JP6536962B2 - オレフィン及びパラフィン混合物の膜分離 - Google Patents
オレフィン及びパラフィン混合物の膜分離 Download PDFInfo
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- JP6536962B2 JP6536962B2 JP2016527112A JP2016527112A JP6536962B2 JP 6536962 B2 JP6536962 B2 JP 6536962B2 JP 2016527112 A JP2016527112 A JP 2016527112A JP 2016527112 A JP2016527112 A JP 2016527112A JP 6536962 B2 JP6536962 B2 JP 6536962B2
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- Prior art keywords
- ionomer
- membrane
- silver
- gas separation
- gas
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- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 14
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- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
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- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 1
- 229940098221 silver cyanide Drugs 0.000 description 1
- YSVXTGDPTJIEIX-UHFFFAOYSA-M silver iodate Chemical compound [Ag+].[O-]I(=O)=O YSVXTGDPTJIEIX-UHFFFAOYSA-M 0.000 description 1
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 1
- 229910000161 silver phosphate Inorganic materials 0.000 description 1
- 229940019931 silver phosphate Drugs 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- NSVHDIYWJVLAGH-UHFFFAOYSA-M silver;n,n-diethylcarbamodithioate Chemical compound [Ag+].CCN(CC)C([S-])=S NSVHDIYWJVLAGH-UHFFFAOYSA-M 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000006478 transmetalation reaction Methods 0.000 description 1
- KAKQVSNHTBLJCH-UHFFFAOYSA-N trifluoromethanesulfonimidic acid Chemical compound NS(=O)(=O)C(F)(F)F KAKQVSNHTBLJCH-UHFFFAOYSA-N 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/12—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
- B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/144—Purification; Separation; Use of additives using membranes, e.g. selective permeation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Aはペルフルオロ化環状又は環化可能有機化合物の重合誘導体であり、
m及びnはイオノマー中の繰り返し単位A及び高フッ素化ビニルエーテル化合物誘導体の総数のそれぞれの分率であり、
XはSO2又はCOであり、
YはNSO2Rf1又はOであり、
Rf及びRf 1はそれぞれ独立に、1〜20個の炭素原子を有するペルフルオロアルキル又はペルフルオロアルキルエーテル基であり、
Mは第11族金属である。
(実施例1)
銀交換PDD−SEFVEコポリマーの形成
ガラス圧力管の中に、4.88gのPDD、17.84gのSEFVE、5mLの2,3−ジヒドロデカフルオロペンタン(Vertrel(登録商標)XF特殊液、DuPont Wilmington、Delaware)、及びCF3CF2CF2OCF(CF3)CFOと塩基性過酸化水素との反応により作られるヘキサフルオロプロピレンオキシド(HFPO)二量体過酸化物のVertrel(登録商標)XF中の1mLの開始剤溶液を入れた。この管をドライアイス/イソプロパノール浴中で−78℃に冷却し、排気及び窒素充填を3回行った。このガラス管を密封し、水浴中で室温まで温めた。反応混合物を一晩振とうすることにより撹拌した。この管を外気に開放し、20mLのアセトンを混合物に加えた。15分間撹拌した後、液体をデカンテーションし、20mLの新しいアセトンを加えた。15分間撹拌した後、液体を再びデカンテーションし、固体残渣を時計皿へ移した。オーブンで100℃にて一晩乾燥させて、6.3gの白色の固体PDD/SEFVEコポリマー生成物を得た。
銀交換PDD−SEFVEポリマーの膜の作成
約60モル%のPDD繰り返し単位及び約40モル%のSEFVE繰り返し単位を有するIEPP(Ag+)コポリマーを実施例1のような手順により作った。コポリマーを室温で70wt%のイソプロピルアルコール及び30wt%のNovec7300液の溶液中に溶解させて1.2wt%のポリマー溶液を作った。ポリアクリロニトリル(PAN)精密ろ過膜の非対称多孔性シートをポリマー溶液中に浸漬した。ウェットシートを取り出し、垂直に持って過剰の液体を排出させた。次いでコポリマー被覆膜をオーブンで100℃にて一晩乾燥させて非多孔性複合膜を得た。
IEPP(Ag+)膜を使用したプロパン及びプロピレンの分離
PDD:SEFVEの異なる比率を有するIEPP(Ag+)で被覆したいくつかのPAN基材膜を、実質的に実施例2に記載のような手順によって作った。各々の膜を透過テストセルに置いた。80wt%プロパン及び20wt%プロピレンの乾燥ガス混合物を、質量流量制御装置により維持される200標準cm3(「scc」)毎分の流量で、69kPa(10psi)でセルの片側に供給した。ガス混合物は非多孔性膜を透過し、透過液流の流量を気泡流量計により測定した。窒素ガスを、25〜200scc/minの範囲の流量で膜の透過液側へスイープさせた。透過液中のプロパン及びプロピレンの濃度を、2mのガスセル光路長を備えたNicolet(登録商標)6700FTIR分析装置(Thermo Fisher Scientific、Waltham MA)を使用してフーリエ変換赤外分光分析によって測定した。ステージカット(すなわち、供給材料の流量に対する透過液の流量)を10%未満に維持するように、流量を調整した。膜の両端の対数平均の分圧の差を使用して、透過性を各成分について独立に計算した。プロピレン透過性対プロパン透過性の比として選択性を計算した。得られるデータを表IIに示す。
供給流及びスイープ流を室温にて25〜200scc/minの範囲の流量で水に通してバブリングしたことを除き、実施例4及び5の手順を繰り返した。加湿流は、表IIに示される結果で見られる透過性の向上をもたらした。
銀交換スルホンイミドコポリマーの形成
100:200のPDD:SEFVEモル比のコモノマー供給混合物からコポリマーを合成した。ガラスビーカー中に、2gのPDD/SEFVEコポリマー、0.43gのトリフルオロメチルスルホンアミドCF3SO2NH2、100mLのNovec HFE 7200フッ素化溶媒、50mLのテトラヒドロフラン、及び0.72gのトリエチルアミンを入れた。この混合物を70℃で24時間撹拌した。その後、溶媒を蒸発させたところ、粒状生成物が残った。多量の水を生成物に加え、次いでそれをろ過した。固体生成物を10mLの3N塩酸水溶液中に浸漬し、3時間撹拌した。ろ過後、生成物を再び水洗、ろ過、及び真空乾燥させて、重合PDDの繰り返し単位A及びCF2−CF(OCF2CF(CF3)OCF2CF2SO2NHSO2CF3)の繰り返し単位Bを有する、1.8gのPDD/SEFVE−イミドコポリマーを得た。
混合溶媒溶液を用いて製造されたPDD−SEFVE−Ag+膜を透過させたエチレン及びエタン純ガス
PDD/SEFVE−銀交換イオノマーを実施例1のように調製した。30wt% Novec HFE 7300/70wt%イソプロピルアルコール溶媒混合物中のこのイオノマーの2wt%溶液をPAN基材上に被覆して実施例2に記載の膜を製造した。純粋なエチレン及びエタンガスを別々に二重反復試験(9a、9b)において同じ圧力で透過させることにより、膜を評価した。同じ組成の第2の膜も調製し、低圧で同じ評価を繰り返した(9c)。結果を表IIIに示す。
混合溶媒溶液を用いて製造されたPDD−SEFVE−VF2−Ag+膜のエチレン/エタン透過
銀交換されたコポリマーが、21.4モル% PDD/57.2モル% SEFVE/21.4モル% フッ化ビニリデン(VF2)、すなわち100:267:100のモル比の供給混合物から生成される組成を有していることを除き、実施例9の手順を繰り返した。3つの異なる膜供給圧力で純粋なエチレン及びエタンガスを別々に透過させることにより、膜を試験した。結果を表IIIに示す。
PDD−POESF−Ag+膜によるプロピレン/プロパンの分離
高フッ素化ビニルエーテル化合物モノマーがペルフルオロ(3−オキサペンタ−4−エン)スルホニルフルオリド「POESF」(SynQuest Laboratories Inc. Alachua、FL)であることを除き、実施例1のコポリマー合成手順を繰り返して100:200のPDD:POESFの反応物のモル比に基づく銀交換イオノマーを得た。このイオノマーの膜を実施例2と同様の手順により製造した。膜を透過試験セル中に取り付けた。80vol.%プロパン/20vol.%プロピレンのガス混合物を約24℃で水に通してバブリングすることにより80%相対湿度(「RH」)まで加湿し、次いで膜の供給側と接触させてセル中に供給した。同様に80%RHに加湿し、2.8kPa(0.4psi)で300mL/minの窒素スイープガス流を透過側でセルに吹き込んだ。二重反復試験(11a、11b)を行い、分離の結果を表IIIに示す。
PDD/SEFVE−Ag+膜によるエチレン/エタンの分離
銀の対イオンを含むPDD/SEFVEコポリマーの膜を実施例2のように製造した。10vol.%エチレン/90vol.%エタンガス混合物を二重反復試験で膜により分離した。結果を表IIIに示す。
混合溶媒溶液を用いて製造されたPDD−SEFVE−VF2−Ag+膜によるプロピレン/プロパンの膜分離
PDD−SEFVE−VF2−Ag+コポリマーの膜を実施例10のように調製した。プロピレン/プロパンガス混合物を分離する数回の試験で膜を使用した。これらの試験の各々において、300mL/minの加湿窒素スイープガス流を膜の透過側に2.8kPa(0.4psi)で吹き込んだ。試験13a〜13cにおけるスイープの湿度はそれぞれ87%、77%、及び81%RHであった。供給ガス混合物は試験13a〜13cにおいてそれぞれ、10℃、15℃、及び23℃であり、85%、84%、及び81%RHに加湿された。データを表IIIに示す。
凝縮性スイープガスによるオレフィン/パラフィン促進輸送膜分離
実施例2のように膜を製造し、414kPa(60psi)に加圧された、10vol.%プロピレン/90vol.%プロパンの室温ガス混合物を分離する逐次試験において使用した。様々なスイープガス構成を試験に採用した。試験14aにおいて、供給混合物は加湿されなかった。水の密封タンクの上方の蒸気を、移送ラインによって試験セルの透過チャンバーへ受け入れ、6.7kPa(50Torr)の絶対圧力の真空下でスイープガスとして膜の透過側へ引いた。この透過側が乾燥真空下で維持され供給側が加湿されないように移送ラインが閉じられることを除き、試験14bは同じであった。試験14cについては、加湿窒素ガススイープを膜セルの透過側に2.8kPa(0.4psi)で吹きこんで使用し、供給混合物も加湿した。データを表IIIに示す。
Claims (16)
- 繰り返し単位A及びBを含むガス分離イオノマーであって、
Aはペルフルオロ化環状又は環化可能有機化合物の重合誘導体であり、
Bは式
前記ガス分離イオノマーは、プロピレン対プロパンの選択性が9.0以上であり、
前記ペルフルオロ化環状又は環化可能有機化合物が、ペルフルオロ−2,2−ジメチル−1,3−ジオキソール、ペルフルオロ−2−メチレン−4−メチル−1,3−ジオキソラン、ペルフルオロ(アルケニルビニルエーテル)、及び2,2,4−トリフルオロ−5トリフルオロメトキシ−1,3ジオキソールから成る群から選択されることを特徴とするガス分離イオノマー。 - Rfは、−CF2CF2−、−CF2 CF(CF3)OCF2CF2−、または、−(CF2)4−の一つ以上であることを特徴とする請求項1に記載のガス分離イオノマー。
- Mは、銀であることを特徴とする請求項1に記載のガス分離イオノマー。
- Mは、銀であることを特徴とする請求項3に記載のガス分離イオノマー。
- 前記単位Aが少なくとも60モル%であることを特徴とする請求項1に記載のガス分離イオノマー。
- 請求項1に記載のイオノマーを本質的に含む非多孔性の選択的透過性膜の層を含むガス分離膜。
- Rfは、−CF2CF2−、−CF2 CF(CF3)OCF2CF2−、または、−(CF2)4−の一つ以上であることを特徴とする請求項6のガス分離膜。
- Mは、銀であることを特徴とする請求項6のガス分離膜。
- Mは、銀であることを特徴とする請求項7のガス分離膜。
- 1以上のオレフィンと1以上のパラフィンの混合物からオレフィンを分離する方法であって、
(A)請求項1に記載のガス分離イオノマーの非多孔性層を含む1以上の膜を提供するステップと、
(B)前記膜の供給側を前記混合物と接触させるステップと、および、
(C)推進力を加え、前記パラフィンに対して前記オレフィンを膜の透過側へ選択的に透過させるステップと、
を含む方法。 - 前記供給混合物および前記透過物は流体であり、前記推進力を加えるステップは、前記膜の透過側でスイープ流体と接触させることを含むことを特徴とする請求項10に記載の方法。
- 前記スイープ流体がオレフィンを含むスイープガスであり、前記透過物は、前記混合物の圧力よりも低圧力あることを特徴とする請求項11に記載の方法。
- 前記供給混合物は、(i)エチレンおよびエタン、(ii)プロピレンおよびプロパン、(iii)ブチレンおよびブタンから成る群から選択されるベアの化合物を含むことを特徴とする請求項12に記載の方法。
- 請求項1に記載のガス分離イオノマーの極性溶媒系中の溶液。
- 前記極性溶媒系が、約10−100vol.%の有機極性溶媒、および、合計で100vol.%になるように相補的な量のフッ素化溶媒を含むことを特徴とする請求項14に記載の溶液。
- 前記極性溶媒系は、有機極性溶媒から本質的に成ることを特徴とする請求項15に記載の溶液。
Applications Claiming Priority (3)
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CA2918287C (en) | 2021-05-04 |
US10029248B2 (en) | 2018-07-24 |
WO2015009969A1 (en) | 2015-01-22 |
JP2016529095A (ja) | 2016-09-23 |
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US20150025293A1 (en) | 2015-01-22 |
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