JP5772275B2 - Method for producing hollow fiber carbon membrane - Google Patents
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- JP5772275B2 JP5772275B2 JP2011137090A JP2011137090A JP5772275B2 JP 5772275 B2 JP5772275 B2 JP 5772275B2 JP 2011137090 A JP2011137090 A JP 2011137090A JP 2011137090 A JP2011137090 A JP 2011137090A JP 5772275 B2 JP5772275 B2 JP 5772275B2
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- 239000012528 membrane Substances 0.000 title claims description 54
- 239000012510 hollow fiber Substances 0.000 title claims description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 38
- 229910052799 carbon Inorganic materials 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 30
- 239000000463 material Substances 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000004804 winding Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 22
- 238000009987 spinning Methods 0.000 claims description 17
- 238000003763 carbonization Methods 0.000 claims description 13
- 238000011282 treatment Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 238000001891 gel spinning Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002243 precursor Substances 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- 238000002166 wet spinning Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229920006380 polyphenylene oxide Polymers 0.000 description 3
- 229920013637 polyphenylene oxide polymer Polymers 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920002852 poly(2,6-dimethyl-1,4-phenylene oxide) polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
- Artificial Filaments (AREA)
- Inorganic Fibers (AREA)
Description
本発明は、中空糸炭素膜の製造方法に関する。さらに詳しくは、中空糸炭素膜製造過程における製造能力の向上、省人力化を可能とする中空糸炭素膜の製造方法に関する。 The present invention relates to a method for producing a hollow fiber carbon membrane. More specifically, the present invention relates to a method for producing a hollow fiber carbon membrane that can improve the production capacity and save labor in the hollow fiber carbon membrane production process.
炭素膜は、種々の無機膜の中でもすぐれた気体分離性を示し、かつ有機膜が適用できない耐熱性、耐薬品性が要求される環境下でも使用可能なことから、その実用性が大いに期待されている。また、中空糸状の炭素膜は耐圧性にすぐれ、かつ単位容積当りに占める膜面積が大きく、コンパクトな分離膜モジュールの作製が可能となる。既にこれらの特徴をあわせもつ中空糸炭素膜が開発され、その製造方法として、特許文献１および同２にはポリフェニレンオキシド誘導体から中空糸炭素膜を製造する方法が開示されている。これらは、中空糸炭素膜の基本的な製造法ともいえるものであるが、これら中空糸炭素膜を用いた分離膜モジュールの製造、中空糸炭素膜および分離膜モジュールの量産、さらには製造能力向上のために、量産化設備を使用した条件での製造可能な技術開発が必要とされている。
Carbon membranes show excellent gas separation properties among various inorganic membranes, and can be used in environments where heat resistance and chemical resistance are not applicable to organic membranes. ing. In addition, the hollow fiber-like carbon membrane is excellent in pressure resistance and has a large membrane area per unit volume, making it possible to produce a compact separation membrane module. A hollow fiber carbon membrane having these characteristics has already been developed. As a production method thereof,
かかる中空糸炭素膜は、下記の如き紡糸工程、乾燥工程、不融化処理工程および炭化処理工程を基本工程とする(特許文献２参照)。
(1) 紡糸工程：ポリフェニレンオキシド誘導体ポリマーの有機溶媒溶液(紡糸原液)を2
重管構造の中空糸紡糸ノズルを用いて、湿式紡糸法または乾湿式紡糸法
によって、無機塩水溶液、水などの芯液と同時に押し出す(特許文献２
図２参照)
(2) 乾燥工程：紡糸工程で得られた誘導体ポリマーの中空糸状物を乾燥する
(3) 不融化処理工程：前駆体である乾燥した中空糸状物を、150〜300℃、0.5〜4時間の
加熱処理条件下で、不融化処理を実施する(但し、この工程は任
意)
(4) 炭化処理工程：前駆体不融化処理膜を10−４気圧以下の減圧下、もしくはヘリウム
、アルゴンガス、窒素ガスなどで置換した不活性ガス雰囲気下で
450〜850℃で0.5〜4時間加熱する
Such a hollow fiber carbon membrane has the following spinning process, drying process, infusibilization process and carbonization process as basic processes (see Patent Document 2).
(1) Spinning process: Polyphenylene oxide derivative polymer organic solvent solution (spinning stock solution) 2
Wet spinning method or dry-wet spinning method using hollow tube spinning nozzle with double tube structure
Extruded simultaneously with a core liquid such as an inorganic salt aqueous solution or water (Patent Document 2)
(See Figure 2)
(2) Drying process: Drying the hollow fiber of derivative polymer obtained in the spinning process
(3) Infusibilization treatment process: The dried hollow fiber material as a precursor is heated at 150 to 300 ° C. for 0.5 to 4 hours.
Perform infusibilization treatment under heat treatment conditions (however, this step is
)
(4) Carbonization process: The precursor infusible film is subjected to reduced pressure of 10-4 atm or less or helium.
In an inert gas atmosphere substituted with argon gas, nitrogen gas, etc.
Heat at 450-850 ° C for 0.5-4 hours
これらの従来の技術による中空糸炭素膜の製造は、得られる中空糸炭素膜の欠陥発生割合が高く、かかる点について改良が求められている。 The production of hollow fiber carbon membranes by these conventional techniques has a high defect generation rate of the obtained hollow fiber carbon membranes, and improvements are demanded in this respect.
ここで、乾燥工程では中空糸状物の乾燥に先立ち、中空糸状物の中空部分に残留する芯液を取り除くことが必要となる。この芯液の除去を容易にするために、本出願人は先に、中空糸状物を所定の長さで切り揃えた後、中空糸状物１本ごとに、重力方向に吊り下げて、中空糸状物の中空部分に残留する芯液を取り除き、その後中空糸状物のポリマー部分から水分を蒸発させて乾燥させる方法を提案している(特開2012-81375号公報)。しかるに、これらの作業はすべて手作業であるため、製造能力の向上や製造時における省人力化を阻む要因となっている。また、不融化処理工程では、乾燥した中空糸状物を加熱処理時に発生する中空糸状物間の付着に起因する破損不良防止を目的として、一本毎に保護管内に設置して加熱処理が実施されており、加熱処理後には不融化処理膜を保護管から取り出す必要があるが、かかる作業もすべて手作業で行わなければならず、この工程も製造能力向上、製造における省人力化を阻む要因となっている。 Here, in the drying step, it is necessary to remove the core liquid remaining in the hollow portion of the hollow fiber-like material before drying the hollow fiber-like material. In order to facilitate the removal of the core liquid, the applicant first cuts the hollow fiber-like material to a predetermined length, and then suspends the hollow fiber-like material in the direction of gravity to form a hollow fiber-like material. A method has been proposed in which the core liquid remaining in the hollow portion of the product is removed, and then water is evaporated from the polymer portion of the hollow fiber-like product to dry it ( Japanese Patent Laid-Open No. 2012-81375 ). However, since these operations are all manual operations, it is a factor that hinders the improvement of manufacturing capability and the labor saving during manufacturing. In addition, in the infusibilization treatment process, the dried hollow fiber-like material is heat-treated by installing it in a protective tube one by one for the purpose of preventing damage due to adhesion between the hollow fiber-like materials generated during the heat treatment. After the heat treatment, it is necessary to remove the infusible film from the protective tube, but all such work must be done manually, and this process is also a factor that hinders the improvement of manufacturing capacity and labor saving in manufacturing. It has become.
以上より、中空糸炭素膜の製造においては、得られる中空糸炭素膜の欠陥発生割合を低く抑えつつ、作業効率を向上させることが求められている。 From the above, in the production of the hollow fiber carbon membrane, it is required to improve the working efficiency while keeping the defect generation rate of the obtained hollow fiber carbon membrane low.
本発明の目的は、中空糸炭素膜を、欠陥発生割合を抑制しつつ、大量かつ迅速に得ることを可能とする中空糸炭素膜の製造方法を提供することにある。 The objective of this invention is providing the manufacturing method of the hollow fiber carbon membrane which makes it possible to obtain a hollow fiber carbon membrane rapidly and in large quantities, suppressing the defect generation rate.
かかる本発明の目的は、湿式または乾湿式紡糸工程、乾燥工程および炭化処理工程を基本工程とする中空糸炭素膜の製造方法において、
紡糸により得られた中空糸状物を、水抜用巻き取りボビンに巻き取り、巻き取られた中空糸状物の一端部を開放した状態で他端部より空気を送り込み、中空部分の水および芯液を排出した後、水抜用巻き取りボビンとこれとは別の乾燥物巻き取りボビンとの間に設置された乾燥機を用いて乾燥処理を施し、その後炭化処理することによって達成される。中空糸状物中に送り込まれる空気としては、ゲージ圧が100〜300kPaGの空気が一般に用いられる。
The object of the present invention is to provide a hollow fiber carbon membrane production method comprising a wet or dry-wet spinning process, a drying process and a carbonization process as basic processes.
The hollow fiber-like material obtained by spinning is wound around a take-up bobbin for draining water, and air is fed from the other end with one end of the wound hollow fiber-like material being opened, and the water and core liquid in the hollow part are discharged. After discharging, it is achieved by performing a drying process using a drier installed between a draining bobbin for draining water and another dried material winding bobbin, and then carbonizing. As the air fed into the hollow fiber material, air having a gauge pressure of 100 to 300 kPaG is generally used.
本発明に係る中空糸炭素膜の製造方法は、1m程度の中空糸状物1本毎ではなく、100m以上の長さの中空糸状物を切断することなく、ボビンを用いてこれを一単位とし、乾燥および不融化処理を可能とせしめる方法であり、欠陥発生割合を抑制しつつ、中空糸炭素膜の量産化、製造能力向上を可能にするといったすぐれた効果を奏する。 The method for producing a hollow fiber carbon membrane according to the present invention is not used for each hollow fiber of about 1 m, but without cutting a hollow fiber of a length of 100 m or more, using a bobbin as a unit, This is a method that enables drying and infusibilization treatments, and has excellent effects such as enabling mass production of hollow fiber carbon membranes and improvement of manufacturing capability while suppressing the defect generation rate.
中空糸炭素膜の製造材料としては、公知の炭素形成材料(ポリマー)のいずれも用いることができるが、好ましくは特許文献１〜２記載のポリフェニレンオキシド系ポリマー、例えばポリフェニレンオキシドあるいはその芳香族環の1〜4個の水素原子がハロゲン原子、スルホン基、カルボキシル基、低級アルキル基、トリ低級アルキルシリル基、ジアリールホスフィノ基で直接または-CH２-基を介して置換された誘導体であるもの等が用いられる。ここで、低級アルキル基は、炭素数1〜5のアルキル基を指している。かかるポリマーを原料とする中空糸炭素膜の製造は、次のような工程に従って製造される。
As a material for producing the hollow fiber carbon membrane, any of known carbon forming materials (polymers) can be used, but preferably a polyphenylene oxide polymer described in
〔紡糸工程〕
ポリマーを任意の可溶性有機溶媒、例えばメタノール、エタノール、テトラヒドロフラン、N,N-ジメチルアセトアミド、N-メチル-2-ピロリドンまたはこれらの混合物などに、約20〜40重量％、好ましくは約25〜35重量％の濃度に溶解させた紡糸原液を調製する。調製された紡糸原液を、湿式紡糸法または乾湿式紡糸法によって、二重管環状構造の中空糸紡糸ノズルの外管から凝固浴中に押し出し、紡糸ノズルの内管からは、製膜原液の溶媒とポリマーに対しては非溶解性の芯液を同時に押し出すことにより、中空糸状物を成形する。このとき、二重管環状構造の中空糸紡糸ノズルの外管の径と巻き取り速度の比などを適宜調節することにより所定の膜外径を有する中空糸炭素膜を形成し得る前駆体高分子中空糸膜を得ることができる。また、芯液および凝固浴は、製膜原液の溶媒と混合するが、ポリマーとは非溶解性の溶媒、例えば上記ポリフェニレンオキシド系ポリマーに対しては、水または硝酸アンモニウム、塩酸アンモニウム、硫酸アンモニウムなどのアンモニウム塩水溶液が用いられる。このとき、芯液および凝固浴の温度は、-20〜60℃、好ましくは0〜30℃に設定される。
[Spinning process]
The polymer is added to any soluble organic solvent, such as methanol, ethanol, tetrahydrofuran, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, or mixtures thereof, about 20-40% by weight, preferably about 25-35%. A stock solution of spinning dissolved to a concentration of% is prepared. The prepared spinning solution is extruded into the coagulation bath from the outer tube of the hollow tube spinning nozzle having a double-pipe annular structure by a wet spinning method or a dry-wet spinning method, and from the inner tube of the spinning nozzle, A hollow fiber-like product is formed by simultaneously extruding an insoluble core liquid to the polymer. At this time, a precursor polymer hollow capable of forming a hollow fiber carbon membrane having a predetermined outer membrane diameter by appropriately adjusting the ratio of the outer tube diameter and the winding speed of the hollow tube spinning nozzle having a double tube annular structure. A yarn membrane can be obtained. In addition, the core solution and the coagulation bath are mixed with the solvent of the film-forming stock solution. However, for the above-mentioned polyphenylene oxide polymer, water or ammonium such as ammonium nitrate, ammonium hydrochloride, or ammonium sulfate is mixed with the polymer. An aqueous salt solution is used. At this time, the temperature of the core liquid and the coagulation bath is set to -20 to 60 ° C, preferably 0 to 30 ° C.
次に、中空糸状物のボビン(水抜用巻き取りボビン)への巻き取りが行われる。水抜用巻き取りボビンとしては、外周0.5〜2.0m、好ましくは0.7〜1.2m程度のものが用いられ、中空糸状物の巻き取り速度は10〜60m/分、好ましくは20〜40m/分程度で行われる。また、巻き取られる中空糸状物の長さは、100〜8000m、好ましくは2000〜4000mとされ、中空糸状物を巻き取ったボビンは、水槽などに水中保管される。 Next, the hollow fiber-like material is wound up on a bobbin (a draining bobbin for draining water). As the take-up bobbin for draining water, one having an outer periphery of 0.5 to 2.0 m, preferably about 0.7 to 1.2 m is used, and the winding speed of the hollow fiber-like material is 10 to 60 m / min, preferably about 20 to 40 m / min. Done. The length of the hollow fiber-like material to be wound is 100 to 8000 m, preferably 2000 to 4000 m, and the bobbin wound with the hollow fiber-like material is stored underwater in a water tank or the like.
〔水抜工程〕
水抜用巻き取りボビンに巻き取られた状態の中空糸状物は、水中に保管されている状態を保ったまま、その一端部を開放し、また他端部を接着剤等を利用して空気圧をかけるためのチューブなどに接続固定した後、中空糸状物の中空部にゲージ圧が20〜300kPaG、好ましくは100〜200kPaGの空気送り込みが行われる。このとき、中空糸状物につぶれなどがみられると、中空部分に空気圧が均一に印加されず、水抜きを十分に行うことができない。以上の操作によって、中空糸状物の中空部分に存在する芯液および水をほぼ排出することができる。水抜きに要する時間は、中空糸の長さに依存するが、例えば長さ2000mの中空糸状物の場合には、100kPaGのゲージ圧条件下で3〜8時間程度となる。空気圧がこれよりも低い空気が送り込まれると、所望される芯液および水を完全に排出することはできず、一方これよりも高い空気圧を有する空気を送り込むと、中空糸の圧力による破断などが発生するおそれがある。
[Draining process]
The hollow fiber-like material that has been wound on the take-up bobbin for draining water is opened in one end while keeping the state stored in water, and air pressure is applied to the other end using an adhesive or the like. After being connected and fixed to a tube or the like for application, air is fed into the hollow portion of the hollow fiber-like material at a gauge pressure of 20 to 300 kPaG, preferably 100 to 200 kPaG. At this time, if the hollow fiber-like material is crushed, air pressure is not uniformly applied to the hollow portion, and water cannot be sufficiently drained. By the above operation, the core liquid and water present in the hollow portion of the hollow fiber-like material can be almost discharged. Although the time required for draining depends on the length of the hollow fiber, for example, in the case of a hollow fiber having a length of 2000 m, it is about 3 to 8 hours under a gauge pressure of 100 kPaG. If air with a lower air pressure is sent, the desired core liquid and water cannot be completely discharged, while if air with a higher air pressure is sent, the hollow fiber may break due to pressure, etc. May occur.
〔ボビン乾燥工程〕
水抜きが行われた中空糸状物は、乾燥機を用いて室温〜80℃、好ましくは25〜35℃の条件下で乾燥処理が行われた後、水抜用巻き取り用ボビンとは別の乾燥物巻き取りボビンに巻き取られる。水抜きが行われた中空糸状物は、これを巻き取った水抜用巻き取りボビンから線速度換算で5〜100cm/秒、好ましくは30〜80cm/秒の送風条件下で、２つのボビン間に設置されている筒状乾燥機を通過させて乾燥処理が行われ、乾燥温度条件にもよるが4〜20m/分、好ましくは8〜14m/分の巻き取り速度で巻き取りボビンに巻き取られる。
[Bobbin drying process]
The hollow fiber-like material that has been drained is dried using a dryer at room temperature to 80 ° C., preferably 25 to 35 ° C., and then dried separately from the drain bobbin for draining. It is wound on a material winding bobbin. The hollow fiber-like material from which water has been drained is drawn between the two bobbins under a blowing condition of 5 to 100 cm / second, preferably 30 to 80 cm / second, in terms of linear velocity, from the winding bobbin for water draining. It is passed through an installed cylindrical dryer and dried, and it is wound on a winding bobbin at a winding speed of 4 to 20 m / min, preferably 8 to 14 m / min, depending on the drying temperature conditions. .
乾燥物巻き取りボビンは、中空糸状物どうしが接触しない状態であれば、任意のものを使用することができ、例えば乾燥物巻き取り部分のシャフトに0.5〜5mm、好ましくは1〜2mmの間隔でコイル状の溝を設けたものなどが用いられる。巻き取りは、このような乾燥用巻き取り用ボビンを１個または２個以上使用して、中空糸状物全長の巻き取りを実施することにより行われる。 Any dry bobbin can be used as long as the hollow fiber-like bobbin is not in contact with each other. A coil provided with a coiled groove is used. Winding is performed by winding the entire length of the hollow fiber-like material by using one or more of such drying bobbins for winding.
〔不融化処理工程〕
乾燥された中空糸状物は、そのまま炭化処理を行うこともできるが、好ましくは炭化処理の前に不融化処理が行われる。不融化処理では、材料の種類、その量などによって異なるが、巻き取り用ボビンに巻き取られた状態で、一般には150〜300℃程度で0.5〜4時間といった炭化温度よりも低い温度で加熱処理を施すことにより行われる。かかる不融化処理により、中空糸炭素膜としての性能が特に改善されることとなる。加熱処理後、不融化処理膜を所定の長さ、例えば0.2m〜1m程度の長さへの切り出しが行われる。
[Infusibilization process]
The dried hollow fiber-like product can be carbonized as it is, but preferably infusibilized before carbonization. The infusibilization treatment varies depending on the type of material and the amount of the material, but the heat treatment is generally performed at a temperature lower than the carbonization temperature of about 150 to 300 ° C. for 0.5 to 4 hours while being wound on a winding bobbin. It is performed by giving. Such an infusibilization treatment particularly improves the performance as a hollow fiber carbon membrane. After the heat treatment, the infusible film is cut into a predetermined length, for example, about 0.2 m to 1 m.
〔炭化処理工程〕
不融化処理後、公知の方法、例えば切り出しした不融化処理膜である前駆体高分子中空糸膜を容器内に収容し、約10Pa以下、好ましくは10〜4Paといった減圧下、あるいはヘリウム、アルゴンガス、窒素ガスなどで置換した不活性ガス雰囲気下で減圧処理することなく加熱することにより炭化処理が行われる。炭化処理は、材料の種類、その量などによって異なるが、一般には450〜850℃、0.5〜4時間といった条件下で行われる。
[Carbonization process]
After the infusibilization treatment, a known method, for example, a precursor polymer hollow fiber membrane which is a cut infusibilized treatment membrane is accommodated in a container, and is about 10 Pa or less, preferably under a reduced pressure of 10 to 4 Pa, or helium, argon gas, Carbonization is performed by heating in an inert gas atmosphere substituted with nitrogen gas or the like without reducing pressure. The carbonization treatment varies depending on the type of material, the amount thereof, and the like, but is generally performed under conditions of 450 to 850 ° C. and 0.5 to 4 hours.
次に、実施例について本発明を説明する。 Next, the present invention will be described with reference to examples.
実施例
〔紡糸工程〕
ポリフェニレンオキシド系ポリマーとしてのスルホン化ポリ(2,6-ジメチル-1,4-フェニレンオキシド)50gをジメチルホルムアミド150gに溶解させて、濃度25重量％の製膜原液を調製した。調製された製膜原液を、外管の外径0.5mm、内径0.25mmの2重管構造のノズルの外管に、また15重量％の硝酸アンモニウム水溶液をノズル内管側を通る芯液として、製膜原液と芯液とを同時に水中に湿式紡糸法により押し出して中空糸状物(前駆体高分子中空糸膜)を得、これを約20m/分の速度で外周1mの回転ボビン(水抜用巻き取りボビン)に巻き取った。中空糸状物の総長は、1,000mであった。
Example [spinning process]
50 g of sulfonated poly (2,6-dimethyl-1,4-phenylene oxide) as a polyphenylene oxide polymer was dissolved in 150 g of dimethylformamide to prepare a film-forming stock solution having a concentration of 25% by weight. The prepared membrane-forming solution is prepared as a core solution that passes through the inner tube side of the nozzle inner tube with a 15% by weight ammonium nitrate aqueous solution in the outer tube of a double tube structure nozzle with an outer tube outer diameter of 0.5 mm and inner diameter of 0.25 mm. The membrane undiluted solution and core solution are simultaneously extruded into water by a wet spinning method to obtain a hollow fiber (precursor polymer hollow fiber membrane), which is rotated at a speed of about 20 m / min with a rotating bobbin with a circumference of 1 m (winding bobbin for draining water). ). The total length of the hollow fiber material was 1,000 m.
〔水抜き工程〕
中空糸状物の一端と内径6mmのチューブとを、エポキシ接着剤を用いて接続、固定した。このチューブから、ゲージ圧100kPaGの空気を送り込み、中空糸状物の中空部分に含まれる芯液および水を排出した。以上の水抜き工程についての所要時間は、準備を含めて約5時間であり、これは作業員1名が1日8時間作業した場合に換算すると、0.6日に相当するものであり、このうち手作業は0.1日相当分であった。
[Draining process]
One end of the hollow fiber and a tube having an inner diameter of 6 mm were connected and fixed using an epoxy adhesive. From this tube, air with a gauge pressure of 100 kPaG was fed, and the core liquid and water contained in the hollow part of the hollow fiber-like material were discharged. The time required for the above draining process is about 5 hours including preparation, which corresponds to 0.6 days when one worker works 8 hours a day. Manual work was equivalent to 0.1 days.
〔乾燥工程〕
中空糸状物は、中空糸状物が巻き取られたボビン(水抜用巻き取りボビン)と乾燥後の中空糸状物を巻き取るためのボビン(乾燥物巻き取りボビン)との間に設置された筒状の加熱空気乾燥機を用い、40℃、線速度換算40cm/秒で通風を行い、10m/分の巻き取り速度で乾燥物巻き取りボビンに巻き取ることによって乾燥処理された。ここで、乾燥物巻き取りボビンとしては、1周が1m、シャフト部分に0.5mm間隔で溝が設けられたボビンが用いられ、ボビン1つ当り200mの中空糸状物を巻き取り、計5個の巻き取りボビンに得られた中空糸状物すべての巻き取りが行われた。以上の乾燥工程についての所要時間は、準備およびボビン交換過程を含めて約2.4時間であり、これは作業員1名が1日8時間作業した場合に換算すると、0.3日に相当するものであり、このうち手作業は0.1日相当分であった。
[Drying process]
The hollow fiber-like material is a cylindrical shape installed between a bobbin around which the hollow fiber-like material is wound up (winding bobbin for draining water) and a bobbin for winding up the hollow fiber-like material after drying (dried material winding bobbin). Using a heated air dryer, the material was ventilated at 40 ° C. at a linear velocity of 40 cm / second, and dried by winding it on a dry matter winding bobbin at a winding speed of 10 m / min. Here, as a dry matter winding bobbin, a bobbin having a circumference of 1 m and a groove provided at intervals of 0.5 mm in the shaft portion is used, and a hollow fiber-like material of 200 m is wound up per bobbin, and a total of five bobbins are taken up. The entire hollow fiber obtained on the winding bobbin was wound. The time required for the above drying process is about 2.4 hours including the preparation and bobbin exchange process, which corresponds to 0.3 days when one worker works 8 hours a day. Of these, manual work was equivalent to 0.1 days.
〔不融化処理工程〕
かかる乾燥を終了した5個の巻き取りボビンは、加熱装置の中に設置され、290℃、2時間、加熱処理されて不融化処理膜とされた後、0.5mの長さに切り出された。不融化処理後における中空糸状物間の付着および中空糸の切れはみられず、すぐれた成形性が確認された。以上の不融化処理工程についての所要時間は、昇温、加熱、降温および切り出しに要する時間を合わせて約5時間であり、これは作業員1名が1日8時間作業した場合に換算すると、0.6日に相当するものであり、このうち手作業は0.1日相当分であった。
[Infusibilization process]
The five take-up bobbins after completion of the drying were placed in a heating device, heated at 290 ° C. for 2 hours to form an infusible film, and then cut into a length of 0.5 m. Adhesion between the hollow fiber-like materials after the infusibilization treatment and breakage of the hollow fiber were not observed, and excellent moldability was confirmed. The time required for the above infusibilization treatment process is about 5 hours in total including the time required for heating, heating, cooling and cutting, and this is converted when one worker works 8 hours a day, This was equivalent to 0.6 days, of which manual work was equivalent to 0.1 days.
〔炭化処理工程〕
切り出された長さ0.5mの中空糸状物2000本について、不活性ガス雰囲気下、600℃、1時間の加熱が行われ、中空糸炭素膜を得た。得られた中空糸炭素膜は、曲がりあるいは折れのない成形性の良いものであった。膜の透過性能としての水／窒素の分離係数、すなわち水の透過速度／窒素の透過速度は10,000以上であり、膜強度は約250gfであった。
[Carbonization process]
About 2000 hollow fiber pieces having a length of 0.5 m that were cut out, heating was performed at 600 ° C. for 1 hour in an inert gas atmosphere to obtain a hollow fiber carbon membrane. The obtained hollow fiber carbon membrane had good moldability without bending or bending. The separation factor of water / nitrogen as the membrane permeation performance, that is, the water permeation rate / nitrogen permeation rate was 10,000 or more, and the membrane strength was about 250 gf.
参考例（−従来法−）
〔紡糸工程〕
実施例の紡糸工程において、中空糸状物をボビンに巻き取ることなく、これを水中で1mの長さに切断して、1000本の中空糸状物を水中に保管した。
Reference example (-conventional method)
[Spinning process]
In the spinning process of the example, the hollow fiber-like material was cut into a length of 1 m in water without being wound around the bobbin, and 1000 hollow fiber-like materials were stored in water.
〔水抜き・乾燥工程〕
長さ1mの中空糸状物1000本について、1本毎に重力方向への吊り下げおよび乾燥を実施した。これらの作業によって、中空糸状物の中空部分に残留する水の除去およびポリマー部分の水分蒸発が行われることとなるが、すべてが手作業で行われるため、以上の水抜き・乾燥工程についての所要時間は22時間であり、これは作業員1名が1日8時間作業した場合に換算すると、2.8日分であった。
[Draining and drying process]
With respect to 1000 hollow fiber-like materials having a length of 1 m, each one was suspended in the direction of gravity and dried. These operations will remove the water remaining in the hollow part of the hollow fiber-like material and evaporate the water in the polymer part. However, since everything is performed manually, the above-mentioned requirements for the draining / drying process are required. The time was 22 hours, which was equivalent to 2.8 days when one worker worked 8 hours a day.
〔不融化処理工程〕
乾燥後の長さ1m中空糸状物1000本は、すべて半分の長さ(0.5m)に切断された後、計2000本すべてを保護管内に設置して、290℃、2時間の加熱処理が行われ、その後不融化処理膜の保護管からの取り出しが行われた。保護管内への設置および取出しは、すべてが手作業で行われるため、以上の不融化処理工程についての所要時間は23時間であり、これは作業員1名が1日8時間作業した場合に換算すると、2.9日分であった。
[Infusibilization process]
After drying, all 1000 1m hollow fiber-like materials after being cut into half lengths (0.5m) were placed in a protective tube and a total of 2000 pieces were heated at 290 ° C for 2 hours. Thereafter, the infusible film was removed from the protective tube. Installation and removal into the protective tube are all performed manually, so the time required for the above infusibilization process is 23 hours, which is converted when one worker works 8 hours a day. Then, it was for 2.9 days.
〔炭化処理工程〕
実施例と同様に炭化処理が行われた。得られた中空糸炭素膜は、曲がりあるいは折れのない成形性の良いものであった。また、膜の透過性能および膜強度は、それぞれ実施例と同じく10,000および約250gfであった。
[Carbonization process]
The carbonization process was performed similarly to the Example. The obtained hollow fiber carbon membrane had good moldability without bending or bending. The membrane permeation performance and membrane strength were 10,000 and about 250 gf, respectively, as in the examples.
以上の実施例および参考例における各工程の所要時間を次の表に示す。
工 程
紡糸 水抜 乾燥 不融化処理 炭化処理 全
〈 実施例 〉
(A)作業時間(日) 1.2 0.6 0.3 0.6 0.5 3.2
(B)手作業時間(日) 0.4 0.1 0.1 0.1 0.2 0.9
(B)手作業時間／
(A)作業時間(％) 33.3 0.2 33.3 16.7 40.0 28.1
〈 参考例 〉
(A)作業時間(日) 1.2 → 2.8 2.9 0.5 7.4
(B)手作業時間(日) 0.4 → 2.8 2.4 0.2 5.8
(B)手作業時間／
(A)作業時間(％) 33.3 → 100.0 82.8 40.0 78.4
The time required for each step in the above Examples and Reference Examples is shown in the following table.
Process
Spinning draining drying infusibilized carbonization total
< Example >
(A) Working time (days) 1.2 0.6 0.3 0.6 0.5 3.2
(B) Manual work time (days) 0.4 0.1 0.1 0.1 0.2 0.9
(B) Manual work time /
(A) Working time (%) 33.3 0.2 33.3 16.7 40.0 28.1
<Reference example>
(A) Working time (days) 1.2 → 2.8 2.9 0.5 7.4
(B) Manual work time (days) 0.4 → 2.8 2.4 0.2 5.8
(B) Manual work time /
(A) Working time (%) 33.3 → 100.0 82.8 40.0 78.4
以上の結果より、次のようなことがいえる。
(1) 実施例で得られた中空糸炭素膜は、参考例で得られた中空糸炭素膜と同様に、曲がりあるいは折れがなく成形性良好であり、また、透過性能および膜強度も全く遜色のないものであった。
(2) 従来法は、参考例の作業時間の結果からも明らかな通り、作業時間および手作業時間が長く、本発明に係る中空糸炭素膜の製造方法と比べて生産性が低い。
すなわち、実施例を参考例と比較すると、中空糸炭素膜1000mに要する全行程の所要日数は3.2日であり、参考例の7.4日と比較して所要時間が55％短縮されており、顕著な製造能力の向上効果が示された。さらに、実施例における全行程の所要日数に占める手作業時間の合計割合は、27.3％であり、参考例の78.4％と比較して、その比率も大幅に低減され、省人力化にすぐれていることが確認された。
From the above results, the following can be said.
(1) The hollow fiber carbon membranes obtained in the examples, like the hollow fiber carbon membranes obtained in the reference examples, are not bent or bent and have good moldability, and the permeation performance and membrane strength are completely inferior. There was nothing.
(2) As is clear from the results of the working time of the reference example, the conventional method has a long working time and manual working time, and is less productive than the method for producing a hollow fiber carbon membrane according to the present invention.
That is, when compared with the reference example, the required time for the entire process required for the hollow fiber carbon membrane 1000m is 3.2 days, and the required time is shortened by 55% compared with 7.4 days of the reference example, which is remarkable. The improvement effect of the production capacity was shown. Furthermore, the total ratio of manual work time to the total number of days required for the entire process is 27.3%, which is significantly reduced compared to 78.4% in the reference example, and is excellent in labor saving. It was confirmed.
１ ボビン
２、２′ ボビン両端部
３ シャフト
４ 中空糸状物
５ 円弧状溝
1
Claims (4)
紡糸により得られた中空糸状物を、水抜用巻き取りボビンに巻き取り、巻き取られた中空糸状物の一端部を開放した状態で他端部より空気を送り込み、中空部分の水および芯液を排出した後、水抜用巻き取りボビンとこれとは別の乾燥物巻き取りボビンとの間に設置された乾燥機を用いて乾燥処理を施し、その後炭化処理することを特徴とする中空糸炭素膜の製造方法。 In the method for producing a hollow fiber carbon membrane having a wet process or a dry-wet spinning process, a drying process and a carbonization process as basic processes,
The hollow fiber-like material obtained by spinning is wound around a take-up bobbin for draining water, and air is fed from the other end with one end of the wound hollow fiber-like material being opened, and the water and core liquid in the hollow part are discharged. A hollow fiber carbon membrane characterized in that after being discharged, it is subjected to a drying treatment using a drier installed between a take-up bobbin for draining water and another dry matter take-up bobbin, and then carbonized. Manufacturing method.
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| JP3219445B2 (en) * | 1992-02-12 | 2001-10-15 | 旭化成株式会社 | Drying method for hollow fiber bundles |
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