CN114028959A - 一种超薄脱盐层反渗透复合膜及其制备方法 - Google Patents
一种超薄脱盐层反渗透复合膜及其制备方法 Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 110
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000010612 desalination reaction Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000011033 desalting Methods 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims description 56
- 239000002585 base Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 22
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 16
- 150000004692 metal hydroxides Chemical class 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 11
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 10
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 9
- 238000012695 Interfacial polymerization Methods 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 238000003828 vacuum filtration Methods 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 7
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical compound [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 4
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229920000768 polyamine Polymers 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
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- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001263 acyl chlorides Chemical class 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 2
- 229910001626 barium chloride Inorganic materials 0.000 claims description 2
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 2
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 2
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 2
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- 229940007718 zinc hydroxide Drugs 0.000 claims description 2
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- 230000000052 comparative effect Effects 0.000 description 5
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- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 4
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 4
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical group ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
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- 230000010354 integration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- -1 metal hydroxide compound Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 239000012224 working solution Substances 0.000 description 1
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Abstract
本发明属于多孔薄膜材料制备技术领域，具体涉及一种超薄脱盐层反渗透复合膜及其制备方法；通过对聚砜基膜进行改性后引入中间层，经改性后的聚砜基膜支撑层可与脱盐层以共价键加强连接，并降低脱盐层的厚度至≤10nm，使得在提高膜片通量的同时，膜片的脱盐率不受较大影响。与传统厚度脱盐层的膜片对比，水通量可提高约0.5倍，而脱盐率变化较小。
Description
技术领域
本发明属于多孔薄膜材料制备技术领域，具体涉及一种超薄脱盐层反渗透复合膜及其制备方法。
背景技术
反渗透膜水处理技术具有集成、便捷的特点，反渗透膜材料作为膜法海水淡化技术的基础和核心材料，其性能是决定水处理技术经济指标的直接因素。降低能耗是该技术应用过程中持续关注的重点，提升通量能够显著降低膜片在同等水处理能力下的能量消耗，随着市场发展，对通量不断提升的要求日益成为反渗透复合膜技术开发的热点问题。
其中，由于透过率作为聚酰胺脱盐层材料本身固有的特征参数无法改变，故减少脱盐层的有效厚度是一种显而易见的提高膜片通量的办法。为了制备得到一种高性能的反渗透复合膜，从功能层的厚度改造角度出发，选择在基膜表面形成的中间层基础上进行界面聚合反应，得到超薄脱盐层。这使得在膜片功能层中的水通道长度减小，利于提高反渗透复合膜的水通量。
申请号为CN202110114270.5的专利文件公开了一种聚酰胺复合反渗透膜的制备方法及所得反渗透膜，其是在聚砜支撑层上设置柔性链交联的碳量子纳米多孔层作为界面聚合调控层，最后再制作功能层。界面聚合调控层由柔性链交联剂将氨基化的碳原子交联固定形成，能对界面聚合过程进行调控并在成膜后作为有效水通道；使形成的芳香聚酰胺层超薄且致密，膜材料的水通量和脱盐率同时提高。
另外，文献如Journal of Membrane Science 576(2019)131–141、Journal ofMembrane Science 564(2018)813–819等也给出过在覆膜过程中于基膜和功能层之间引入中间层的报道。由以上专利和文献可知，在支撑层上覆膜得到脱盐层之前引入中间层来调控界面聚合反应的条件已有相关研究。但现有技术中所制备的功能层厚度还达不到理想程度，或者是厚度与功能性无法同时兼顾。
发明内容
本发明为解决上述问题，提供了一种超薄脱盐层反渗透复合膜及其制备方法。
具体是通过以下技术方案来实现的：
1、一种超薄脱盐层反渗透复合膜，所述的反渗透复合膜是由无纺布、改性聚砜基膜支撑层、中间层和脱盐层组成。
进一步，所述的改性聚砜基膜支撑层，是采用浓度为10wt.％-99wt.％的氯磺酸溶液对聚砜基膜进行接枝改性处理得到。
进一步，通过SEM照片检测发现，所述的聚砜基膜平均孔径大小为10-50nm。
进一步，所述的中间层，是由金属氢氧化合物纳米线溶液经真空过滤后堆叠于改性聚砜基膜支撑层表面的。通过SEM照片检测发现，其厚度为1-10μm。
进一步，所述的脱盐层，是以多元胺作为水相单体，以多元酰氯作为油相单体，通过界面聚合反应得到，复合在聚砜基膜支撑层上的。通过SEM照片检测发现，其厚度为≤10nm。
2、所述金属氢氧化合物纳米线溶液的制备方法如下：
(1)将可溶性金属盐溶解在去离子水中，形成浓度为1-10wt.％的溶液，再加入碱或氨水溶液调节pH值为10-14，搅拌生成金属氢氧化物沉淀；
(2)将氢氧化物沉淀离心洗涤至pH值为中性，再将沉淀重新分散在去离子水中，加入1-10g与步骤(1)相应的可溶性金属盐，在密闭容器内进行在常压、200-250℃温度条件下进行的水热反应，反应时间为10-15h，得到金属氢氧化物纳米线溶液。
进一步，所述的可溶性金属盐为氯化隔、氯化钡、氯化锶、氯化锌中的任意一种。
3、上述超薄脱盐层反渗透复合膜的制备方法，具体包括以下步骤：
(1)基膜改性：将聚砜基膜浸泡在氯磺酸溶液中1-24h，聚砜基膜与氯磺酸溶液的比例为20cm2：1L，氯磺酸溶液浓度为10wt.％-99wt.％；并在溶液中加入钯催化剂，加入量为2g/L，浸泡完成后经超纯水洗涤、晾干，得到改性聚砜基膜支撑层；
(2)形成中间层：将金属氢氧化合物纳米线溶液经真空过滤堆叠于改性聚砜基膜支撑层表面，压实；
进一步，所述的金属氢氧化合物纳米线为氢氧化镉、氢氧化钡、氢氧化锶、氢氧化锌中的任意一种，浓度为1-10wt.％；
(3)形成脱盐层：将覆盖有中间层的改性聚砜基膜支撑层浸入含多元胺的水相溶液中，处理5-300s，取出，除去表面水滴，再浸入含多元酰氯的油相溶液中，处理5-300s，形成聚酰胺脱盐层；
进一步，所述的水相溶液为间苯二胺、对苯二胺、乙二胺、哌嗪中的一种或几种，浓度为3-5wt.％。
进一步，所述的油相溶液为苯三甲酰氯、对苯二甲酰氯、草酰氯中的一种或几种，浓度为0.15-0.25wt.％。
进一步，所述油相溶液的溶剂为二氯甲烷、氯仿、二氯乙烷、正己烷、乙基环己烷、环氧丙烷等中的一种或几种。
(4)成膜制备：将形成脱盐层的改性聚砜基膜支撑层在50-70℃条件下进行表面烘干热处理1-10min，即得到超薄脱盐层反渗透复合膜。
综上所述，本发明的有益效果在于：本发明通过对聚砜基膜进行改性后引入中间层，经改性后的聚砜基膜支撑层可与脱盐层以共价键加强连接，并降低脱盐层的厚度，使得在提高膜片通量的同时，膜片的脱盐率不受较大影响。与传统厚度脱盐层的膜片对比，水通量可提高约0.5倍，而脱盐率变化较小。
引入中间层可以改变界面聚合反应过程中的水相单体与油相单体反应的混溶区溶剂环境，从而得到超薄脱盐层。这是因为在界面聚合过程中只有中间层中引入的水相才能参与形成混溶区，而且，采用金属氢氧化合物纳米线经过真空过滤堆叠于基膜表面压密形成的中间层，可在界面聚合反应进行的同时被生成的氯化氢中和反应去除。所以，显然的，在中间层中的水相传递至混溶区的量就很受限制，参与界面聚合反应形成功能层的水相单体很少。综上所述，界面聚合反应最初形成很薄的一层聚酰功能层初生膜会被固定下来不再增厚，从而导致复合膜具有超薄的脱盐层结构。
由于引入了中间层会导致基膜与脱盐层之间的连接变弱，为了在提高反渗透复合膜通量的同时保证较高的脱盐率，本发明通过对基膜的聚砜苯环进行磺酰氯基团接枝，使得在界面聚合水相单体多元苯胺与油相单体多元酰氯反应生成脱盐层的同时，部分水相单体多元苯胺与基团表面的磺酰氯基团反应，从而实现基膜与脱盐层以共价键的方式加强连接。这保证了功能层在复合膜上的强度，使得在提高膜片通量的同时，膜片脱盐率不受较大影响。不过引入可牺牲的中间层只是手段，而以此来制备厚度≤10nm的超薄功能层才是本发明的核心内容，在此基础上又为保证功能层与支撑层之间的连接强度而引进基膜支撑层改性过程。
采用本发明方法制备得到反渗透复合膜的聚酰胺功能层(即脱盐层)可以达到≤10nm的厚度，且通过与传统厚度聚酰胺功能层的膜片对比，发现膜片在以下条件下：1500ppm的NaCl水溶液，在操作压力为0.70MPa下(浓水循环)运行时，水通量从42gfd左右提升至60gfd左右，增加了约0.5倍，且脱盐率仅从99.2％降至98.8％；在水效条件下：水效溶液的配制是在40L纯水中分别添加11.10g CaCl2、10.75g NaHCO3、2.00g NaCl，然后加入40ml的按照6-8ml次氯酸溶解在1L纯水中比例稀释的次氯酸溶液，在操作压力为0.70MPa下(浓水循环)运行时，水通量从36gfd左右提升至56gfd左右，亦增加了约0.5倍，且脱盐率仅从96.2％降至95.0％。
此外，采用本发明方法制备得到的反渗透复合膜基膜与脱盐层之间的连接强度与常规方法得到的反渗透复合膜基本一致。表征基膜和脱盐层之间的连接强度的方法为测量膜片剥离强度(或称为平均剥离力)，它表示的是宽度尺寸固定时基膜和脱盐层之间呈180°连续剥离时用力大小。而采用本发明方法制备得到的膜片与常规膜片的剥离强度均在0.3N-0.5N的范围之内变化，均属于基膜与脱盐层之间的连接强度较好范围。相较而言，本发明方法制备得到的膜片水通量有较大的提升效果，此技术有望应用到大批量的反渗透膜生产中，易于推行工厂化生产。
具体实施方式
下面对本发明的具体实施方式作进一步详细的说明，但本发明并不局限于这些实施方式，任何在本实施例基本精神上的改进或代替，仍属于本发明权利要求所要求保护的范围。
一、实施例与对比例
实施例1
1、一种超薄脱盐层反渗透复合膜，所述的反渗透复合膜是由无纺布、改性聚砜基膜支撑层、中间层和脱盐层组成。
进一步，通过SEM照片检测发现，所述的聚砜基膜平均孔径大小为10nm。
进一步，所述的中间层，是由金属氢氧化合物纳米线溶液经真空过滤后堆叠于改性聚砜基膜支撑层表面的。
2、所述金属氢氧化合物纳米线溶液的制备方法如下：
(1)将氯化镉溶解在去离子水中形成10wt.％的溶液，再缓慢加入氨水溶液调节pH值为14，搅拌生成氢氧化镉沉淀；
(2)将氢氧化镉沉淀离心洗涤至pH值为中性，再将沉淀重新分散在去离子水中，加入适量无机盐氯化镉，在密闭容器内进行在200℃下进行水热反应10h，得到5wt.％的氢氧化镉纳米线溶液。
3、上述超薄脱盐层反渗透复合膜的制备方法，具体包括以下步骤：
(1)基膜改性：将聚砜基膜(10cm×10cm)浸泡在5L氯磺酸溶液中2h，氯磺酸溶液的浓度为50wt.％，并在溶液中加入10g钯催化剂，浸泡完成后经超纯水洗涤、晾干，得到改性聚砜基膜支撑层；
(2)形成中间层：将氢氧化镉纳米线溶液经真空过滤堆叠于改性聚砜基膜支撑层表面，压实，厚度约2μm；
(3)形成脱盐层：将覆盖有中间层的改性聚砜基膜支撑层浸入含3.0wt.％间苯二胺的水相溶液中，处理20s，取出，除去表面水滴，再浸入含0.15wt.％均苯三甲酰氯的油相溶液中，处理20s，形成聚酰胺脱盐层；进一步，所述的水相溶液中含有浓度为4wt.％的樟脑磺酸、2wt.％的三乙胺。进一步，所述油相溶液的溶剂为乙基环己烷。
(4)成膜制备：将形成脱盐层的改性聚砜基膜支撑层在70℃条件下热处理5min，即得到超薄脱盐层反渗透复合膜。
实施例2
与实施例1的制备方法相同，区别在于，在基膜改性步骤中，将聚砜基膜采用75％的氯磺酸溶液浸泡2h，并在溶液中加入钯催化剂，浸泡完成后经超纯水洗涤、晾干，得到改性聚砜基膜支撑层。其他制备步骤和条件完全相同，此不赘述。
实施例3
与实施例1的制备方法相同，区别在于，在改性聚砜基膜支撑层上真空过滤堆叠的是氢氧化钡纳米线，其中氢氧化钡纳米线溶液的制备方法类似于氢氧化隔纳米线溶液。其他制备步骤和条件完全相同，此不赘述。
对比例1
采用实施例1的方法制备反渗透复合膜，区别在于，没有基膜的经氯磺酸溶液浸泡改性和不引入金属氢氧化合物纳米线中间层。
二、膜片性能测试
2.1实验材料
采用实施例1-2及对比例1的方法制备的反渗透复合膜。
2.2实验方法
用1500ppm的NaCl水溶液，在操作压力为0.70MPa、温度为25℃的条件下测试膜片的脱盐率和通量，结果如表1所示(浓水循环)。
用水效溶液，在操作压力为0.70MPa、温度为25℃的条件下测试膜片的脱盐率和通量，结果如表2所示(浓水循环)。
水效溶液的配制方法：在40L纯水中分别添加11.10g CaCl2、10.75g NaHCO3、2.00gNaCl，然后加入40ml的按照6-8ml次氯酸溶解在1L纯水中比例稀释的次氯酸溶液。
2.3实验结果
表1
表2
由以上表1和表2的实验结果可知，在实施例1、实施例2和实施例3中分别采用本发明方法制备得到的超薄脱盐层反渗透复合膜，无论在NaCl溶液或是在水效溶液中运行时，通量均大大提高，同时脱盐率几乎不变。长时间运行条件下，膜片在NaCl溶液中运行的脱盐率略有提升，而通量稳定；在水效溶液中运行的脱盐率亦略有提升，而通量衰减较快。但水效运行条件下，实施例1、2、3与对比例1均保持相同的通量衰减趋势，且实施例1、2、3的膜片通量始终高于对比例1的膜片通量。
亦即，采用本发明所述的权利要求范围内的方法可以制备得到一种高性能的超薄脱盐层反渗透复合膜，其功能层厚度较薄，与传统厚度脱盐层的膜片对比，水通量可提高约0.5倍，而脱盐率变化较小。
Claims (10)
1.一种超薄脱盐层反渗透复合膜，其特征在于，所述的反渗透复合膜是由无纺布、改性聚砜基膜支撑层、中间层和脱盐层组成；其中，所述的中间层，是由金属氢氧化合物纳米线溶液经真空过滤后堆叠于改性聚砜基膜支撑层表面的，厚度为1-10μm；所述的脱盐层，是以多元胺作为水相单体，以多元酰氯作为油相单体，通过界面聚合反应得到，复合在聚砜基膜支撑层上的，厚度≤10nm。
2.如权利要求1所述的一种超薄脱盐层反渗透复合膜，其特征在于，所述的改性聚砜基膜支撑层，是采用浓度为10wt.％-99wt.％的氯磺酸溶液对聚砜基膜进行接枝改性处理得到。
3.一种超薄脱盐层反渗透复合膜的制备方法，其特征在于，包括以下步骤：
(1)基膜改性：将聚砜基膜浸泡在氯磺酸溶液中1-24h，聚砜基膜与氯磺酸溶液的比例为20cm2：1L；并在溶液中加入钯催化剂，加入量为2g/L，浸泡完成后经超纯水洗涤、晾干，得到改性聚砜基膜支撑层；
(2)形成中间层：将金属氢氧化合物纳米线溶液经真空过滤堆叠于改性聚砜基膜支撑层表面，压实；
(3)形成脱盐层：将覆盖有中间层的改性聚砜基膜支撑层浸入含多元胺的水相溶液中，处理5-300s，取出，除去表面水滴，再浸入含多元酰氯的油相溶液中，处理5-300s，形成聚酰胺脱盐层；
(4)成膜制备：将形成脱盐层的改性聚砜基膜支撑层在50-70℃条件下进行表面烘干热处理，处理时间为1-10min，即得到超薄脱盐层反渗透复合膜。
4.如权利要求3所述的一种超薄脱盐层反渗透复合膜的制备方法，其特征在于，所述的氯磺酸溶液，其浓度为10wt.％-99wt.％。
5.如权利要求3所述的一种超薄脱盐层反渗透复合膜的制备方法，其特征在于，所述的金属氢氧化合物纳米线为氢氧化镉、氢氧化钡、氢氧化锶、氢氧化锌中的任意一种，其中氢氧化物的浓度为1-10wt.％。
6.如权利要求3所述的一种超薄脱盐层反渗透复合膜的制备方法，其特征在于，所述的水相溶液为间苯二胺、对苯二胺、乙二胺、哌嗪中的一种或几种，浓度为3-5wt.％。
7.如权利要求3所述的一种超薄脱盐层反渗透复合膜的制备方法，其特征在于，所述的油相溶液为苯三甲酰氯、对苯二甲酰氯、草酰氯中的一种或几种，浓度为0.15-0.25wt.％。
8.如权利要求3或5所述的一种超薄脱盐层反渗透复合膜的制备方法，其特征在于，所述的金属氢氧化物纳米线溶液的制备方法如下：
(1)将可溶性金属盐溶解在去离子水中，形成浓度为1-10wt.％的溶液，再在其中加入碱或氨水溶液调节pH值为10-14，搅拌生成金属氢氧化物沉淀；
(2)将氢氧化物沉淀离心洗涤至pH值为中性，再将沉淀重新分散在去离子水中，加入1-10g与步骤(1)相应的可溶性金属盐，在密闭容器内进行水热反应，得到金属氢氧化物纳米线溶液。
9.如权利要求8所述的一种超薄脱盐层反渗透复合膜的制备方法，其特征在于，所述的可溶性金属盐为氯化隔、氯化钡、氯化锶、氯化锌中的任意一种。
10.如权利要求8所述的一种超薄脱盐层反渗透复合膜的制备方法，其特征在于，所述的水热反应，是在常压下，于200-250℃条件下反应10-15h。
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