JP2015139742A - 複合分離膜とこれを用いた分離膜エレメント - Google Patents
複合分離膜とこれを用いた分離膜エレメント Download PDFInfo
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- JP2015139742A JP2015139742A JP2014013700A JP2014013700A JP2015139742A JP 2015139742 A JP2015139742 A JP 2015139742A JP 2014013700 A JP2014013700 A JP 2014013700A JP 2014013700 A JP2014013700 A JP 2014013700A JP 2015139742 A JP2015139742 A JP 2015139742A
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- Prior art keywords
- separation membrane
- polyfunctional amine
- polyfunctional
- composite separation
- amine
- 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.)
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- 239000012528 membrane Substances 0.000 title claims abstract description 103
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 150000001412 amines Chemical class 0.000 claims abstract description 112
- 239000002253 acid Substances 0.000 claims abstract description 44
- 150000004820 halides Chemical class 0.000 claims abstract description 42
- 239000004952 Polyamide Substances 0.000 claims abstract description 41
- 229920002647 polyamide Polymers 0.000 claims abstract description 41
- 125000003118 aryl group Chemical group 0.000 claims abstract description 21
- 150000001875 compounds Chemical group 0.000 claims abstract description 16
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000002346 layers by function Substances 0.000 claims description 68
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 18
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 11
- -1 amidole Chemical compound 0.000 claims description 9
- 125000002723 alicyclic group Chemical group 0.000 claims description 8
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 8
- OCIDXARMXNJACB-UHFFFAOYSA-N n'-phenylethane-1,2-diamine Chemical compound NCCNC1=CC=CC=C1 OCIDXARMXNJACB-UHFFFAOYSA-N 0.000 claims description 4
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- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
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- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 claims description 2
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 claims description 2
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- NSMWYRLQHIXVAP-UHFFFAOYSA-N 2,5-dimethylpiperazine Chemical compound CC1CNC(C)CN1 NSMWYRLQHIXVAP-UHFFFAOYSA-N 0.000 description 1
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- FPFCYBCBFOAYRH-UHFFFAOYSA-N 6-sulfonylcyclohexa-2,4-diene-1,2-dicarbonyl chloride Chemical compound S(=O)(=O)=C1C(C(=CC=C1)C(=O)Cl)C(=O)Cl FPFCYBCBFOAYRH-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- B01D71/06—Organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
- B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
【解決手段】多孔性支持体と多孔性支持体上に形成された分離機能層とを備え、分離機能層は、芳香環を有する多官能アミンと、当該多官能アミンを除く脂肪族多官能アミンと、多官能酸ハライドとを含む化合物群の反応により形成されたポリアミドから構成され、当該ポリアミドの多官能アミン単位に占める、芳香環を有する多官能アミンに由来する単位の割合が30モル%以下である複合分離膜とする。
【選択図】図1
Description
分離機能層を構成するポリアミドにおけるアミン単位のモル組成比(ポリアミドの全アミン単位に占める各アミン単位の割合の比)は、作製した複合分離膜から分離機能層を機械的に分離した後、分離した分離機能層に対して1H−NMR測定を実施して求めた。
作製した複合分離膜の塩阻止率は、以下のようにして求めた。複合分離膜に硫酸マグネシウム(MgSO4)水溶液(濃度0.20重量%、温度25℃、pH6.5)を操作圧力1.0MPaで30分間透過させた。電導度測定装置(京都電子製、CM−117)を用いて膜透過液および供給液の電導度測定を行い、その結果および検量線(濃度−電導度)から、下記式に基づいて、MgSO4の阻止率を算出した。
阻止率=(1−(膜透過液中のMgSO4濃度/供給液中のMgSO4濃度))×100(%)
作製した複合分離膜の透過流束を、塩阻止率を評価する際に併せて測定した膜透過液量から、以下の式により求めた。
透過流束(m3/(m2・day))=透過液量/(膜面積×サンプリング時間)
ピペラジン3.582重量%、m−フェニレンジアミン(MPD)0.018重量%、ラウリル硫酸ナトリウム0.15重量%、水酸化ナトリウム0.45重量%、カンファスルホン酸6重量%を含有するアミン水溶液を、多孔性支持体である多孔性ポリスルホン酸支持体(分離機能層を形成する側の平均孔径20μm、当該側と反対側とで平均孔径が異なる非対称膜)に塗布した後、余分の水溶液を除去した。次に、支持体におけるアミン水溶液の塗布面にトリメシン酸クロライド0.4重量%を含有するイソオクタン溶液を接触させて界面縮合重合反応を進行させ、多孔性支持体上にポリアミドの分離機能層(厚さ1μm)を形成して、複合分離膜を得た。
以下の表1に示す値となるように、アミン水溶液におけるピペラジンおよびMPDの仕込み比を制御した以外は実施例1と同様にして、複合分離膜を得た。
MPDの代わりにN−フェニルエチレンジアミン(FED)を用いるとともに、分離機能層におけるアミン単位の組成比が以下の表2に示す値となるようにアミン水溶液におけるピペラジンおよびFEDの仕込み比を制御した以外は実施例1と同様にして、複合分離膜を得た。
実施例1,2および比較例1〜4で作製した複合分離膜を、遊離塩素濃度100mg/Lの次亜塩素酸ナトリウム水溶液に72時間浸漬することで塩素処理を実施し、それぞれ実施例5,6および比較例7〜10とした。
実施例4、比較例5,6で作製した複合分離膜を、遊離塩素濃度100mg/Lの次亜塩素酸ナトリウム水溶液に72時間浸漬することで塩素処理を実施し、それぞれ実施例7および比較例11,12とした。
アミン水溶液にポリビニルアルコール(けん化度99%)を濃度0.25重量%で添加するとともに、分離機能層におけるアミン単位の組成比が以下の表5に示す値となるようにアミン水溶液におけるピペラジンおよびMPDの仕込み比を制御した以外は実施例1と同様にして、複合分離膜を得た。
実施例8〜12、比較例13で作製した複合分離膜を、遊離塩素濃度100mg/Lの次亜塩素酸ナトリウム水溶液に72時間浸漬することで塩素処理を実施し、それぞれ実施例13〜17、比較例14とした。
31 複合分離膜
32 供給側流路材
33 透過側流路材
35 集水管
Claims (9)
- 多孔性支持体と、前記多孔性支持体上に形成された分離機能層と、を備え、
前記分離機能層は、芳香環を有する多官能アミンと、前記多官能アミンを除く脂肪族多官能アミンと、多官能酸ハライドとを含む化合物群の反応により形成されたポリアミドから構成され、
前記ポリアミドの多官能アミン単位に占める、前記芳香環を有する多官能アミンに由来する単位の割合が30モル%以下である、複合分離膜。 - 前記脂肪族多官能アミンが脂環式多官能アミンである、請求項1に記載の複合分離膜。
- 前記脂肪族多官能アミンが、ピペラジンまたはピペラジン誘導体である、請求項1に記載の複合分離膜。
- 前記芳香環を有する多官能アミンが、m−フェニレンジアミン、p−フェニレンジアミン、o−フェニレンジアミン、1,3,5−トリアミノベンゼン、1,2,4−トリアミノベンゼン、3,5−ジアミノ安息香酸、2,4−ジアミノトルエン、2,6−ジアミノトルエン、N−フェニルエチレンジアミン、N,N’−ジメチル−m−フェニレンジアミン、2,4−ジアミノアニソール、アミドール、およびキシリレンジアミンから選ばれる少なくとも1種である、請求項1〜3のいずれかに記載の複合分離膜。
- 前記ポリアミドの多官能アミン単位に占める、前記芳香環を有する多官能アミンに由来する単位の割合が15モル%以下である、請求項1〜4のいずれかに記載の複合分離膜。
- 前記化合物群が、親水性ポリマーをさらに含む、請求項1〜5のいずれかに記載の複合分離膜。
- 前記親水性ポリマーがポリビニルアルコールである、請求項6に記載の複合分離膜。
- 請求項1〜7のいずれかに記載の複合分離膜にさらに塩素処理を施した複合分離膜。
- 請求項1〜8のいずれかに記載の複合分離膜を用いた分離膜エレメント。
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