化分離方法において使用する非対称性分
離膜は、概略、前述一般弐Ｉを主として有する可溶性の
芳香族ポリイミドから形成されており、選択的な分離性
能に直接的に係わる極めて薄い均質層（好ましくは厚さ
約０．００１〜５μｍの均質層）と、その均質層の支持
を行っている比較的厚いポーラスな多孔質層（好ましく
は厚さ約１０〜２０００μｍの多孔質層）とを連続的に
一体に有していて、有機物水溶液中の水分を選択的に透
過させる性能を有する、例えば、平膜状、中空糸状など
の形状の非対称性分離膜（厚さ方向において、均質でな
く、非対称性な微細孔状態を有する分離膜）である。The asymmetric separation membrane used in the pervaporation separation method of the present invention is generally formed from a soluble aromatic polyimide mainly having the above-mentioned general compound I, and is an extremely thin homogeneous layer that is directly related to selective separation performance. (preferably a homogeneous layer with a thickness of about 0.001-5 μm) and a relatively thick porous layer (preferably a porous layer with a thickness of about 10-2000 μm) supporting the homogeneous layer. An asymmetrical separation membrane (not homogeneous in the thickness direction) that has a continuous integral structure and has the ability to selectively permeate water in an organic aqueous solution, for example, in the shape of a flat membrane or hollow fiber. , a separation membrane with asymmetric micropore conditions).
前記の非対称性分離膜を形成している可溶性の芳香族ポ
リイミドは、前述の一般式Ｉで示される反復単位を、６
０モル％以上、好ましくは６５〜９５モル％、特に７０
〜９０モル％含有しており、反復単位の残部がビフェニ
ルテトラカルボン酸類とベンゼン環を２〜５個、特に２
〜４個有する他の芳香族ジアミン化合物である芳香族ジ
アミン成分とから形成された反復単位であるようなｒフ
ェノール系の有機溶媒などに可溶性である高分子量の芳
香族ポリイミドＪである。The soluble aromatic polyimide forming the asymmetric separation membrane has 6 repeating units represented by the general formula I.
0 mol% or more, preferably 65 to 95 mol%, especially 70 mol%
It contains ~90 mol%, and the remainder of the repeating unit consists of biphenyltetracarboxylic acids and 2 to 5 benzene rings, especially 2
It is a high molecular weight aromatic polyimide J that is soluble in phenolic organic solvents, etc., and is a repeating unit formed from an aromatic diamine component, which is another aromatic diamine compound having ~4 units.
前記の芳香族ポリイミドは、例えば、ビフェニルテトラ
カルボン酸類を６０モル％以上、好ましくは８０モル％
以上含有するｒ芳香族テトラカルボン酸成分ｊと、
ジ〔（アミノフェノキシ）フェニル〕プロパン類を６０
モル％以上、好ましくは８０モル％以上含有するｒ芳香
族ジアミン成分Ｊとを、略等モル、フェノール系有機溶
媒中に添加し均一に溶解させながら、その溶液を約１５
０〜２５０°Ｃの高温に加熱するか、あるいは、約１０
〜１００°Ｃ程度の低温でイミド化剤の存在下に反応さ
せるかして、前記溶液中の両成分を重合およびイミド化
することによって生成することができる。The aromatic polyimide contains, for example, 60 mol% or more of biphenyltetracarboxylic acids, preferably 80 mol%.
r aromatic tetracarboxylic acid component j containing 60% or more of di[(aminophenoxy)phenyl]propanes;
R aromatic diamine component J containing mol% or more, preferably 80 mol% or more, is added to a phenolic organic solvent in approximately equal moles, and while uniformly dissolving the solution, about 15%
Heat to a high temperature of 0 to 250°C or about 10
It can be produced by polymerizing and imidizing both components in the solution by reacting in the presence of an imidizing agent at a low temperature of about 100°C.
前記のビフェニルテトラカルボン酸類としては、２．３
．３’、４’−又は３．３’、４．４’−ビフェニルテ
トラカルボン酸又はそれらの酸二無水物、あるいは、そ
れらの酸の塩または低級アルコールエステル化物等を挙
げることができる。The above biphenyltetracarboxylic acids include 2.3
．． Examples include 3', 4'- or 3.3', 4.4'-biphenyltetracarboxylic acids, acid dianhydrides thereof, salts of these acids, and lower alcohol esters thereof.
前記のビフェニルテトラカルボン酸類としては、特に、
２．３，３“、４”−または３．３’、４，４°−ビフ
ェニルテトラカルボン酸二無水物が、可溶性の芳香族ポ
リイミドを製造する上で好ましい。The above-mentioned biphenyltetracarboxylic acids include, in particular,
2.3,3", 4"- or 3.3', 4,4[deg.]-biphenyltetracarboxylic dianhydride is preferred for producing soluble aromatic polyimides.
前記のテトラカルボン酸成分としては、前記のビフェニ
ルテトラカルボン酸類と共に、例えば、ピロメリットＭ
、３＋３’＋４＋４’−ビフェニルエーテルテトラカル
ボン酸、３．３”、 ４．４’−ベンゾフェノンテトラ
カルボン酸、２．２−ビス（３，４−ジカルボキシフェ
ニル）プロパン、ビス（３，４−ジカルボキシフェニル
）メタン、又はそれらの酸無水物などを、少ない割合（
特に好ましくは２０モル％以下、さらに好ましくは１０
モル％以下の割合）で併用されているものであってもよ
い。As the tetracarboxylic acid component, in addition to the biphenyltetracarboxylic acids, for example, pyromellit M
, 3+3'+4+4'-biphenyl ether tetracarboxylic acid, 3.3", 4.4'-benzophenone tetracarboxylic acid, 2.2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)propane, carboxyphenyl)methane, or their acid anhydrides, etc., in a small proportion (
Particularly preferably 20 mol% or less, more preferably 10
They may be used together in a ratio of mol % or less.
前記の各芳香族ポリイミドの製法において、テトラカル
ボン酸成分中のビフェニルテトラルボン酸類の含有割合
が余りに少なくなり過ぎると、得られる芳香族ポリイミ
ドは、フェノール系有機溶媒に対して溶解性の低いもの
となったり、品質の安定した非対称性分離膜を製造する
ことができなくなったり、得られた非対称性分離膜の浸
透気化法における分離性能が劣るので好ましくない。In each of the above aromatic polyimide production methods, if the content of biphenyltetralboxylic acids in the tetracarboxylic acid component becomes too low, the resulting aromatic polyimide will have low solubility in phenolic organic solvents. This is not preferable because it may become impossible to produce an asymmetric separation membrane with stable quality, or the separation performance of the obtained asymmetric separation membrane in pervaporation method will be poor.
前記の一般式Ｉで示される反復単位を形成するための芳
香族ジアミン成分の主成分として使用されるジ〔（アミ
ノフェノキシ）フェニル〕ピロパン類は、一般式■
で示される芳香族ジアミン化合物であり、例えば、２．
２−ビス（４−（４−アミノフェノキシ）フェニル〕プ
ロパン、２．２−ビス（４−（３−アミノフェノキシ）
フェニル〕プロパン、２．２−ビス（３−（４−アミノ
フェノキシ）フェニル〕プロパン、２．２−ビス〔３（
３−アミノフェノキシ）フェニル〕プロパンなどの２．
２−ビス〔（アミノフェノキシ）フェニル〕プロパン類
を好適に挙げることができる。The di[(aminophenoxy)phenyl]pyropanes used as the main component of the aromatic diamine component for forming the repeating unit represented by the general formula I above are aromatic diamine compounds represented by the general formula (■). , for example, 2.
2-bis(4-(4-aminophenoxy)phenyl)propane, 2.2-bis(4-(3-aminophenoxy)
Phenyl]propane, 2.2-bis(3-(4-aminophenoxy)phenyl)propane, 2.2-bis[3(
2. such as 3-aminophenoxy)phenyl]propane.
Preferred examples include 2-bis[(aminophenoxy)phenyl]propanes.
この発明の非対称性分離膜を形成している芳香族ポリイ
ミドにおいては、前述の一般式ｌで示される反復単位６
０モル％以上含有していて、その残部が、ビフェニルテ
トラカルボン酸類とベンゼン環を２〜５個有する他の芳
香族ジアミン化合物である芳香族ジアミン成分とから形
成された反復単位である。In the aromatic polyimide forming the asymmetric separation membrane of the present invention, the repeating unit 6 represented by the above general formula l is
The remainder is a repeating unit formed from biphenyltetracarboxylic acids and an aromatic diamine component which is another aromatic diamine compound having 2 to 5 benzene rings.
前記のベンゼン環を２〜５個有する他の芳香族ジアミン
化合物としては、
（ａ）ベンゼン ２ する ジアミン 人４．
４′−ジアミノジフェニルエーテル、３，４゛−ジアミ
ノジフェニルエーテル、３，３”−ジアミノジフエニル
エーテルなどのジアミノジフェニルエーテル類、４．４
゛−ジアミノジフェニルメタン、３．４’−ジアミノジ
フェニルメタン、 ３．３’−ジアミノジフェニルメタ
ンなどのジアミノジフェニルメタン類、ジアミノジフェ
ニルプロパン？’４、ｏ−ジアニシジン、０−トリジン
、ｍ−）リジンなどのジアミノビフェニル類、ジアミノ
ジフェニルチオエーテル類、ジアミノジフェニルスルホ
ン類、ジアミノジフェニレンスルホン類、ジアミノジベ
ンゾチオフェン類、ジアミノチオキサンチン類など、
（ｂ）ベンゼン を３ する ジアミン 人１．
４−ビス（３−アミノフェノキシ）ベンゼン、Ｉ。Other aromatic diamine compounds having 2 to 5 benzene rings include (a) benzene 2 diamine 4.
Diaminodiphenyl ethers such as 4'-diaminodiphenyl ether, 3,4''-diaminodiphenyl ether, 3,3''-diaminodiphenyl ether, 4.4
Diaminodiphenylmethanes such as ゛-diaminodiphenylmethane, 3.4'-diaminodiphenylmethane, 3.3'-diaminodiphenylmethane, diaminodiphenylpropane? Diaminobiphenyls such as 4,o-dianisidine, 0-tolidine, m-)lysine, diaminodiphenylthioethers, diaminodiphenylsulfones, diaminodiphenylenesulfones, diaminodibenzothiophenes, diaminothioxanthines, etc. (b ) Diamine that makes benzene 3 1.
4-bis(3-aminophenoxy)benzene, I.
４−ビス（４−アミノフェノキシ）ベンゼン、１．３−
ビス（３−アミノフェノキシ）ベンゼン、■、３−ビス
（４−アミノフェノキシ）ベンゼンなどのビス（アミノ
フェノキシ）ベンゼン類などのベンゼン環を３個有する
芳香族ジアミン化合物など、あるいは、（Ｃ）ベンゼン
を４ する ジアミン 人ビス（４−（４−ア
ミノフェノキシ）フェニル〕エーテル、ビス（４−（３
−アミノフェノキシ）フェニル〕エーテル、ビス（３−
（４−アミノフェノキシ）フェニル］エーテル、ビス（
３−（３−アミノフェノキシ）フェニル〕エーテルなど
のビス〔（アミノフェノキシ）フェニル〕エーテル類、
４，４”−ビス（４−アミノフェノキシ）ビフェニル、
４．４゛−ビス（３−アミノフェノキシ）ビフェニルな
どの４，４−ジ（アミノフェノキシ）ビフェニル類、ジ
〔（アミノフェノキシ）フェニル〕メタン類などを挙げ
ることができる。4-bis(4-aminophenoxy)benzene, 1.3-
(C) benzene Diamine Bis(4-(4-aminophenoxy)phenyl)ether, Bis(4-(3-aminophenoxy)phenyl)
-aminophenoxy)phenyl]ether, bis(3-
(4-aminophenoxy)phenyl]ether, bis(
Bis[(aminophenoxy)phenyl]ethers such as 3-(3-aminophenoxy)phenyl]ether,
4,4”-bis(4-aminophenoxy)biphenyl,
Examples include 4,4-di(aminophenoxy)biphenyls such as 4.4'-bis(3-aminophenoxy)biphenyl, and di[(aminophenoxy)phenyl]methanes.
なお、前記の芳香族ジアミン成分は、フェニレンジアミ
ン類、ジアミノ安息香酸類などの？ベンゼン環を１個有
する芳香族ジアミン化合物１などが少い割合（１０モル
％以下の含有割合）で含有されていてもよい。The aromatic diamine components mentioned above include phenylene diamines, diaminobenzoic acids, etc. Aromatic diamine compound 1 having one benzene ring may be contained in a small proportion (content of 10 mol% or less).
この発明において使用される前述の芳香族ポリイミドか
らなる各非対称性分離膜は、芳香族ポリイミドのフェノ
ール系溶媒溶液を使用して、その溶液の薄膜（平膜状、
中空糸状）を、流延法、押出し法などによって形成し、
次いで、その薄膜を比較的低温の凝固液と接触させてそ
の薄膜を凝固させて平膜状又は中空糸状の非対称性分Ｍ
膜を形成する湿式製膜法で製造することができ、例えば
、特開昭５６−２１６０２号、特開昭５６−１５７４３
５号公報などに記載されているような従来公知の製膜方
法によって製造することができる。Each of the asymmetric separation membranes made of aromatic polyimide used in this invention is prepared by using a solution of aromatic polyimide in a phenolic solvent, forming a thin film (flat film shape,
hollow fiber) is formed by a casting method, an extrusion method, etc.
Next, the thin film is brought into contact with a relatively low-temperature coagulation liquid to solidify the thin film to form an asymmetrical component M in the form of a flat film or hollow fiber.
It can be manufactured by a wet film forming method to form a film, for example, JP-A-56-21602, JP-A-56-15743.
It can be manufactured by a conventionally known film forming method such as that described in Japanese Patent No. 5.
前記の非対称性分離膜の製造法において、湿式製膜法で
製造された非対称性分離膜は、適当な有機溶媒（例えば
、炭素数１〜６の低級アルコール類、および、炭素数１
〜８の低級脂肪族又は脂環式炭化水素溶媒など）で洗浄
し、さらに、充分に乾燥した後、さらに、窒素、空気な
どの気体の雰囲気下、約１５０〜４２０°Ｃ１特に１８
０〜４００°Ｃの温度で０．１〜５時間程度の熱処理す
ることが適当である。In the above method for producing an asymmetric separation membrane, the asymmetric separation membrane produced by the wet membrane forming method is prepared using a suitable organic solvent (for example, a lower alcohol having 1 to 6 carbon atoms, and a lower alcohol having 1 to 6 carbon atoms).
~8 lower aliphatic or alicyclic hydrocarbon solvents, etc.), and further dried thoroughly, and further heated at about 150 to 420 °C, especially 18 in an atmosphere of gas such as nitrogen or air.
It is appropriate to carry out the heat treatment at a temperature of 0 to 400°C for about 0.1 to 5 hours.
この発明で使用する非対称性分離膜は、有機物水溶液（
有機物濃度が５０重量％である）を使用して浸透気化分
離を行った場合に、選択的に透過する水分の透過速度Ｑ
が、約０．２ｋｇ／ｆＴｆ・ｌｌｒ以上、特に約０．４
〜５．０ ｋｇ／ ｒｒｆ−Ｈｒ程度であって、透過し
た水分と透過しなかった有機物との分離性能（後で述べ
る分離係数α＝水の透過速度／エタノールの透過速度）
が、２０以上、特に２５〜２００程度であることが好ま
しい。The asymmetric separation membrane used in this invention is an organic matter aqueous solution (
The permeation rate Q of selectively permeated water when pervaporative separation is performed using organic matter concentration of 50% by weight
However, about 0.2 kg/fTf・llr or more, especially about 0.4
~5.0 kg/rrf-Hr, separation performance between permeated water and unpermeated organic matter (separation coefficient α = water permeation rate/ethanol permeation rate, which will be described later)
is preferably 20 or more, particularly about 25 to 200.
この発明の浸透気化分離方法は、
（ａ） 前述の芳香族ポリイミドからなる非対称性分
離膜（平膜状、中空糸状）が内蔵されている分離膜モジ
ュールに、有機物水溶液を供給し、そして、を機吻水溶
液を分離膜モジュール内の前記非対称性分離膜の供給側
と直接に接触させ、（ｂ） 前記非対称性分離膜の透
過側を、必要であれば、キャリヤーガス（スィーブガス
）を流しながら、あるいは、分離膜モジュールの外部に
設置された減圧ポンプなどと連結して減圧状態としてお
き、前記の供給された有機物水溶液から、前記非対称性
分離膜を介して、水分を選択的に浸透・透過させ、そし
て、気化させて分離し、（Ｃ） 最後に、前記の非対
称性分離膜の未透過側（供給側）から分離膜モジュール
の外部へ、前記分離膜を透過しなかった濃縮された残部
の有機物水溶液を取り出して回収し、同時に、非対称性
分離脱の透過側から分離膜モジュールの外部へ、前記の
分離膜を選択的に透過した水分を主成分とする透過蒸気
（透過物）を取り出し、必要であればその透過蒸気（透
過物）を冷却し凝縮して回収するのである。The pervaporation separation method of the present invention includes: (a) supplying an organic substance aqueous solution to a separation membrane module incorporating the asymmetric separation membrane (flat membrane type, hollow fiber type) made of the above-mentioned aromatic polyimide; (b) bringing the aqueous solution into direct contact with the feed side of the asymmetric separation membrane in the separation membrane module; (b) flowing a carrier gas (sweve gas) through the permeate side of the asymmetric separation membrane, if necessary; Alternatively, the separation membrane module is connected to a vacuum pump or the like installed outside the separation membrane module to maintain a reduced pressure state, and water is selectively permeated and permeated from the supplied organic aqueous solution through the asymmetric separation membrane. , and then vaporized and separated, (C) Finally, the concentrated remainder that did not pass through the separation membrane is transferred from the unpermeated side (supply side) of the asymmetric separation membrane to the outside of the separation membrane module. Taking out and recovering the organic matter aqueous solution, and at the same time taking out the permeated vapor (permeate) mainly composed of water that has selectively permeated the separation membrane from the permeation side of the asymmetric separation/desorption to the outside of the separation membrane module, If necessary, the permeated vapor (permeate) is cooled, condensed, and recovered.
この発明では、分離膜モジュールへ供給される有機物水
溶液は、約２５〜１２０°Ｃ１特に好ましくは５０〜ｌ
ＯＯ°Ｃ程度の温度であることが好ましい。In this invention, the organic aqueous solution supplied to the separation membrane module is about 25 to 120°C, particularly preferably 50 to 120°C.
Preferably, the temperature is around OO°C.
この発明の浸透気化分離方法では、分離方法に適用され
る圧力が、通常、分離膜の透過側の圧を供給側の圧より
も低圧とし、しかも、供給側の圧を大気圧〜６０ｋｇ１
０ｆ？、好ましくは大気圧〜３０ｋｇ ／ ｃｒＡと程
度することが好ましい。In the pervaporation separation method of the present invention, the pressure applied to the separation method is usually such that the pressure on the permeate side of the separation membrane is lower than the pressure on the supply side, and the pressure on the supply side is from atmospheric pressure to 60 kg1.
0f? , preferably about atmospheric pressure to 30 kg/crA.
前記の分離膜モジュール内の非対称性分離膜の透過側は
、有機物水溶液の浸透気化分離を行う際に、スィーブガ
スを流すか、または、減圧状態とすればよいが、その減
圧状態は、大気圧より低圧となっていればよく、特に好
ましくは約２００トール以下、さらに好ましくは１００
１−−ル以下に減圧されていることが好ましい。The permeation side of the asymmetric separation membrane in the separation membrane module may be subjected to a sweep gas or to a reduced pressure state when performing pervaporation separation of an aqueous organic solution, but the reduced pressure state is lower than atmospheric pressure. It is sufficient that the pressure is low, particularly preferably about 200 torr or less, and even more preferably about 100 torr or less.
It is preferable that the pressure is reduced to 1-liter or less.
この発明における有機物水溶液の浸透気化分離方法を適
用することができる有機物水溶液としては、種々の有機
物の水溶液を使用することができるが、例えば、前記有
機物としては、例えば、メタノール、エタノール、ｎ−
プロパツール、イソプロパツール、ｎ−ブタノール、５
ｅｃ−ブタノール１、ｔｅｒｔ−７’タノール、エチレ
ングリコールなどの脂肪族アルコール、シクロヘキサノ
ールの脂環式アルコール、ベンジルアルコールなどの芳
香族アルコール、ギ酸、酢酸、プロピオン酸、酪酸なと
の有機カルボン酸、酢酸ブチル、酢酸エチル、マロン酸
メチルエステルなどの有機カルボン酸エステル、アセト
ン、メチルエチルケトンなどのケトン類、テトラヒドロ
フラン、ジオキサンなの環状エーテル類、アセトニトリ
ル、アクリルニトリルなどのニトリル類、ホルムアルデ
ヒド、セトアルデヒドなどのアルデヒド類などを挙げる
ことができ、それらの二種以上の混合物であってもよい
。Various organic aqueous solutions can be used as the organic aqueous solution to which the pervaporative separation method of an organic aqueous solution according to the present invention can be applied, and examples of the organic matter include methanol, ethanol, n-
Propatool, Isopropatool, n-butanol, 5
Aliphatic alcohols such as ec-butanol 1, tert-7'tanol, ethylene glycol, alicyclic alcohols such as cyclohexanol, aromatic alcohols such as benzyl alcohol, organic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, Organic carboxylic acid esters such as butyl acetate, ethyl acetate, and methyl malonate, ketones such as acetone and methyl ethyl ketone, cyclic ethers such as tetrahydrofuran and dioxane, nitriles such as acetonitrile and acrylonitrile, and aldehydes such as formaldehyde and cetaldehyde. etc., and a mixture of two or more thereof may be used.
本発明の浸透気化分離方法では、前記の有機物水溶液の
濃度は、特に限定されるものではなく、任意の割合で有
機物が含有されている有機物水溶液を分離又は濃縮する
ことができる。In the pervaporative separation method of the present invention, the concentration of the organic substance aqueous solution is not particularly limited, and an organic substance aqueous solution containing organic substances in any proportion can be separated or concentrated.
前記の分離膜モジュールの構造、形式などは、特に限定
されるものではないが、特に限定されるものではないが
、例えば、プレートアンドフレーム型モジュール、スパ
イラル型モジュール、中空糸膜型モジュールなどである
ことが好ましい。The structure, format, etc. of the separation membrane module described above are not particularly limited, but examples thereof include a plate-and-frame type module, a spiral type module, a hollow fiber membrane type module, etc. It is preferable.
以下、この発明の浸透気化分離方法に関する実施例、お
よび比較例を示し、さらに詳しくこの発明を説明する。EXAMPLES Hereinafter, the present invention will be explained in more detail by showing examples and comparative examples regarding the pervaporative separation method of the present invention.
実施例および比較例において、透過速度Ｑおよび分離係
数αは、膜を透過した気化成分を冷却・凝縮させて採集
し、その重量を測定し、そして、凝縮液中に内部標準液
として脱水ｎ−プロパツールを加え、ＴＣＤ−ガスクロ
マトグラフィーによって水と有機物との重量比が測定さ
れ、次に示す計算式によって算出された。In Examples and Comparative Examples, the permeation rate Q and separation coefficient α are determined by cooling and condensing the vaporized components that have passed through the membrane, collecting them, measuring their weight, and adding dehydrated n- Propatool was added, and the weight ratio of water to organic matter was measured by TCD-gas chromatography, and calculated using the formula shown below.
参考例において、芳香族テトラカルボン酸成分および芳
香族ジアミン成分に使用される各化合物の略記号を以下
に示す。In the reference examples, the abbreviations of each compound used for the aromatic tetracarboxylic acid component and the aromatic diamine component are shown below.
４．４’−ＤＡＤＥ ； ４，４’−ジアミノジフェニ
ルエーテルＤＭ ；４＋４’−ジアミノジフェニル
メタンＴＳＮ ；ｏ−）リジンスルホン
ＤＡＢへ ；３，５−ジアミノ安息香酸参考例１
〔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酸二無
水物１００モル％からなるテトラカルボン酸成分と、２
．２−ビス（４−（４−アミノフェノキシ）フヱニル〕
プロパン（ＢＡＰＰ）１００モル％からなるジアミン成
分とを、等モル、パラクロルフェノール（ＰＣＰ）中、
１８０°Ｃの温度で１４時間重合して得られた高分子量
の芳香族ポリイミドのＰＣＰ溶液（濃度＝１７重量％）
を調製した。4.4'-DADE;4,4'-diaminodiphenyl ether DM; 4+4'-diaminodiphenylmethane TSN; o-) To lysine sulfone DAB; 3,5-diaminobenzoic acid Reference Example 1 [Preparation of aromatic polyimide solution] 3 .3',4.4'-A tetracarboxylic acid component consisting of 100 mol% of biphenyltetracarboxylic dianhydride;
．． 2-bis(4-(4-aminophenoxy)fenyl)
A diamine component consisting of 100 mol% of propane (BAPP) is equimolar in parachlorophenol (PCP),
PCP solution of high molecular weight aromatic polyimide obtained by polymerization at a temperature of 180°C for 14 hours (concentration = 17% by weight)
was prepared.
〔芳香族ポリイミド製の中空糸膜の紡糸〕中空糸紡糸用
ノズルを備えた紡糸装置に、前記の芳香族ポリイミド溶
液を供給し、凝固液（温度＝５゛Ｃ、エタノール−水系
凝固液）を用いる湿式製膜法によって、非対称性の中空
糸分離膜を形成し、第１表に示す熱処理温度で熱処理し
て、芳香族ポリイミド製の中空糸分離膜を製造した。[Spinning of hollow fiber membrane made of aromatic polyimide] The above-mentioned aromatic polyimide solution was supplied to a spinning device equipped with a hollow fiber spinning nozzle, and a coagulation liquid (temperature = 5°C, ethanol-water coagulation liquid) was added. An asymmetric hollow fiber separation membrane was formed by the wet membrane forming method used, and heat treated at the heat treatment temperature shown in Table 1 to produce an aromatic polyimide hollow fiber separation membrane.
その中空糸膜は、外径が６２０ａｍであって、内径が３
７０μｍである（膜厚が１２５μｍである）連続した長
尺の中空糸であった。The hollow fiber membrane has an outer diameter of 620 am and an inner diameter of 3.
It was a continuous long hollow fiber with a thickness of 70 μm (film thickness: 125 μm).
前記中空糸膜の引張り強度（ｋｇ／糸）および伸び率（
％）、並びに、１５０°Ｃの熱エタノール水溶液に２０
時間浸漬した後の引張り強度と伸び率の保持率（％）を
、第１表に示す。The tensile strength (kg/fiber) and elongation rate (
%), and 20% in hot ethanol aqueous solution at 150°C.
Table 1 shows the tensile strength and elongation retention (%) after soaking for a time.
参考例２〜７
第１表に示した種類と、組成とを有するジアミン成分を
使用したほかは、参考例１と同様にして、第１表に示す
濃度および回転粘度の芳香族ポリイミドのＰＣＰ溶液を
、それぞれ調製し、得られた芳香族ポリイミド溶液を使
用し、第１表に示す熱処理温度での熱処理をしたほかは
参考例１と同様の湿式製膜法によって、参考例１と同じ
程度の外径、内径および肉厚の芳香族ポリイミド製の非
対称性分離膜からなる中空糸膜をそれぞれ製造した。Reference Examples 2 to 7 A PCP solution of aromatic polyimide having the concentration and rotational viscosity shown in Table 1 was prepared in the same manner as in Reference Example 1, except that a diamine component having the type and composition shown in Table 1 was used. were prepared, respectively, and the obtained aromatic polyimide solution was used, and the same wet film forming method as in Reference Example 1 was performed except that heat treatment was performed at the heat treatment temperature shown in Table 1. Hollow fiber membranes each consisting of an asymmetric separation membrane made of aromatic polyimide having an outer diameter, an inner diameter, and a wall thickness were manufactured.
それらの各中空糸膜について、引張り強度および伸び率
、並びに、１５０°Ｃの熱エタノール水溶液に２０時間
浸漬した後の引張り強度と伸び率の保持率を、第１表に
示す。Table 1 shows the tensile strength and elongation of each hollow fiber membrane, as well as the retention of the tensile strength and elongation after being immersed in a hot ethanol aqueous solution at 150° C. for 20 hours.
実施例１〜３および比較例１〜６
各参考例で製造された非対称性中空糸分離膜を第１表に
示した熱処理温度で熱処理した後、４本束ねて糸束を形
成し、その糸束の一方の端部をエポキシ樹脂で封止し、
中空系束エレメントを作成し、有機物水溶液を供給する
導入口と、未透過物の取出し口および透過物の取り出し
口を有する容器内へ前記中空系束エレメントを内設して
、分離膜モジュールを製造した。Examples 1 to 3 and Comparative Examples 1 to 6 After heat treating the asymmetric hollow fiber separation membranes manufactured in each reference example at the heat treatment temperature shown in Table 1, four fibers were bundled to form a fiber bundle, and the fibers were Seal one end of the bundle with epoxy resin,
A separation membrane module is manufactured by creating a hollow bundle element and placing the hollow bundle element inside a container having an inlet for supplying an aqueous organic solution, an outlet for taking out unpermeated matter, and an outlet for taking out permeated matter. did.
前記の分離膜モジュールへ８０重量％のエタノール水溶
液を９０°Ｃで供給し、分離膜モジュール内の中空糸エ
レメントの中空糸内部を３トール以下の減圧状態で、浸
透気化を行い、透過物薄気を冷却し、回収した。An 80% by weight ethanol aqueous solution is supplied to the separation membrane module at 90°C, and pervaporation is performed inside the hollow fibers of the hollow fiber elements in the separation membrane module under a reduced pressure of 3 torr or less. was cooled and collected.
その浸透気化における透過速度Ｑおよび水分と有機物と
の分離係数αを第２表に示す。Table 2 shows the permeation rate Q in pervaporation and the separation coefficient α between water and organic matter.
第
表
実施例４および比較例７〜８
参考例２、参考例４および参考例６で得られ芳香族ポリ
イミド類の非対称性の中空糸分離膜を、１５０°Ｃの水
、又は６０重量％のエタノール水溶液中に２０時間浸漬
処理した。Table Example 4 and Comparative Examples 7 to 8 The asymmetric hollow fiber separation membranes made of aromatic polyimides obtained in Reference Example 2, Reference Example 4, and Reference Example 6 were soaked in water at 150°C or 60% by weight. It was immersed in an ethanol aqueous solution for 20 hours.
前述のように熱処理した芳香族ポリイミド類の非対称性
中空糸分離膜を、６０°Ｃ，減圧下、乾燥させた後、実
施例１と同様の方法で、中空系束エレメント、分離膜モ
ジュールを制作し、８０重量％のエタノール水溶液を９
０°Ｃで供給し、浸透気化における透過速度Ｑおよび水
分と有機物との分離係数αを第３表に示す。After drying the asymmetric hollow fiber separation membrane made of aromatic polyimide heat-treated as described above at 60°C under reduced pressure, a hollow system bundle element and a separation membrane module were produced in the same manner as in Example 1. Then, add 80% by weight ethanol aqueous solution to 9
Table 3 shows the permeation rate Q and the separation coefficient α between water and organic matter in pervaporation when the water is supplied at 0°C.
Ｃ本発明の作用効果〕
この発明の浸透気化分離方法は、特定の芳香族ポリイミ
ド製の非対称性分離膜を用いる浸透気化法に係わる分離
法であるので、種々の有機物質の水溶液の分離、濃縮に
使用することができ、そして、広範囲な濃度の有機物水
溶液について使用可能であって、しかも、充分な耐熱性
、耐水性、耐溶剤性および耐久性を有しており、さらに
、高い透水性を有する特定のポリイミド製の非対称性膜
を使用しているので、長時間、安定した浸透気化法によ
る分離を行うことができる。C Effects of the present invention] The pervaporation separation method of the present invention is a separation method related to pervaporation using an asymmetric separation membrane made of a specific aromatic polyimide, so it can be used for separation and concentration of aqueous solutions of various organic substances. It can be used for organic substance aqueous solutions with a wide range of concentrations, has sufficient heat resistance, water resistance, solvent resistance, and durability, and has high water permeability. Since it uses an asymmetric membrane made of a specific polyimide, it is possible to perform stable separation by pervaporation for a long period of time.
特許出願人 宇部興産株式会社Patent applicant: Ube Industries Co., Ltd.
Claims (1)
と接触させて、有機物水溶液から主として水分を選択的
に浸透気化させる浸透気化分離方法において、 前記の耐熱性重合体が、 一般式 I ▲数式、化学式、表等があります▼（ I ） で示される反復単位を６０〜１００モル含有し、そして
、残部の反復単位がビフェニルテトラカルボン酸類とベ
ンゼン環を２〜５個有する他の芳香族ジアミン化合物で
ある芳香族ジアミン成分とから形成された反復単位であ
る可溶性の芳香族ポリイミドであることを特徴とする有
機物水溶液の浸透気化分離方法。[Scope of Claims] A pervaporation separation method in which an aqueous solution of organic matter is brought into contact with an asymmetric separation membrane made of a heat-resistant polymer to selectively pervaporate mainly water from the aqueous solution of organic matter, wherein the heat-resistant polymer is , General formula I ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Contains 60 to 100 moles of repeating units represented by (I), and the remaining repeating units have biphenyltetracarboxylic acids and 2 to 5 benzene rings. A method for pervaporative separation of an aqueous solution of an organic substance, characterized in that the soluble aromatic polyimide is a repeating unit formed from an aromatic diamine component which is another aromatic diamine compound.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1087079A JP2782769B2 (en) | 1989-04-07 | 1989-04-07 | Pervaporation separation method of organic matter aqueous solution |
| EP90303637A EP0391699B1 (en) | 1989-04-07 | 1990-04-04 | Pervaporation method of selectively separating water from an organic material aqueous solution through aromatic imide polymer asymmetric membrane |
| DE69014958T DE69014958T2 (en) | 1989-04-07 | 1990-04-04 | Pervaporation process for the selective separation of water from an aqueous solution containing organic compounds by means of an asymmetric membrane made of an aromatic polyimide. |
| US07/505,443 US4997462A (en) | 1989-04-07 | 1990-04-05 | Pervaporation method of selectively separating water from an organic material aqueous solution through aromatic imide polymer asymmetric membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1087079A JP2782769B2 (en) | 1989-04-07 | 1989-04-07 | Pervaporation separation method of organic matter aqueous solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02268819A true JPH02268819A (en) | 1990-11-02 |
| JP2782769B2 JP2782769B2 (en) | 1998-08-06 |
Family
ID=13904939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1087079A Expired - Lifetime JP2782769B2 (en) | 1989-04-07 | 1989-04-07 | Pervaporation separation method of organic matter aqueous solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2782769B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0586789A3 (en) * | 1992-04-11 | 1994-07-27 | Boehringer Mannheim Gmbh | Asymmetric porous membranes |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63166415A (en) * | 1986-12-26 | 1988-07-09 | Ube Ind Ltd | Polyimide gas separating membrane |
| JPS63264121A (en) * | 1987-04-21 | 1988-11-01 | Ube Ind Ltd | Polyimide membrane for separating gas |
-
1989
- 1989-04-07 JP JP1087079A patent/JP2782769B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63166415A (en) * | 1986-12-26 | 1988-07-09 | Ube Ind Ltd | Polyimide gas separating membrane |
| JPS63264121A (en) * | 1987-04-21 | 1988-11-01 | Ube Ind Ltd | Polyimide membrane for separating gas |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0586789A3 (en) * | 1992-04-11 | 1994-07-27 | Boehringer Mannheim Gmbh | Asymmetric porous membranes |
| JPH0772145A (en) * | 1992-04-11 | 1995-03-17 | Boehringer Mannheim Gmbh | Asymmetrical porous film |
| US6287867B1 (en) | 1992-04-11 | 2001-09-11 | Roche Diagnostics Gmbh | Asymmetric porous membranes |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2782769B2 (en) | 1998-08-06 |
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