CN117018867A - 一种多巴胺原位生长zif-8的染料/盐分离疏松纳滤膜及其制备方法 - Google Patents
一种多巴胺原位生长zif-8的染料/盐分离疏松纳滤膜及其制备方法 Download PDFInfo
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- CN117018867A CN117018867A CN202311136676.9A CN202311136676A CN117018867A CN 117018867 A CN117018867 A CN 117018867A CN 202311136676 A CN202311136676 A CN 202311136676A CN 117018867 A CN117018867 A CN 117018867A
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- 239000012528 membrane Substances 0.000 title claims abstract description 64
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 30
- 238000000926 separation method Methods 0.000 title claims abstract description 30
- 229960003638 dopamine Drugs 0.000 title claims abstract description 27
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 title claims abstract description 26
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 24
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- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000007983 Tris buffer Substances 0.000 claims abstract description 26
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
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- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 5
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 26
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000002346 layers by function Substances 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- DEPDDPLQZYCHOH-UHFFFAOYSA-N 1h-imidazol-2-amine Chemical compound NC1=NC=CN1 DEPDDPLQZYCHOH-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
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- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 claims description 2
- JWYUFVNJZUSCSM-UHFFFAOYSA-N 2-aminobenzimidazole Chemical compound C1=CC=C2NC(N)=NC2=C1 JWYUFVNJZUSCSM-UHFFFAOYSA-N 0.000 claims description 2
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 claims description 2
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- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
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- 238000011161 development Methods 0.000 abstract description 3
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 abstract description 3
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 2
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- 239000012621 metal-organic framework Substances 0.000 description 5
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 5
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 4
- 238000010612 desalination reaction Methods 0.000 description 4
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- 239000011734 sodium Substances 0.000 description 4
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- 238000004132 cross linking Methods 0.000 description 3
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- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 2
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- WCSMZAHKVXOYLH-UHFFFAOYSA-N 6-fluoro-1h-quinazolin-4-one Chemical compound N1C=NC(=O)C2=CC(F)=CC=C21 WCSMZAHKVXOYLH-UHFFFAOYSA-N 0.000 description 1
- 208000029422 Hypernatremia Diseases 0.000 description 1
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- GMMSTIGHDDLCMI-UHFFFAOYSA-N zinc;imidazol-3-ide Chemical compound [Zn+2].C1=C[N-]C=N1.C1=C[N-]C=N1 GMMSTIGHDDLCMI-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/60—Polyamines
- B01D71/601—Polyethylenimine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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Abstract
本发明公开了一种多巴胺原位生长ZIF‑8的染料/盐分离疏松纳滤膜及其制备方法,包括:将三羟甲基氨基甲烷用醇水混合溶液作为溶剂配制成Tris缓冲溶液;将多巴胺、聚乙烯亚胺、金属离子化合物加入到缓冲溶液中配制成前驱体溶液;将前驱体溶液加入到聚砜膜表面沉积;将2‑甲基咪做加入到醇水混合溶液中溶解后并加入到聚砜膜表面沉积;将多余的溶液倒掉,将膜烘干后放入去离子水中保存,得到滤膜。本发明制备的纳滤膜可以截留染料而二价无机盐几乎完全通过,能够充分分离刚果红、甲基蓝与硫酸钠的混合溶液。同时,本发明操作简单,并且可推广到多种材质的基底上使用,具有巨大的应用价值和发展前景。
Description
技术领域
本发明涉及滤膜领域,具体涉及一种多巴胺原位生长ZIF-8的染料/盐分离疏松纳滤膜及其制备方法。
背景技术
近年来,我国印染行业发展迅速,在其工业生产的过程中,通常会添加无机盐(如NaCl、Na2SO4)来降低纤维表面的电荷,以此增强染料与织物上的结合力。但由此产生的高盐度染料废水,如果处理不当,会严重破坏生态系统平衡,危害人类健康。随着我国相关环保政策日益严格,可持续发展的理念逐渐深入人心,对高盐染料废水进行处理也不仅仅停留在去除的层面上。将“废物”进行有效的分离,将废水中的染料和盐转化为可循环利用的资源,是目前废水处理领域的研究重点。由于无机盐的加入,使得絮凝、氧化、吸附、降解等常规的处理方法运用起来更加困难,膜分离技术因其具有低能耗、高效、操作简单等优点在分离领域得到广泛的应用。对于染料脱盐而言,超滤虽然具有较大的通量,但是染料和盐的截留率均较低且选择性差。纳滤作为膜技术中的一种,可以在低压力下有效分离溶液中的小分子物质,对于低分子量有机物去除率比超滤高,渗透性比反渗透高而得到广泛的应用。然而,为了获得高截留性能,传统的纳滤膜被设计成致密的选择层,这将导致染料与盐截留率虽高,但两者的选择性依旧不理想。因此,开发出适用于染料/盐分离领域的具有高选择性、高通量的疏松纳滤膜具有重要的实际意义。
金属-有机框架(Metal-Organic Frameworks),简称MOFs,是由有机配体和金属离子或团簇通过配位键自组装形成的具有分子内孔隙的有机-无机杂化材料。沸石咪唑酯骨架材料(Zinc Imidazole Frameworks)ZIFs作为MOF材料中的一种,具有比表面积大、高孔隙率、孔径可调等特点,广泛应用于气体吸附、分离、催化、药物传递等领域。目前,越来越多的研究人员通过将ZIFs材料与高分子膜材料相结合来制备高性能膜材料,基于ZIFs的高孔隙率,创建额外的渗透水通道,希望打破截留与渗透通量之间的权衡效应。然而,由于MOF材料在膜表面易团聚、与基底相互作用力弱,存在运行过程中易脱落等特点,会影响膜的选择性能与稳定性。因此,开发出高选择性、高稳定性的MOF高性能膜材料面临着重大挑战。
发明内容
针对以上问题,本发明提供了一种多巴胺原位生长ZIF-8的染料/盐分离疏松纳滤膜及其制备方法,通过多巴胺聚乙烯亚胺共价交联锚定原位生长的ZIF-8制备用于染料脱盐的疏松纳滤膜。通过此方法,ZIF-8颗粒在膜表面原位形成,通过多巴胺(PDA)的自聚和其与聚乙烯亚胺(PEI)分子之间的席夫碱、迈克尔加成反应,以及PEI与锌离子络合反应,将ZIF-8粒子均匀分散且锚定在聚砜超滤膜表面,通过ZIFs粒子之间的堆叠形成纳米孔道,制备出的染料脱盐膜具有较高的染料通量与截留、优异的稳定性、较高的分离比、工艺简单等特点。
一种多巴胺原位生长ZIF-8的染料/盐分离疏松纳滤膜及其制备方法,疏松纳滤膜分为聚合物支撑层和功能层,其中聚砜为聚合物支撑层,多巴胺(PDA)、聚乙烯亚胺(PEI)、锌离子共沉积后原位生长ZIFs的PDA-PEI-ZIFs为功能层;
所述聚合物支撑层为由聚酯、聚烯烃、聚四氟乙烯、聚偏二氟乙烯、尼龙、聚砜、聚醚砜、聚丙烯腈等聚合物中的一种或多种组成的纤维无纺布或纺织材料组成,其厚度为30-300微米;
所述的聚合物支撑层,包括平板膜、中空纤维均质膜、或中空复合膜与管式膜;
所述PDA-PEI-ZIFs功能层由多巴胺、聚乙烯亚胺、锌离子交联后再加入咪唑原位生长ZIFs纳米粒子,制备的功能层通过原位生长的ZIFs纳米粒子的堆积形成纳米级孔道,该膜表面均匀,具有高孔隙率;
一种多巴胺原位生长ZIF-8的染料/盐分离疏松纳滤膜及其制备方法包括以下步骤;
1)将三羟甲基氨基甲烷(Tris)用体积分数为0.1-50%v/v(优选10-30%v/v)的醇/水混合溶液溶解后,再用0.1mol/L的HCl调节Tris溶液pH至8.5后均分为两份备用,分别记为Tris缓冲液A和B;
2)前驱体溶液分别由PDA、PEI、金属离子化合物加入到A溶液中组成;
3)将支撑层用方形板框固定在底板上,将步骤2)中的前驱体溶液加入到板框压在底板上的支撑层上静置沉积一段时间;
4)以B溶液为溶剂,取咪唑类配体配成溶液,并将其加入到上述板框内的前驱体溶液中,在一定温度下沉积反应一段时间;
5)倒出板框内溶液后放入烘箱干燥一定时间后放入去离子水中保存。
步骤1)中所用醇/水溶液包含甲醇水溶液、乙醇水溶液、丙醇水溶液、丁醇水溶液、乙二醇水溶液、丙三醇、异丙醇水溶液的一种或多种;
步骤1)中醇水溶液的体积分数为0.1~50%v/v;
步骤2)中PDA的质量体积比为0.01~2%wt/v;
步骤2)中PEI的质量体积比为0.01~2%wt/v;
步骤2)中金属离子化合物的质量体积比为0.01~3%wt/v;
步骤2)中金属离子化合物包括硝酸锌、氯化锌、硫酸锌、醋酸锌、硝酸钴、氧化钴、醋酸钴等中的一种或多种;
步骤3)中静置沉积时间为0.01~6小时;
步骤4)中咪唑类配体包含2-甲基咪唑、苯并咪唑、2-氨基苯并咪唑、2-氨基咪唑、咪唑-2-甲醛、2-乙基咪唑等其他含有咪唑类的化合物的一种或或者多种;
步骤4)中咪唑类配体的质量体积比为0.01-10%wt/v;反应温度为2~90℃,反应时间0.1~24小时;
步骤5)中干燥时间为0.01~2小时。
进一步,本发明的技术方案按照以下步骤进行:
(1)将三羟甲基氨基甲烷(Tris)用体积分数为0.1-50%v/v(优选10-30%v/v)的醇/水混合溶液溶解后,再用0.1mol/L的HCl调节Tris溶液pH至8.5后均分为两份备用,分别记为Tris缓冲液A和B;
(2)前驱体溶液分别由PDA、PEI、金属离子化合物先后加入到A溶液中组成;
其中PDA的质量体积比为0.01-2%wt/v(优选0.1-1%wt/v),PEI质量体积比为0.01-2%wt/v(优选0.3-0.9%wt/v),金属离子类化合物质量体积比为0.01-3%wt/v的溶液;
(3)以聚砜超滤膜为支撑层,将其用方形板框固定在底板上,将上述混合溶液覆盖在膜表面沉积0.01-6小时(优选2-4小时);
(4)取Tris缓冲液B,将2-甲基咪唑配制质量体积比为0.01-10wt/v的溶液,并将其加入到上述板框内的溶液中,并充分反应0.01-24小时(优选4-10小时);
(5)倒出板框内上清液,将膜放入烘箱中20-90℃(优选30-60℃)条件下烘干0.01-2小时(优选10-30分钟)后放入去离子水中保存;
所述醇水混合溶液为甲醇水溶液、乙醇水溶液、丙醇水溶液、丁醇水溶液、乙二醇水溶液、丙三醇、异丙醇水溶液中的一种(优选甲醇水溶液);
所述金属离子化合物为硝酸锌、氯化锌、醋酸锌、氧化锌、硫化锌、硝酸钴、氧化钴、醋酸钴中的一种(优选六水合硝酸锌);
所述疏松纳滤膜膜表面的ZIF纳米粒子均匀覆盖在支撑层上,所述的疏松纳滤膜具有均匀平整的膜表面,分为功能分离层和支撑层。保存方式为浸泡于去离子水中;
本发明的技术优势在于:
1)过程简单,操作简洁,合成方法与制备条件容易;
2)通过使用醇水混合溶液作为溶剂,可以降低前驱体溶液与基膜之间的表面张力,在一定程度上解决了纳米粒子不易沉积、沉积不均匀等问题,使膜更平整;
3)涂层具有优异的化学稳定性,为基膜与纳米粒子之间起到良好的锚定作用;
4)ZIFs粒子堆积而产生的纳米级孔道有利于同时获得优异的分离性能和选择性。
附图说明
图1是实施例13的平面扫描电镜图;
图2是实施例13的断面扫描电镜图;
图3是对比例1的平面扫描电镜图;
图4是对比例1、对比例2、实施例3、实施例7、实施例11、实施例15的红外光谱图;
图5是该疏松纳滤膜的制作流程图。
具体实施方式
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此。
实施例中所有纳滤膜的制备环境为:30℃,湿度为40-45%,常压。
实施例中所使用的聚砜超滤膜支撑层购自杭州水处理中心。
对比例1:
未经改性的商用聚砜超滤膜支撑层(杭州水处理中心)
对比例2:
将Tris用体积分数为10%v/v%的甲醇水混合溶液溶解后,再用0.1mol/L的HCl调节Tris溶液pH至8.5后备用,均分为两份,分别记为溶液A与溶液B;
取0.15g PDA溶解于A溶液中后记为溶液C,取0.3g PEI加入上述溶液C;
以聚砜超滤膜为支撑层,将其用方形板框固定在底板上,将上述溶液加入到板框压在底板上的支撑层上沉积2小时后,再倒入溶液B沉积反应10小时;
沉积完成后倒出板框内溶液后放入烘箱60℃干燥20min后放入去离子水中保存,制得无ZIF的PDA-PEI膜。
对比例3:
商业纳滤膜NF-270(陶氏纳滤膜)
实施例1:
制备覆盖有PDA-PEI锚定的ZIF-8染料/盐分离疏松纳滤膜材料,具体步骤如下:
将Tris用体积分数为10%v/v的甲醇水混合溶液溶解后,再用0.1mol/L的HCl调节Tris溶液pH至8.5后备用,均分为两份,分别记为溶液A与溶液B;
取0.15g PDA溶解于A溶液中后记为溶液C,再取0.15g PEI加入上述溶液C,记为溶液D;
取0.475g六水合硝酸锌溶解在上述D溶液中后记为溶液E;
溶液E中多巴胺的质量体积比为0.3%wt/v;
溶液E中聚乙烯亚胺的质量体积比为0.3%wt/v;
溶液E中金属离子化合物的质量体积比为0.95%wt/v。
以聚砜超滤膜(杭州水处理中心)为支撑层,将其用方形板框固定在底板上,将上述E溶液加入到板框压在底板上的支撑层上沉积2小时;
以B溶液为溶剂,取1.97g 2-甲基咪唑配制成溶液命名为溶液F,并将其加入到上述板框内的E溶液中,30℃充分沉积反应10小时;
溶液F中2-甲基咪唑配的质量体积比为3.94%wt/v。
沉积完成后倒出板框内溶液后干燥20min后放入去离子水中保存。
实施例2-6
实施例2-6与实施例1的方法相同,不同之处为Tris缓冲溶液的配置。将Tris用体积分数分别为5v/v%、10v/v%、15v/v%、20v/v%、30v/v%的甲醇水混合溶液溶解后,再用0.1mol/L的HCl调节Tris溶液pH至8.5后备用。
实施例7-10
实施例7-10与实施例1的方法相同,不同之处为加入的PEI质量分别为0.3g、0.45g、0.6g、1.0g,通过改变PEI的加入量调控其与PDA的交联程度以及与锌离子的络合反应,以此调控膜的性能。
实施例11-13
实施例11-13与实施例1的方法相同,不同之处为PDA的加入量为0.3g、0.45g、0.6g,PEI的加入量为0.3g,通过改变PDA的加入量影响其与PEI的加成反应以及自聚,以此调控膜的性能。
实施例14-15
实施例14-15与实施例1的方法相同,不同之处为PEI的加入量为0.3g,加入的六水合硝酸锌的质量分别为0.2375g、0.7125g,相对应加入的二甲基咪唑的质量分别为0.985g、2.955g。在保持六水合硝酸锌和二甲基咪唑两者摩尔比为1:15的条件下,改变锌离子的加入量,控制ZIF-8在膜上的负载量,以此调控膜性能。
如图1所示,表明膜表面的ZIF-8粒子形貌为十字针状型,且可以看到粒子间的堆积所形成的孔隙。
如图2所示,表明ZIF-8粒子在膜表面形成了堆积层。
如图3所示,表明未经改性的超滤膜表面光滑且有明显孔隙。
如图4所示,实施例7、11、15中出现1640cm-1,996cm-1,430cm-1为ZIF-8粒子的特征峰,可证明ZIFs粒子已经成功引入到膜表面。
测试例:
将实施例3,7,13,对比例1、2制备的染料脱盐疏松纳滤膜通过错流过滤装置在常温、压力为2bar的条件下进行测试,测试结果如表1所示。表中的R(Na2SO4)、R(CR)、R(MB)分别为硫酸钠、刚果红、甲基蓝的截留率,PWP、S(Na2SO4/CR)、S(Na2SO4/MB)分别为纯水通量、硫酸钠与刚果红渗透分离比、硫酸钠与甲基蓝渗透分离比。其中,s渗透分离比。
表1
从上述表格数据可以看出,添加了ZIF-8纳米粒子与未添加时相比,在对染料保持高截留、对硫酸钠保持低截留的同时,通量有较大幅度的提升,性能优异,可以适用于染料/盐分离的体系中。
各位技术人员须知:虽然本发明已按照上述具体实施方式做了描述,但是本发明的发明思想并不仅限于此发明,任何运用本发明思想的改装,都将纳入本发明保护范围内。
Claims (10)
1.一种多巴胺原位生长ZIF-8的染料/盐分离疏松纳滤膜,其特征在于,包括聚合物支撑层以及设置在所述聚合物支撑层上的PDA-PEI-ZIFs功能层,所述PDA-PEI-ZIFs功能层为多巴胺、聚乙烯亚胺、锌离子共沉积后原位生长ZIFs的功能层。
2.根据权利要求1所述的多巴胺原位生长ZIF-8的染料/盐分离疏松纳滤膜,其特征在于,所述的聚合物支撑层为由聚酯、聚烯烃、聚四氟乙烯、聚偏二氟乙烯、尼龙、聚砜、聚醚砜、聚丙烯腈中的一种或多种组成的纤维无纺布或纺织材料,所述的聚合物支撑层的厚度为30-300微米。
3.根据权利要求1所述的多巴胺原位生长ZIF-8的染料/盐分离疏松纳滤膜的制备方法,其特征在于,包括以下步骤;
1)将三羟甲基氨基甲烷用体积分数为0.1-50%的醇/水混合溶液溶解后,再用HCl调节溶液pH至8~9后分为两份,分别记为Tris缓冲液A和Tris缓冲液B;
2)前驱体溶液由多巴胺、聚乙烯亚胺、金属离子化合物加入到Tris缓冲液A中制成;
3)将聚合物支撑层用方形板框固定在底板上,将步骤2)中的前驱体溶液加入到板框压在底板上的聚合物支撑层上静置沉积;
4)取咪唑类配体以Tris缓冲液B为溶剂配成混合溶液,并将混合溶液加入到板框内步骤3)静置沉积后的前驱体溶液上,沉积反应,经后处理得到多巴胺原位生长ZIF-8的染料/盐分离疏松纳滤膜。
4.根据权利要求3所述的多巴胺原位生长ZIF-8的染料/盐分离疏松纳滤膜的制备方法,其特征在于,步骤2)中,所述的金属离子化合物为硝酸锌、氯化锌、硫酸锌、醋酸锌、硝酸钴、氧化钴、醋酸钴中的一种或多种。
5.根据权利要求3所述的多巴胺原位生长ZIF-8的染料/盐分离疏松纳滤膜的制备方法,其特征在于,步骤2)中,所述的前驱体溶液中多巴胺的质量体积比为0.01~2%wt/v;
所述的前驱体溶液中聚乙烯亚胺的质量体积比为0.01~2%wt/v;
所述的前驱体溶液中金属离子化合物的质量体积比为0.01~3%wt/v。
6.根据权利要求3所述的多巴胺原位生长ZIF-8的染料/盐分离疏松纳滤膜的制备方法,其特征在于,步骤3)中,静置沉积的时间为0.01~6小时。
7.根据权利要求3所述的多巴胺原位生长ZIF-8的染料/盐分离疏松纳滤膜的制备方法,其特征在于,步骤4)中,所述的咪唑类配体为2-甲基咪唑、苯并咪唑、2-氨基苯并咪唑、2-氨基咪唑、咪唑-2-甲醛、2-乙基咪唑中的一种或或者多种。
8.根据权利要求3所述的多巴胺原位生长ZIF-8的染料/盐分离疏松纳滤膜的制备方法,其特征在于,步骤4)中,所述的混合溶液中咪唑类配体的质量体积比为0.01-10%wt/v。
9.根据权利要求3所述的多巴胺原位生长ZIF-8的染料/盐分离疏松纳滤膜的制备方法,其特征在于,步骤4)中,沉积反应的条件为:反应温度2~90℃,反应时间0.1~24小时。
10.根据权利要求3所述的多巴胺原位生长ZIF-8的染料/盐分离疏松纳滤膜的制备方法,其特征在于,步骤4)中,所述的后处理包括:沉积反应后倒出板框内溶液,之后放入烘箱干燥,最后放入去离子水中保存。
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