CN103524965B - 一种具有吸附催化双功能水凝胶的制备方法 - Google Patents
一种具有吸附催化双功能水凝胶的制备方法 Download PDFInfo
- Publication number
- CN103524965B CN103524965B CN201210226921.0A CN201210226921A CN103524965B CN 103524965 B CN103524965 B CN 103524965B CN 201210226921 A CN201210226921 A CN 201210226921A CN 103524965 B CN103524965 B CN 103524965B
- Authority
- CN
- China
- Prior art keywords
- hydrogel
- preparation
- support type
- initator
- crosslinking agent
- 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.)
- Expired - Fee Related
Links
- 239000000017 hydrogel Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 239000010970 precious metal Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 239000001263 FEMA 3042 Substances 0.000 claims description 4
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 150000004676 glycans Chemical class 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229920001282 polysaccharide Polymers 0.000 claims description 4
- 239000005017 polysaccharide Substances 0.000 claims description 4
- 229920002258 tannic acid Polymers 0.000 claims description 4
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 4
- 229940033123 tannic acid Drugs 0.000 claims description 4
- 235000015523 tannic acid Nutrition 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229940037003 alum Drugs 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 229960000892 attapulgite Drugs 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052625 palygorskite Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 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 description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- 241000206575 Chondrus crispus Species 0.000 claims description 2
- 229920002907 Guar gum Polymers 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 2
- 235000003421 Plantago ovata Nutrition 0.000 claims description 2
- 244000134552 Plantago ovata Species 0.000 claims description 2
- 239000009223 Psyllium Substances 0.000 claims description 2
- 239000004113 Sepiolite Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 239000000499 gel Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 239000000665 guar gum Substances 0.000 claims description 2
- 235000010417 guar gum Nutrition 0.000 claims description 2
- 229960002154 guar gum Drugs 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 2
- 229910052900 illite Inorganic materials 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 2
- 229940070687 psyllium Drugs 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- -1 shitosan Polymers 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 229940032147 starch Drugs 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 229910052902 vermiculite Inorganic materials 0.000 claims description 2
- 239000010455 vermiculite Substances 0.000 claims description 2
- 235000019354 vermiculite Nutrition 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 150000001450 anions Chemical class 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 238000004043 dyeing Methods 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 235000020679 tap water Nutrition 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 241000894007 species Species 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 241000907663 Siproeta stelenes Species 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 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 description 1
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000021384 green leafy vegetables Nutrition 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
本发明公开了一种具有吸附催化双功能水凝胶的制备方法,其包括:制备水凝胶将至少一种贵金属负载到水凝胶载体上;干燥所得负载型水凝胶。该负载型水凝胶材料的制备工艺简单,条件温和,适合工业生产;所得产物可有效降解水体中的有机染料,包括阴离子和阳离子染料;同时多次循环使用后仍有较好的催化性能。
Description
技术领域
本发明涉及环保水处理领域,具体地讲,本发明涉及一种可降解有机染料的具有吸附催化双功能的水凝胶的制备方法。
背景技术
环境污染控制与治理是人类面临和亟待解决的重大课题。我国是纺织业的第一大国,而印染是纺织业的核心工艺。由印染排放的废水约占纺织行业废水排放的80%以上,约占整个工业废水排放量的35%。印染行业是工业废水排放的大户,由此造成的生态破坏及经济损失是不可估量的。
印染废水色度高、毒性强、水量大、可生化性差。废水中的偶氮染料能使生物致畸、致癌、致突变。染料在环境中具有相对稳定性和难降解性,很难从环境中清除出来。此外,随着科技的发展,染料品种日益增多,染料成分日益复杂,这些使得印染废水治理十分困难。印染废水已经成为环境综合治理工作中的新难点和新课题。
常见的印染废水的治理方法主要有化学、物理和生物三大方法。吸附法作为一种物理化学方法被认为是有效、经济实用的处理染料的方法,而且已经得到了广泛的应用。活性炭是最早也是迄今为止应用最多的脱色吸附剂。活性炭表面及内部存在由细孔相互连通形成的空间结构,比表面积大,因此活性炭能够有效去除废水中许多种类的染料。但活性炭价格贵、不易再生使其实际应用受到限制。
水凝胶属于功能高分子材料,通常是以烯类物质为单体,在引发剂和交联剂作用下,经聚合、水解、交联等化学反应形成的三维网状聚合物。水凝胶良好的亲水性能使其遇水溶胀,三维网格尺寸随之增大,进而降低吸附过程中的传质阻力,使吸附体系很快达到吸附平衡。通过分子设计,可在水凝胶中引入不同的功能基团,实现对水体中不同染料的高效去除。同其它吸附剂相比,水凝胶具有吸附速度快、吸附容量高、易分离等明显优势。
尽管如此,水凝胶吸附染料之后,脱附率较低,使得染料仅从印染废水中吸附至水凝胶而转化为固体废物,无法达到理想的处理效果。水凝胶良好的三维网络可视为微反应器,通过原位还原,将具有室温催化活性的贵金属纳米粒子负载到其中,制备具有吸附催化双功能的水凝胶。该水凝胶可实现对水体中不同有机染料的高效降解,且多次循环使用后催化活性没有降低。
发明内容
本发明的目的在于,制备一种负载贵金属纳米粒子的具有吸附催化双功能的水凝胶,该负载型水凝胶在可见光下,实现对水体中有机染料的高效降解。
一种具有吸附催化双功能水凝胶的制备方法,其特征在于,包括如下步骤:
a)制备水凝胶;
b)将至少一种贵金属负载到水凝胶载体上;
c)干燥所得负载型水凝胶。
为了本发明的目的,术语“水凝胶”指以烯类物质为单体,在引发剂和交联剂作用下,经聚合、水解、交联等化学反应形成的三维网状聚合物。术语“水凝胶”优选以含单一双键的原材料为基础的水凝胶,尤其优选以丙烯酸为基础的水凝胶。
其中在a步骤中水凝胶的制备,采用丙烯酸为单体,添加引发剂和交联剂,在水溶液中经0-90℃聚合而成。
水凝胶的形状可为块状,也可为粒状。
交联剂可选自N,N’-亚甲基双丙烯酰胺、硫酸铝、硫酸铝钾中的一种;引发剂可选自硝酸铈铵、高锰酸钾、双氧水、过硫酸铵、重铬酸钾、氯化亚铁、氯化亚铁铵、抗坏血酸、硼氢化钠中的一种或两种。
根据需要可以添加一种天然多糖,可选自羧甲基纤维素、羟乙基纤维素、羟丙基纤维素、壳聚糖、羧甲基壳聚糖、卡拉胶、淀粉、海藻酸钠、瓜尔胶、欧车前、沙蒿胶。
根据需要还可以添加一种无机组份,可选自蒙脱土、云母、蛭石、高岭土、凹凸棒土、伊利石、海泡石、麦饭石。
水凝胶中原料的质量份数为:丙烯酸100份,交联剂0.2-30份,引发剂0.1-20份,天然多糖0-30份,无机组份0-80份。
其中在b步骤中负载型水凝胶的制备,是将a步骤中制备所得水凝胶切为长宽高均位于0.2~3厘米之间的块状,或者直接利用所制备的粒状水凝胶,浸入一种贵金属离子溶液中,1-24小时后分离水凝胶,再以还原剂进行还原1-10小时后制备。
贵金属离子可选自金、银、铂中的一种;还原剂可选自单宁酸、抗坏血酸、水合肼、硼氢化钠中的一种。
贵金属离子的浓度为0.1-20毫摩尔/升,还原剂的浓度为0.1-20毫摩尔/升。
其中在c步骤中负载型水凝胶的干燥,是将b步骤中制备所得负载型水凝胶,置于温度60-90℃,干燥而成。
与现有技术相比,本发明具有以下优点:
1、制备方法简单,对设备要求不高,可实现工业化;
2、该负载型水凝胶对水体中的有机染料有高效的降解能力。
具体实施方式
下面结合实施例对本发明进行详细描述。
实施例1
将0.1克N,N’-亚甲基双丙烯酰胺置于四口烧瓶中,加入50毫升自来水,搅拌30分钟;将7.2克丙烯酸加入上述烧瓶中,搅拌下滴加6摩尔/升氢氧化钠溶液5毫升;搅拌30分钟后加入0.1克硝酸铈铵,升温至60℃,保持4小时;将制备的水凝胶切成长宽高均位于0.2~3厘米之间的块状,置于200毫升1毫摩尔/升金氯酸溶液中浸泡4小时;水凝胶经分离后再置于300毫升10毫摩尔/升单宁酸溶液中还原1小时;将水凝胶滤出,于70℃烘箱中干燥至恒重。产品可在15分钟内,对20毫克/升亚甲基兰实现完全降解。
实施例2
将0.5克硫酸铝置于四口烧瓶中,加入50毫升自来水,搅拌30分钟;将10克丙烯酸加入上述烧瓶中,搅拌下滴加6摩尔/升氢氧化钠溶液10毫升;搅拌30分钟后加入0.1克过硫酸铵,升温至70℃,保持4小时;将制备的水凝胶切成长宽高均位于0.2~3厘米之间的块状,置于200毫升5毫摩尔/升硝酸银溶液中浸泡10小时;水凝胶经分离后再置于300毫升2毫摩尔/升抗坏血酸溶液中还原2小时;将水凝胶滤出,于80℃烘箱中干燥至恒重。产品可在15分钟内,对20毫克/升刚果红实现完全降解。
实施例3
将0.5克壳聚糖、0.3克N,N’-亚甲基双丙烯酰胺置于四口烧瓶中,加入50毫升自来水,搅拌30分钟;将4克丙烯酸加入上述烧瓶中,搅拌下滴加6摩尔/升氢氧化钠溶液2毫升;搅拌30分钟后加入0.1克双氧水和0.2克抗坏血酸,20度保持4小时;将制备的粒状水凝胶直接置于200毫升2毫摩尔/升氯铂酸溶液中浸泡24小时;水凝胶经分离后再置于300毫升5毫摩尔/升硼氢化钠溶液中还原4小时;将水凝胶滤出,于60℃烘箱中干燥至恒重。产品可在15分钟内,对20毫克/升孔雀石绿实现完全降解。
实施例4
将0.5克硫酸铝钾置于四口烧瓶中,加入50毫升自来水,搅拌30分钟;将8克丙烯酸加入上述烧瓶中,搅拌下滴加6摩尔/升氢氧化钠溶液8毫升;搅拌30分钟后加入0.4克高锰酸钾,升温至70℃,保持4小时;将制备的水凝胶切成长宽高均位于0.2~3厘米之间的块状,置于200毫升6毫摩尔/升硝酸银溶液中浸泡10小时;水凝胶经分离后再置于300毫升5毫摩尔/升水合肼溶液中还原3小时;将水凝胶滤出,于90℃烘箱中干燥至恒重。产品可在15分钟内,对20毫克/升灿烂甲酚蓝实现完全降解。
实施例5
将0.4克N,N’-亚甲基双丙烯酰胺置于四口烧瓶中,加入50毫升自来水,搅拌30分钟;将10.8克丙烯酸加入上述烧瓶中,搅拌下滴加6摩尔/升氢氧化钠溶液15毫升;将1克凹凸棒土分散在10毫升自来水中,加入上述溶液中;搅拌30分钟后加入0.3克过硫酸铵和0.2克氯化亚铁,升温至70℃,保持4小时;将制备的水凝胶切成长宽高均位于0.2~3厘米之间的块状,置于200毫升3毫摩尔/升金氯酸溶液中浸泡20小时;水凝胶经分离后再置于300毫升5毫摩尔/升单宁酸溶液中还原2小时;将水凝胶滤出,于70℃烘箱中干燥至恒重。产品可在15分钟内,对20毫克/升橙黄II实现完全降解。
Claims (6)
1.一种具有吸附催化双功能水凝胶的制备方法,其特征在于,包括如下步骤:
a)制备水凝胶:采用丙烯酸为单体,添加引发剂和交联剂,在自来水中经0-90℃聚合得到块状或粒状水凝胶;所述交联剂选自N,N’-亚甲基双丙烯酰胺、硫酸铝、硫酸铝钾中的一种;所述引发剂选自硝酸铈铵、高锰酸钾、双氧水、过硫酸铵、重铬酸钾、氯化亚铁、氯化亚铁铵、抗坏血酸、硼氢化钠中的一种或两种;所述水凝胶中原料的质量份数为:丙烯酸100份,交联剂0.2-30份,引发剂0.1-20份,天然多糖0-30份,无机组份0-80份;
b)将贵金属负载到水凝胶载体上:将a)步骤中制备所得水凝胶切为长宽高均位于0.2~3厘米之间的块状,或者直接利用所制备的粒状水凝胶,浸入贵金属离子溶液中,1-24小时后分离水凝胶,再以还原剂进行还原1-10小时;
c)干燥所得负载型水凝胶。
2.如权利要求1所述的制备方法,其特征在于所述天然多糖为羧甲基纤维素、羟乙基纤维素、羟丙基纤维素、壳聚糖、羧甲基壳聚糖、卡拉胶、淀粉、海藻酸钠、瓜尔胶、欧车前或沙蒿胶。
3.如权利要求1所述的制备方法,其特征在于所述无机组份为蒙脱土、云母、蛭石、高岭土、凹凸棒土、伊利石、海泡石或麦饭石。
4.如权利要求1所述的制备方法,其特征在于所述贵金属离子选自金、银、铂中的一种;还原剂选自单宁酸、抗坏血酸、水合肼、硼氢化钠中的一种。
5.如权利要求1所述的制备方法,其特征在于所述贵金属离子的浓度为0.1-20毫摩尔/升,还原剂的浓度为0.1-20毫摩尔/升。
6.如权利要求1所述的制备方法,其特征在于c)步骤中负载型水凝胶的干燥,是将b)步骤中制备所得负载型水凝胶置于温度60-90℃干燥。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201210226921.0A CN103524965B (zh) | 2012-07-03 | 2012-07-03 | 一种具有吸附催化双功能水凝胶的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201210226921.0A CN103524965B (zh) | 2012-07-03 | 2012-07-03 | 一种具有吸附催化双功能水凝胶的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103524965A CN103524965A (zh) | 2014-01-22 |
CN103524965B true CN103524965B (zh) | 2016-05-25 |
Family
ID=49927338
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201210226921.0A Expired - Fee Related CN103524965B (zh) | 2012-07-03 | 2012-07-03 | 一种具有吸附催化双功能水凝胶的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103524965B (zh) |
Families Citing this family (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104383887B (zh) * | 2014-11-12 | 2017-02-15 | 青岛海洋生物医药研究院股份有限公司 | 壳聚糖、壳寡糖及其衍生物在制备吸附大气污染物的吸附剂中的应用 |
CN104826604A (zh) * | 2015-05-25 | 2015-08-12 | 西北大学 | 一种应用于污水处理的双离子型秸秆基水凝胶的制备方法 |
CN105153459A (zh) * | 2015-10-19 | 2015-12-16 | 高大元 | 一种微导电水凝胶的制备方法 |
CN105903442A (zh) * | 2016-05-10 | 2016-08-31 | 西北师范大学 | 一种多糖基水凝胶的制备及作为吸附剂在废水处理中的应用 |
CN106009458B (zh) * | 2016-06-20 | 2018-09-14 | 华南理工大学 | 一种菠萝皮渣纤维素-g-丙烯酸/高岭土/乌贼墨水凝胶及其制备方法与应用 |
CN106111193B (zh) * | 2016-06-21 | 2018-07-27 | 西安交通大学 | 一种负载银纳米颗粒催化剂水凝胶的制备方法 |
CN106732423B (zh) * | 2016-12-28 | 2019-10-01 | 西北师范大学 | 一种羟乙基纤维素/凹凸棒/腐殖酸钠复合水凝胶的制备及应用 |
CN106824091A (zh) * | 2017-01-12 | 2017-06-13 | 北京林业大学 | 一种磁性阳离子水凝胶基复合吸附材料的制备及其应用 |
CN106830259B (zh) * | 2017-02-28 | 2019-04-09 | 华南理工大学 | 一种氯代有机物的降解方法 |
CN106902748A (zh) * | 2017-03-29 | 2017-06-30 | 青岛辰达生物科技有限公司 | 一种重金属离子吸附剂的制备方法和污水处理剂 |
CN107376857B (zh) * | 2017-08-02 | 2020-12-18 | 刘庆玉 | 一种用于吸附重金属的复合水凝胶材料及其制备方法 |
CN107442082B (zh) * | 2017-08-30 | 2019-10-29 | 广州大学 | 一种磁性聚丙烯酰胺/海藻酸锆凝胶球及其制备方法和应用 |
CN107694534A (zh) * | 2017-09-29 | 2018-02-16 | 周玲玲 | 一种聚天冬氨酸改性阴离子纤维基滤料的制备方法 |
CN108341906B (zh) * | 2018-03-12 | 2020-03-17 | 福州大学 | 一种阳离子染料复合吸附材料的制备方法及应用 |
CN108191034B (zh) * | 2018-03-15 | 2020-11-03 | 哈尔滨工业大学 | 一种催化NaBH4同步产氢、除Cr(Ⅵ)的方法 |
CN108499542A (zh) * | 2018-05-03 | 2018-09-07 | 石狮纳通新材料科技有限公司 | 一种高效处理环境废水的基于鸡蛋壳的复合材料及其制备方法 |
CN108862727B (zh) * | 2018-07-16 | 2021-01-26 | 中国科学院合肥物质科学研究院 | 污水处理方法 |
CN109046341B (zh) * | 2018-08-28 | 2021-07-13 | 中国科学院兰州化学物理研究所 | 一种可见光响应的硅酸银/凹凸棒复合催化剂的制备方法 |
CN109158058B (zh) * | 2018-09-11 | 2020-05-22 | 淮阴工学院 | 凹土-壳聚糖复合凝胶及其制备方法 |
CN109942071B (zh) * | 2019-04-23 | 2022-07-01 | 天津大学 | 一种单宁酸稳定的纳米级零价铁强化过硫酸盐降解开链氯代烃的方法 |
CN110358016A (zh) * | 2019-07-18 | 2019-10-22 | 牡丹江师范学院 | 一种具有吸附催化双功能水凝胶的制备方法 |
CN110665457A (zh) * | 2019-09-30 | 2020-01-10 | 广西民族大学 | 一种蔗糖碳化物/海泡石复合材料及其制备方法 |
CN110665459A (zh) * | 2019-09-30 | 2020-01-10 | 广西民族大学 | 一种淀粉碳化物/海泡石复合材料及其制备方法 |
CN110628090B (zh) * | 2019-10-17 | 2021-06-22 | 陕西科技大学 | 一种阳离子瓜尔胶/壳聚糖复合水凝胶及其制备方法 |
CN111019171B (zh) * | 2019-12-27 | 2021-04-27 | 福州大学 | 一种改性硅铝酸盐掺杂羧基化壳聚糖的抗菌阻隔性pet保护膜的制备方法 |
CN113288820B (zh) * | 2021-05-25 | 2022-07-01 | 台州学院 | 一种有机改性凹凸棒-染料杂化颜料及其制备方法和应用 |
CN115999521A (zh) * | 2023-02-28 | 2023-04-25 | 陕西科技大学 | 一种废水中氨氮的高效吸附材料、制备方法及其应用 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101735396B (zh) * | 2009-12-31 | 2011-10-26 | 陕西科技大学 | 采用麦秸秆制备高吸水性树脂的方法 |
-
2012
- 2012-07-03 CN CN201210226921.0A patent/CN103524965B/zh not_active Expired - Fee Related
Non-Patent Citations (2)
Title |
---|
Hydrogel networks as nanoreactors: A novel approach to silver nanoparticles for antibacterial applications;Y. Murali Mohan,etc.;《Polymer》;20061122;第48卷(第1期);第158-164页 * |
Response Surface Methodology for Optimizing Adsorption Process Parameters for Methylene Blue Removal by a Hydrogel Composite;Aiqin Wang,etc.;《Adsorption Science & Technology》;20110427;第28卷(第10期);第913-922页 * |
Also Published As
Publication number | Publication date |
---|---|
CN103524965A (zh) | 2014-01-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103524965B (zh) | 一种具有吸附催化双功能水凝胶的制备方法 | |
Jiang et al. | Preparation of a novel bio-adsorbent of sodium alginate grafted polyacrylamide/graphene oxide hydrogel for the adsorption of heavy metal ion | |
Kong et al. | Dye removal by eco-friendly physically cross-linked double network polymer hydrogel beads and their functionalized composites | |
Wang et al. | Equilibrium, kinetics and mechanism of Au3+, Pd2+ and Ag+ ions adsorption from aqueous solutions by graphene oxide functionalized persimmon tannin | |
Subhan et al. | Sodium alginate grafted poly (N-vinyl formamide-co-acrylic acid)-bentonite clay hybrid hydrogel for sorptive removal of methylene green from wastewater | |
CN106799211B (zh) | 一种凹凸棒土-交联壳聚糖复合除汞吸附剂及其固相合成方法 | |
Liu et al. | Removal of Pb (II) from aqueous solution using dithiocarbamate modified chitosan beads with Pb (II) as imprinted ions | |
Ngah et al. | Adsorption of dyes and heavy metal ions by chitosan composites: A review | |
Li et al. | Synthesis of ion-imprinted chitosan-TiO2 adsorbent and its multi-functional performances | |
CN108201878B (zh) | 一种碳点改性金属有机骨架吸附材料的制备方法及水体污染物治理应用 | |
Zhang et al. | Improvement of Ag (I) adsorption onto chitosan/triethanolamine composite sorbent by an ion-imprinted technology | |
Dong et al. | Three-dimensional porous sodium alginate/gellan gum environmentally friendly aerogel: Preparation, characterization, adsorption, and kinetics studies | |
CN108355611B (zh) | 一种mof配合物及其合成和在吸附废水中有机染料的应用 | |
Mohrazi et al. | Removal of methylene blue dye from aqueous solution using an efficient chitosan-pectin bio-adsorbent: kinetics and isotherm studies | |
Hong et al. | Cellulose-derived polyols as high-capacity adsorbents for rapid boron and organic pollutants removal from water | |
CN106082211A (zh) | 一种木质素基多级孔碳材料的制备方法及其用途 | |
CN109482158B (zh) | “半干法”制备高性能三维网络吸附剂的方法 | |
Song et al. | Adsorption of crystal violet onto epichlorohydrin modified corncob | |
Shao et al. | Adsorption of Ag/Au nanoparticles by ordered macro-microporous ZIF-67, and their synergistic catalysis application | |
Su et al. | Adsorption mechanism for imprinted ion (Ni2+) of the surface molecular imprinting adsorbent (SMIA) | |
Coşkun | Removal of cationic dye from aqueous solution by adsorption onto crosslinked poly (4-vinylpyridine/crotonic acid) and its N-oxide derivative | |
Tang et al. | Paddle-Wheel-Shaped Porous Cu (II)–Organic Framework with Two Different Channels as an Absorbent for Methylene Blue | |
Yang et al. | Au/Boron organic frameworks for efficient removal and degradation of azo dye pollutants | |
Wang et al. | Fabrication of β-cyclodextrin-polyacrylamide/covalent organic framework hydrogel at room temperature for the efficient removal of triazole fungicides from environmental water | |
Xu et al. | Facile in-situ growth of ZIF-67 nanoparticles and in-situ polymerization of polyacrylamide on chitosan aerogel spheres and their high-efficient adsorption of tetracycline |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160525 |