CN109529947A - 离子交换树脂为载体的非均相芬顿催化剂及其制备方法与应用 - Google Patents
离子交换树脂为载体的非均相芬顿催化剂及其制备方法与应用 Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/30—Organic compounds
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Abstract
一种离子交换树脂为载体的非均相芬顿催化剂，其特征在于，按如下方法制备得到：将离子交换树脂加到0.01～0.05mol/L金属盐的水溶液中，密封浸渍3～8h，之后离心去除上清液，离心所得固体烘干，得到所述非均相芬顿催化剂；本发明制备催化剂的步骤简单，制得的催化剂催化效率高，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，而以离子交换树脂作为载体，由于其中含有的大量功能基团，不仅提高了催化剂的机械强度和活性位的稳定性，而且保证了催化剂具有较大的比表面积和孔隙率。
Description
(一)技术领域
本发明涉及一种离子交换树脂为载体的非均相芬顿催化剂及其制备方法与应用。
(二)背景技术
近年来，离子交换材料由于其独特的表面特性和空间结构常被作为持续释放金属催化剂的新型载体。专利CN200710072473.2说明了三氯化铁改性离子交换树脂催化剂、其制备方法及应用，其是为了解决现有的乳酸铵催化剂制备工艺复杂、造价高及用现有的催化剂催化乳酸铵酯化时效率低的问题；专利CN201210545927.4公开了一种刺猬状的金-离子交换树脂核壳微球催化剂的制备方法，属于化工技术领域。该发明是将水溶性的氯金酸(盐)在阴离子交换树脂微球表面经还原赋形一步室温反应，即可制备得到刺猬状的金-离子交换树脂核壳微球。该发明所述刺猬状金-离子交换树脂核壳微球可用作液相催化还原反应的可重复使用催化剂。
负载型非均相芬顿催化剂由于降解效率高，产生铁污泥量少，可拓宽均相芬顿反应pH，减少二次污染等特性，被研究者和相关环境企业广泛关注。据已公开的专利可知，专利CN201310442419公开了一种应用于非均相芬顿体系的铁碳催化剂制备方法，是以聚四氟乙烯为改性原料，将铁碳浸渍后于氮气中煅烧制成负载型催化剂。专利201310036533公开了一种载铁分子筛型类芬顿催化剂的制备方法及其应用，以3A分子筛为载体，硫酸亚铁为前驱体，通过控制3A分子筛高温焙烧温度制成载铁分子筛催化剂，并实现硝基苯废水的高效去除与矿化。专利201410164298.X公开了降解偶氮染料废水的非均相芬顿催化剂制备方法及其用途，其以介孔TiO2为载体铜锰盐溶液为金属活性物种制备成非均相芬顿催化剂，催化剂的水热稳定性好，能够再生循环利用，无二次污染。
因此，结合离子交换树脂特性制备稳定性好、回用效率高的催化剂在染料废水中的降解效果也很好，这是具有良好潜在应用前景的实用型催化剂。
(三)发明内容
针对现有均相芬顿处理染料废水中存在的二次污染多，药剂消耗大等缺点，本发明提供了一种离子交换树脂为载体的非均相芬顿催化剂及其制备方法，以及在染料废水处理中的应用。
本发明的技术方案如下：
一种离子交换树脂为载体的非均相芬顿催化剂，按如下方法制备得到：
将离子交换树脂加到0.01～0.05mol/L金属盐的水溶液中，密封浸渍3～8h，之后离心去除上清液，离心所得固体烘干，得到所述非均相芬顿催化剂；
所述离子交换树脂的形状为直径0.7～1mm的球体颗粒，类型为强酸型阳离子交换树脂、弱酸型阳离子交换树脂，具体例如001X4、001X7、001X8、001X10、D001、D113阳离子交换树脂，优选D001、D113阳离子交换树脂；
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，优选硫酸锰、氯化锰。
本发明制得的离子交换树脂为载体的非均相芬顿催化剂中，金属元素的负载量在1～3wt％。
本发明制得的离子交换树脂为载体的非均相芬顿催化剂可应用于降解染料废水。具体的，所述应用的方法为：
(1)配制模拟染料废水
称取染料加到去离子水中，超声溶解完全，调节pH至5～6，得到模拟染料废水；
所述染料例如：亚甲基蓝、活性艳红X-3B、活性大红4-BS；
所述模拟染料废水中染料的浓度为10～100mg/L；
(2)非均相芬顿降解
在步骤(1)所得模拟染料废水中加入所述非均相芬顿催化剂，搅拌30min后，加入双氧水进行降解反应，间隔时间取样测量废水的吸光度；
所述双氧水为30wt％H2O2的水溶液，所述双氧水的体积用量以模拟染料废水的体积计为0.2～1.25mL/L；
所述非均相芬顿催化剂的质量用量以模拟染料废水的体积计为1～3.5g/L；
反应结束后，离心分离催化剂，用乙醇和去离子水清洗，再于105℃下烘干，回收的催化剂可重复套用。
相对于现有技术，本发明的有益效果在于：
本发明制备催化剂的步骤简单，制得的催化剂催化效率高，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。而以离子交换树脂作为载体，由于其中含有的大量功能基团，不仅提高了催化剂的机械强度和活性位的稳定性，而且保证了催化剂具有较大的比表面积和孔隙率。
(四)附图说明
图1：实施例1、2、3中催化剂对不同染料的吸附-降解效果；
图2：实施例1中催化剂降解亚甲基蓝回用三次效果；
图3：实施例2中催化剂降解X-3B回用三次效果；
图4：实施例3中催化剂降解4-BS回用三次效果。
(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：
将D001阳离子交换树脂0.075g(购自陕西蓝深特种树脂有限公司)加到50mL0.03mol/L MnSO4的水溶液中，密封浸渍6h，之后离心去除上清液，离心所得固体于105℃烘干，得到非均相芬顿催化剂。
降解染料废水的实验的方法是：取10mg/L的亚甲基蓝溶液50mL，pH调节为5.0，搅拌、同时加入催化剂(催化剂用量为1.5g/L)，开始计时，前30min为吸附饱和实验，取样后加入双氧水(30wt％水溶液，双氧水用量为1.25mL/L)，每隔20min取样，共取5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离心分离后，分别用乙醇和去离子水清洗三次，然后于烘箱中105℃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：
将D001阳离子交换树脂0.075g(购自陕西蓝深特种树脂有限公司)加到100mL0.03mol/L MnSO4的水溶液中，密封浸渍6h，之后离心去除上清液，离心所得固体于105℃烘干，得到非均相芬顿催化剂。
降解染料废水的实验的方法是：取100mg/L的X-3B溶液50mL，pH调节为5.0，搅拌、同时加入催化剂(催化剂用量为1.5g/L)，开始计时，前30min为吸附饱和实验，取样后加入双氧水(30wt％水溶液，双氧水用量为1.25mL/L)，每隔20min取样，共取5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离心分离后，分别用乙醇和去离子水清洗三次，然后于烘箱中105℃烘干备用。重复以该催化剂降解X-3B实验，共重复三次。
实施例3：
将D001阳离子交换树脂0.075g(购自陕西蓝深特种树脂有限公司)加到50mL0.03mol/L MnSO4的水溶液中，密封浸渍6h，之后离心去除上清液，离心所得固体于105℃烘干，得到非均相芬顿催化剂。
降解染料废水的实验的方法是：取100mg/L的4-BS溶液50mL，pH调节为5.0，搅拌、同时加入催化剂(催化剂用量为1.5g/L)，开始计时，前30min为吸附饱和实验，取样后加入双氧水(30wt％水溶液，双氧水用量为1.25mL/L)，每隔20min取样，共取5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离心分离后，分别用乙醇和去离子水清洗三次，然后于烘箱中105℃烘干备用。重复以该催化剂降解4-BS实验，共重复三次。
对比例
目前，芬顿催化剂有机载体研究的比较多的是海藻酸钠球凝胶珠，例如文献“Chemical oxidation of a malodorous compound,indole,using iron entrapped incalcium alginate beads”(J.Hazard.Mater.,2016,301,350-361)以铁凝胶珠来降解吲哚，“Optimisation of decolourisation and degradation of Reactive Black 5 dyeunder electro-Fenton process using Fe alginate gel beads”(Environ.Sci.Pollut.R.,2013,20,2172-2183)以铁凝胶珠来降解有机染料，虽然能够达到比较好的效果，但是催化剂制备效率低，成本高，无法大规模生产，而且凝胶珠含水率高，机械强度低，不易储存和运输。而离子交换树脂机械强度高，官能团丰富，可大规模工业化生产，以其作为载体制备芬顿催化剂过程简单，具有实现工业化的潜力。
Claims (6)
1.一种离子交换树脂为载体的非均相芬顿催化剂，其特征在于，按如下方法制备得到：
将离子交换树脂加到0.01～0.05mol/L金属盐的水溶液中，密封浸渍3～8h，之后离心去除上清液，离心所得固体烘干，得到所述非均相芬顿催化剂；
所述离子交换树脂为强酸型阳离子交换树脂或弱酸型阳离子交换树脂；
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所述的离子交换树脂为载体的非均相芬顿催化剂，其特征在于，所述离子交换树脂为001X4、001X7、001X8、001X10、D001或D113阳离子交换树脂。
3.如权利要求1所述的离子交换树脂为载体的非均相芬顿催化剂，其特征在于，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，优选硫酸锰、氯化锰。
4.如权利要求1所述的离子交换树脂为载体的非均相芬顿催化剂在降解染料废水中的应用。
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：
(1)配制模拟染料废水
称取染料加到去离子水中，超声溶解完全，调节pH至5～6，得到模拟染料废水；
所述模拟染料废水中染料的浓度为10～100mg/L；
(2)非均相芬顿降解
在步骤(1)所得模拟染料废水中加入所述非均相芬顿催化剂，搅拌30min后，加入双氧水进行降解反应，间隔时间取样测量废水的吸光度；
所述双氧水为30wt％H2O2的水溶液，所述双氧水的体积用量以模拟染料废水的体积计为0.2～1.25mL/L；
所述非均相芬顿催化剂的质量用量以模拟染料废水的体积计为1～3.5g/L。
6.如权利要求5所述的应用，其特征在于，所述染料为：亚甲基蓝、活性艳红X-3B或活性大红4-BS。
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