CN112121644B - 一种草酸交联海藻酸盐水凝胶过滤膜的制备方法及在分子离子分离中的应用 - Google Patents
一种草酸交联海藻酸盐水凝胶过滤膜的制备方法及在分子离子分离中的应用 Download PDFInfo
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- oxalic acid
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 193
- 239000012528 membrane Substances 0.000 title claims abstract description 68
- 235000006408 oxalic acid Nutrition 0.000 title claims abstract description 64
- 238000001914 filtration Methods 0.000 title claims abstract description 63
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229940072056 alginate Drugs 0.000 title claims abstract description 56
- 235000010443 alginic acid Nutrition 0.000 title claims abstract description 56
- 229920000615 alginic acid Polymers 0.000 title claims abstract description 56
- 239000000017 hydrogel Substances 0.000 title claims abstract description 52
- 238000000926 separation method Methods 0.000 title claims abstract description 29
- 150000001793 charged compounds Chemical class 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 35
- 238000004132 cross linking Methods 0.000 claims abstract description 31
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 238000005266 casting Methods 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 16
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 12
- 239000000661 sodium alginate Substances 0.000 claims abstract description 12
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 12
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 10
- 238000007790 scraping Methods 0.000 claims abstract description 8
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 10
- 235000002639 sodium chloride Nutrition 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 claims description 5
- 229930003779 Vitamin B12 Natural products 0.000 claims description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- AGVAZMGAQJOSFJ-WZHZPDAFSA-M cobalt(2+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+2].N#[C-].[N-]([C@@H]1[C@H](CC(N)=O)[C@@]2(C)CCC(=O)NC[C@@H](C)OP(O)(=O)O[C@H]3[C@H]([C@H](O[C@@H]3CO)N3C4=CC(C)=C(C)C=C4N=C3)O)\C2=C(C)/C([C@H](C\2(C)C)CCC(N)=O)=N/C/2=C\C([C@H]([C@@]/2(CC(N)=O)C)CCC(N)=O)=N\C\2=C(C)/C2=N[C@]1(C)[C@@](C)(CC(N)=O)[C@@H]2CCC(N)=O AGVAZMGAQJOSFJ-WZHZPDAFSA-M 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- 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 claims description 5
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
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- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- ULGZDMOVFRHVEP-RWJQBGPGSA-N Erythromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=O)[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 ULGZDMOVFRHVEP-RWJQBGPGSA-N 0.000 claims description 4
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- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 108091003079 Bovine Serum Albumin Proteins 0.000 claims description 2
- 102000016943 Muramidase Human genes 0.000 claims description 2
- 108010014251 Muramidase Proteins 0.000 claims description 2
- 108010062010 N-Acetylmuramoyl-L-alanine Amidase Proteins 0.000 claims description 2
- 229940098773 bovine serum albumin Drugs 0.000 claims description 2
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims description 2
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- 235000011147 magnesium chloride Nutrition 0.000 claims description 2
- ZDYUUBIMAGBMPY-UHFFFAOYSA-N oxalic acid;hydrate Chemical compound O.OC(=O)C(O)=O ZDYUUBIMAGBMPY-UHFFFAOYSA-N 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 235000010410 calcium alginate Nutrition 0.000 description 3
- 239000000648 calcium alginate Substances 0.000 description 3
- 229960002681 calcium alginate Drugs 0.000 description 3
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical class [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 3
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 3
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241000199919 Phaeophyceae Species 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 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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- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
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Abstract
本发明报道了一种草酸交联海藻酸盐水凝胶过滤膜的制备方法及在分子离子分离中的应用。首先配制海藻酸钠和高分子增强剂的混合物水溶液作为铸膜液，将铸膜液刮成膜后用草酸水溶液交联。草酸同时交联高分子增强剂上的羟基和海藻酸盐上的羟基，得到草酸交联海藻酸盐水凝胶过滤膜。该过滤膜具有良好的亲水性和抗污染性能，可耐受高浓度无机盐溶液。该过滤膜对于无机盐的截留率低，而对分子量大于650的体型分子具有较高的截留率，因此特别适合用于分子离子的分离，在染料、多肽、药物和蛋白质等分离纯化中有广泛应用前景。
Description
技术领域
本发明涉及一种草酸交联海藻酸盐水凝胶过滤膜的制备方法及在分子离子分离中的应用，属于功能材料和膜分离领域。
本发明涉及过滤膜、水凝胶、分子离子分离等技术领域。具体涉及一种草酸交联海藻酸盐水凝胶过滤膜的制备方法及在分子离子分离中的应用。
背景技术
目前，我国每年生产大约7×105吨染料，种类繁多，并在纺织，塑料，橡胶和皮革工业得到了广泛的应用。然而，在染料的合成过程当中，由于无机盐的存在，染料的稳定性及纯度会受到很严重的影响，除此之外，氯化钠，硫酸钠等无机盐常用来提高上染率。纺织品染色过程中产生的高盐废水不仅严重危害水体环境及人类健康，而且浪费了大量的资源。因此，对染料废水的脱盐处理迫在眉睫。
膜分离技术可以对小分子、无机盐以及水进行有效分离，提高染料的浓度，相对于传统的盐析压滤工艺减少了废水排放，缩短了工艺过程，降低产品的含盐量，在经济方面还可以降低生产成本，提高经济效益。水凝胶是以水为分散介质的凝胶，可以保持一定的形状，能吸收大量的水。海藻酸钠是一种可从海带或褐藻中提取的天然高分子物质，不仅来源广泛，而且价格低廉，目前已经广泛应用于食品、生物医药和废水处理等领域。海藻酸钠与钙离子可通过离子交联形成水凝胶。赵孔银等制备了一系列的海藻酸钙基水凝胶过滤膜【发明专利ZL201310424398.7，ZL201310424399.1，ZL201310424397.2】，这些海藻酸钙基过滤膜具有良好的抗污染性能，但存在力学性能差、机械强度低且易被细菌降解的缺点。
Pérez-Madrigal Maria M等人以海藻酸钠和草酸为载体制备出的膜具有更好的弹性，而且具有良好的协同抗癌药物载体的潜力。草酸基凝胶的内聚性是多种离子缔合物共存的结果，这些离子缔合物包括草酸、海藻酸钠和钠离子，这些离子缔合物稳定了体系，并使所有相互作用的物种保持在一起。Subbaiah Muthu Prabhu等人以草酸、丙二酸和琥珀酸为介质制备海藻酸锆络合物，对水溶液中氟的去除进行了研究。合成了海藻酸-草酸-锆(Alg-Ox-Zr)、海藻酸-丙二酸-锆和海藻酸-琥珀酸-锆配合物，并对其除氟性能进行了研究。用FTIR、XRD、SEM、EDAX和mapping图像对合成的配合物进行了表征。优化了各种操作参数的影响。结果表明，在酸性pH条件下，Alg-Ox-Zr络合物对氟化物的最大去除率为9653mgF-/kg。Alg-Ox-Zr配合物的平衡数据与Freundlich等温线吻合较好。热力学参数的计算值表明，氟的吸附是自发的、吸热的。详细分析了Alg-Ox-Zr复合物的除氟机理。Alg-Ox-Zr复合物的适用性已通过在附近氟化物流行区采集的现场样本进行了测试。
本发明报道了一种草酸交联海藻酸盐水凝胶过滤膜的制备方法及在分子离子分离中的应用。首先配制海藻酸钠和高分子增强剂的混合物水溶液作为铸膜液，将铸膜液刮成膜后用草酸水溶液交联。草酸同时交联高分子增强剂上的羟基和海藻酸盐上的羟基，得到草酸交联海藻酸盐水凝胶过滤膜。该过滤膜具有良好的亲水性和抗污染性能，可耐受高浓度无机盐溶液。该过滤膜对于无机盐的截留率低，而对分子量大于650的体型分子具有较高的截留率，因此特别适合用于分子离子的分离，在染料、多肽、药物和蛋白质等分离纯化中有广泛应用前景。
发明内容
针对现有技术的不足，本发明拟解决的技术问题是传统膜不耐污染、亲水性差、海藻酸钙水凝胶过滤膜易溶胀、在高浓度无机盐中不稳定等问题。
本发明解决所述传统膜不耐污染、亲水性差、海藻酸钙水凝胶过滤膜易溶胀、在高浓度无机盐中不稳定等问题的技术方案是提供一种草酸交联海藻酸盐水凝胶过滤膜的制备方法及在分子离子分离中的应用。
本发明提供了一种草酸交联海藻酸盐水凝胶过滤膜的制备方法及在分子离子分离中的应用，其特征是包括以下步骤：
a)配制质量百分比浓度1％-5％的海藻酸钠和0.5％-3.5％的高分子增强剂的混合物水溶液，静置脱泡得到铸膜液；
b)配制质量百分比浓度1％-10％的草酸水溶液，作为交联溶液；
c)将步骤a)得到的铸膜液倒在干燥清洁的玻璃板上，用两端缠绕直径为20-1500μm铜丝的玻璃棒刮平，然后立即将玻璃板和刮好的膜浸泡入步骤b)得到的交联溶液中交联5-600min，草酸同时交联高分子增强剂上的羟基和海藻酸盐上的羟基，起到增强海藻酸盐水凝胶的作用，随后用去离子水充分洗涤膜去除残余的草酸，得到草酸交联海藻酸盐水凝胶过滤膜，在去离子水中保存；
d)配制质量百分比浓度4％-80％的无机盐和质量百分比浓度0.1％-10％的体型分子的混合水溶液作为料液，采用错流过滤的方式，用步骤c)得到的草酸交联海藻酸盐水凝胶过滤膜对料液进行过滤；草酸交联海藻酸盐水凝胶过滤膜可允许无机盐的离子通过，而不允许分子量大于650的体型分子通过，因此对于分子量大于650的体型分子和无机盐具有良好的分离效果，分离系数达到90-310。
本发明所述的体型分子为亮蓝、甲基蓝、直接黑、刚果红、溶菌酶、牛血清白蛋白、维生素B12、红霉素中的任意一种；所述的高分子增强剂为羧甲基壳聚糖、羧甲基纤维素、聚乙烯醇、水溶性淀粉中的任意一种或两种及以上混合物；所述的无机盐为氯化钠、氯化钾、氯化镁、硫酸钠、硫酸铵、硫酸钾、硝酸镁、硝酸钾中的任意一种或两种及以上混合物。
在本发明中，该过滤膜对于无机盐的截留率低，而对分子量大于650的体型分子具有较高的截留率，对于高浓度无机盐溶液有很好的耐受性，特别适合用于分子离子的分离，具有良好的亲水性和抗污染性能，在染料、多肽、药物和蛋白质等分离纯化中有广泛应用前景。
具体实施方式
下面介绍本发明的具体实施例，但本发明不受实施例的限制。
实施例1.
a)配制质量百分比浓度1％的海藻酸钠和0.5％的羧甲基壳聚糖的混合物水溶液，静置脱泡得到铸膜液；
b)配制质量百分比浓度1％的草酸水溶液，作为交联溶液；
c)将步骤a)得到的铸膜液倒在干燥清洁的玻璃板上，用两端缠绕直径为20μm铜丝的玻璃棒刮平，然后立即将玻璃板和刮好的膜浸泡入步骤b)得到的交联溶液中交联5min，草酸同时交联羧甲基壳聚糖上的羟基和海藻酸盐上的羟基，起到增强海藻酸盐水凝胶的作用，随后用去离子水充分洗涤膜去除残余的草酸，得到草酸交联海藻酸盐水凝胶过滤膜，在去离子水中保存；
d)配制质量百分比浓度4％的氯化钠和质量百分比浓度0.1％的亮蓝的混合水溶液作为料液，采用错流过滤的方式，用步骤c)得到的草酸交联海藻酸盐水凝胶过滤膜对料液进行过滤；草酸交联海藻酸盐水凝胶过滤膜可允许氯化钠的离子通过，而不允许分子量大于650的亮蓝通过，因此对于分子量大于650的亮蓝和氯化钠具有良好的分离效果，分离系数达到90。
实施例2.
a)配制质量百分比浓度5％的海藻酸钠和3.5％的羧甲基纤维素的混合物水溶液，静置脱泡得到铸膜液；
b)配制质量百分比浓度10％的草酸水溶液，作为交联溶液；
c)将步骤a)得到的铸膜液倒在干燥清洁的玻璃板上，用两端缠绕直径为1500μm铜丝的玻璃棒刮平，然后立即将玻璃板和刮好的膜浸泡入步骤b)得到的交联溶液中交联600min，草酸同时交联羧甲基纤维素上的羟基和海藻酸盐上的羟基，起到增强海藻酸盐水凝胶的作用，随后用去离子水充分洗涤膜去除残余的草酸，得到草酸交联海藻酸盐水凝胶过滤膜，在去离子水中保存；
d)配制质量百分比浓度80％的氯化钾和质量百分比浓度10％的甲基蓝的混合水溶液作为料液，采用错流过滤的方式，用步骤c)得到的草酸交联海藻酸盐水凝胶过滤膜对料液进行过滤；草酸交联海藻酸盐水凝胶过滤膜可允许氯化钾的离子通过，而不允许分子量大于650的甲基蓝通过，因此对于分子量大于650的甲基蓝和氯化钾具有良好的分离效果，分离系数达到310。
实施例3.
a)配制质量百分比浓度4％的海藻酸钠和2.5％的聚乙烯醇的混合物水溶液，静置脱泡得到铸膜液；
b)配制质量百分比浓度8％的草酸水溶液，作为交联溶液；
c)将步骤a)得到的铸膜液倒在干燥清洁的玻璃板上，用两端缠绕直径为1200μm铜丝的玻璃棒刮平，然后立即将玻璃板和刮好的膜浸泡入步骤b)得到的交联溶液中交联400min，草酸同时交联聚乙烯醇上的羟基和海藻酸盐上的羟基，起到增强海藻酸盐水凝胶的作用，随后用去离子水充分洗涤膜去除残余的草酸，得到草酸交联海藻酸盐水凝胶过滤膜，在去离子水中保存；
d)配制质量百分比浓度60％的氯化镁和质量百分比浓度8％的直接黑的混合水溶液作为料液，采用错流过滤的方式，用步骤c)得到的草酸交联海藻酸盐水凝胶过滤膜对料液进行过滤；草酸交联海藻酸盐水凝胶过滤膜可允许氯化镁的离子通过，而不允许分子量大于650的直接黑通过，因此对于分子量大于650的直接黑和氯化镁具有良好的分离效果，分离系数达到220。
实施例4.
a)配制质量百分比浓度2％的海藻酸钠和1.5％的水溶性淀粉的混合物水溶液，静置脱泡得到铸膜液；
b)配制质量百分比浓度4％的草酸水溶液，作为交联溶液；
c)将步骤a)得到的铸膜液倒在干燥清洁的玻璃板上，用两端缠绕直径为800μm铜丝的玻璃棒刮平，然后立即将玻璃板和刮好的膜浸泡入步骤b)得到的交联溶液中交联200min，草酸同时交联水溶性淀粉上的羟基和海藻酸盐上的羟基，起到增强海藻酸盐水凝胶的作用，随后用去离子水充分洗涤膜去除残余的草酸，得到草酸交联海藻酸盐水凝胶过滤膜，在去离子水中保存；
d)配制质量百分比浓度40％的硫酸铵和质量百分比浓度4％的维生素B12的混合水溶液作为料液，采用错流过滤的方式，用步骤c)得到的草酸交联海藻酸盐水凝胶过滤膜对料液进行过滤；草酸交联海藻酸盐水凝胶过滤膜可允许硫酸铵的离子通过，而不允许分子量大于650的维生素B12通过，因此对于分子量大于650的维生素B12和硫酸铵具有良好的分离效果，分离系数达到180。
Claims (3)
1.一种草酸交联海藻酸盐水凝胶过滤膜在分子离子分离中的应用，其特征是草酸交联海藻酸盐水凝胶过滤膜的制备方法包括以下步骤：
a)配制质量百分比浓度1％-5％的海藻酸钠和0.5％-3.5％的高分子增强剂的混合物水溶液，静置脱泡得到铸膜液，所述的高分子增强剂为羧甲基纤维素、聚乙烯醇、水溶性淀粉中的任意一种或两种及以上混合物；
b)配制质量百分比浓度1％-10％的草酸水溶液，作为交联溶液；
c)将步骤a)得到的铸膜液倒在干燥清洁的玻璃板上，用两端缠绕直径为20-1500μm铜丝的玻璃棒刮平，然后立即将玻璃板和刮好的膜浸泡入步骤b)得到的交联溶液中交联5-600min，草酸同时交联高分子增强剂上的羟基和海藻酸盐上的羟基，起到增强海藻酸盐水凝胶的作用，随后用去离子水充分洗涤膜去除残余的草酸，得到草酸交联海藻酸盐水凝胶过滤膜，在去离子水中保存；
d)配制质量百分比浓度40％-80％的无机盐和质量百分比浓度4％-10％的体型分子的混合水溶液作为料液，采用错流过滤的方式，用步骤c)得到的草酸交联海藻酸盐水凝胶过滤膜对料液进行过滤；草酸交联海藻酸盐水凝胶过滤膜允许无机盐的离子通过，而不允许分子量大于650的体型分子通过，因此对于分子量大于650的体型分子和无机盐具有良好的分离效果，分离系数达到180-310。
2.如权利要求1所述的一种草酸交联海藻酸盐水凝胶过滤膜在分子离子分离中的应用，其特征是所述的体型分子为亮蓝、甲基蓝、直接黑、刚果红、溶菌酶、牛血清白蛋白、维生素B12、红霉素中的任意一种。
3.如权利要求1所述的一种草酸交联海藻酸盐水凝胶过滤膜在分子离子分离中的应用，其特征是所述的无机盐为氯化钠、氯化钾、氯化镁、硫酸钠、硫酸铵、硫酸钾、硝酸镁、硝酸钾中的任意一种或两种及以上混合物。
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