JPS63151333A - Gas separation membrane and its preparation - Google Patents
Gas separation membrane and its preparationInfo
- Publication number
- JPS63151333A JPS63151333A JP61296586A JP29658686A JPS63151333A JP S63151333 A JPS63151333 A JP S63151333A JP 61296586 A JP61296586 A JP 61296586A JP 29658686 A JP29658686 A JP 29658686A JP S63151333 A JPS63151333 A JP S63151333A
- Authority
- JP
- Japan
- Prior art keywords
- surfactant
- membrane
- gas separation
- separation membrane
- cellulose acetate
- 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 77
- 238000000926 separation method Methods 0.000 title claims abstract description 32
- 239000004094 surface-active agent Substances 0.000 claims abstract description 32
- 229920002301 cellulose acetate Polymers 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 238000011282 treatment Methods 0.000 claims abstract description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 13
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims abstract description 11
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229920001747 Cellulose diacetate Polymers 0.000 claims abstract description 6
- 229920002284 Cellulose triacetate Polymers 0.000 claims abstract description 6
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims abstract description 6
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims abstract description 6
- 238000006467 substitution reaction Methods 0.000 claims abstract description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 5
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 5
- 239000003495 polar organic solvent Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000012510 hollow fiber Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000007789 gas Substances 0.000 description 24
- 239000010408 film Substances 0.000 description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 238000001223 reverse osmosis Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- -1 polyoxyethylene nonylphenyl ether Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 2
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、気体分離膜およびその製造方法に関するもの
であり、特に炭酸ガスとメタンの分離に有効な気体分離
膜およびその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a gas separation membrane and a method for manufacturing the same, and particularly to a gas separation membrane effective in separating carbon dioxide and methane and a method for manufacturing the same.
［従来の技術］
セルロースアセテート膜はすでに逆浸透法による水の脱
塩に広く実用化されている。そこでこの含水セルロース
アセテート膜の非対称構造を破壊することなく乾燥し、
再湿潤しても元の逆浸透性能が損われない乾燥膜あるい
は気体分離膜およびその乾燥方法が種々検討されてきた
。[Prior Art] Cellulose acetate membranes have already been widely put into practical use for water desalination by reverse osmosis. Therefore, drying without destroying the asymmetric structure of this hydrous cellulose acetate membrane,
Various studies have been conducted on dry membranes or gas separation membranes whose original reverse osmosis performance is not impaired even after rewetting, and on drying methods thereof.
その代表的なものは、まず水混和性の有機溶剤で処理し
次いで非極性有機溶剤で処理した後に乾燥するという方
法で得られ、例えばＵＳＰ−３，８４２，５１５号明細
書、特開昭６０−１９７２０４号公報に開示されている
。この方法により湿潤膜を乾燥すれば膜構造を大きく破
壊せずに乾燥膜を得ることができる。A typical example thereof is obtained by first treating with a water-miscible organic solvent, then treating with a non-polar organic solvent, and then drying. It is disclosed in Japanese Patent No.-197204. By drying a wet film using this method, a dry film can be obtained without significantly destroying the film structure.
Ｕ発明が解決しようとする問題点」
しかしながら、この方法で得られる乾燥膜は、水混和性
の有機溶剤による置換処理を数段階性ない、その後非極
性有機溶剤でさらに数段階置換処理する必要があった。However, the dried film obtained by this method requires several steps of replacement treatment with a water-miscible organic solvent, and then several more steps of replacement treatment with a non-polar organic solvent. there were.
そのため、連続処理、バッチ処理を問わず置換処理装置
が過大なものとなるばかりか、使用溶剤量が多くなり処
理時間も長く、そのために、乾燥膜の製造コストが高く
なるという欠点を有していた。Therefore, regardless of whether continuous processing or batch processing is being carried out, the replacement processing equipment becomes too large, and the amount of solvent used is large, the processing time is also long, and therefore the manufacturing cost of the dry membrane increases. Ta.
本発明は、かかる従来技術の欠点を解決しようとするも
のであり、製造プロセスを簡略化することにより、処理
時間が短く、製造コストの低い気体分離膜およびその製
造方法を提供することを目的とする。The present invention aims to solve the drawbacks of the prior art, and aims to provide a gas separation membrane and a method for manufacturing the same that have short processing times and low manufacturing costs by simplifying the manufacturing process. do.
［問題点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。[Means for Solving the Problems] In order to achieve the above object, the present invention has the following configuration.
［（１）乾燥セルロースアセテ−■・膜からなり、該膜
中に界面活性剤を含有することを特徴とする気体分離膜
。[(1) A gas separation membrane comprising a dry cellulose acetate membrane and containing a surfactant therein.
（２）含水セルロースアセテート膜を界面活性剤を含む
非極性有機溶剤で１段置換処理した後乾燥することを特
徴とする気体分離膜の製造方法。」本発明におけるセル
ロースアセテート膜としては、セルロースジアセテート
膜、セルローストリアセテート膜または、セルロースジ
アセテートとセルローストリアセテートの混合物を主体
とした膜が好ましく用いられるが、セルロースジアセテ
ートとセルローストリアセテートの混合物を主体とした
膜が気体分離性能と製膜性のバランスに優れ好ましい。(2) A method for producing a gas separation membrane, which comprises subjecting a hydrous cellulose acetate membrane to one-stage substitution treatment with a nonpolar organic solvent containing a surfactant and then drying it. As the cellulose acetate membrane in the present invention, a cellulose diacetate membrane, a cellulose triacetate membrane, or a membrane mainly composed of a mixture of cellulose diacetate and cellulose triacetate is preferably used. A membrane having an excellent balance between gas separation performance and film formability is preferable.
また、含水セルロースアセテート膜の逆浸透膜としての
性能が塩排除率９０％以上（１５００ｐｐｍの食塩水を
用い評価圧力３０ ｋｇ／ｃｎｆ、２５℃で測定）のも
のが好ましい。つまり塩排除率の高い膜はど気体分離性
能、特に炭酸ガス／メタンの分離性能に優れた乾燥膜を
得やすいので適している。Further, it is preferable that the performance of the hydrous cellulose acetate membrane as a reverse osmosis membrane is 90% or more in salt rejection rate (measured using 1500 ppm saline solution at an evaluation pressure of 30 kg/cnf and 25° C.). In other words, a membrane with a high salt rejection rate is suitable because it is easy to obtain a dry membrane with excellent gas separation performance, especially carbon dioxide/methane separation performance.
また、本発明において、乾燥セルロースアセテート膜に
含有される界面活性剤は非極性有機溶剤と混和あるいは
一部混和するもので、界面活性剤を含む非極性有機溶剤
に水を加えた時、乳化あるいは可溶化するものであれば
特に限定されない。In addition, in the present invention, the surfactant contained in the dried cellulose acetate film is miscible or partially miscible with the non-polar organic solvent, and when water is added to the non-polar organic solvent containing the surfactant, it emulsifies or There are no particular limitations as long as it can be solubilized.
具体的には、ノニオン系界面活性剤、アニオン系界面活
性剤、カチオン系界面活性剤を用いることができ、特に
ノニオン系界面活性剤ではポリエチレングリコール型界
面活性剤であるポリオキシエチレンノニルフェニルエー
テルのエチレンオキサイド基６３〜８モル付加物が適し
ている。またアニオン系界面活性剤では、ジアルキルス
ルホコハク酸ナトリウムのアルキル基がヘキシル基およ
びオクチル基のものが適している。Specifically, nonionic surfactants, anionic surfactants, and cationic surfactants can be used. In particular, nonionic surfactants include polyoxyethylene nonylphenyl ether, which is a polyethylene glycol type surfactant. Adducts with 63 to 8 moles of ethylene oxide groups are suitable. As anionic surfactants, sodium dialkyl sulfosuccinates in which the alkyl group is a hexyl group or an octyl group are suitable.
本発明における気体分離膜の膜中の界面活性剤の含有濃
度としては、使用する界面活性剤により異なるが少なく
とも１重量％が好ましく、通常１゜〜３０重量％、さら
に好ましくは５〜２０重量％である。含有濃度が］１重
量％より低い場合は、分離膜の製法上のメリッ■〜が得
られなくなる傾向となる。The concentration of surfactant in the gas separation membrane of the present invention varies depending on the surfactant used, but is preferably at least 1% by weight, usually 1° to 30% by weight, more preferably 5 to 20% by weight. It is. If the content concentration is lower than 1% by weight, the advantages (1) to (1) in terms of the separation membrane manufacturing method tend not to be obtained.
また、本発明における気体分離膜の製造に用いる非極性
有機溶剤としては、セルロースアセチート膜に対して非
溶剤であることが必要である。すなわち、膜を溶解ある
いは膜構造を緻密にする溶剤は適さない。具体的には、
ペンタン、イソペンタン、ｎ−ヘキサン、ｎ−ヘプタン
等の脂肪族炭化水素類、シクロペンタン、シクロヘキサ
ン、シクロヘプタン等の脂環族炭化水素類、ベンゼン、
トルエン等の芳香族炭化水素類等が用いられるが特にｎ
−ヘキサン、ｎ−ヘプタン、シクロヘプタン、およびシ
クロヘキサンが適している。また、これらの非極性有機
溶剤は単独でもよいが数種類の混合溶剤でもよい。Further, the non-polar organic solvent used in the production of the gas separation membrane in the present invention needs to be a non-solvent for the cellulose acetate membrane. That is, solvents that dissolve the film or make the film structure dense are not suitable. in particular,
Aliphatic hydrocarbons such as pentane, isopentane, n-hexane, n-heptane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane, benzene,
Aromatic hydrocarbons such as toluene are used, but especially n
-Hexane, n-heptane, cycloheptane and cyclohexane are suitable. Further, these non-polar organic solvents may be used alone or in a mixture of several types.
界面活性剤を含む非極性溶剤による含水セルロースアセ
テート膜の溶剤置換処理は非極性有機溶剤中の界面活性
剤の濃度および水／界面活性剤の比率をコントロールす
れば１段置換処理のみでよい。Solvent replacement treatment of a hydrous cellulose acetate membrane with a non-polar solvent containing a surfactant only requires one-stage replacement treatment if the concentration of the surfactant in the non-polar organic solvent and the water/surfactant ratio are controlled.
その界面活性剤の濃度は非極性有機溶剤中でミセルが形
成できる濃度（ｃ、ｍ、ｃ）以上必要であり、界面活性
剤の種類によって異なるが通常非極性有機溶剤に対して
、１〜１０重量％であることが好ましく、さらに好まし
くは１−〜３重量％である。また、水／界面活性剤の比
率は界面活性剤の種類および濃度により異なるが、通常
水が非極性有機溶剤中から分離しない比率である０、１
〜５が好ましく、さらに好ましくは０．５〜２である。The concentration of the surfactant must be at least the concentration (c, m, c) at which micelles can be formed in the non-polar organic solvent, and although it varies depending on the type of surfactant, it is usually 1 to 10 It is preferably 1% to 3% by weight, more preferably 1-3% by weight. The water/surfactant ratio varies depending on the type and concentration of the surfactant, but is usually 0 or 1, which is the ratio at which water does not separate from the non-polar organic solvent.
-5 is preferable, and 0.5-2 is more preferable.
また、置換処理時間および温度は、使用する非極性有機
溶剤、界面活性剤の種類および処理液組成によって異な
るが、時間は通常５〜３０分で充分であり、温度は２０
〜６０℃が好ましい。なぜならこの温度範囲では界面活
性剤を含む非極性有機溶剤に水が可溶化した状態、すな
わち有機溶剤、界面活性剤、水の三者が均一層になるか
らである。The replacement treatment time and temperature vary depending on the nonpolar organic solvent used, the type of surfactant, and the treatment liquid composition, but usually 5 to 30 minutes is sufficient, and the temperature is 20 minutes.
~60°C is preferred. This is because, in this temperature range, water is solubilized in a nonpolar organic solvent containing a surfactant, that is, the organic solvent, surfactant, and water form a uniform layer.
乾燥温度は、セルロースアセテート膜が緻密化しない温
度であり、界面活性剤が蒸発しない温度であればよく１
０〜５０℃で乾燥するのが好ましい。The drying temperature may be a temperature at which the cellulose acetate film does not become densified and at which the surfactant does not evaporate.
It is preferable to dry at 0 to 50°C.
乾燥時間は、セルロースアセテート膜中の非極性有機溶
剤が完全に蒸発するのに要する時間であればよく、乾燥
温度、非極性有機溶剤により異なるが通常、数分〜数時
間もあればよい。The drying time may be any time required for the non-polar organic solvent in the cellulose acetate film to completely evaporate, and usually takes several minutes to several hours, although it varies depending on the drying temperature and the non-polar organic solvent.
膜形態としては、平膜に限らず中空糸膜でもよく置換形
態も膜状態に限らずエレメントあるいはモジュール形態
でも実施できる。The membrane form is not limited to a flat membrane, but may also be a hollow fiber membrane, and the substitution form is not limited to a membrane form, but may also be implemented in an element or module form.
［実施例］
以下の実施例により更に詳細に説明するが、本発明はこ
れらに限定されるものではない。[Example] The present invention will be explained in more detail with reference to the following examples, but the present invention is not limited thereto.
なお、実施例中の含水セルロースアセデート膜としては
、東しく株）製゛′ロメンブラ′″ （商品名）エレメ
ント、５Ｃ−３１００タイプに使用されているものを実
施例１に、５Ｃ−Ｌ１００Ｓタイプに使用されているも
のを実施例２．実施例３に用いた。In addition, the hydrous cellulose acedate membrane used in Example 1 is that used in Toshiku Co., Ltd.'s ``Romembra'' (trade name) element, 5C-3100 type, and 5C-L100S type. Those used in Example 2 and Example 3 were used.
なお、これらの膜は、セルロースジアセテートとセルロ
ーストリアセテートとの混合物からなり、逆浸透膜とし
ての性能は実施例１の使用膜で塩排除率９７％、実施例
２、実施例３の使用膜で塩排除率７０％であった。（１
５００ｐｐｍの食塩水を用い評価圧力３０’Ｋ（Ｊ／ｃ
ｌで測定した。）また、乾燥膜の気体透過性能は、各種
純ガスを３．０ｋｇ／ｃｎｔに加圧し測定温度２５℃で
膜（面積約３０ｃ／）を透過したガスの流量を薄膜式流
量計を用いて測定した。透過流量を換算して、各種気体
の透過速度（浦！ ／ Ｔｒ１２・ｈｒ−ａｔｍ）を求
め、その透過速度の比から分離係数αを算出した。These membranes are made of a mixture of cellulose diacetate and cellulose triacetate, and the performance as a reverse osmosis membrane is that the membrane used in Example 1 has a salt rejection rate of 97%, and the membranes used in Examples 2 and 3 have a salt rejection rate of 97%. The salt rejection rate was 70%. (1
Evaluation pressure was 30'K (J/c) using 500ppm saline solution.
Measured in l. ) Also, the gas permeation performance of the dry membrane is determined by pressurizing various pure gases to 3.0 kg/cnt and measuring the flow rate of gas that permeates through the membrane (area: approximately 30 c/c) at a measurement temperature of 25°C using a thin film flow meter. did. The permeation flow rate was converted to determine the permeation rate (Ura!/Tr12·hr-atm) of various gases, and the separation coefficient α was calculated from the ratio of the permeation rates.
膜中の界面活性剤の含有量は、実施例１、実施例２では
ｒ−ｓｏ法（ＡＳＴＨＤ ３０４９−７２Ｔ参照）によ
り測定した。また実施例３については、ガスクロ法（パ
ラトルエンスルホン酸／無水酢酸による加水分解）によ
り測定した。The content of surfactant in the film was measured in Examples 1 and 2 by the r-so method (see ASTHD 3049-72T). Further, in Example 3, the measurement was performed by a gas chromatography method (hydrolysis with para-toluenesulfonic acid/acetic anhydride).
実施例１
ｎ−ヘキサン、ジオクチルスルホコハク酸ナトリウムを
９９／１の割合からなる処理液を作り４０℃に加熱した
。これに、含水セルロースアセテート膜を浸漬し時々溶
液を撹拌しながら２０分間保持しな。この置換処理に用
いた液量は含水膜ｌＴ１１２に対して１］１であった。Example 1 A treatment solution containing n-hexane and sodium dioctyl sulfosuccinate in a ratio of 99/1 was prepared and heated to 40°C. The hydrated cellulose acetate membrane was immersed in this and kept for 20 minutes while occasionally stirring the solution. The amount of liquid used for this replacement treatment was 1]1 for the water-containing film IT112.
その後、４０℃で３時間乾煤し乾燥膜を得た。Thereafter, the soot was dried at 40° C. for 3 hours to obtain a dry film.
この乾燥膜中の界面活性剤含有濃度と気体透過性能を測
定した結果を表１−に示しな。Table 1 shows the results of measuring the concentration of surfactant and gas permeability in this dry membrane.
比鮫例１
−１〇 −
実施例１に使用した物と同じセルロースアセテート膜を
２５℃とイソプロピルアルコールに１時間浸漬し、時々
液を撹拌した。次いでイソプロピルアルコールを交換し
同操作を２回繰り返し行った。さらに、２５℃のｎ−ヘ
キサンに１時間浸漬した後４０℃で３時間乾燥し、乾燥
膜を得た。Example 1 - 10 - The same cellulose acetate membrane used in Example 1 was immersed in isopropyl alcohol at 25° C. for 1 hour, and the solution was stirred occasionally. Next, the isopropyl alcohol was replaced and the same operation was repeated twice. Furthermore, it was immersed in n-hexane at 25°C for 1 hour and then dried at 40°C for 3 hours to obtain a dry film.
この乾燥膜の気体透過性能を測定した結果を表１に示し
た。Table 1 shows the results of measuring the gas permeability of this dry membrane.
本発明の乾燥膜（実施例１の気体分離膜）は気体透過速
度、気体分離係数はともに従来法である比較例１で置換
処理した乾燥膜とほぼ同等であった。しかし、置換処理
回数が減少したため、使用溶剤量も大幅に減少した。The dry membrane of the present invention (the gas separation membrane of Example 1) had substantially the same gas permeation rate and gas separation coefficient as the dry membrane subjected to displacement treatment in Comparative Example 1, which is a conventional method. However, because the number of replacement treatments was reduced, the amount of solvent used was also significantly reduced.
実施例２
シクロヘキサン、ジオクチルスルホコハク酸ナトリウム
を９８／２の割合からなる処理液を６０℃に加熱した、
これに含水セルロースアセテート膜を浸漬し、時々液を
撹拌しながら２０分間保持した。この置換処理に用いた
液量は含水膜１−？ｎ２に対して］−〇ａであった。そ
の後５０℃で２時間乾−１１＝
燥し乾燥膜を得な。この乾燥膜中の界面活性剤含有濃度
と気体透過性能を測定した結果を表１に示しな。Example 2 A treatment solution consisting of cyclohexane and sodium dioctyl sulfosuccinate in a ratio of 98/2 was heated to 60°C.
A hydrous cellulose acetate membrane was immersed in this solution, and the solution was maintained for 20 minutes while stirring occasionally. The amount of liquid used for this replacement treatment was 1-? n2] -○a. Then dry at 50°C for 2 hours to obtain a dry film. Table 1 shows the results of measuring the concentration of surfactant and gas permeability in this dry membrane.
実施例３
ｎ−ヘキサン、ポリオキシエチレンノニルフェニルエー
テルのエチレンオキサイド基６モル付加物を９８／２の
割合からなる処理液を６０’Ｃに加熱しな。これに含水
セルロースアセテート膜を浸漬し時々液を撹拌しながら
１０分間保持しな。この置換処理に用いた液量は、含水
膜ＩＴｎ２に対して１０Ｄ、であった。その後４０’Ｃ
で３時間乾燥し乾燥膜を得な。この乾燥膜中の界面活性
剤濃度と気体透過性能を測定した結果を表１に示しな。Example 3 A treatment solution consisting of a 98/2 ratio of 6 moles of ethylene oxide group adduct of n-hexane and polyoxyethylene nonylphenyl ether was heated to 60'C. The hydrated cellulose acetate membrane was immersed in this and kept for 10 minutes while stirring the solution occasionally. The amount of liquid used in this replacement process was 10D for the water-containing film ITn2. Then 40'C
Dry for 3 hours to obtain a dry film. Table 1 shows the results of measuring the surfactant concentration and gas permeability in this dried membrane.
［発明の効果］
本発明の気体分離膜は、界面活性剤の採用により、従来
の含水セルロースアセテート膜の乾燥法に比べ製造プロ
セスを大幅に簡略化することができる。そのために、使
用溶剤量の減少、処理時間の短縮が可能となり、製造コ
ストの安い気体分離膜およびその製造方法を提供するこ
とができる。[Effects of the Invention] By employing a surfactant, the gas separation membrane of the present invention can greatly simplify the manufacturing process compared to the conventional method of drying a hydrous cellulose acetate membrane. Therefore, the amount of solvent used can be reduced and the processing time can be shortened, making it possible to provide a gas separation membrane and a method for manufacturing the same that are inexpensive to manufacture.
また、これらの膜を利用し、天然ガス中の炭酸ガスの除
去、酸素と窒素の分離、水素と一酸化炭素等の気体分離
膜として広い用途に利用できる。Furthermore, these membranes can be used in a wide range of applications as gas separation membranes for removing carbon dioxide from natural gas, separating oxygen and nitrogen, and separating hydrogen and carbon monoxide.
Claims (11)
界面活性剤を含有することを特徴とする気体分離膜。(1) A gas separation membrane comprising a dry cellulose acetate membrane and containing a surfactant in the membrane.
れること特徴とする特許請求の範囲第（１）項記載の気
体分離膜。(2) The gas separation membrane according to claim (1), wherein the membrane contains at least 1% by weight of a surfactant.
トとセルローストリアセテートとの混合物であることを
特徴とする特許請求の範囲第（１）項記載の気体分離膜
。(3) The gas separation membrane according to claim (1), wherein the cellulose acetate is a mixture of cellulose diacetate and cellulose triacetate.
オン系界面活性剤であることを特徴とする特許請求の範
囲第（１）項記載の気体分離膜。(4) The gas separation membrane according to claim (1), wherein the surfactant is a nonionic surfactant or an anionic surfactant.
非極性有機溶剤で１段置換処理した後乾燥することを特
徴とする気体分離膜の製造方法。(5) A method for producing a gas separation membrane, which comprises subjecting a hydrous cellulose acetate membrane to one-stage substitution treatment with a nonpolar organic solvent containing a surfactant and then drying it.
トとセルローストリアセテートとの混合物であることを
特徴とする特許請求の範囲第（５）項記載の気体分離膜
の製造方法。(6) The method for producing a gas separation membrane according to claim (5), wherein the cellulose acetate is a mixture of cellulose diacetate and cellulose triacetate.
オン系界面活性剤であることを特徴とする特許請求の範
囲第（５）項記載の気体分離膜の製造方法。(7) The method for producing a gas separation membrane according to claim (5), wherein the surfactant is a nonionic surfactant or an anionic surfactant.
ン、シクロヘキサン、ｎ−ヘプタン、シクロヘプタンか
ら選ばれる１種以上の溶剤であることを特徴とする特許
請求の範囲第（５）項記載の気体分離膜の製造方法。(8) Claim (5) characterized in that the non-polar organic solvent is one or more solvents selected from cyclopentane, n-hexane, cyclohexane, n-heptane, and cycloheptane. A method for manufacturing a gas separation membrane.
％以上含まれていることを特徴とする特許請求の範囲第
（５）項記載の気体分離膜の製造方法。(9) The method for producing a gas separation membrane according to claim (5), wherein the surfactant is contained in an amount of 1% by weight or more based on the non-polar organic solvent.
処理されることを特徴とする特許請求の範囲第（５）項
記載の気体分離膜の製造方法。(10) The method for producing a gas separation membrane according to claim (5), wherein the first-stage substitution treatment is performed at a temperature in the range of 20 to 60°C.
空糸膜であることを特徴とする特許請求の範囲第（５）
項記載の気体分離膜の製造方法。(11) Claim (5), wherein the hydrous cellulose acetate membrane is a flat membrane or a hollow fiber membrane.
A method for producing a gas separation membrane as described in Section 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61296586A JPS63151333A (en) | 1986-12-15 | 1986-12-15 | Gas separation membrane and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61296586A JPS63151333A (en) | 1986-12-15 | 1986-12-15 | Gas separation membrane and its preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63151333A true JPS63151333A (en) | 1988-06-23 |
Family
ID=17835462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61296586A Pending JPS63151333A (en) | 1986-12-15 | 1986-12-15 | Gas separation membrane and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63151333A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4968470A (en) * | 1989-11-15 | 1990-11-06 | Air Products And Chemicals, Inc. | Asymmetric permselective polyacetylene membranes and process for the formation thereof |
| US5032149A (en) * | 1989-10-10 | 1991-07-16 | E. I. Du Pont De Nemours And Company | Surfactant treatment of polyaramide gas separation membranes |
| US5034024A (en) * | 1989-10-10 | 1991-07-23 | E. I. Du Pont De Nemours And Company | Surfactant treatment of aromatic polyimide gas separation membranes |
-
1986
- 1986-12-15 JP JP61296586A patent/JPS63151333A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5032149A (en) * | 1989-10-10 | 1991-07-16 | E. I. Du Pont De Nemours And Company | Surfactant treatment of polyaramide gas separation membranes |
| US5034024A (en) * | 1989-10-10 | 1991-07-23 | E. I. Du Pont De Nemours And Company | Surfactant treatment of aromatic polyimide gas separation membranes |
| US4968470A (en) * | 1989-11-15 | 1990-11-06 | Air Products And Chemicals, Inc. | Asymmetric permselective polyacetylene membranes and process for the formation thereof |
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