JPH0445829A - Pervaporization separating membrane, pervaporization separating device and pervaporization separation method - Google Patents
Pervaporization separating membrane, pervaporization separating device and pervaporization separation methodInfo
- Publication number
- JPH0445829A JPH0445829A JP15231590A JP15231590A JPH0445829A JP H0445829 A JPH0445829 A JP H0445829A JP 15231590 A JP15231590 A JP 15231590A JP 15231590 A JP15231590 A JP 15231590A JP H0445829 A JPH0445829 A JP H0445829A
- Authority
- JP
- Japan
- Prior art keywords
- zeolite
- membrane
- pervaporization
- hydrophobic
- separation
- 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 52
- 238000000926 separation method Methods 0.000 title claims description 50
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000010457 zeolite Substances 0.000 claims abstract description 53
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 52
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- 238000005373 pervaporation Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000009834 vaporization Methods 0.000 claims 1
- 230000008016 vaporization Effects 0.000 claims 1
- 230000002209 hydrophobic effect Effects 0.000 abstract description 29
- 239000012510 hollow fiber Substances 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 9
- 238000013329 compounding Methods 0.000 abstract description 4
- 229920001600 hydrophobic polymer Polymers 0.000 abstract description 3
- 239000002808 molecular sieve Substances 0.000 abstract description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract description 2
- 230000008020 evaporation Effects 0.000 abstract 1
- 230000003204 osmotic effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- -1 poly(4-methylpentene-1) Polymers 0.000 description 13
- 230000007423 decrease Effects 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920003242 poly[1-(trimethylsilyl)-1-propyne] Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 125000005386 organosiloxy group Chemical group 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 229920002379 silicone rubber Polymers 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229920000306 polymethylpentene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 102100039121 Histone-lysine N-methyltransferase MECOM Human genes 0.000 description 1
- 101001033728 Homo sapiens Histone-lysine N-methyltransferase MECOM Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102400001019 Intermedin-short Human genes 0.000 description 1
- 101800001379 Intermedin-short Proteins 0.000 description 1
- LFVLUOAHQIVABZ-UHFFFAOYSA-N Iodofenphos Chemical compound COP(=S)(OC)OC1=CC(Cl)=C(I)C=C1Cl LFVLUOAHQIVABZ-UHFFFAOYSA-N 0.000 description 1
- 239000004944 Liquid Silicone Rubber Substances 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 244000292604 Salvia columbariae Species 0.000 description 1
- 235000012377 Salvia columbariae var. columbariae Nutrition 0.000 description 1
- 235000001498 Salvia hispanica Nutrition 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- WYUIWUCVZCRTRH-UHFFFAOYSA-N [[[ethenyl(dimethyl)silyl]amino]-dimethylsilyl]ethene Chemical compound C=C[Si](C)(C)N[Si](C)(C)C=C WYUIWUCVZCRTRH-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000014167 chia Nutrition 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 208000013057 hereditary mucoepithelial dysplasia Diseases 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 208000037909 invasive meningococcal disease Diseases 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- ZSMNRKGGHXLZEC-UHFFFAOYSA-N n,n-bis(trimethylsilyl)methanamine Chemical compound C[Si](C)(C)N(C)[Si](C)(C)C ZSMNRKGGHXLZEC-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は浸透気化法（パーベイボレーション法）による
液−ガス分離等に有用な新規な浸透気化分離膜、同分離
装置および同分離方法に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention provides a novel pervaporation separation membrane useful for liquid-gas separation by pervaporation, a separation device thereof, and a separation method thereof. It is related to.
（従来の技術）
浸透気化法は、通常の蒸留法では分離不可能な液状混合
物の分離を目的として考え出された方法で、このような
混合物としては、共沸および近沸点混合物や熱変成し易
い化合物を含む混合物がある。これらの分離方法は米国
特許第２９５３５０２号等に開示されている。近年、省
エネルギー化、バイオマス技術の進歩から、低エネルギ
ーで連続的にン昆合系の中から必要な成分を取り出せる
この浸透気化法が注目されており、実用化の検討かなさ
れているが、混合系から水などの不要成分を取り除いて
必要成分を濃縮する膜は実用化されているのに対し、混
合系から必要成分のみを濃縮して取り出す膜は、その分
離係数が低いことや、必要成分の透過量が少ない等の問
題があり、商業的な実用化に至っていないのが現状であ
る。(Prior art) Pervaporation is a method devised for the purpose of separating liquid mixtures that cannot be separated by ordinary distillation methods. Such mixtures include azeotropic and near-boiling point mixtures, and thermally modified There are mixtures that contain easy-to-understand compounds. These separation methods are disclosed in US Pat. No. 2,953,502 and the like. In recent years, due to advances in energy conservation and biomass technology, this pervaporation method, which can continuously extract the necessary components from the agglomeration system with low energy, has been attracting attention, and practical application is being considered. Membranes that remove unnecessary components such as water from a system and concentrate necessary components are in practical use, whereas membranes that concentrate and extract only the necessary components from a mixed system have a low separation coefficient and Currently, it has not been commercially put into practical use due to problems such as a small amount of permeation.
（本発明が解決しようとする課題）
これに対し、必要成分を選択的に吸着する分子篩特性を
もつゼオライトを用いて、分離係数と透過量の向上を計
る試み（特開昭６３−１１６７０５号公報参照）がなさ
れているが、使用するゼオライトが吸水性を有するため
、長期の使用においてその分離係数や透過量が著しく低
下してしまうという問題点を有していた。(Problem to be solved by the present invention) To solve this problem, an attempt was made to improve the separation coefficient and permeation amount by using zeolite that has molecular sieve properties that selectively adsorb necessary components (Japanese Patent Application Laid-open No. 116705/1983). However, since the zeolite used has water absorption properties, the separation coefficient and permeation amount decrease significantly during long-term use.
本発明は、このような従来の問題点を解決するものであ
り、高い分離係数と透過量が得られ、安価で長期の使用
においても性能の低下のない浸透気化分離膜を提供する
ことを課題とする。The present invention solves these conventional problems, and an object of the present invention is to provide a pervaporation separation membrane that can obtain a high separation coefficient and permeation amount, is inexpensive, and does not deteriorate in performance even during long-term use. shall be.
（課題を解決するための手段）
本発明者等は、かかる問題点を解決するためにはゼオラ
イトの吸水性を排除すれば可能であるとの観点から、ゼ
オライトの疎水化処理について種々検討した結果、分子
篩特性を有するゼオライトを高分子マトリックス中に配
合、分散して成る浸透気化膜において、Ｓｉ／Ａ、ｅの
原子比率が１０以上である該ゼオライトを少な（ども１
つ以上のシラザン結合を有するオルガノシラザンによっ
て疎水化処理すること。分離膜を構成する高分子７トリ
ツクスが溶解度パラメーター（ＳＰ値）＝１３以下の疎
水性ポリマーであり、該ポリマーがポリオルガノシロキ
サン、ポリ［１−Ｄリメチルシリル）１−プロピン］、
ポリ（４−メチルペンテン−１）、ポリオレフィン、ポ
リオルガノシロキサン・ポリカーボネート共重合体、ポ
リ（トリメチルビニルシラン）の１種または２種以上か
らなり、粒子径が１００μｍ未満の疎水化処理ゼオライ
トの含有量が４０〜８５重量％であり、該膜の厚さが３
〜５００μｍで膜の形状が中空糸状のもの、または膜の
厚さが２０μｍ未満の平膜で多孔質支持体上に設けられ
たものとすれば分離係数および透過量を飛躍的に向上さ
せることができ、さらに長期間の使用においても性能が
低下しないことを見出し、本発明を完成させた。(Means for Solving the Problems) The present inventors have conducted various studies on hydrophobic treatment of zeolite from the viewpoint that it is possible to solve this problem by eliminating the water absorbing property of zeolite. In a pervaporation membrane formed by blending and dispersing zeolite having molecular sieving properties in a polymer matrix, a small amount of the zeolite having an atomic ratio of Si/A, e of 10 or more is used.
Hydrophobizing treatment with an organosilazane having three or more silazane bonds. The polymer 7 trix constituting the separation membrane is a hydrophobic polymer with a solubility parameter (SP value) of 13 or less, and the polymer is polyorganosiloxane, poly[1-D-limethylsilyl)-1-propyne],
The content of hydrophobized zeolite, which is composed of one or more of poly(4-methylpentene-1), polyolefin, polyorganosiloxane/polycarbonate copolymer, and poly(trimethylvinylsilane), and has a particle size of less than 100 μm. 40 to 85% by weight, and the thickness of the film is 3
If the membrane is ~500 μm in shape and has a hollow fiber shape, or if the membrane is a flat membrane with a thickness of less than 20 μm and is provided on a porous support, the separation coefficient and permeation amount can be dramatically improved. The present invention was completed based on the discovery that the performance does not deteriorate even after long-term use.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
先ず本発明に使用されるゼオライト疎水化処理剤である
オルガノシラザンとしては、少なくとも５ｉ−Ｎ （Ｒ
） −３ｉ （ここにＲは水素、または炭素数１〜３の
アルキル基）で示されるシラザン結合を少なくとも１つ
以上有すれば良く、このシラザン結合が水分の存在下で
ゼオライト表面にイオン吸着している親水性の一〇Ｈ基
（＝Ｓｉ−Ｏ１１）と反応し、脱ＮＨａによりオルガノ
シロキシ基（Ｏ３ｉ、Ｒａ）をゼオライト表面に化学的
に導入することができる。さらに、導入されるオルガノ
シロキシ基は、これが疎水性を示すことが必要であるこ
とから、本発明に用いるオルガノシラザンは下記式（ｉ
）で示されるシラザンの水素を疎水性の有機基で置換し
たもの（ｎが１のときジシラザン、ｎが２の時トリシラ
ザン等と呼ぶ）であり、１．１．３．３−テトラメチル
ジシラザン（下記式（ｊｉ）） 、ヘキサメチルジシラ
ザン（下記式（ｉｉｉ））、ヘプタメチルジシラザン（
下記式（ｉｖ）） 、 １．３−ジビニル−１，１，３
，３−テトラメチルジシラザン（下記式（ｖ） ）、
１．３−ビス（クロルメチル）−１，１，３，３−テト
ラメチルジシラザン（下記式（ｖｉ）） 、 １，１，
３，３，５．５−ヘキサメグ・ルシクロトリシラザン（
下記式（ｖｉｉ） ）ｊ、］、３，３，５゜５、７．７
．−オクタメチルシクロテトラシラザン（下記式（ｖｉ
ｉｉ）） 、１．３−ビス（２−パーフロロオクチル）
エチル−１，１，３，３−テトラメチル−１，３−ジシ
ラザン（下記式（ｉｘ） ）等が例示されるが、疎水性
のトリメデルシロキシ基（−０ＳｉＣ）１３）を導入す
ることができ製法が容易で最も安価なヘキサメチルジシ
ラザン（以下ＨＭ Ｄ Ｓと略記する）、またはより高
い疎水性を有するパーフロロアルキルシロキシ基を導入
することができる１、３−ビス（パーフロロアルキル）
エチル−１，１，３，３−テトラメチル−１，３−ジシ
ラザンの使用が望ましい。First, the organosilazane which is the zeolite hydrophobizing agent used in the present invention is at least 5i-N (R
) -3i (where R is hydrogen or an alkyl group having 1 to 3 carbon atoms), and this silazane bond is capable of adsorbing ions on the zeolite surface in the presence of water. It is possible to chemically introduce organosiloxy groups (O3i, Ra) onto the zeolite surface by reacting with the hydrophilic 10H group (=Si-O11) in the zeolite and removing NHa. Furthermore, since the organosiloxy group to be introduced needs to exhibit hydrophobicity, the organosilazane used in the present invention has the following formula (i
) in which the hydrogen of the silazane is replaced with a hydrophobic organic group (when n is 1, it is called disilazane, when n is 2, it is called trisilazane, etc.), and is 1.1.3.3-tetramethyldisilazane. (formula (ji) below), hexamethyldisilazane (formula (iii) below), heptamethyldisilazane (formula (iii) below),
The following formula (iv)), 1,3-divinyl-1,1,3
, 3-tetramethyldisilazane (formula (v) below),
1.3-bis(chloromethyl)-1,1,3,3-tetramethyldisilazane (formula (vi) below), 1,1,
3,3,5,5-hexameg luciclotrisilazane (
The following formula (vii) )j, ], 3, 3, 5°5, 7.7
．． -Octamethylcyclotetrasilazane (formula (vi)
ii)) , 1,3-bis(2-perfluorooctyl)
Examples include ethyl-1,1,3,3-tetramethyl-1,3-disilazane (formula (ix) below), but it is also possible to introduce a hydrophobic trimedelsiloxy group (-0SiC)13). Hexamethyldisilazane (hereinafter abbreviated as HMDS), which is easily manufactured and the cheapest, or 1,3-bis(perfluoroalkyl) into which a perfluoroalkylsiloxy group with higher hydrophobicity can be introduced.
Preference is given to using ethyl-1,1,3,3-tetramethyl-1,3-disilazane.
□ ＣＨ３ ＣＨ。□ CH3 CH.
以下、上記に例示したオルガノシラザンのうちＨＭＤＳ
を例にとって説明すると、ＨＭ Ｄ Ｓは沸点１２６°
Ｃ（蒸気圧７９ｍｍＨｇ ａｔ５０℃）、密度０．７７
ｇ／ａｍ”、粘度： ０．７ｃＰの液体であり、水分
の存在下でＨＭＤＳの液体または気体とゼオライト粒子
を接触させることにより、容易にゼオライト表面にイオ
ン吸着している親水性の一〇Ｈ基２分子とＩ（ＭＤＳ１
分子が反応でアンモニアを放出し、疎水性のトリメチル
シロキシ基をゼオライト表面に簡単に、しかも均一で単
分子的に導入することができる。Below, among the organosilazanes exemplified above, HMDS
To explain this using an example, HMDS has a boiling point of 126°
C (vapor pressure 79 mmHg at 50°C), density 0.77
g/am”, viscosity: 0.7 cP, and is a hydrophilic 10H that easily adsorbs ions on the zeolite surface by bringing the HMDS liquid or gas into contact with the zeolite particles in the presence of water. Group 2 molecules and I (MDS1
The molecules release ammonia during the reaction, and hydrophobic trimethylsiloxy groups can be easily, uniformly, and monomolecularly introduced onto the zeolite surface.
疎水化処理方法としては、密閉容器内にＨＭＤＳとゼオ
ライトおよび水を投入しておけばよいが、ゼオライト粒
子が二次凝集を形成していることが多く、処理が不完全
となり良好な疎水性が得られないことがあるので、ボー
ルミル等の装置を用いて二次凝集を解砕しながら同時に
反応処理するのが好ましい。オルガノシラザンの添加量
は、使用するゼオライトの粒径が異なると、その比表面
積が異なるため粒度分布から全表面積を求め、計算値よ
り若干過剰に加え、ゼオライト表面の一〇Ｈ基をオルガ
ノシロキシ基に完全に置換した後に、使用するオルガノ
シラザンの沸点以上の雰囲気、もしくはオルガノシラザ
ンの沸点が水の沸点１００°Ｃより低い場合は１００°
Ｃ以上の雰囲気中に投入して、余剰のオルガノシラザン
および水を揮発させることによって処理を完結すること
ができる。As a hydrophobic treatment method, it is sufficient to put HMDS, zeolite, and water into a closed container, but zeolite particles often form secondary agglomerations, resulting in incomplete treatment and poor hydrophobicity. Since this may not be possible, it is preferable to use a device such as a ball mill to disintegrate secondary agglomerates and perform the reaction treatment at the same time. The amount of organosilazane to be added is determined by calculating the total surface area from the particle size distribution, since the specific surface area differs depending on the particle size of the zeolite used, and adding a slightly excess amount than the calculated value, replacing the 10H groups on the zeolite surface with organosiloxy groups. After completely substituting with
The treatment can be completed by evaporating the excess organosilazane and water by placing it in an atmosphere of C or higher.
本発明に用いるゼオライトは、目的とする分離物質を選
択的に吸着するものであれば良く、その目的のためにゼ
オライトのＳＬ／ＡＩ２の原子比率や孔径を任意に選択
することができる。しかし、ゼオライトのＳＬ／Ａβの
原子比率がｌＯ未滴になると、その吸水性が著しく大き
くなり、ゼオライト表面をオルガノシラザンで疎水化し
ても尚、ゼオライト粒子内部の吸水性による性能低下が
あることから、 Ｓｉ／ＡＪ２の原子比率が１０以上で
あることが好ましい。また、使用するゼオライト粒子径
は、これを高分子マトリックスに配合して得られる分離
膜の膜厚との関係で述べると、膜厚よりも小さい必要が
あり、膜厚が厚過ぎると膜を透過する単位時間当たりの
透過量が少なくなり分離効率が悪化することから、膜厚
は５００μｍ未満とするのが好ましく、これが３μｍ未
満では膜強度が不足し、膿単体として取扱うことが困難
となることから３〜５００μｍとするのが好ましい。従
って使用するゼオライトの大きさは、その膜厚の５分の
１以下でかつ１００μｍ以下とするのが好ましい。また
、ゼオライトを高分子マトリックスに高充填する目的か
ら、粒度分布の異なる２種以上のゼオライ１〜を混合し
て用いても良い。The zeolite used in the present invention may be one that selectively adsorbs the target separation substance, and the SL/AI2 atomic ratio and pore diameter of the zeolite can be arbitrarily selected for that purpose. However, when the atomic ratio of SL/Aβ of zeolite becomes less than 100, its water absorption becomes significantly large, and even if the zeolite surface is hydrophobized with organosilazane, there is still a decrease in performance due to the water absorption inside the zeolite particles. , The atomic ratio of Si/AJ2 is preferably 10 or more. In addition, the diameter of the zeolite particles used must be smaller than the membrane thickness, which is obtained by blending it into a polymer matrix. The membrane thickness is preferably less than 500 μm because the permeation amount per unit time decreases and the separation efficiency deteriorates. If it is less than 3 μm, the membrane strength is insufficient and it becomes difficult to handle it as a single pus. It is preferable to set it as 3-500 micrometers. Therefore, the size of the zeolite used is preferably one-fifth or less of the film thickness and 100 μm or less. Furthermore, for the purpose of highly filling the polymer matrix with zeolite, two or more types of zeolites 1 to 1 with different particle size distributions may be mixed and used.
本発明に用いる高分子マトリックスとしては、分子篩特
性を有するゼオライトを疎水化することにより、混合液
体中から疎水性成分のみを選択的に分離することを目的
とすることから、疎水性を示すマトリックスが好ましく
、より具体的には疎水性の指標となる溶解度パラメータ
ー（ＳＰ値）が１３以下の疎水性ポリマーであることが
好ましい。The polymer matrix used in the present invention is a hydrophobic matrix because the purpose is to selectively separate only hydrophobic components from a mixed liquid by making zeolite with molecular sieving properties hydrophobic. Preferably, it is more specifically a hydrophobic polymer having a solubility parameter (SP value), which is an index of hydrophobicity, of 13 or less.
この高分子マトリックスは最終的には分離膜として分離
装置に組込むことになるため、その膜厚は分離効率を高
める観点から可能な限り薄い方が好ましく、膜化が可能
で薄膜でも充分な強度を有するものが好ましい。このよ
うな高分子マトリックスとしては、ポリエチレン、ポリ
プロピレン、ポリスチレン、ポリ塩化ビニル、ポリ塩化
ビニリデン、ふっ素樹脂、ポリカーボネート、ポリエチ
レンテレフタレート、飽和ポリエステル樹脂、ポリアミ
ド、ポリフェニレンオキサイド、ポリスルポン、ポリウ
レタン、ニトロセルロース、セルロースアセテート、ポ
リ酢酸ビニル、ポリビニルアセタール等の一般的な合成
樹脂フィルム材料やアクリロニトリル・ブタジェン・ス
チレン（ＡＢＳ）樹脂、スチレン・ブタジェン・スチレ
ン（ＳＢＳ）樹脂、エチレン・酢酸ビニル共重合樹脂等
の共重合樹脂、天然ゴム、ブチルゴム、クロロプレンゴ
ム、アクリロニトリル・ブタジェンゴム、エチレン・プ
ロピレンゴム、アクリルゴム、エピクロルヒドリンゴム
、シリコーンゴム、フッ素ゴム等のゴムマトリックスが
挙げられる。さらに詳しくは、この浸透気化分離膜はそ
の面積と処理量とが比例関係にあることから、透過量の
少ない高分子マトリックスを使用すると必要な透過量を
得るのに大きな膜面積を必要とし、装置が大型化して実
用的でないことから、透過量のある程度大きなマトリッ
クスを使用するのが好ましく、このような樹脂としては
ポリオルガノシロキサン、ポリ［１−（＋−リ■
メチルシリル）−１−プロピン］、ポリ（４−メチルペ
ンテン−１）、ポリオルガノシロキサン・ポリカーボネ
ート共重合体、ポリ（トリメチルビニルシラン）および
ポリオレフィン等が挙げられる。Since this polymer matrix will ultimately be incorporated into a separation device as a separation membrane, it is preferable that the membrane be as thin as possible from the perspective of increasing separation efficiency. It is preferable to have one. Such polymer matrices include polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, fluororesin, polycarbonate, polyethylene terephthalate, saturated polyester resin, polyamide, polyphenylene oxide, polysulfone, polyurethane, nitrocellulose, cellulose acetate, General synthetic resin film materials such as polyvinyl acetate and polyvinyl acetal, copolymer resins such as acrylonitrile-butadiene-styrene (ABS) resin, styrene-butadiene-styrene (SBS) resin, ethylene-vinyl acetate copolymer resin, and natural Rubber matrices include rubber, butyl rubber, chloroprene rubber, acrylonitrile-butadiene rubber, ethylene-propylene rubber, acrylic rubber, epichlorohydrin rubber, silicone rubber, fluororubber, and the like. More specifically, the area of this pervaporation separation membrane is proportional to the throughput, so if a polymer matrix with a small permeation rate is used, a large membrane area is required to obtain the necessary permeation rate, and the equipment It is preferable to use a matrix with a certain amount of permeation, since it is too large to be practical. Examples of such resins include polyorganosiloxane, poly[1-(+-methylsilyl)-1-propyne], Examples include poly(4-methylpentene-1), polyorganosiloxane/polycarbonate copolymer, poly(trimethylvinylsilane), and polyolefin.
次に、この疎水化処理したゼオライトの高分子マトリッ
クスに対する配合量は、これが４０重量％未満では充分
な分離係数や透過量が得られず、８５重量％を越えると
膜強度が低下して膜単体として取扱うことが困難になる
と共に、配合工程における混合分散が難しく、さらには
膜にピンホール、スクラッチ等が発生し易くなる等の不
具合を生じることから、４０〜８５重量％とするのが良
く、さらに好ましくは５０〜８０重量％である。Next, if the amount of hydrophobized zeolite added to the polymer matrix is less than 40% by weight, a sufficient separation coefficient and permeation rate will not be obtained, and if it exceeds 85% by weight, the membrane strength will decrease and the membrane alone It is recommended that the amount be 40 to 85% by weight, since it becomes difficult to handle as a liquid, difficult to mix and disperse in the compounding process, and furthermore causes problems such as pinholes, scratches, etc. in the film. More preferably, it is 50 to 80% by weight.
膜厚については、先にゼオライト粒子径との関係で述べ
たが、上記高分子マトリックスの中でも強度的にさほど
強（ない例えばシリコーンゴム等のゴム材料やポリオレ
フィン等の場合には、この膜を多孔質支持体上に形成す
ることにより強度の不足を補うことができる。この場合
、膜厚としては、多孔質支持体の開口面積が小さいと、
膜の実質的有効面積が小さ（なることから、膜厚を薄（
する必要があり、好ましくは用いられるゼオライト粒子
径の５倍以下とするのが良い。また、膜の形状としては
平膜以外に、装置への装着方法や設計のし易さ等の観点
から、中空糸状としても良い。Regarding the membrane thickness, as mentioned above in relation to the zeolite particle size, in the case of a rubber material such as silicone rubber or polyolefin, which is not particularly strong among the polymer matrices mentioned above, the membrane is porous. The lack of strength can be compensated for by forming the film on a porous support.In this case, if the film thickness is small, the opening area of the porous support is small.
Since the actual effective area of the membrane is small, the thickness of the membrane can be reduced (
The diameter of the zeolite particles used should preferably be 5 times or less. In addition, the shape of the membrane may be in the form of a hollow fiber other than a flat membrane from the viewpoint of ease of attachment to the device and ease of design.
本発明の浸透気化分離膜を製造する方法としては、高分
子マトリックス中に疎水化処理をしたゼオライトを所定
量、公知の混合分散装置、例えば加圧式ニーダー、ヘン
シェルミキサー、バンバリーミキサー、スパイラルミキ
サー、エクストルーダー等の混合分散装置により、加熱
熔融状態で混合、分散し、続いて公知の膜化方法、例え
ばＴダイ法、インフレーション法、カレンダー法等の溶
融押出し法（エキストルージョン法）を用いれば良い。As a method for manufacturing the pervaporation separation membrane of the present invention, a predetermined amount of hydrophobized zeolite is added to a polymer matrix using a known mixing and dispersing device such as a pressure kneader, Henschel mixer, Banbury mixer, spiral mixer, They may be mixed and dispersed in a heated molten state using a mixing and dispersing device such as a Ruder, and then a known film-forming method, such as a melt extrusion method such as a T-die method, an inflation method, or a calendar method, may be used.
また、高分子マトリックスがゴム材料等である場合は、
２本ロール、３本ロール等のロールミル、エクストル−
グー、加圧式ニーダー等を用いて混合分散したのち、カ
レンダーやＴダイ押出し法等により膜化することができ
る。さらに、高分子マトリックスが溶剤等に可溶である
場合は、溶剤等に溶解したワニスを作製し、これに疎水
化処理したゼオライトを配合した後、ボールミル、サン
ドグラインダー等のボール型混合分散装置や３本ロール
ミル、加圧式ニーダ−等を用いて混合分散した後、ガラ
ス板等のキャリアー上にキャスティング法により成膜す
れば良い。このキャスティング法は比較的容易に薄膜を
得ることが出来るため、本発明の浸透気化分離膜を得る
方法として好ましい。In addition, if the polymer matrix is a rubber material etc.
Roll mills such as 2 rolls, 3 rolls, etc.
After mixing and dispersing using a goo, a pressure kneader, etc., it can be formed into a film by a calender, T-die extrusion method, etc. Furthermore, if the polymer matrix is soluble in a solvent, etc., prepare a varnish dissolved in a solvent, etc., add hydrophobized zeolite to this, and then use a ball-type mixing and dispersing device such as a ball mill or sand grinder. After mixing and dispersing using a three-roll mill, pressure kneader, etc., a film may be formed on a carrier such as a glass plate by a casting method. This casting method is preferable as a method for obtaining the pervaporation separation membrane of the present invention because a thin film can be obtained relatively easily.
また、中空糸状とする方法は高分子マトリックス中に疎
水化処理したゼオライトを上記混合分散装置を用いて分
散したのち、これを押出機にてダイスより押出し、一定
のテンションを掛けて紡糸すれば良い。この中空糸の形
状は、その肉厚か厚すぎると前記したように透過量が低
下し分離効率が低下するので、出来る限り薄いことが好
ましく、その厚みは平膜と同様に３〜５００μｍの範囲
とすればよく、この範囲内で前記した理由から、使用す
る疎水化したゼオライトの粒径および用いる高分子マト
リックスの強度等から決定すれば良い。さらに、中空糸
の外形および内径は、径か太き（なると中空糸の比表面
積が減少し、大型の装置となることから、できるだけ小
径のものか好ましく、その外形は０．０３〜５ｍｍ、内
径ｉ；Ｉ：０．０２〜４．９ｍｍの範囲、好ましくは外
形０．０５ｍｍ〜１．０ｍｍ、内径は０．０３〜０．９
ｍｍの範囲とするのが良い。In addition, to form a hollow fiber, after dispersing hydrophobized zeolite in a polymer matrix using the above-mentioned mixing and dispersing device, extrude it through a die using an extruder and spin it under a certain tension. . The shape of this hollow fiber is preferably as thin as possible, as if it is too thick, the amount of permeation will decrease and the separation efficiency will decrease as described above, and the thickness is in the range of 3 to 500 μm, similar to the flat membrane. It may be determined within this range based on the particle size of the hydrophobized zeolite used, the strength of the polymer matrix used, etc. for the reasons described above. Furthermore, the outer and inner diameters of the hollow fibers are preferably as small as possible because the diameter or the diameter is large (the specific surface area of the hollow fibers decreases, resulting in a large device), and the outer diameter is 0.03 to 5 mm, and the inner diameter is 0.03 to 5 mm. i; I: range of 0.02 to 4.9 mm, preferably outer diameter of 0.05 mm to 1.0 mm, inner diameter of 0.03 to 0.9
It is preferable to set it in the range of mm.
本発明の浸透気化分離膜を装着する装置（Ｊ、公知の技
術に依れば良く、その構造は平膜を利用したザントイッ
チ型、スパイラル型、中空糸を利用した中空糸型が挙げ
られるか、処理物質、処理能力、設置条件等に応じて適
宜設計すれば良い。An apparatus for mounting the pervaporation separation membrane of the present invention (J) may be based on a known technique, and its structure may include a Zantwich type using a flat membrane, a spiral type, a hollow fiber type using a hollow fiber, It may be designed as appropriate depending on the processing substance, processing capacity, installation conditions, etc.
本発明の浸透気化分離膜による処理対象物は、疎水性液
体と水との混合系であって、この混合系から疎水性液体
を選択的に分離する方式である。The object to be treated by the pervaporation separation membrane of the present invention is a mixed system of a hydrophobic liquid and water, and the method is such that the hydrophobic liquid is selectively separated from this mixed system.
疎水性液体どしては、脂肪族炭化水素類、芳香族炭化水
素類、アルコール類、グリコール類、エステル類、ケト
ン類等が挙げられるが、実用的に分離効率か高く、透過
量の大きいものＴＲＩ、炭素数１〜５のアルコール類で
ある。Hydrophobic liquids include aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, glycols, esters, ketones, etc., but those with high separation efficiency and large permeation amount are recommended for practical use. TRI, alcohols having 1 to 5 carbon atoms.
（イ乍用） 本発明の疎水化処理の作用を説明する。(for I) The effect of the hydrophobization treatment of the present invention will be explained.
従来のゼオライトを用いた浸透気化分１１１ｆｔ ｌ］
Ｉｆｉでは、使用するゼオライトのＳｉ／ｌ！の原子比
率を大きくすることにより、ゼオライト表面を疎水化す
ることで分離係数、透過量の向上、および水分子の吸着
による分離性能の低下を防止しようとしてきた。しかし
ながら、混合液体中特には疎水性物質と水との混合系に
おいては、水分子の方がその分子径（２，６５人）が疎
水性！Ｉ勿質の分子径（例えばメタノール３．８人、ｎ
−ヘキ→ナン４．３人）よりも小さく、よって分離を目
的とする物質を選択的に吸着さぜ冒い分離係数を得るた
め、ゼオライトの孔径を分離しようとする物質の分子径
に一致さ七た場合、ゼオライト内部にも水分が侵入して
吸着されるため、目的とする疎水性分子の吸着能力が低
下し、膜自体の分離、透過能力が低下するという問題が
あった。そこで、本発明者等はこのゼオライト表面に疎
水性の薄膜を形成することにより性能］
低下を防止することを試み、疎水性処理試薬として種々
のシランカップリング剤、含フツ素シラン、デクネート
カップリング剤等を検討した結果、いずれの処理剤もゼ
オライト表面に厚い被膜を形成し、その分離特性、透過
特性が著しく低下した。これらの検討おいて、本発明の
ジメチルシラザンを代表とするオルガノシラザンは、ゼ
オライト表面にイオン吸着している一０１１基とのみ反
応し、単分子的疎水性被膜を形成するため、その分離、
透過能力に著しい低下は見られなかった。このオルガノ
シラザンによる疎水化処理により導入されたアルキルシ
ロキシ基は、その疎水性により水分子かゼオライト表面
に接近するのを阻止することにより水分子の吸着による
性能低下を防止し、長期間連続使用しても分離膜の性能
低下がなく、その被処理疎水物質との親和力から、疎水
性物質を選択的に透過することで、その分離係数を向上
させるという作用を有する。Pervaporation content using conventional zeolite: 111ftl]
Ifi uses zeolite Si/l! By increasing the atomic ratio of zeolite, attempts have been made to make the zeolite surface hydrophobic, thereby improving the separation coefficient and permeation rate, and preventing deterioration in separation performance due to adsorption of water molecules. However, in a mixed liquid, especially in a mixed system of a hydrophobic substance and water, the water molecule has a more hydrophobic molecular diameter (2.65 people)! I have a molecular size of 3.8 methanol (e.g. methanol, n
The pore size of the zeolite must match the molecular diameter of the substance to be separated in order to selectively adsorb the substance to be separated and obtain a separation coefficient. In this case, water also enters the zeolite and is adsorbed, resulting in a decrease in the adsorption ability of the target hydrophobic molecules and a decrease in the separation and permeation ability of the membrane itself. Therefore, the present inventors attempted to prevent this deterioration in performance by forming a hydrophobic thin film on the surface of this zeolite, and used various silane coupling agents, fluorine-containing silanes, and decnate cups as hydrophobic treatment reagents. As a result of examining ring agents, etc., it was found that all treatment agents formed a thick film on the zeolite surface, and the separation and permeation characteristics were significantly reduced. In these studies, the organosilazane represented by the dimethylsilazane of the present invention reacts only with the 1011 groups ionically adsorbed on the zeolite surface and forms a monomolecular hydrophobic film.
No significant decrease in permeability was observed. The alkylsiloxy groups introduced by this hydrophobic treatment with organosilazane prevent water molecules from approaching the zeolite surface due to their hydrophobicity, thereby preventing performance deterioration due to adsorption of water molecules and allowing continuous use for long periods of time. However, due to its affinity with the hydrophobic substance to be treated, it has the effect of selectively permeating the hydrophobic substance and improving its separation coefficient.
以下、本発明の具体的な実施態様を実施例と比較例を挙
げて説明するが、本発明はこれらに限定されるものでは
ない。Hereinafter, specific embodiments of the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
（実施例１）
Ｓｊ／Ａ、ｆ２の原子比率が２５、細孔径が６人、平均
粒径５．ＯＩＪ、ｍである ＺＭＳ−５型ゼオライｌ−
； ＥＸ−１０７（水沢化学工業■製部品名）１００重
量部に刻し、ヘキザメチルジシラザシ（ＨＭＤＳ）
； ＬＳ−７１５０（信越化学工業（摺装商品名）を１
０重量部、純水を５．０重量部加え、この混合物をボー
ルミル容器中に投入して１時間混合、解砕を行いながら
処理をし、その後この混合物を密閉したボールミル容器
内にて室温中で７２時間放置し、処理を完全なものとし
た。その後、ステンレスバット上に移し）ＩＭＤＳの沸
点（１２６°Ｃ）以上の温度である １５０°Ｃの雰囲
気中に２時間放置し、余剰のＨＭ Ｄ Ｓおよび水を蒸
発させた。この時のＥＸ−１，［１７の重量増加は１．
２ｇであった。(Example 1) Sj/A, atomic ratio of f2 is 25, pore size is 6, average particle size is 5. ZMS-5 type zeolite l-
; Cut into 100 parts by weight of EX-107 (part name manufactured by Mizusawa Chemical Industry ■) and hexamethyl disilazashi (HMDS)
; LS-7150 (Shin-Etsu Chemical Co., Ltd. (sliding product name))
0 parts by weight and 5.0 parts by weight of pure water were added, and this mixture was put into a ball mill container and treated while being mixed and crushed for 1 hour, and then this mixture was placed in a sealed ball mill container at room temperature. The mixture was left for 72 hours to complete the treatment. Thereafter, the mixture was transferred onto a stainless steel vat and left in an atmosphere at 150°C, which is higher than the boiling point of IMDS (126°C), for 2 hours to evaporate excess HMDS and water. At this time, the weight increase of EX-1, [17 was 1.
It was 2g.
つぎに、室温硬化型液状シリコーンゴム化合物ＲＴＶ−
ＫＥ−１０３（信越化学工業（掬製商品名）２４０重量
部にイ」加型硬化剤Ｃａｔ−１０３１，２重量部と上記
ＨＭ Ｄ Ｓ処理をしたＥＸ−１０７７５重量部を配合
し、こオ］を１雷潰機を用いて３０分（見合、分散後、
三本ロールにて３回通過させて分散を完全なものとし、
ペースト状の配合物を得た。次いでこのペース１−を厚
さ １００μｍの四フッ化エチレン（ＰＴＦＥ）シーｉ
・・テフロンテープ・トンボ９００１ にチアス■製商
品名）上にナイフコーターを用いて塗工し、１８０℃で
３０分間硬化させて膜厚的５０μｍの膜とした。Next, a room temperature curable liquid silicone rubber compound RTV-
240 parts by weight of KE-103 (trade name manufactured by Shin-Etsu Chemical Co., Ltd. (Kiyomi)) was blended with 2 parts by weight of the mold hardening agent Cat-1031 and 2 parts by weight of EX-10775 treated with the above HM D S. 1 for 30 minutes using a lightning crusher (after dispersion,
Complete the dispersion by passing it through three rolls three times,
A pasty formulation was obtained. Next, this paste 1- was coated with a 100 μm thick polytetrafluoroethylene (PTFE) sheet.
It was coated on Teflon tape Tombo 9001 (trade name, manufactured by Chias ■) using a knife coater and cured at 180° C. for 30 minutes to form a film with a thickness of 50 μm.
（比較例１）
旧１１ＤＳ処理をしていないゼオライ１−ＥＸ−１０７
を使用した以外は実施例１ど同様の配合物を処理し膜厚
的５０μｍの嘆を作製した。(Comparative Example 1) Zeolite 1-EX-107 without old 11DS treatment
A film having a film thickness of 50 μm was prepared by processing the same formulation as in Example 1 except that .
（実施例２）
実施例１のゼオライトＥＸ−１０７に代えて、ＳＬ／Ａ
ρの原子比率が約９００である高シリカゼオライトのシ
リカライト（ＵＣＣ社製商品名；平均粒径１．ｌｕｍ、
細孔径；５．４人）を使用し、実施例１と同様の方法で
）ＩＭＤｓ処理を施した。この時のシリカライトの重量
増加は２．４ｇであった。つぎに、実施例１と同じ処方
のペーストを同様に処理して膜厚５０１１ｍの膜とした
。(Example 2) In place of zeolite EX-107 in Example 1, SL/A
Silicalite, a high-silica zeolite with an atomic ratio of ρ of about 900 (product name manufactured by UCC; average particle size 1.lum,
The IMDs treatment was performed in the same manner as in Example 1 using a pore size of 5.4. The weight increase of silicalite at this time was 2.4 g. Next, a paste with the same formulation as in Example 1 was treated in the same manner to form a film with a thickness of 5011 m.
（比較例２）
実施例２においてＨＭ Ｄ Ｓ処理を行わないシリカラ
イトを用いた以外は実施例２とすべて同一の処方および
処理方法で膜厚的５０μｍの膜を作製した。(Comparative Example 2) A film with a thickness of 50 μm was produced using the same recipe and treatment method as in Example 2, except that silicalite without HMDS treatment was used in Example 2.
（実施例３）
実施例２で使用したシリカライト １．００重量部に、
ＨＭＤＳに代えて含ふっ素シラザンである １−３ビス
（２−パーフロロアルキル）エチル−１，１，３’、３
−テトラメチル−１３−ジシラザンのフロン１１３ ｍ
ｉｄ （固形分；９．５重量％）１０５重量部、フロン
１１３溶剤８９．５重量部を加え、ボールミル容器中に
投入し、１時間混合、解砕を行いながら処理をしたのち
、密閉したボールミル容器内に室温にて２４時間放置し
、シリカライトの一〇Ｈ基との反応を完全なものとした
。次いで、ステンレスバットに移し、６０°Ｃ×２時間
加熱してフロン１１３溶剤を揮発させた。(Example 3) To 1.00 parts by weight of silicalite used in Example 2,
1-3bis(2-perfluoroalkyl)ethyl-1,1,3',3 which is a fluorine-containing silazane in place of HMDS
-Tetramethyl-13-disilazane Freon 113 m
105 parts by weight of id (solid content; 9.5% by weight) and 89.5 parts by weight of Freon 113 solvent were added, placed in a ball mill container, mixed and crushed for 1 hour, and then sealed in a ball mill. The mixture was left in the container at room temperature for 24 hours to complete the reaction with the 10H group of silicalite. Next, the mixture was transferred to a stainless steel vat and heated at 60°C for 2 hours to volatilize the Freon 113 solvent.
その後、シリカライトの二次凝集をほぐすため再度ボー
ルミル容器に投入し、１５分解砕を行った。Thereafter, in order to loosen the secondary agglomeration of silicalite, it was again put into the ball mill container and subjected to decomposition and crushing for 15 minutes.
次いでこれをステンレスバットに移し、これを１５０°
Ｃで３０分加熱処理することにより処理を完全なものと
−した。この処理を行ったシリカライトを実施例１と同
じ処方のペーストを作り、同じように処理し、膜厚的５
０μｍの膜を作製した。Next, transfer this to a stainless steel vat and heat it at 150°.
The treatment was completed by heating at C for 30 minutes. A paste with the same formulation as in Example 1 was made from the silicalite subjected to this treatment, treated in the same way, and the film thickness was 5.
A 0 μm film was produced.
（実施例４）
ポリ ［１−（ｈリメチルシリル）−１−プロピン］（
ＰＴＭＳＰと略記；信越化学工業■製）を５重量％の固
形分濃度にてトルエンに溶解してＰＴＭＳＰフェスを作
製した。このＰＴＭＳＰワニス１００重量部に実施例２
で使用したＨＭＤｓ処理シ処理シリカライラフ量部を配
合し、これをボールミル容器に投入して２時間混合、分
散を行った。分散終了後、目開き２２（ｉ ｍのステン
レスメツシュを使用して濾過した後、実施例２と同様に
テフロンシート上にナイフコーターを用いて塗工した。(Example 4) Poly[1-(h-limethylsilyl)-1-propyne](
A PTMSP face was prepared by dissolving PTMSP (abbreviated as PTMSP; manufactured by Shin-Etsu Chemical Co., Ltd.) in toluene at a solid content concentration of 5% by weight. Example 2 was added to 100 parts by weight of this PTMSP varnish.
A portion of the HMDs-treated silica lye rough used in the above was blended, and this was put into a ball mill container and mixed and dispersed for 2 hours. After the dispersion was completed, the mixture was filtered using a stainless steel mesh with an opening of 22 (i m), and then coated on a Teflon sheet using a knife coater in the same manner as in Example 2.
塗工後、トルエン溶剤を風乾により揮発させたのち、
１２０℃で６０分加熱処理をして溶剤を完全に揮発させ
て１ＩＩＪ厚約１１０４ｚの膜を作製した。After coating, the toluene solvent was evaporated by air drying, and then
A heat treatment was performed at 120° C. for 60 minutes to completely volatilize the solvent, thereby producing a film having a thickness of 1IIJ and about 1104z.
以上実施例１〜４、比較例１．２で作製した各分離膜を
第１図に示す構成の浸透気化分離装置により性能評価を
実施した。第１図に示された浸透気化分離装置は、セル
４内部の３２５メツシユのステンレスメツシュ２上に分
離膜１を保持させ、これをセル内部にバッキング３を介
して固定したもので、付属装置として被処理物質を含む
混合液体（原液）貯ＩＩ ５と、循環ポンプ６および分
離膜によって分離された疎水性液体を補集するトラップ
７と１〜クラップ却用液体窒素ボトル８、透過側の系を
真空とする真空装置（図示せず）から成っている。The performance of each of the separation membranes produced in Examples 1 to 4 and Comparative Examples 1 and 2 was evaluated using a pervaporation separation apparatus having the configuration shown in FIG. The pervaporation separation device shown in FIG. 1 has a separation membrane 1 held on a 325-mesh stainless steel mesh 2 inside a cell 4, and this is fixed inside the cell via a backing 3. A mixed liquid (undiluted solution) storage II 5 containing the substance to be treated, a circulation pump 6 and a trap 7 for collecting the hydrophobic liquid separated by the separation membrane 1 to a liquid nitrogen bottle 8 for scrap disposal, and a system on the permeate side. It consists of a vacuum device (not shown) that creates a vacuum.
分離膜の評価方法としては、膜の単位面積（１ｍ２）、
単位厚み（１ｍｍ）、単位時間（１時間）当たりの各分
離物質の透過率Ｋ （ｇ／ｍｍｍ″Ｈｒ）をセル面積、
膜厚、分離時間、透過物質の重量から算出した。ポンプ
圧はほぼ大気圧とし、真空圧は７５０ ｍ ｍ Ｈｇ
Ｉｌｌ、下とした。また、疎水性成分の透過選択性αは
下式により求めた。The evaluation method for separation membranes is based on the unit area of the membrane (1 m2),
The transmittance K (g/mmm″Hr) of each separated substance per unit thickness (1 mm) and unit time (1 hour) is expressed as the cell area,
Calculated from membrane thickness, separation time, and weight of permeated material. The pump pressure is approximately atmospheric pressure, and the vacuum pressure is 750 mm Hg.
Ill, below. Further, the permselectivity α of the hydrophobic component was determined by the following formula.
α＝Ｘ、（１−ＸＩ）／Ｘ、（１−Ｘｐ）ここにＸｐお
よびＸｌはそれぞれ原液中の疎水性成分の重量分率と透
過物質中の疎水甥成分の重量分率を表す。これら重量分
率はガスクロマトグラフィーにより測定した。α=X, (1-XI)/X, (1-Xp) where Xp and Xl represent the weight fraction of the hydrophobic component in the stock solution and the weight fraction of the hydrophobic component in the permeate, respectively. These weight fractions were measured by gas chromatography.
さらに、分離膜の信頼性評価方法どして、分離膜を４０
°Ｃの水中に２４０時間浸漬した後、上記透過量と透過
選択性に関する評価を実施した。ここで評価に使用した
液分１１１１１物質としては、メタノールエタノール、
プロパツールの３種とし、７＄４ Ｗ５０重量％の水溶
液とした。これらの評価結果を第１表（初期値）、第２
表（４０℃×２４０時間値）に示す。Furthermore, the reliability evaluation method of separation membranes was
After being immersed in water at °C for 240 hours, the permeation amount and permeation selectivity were evaluated. The 11111 liquid substances used for evaluation here include methanol, ethanol,
Three types of propatool were used, and an aqueous solution of 7$4 W and 50% by weight was prepared. These evaluation results are shown in Table 1 (initial values) and Table 2.
It is shown in the table (40°C x 240 hour values).
（発明の効果）
本発明の疎水化処理を施したゼオライトを、高分子７ト
リツクス中に配合した浸透気化分離膜を使用することに
よって、従来問題となっていたゼオライトの吸水性によ
る透過量および分離係数等の性能低下がなく、かつその
分離係数がより大きいことから、高濃度の疎水性成分を
得ることができ、分離、精製コストの低下に繋り、さら
に分離膜の信頼性と相まって実用状その利用価値は極め
て高い。(Effects of the invention) By using a pervaporation separation membrane in which the hydrophobized zeolite of the present invention is blended into the polymer 7trix, the amount of permeation and separation due to the water absorption of zeolite, which has been a problem in the past, has been improved. Since there is no decrease in performance such as coefficient, and the separation coefficient is larger, it is possible to obtain a high concentration of hydrophobic components, leading to a reduction in separation and purification costs, and combined with the reliability of the separation membrane, it is suitable for practical use. Its utility value is extremely high.
〈初期値〉 第 表 ＜４０℃ ２４ＯＨｒ後〉 第 表 ［註］透過率 （ｇ／ｍｖｍ２１１ｒ）、選択性<initial value> No. table <40℃ After 24OHr> No. table [Note] Transmittance (g/mvm211r), selectivity
第１図は浸透気化分離膜の性能評価用浸透気化分離装置
の概要図である。
主な記号の説明
１・・・浸透気化分離膜
２・・・ステンレスメツシュ
３・・・バッキング、 ４・・・セル
５・・・貯槽、 ６・・・循環ポンプ７・・・
トラップ
８・・・液体窒素ボトル
特許出願人 信越ポリマー株式会社FIG. 1 is a schematic diagram of a pervaporation separation device for performance evaluation of pervaporation separation membranes. Explanation of main symbols 1... Pervaporation separation membrane 2... Stainless steel mesh 3... Backing, 4... Cell 5... Storage tank, 6... Circulation pump 7...
Trap 8...Liquid nitrogen bottle patent applicant Shin-Etsu Polymer Co., Ltd.
Claims (1)
ス中に配合、分散して成る浸透気化分離膜において、疎
水化処理した該ゼオライトを配合、分散して成ることを
特徴とする浸透気化分離膜。 ２）請求項１に記載の浸透気化分離膜を装着してなるこ
とを特徴とする浸透気化分離装置。 ３）請求項１または２に記載の浸透気化分離膜または浸
透気化分離装置によって水との混合系から分離される物
質が炭素数１〜５のアルコールであることを特徴とする
浸透気化分離方法。[Scope of Claims] 1) A pervaporation separation membrane formed by blending and dispersing zeolite having molecular sieving properties in a polymer matrix, characterized in that the zeolite that has been subjected to hydrophobization treatment is blended and dispersed. Vaporization separation membrane. 2) A pervaporative separation device equipped with the pervaporative separation membrane according to claim 1. 3) A pervaporative separation method, characterized in that the substance separated from the mixed system with water by the pervaporative separation membrane or pervaporative separation device according to claim 1 or 2 is an alcohol having 1 to 5 carbon atoms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15231590A JPH0445829A (en) | 1990-06-11 | 1990-06-11 | Pervaporization separating membrane, pervaporization separating device and pervaporization separation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15231590A JPH0445829A (en) | 1990-06-11 | 1990-06-11 | Pervaporization separating membrane, pervaporization separating device and pervaporization separation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0445829A true JPH0445829A (en) | 1992-02-14 |
Family
ID=15537840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15231590A Pending JPH0445829A (en) | 1990-06-11 | 1990-06-11 | Pervaporization separating membrane, pervaporization separating device and pervaporization separation method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0445829A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996002322A1 (en) * | 1994-07-15 | 1996-02-01 | Minnesota Mining And Manufacturing Company | Composite membranes for solid phase extractions and reactions |
| US5678134A (en) * | 1995-03-31 | 1997-10-14 | Olympus Optical Co., Ltd. | Cleaning device for an image forming apparatus |
| WO1999062624A1 (en) * | 1998-06-03 | 1999-12-09 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Hydrophobic permeable composite, method for producing said composite and use of the same |
| JP2008055326A (en) * | 2006-08-31 | 2008-03-13 | National Institute Of Advanced Industrial & Technology | Membrane and method for separation of organic compound |
| JP2010521290A (en) * | 2007-03-12 | 2010-06-24 | ボード オブ リージェンツ， ザ ユニバーシティ オブ テキサス システム | Highly selective polymer-nanoporous particle membrane structure |
| JP2012527340A (en) * | 2009-05-18 | 2012-11-08 | ヴィト ナームロゼ ベンノートチャップ | Thin film-containing pervaporation film |
| WO2024070573A1 (en) * | 2022-09-26 | 2024-04-04 | 日東電工株式会社 | Pervaporation membrane |
-
1990
- 1990-06-11 JP JP15231590A patent/JPH0445829A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996002322A1 (en) * | 1994-07-15 | 1996-02-01 | Minnesota Mining And Manufacturing Company | Composite membranes for solid phase extractions and reactions |
| US5529686A (en) * | 1994-07-15 | 1996-06-25 | Minnesota Mining And Manufacturing Company | Composite membranes for solid phase extractions and reactions |
| US5639372A (en) * | 1994-07-15 | 1997-06-17 | Minnesota Mining And Manufacturing Company | Composite membranes for solid phase extractions and reactions |
| US5738790A (en) * | 1994-07-15 | 1998-04-14 | Minnesota Mining And Manufacturing Company | Composite membranes for solid phase extractions and reactions |
| US5678134A (en) * | 1995-03-31 | 1997-10-14 | Olympus Optical Co., Ltd. | Cleaning device for an image forming apparatus |
| WO1999062624A1 (en) * | 1998-06-03 | 1999-12-09 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Hydrophobic permeable composite, method for producing said composite and use of the same |
| JP2008055326A (en) * | 2006-08-31 | 2008-03-13 | National Institute Of Advanced Industrial & Technology | Membrane and method for separation of organic compound |
| JP2010521290A (en) * | 2007-03-12 | 2010-06-24 | ボード オブ リージェンツ， ザ ユニバーシティ オブ テキサス システム | Highly selective polymer-nanoporous particle membrane structure |
| KR101137989B1 (en) * | 2007-03-12 | 2012-04-20 | 보오드 오브 리젠츠, 더 유니버시티 오브 텍사스 시스템 | High selectivity polymer-nano-porous particle membrane structures |
| JP2012527340A (en) * | 2009-05-18 | 2012-11-08 | ヴィト ナームロゼ ベンノートチャップ | Thin film-containing pervaporation film |
| KR101341608B1 (en) * | 2009-05-18 | 2013-12-13 | 비토 엔브이 | Thin film pervaporation membranes |
| US9339771B2 (en) | 2009-05-18 | 2016-05-17 | Vito N.V. | Thin film pervaporation membranes |
| WO2024070573A1 (en) * | 2022-09-26 | 2024-04-04 | 日東電工株式会社 | Pervaporation membrane |
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