CN107126851B - 一种复合反渗透膜及其制备方法 - Google Patents
一种复合反渗透膜及其制备方法 Download PDFInfo
- Publication number
- CN107126851B CN107126851B CN201710305570.5A CN201710305570A CN107126851B CN 107126851 B CN107126851 B CN 107126851B CN 201710305570 A CN201710305570 A CN 201710305570A CN 107126851 B CN107126851 B CN 107126851B
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- layer
- reverse osmosis
- paek
- osmosis membrane
- chloride
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- 239000012528 membrane Substances 0.000 title claims abstract description 66
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920006260 polyaryletherketone Polymers 0.000 claims abstract description 45
- -1 ether ketone Chemical class 0.000 claims abstract description 30
- 238000005266 casting Methods 0.000 claims abstract description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920000412 polyarylene Polymers 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 10
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 150000001263 acyl chlorides Chemical class 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 229910021389 graphene Inorganic materials 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 238000007872 degassing Methods 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 6
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004760 aramid Substances 0.000 claims description 4
- 150000004982 aromatic amines Chemical class 0.000 claims description 4
- 229920003235 aromatic polyamide Polymers 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 claims description 4
- 229940094989 trimethylsilane Drugs 0.000 claims description 4
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical class NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 claims description 3
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000002608 ionic liquid Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- RWAWMKWJDOUNKY-UHFFFAOYSA-N 1-piperidin-3-ylpiperidine Chemical compound C1CCCCN1C1CNCCC1 RWAWMKWJDOUNKY-UHFFFAOYSA-N 0.000 claims description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- RUOKPLVTMFHRJE-UHFFFAOYSA-N benzene-1,2,3-triamine Chemical compound NC1=CC=CC(N)=C1N RUOKPLVTMFHRJE-UHFFFAOYSA-N 0.000 claims description 2
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical group ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 claims description 2
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- BQFCCCIRTOLPEF-UHFFFAOYSA-N chembl1976978 Chemical compound CC1=CC=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 BQFCCCIRTOLPEF-UHFFFAOYSA-N 0.000 claims description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 2
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical class NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 claims description 2
- WMPOZLHMGVKUEJ-UHFFFAOYSA-N decanedioyl dichloride Chemical compound ClC(=O)CCCCCCCCC(Cl)=O WMPOZLHMGVKUEJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims description 2
- GHAIYFTVRRTBNG-UHFFFAOYSA-N piperazin-1-ylmethanamine Chemical class NCN1CCNCC1 GHAIYFTVRRTBNG-UHFFFAOYSA-N 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 claims description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical class NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 claims 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical class NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 claims 1
- YLFCXTJHZOZFFI-UHFFFAOYSA-N n'-ethoxyethane-1,2-diamine Chemical compound CCONCCN YLFCXTJHZOZFFI-UHFFFAOYSA-N 0.000 claims 1
- 238000010612 desalination reaction Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 6
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- 238000003756 stirring Methods 0.000 description 5
- GGBJHURWWWLEQH-UHFFFAOYSA-N butylcyclohexane Chemical compound CCCCC1CCCCC1 GGBJHURWWWLEQH-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
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- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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Classifications
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- B01D—SEPARATION
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- 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
- B01D69/1216—Three or more layers
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- 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
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B01D67/0011—Casting solutions therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
- B01D67/00111—Polymer pretreatment in the casting solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
- B01D67/00113—Pretreatment of the casting solutions, e.g. thermal treatment or ageing
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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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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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
- B01D69/10—Supported membranes; Membrane supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明公开了一种复合反渗透膜及其制备方法。该方法为:将一定浓度的含氟聚芳醚酮和含有硅烷改性的聚芳醚酮混合均匀后作为铸膜液,涂覆在无纺布为基材上面形成支撑层,然后在支撑层表面先后涂覆上溶液A和溶液B,经过反应形成聚酰胺脱盐层,聚酰胺脱盐层再涂覆上改性聚乙烯醇抗污染层。即制成所述的复合反渗透膜;与现有技术相比,本发明以复合改性聚芳醚酮为支撑层,可以制备获得耐高温、高强度的复合反渗透膜,同时采用聚乙烯醇作为抗污染层成分,具有良好的抗污染性。
Description
技术领域
本发明涉及一种复合反渗透膜及其制备方法,尤其是一种高通量复合反渗透膜及其制备方法,属于水处理膜分离技术领域。
背景技术
反渗透技术是一种采用半透膜,以压力为推动力,截留溶液中溶质的膜分离技术。相比于普通的过滤技术,反渗透具有操作过程简单以及脱除效率高和环境友好等优点并广泛的用于海水及苦咸淡化,硬水软化,中水回收,工业废水处理,超纯水制备等广泛领域。其中复合膜因其可将膜的截留率,水通量,稳定性等性能优化而成为当前发展最快、应用最多的膜品种,目前市场上超过90%的纳滤和反渗透膜是复合膜。复合膜是指在多孔的支撑底膜上复合一层很薄的、致密的、有特种分离功能的不同材料。与一体化膜比较,复合膜的表面致密层厚度更薄,从而使膜同时具有高的溶质分离率和水的透过速率,及可优化的物理化学结构,可满足各种不同的选择性分离需求。
最先商业化的反渗透膜是由改性醋酸纤维素制备的,所生产的反渗透膜水通量和脱盐率都比较低,耐氯性能较好,后经工艺优化,脱盐率得到改善,但是水通量始终较低,应用受到很大限制。后来以聚酰胺结构为主的复合反渗透膜得到商业化应用,并以其高通量、高脱盐、低能耗的优势,迅速获得广泛应用,成为使用最多的反渗透膜。现有复合反渗透膜通用的制备方法为两步:第一步在PET无纺布上刮涂一层高分子材料作为多孔支撑层,第二步在支撑层上进行界面缩聚反应生成聚酰胺三维交联结构,形成脱盐功能层。现有的复合反渗透膜虽然具有较高的水通量和脱盐率,但是由于特有的三层复合结构,导致其总厚度达到140微米,甚至更厚。不利于反渗透组件进一步节约空间,单位体积内有效膜面积难以提升,是组件设计优化的主要制约因素。
目前反渗透膜虽然已经大规模使用,但仍存在不少问题,如耐高温性能不好,一般的反渗透膜并不具备耐高温性能,由于在工业过滤中很多地方的水是具有高于室温下的温度,甚至达到50度以上,在这种条件下采用反渗透膜对膜的损害非常大,膜在高温下运行会加速其老化,同时膜的强度会大大降低,超过其运行温度时,反渗透膜的性能会很快下降,严重时导致不能够正常工作,因此,提高反渗透膜的耐高温性能也是亟待解决的一个问题,目前提高反渗透膜的方法也有不少,比如增加膜厚度,通过加入添加剂来提高支撑体的耐高温性能,通过对支撑体材料进行改性等,虽然都取得了一定的效果,但仍不能够满足各种情况的要求。
另外,反渗透膜作为过滤膜的一种,其使用寿命和通水性能一直是人们关注点之一,好多复合反渗透膜的结构由于是多层,虽然脱盐性能有所提高,但是长时间使用后由于积累污垢导致水通量变小,使得反渗透效率降低,而在膜材料中掺杂增加亲水性物质可以提高反渗透膜的通水量,如通过亲水基团改性。而近几年石墨烯及改性石墨烯作为一种新材料出现在人们眼中,石墨烯是人们发现的一种由碳原子以sp2杂化形成的、具有单原子层的、二维蜂窝状结构的原子晶体。在石墨烯中,除了纯粹引入氧原子的过氧键外,结构中还存在其他种类官能团,比如羰基(=CO)、羟基(-OH)和酚羟基,使石墨烯具有极强的亲水性和极好的抑菌性。本发明的申请人通过实验研究发现石墨烯和改性石墨烯都具有非常良好的亲水性能,将其掺杂到反渗透膜和过滤膜中竟然有意想不到的增强水通量的效果。
本发明致力于解决现有技术中反渗透膜的耐高温性能差、寿命短、通水量低等问题,以提供能够增强使用耐高温的、使用寿命长的、高通水量的复合反渗透膜及其制备方法。
发明内容
本发明的目的是提供一种复合反渗透膜及其制备方法。
一种复合反渗透膜,包括支撑体层、功能膜层和抗污染层,其特征在于:支撑体层为氟聚芳醚酮和硅烷改性的聚芳醚酮的混合物,功能膜层为聚酰胺层;
进一步的,所述的抗污染层为改性聚乙烯层;
进一步的,所述含氟聚芳醚酮为三氟甲烷基聚芳醚酮或二氟甲烷基聚芳醚酮;
进一步的,所述硅烷改性的聚芳醚酮为三甲基硅烷、三乙基硅烷、三丙基硅烷改性的聚芳醚酮;
进一步的,所述氟聚芳醚酮和硅烷改性的聚芳醚酮的质量比例为1:3—3:1。
进一步的,所述的功能膜层中还掺杂有氧化石墨烯,氧化石墨烯掺杂量为该膜层质量含量的0.01-0.1%,优选0.02-0.05%。
进一步的,所述支撑体层的厚度为10~100μm;所述聚酰胺层的厚度为50~500nm;改性聚乙烯层为10-100μm。
本发明还提供的上述复合反渗透膜的制备方法,具体如下:
1)将含氟聚芳醚酮、硅烷改性的聚芳醚酮和有机溶剂按一定比例配置成铸膜液,搅拌均匀,静置1-3h后超声脱气10-30min,作为支撑体铸膜液;
2)将步骤1)制得的铸膜液利用刮膜机涂抹到无纺布上,厚度为10-150μm,然后室温下蒸发5-30s后浸入15-25℃超纯水中凝胶固化成膜,然后在50-80℃烤箱中干燥4-8小时,制得支撑体层;
3)分别配置溶液A和溶液B中,所述溶液A的溶质为芳香胺和/或脂肪胺,溶剂为水,所述溶液B的溶质为芳香酰氯和/或脂肪酰氯,溶剂为有机溶剂;
4)将步骤2)制得的支撑体层表面先浸渍溶液A中5-30s,然后在室温下静置5-30s,再浸渍溶液B中5-30s,后在室温下静置反应1-10min后,置于干燥箱中40-60℃中干燥2-6小时;
5)将步骤4)所制得的复合膜层表面涂覆一层改性聚乙烯醇和离子液体的溶液,厚度为30-80μm,在40-80℃干燥箱中干燥2-6小时,制得复合反渗透膜。
进一步的,所述含氟聚芳醚酮为三氟甲烷基聚芳醚酮或二氟甲烷基聚芳醚酮;所述硅烷改性的聚芳醚酮为三甲基硅烷、三乙基硅烷、三丙基硅烷改性的聚芳醚酮。
进一步的,所述步骤1中含氟聚芳醚酮和硅烷改性的聚芳醚酮质量比例为1:3—3:1。
进一步的,所述溶剂A中添加有氧化石墨烯,添加量为溶液A和B溶质总量的0.01-0.1%,优选0.02-0.05%。
进一步的,所述芳香胺为对苯二胺、间苯二胺、均苯三胺、4,4‘-二氨基二本醚,3,5-二氨基苯甲酸和1,2,4-三胺基本中的至少一种,所述脂肪胺为乙二胺、丙二胺、丁二胺、戊二胺、三(2-氨乙基)胺、二乙烯三胺、N-(2-羟乙基)乙二胺、己二胺、1,3-二胺基环己烷、1,2-二胺基环己烷、1,4-二氨基环己烷、哌嗪、1,3-双哌啶基丙烷和4-氨基甲基哌嗪中的至少一种;
所述芳香酰氯为苯二甲酰氯、间苯二甲酰氯、邻苯二甲酰氯、联苯二甲酰氯、苯二磺酰氯、1,2,4-偏苯三酸酐酰氯,均苯三甲酰氯中的至少一种,所述脂肪酰氯为丁三酰氯、丁二酰氯、戊三酰氯、戊二酰氯、己三酰氯、己二酰氯、癸二酰氯、癸三酰氯、环丙烷三酰氯、环丁烷二酰氯、环丁烷四酰氯、环戊烷二酰氯、环戊烷三酰氯、环戊烷四酰氯、环己烷二酰氯、环己烷三酰氯、环己烷四酰氯、四氢呋喃二酰氯和四氢呋喃四酰氯中的至少一种。
进一步的,所述步骤1)中的有机溶剂为:三氯甲烷、二氯甲烷、二甲亚砜、DMF或者DMAc。
进一步的,所述步骤3)中所述有机溶剂为含有4~10个碳原子的脂肪烃、环脂烃和芳香烃中的一种或几种。
进一步的,所述的支撑体层的孔径为0~200nm,优选为5~100nm;更优选为15~50nm
进一步的,所述的支撑体层浸渍在所述溶液A中的时间为10-20秒;支撑体浸渍在所述溶液B中的时间为10-20秒。
进一步的,所述的离子液体为N-甲基吡咯烷酮、羧基咪唑类离子液体。
进一步的,所述的致孔剂选自聚乙烯醇,聚乙二醇、聚乙烯吡咯烷酮、乙二醇单甲醚、乙二醇二甲醚中任意一种或者任意几种的混合物,浓度为1-20%wt。
本发明具有显著的效果,主要在于:
本发明以含氟聚芳醚酮支撑层和硅烷改性聚芳醚酮为主体材料,即采用复合的改性聚芳醚酮,其中经过氟原子改性的聚芳醚酮,由于氟原子具有较小的原子半径和很高的负电势能,可以提高聚芳醚酮的热稳定性和溶解性能,同时,硅烷改性的聚芳醚酮由于硅烷基的存在,硅烷基具有高稳定性和化学平衡性能,能够使聚芳醚酮具有更加高的热稳定性,具备了耐高温性能和强度。含氟聚芳醚酮支撑层和硅烷改性聚芳醚酮在分别单独使用时已经具有良好的耐热性能,而通过实验发现,将同样具备耐高温性能的含氟聚芳醚酮和硅烷改性的聚芳醚酮混合在一起使用时,其耐热性能和强度具有更加显著的提高,通过分析认为是硅烷基团的硅原子构成网状结构与氟原子交叉后形成了更加稳定的空间结构,并能够借助原子间作用力加强结构强度。
另外,氧化石墨烯本身就是一种高强度、耐高温材料,同时氧化石墨烯表面具有很多活性羟基等基团,具有良好的亲水性,在铸膜材料中添加了氧化石墨烯,在成膜过程中能够与成膜聚合物有机结合,进一步强度复合反渗透膜的强度、耐高温性能和水通量。再借助外层改性聚乙二醇的抗菌性能,可以避免反渗透膜的生物污染,提高反渗透膜的使用寿命。
具体实施方式
为了更好地理解本发明,下面结合实施例进一步阐明本发明的内容,但本发明的内容不仅仅局限于下面的实施例。
实施例1、
制备含有10%含氟聚芳醚酮、8%硅烷改性聚芳醚酮的复合反渗透膜,具体步骤如下:
1)将三氟甲烷基聚芳醚酮、三甲基硅烷基聚芳醚酮、DMF(二甲基甲酰胺)和聚乙烯吡咯烷酮按重量比例10:8:68:14配置成铸膜液,搅拌均匀,静置30min后超声脱气8min,作为支撑体层铸膜液;
2)将步骤1)制得的铸膜液利用刮膜机涂抹到无纺布上,厚度为60μm,然后室温下蒸发10s后浸入20℃去离子水中凝胶固化成膜,然后在50℃烤箱中干燥6小时,制得支撑体层;
3)分别配置溶液A:溶质为对二苯胺,溶剂为水,浓度5%wt;配置溶液B:溶质为四氢呋喃二酰氯,溶剂为甲苯,浓度5%wt;
4)将步骤2)制得的支撑体层表面先浸渍溶液A中20s,然后在室温下静置15s,再浸渍溶液B中20s,后在室温下静置反应8min后,置于干燥箱中50℃中干燥3小时;
步骤5),配置含15%聚乙烯醇和5%N-甲基吡咯烷酮的水溶液,涂覆到步骤4)所制得的复合膜层表面,厚度为50μm,在60℃干燥箱中干燥4h,制得复合反渗透膜。
所制备的复合反渗透膜支撑层基膜厚度60μm、脱盐层35μm、抗污染层50μm,支撑层平均孔径30-60nm。
实施例2、
制备含有10%含氟聚芳醚酮、10%硅烷基聚芳醚酮的复合反渗透膜,脱盐层掺杂0.03%氧化石墨烯,具体步骤如下:
1)将二氟甲烷基聚芳醚酮、三乙基硅烷基聚芳醚酮、DMAc(二甲基乙酰胺)、聚乙二醇按比例10:10:68:12配置成铸膜液,搅拌均匀,静置45min后超声脱气20min,作为支撑体层铸膜液;
2)将步骤1)制得的铸膜液利用刮膜机涂抹到无纺布上,厚度为90μm,然后室温下蒸发10s后浸入25℃去离子水中凝胶固化成膜,然后在60℃烤箱中干燥4小时,制得支撑体层;
3)分别配置溶液A:溶质为3,5-二氨基苯甲酸,溶剂为水、浓度8%wt、掺杂氧化石墨烯0.03%wt;配置溶液B:溶质为环丙烷三酰氯,溶剂为正己烷、浓度8%wt、掺杂氧化石墨烯0.03%wt;
4)将步骤2)制得的支撑体层表面先浸渍溶液A中15s,然后在室温下静置15s,再浸渍溶液B中20s,后在室温下静置反应5min后,置于干燥箱中50℃中干燥2小时;
步骤5),配置含12%聚乙烯醇和8%N-甲基吡咯烷酮的水溶液,涂覆到步骤4)所制得的复合膜层表面,厚度为50μm,在60℃干燥箱中干燥4h,制得复合反渗透膜。
所制备的复合反渗透膜支撑层基膜厚度90μm、脱盐层40μm、抗污染层50μm,支撑层平均孔径30-60nm。
实施例3、
制备含有5%含氟聚芳醚酮、15%硅烷基聚芳醚酮的复合反渗透膜,脱盐层掺杂0.05%氧化石墨烯,具体步骤如下:
1)将含三氟甲烷改性聚芳醚酮、三丙基硅烷改性聚芳醚酮、DMF和聚乙二醇按比例5:15:65:15配置成铸膜液,搅拌均匀,静置1h后超声脱气15min,作为支撑体层铸膜液。
2)将步骤1)制得的铸膜液利用刮膜机涂抹到无纺布上,厚度为100μm,然后室温下蒸发15s后浸入20℃去离子水中凝胶固化成膜,然后在55℃烤箱中干燥3小时,制得支撑体层;
3)分别配置溶液A:溶质为己二胺,浓度8%wt,溶剂为水,并添加有0.05%的氧化石墨烯;配置溶液B:溶质为四氢呋喃四酰氯,溶剂为正戊烷,浓度为8%wt,并添加有0.05%的氧化石墨烯;
4)将步骤2)制得的支撑体层表面先浸渍溶液A中15s,然后在室温下静置8s,再浸渍溶液B中20s,后在室温下静置反应5min后,置于干燥箱中45℃中干燥4小时;
步骤5),配置含12%聚乙烯醇和6%N-甲基吡咯烷酮的水溶液,涂覆到步骤4)所制得的复合膜层表面,厚度为50μm,在60℃干燥箱中干燥4h,制得复合反渗透膜。
所制备的复合反渗透膜支撑层基膜厚度100μm、脱盐层50μm、抗污染层50μm,支撑层平均孔径30-80nm。
对照例、
制备基膜为18%聚砜的复合反渗透膜,具体步骤如下:
1)按比例配置含18%wt的聚砜树脂和溶剂N-甲基吡咯烷酮配成水溶液。在60℃下搅拌5小时,配制成均匀分散的铸膜液。铸膜液经过滤、脱气后,在刮膜机上均匀涂布于无纺布上,湿膜厚度为120μm,在室温下静置5s后,浸入25℃的去离子水中凝胶固化成膜,将膜在60℃烤箱中干燥得到基膜;
2)分别配置溶液A:溶质为1,4-二氨基环己烷,溶剂为正己烷,浓度6%wt;配置溶液B:溶质为苯三甲酰氯,溶剂为正己烷,浓度5%wt;
4)将步骤2)制得的支撑体层表面先浸渍溶液A中15s,然后在室温下静置5s,再浸渍溶液B中20s,后在室温下静置反应5min后,置于干燥箱中50℃中干燥2.5小时;
步骤5),配置含12%聚乙烯醇和6%N-甲基吡咯烷酮的水溶液,涂覆到步骤4)所制得的复合膜层表面,厚度为50μm,室温晾干,用去离子水冲洗三次,在60℃干燥箱中干燥4h,制得复合反渗透膜。
所制备的复合反渗透膜支撑层基膜厚度120μm、脱盐层40μm、抗污染层50μm,支撑层平均孔径40-100nm。
实施例4:测试实验
将实施例1-3和对比例所制得的复合反渗透膜在较高温度下进行反渗透操作实验,测试相应的渗透流率(GFD)、脱盐率(REJ)和水通量。
测试初始条件:原水含盐量(NaCL)1500PPM,原水温度25℃,操作压力150PSI
耐高温测试条件:原水含盐量(NaCL)1500PPM,原水温度40℃,操作压力150PSI
表1膜片的渗透流率(GFD)、脱盐率(REJ)和水通量
由上述测试结果可以明显看出,本发明实施例1-3的复合反渗透膜具有较好的耐高温性能,具有高通水量,稳定的脱盐率和渗透流率,在高温下反渗透膜的各个性能非常稳定并具有较长的使用寿命,而这都依赖于采用了提高性能的含氟聚芳醚酮、硅烷改性聚芳醚酮基膜材料以及掺杂了增强耐热性能和透水性能的氧化石墨烯成分。
以上所述,以上实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
Claims (11)
1.一种复合反渗透膜,包括支撑体层、功能膜层和抗污染层,其特征在于:支撑体层为氟聚芳醚酮和硅烷改性的聚芳醚酮的混合物,功能膜层为聚酰胺层;所述的抗污染层为改性聚乙烯醇层。
2.根据权利要求1所述的复合反渗透膜,其特征在于:所述含氟聚芳醚酮为三氟甲烷基聚芳醚酮或二氟甲烷基聚芳醚酮;所述硅烷改性的聚芳醚酮为三甲基硅烷、三乙基硅烷或三丙基硅烷改性的聚芳醚酮。
3.根据权利要求1所述的复合反渗透膜,其特征在于:所述氟聚芳醚酮和硅烷改性的聚芳醚酮的质量比例为1:3—3:1。
4.根据权利要求1-3任意一项所述的复合反渗透膜,其特征在于:所述的功能膜层中还掺杂有氧化石墨烯,氧化石墨烯掺杂量为该膜层质量含量的0.01-0.1%。
5.根据权利要求1-3任意一项所述的复合反渗透膜,其特征在于:所述支撑体层的厚度为10~100μm;所述聚酰胺层的厚度为50~500nm;改性聚乙烯层的厚度为10-100μm。
6.一种如权利要求1-5任一项所述的复合反渗透膜的制备方法:
1)将含氟聚芳醚酮、硅烷改性的聚芳醚酮和有机溶剂按一定比例配置成铸膜液,搅拌均匀,静置1-3h后超声脱气10-30min,作为支撑体铸膜液;
2)将步骤1)制得的铸膜液利用刮膜机涂抹到无纺布上,厚度为10-150μm,然后室温下蒸发5-30s后浸入15-25℃超纯水中凝胶固化成膜,然后在50-80℃烤箱中干燥4-8小时,制得支撑体层;
3)分别配置溶液A和溶液B中,所述溶液A的溶质为芳香胺和/或脂肪胺,溶剂为水,所述溶液B的溶质为芳香酰氯和/或脂肪酰氯,溶剂为有机溶剂;
4)将步骤2)制得的支撑体层表面先浸渍溶液A中5-30s,然后在室温下静置5-30s,再浸渍溶液B中5-30s,后在室温下静置反应1-10min后,置于干燥箱中40-60℃中干燥2-6小时;
5)将步骤4)所制得的复合膜层表面涂覆一层改性聚乙烯醇和离子液体的溶液,厚度为30-80μm,在40-80℃干燥箱中干燥2-6小时,制得复合反渗透膜;
其中所述步骤1)中含氟聚芳醚酮和硅烷改性的聚芳醚酮质量比例为1:3—3:1。
7.根据权利要求6所述的制备方法,其特征在于:所述含氟聚芳醚酮为三氟甲烷基聚芳醚酮或二氟甲烷基聚芳醚酮;所述硅烷改性的聚芳醚酮为三甲基硅烷、三乙基硅烷或三丙基硅烷改性的聚芳醚酮。
8.根据权利要求6所述的制备方法,其特征在于:所述溶剂A中也添加有氧化石墨烯,添加量为溶液A和B溶质总量的0.01-0.1%。
9.根据权利要求6-8任一一项所述的制备方法,其特征在于:所述芳香胺为对苯二胺、间苯二胺、均苯三胺、4,4’ -二氨基二苯醚,3,5-二氨基苯甲酸和1,2,4-三胺基苯中的至少一种,所述脂肪胺为乙二胺、丙二胺、丁二胺、戊二胺、三(2-氨乙基)胺、二乙烯三胺、N-(2-羟乙基)乙二胺、己二胺、1,3-二氨 基环己烷、1,2-二氨 基环己烷、1,4-二氨基环己烷、哌嗪、1,3-双哌啶基丙烷和4-氨基甲基哌嗪中的至少一种;
所述芳香酰氯为苯二甲酰氯、间苯二甲酰氯、邻苯二甲酰氯、联苯二甲酰氯、苯二磺酰氯、1,2,4-偏苯三酸酐酰氯,均苯三甲酰氯中的至少一种,所述脂肪酰氯为丁三酰氯、丁二酰氯、戊三酰氯、戊二酰氯、己三酰氯、己二酰氯、癸二酰氯、癸三酰氯、环丙烷三酰氯、环丁烷二酰氯、环丁烷四酰氯、环戊烷二酰氯、环戊烷三酰氯、环戊烷四酰氯、环己烷二酰氯、环己烷三酰氯、环己烷四酰氯、四氢呋喃二酰氯和四氢呋喃四酰氯中的至少一种。
10.根据权利要求6-8任一一项所述的制备方法,其特征在于:步骤1)中的有机溶剂为:三氯甲烷、二氯甲烷、二甲亚砜、DMF或者DMAc。
11.根据权利要求6-8任一一项所述的制备方法,其特征在于:步骤3)中所述有机溶剂为含有4~10个碳原子的脂肪烃、环脂烃和芳香烃中的一种或几种。
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