JPH06246126A - Hollow fiber type organic vapor separating membrane and module using the same - Google Patents
Hollow fiber type organic vapor separating membrane and module using the sameInfo
- Publication number
- JPH06246126A JPH06246126A JP19980693A JP19980693A JPH06246126A JP H06246126 A JPH06246126 A JP H06246126A JP 19980693 A JP19980693 A JP 19980693A JP 19980693 A JP19980693 A JP 19980693A JP H06246126 A JPH06246126 A JP H06246126A
- Authority
- JP
- Japan
- Prior art keywords
- hollow fiber
- organic vapor
- membrane
- vapor
- org
- 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 98
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 84
- 238000000926 separation method Methods 0.000 claims description 35
- 239000002346 layers by function Substances 0.000 claims description 14
- 239000010410 layer Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 45
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- 239000002131 composite material Substances 0.000 description 15
- 229920001296 polysiloxane Polymers 0.000 description 15
- 239000012466 permeate Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 229920002239 polyacrylonitrile Polymers 0.000 description 10
- 238000011084 recovery Methods 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000009987 spinning Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- KQNZLOUWXSAZGD-UHFFFAOYSA-N benzylperoxymethylbenzene Chemical compound C=1C=CC=CC=1COOCC1=CC=CC=C1 KQNZLOUWXSAZGD-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、有機蒸気の分離回収に
有用な有機蒸気分離膜およびそれを用いたモジュールに
関し、詳しくは、飽和又は不飽和の脂肪族炭化水素類、
芳香族炭化水素類、ハロゲン化炭化水素類、ケトン類、
アルコール類、カルボン酸エステル類等の有機溶剤の蒸
気を含む気体、例えば、空気からかかる有機溶剤蒸気を
効率よく分離回収するのに有用な有機蒸気分離膜に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic vapor separation membrane useful for separating and recovering organic vapor and a module using the same, and more specifically, saturated or unsaturated aliphatic hydrocarbons,
Aromatic hydrocarbons, halogenated hydrocarbons, ketones,
The present invention relates to an organic vapor separation membrane useful for efficiently separating and recovering a gas containing an organic solvent vapor such as alcohols and carboxylic acid esters, for example, such an organic solvent vapor from air.
【０００２】[0002]
【従来の技術】比較的高濃度の有機溶剤の蒸気（以下有
機蒸気と称する。）を含む空気は、例えば、電子部品や
金属部品などの洗浄機からや、ドライクリーニング機か
ら、または、油槽所から多量に排出される。2. Description of the Related Art Air containing a relatively high concentration of organic solvent vapor (hereinafter referred to as "organic vapor") is used, for example, from a washing machine for electronic parts or metal parts, a dry cleaning machine, or an oil tank. Is discharged in large quantities from.
【０００３】例えば、金属部品の洗浄溶媒として広く使
用されているトリクロロエタンは、洗浄機内で加熱され
蒸気として使われているが、洗浄機の上部開口部から高
濃度の蒸気として大気に排出されており、その結果、オ
ゾン層を破壊し、地球規模での環境破壊につながってい
る。For example, trichloroethane, which is widely used as a cleaning solvent for metal parts, is heated in a cleaning machine and used as steam, but it is discharged to the atmosphere as a high-concentration steam from the upper opening of the cleaning machine. As a result, it destroys the ozone layer, leading to global environmental damage.
【０００４】そこで、有機蒸気を含む気体混合物から有
機蒸気を回収するために、シリコーンからなる平膜型気
体分離膜を使用する方法（特開平１−２３６９１８号）
が知られている。通常この平膜型気体分離膜はスパイラ
ル型膜モジュールとして使用されるが、スパイラル型膜
モジュールでは有機蒸気の十分な分離を実現することが
困難であった。Therefore, in order to recover the organic vapor from the gas mixture containing the organic vapor, a method of using a flat membrane type gas separation membrane made of silicone (Japanese Patent Laid-Open No. 1-236918).
It has been known. Usually, this flat membrane type gas separation membrane is used as a spiral membrane module, but it has been difficult to realize sufficient separation of organic vapor with the spiral membrane module.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、有機
蒸気に対して十分な分離が実現できる有機蒸気分離膜お
よびモジュールを提供することである。SUMMARY OF THE INVENTION An object of the present invention is to provide an organic vapor separation membrane and a module capable of realizing sufficient separation of organic vapor.
【０００６】[0006]
【課題を解決するための手段】本発明は、上記目的を達
成するために下記の構成を有する。The present invention has the following constitution in order to achieve the above object.
【０００７】「内径５０ミクロン以上、１０００ミクロ
ン以下の中空糸膜構造を有する有機蒸気分離膜。」有機
蒸気分離膜とは、有機蒸気を含む気体混合物から有機蒸
気を濃縮することが可能な気体分離膜である。有機蒸気
とは有機溶剤の蒸気をいう。"Organic vapor separation membrane having a hollow fiber membrane structure having an inner diameter of 50 microns or more and 1000 microns or less." Organic vapor separation membrane is a gas separation capable of concentrating organic vapor from a gas mixture containing organic vapor. It is a film. Organic vapor means vapor of an organic solvent.
【０００８】本発明の中空糸膜とは、繊維の内部に長手
方向に連続して存在するチャンネルを有する繊維すなわ
ち実質的に軸方向の中空部を有する管状分離膜である
が、中心部分の中空の径を内径と称するが、本発明の中
空糸の内径は５０ミクロン以上、１０００ミクロン以下
である。有機蒸気の分離特性は、機能層の分離性に依存
するところが大きいが、この中空糸の内径にも大きく依
存し、本発明の内径の範囲内であれば良好な分離特性を
発現するが、さらに好ましい内径は、５０ミクロン以上
５００ミクロン以下である。The hollow fiber membrane of the present invention is a fiber having a continuous channel in the inside of the fiber in the longitudinal direction, that is, a tubular separation membrane having a hollow portion substantially in the axial direction. The inner diameter of the hollow fiber of the present invention is 50 microns or more and 1000 microns or less. The separation property of the organic vapor largely depends on the separability of the functional layer, but also largely depends on the inner diameter of this hollow fiber, and if it is within the range of the inner diameter of the present invention, good separation property is expressed. The preferred inner diameter is 50 microns or more and 500 microns or less.
【０００９】本発明の中空糸膜は、最外層に有機蒸気を
実質的に分離する機能層を有し、内部層に多孔質構造を
有することが好ましく、機能層が０．０１ミクロン以
上、１０ミクロン以下の厚みを有していることが好まし
い。The hollow fiber membrane of the present invention preferably has a functional layer that substantially separates organic vapors in the outermost layer and a porous structure in the inner layer. It preferably has a thickness of micron or less.
【００１０】内側の多孔質構造を有する中空糸部分は、
機能層に近い部分は、孔径が小さく内部にいくに従って
大きい孔を有する、いわゆる非対称構造を有すること
が、良好な機能層を形成できるということと、圧損が小
さくなるということから好ましい。また、多孔質構造を
有する中空糸部分の膜厚は、厚損と耐圧性の点で１０ミ
クロン以上１００ミクロン以下、さらには２０ミクロン
以上８０ミクロン以下が好ましい。The hollow fiber portion having the inner porous structure is
It is preferable that the portion near the functional layer has a so-called asymmetric structure in which the pore diameter is small and the pores are large toward the inside, so that a good functional layer can be formed and the pressure loss becomes small. The thickness of the hollow fiber portion having a porous structure is preferably 10 microns or more and 100 microns or less, more preferably 20 microns or more and 80 microns or less in terms of thickness loss and pressure resistance.
【００１１】この様な非対称構造の多孔質中空糸を具体
的に挙げると、ポリスルホン多孔質中空糸、ポリエーテ
ルスルホン多孔質中空糸、ポリアクリロニトリル多孔質
中空糸、超高重合度ポリアクリロニトリル多孔質中空
糸、ポリイミド多孔質中空糸、ポリフェニレンスルフィ
ドスルホン多孔質中空糸などが挙げられる。Specific examples of the porous hollow fiber having such an asymmetric structure include polysulfone porous hollow fiber, polyether sulfone porous hollow fiber, polyacrylonitrile porous hollow fiber, and ultra-high degree of polymerization polyacrylonitrile porous hollow fiber. Examples thereof include a thread, a polyimide porous hollow fiber, a polyphenylene sulfide sulfone porous hollow fiber, and the like.
【００１２】本発明の機能層は、実質的に有機蒸気を分
離する素材であれば特に限定されるものではないが、具
体的に架橋型シリコーン、ポリブタジエン、ポリアクリ
ロニトリルブタジエン、エチレンプロピレンラバー、ネ
オプレンゴム等のゴム状高分子を挙げることができる。The functional layer of the present invention is not particularly limited as long as it is a material that substantially separates organic vapors, but specifically, cross-linking type silicone, polybutadiene, polyacrylonitrile butadiene, ethylene propylene rubber, neoprene rubber. Rubber-like polymers such as
【００１３】本発明の機能層は、単一素材の単層でも、
異なる素材の層を積層していてもどちらでも良いが、多
孔質中空糸の外表面にピンホールフリーの機能層を形成
するためには、多孔質中空糸の外表面に架橋型シリコー
ンを設けさらにその外表面に実質的に有機蒸気を分離す
る素材からなる機能層を設けた構造が好ましい。The functional layer of the present invention may be a single layer made of a single material,
Both layers of different materials may be laminated, but in order to form a pinhole-free functional layer on the outer surface of the porous hollow fiber, a crosslinkable silicone is provided on the outer surface of the porous hollow fiber. A structure in which a functional layer made of a material that substantially separates organic vapors is provided on the outer surface is preferable.
【００１４】多孔質中空糸の外表面に架橋構造を有する
ポリオルガノシロキサンを形成する方法は、末端にシラ
ノールを有するポリオルガノシロキサンとシラン架橋剤
または側鎖にアミノ基を有するポリオルガノシロキサン
とイソシアネート架橋剤を溶媒に溶解せしめて溶液を調
製し、多孔質中空糸上に塗工して溶媒を蒸発せしめて形
成する方法が挙げられる。The polyorganosiloxane having a crosslinked structure on the outer surface of the porous hollow fiber is formed by a polyorganosiloxane having silanol at the terminal and a silane crosslinking agent, or a polyorganosiloxane having an amino group at the side chain and isocyanate crosslinking. A method may be mentioned in which the agent is dissolved in a solvent to prepare a solution, which is applied on a porous hollow fiber and the solvent is evaporated to form the solution.
【００１５】多孔質中空糸の外表面に架橋型シリコーン
層を設けた中空糸のさらに外表面に機能層を設ける方法
としては、機能層の素材を適当な可溶性の溶媒に溶解し
た溶液を塗工して形成することができる。As a method for providing a functional layer on the outer surface of a hollow fiber having a crosslinked silicone layer on the outer surface of a porous hollow fiber, a solution of the material for the functional layer in a suitable soluble solvent is applied. Can be formed.
【００１６】機能層の厚みは、薄ければ薄い程透過性が
高くなるため好ましいが、薄いとピンホールを発生しや
すくなるので、０．０１ミクロン以上１０ミクロン以下
の範囲にすることが好ましい。The thinner the functional layer is, the more preferable it is because the higher the transparency is. However, the thinner the thickness, the more easily pinholes are formed. Therefore, the thickness is preferably in the range of 0.01 to 10 microns.
【００１７】この様にして得られた中空糸は、中空糸の
外側あるいは内側から有機蒸気を含有した混合ガスを供
給することにより用いられるが、特に、有機蒸気を含有
した混合ガスを内側から供給し、中空糸の内側を中空糸
の外側より圧力を高く設定することによって、有機蒸気
は選択的に中空糸の内側から外側に透過していくので、
濃縮された有機蒸気を得ることができ、これを冷却凝縮
することにより有機溶剤として回収することができるの
である。The hollow fiber thus obtained is used by supplying a mixed gas containing an organic vapor from the inside or outside of the hollow fiber. Particularly, a mixed gas containing an organic vapor is supplied from the inside. However, by setting the pressure inside the hollow fiber higher than that outside the hollow fiber, the organic vapor selectively permeates from the inside to the outside of the hollow fiber.
A concentrated organic vapor can be obtained and can be recovered as an organic solvent by cooling and condensing.
【００１８】通常、透過側の有機蒸気の濃縮倍率（透過
側の有機蒸気濃度と供給側の有機蒸気濃度の比）は、機
能層の有機蒸気分離性と回収率（透過ガス流量と供給ガ
ス流量の比）と圧力比（供給側の圧力と透過側の圧力の
比）で決定されるといわれている。本発明者らは、鋭意
検討した結果、同じ機能層を有する複合膜で回収率と圧
力比を同じ条件にして有機蒸気を分離した際、複合膜の
形態が中空糸でしかも内側に有機蒸気を供給した場合
と、複合膜の形態が平膜でスパイラルモジュールにし有
機蒸気を供給した場合とでは、濃縮倍率が前者の方がは
るかに大きい、すなわち分離特性がはるかに高いことを
見出したのである。Usually, the concentration ratio of the organic vapor on the permeate side (ratio between the organic vapor concentration on the permeate side and the organic vapor concentration on the feed side) is determined by the organic vapor separability of the functional layer and the recovery rate (permeate gas flow rate and feed gas flow rate). Ratio) and pressure ratio (the ratio of the pressure on the supply side to the pressure on the permeation side). As a result of diligent studies, the inventors of the present invention have found that when the organic vapor is separated in a composite membrane having the same functional layer under the same conditions of recovery rate and pressure ratio, the composite membrane is a hollow fiber and the organic vapor is present inside. It has been found that the concentration ratio is much higher in the former case, that is, the separation characteristic is much higher, in the case of supplying the compound and in the case of supplying the organic vapor in the form of a spiral membrane in which the composite film has a flat film form.
【００１９】本発明の中空糸膜は通常中空糸膜モジュー
ルに組まれて使用される。中空糸膜モジュールとは、例
えば、多数の中空糸膜が配列された状態で外筒の中に充
填され、該中空糸膜束の両端部が接着剤で外筒の両端部
に固定され、かつ該接着剤が外筒の内表面と中空糸膜の
外表面でかこまれた空間と外筒の外の空間とを完全にさ
えぎり、かつ該中空糸膜束の固定された両端部が切断に
より中空糸膜内部を開孔状態とされている構造物の外筒
の一部に外筒の中と外筒の外をつなげる口が設けられて
いる構造である。The hollow fiber membrane of the present invention is usually assembled into a hollow fiber membrane module for use. The hollow fiber membrane module is, for example, filled in an outer cylinder in a state where a large number of hollow fiber membranes are arranged, and both ends of the bundle of hollow fiber membranes are fixed to both ends of the outer cylinder with an adhesive, and The adhesive completely blocks the space surrounded by the inner surface of the outer cylinder and the outer surface of the hollow fiber membrane and the space outside the outer cylinder, and the fixed both ends of the hollow fiber membrane bundle are hollow by cutting. This is a structure in which a port that connects the inside of the outer cylinder to the outside of the outer cylinder is provided in a part of the outer cylinder of the structure in which the inside of the thread film is open.
【００２０】本発明の中空糸膜モジュールを構成する容
器外筒としては、金属、プラスチック類等の適当な材質
のものから適宜選定することができる。また、特に好ま
しくはアクリル樹脂、塩化ビニル樹脂、ポリスルホン、
変性ポリフェニレンオキサイド、ポリカーボネート樹脂
などが適当である。The outer cylinder of the container constituting the hollow fiber membrane module of the present invention can be appropriately selected from those made of appropriate materials such as metals and plastics. Further, particularly preferably, acrylic resin, vinyl chloride resin, polysulfone,
Modified polyphenylene oxide, polycarbonate resin and the like are suitable.
【００２１】該中空糸膜モジュールの一方の端部から有
機蒸気の混合ガスを供給して、中空糸膜内部を経由し
て、もう一方の端部からガスを出す様に流す。この時、
中空糸内部と中空糸外部との間に差圧を設け、中空糸内
部の方が圧力が高くなるように設定する。この中空糸内
部の圧力と中空糸外部の圧力の比を圧力比と呼ぶが、圧
力比を２０以上１００以下とすることが好ましく、さら
に、透過ガス量と供給ガス量の比を回収率と呼ぶが、こ
の回収率を５％以上５０％以下の適当な条件になる様に
供給ガス量を設定することが好ましい。この様に有機蒸
気を分離すると、本発明の中空糸膜モジュールは、分離
特性が平膜スパイラルモジュールに比べて非常に優れて
いるので、有機蒸気を効率良く回収することができるの
である。A mixed gas of organic vapor is supplied from one end of the hollow fiber membrane module and flows through the inside of the hollow fiber membrane so that the gas is discharged from the other end. At this time,
A pressure difference is provided between the inside of the hollow fiber and the outside of the hollow fiber, and the pressure is set to be higher inside the hollow fiber. The ratio between the pressure inside the hollow fiber and the pressure outside the hollow fiber is called a pressure ratio, but the pressure ratio is preferably 20 or more and 100 or less, and the ratio of the amount of permeated gas and the amount of supplied gas is called the recovery rate. However, it is preferable to set the supply gas amount so that the recovery rate becomes an appropriate condition of 5% or more and 50% or less. When the organic vapor is separated in this manner, the hollow fiber membrane module of the present invention has much better separation characteristics than the flat membrane spiral module, so that the organic vapor can be efficiently recovered.
【００２２】[0022]
【実施例】以下に、実施例に基いてさらに詳細に説明す
るが、本発明はこれに限定されるものではない。The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto.
【００２３】実施例１ アクリロニトリル１００モル％、［η］＝３．２の重合
体をＤＭＳＯ中で重合し、さらに希釈して重合体濃度１
４．０重量％の紡糸原液を得た。内径０．３ｍｍ、スリ
ット巾０．１ｍｍの鞘芯型中空糸用口金を用いて鞘部よ
りこの紡糸原液を１．２ｃｃ／ｍｉｎの速度で吐出し、
芯部より水を吐出した。紡糸温度は３０℃で、吐出した
糸条をいったん空気中（室温）を３０ｍｍ通過させたの
ち３０℃の水からなる凝固浴中に導いて凝固させ、３５
℃の水中で洗浄してから巻き取った。中空糸膜の寸法
は、内径２４０ミクロン、膜厚３０ミクロンであった。
膜の外表面から０．１〜０．３ミクロンの内部に２００
〜３００オングストロームの緻密層、さらに内部へ数ミ
クロンは多孔質層、さらに内部は１０ミクロン以上の径
をもつ巨大ボイドを有する網状層となっている。両末端
シラノールポリジメチルシロキサン（数平均分子量３０
０００）５重量部、テトラオキシムシラン２．５重量
部、ジブチル錫ジアセテート０．５重量部をトリフルオ
ロトリクロロエタンに溶解して溶液を調製し、ポリマ濃
度が１．０％になるまでトリフルオロトリクロロエタン
で塗液を調製した。本溶液を、得られているポリアクリ
ロニトリル多孔質中空糸の外表面に塗工して乾燥させる
ことを７回繰り返す。得られたシリコーン複合中空糸膜
の窒素透過速度は、０．２（ｍ3 ／ｍ2 ・ｈ・ａｔｍ）
であり、酸素／窒素分離係数＝２．１であった。Example 1 A polymer having 100 mol% of acrylonitrile and [η] = 3.2 was polymerized in DMSO and further diluted to give a polymer concentration of 1
A spinning dope of 4.0% by weight was obtained. This spinning solution was discharged from the sheath at a rate of 1.2 cc / min using a sheath-core type hollow fiber spinneret having an inner diameter of 0.3 mm and a slit width of 0.1 mm.
Water was discharged from the core. The spinning temperature was 30 ° C, the discharged yarn was once passed through the air (room temperature) for 30 mm, and then introduced into a coagulation bath consisting of water at 30 ° C to coagulate the yarn.
It was washed in water at ℃ and wound up. The hollow fiber membrane had an inner diameter of 240 μm and a film thickness of 30 μm.
200 inside from 0.1 to 0.3 microns from the outer surface of the membrane
A dense layer of 300 angstroms, a porous layer of several microns inside, and a mesh layer having huge voids with a diameter of 10 microns or more inside. Both terminal silanol polydimethyl siloxane (number average molecular weight 30
000) 5 parts by weight, tetraoxime silane 2.5 parts by weight, and dibutyltin diacetate 0.5 parts by weight are dissolved in trifluorotrichloroethane to prepare a solution, and trifluorotrichloroethane is added until the polymer concentration becomes 1.0%. To prepare a coating liquid. This solution is applied to the outer surface of the obtained polyacrylonitrile porous hollow fiber and dried, which is repeated 7 times. The nitrogen permeation rate of the obtained silicone composite hollow fiber membrane was 0.2 (m 3 / m 2 · h · atm).
And the oxygen / nitrogen separation coefficient = 2.1.
【００２４】得られた中空糸膜８０００本からなる中空
糸膜束を、外径１１４ｍｍ、内径１０４ｍｍの透明硬質
塩化ビニルパイプの外筒内部に挿入して両端を接着剤で
固定した。次に、接着固定部の両端を切断し、中空糸膜
の内部孔を開孔させた後に、長さ１．２ｍ、中空糸膜有
効長８５ｃｍの中空糸膜モジュールを製作した。この中
空糸膜モジュールの有効膜面積は、０．４８ｍ2 であっ
た。この中空糸膜モジュールの一端にトリクロロエタン
蒸気を５％混合した空気を１６リットル／分で供給し、
外筒の側壁にある透過ガス排出口を真空ポンプに接続
し、真空度−７４７Ｔｏｒｒに設定すると、透過ガス流
量は、１．６リットル／分でトリクロロエタン蒸気濃度
は、４５．５％であり、中空糸膜モジュールのもう一つ
の一端から排出される非透過ガスの流量は１４．４リッ
トル／分でトリクロロエタン蒸気濃度は、０．５％であ
った。本条件での回収率（透過ガス流量／供給ガス流
量）は１０％であるが、この分離効率（透過ガス中のト
リクロロエタン重量／供給ガス中のトリクロロエタン重
量）＝９１％であった。The hollow fiber membrane bundle consisting of 8000 hollow fiber membranes thus obtained was inserted into the outer cylinder of a transparent hard vinyl chloride pipe having an outer diameter of 114 mm and an inner diameter of 104 mm, and both ends were fixed with an adhesive. Next, both ends of the adhesive fixing part were cut, the inner holes of the hollow fiber membrane were opened, and then a hollow fiber membrane module having a length of 1.2 m and an effective length of the hollow fiber membrane of 85 cm was manufactured. The effective membrane area of this hollow fiber membrane module was 0.48 m 2 . Air mixed with 5% trichloroethane vapor was supplied to one end of this hollow fiber membrane module at 16 liters / minute,
When the permeated gas discharge port on the side wall of the outer cylinder is connected to a vacuum pump and the degree of vacuum is set to -747 Torr, the permeated gas flow rate is 1.6 liters / minute, and the trichloroethane vapor concentration is 45.5%. The flow rate of the non-permeable gas discharged from the other end of the fiber membrane module was 14.4 l / min, and the trichloroethane vapor concentration was 0.5%. The recovery rate (permeate gas flow rate / supply gas flow rate) under these conditions was 10%, but this separation efficiency (trichloroethane weight in permeate gas / trichloroethane weight in supply gas) was 91%.
【００２５】比較例１ 実施例１で使用した１４．０重量％のポリアクリロニト
リル溶液をポリエステルタフター上に２００ミクロン塗
工し、水凝固浴に浸漬して１ｍ幅の平膜のポリアクリロ
ニトリル多孔質支持膜を作成した。実施例１と同様に、
両末端シラノールポリジメチルシロキサン（数平均分子
量３００００）５重量部、テトラオキシムシラン２．５
重量部、ジブチル錫ジアセテート０．５重量部をトリフ
ルオロトリクロロエタンに溶解して溶液を調製し、ポリ
マ濃度が１．０％になるまでトリフルオロトリクロロエ
タンで塗液を調製した。本溶液を、得られている平膜の
ポリアクリロニトリル多孔質支持膜の表面に塗工して乾
燥させることを７回繰り返す。得られた平膜のシリコー
ン複合膜の窒素透過速度は、０．２１（ｍ3 ／ｍ2・ｈ
・ａｔｍ）であり、酸素／窒素分離係数＝２．２であっ
た。Comparative Example 1 Polyester acrylonitrile solution of 14.0% by weight used in Example 1 was coated on a polyester tuft for 200 μm and immersed in a water coagulation bath to form a flat film of polyacrylonitrile having a width of 1 m. A supporting film was prepared. Similar to Example 1,
5 parts by weight of silanol polydimethyl siloxane with both ends (number average molecular weight 30,000), tetraoxime silane 2.5
By weight, 0.5 part by weight of dibutyltin diacetate was dissolved in trifluorotrichloroethane to prepare a solution, and a coating solution was prepared with trifluorotrichloroethane until the polymer concentration became 1.0%. This solution is applied to the surface of the obtained flat membrane polyacrylonitrile porous support membrane and dried to repeat 7 times. The nitrogen permeation rate of the obtained flat membrane silicone composite membrane was 0.21 (m 3 / m 2 · h
-Atm), and the oxygen / nitrogen separation coefficient = 2.2.
【００２６】本平膜のシリコーン複合膜を用い、供給側
流路材および透過側流路材に厚み０．８ｍｍのポリエチ
レン製ネットを使用して、長さ１ｍ、有効膜面積０．４
８ｍ2 のスパイラルモジュールを作成した。Using the silicone composite membrane of this flat membrane, a polyethylene net having a thickness of 0.8 mm is used for the flow channel material on the supply side and the flow channel material on the permeate side, and the length is 1 m and the effective membrane area is 0.4.
An 8 m 2 spiral module was created.
【００２７】このスパイラルモジュールの一端にトリク
ロロエタン蒸気濃度５％の混合空気を１６リットル／分
で供給し、スパイラルモジュールの透過側に通じる中心
パイプより真空ポンプによって、透過側の真空度−７４
７Ｔｏｒｒに設定すると、透過ガス流量は、１．６リッ
トル／分でトリクロロエタン蒸気濃度は、３６．５％で
あり、スパイラルモジュールのもう一端から排出される
非透過ガスの流量は、１４．４リットル／分でトリクロ
ロエタン蒸気濃度は、１．５％であった。本条件での回
収率（透過ガス流量／供給ガス流量）は１０％である
が、この分離効率（透過ガス中のトリクロロエタン重量
／供給ガス中のトリクロロエタン重量）＝７３％であっ
た。A mixed air having a trichloroethane vapor concentration of 5% was supplied to one end of the spiral module at a rate of 16 liters / minute, and a vacuum degree of -74 on the permeate side was obtained by a vacuum pump from a central pipe leading to the permeate side of the spiral module.
When set to 7 Torr, the permeated gas flow rate is 1.6 l / min, the trichloroethane vapor concentration is 36.5%, and the non-permeated gas flow rate discharged from the other end of the spiral module is 14.4 l / min. The trichloroethane vapor concentration in minutes was 1.5%. The recovery rate (permeation gas flow rate / supply gas flow rate) under these conditions was 10%, but this separation efficiency (trichloroethane weight in permeation gas / trichloroethane weight in supply gas) was 73%.
【００２８】実施例２ ポリ１、２ブタジエン（日本合成ゴム（株）製 ＪＳＲ
ＲＢ８２０）を５重量部、ビニルトリメトキシシラン
を１０重量部キシレンに溶解する。さらに、ベンジルパ
ーオキサイドを０．１重量部キシレンに溶解し、１５０
℃で３０分窒素ガス中で撹拌して反応せしめる。得られ
た溶液よりメタノールで高分子を析出させ、トリメトキ
シシリルグラフトポリ１、２ブタジエンを得た。該高分
子のトリメトキシシリル基のグラフト率は、０．８モル
％であった。Example 2 Poly 1,2 butadiene (JSR manufactured by Japan Synthetic Rubber Co., Ltd.)
5 parts by weight of RB820) and 10 parts by weight of vinyltrimethoxysilane are dissolved in xylene. Further, benzyl peroxide was dissolved in 0.1 part by weight of xylene to obtain 150
The reaction is carried out by stirring in nitrogen gas at 30 ° C. for 30 minutes. A polymer was precipitated from the obtained solution with methanol to obtain trimethoxysilyl graft poly 1,2 butadiene. The graft ratio of trimethoxysilyl group of the polymer was 0.8 mol%.
【００２９】実施例１で用いた反応性シリコーン１％溶
液を、実施例１で用いたポリアクリロニトリル多孔質中
空糸膜の表面に塗工して乾燥することを２回繰り返す。
トリメトキシシリルグラフトポリ１、２ブタジエンをシ
クロヘキサンに５重量部に調製し、さらにトリフルオロ
トリクロロエタンで希釈してポリマ濃度０．５重量部に
調製し、さらにオクチル酸錫を０．１重量部加えて溶液
を調製した。本溶液を上記で得た架橋型シリコーン複合
中空糸膜上に塗工し乾燥することを２回繰り返す。この
複合中空糸膜の窒素透過速度は、０．３（ｍ3 ／ｍ2 ・
ｈ・ａｔｍ）であり、酸素／窒素分離係数＝２．８であ
った。この様にして得られた複合中空糸膜８０００本か
らなる中空糸膜束を、外径１１４ｍｍ、内径１０４ｍｍ
の透明硬質塩化ビニルパイプの外筒内部に挿入して両端
を接着剤で固定した。次に接着剤固定部の両端を切断
し、中空糸膜の内部孔を開孔させた後に、長さ１．２
ｍ、中空糸膜有効長８５ｃｍの中空糸膜モジュールを製
作した。この中空糸膜モジュールの有効膜面積は０．４
８ｍ2 であった。この中空糸膜モジュールの一端にトリ
クロロエタン蒸気を５％混合した空気を２４リットル／
分で供給し、外筒の側壁にある透過ガス排出口を真空ポ
ンプに接続し、真空度−７００Ｔｏｒｒに設定する。透
過ガス流量は２．４リットル／分でトリクロロエタン蒸
気濃度は、３６．５％であり、中空糸膜モジュールのも
う一つの一端から排出される非透過ガスの流量は２１．
６リットル／分でトリクロロエタン蒸気濃度は、１．５
％であった。本条件での回収率（透過ガス流量／供給ガ
ス流量）は１０％であるが、この分離効率（透過ガス中
のトリクロロエタン重量／供給ガス中のトリクロロエタ
ン重量）＝７３％であった。The reactive silicone 1% solution used in Example 1 is applied to the surface of the polyacrylonitrile porous hollow fiber membrane used in Example 1 and dried, which is repeated twice.
Trimethoxysilyl grafted poly-1,2 butadiene was prepared in cyclohexane to 5 parts by weight, further diluted with trifluorotrichloroethane to a polymer concentration of 0.5 parts by weight, and 0.1 parts by weight of tin octylate was added. A solution was prepared. The application of this solution onto the crosslinked silicone composite hollow fiber membrane obtained above and drying is repeated twice. The nitrogen permeation rate of this composite hollow fiber membrane was 0.3 (m 3 / m 2 ·
h · atm), and the oxygen / nitrogen separation coefficient = 2.8. A hollow fiber membrane bundle consisting of 8000 composite hollow fiber membranes thus obtained was used to obtain an outer diameter of 114 mm and an inner diameter of 104 mm.
The transparent hard vinyl chloride pipe was inserted into the outer cylinder and both ends were fixed with an adhesive. Next, after cutting both ends of the adhesive fixing portion and opening the inner holes of the hollow fiber membrane,
m, a hollow fiber membrane module having an effective length of 85 cm was produced. The effective membrane area of this hollow fiber membrane module is 0.4
It was 8 m 2 . 24 liters of air mixed with 5% trichloroethane vapor was added to one end of this hollow fiber membrane module.
The permeated gas outlet on the side wall of the outer cylinder is connected to a vacuum pump, and the degree of vacuum is set to -700 Torr. The permeated gas flow rate was 2.4 liters / minute, the trichloroethane vapor concentration was 36.5%, and the flow rate of the non-permeated gas discharged from the other end of the hollow fiber membrane module was 21.
At 6 liters / minute, the trichloroethane vapor concentration is 1.5
%Met. The recovery rate (permeation gas flow rate / supply gas flow rate) under these conditions was 10%, but this separation efficiency (trichloroethane weight in permeation gas / trichloroethane weight in supply gas) was 73%.
【００３０】比較例２ 実施例１で使用した１４．０重量％のポリアクリロニト
リル溶液をポリエステルタフータ上に２００ミクロン塗
工し、水凝固浴に浸漬して１ｍ幅の平膜のポリアクリロ
ニトリル多孔質支持膜を作成した。実施例１で用いた反
応性シリコーン１％溶液を、本ポリアクリロニトリル多
孔質支持膜の表面に塗工して乾燥することを２回繰り返
す。実施例２で用いたトリメトキシシリルシラングラフ
トポリ１、２ブタジエンをシクロヘキサンに５重量部に
調製し、さらにトリフルオロトリクロロエタンで希釈し
てポリマ濃度０．５重量部に調製し、さらにオクチル酸
錫を１重量部加えて溶液を調製した。本溶液を上記で得
た架橋型シリコーン複合膜上に塗工し乾燥することを２
回繰り返す。この複合膜の窒素透過速度は、０．３（ｍ
3 ／ｍ2 ・ｈ・ａｔｍ）であり、酸素／窒素分離係数＝
２．８５であった。この様にして得られた複合膜を用
い、供給側流路材および透過側流路材に厚み０．８ｍｍ
のポリエチレン製ネットを使用して、長さ１ｍ、有効膜
面積０．４８ｍ2 のスパイラルモジュールを作成した。
このスパイラルモジュールに一端にトリクロロエタン蒸
気を５％混合した空気を２４リットル／分で供給し、ス
パイラルモジュールの透過側に通じる中心パイプより真
空ポンプによって、透過側の真空度−７００Ｔｏｒｒに
設定すると、透過ガス流量は、２．４リットル／分でト
リクロロエタン蒸気濃度２７．５％であり、スパイラル
モジュールのもう一つの一端から排出される非透過ガス
の流量は２１．６リットル／分でトリクロロエタン蒸気
濃度は、２．５％であった。本条件での回収率（透過ガ
ス流量／供給ガス流量）は１０％であるが、この分離効
率（透過ガス中のトリクロロエタン重量／供給ガス中の
トリクロロエタン重量）＝５５％であった。Comparative Example 2 Polyester acrylonitrile solution of 14.0% by weight used in Example 1 was coated on polyester tufts in an amount of 200 μm and immersed in a water coagulation bath to form a flat film of polyacrylonitrile porous having a width of 1 m. A supporting film was prepared. The application of the reactive silicone 1% solution used in Example 1 to the surface of the present polyacrylonitrile porous support membrane and drying are repeated twice. The trimethoxysilylsilane-grafted poly 1,2 butadiene used in Example 2 was prepared in cyclohexane to 5 parts by weight and further diluted with trifluorotrichloroethane to prepare a polymer concentration of 0.5 parts by weight, and tin octylate was further added. A solution was prepared by adding 1 part by weight. Applying this solution onto the crosslinked silicone composite film obtained above and drying it
Repeat times. The nitrogen permeation rate of this composite membrane is 0.3 (m
3 / m 2 · h · atm), and the oxygen / nitrogen separation coefficient =
It was 2.85. Using the composite membrane thus obtained, the feed-side channel material and the permeate-side channel material have a thickness of 0.8 mm.
A polyethylene module having a length of 1 m and an effective membrane area of 0.48 m 2 was prepared using the polyethylene net.
The air mixed with 5% of trichloroethane vapor at one end is supplied to this spiral module at a rate of 24 liters / minute, and when the vacuum degree on the permeation side is set to -700 Torr by the vacuum pump from the central pipe leading to the permeation side of the spiral module, the permeation gas The flow rate was 2.4 liters / minute and the trichloroethane vapor concentration was 27.5%. The flow rate of the non-permeate gas discharged from the other end of the spiral module was 21.6 liters / minute and the trichloroethane vapor concentration was 2%. It was 0.5%. The recovery rate (permeate gas flow rate / supply gas flow rate) under these conditions was 10%, but this separation efficiency (trichloroethane weight in permeate gas / trichloroethane weight in supply gas) was 55%.
【００３１】実施例３ アクリロニトリル１００モル％、［η］＝３．２の重合
体をＤＭＳＯ中で重合し、さらに希釈して重合体濃度１
３．５重量％の紡糸原液を得た。内径０．３ｍｍ、スリ
ット幅０．１５ｍｍの鞘芯型中空糸用口金を用いて鞘部
よりこの紡糸原液を３．５ｃｃ／ｍｉｎの速度で吐出し
た。紡糸温度６０℃で、吐出した糸条をいったん空気中
（室温）を１５０ｍｍ通過させたのち６０の水からなる
凝固浴中に導いて凝固させ、６０℃の水中で洗浄してか
ら巻き取った。中空糸膜の寸法は、内径３４０ミクロ
ン、膜厚５０ミクロンであった。膜の外表面から０．１
〜０．３ミクロンの内部に２００〜３００オングストロ
ームの孔径を有する緻密層、さらに内部へ数ミクロンの
孔を有する多孔質層、さらに内部は１０ミクロン以上の
径をもつ巨大ボイドを有する網状層となっている。側鎖
アミノ基ポリジメチルシロキサン（数平均分子量１０
万、アミノ基含有率＝０．８モル％トーレシリコーン
（株）製ＢＹ１６−８４７）２．５重量部、トリレンジ
イソシアネート０．５重量部をシクロヘキサンに溶解し
て溶液を調製した。本溶液を、上記で得られたポリアク
リロニトリル多孔質中空糸の外表面に塗工して乾燥させ
ることを２回繰り返した。得られた複合中空糸膜に両末
端アミノ変性シリコーン（数平均分子量３０００、アミ
ン当量＝１５００、信越シリコーン（株）製Ｘ−２２−
１６１Ｂ）２重量部、ヘキサメチレンジイソシアネート
０．１４重量部、ジブチル錫ジアセテート０．０４重量
部をシクロヘキサンに溶解して溶液を調製し、上記複合
中空糸膜の表面に塗工して乾燥させることを２回繰り返
した。得られた架橋型シリコーン複合中空糸膜の窒素透
過速度は、０．４（ｍ3 ／ｍ2 ・ｈ・ａｔｍ）であり、
酸素／窒素分離係数＝２．１であった。Example 3 A polymer having 100 mol% of acrylonitrile and [η] = 3.2 was polymerized in DMSO and further diluted to give a polymer concentration of 1
A spinning dope of 3.5% by weight was obtained. This spinning dope was discharged from the sheath portion at a rate of 3.5 cc / min using a sheath-core type hollow fiber spinneret having an inner diameter of 0.3 mm and a slit width of 0.15 mm. At a spinning temperature of 60 ° C., the discharged yarn was once passed through air (room temperature) for 150 mm, then introduced into a coagulation bath of 60 water to coagulate, washed in water at 60 ° C., and then wound. The hollow fiber membrane had an inner diameter of 340 microns and a film thickness of 50 microns. 0.1 from the outer surface of the membrane
~ 0.3 micron with a dense layer with a pore size of 200-300 angstroms inside, a porous layer with pores of a few microns inside, and a net-like layer with huge voids with a diameter of 10 microns or more inside ing. Side chain amino group polydimethylsiloxane (number average molecular weight 10
Amino group content = 0.8 mol% BY16-847 manufactured by Toray Silicone Co., Ltd. 2.5 parts by weight and tolylene diisocyanate 0.5 parts by weight were dissolved in cyclohexane to prepare a solution. The application of this solution to the outer surface of the polyacrylonitrile porous hollow fiber obtained above and drying was repeated twice. Both ends amino-modified silicone (number average molecular weight 3000, amine equivalent = 1500, Shin-Etsu Silicone Co., Ltd. X-22-) was added to the obtained composite hollow fiber membrane.
161B) 2 parts by weight, 0.14 parts by weight of hexamethylene diisocyanate, and 0.04 parts by weight of dibutyltin diacetate are dissolved in cyclohexane to prepare a solution, which is coated on the surface of the composite hollow fiber membrane and dried. Was repeated twice. The nitrogen permeation rate of the obtained crosslinked silicone composite hollow fiber membrane was 0.4 (m 3 / m 2 · h · atm),
The oxygen / nitrogen separation coefficient was 2.1.
【００３２】得られた中空糸膜８０００本からなる中空
糸膜束を、外径１１４ｍｍ、内径１０４ｍｍのナイロン
パイプの外筒内部に挿入して両端を接着剤で固定した。
次に、接着固定部の両端を切断し、中空糸膜の内部孔を
開孔させた後に、長さ１．２ｍ、中空糸膜有効長８５ｃ
ｍの中空糸膜モジュールを作成した。この中空糸膜モジ
ュールの有効膜面積は、０．４８ｍ2 であった。この中
空糸膜モジュールの一端にトリクロロエタン蒸気を１０
％混合した空気を３２リットル／分で供給し、外筒の側
壁にある透過ガス排出口を真空ポンプに接続し、真空度
−７４７Ｔｏｒｒに設定すると、透過ガス流量は、３．
２リットル／分で、トリクロロエタン蒸気濃度は、９５
％であり、中空糸膜モジュールのもう一つの一端から排
出される非透過ガスの流量は、２８．８リットル／分で
トリクロロエタン蒸気濃度は０．５５％であった。この
分離効率（透過ガス中のトリクロロエタン重量／供給ガ
ス中のトリクロロエタン重量）＝９５％であった。A hollow fiber membrane bundle consisting of 8000 hollow fiber membranes thus obtained was inserted into the outer cylinder of a nylon pipe having an outer diameter of 114 mm and an inner diameter of 104 mm, and both ends were fixed with an adhesive.
Next, after cutting both ends of the adhesive fixing part and opening the inner hole of the hollow fiber membrane, the length is 1.2 m and the hollow fiber membrane effective length is 85 c.
m hollow fiber membrane module was prepared. The effective membrane area of this hollow fiber membrane module was 0.48 m 2 . Trichloroethane vapor was added to one end of this hollow fiber membrane module at 10
% Mixed air is supplied at 32 liters / minute, the permeated gas outlet on the side wall of the outer cylinder is connected to a vacuum pump, and the degree of vacuum is set to -747 Torr.
At 2 liters / minute, the trichloroethane vapor concentration is 95
%, The flow rate of the non-permeable gas discharged from the other end of the hollow fiber membrane module was 28.8 l / min, and the trichloroethane vapor concentration was 0.55%. This separation efficiency (weight of trichloroethane in permeated gas / weight of trichloroethane in feed gas) was 95%.
【００３３】[0033]
【発明の効果】本発明により、有機蒸気分離性が高く、
有機蒸気の分離効率の高い有機蒸気分離膜および有機蒸
気分離膜モジュールを提供することができ、膜分離法で
有機蒸気回収の設備費および運転費を小さくすることが
可能である。According to the present invention, the organic vapor separation property is high,
It is possible to provide an organic vapor separation membrane and an organic vapor separation membrane module having a high organic vapor separation efficiency, and it is possible to reduce the facility cost and operating cost of the organic vapor recovery by the membrane separation method.
Claims (5)
以下の中空糸膜構造を有する有機蒸気分離膜。1. An organic vapor separation membrane having a hollow fiber membrane structure having an inner diameter of 50 μm or more and 1000 μm or less.
を有する０．０１ミクロン以上、１０ミクロン以下の厚
みの機能層であり、内部層が１０ミクロン以上、１００
ミクロン以下の厚みを有する多孔質構造であることを特
徴とする請求項１記載の有機蒸気分離膜。2. A hollow fiber membrane structure, wherein the outermost layer is a functional layer having an organic vapor separation property and having a thickness of 0.01 micron or more and 10 micron or less, and an inner layer is 10 micron or more, 100.
The organic vapor separation membrane according to claim 1, which has a porous structure having a thickness of not more than micron.
混合ガスが中空糸内側に供給されることを特徴とする有
機蒸気分離膜。3. An organic vapor separation membrane having a hollow fiber membrane structure, wherein a mixed gas containing organic vapor is supplied to the inside of the hollow fiber.
離膜を組み込んだモジュール。4. A module incorporating the organic vapor separation membrane according to claim 1 or 2.
に供給されることを特徴とする請求項４記載のモジュー
ル。5. The module according to claim 4, wherein the mixed gas containing organic vapor is supplied to the inside of the hollow fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19980693A JPH06246126A (en) | 1992-12-28 | 1993-08-11 | Hollow fiber type organic vapor separating membrane and module using the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4-348793 | 1992-12-28 | ||
| JP34879392 | 1992-12-28 | ||
| JP19980693A JPH06246126A (en) | 1992-12-28 | 1993-08-11 | Hollow fiber type organic vapor separating membrane and module using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06246126A true JPH06246126A (en) | 1994-09-06 |
Family
ID=26511763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19980693A Pending JPH06246126A (en) | 1992-12-28 | 1993-08-11 | Hollow fiber type organic vapor separating membrane and module using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06246126A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8388743B2 (en) | 2008-10-30 | 2013-03-05 | Aisan Kogyo Kabyshiki Kaisha | Separation membrane module and fuel vapor processing apparatus incorporating the same |
-
1993
- 1993-08-11 JP JP19980693A patent/JPH06246126A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8388743B2 (en) | 2008-10-30 | 2013-03-05 | Aisan Kogyo Kabyshiki Kaisha | Separation membrane module and fuel vapor processing apparatus incorporating the same |
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