CN109317209A - 一种螯合树脂基电芬顿催化剂及其制备方法与应用 - Google Patents
一种螯合树脂基电芬顿催化剂及其制备方法与应用 Download PDFInfo
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000000706 filtrate Substances 0.000 claims abstract description 6
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- 238000006243 chemical reaction Methods 0.000 claims description 21
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 10
- 235000011152 sodium sulphate Nutrition 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 7
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
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- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 5
- 229940012189 methyl orange Drugs 0.000 claims description 5
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 5
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- 229910052802 copper Inorganic materials 0.000 claims description 4
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 3
- 241000040710 Chela Species 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 150000005005 aminopyrimidines Chemical class 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
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- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 150000002923 oximes Chemical class 0.000 claims description 2
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 claims description 2
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- 238000012545 processing Methods 0.000 claims description 2
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- 239000000203 mixture Substances 0.000 claims 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 abstract description 10
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- 238000004064 recycling Methods 0.000 abstract description 3
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- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- TVMUHOAONWHJBV-UHFFFAOYSA-N dehydroglycine Chemical compound OC(=O)C=N TVMUHOAONWHJBV-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- QDLZHJXUBZCCAD-UHFFFAOYSA-N [Cr].[Mn] Chemical compound [Cr].[Mn] QDLZHJXUBZCCAD-UHFFFAOYSA-N 0.000 description 2
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
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- 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 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 description 1
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- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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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
- C02F2101/00—Nature of the contaminant
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Abstract
一种螯合树脂基电芬顿催化剂，按如下方法制备得到：将螯合树脂浸没于盐酸水溶液中，室温搅拌，之后过滤并用去离子水洗涤至滤液呈中性，重复上述过程3～5次，完成螯合树脂的预处理，烘干备用；将经过预处理的螯合树脂浸没于金属盐的水溶液中，调节pH为2～4，在50～80℃下搅拌10～18h，之后过滤，用去离子水清洗，干燥即得；本发明制备催化剂的步骤简单，所得催化剂的催化效率高，可循环使用，在工业废水，特别是染料废水领域具有显著效果；本发明所述催化剂以螯合树脂作为载体来固载金属离子，不仅可以重复使用，而且不需要额外添加双氧水，此外树脂较高的机械强度和较大的尺寸，使得催化剂具有回收方便和稳定性好的优点。
Description
(一)技术领域
本发明涉及一种螯合树脂基电芬顿催化剂及其制备方法，以及在内环流式电化学反应体系中处理有机染料废水的应用。
(二)背景技术
螯合树脂是在离子交换树脂基础上发展起来的，它是一种能与金属离子形成螯合物的树脂，它和一般的离子交换树脂一样，并且具有吸附量变化小等优点。但是螯合树脂与离子交换树脂也存在较大的区别，主要表现在以下几点：首先，离子交换树脂同离子发生的是交换反应，螯合树脂主要是以配价键的形式与金属离子形成稳定的螯合物，它对金属离子具有特殊的选择螯合能力；其次，离子交换树脂同金属离子是以离子键结合的，而螯合树脂可以同时以离子键及配位键与金属离子结合，其键能远远大于离子交换树脂。可见，螯合树脂与金属离子形成的螯合物更为稳定；最后，不同的螯合基团对不同的金属离子具有不同的选择吸附能力，选择吸附性大，与金属离子结合稳定，金属离子选择性好就是螯合树脂的最大特点。专利CN201310411464.7公开了一种电解锰铬废水处理过程中利用螯合树脂吸附锰铬的回收方法，通过调控吸附过程中pH，再生时间，回用时间等工艺指标达到对铬、锰的回用；专利CN200710021084.7说明了利用金属螯合树脂吸附剂分离回收水体中脂肪酸的方法，该方法将脂肪酸类高盐生产废水经过预处理后，调整pH到5～8，在5～40℃的温度和0.5～5BV/h的流量条件下，通过装填有金属螯合吸附剂的吸附塔，使水体中的脂肪酸类有机物选择性吸附在吸附剂上，从而达到高效去除有机物的目的。
螯合树脂作为催化剂载体并应用于芬顿催化降解实验中，可有效减少铁污泥量，提高催化剂的回收率，减少二次污染等，被研究者和相关企业广泛关注。据已公开的专利可知，专利JP2008190903公开了一种树脂劣化的评价方法，通过树脂吸附芬顿试剂的铁离子将其作为类芬顿催化剂，加入不同浓度的H2O2反应后来观察树脂表面结构的变化并评判树脂的优劣情况。专利CN201510074499.5公开了一种竹浆纤维素基集成芬顿催化剂Fe3+C2O4/树脂的制备方法，是将三价铁与草酸配位形成络合物Fe3+C2O4，再将其负载于竹浆纤维素多孔树脂上，形成的类芬顿催化剂Fe3+C2O4/树脂，再应用于可见光降解印染废水的研究中，实现了高效降解和催化剂回收简便的目的。
因此，结合螯合树脂球体颗粒的催化剂具有溶胀度小、稳定性高、回用效率高的特点，在染料废水中的降解效果也很好，这是具有现实意义的实用型催化剂。
(三)发明内容
为了解决现有均相芬顿处理染料废水中存在的催化剂不易回收、产生二次污染多以及药剂消耗大等问题，本发明提供了一种螯合树脂基电芬顿催化剂及其制备方法，以及在内环流式电化学反应体系中处理有机染料废水的应用。
本发明的技术方案如下：
一种螯合树脂基电芬顿催化剂，按如下方法制备得到：
(1)将螯合树脂浸没于0.02～0.1mol/L的盐酸水溶液中，室温(20～30℃)搅拌4～8h，之后过滤并用去离子水洗涤至滤液呈中性，重复上述过程3～5次，完成螯合树脂的预处理，烘干备用；
所述螯合树脂可通过常规途径商购获得，为直径0.7±0.2mm的球体颗粒，种类例如：氨基羧酸螯合树脂、氨基磷酸螯合树脂、硫脲螯合树脂、肟类螯合树脂、氨基嘧啶螯合树脂等；
(2)将步骤(1)准备好的螯合树脂浸没于0.05～0.3mol/L金属盐的水溶液中，调节pH为2～4，在50～80℃下搅拌10～18h，之后过滤，用去离子水清洗，干燥，得到所述螯合树脂基电芬顿催化剂；
所述金属盐为Fe、Ni、Cu、Co、Mn的可溶性金属盐中的一种或两种以任意比例的混合物，所述Fe、Ni、Cu、Co、Mn的可溶性金属盐例如三氯化铁、硫酸亚铁、硝酸铁、硫酸镍、硝酸镍、氯化镍、硫酸铜、硝酸铜、氯化铜、硫酸钴、硝酸钴、氯化钴、硫酸锰、氯化锰、乙酸锰。
本发明制得的螯合树脂基电芬顿催化剂可应用于内环流式电化学反应体系以处理有机染料废水。具体的，所述应用方法例如：
(a)将有机染料溶于水中，再加入硫酸钠，配制得到模拟废水；
所述有机染料例如：亚甲基蓝、甲基橙或酸性大红GR染料；
所述模拟废水中有机染料的浓度为20～100mg/L，硫酸钠的浓度为0.01～0.05mol/L；
(b)以内环流式电化学反应器为反应容器，石墨板作为阴、阳极连接直流电源构建电芬顿反应装置(为本领域常规技术)，将步骤(a)配制的模拟废水加到反应容器中，并调节pH为2～7，持续通入空气，空气流量为0.6L/min，取螯合树脂基电芬顿催化剂加到反应器中，在搅拌条件下，开启直流电源通电反应，间隔时间取样测量降解废水的吸光度；
所述螯合树脂基电芬顿催化剂的质量用量以模拟废水的体积计为1～5g/L；
所述通电反应的电流强度为0.05～0.35A；
反应结束后，过滤回收催化剂，用乙醇和去离子水清洗，烘干后催化剂可重复套用。
本申请的有益效果在于：本发明制备催化剂的步骤简单，所得催化剂的催化效率高，可循环使用，在工业废水，特别是染料废水领域具有显著效果。本发明所述催化剂以螯合树脂作为载体来固载金属离子，不仅可以重复使用，而且不需要额外添加双氧水，此外树脂较高的机械强度和较大的尺寸，使得催化剂具有回收方便和稳定性好的优点。
(四)附图说明
图1是实施例1中催化剂对不同染料的降解效果；
图2是实施例2中催化剂降解亚甲基蓝、甲基橙、酸性大红GR回用三次效果；
图3是氨基羧酸树脂的表面形貌图。
(五)具体实施方式
下面通过具体实施例对本发明作进一步的说明，但本发明的保护范围并不仅限于此。
实施例1：
(1)将胺基羧酸螯合树脂(LS-100，购自陕西蓝深特种树脂有限公司)浸没于0.02mol/L的盐酸水溶液中，室温搅拌4h，之后过滤并用去离子水洗涤至滤液呈中性，重复上述过程3次，完成螯合树脂的预处理，烘干备用。
(2)将预处理好的螯合树脂浸没于0.05mol/L MnSO4的水溶液中，调节pH为2，在50℃下搅拌10h，之后过滤，用去离子水清洗，干燥，得到螯合树脂基电芬顿催化剂。
(3)将亚甲基蓝溶于水中，再加入硫酸钠，配制得到模拟废水；所得模拟废水中亚甲基蓝的浓度为20mg/L，硫酸钠的浓度为0.01mol/L。
(4)以内环流式电化学反应器为反应容器，石墨板作为阴、阳极连接直流电源构建电芬顿反应装置，将350mL模拟废水加到反应容器中，并调节pH为3，持续通入空气，空气流量为0.6L/min，取螯合树脂基电芬顿催化剂加到反应器中，催化剂用量3g/L，在搅拌条件下，开启直流电源通电反应，电流强度为0.2A，接通电源开始计时并每隔30min取样，共取6个样，测每个样的吸光度。
催化剂回收实验：在上述实验结束后将催化剂过滤分离，分别用乙醇和去离子水清洗三次，然后于烘箱中60℃烘干备用。重复以该催化剂降解亚甲基蓝实验，共重复三次。
实施例2：
(1)将胺基羧酸螯合树脂(LS100，购自陕西蓝深特种树脂有限公司)浸没于0.06mol/L的盐酸水溶液中，室温搅拌6h，之后过滤并用去离子水洗涤至滤液呈中性，重复上述过程4次，完成螯合树脂的预处理，烘干备用。
(2)将预处理好的螯合树脂浸没于0.2mol/L MnSO4的水溶液中，调节pH为3，在65℃下搅拌14h，之后过滤，用去离子水清洗，干燥，得到螯合树脂基电芬顿催化剂。
(3)将甲基橙溶于水中，再加入硫酸钠，配制得到模拟废水；所得模拟废水中甲基橙的浓度为20mg/L，硫酸钠的浓度为0.03mol/L。
(4)以内环流式电化学反应器为反应容器，石墨板作为阴、阳极连接直流电源构建电芬顿反应装置，将350mL模拟废水加到反应容器中，并调节pH为3，持续通入空气，空气流量为0.6L/min，取螯合树脂基电芬顿催化剂加到反应器中，催化剂用量3g/L，在搅拌条件下，开启直流电源通电反应，电流强度为0.2A，接通电源开始计时并每隔30min取样，共取6个样，测每个样的吸光度。
催化剂回收实验：在上述实验结束后将催化剂过滤分离，分别用乙醇和去离子水清洗三次，然后于烘箱中60℃烘干备用。重复以该催化剂降解甲基橙实验，共重复三次。
实施例3：
(1)将胺基羧酸螯合树脂(LS-100，购自陕西蓝深特种树脂有限公司)浸没于0.1mol/L的盐酸水溶液中，室温搅拌8h，之后过滤并用去离子水洗涤至滤液呈中性，重复上述过程5次，完成螯合树脂的预处理，烘干备用。
(2)将预处理好的螯合树脂浸没于0.3mol/L MnSO4的水溶液中，调节pH为4，在80℃下搅拌18h，之后过滤，用去离子水清洗，干燥，得到螯合树脂基电芬顿催化剂。
(3)将酸性大红GR溶于水中，再加入硫酸钠，配制得到模拟废水；所得模拟废水中酸性大红GR的浓度为100mg/L，硫酸钠的浓度为0.05mol/L。
(4)以内环流式电化学反应器为反应容器，石墨板作为阴、阳极连接直流电源构建电芬顿反应装置，将350mL模拟废水加到反应容器中，并调节pH为3，持续通入空气，空气流量为0.6L/min，取螯合树脂基电芬顿催化剂加到反应器中，催化剂用量3g/L，在搅拌条件下，开启直流电源通电反应，电流强度为0.2A，接通电源开始计时并每隔30min取样，共取6个样，测每个样的吸光度。
催化剂回收实验：在上述实验结束后将催化剂过滤分离，分别用乙醇和去离子水清洗三次，然后于烘箱中60℃烘干备用。重复以该催化剂降解酸性大红GR实验，共重复三次。
对比例
例如，文献“Heterogeneous photo-electro-Fenton process using differentiron supporting materials”(J.Appl.Electrochem.,2010,40,1729-1736)中提到，以Purolite和amberlite离子交换树脂作为载体制备芬顿催化剂，Fe3+泄漏量分别为1.1mg/L和4.8mg/L。而本发明中以螯合树脂为载体金属离子的泄漏量小于0.1mg/L，提高了金属离子的结合力和催化剂稳定性。
Claims (6)
1.一种螯合树脂基电芬顿催化剂，其特征在于，按如下方法制备得到：
(1)将螯合树脂浸没于0.02～0.1mol/L的盐酸水溶液中，室温搅拌4～8h，之后过滤并用去离子水洗涤至滤液呈中性，重复上述过程3～5次，完成螯合树脂的预处理，烘干备用；
(2)将步骤(1)准备好的螯合树脂浸没于0.05～0.3mol/L金属盐的水溶液中，调节pH为2～4，在50～80℃下搅拌10～18h，之后过滤，用去离子水清洗，干燥，得到所述螯合树脂基电芬顿催化剂；
所述金属盐为Fe、Ni、Cu、Co、Mn的可溶性金属盐中的一种或两种以任意比例的混合物。
2.如权利要求1所述的螯合树脂基电芬顿催化剂，其特征在于，步骤(1)中，所述螯合树脂为：氨基羧酸螯合树脂、氨基磷酸螯合树脂、硫脲螯合树脂、肟类螯合树脂或氨基嘧啶螯合树脂。
3.如权利要求1所述的螯合树脂基电芬顿催化剂，其特征在于，步骤(2)中，所述Fe、Ni、Cu、Co、Mn的可溶性金属盐选自：三氯化铁、硫酸亚铁、硝酸铁、硫酸镍、硝酸镍、氯化镍、硫酸铜、硝酸铜、氯化铜、硫酸钴、硝酸钴、氯化钴、硫酸锰、氯化锰、乙酸锰。
4.如权利要求1所述的螯合树脂基电芬顿催化剂在处理有机染料废水中的应用。
5.如权利要求4所述的应用，其特征在于，所述应用的方法为：
(a)将有机染料溶于水中，再加入硫酸钠，配制得到模拟废水；
所述模拟废水中有机染料的浓度为20～100mg/L，硫酸钠的浓度为0.01～0.05mol/L；
(b)以内环流式电化学反应器为反应容器，石墨板作为阴、阳极连接直流电源构建电芬顿反应装置，将步骤(a)配制的模拟废水加到反应容器中，并调节pH为2～7，持续通入空气，空气流量为0.6L/min，取螯合树脂基电芬顿催化剂加到反应器中，在搅拌条件下，开启直流电源通电反应，间隔时间取样测量降解废水的吸光度；
所述螯合树脂基电芬顿催化剂的质量用量以模拟废水的体积计为1～5g/L；
所述通电反应的电流强度为0.05～0.35A。
6.如权利要求5所述的应用，其特征在于，所述有机染料为：亚甲基蓝、甲基橙或酸性大红GR染料。
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| CN113828314A (zh) * | 2021-10-25 | 2021-12-24 | 广西科学院 | 基于edta螯合技术制备淀粉炭基类芬顿催化剂的方法 |
| CN113828314B (zh) * | 2021-10-25 | 2023-06-09 | 广西科学院 | 基于edta螯合技术制备淀粉炭基类芬顿催化剂的方法 |
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