CN107008354A - 臭氧非均相氧化固体催化剂的制备方法 - Google Patents

臭氧非均相氧化固体催化剂的制备方法 Download PDF

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CN107008354A
CN107008354A CN201710274620.8A CN201710274620A CN107008354A CN 107008354 A CN107008354 A CN 107008354A CN 201710274620 A CN201710274620 A CN 201710274620A CN 107008354 A CN107008354 A CN 107008354A
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朱明�
石雨晴
王希雅
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Sichuan Normal University
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Abstract

本发明涉及一种臭氧非均相氧化固体催化剂的制备方法，属环保和化工催化剂技术领域。该制备方法是用活性炭、光卤石、伊利石、钠硼解石、氢氧化铝和天青石多孔矿物材料作载体，载体经次氯酸锂和双(乙酰丙酮)铍扩孔改性后，加入表面活性剂二甲基十六烷基乙基硫酸乙酯铵在超声波作用下进行表面活化处理，然后超声表面活化载体在水热反应釜中与硼砂和硫酸钾构成的复合矿化剂，乙酰丙酮钐、三(4,4,4‑三氟‑1‑(2‑噻吩)‑1,3‑丁二酮)铕、三氟甲烷磺酸铥(III)、碳酸镥水合物稀土金属化合物催化活性助剂，葡萄糖酸钴、L‑天门冬氨基酸钼、四氯金钾、六亚硝基铑三钠过渡金属催化活性中心组分，在乳化剂十二酰胺丙基二甲基二羟丙基氯化铵作用下进行水热反应，反应产物烘干除去水分后，在马弗炉内，一定温度下灼烧得到臭氧非均相氧化固体催化剂。

Description

臭氧非均相氧化固体催化剂的制备方法
技术领域
本发明涉及一种臭氧非均相氧化固体催化剂的制备方法，属环保和化工催化剂技术领域。
背景技术
臭氧氧化技术利用臭氧氧化能力强的特点，能将许多有机污染物氧化分解，广泛用于废水处理。臭氧催化氧化技术分为臭氧均相催化氧化和臭氧非均相催化氧化，臭氧均相催化氧化存在催化剂较难分离回收重复使用、臭氧利用率低导致水处理运行成本较高，同时有机污染物去除率较低和易造成水体二次污染使其应用受到局限；臭氧非均相催化氧化技术具有催化剂易于分离回收并可重复使用、臭氧利用率高、有机污染物去除率较高，降低了水处理运行成本和不会造成二次污染等优点使其应用受到广泛关注。臭氧非均相催化氧化有机物分解是经过催化剂表面吸附有机物达到局部有机物富集，同时臭氧分子吸附在催化剂表面在催化剂作用下产生高活性的羟基自由基使有机物分解。臭氧非均相催化氧化处理废水技术中，核心技术是臭氧非均相氧化固体催化剂的制备。
臭氧非均相氧化固体催化剂通常由载体、活性中心和助剂组成。由于废水中污染物种类繁多、化学成分复杂的特征，会对催化剂的使用性能如吸附、抗毒性产生不良影响，导致催化剂容易失去催化活性。目前臭氧非均相氧化固体催化剂的制备方法主要存在的问题是吸附容量较小、吸附选择性较低，催化剂的抗毒性较差、容易失去催化活性；开发采用多组分多孔载体增加催化剂的吸附容量、增强吸附选择性，使用稀土金属、过渡金属与贵金属形成多元金属催化活性中心以提高催化剂抗毒性和催化活性的臭氧非均相氧化固体催化剂的制备方法具有较大的环境效益和较高的实用价值。
发明内容
针对目前臭氧非均相氧化固体催化剂的制备方法存在的问题，本发明的目的是提供一种采用多组分多孔载体增加催化剂的吸附容量、增强吸附选择性，使用稀土金属、过渡金属与贵金属形成多元金属催化活性中心以提高催化剂抗毒性和催化活性的臭氧非均相氧化固体催化剂的制备方法，其特征是在可密闭反应器中加入A组分和去离子水搅拌制备水溶液，控制A组分的重量浓度为2%～6%，溶液制备完成后，在搅拌下加入B组分，升温至35℃～50℃，继续搅拌反应3h～6h，洗涤过滤，干燥恒重后得到扩孔改性载体；扩孔改性载体投入超声波反应器，加入由C组分和去离子水配制的水溶液，C组分的重量浓度为3%～8%，搅拌混合均匀，控制超声功率密度为0.3～0.8W/m3、频率20kHz～30kHz、40℃～55℃，超声振荡2h～5h，得到超声表面活化载体混合液；超声表面活化载体混合液转移至水热反应釜中，再加入D组分和去离子水配制的水溶液，D组分的重量浓度为40%～55%，按重量计，D组分去离子水溶液:超声表面活化载体混合液的重量比=1:（1.5～2），控制温度120℃～180℃，水热反应时间为8h～16h，然后进行冷却，烘干得细颗粒物；细颗粒物在马弗炉内，600℃～950℃，灼烧3h～8h，得到臭氧非均相氧化固体催化剂。所述A组分由次氯酸锂、双(乙酰丙酮)铍组成，按重量计，次氯酸锂:双(乙酰丙酮)铍的重量之比=1:（1～1.6），B组分由活性炭、光卤石、伊利石、钠硼解石、氢氧化铝、天青石组成，按重量计，活性炭:光卤石:伊利石:钠硼解石:氢氧化铝:天青石的重量之比=（5～15）:（7～17）:（9～19）:（11～21）:（13～23）:（15～25），按重量计，A组分:B组分的重量之比=1:（10～20），C组分是二甲基十六烷基乙基硫酸乙酯铵，按重量计，C组分:扩孔改性载体的重量之比=1:（5～10），D组分由硼砂、硫酸钾、乙酰丙酮钐、三(4,4,4-三氟-1-(2-噻吩)-1,3-丁二酮)铕、三氟甲烷磺酸铥(III)、碳酸镥水合物稀土金属化合物催化活性助剂，葡萄糖酸钴、L -天门冬氨基酸钼、四氯金钾、六亚硝基铑三钠、十二酰胺丙基二甲基二羟丙基氯化铵组成，按重量计，硼砂:硫酸钾:乙酰丙酮钐:三(4,4,4-三氟-1-(2-噻吩)-1,3-丁二酮)铕:三氟甲烷磺酸铥(III):碳酸镥水合物:葡萄糖酸钴:L -天门冬氨基酸钼:四氯金钾:六亚硝基铑三钠:十二酰胺丙基二甲基二羟丙基氯化铵的重量之比=（4～8）:（6～10）:（3～6）:（4～7）:（5～8）:（6～9）:（10～15）:（12～18）:（4～7）:（6～9）:（6～20）。所述B组分中的活性炭、光卤石、伊利石、钠硼解石、氢氧化铝、天青石分别进行粉碎，去离子水洗涤干燥除去水分后，经标准筛进行-200目、+400目筛分，控制粒径为0.0370mm～0.0750 mm。
本发明的技术方法是这样实现的：在可密闭反应器中加入次氯酸锂LiClO、双(乙酰丙酮)铍C10H14BeO4和去离子水搅拌制备水溶液，加入筛分后粒径为0.0370mm～0.0750mm的活性炭、光卤石、伊利石、钠硼解石、氢氧化铝、天青石等多孔矿物材料载体，在一定温度和搅拌条件下，水溶液中离子半径小的Be2+（0.31Å）、Li+（0.60Å）置换出多孔矿物材料中部分离子半径大的Ca2+（0.99Å）、K+（1.33Å）、Ba2+（1.35Å）等离子，多孔矿物材料载体的孔径变大、表面粗糙度增加，因此催化剂的吸附容量提高；洗涤过滤、干燥恒重后的扩孔改性载体投入超声波反应器，再加入二甲基十六烷基乙基硫酸乙酯铵[C16H33N(CH3)2C2H5]+C2H5SO4 -水溶液，控制超声功率密度、超声波频率、温度和超声振荡时间，在超声波空化作用下，二甲基十六烷基乙基硫酸乙酯铵[C16H33N(CH3)2C2H5]+C2H5SO4 -易于从水溶液逸出进入扩孔改性载体孔道或附着在扩孔改性载体表面，有益于载体孔道的相互连通和载体表面活化，提高了吸附选择性；超声活化完成后，超声表面活化载体混合液转移至水热反应釜中，与硼砂Na2B4O7·10H2O、硫酸钾K2SO4复合矿化剂，催化活性助剂乙酰丙酮钐C15H25O8Sm、三(4,4,4-三氟-1-(2-噻吩)-1,3-丁二酮)铕C24H18EuF9O6S3、三氟甲烷磺酸铥(III)C3F9O9S3Tm、碳酸镥水合物C3H2Lu2O10稀土金属化合物，催化活性中心组分过渡金属葡萄糖酸钴[VO2(C9H8N3O5)](C5H5N)、L -天门冬氨基酸钼Mo[OOCCH2CH(NH2)COO]3(H2O)3、四氯金钾KAuCl4和六亚硝基铑三钠Na3Rh(NO2)6贵金属化合物，乳化剂十二酰胺丙基二甲基二羟丙基氯化铵[C11H23CONHCH2CH2N(CH3)2CH2CH(OH)CH2OH]+ Cl-进行水热反应，矿化剂加速扩散作用、使反应物晶格活化，促进了固相反应的进行，稀土金属化合物作催化活性助剂与多组分过渡金属和贵金属反应均匀掺杂，乳化剂十二酰胺丙基二甲基二羟丙基氯化铵使反应液形成准稳态的乳液防止了固液分离、沉降，同时对多孔矿物载体进一步表面活化，通过在一定温度、时间的水热反应，冷却、烘干得到均匀掺杂的细粉粒物；均匀掺杂的细粉粒物在马弗炉内，经高温灼烧，其中的有机物完全碳化进一步强化了多孔载体的微孔结构，得到多孔载体负载稀土金属氧化物、过渡金属氧化物和贵金属形成的催化活性中心的臭氧非均相氧化固体催化剂，增强了催化剂的抗毒性，提高了催化活性。
相对于现有技术方法，本发明突出优点是制备技术中使用活性炭、光卤石、伊利石、钠硼解石、氢氧化铝、天青石等多孔矿物材料作载体，由于次氯酸锂LiClO和双(乙酰丙酮)铍C10H14BeO4的扩孔效应，二甲基十六烷基乙基硫酸乙酯铵[C16H33N(CH3)2C2H5]+C2H5SO4 -、十二酰胺丙基二甲基二羟丙基氯化铵[C11H23CONHCH2CH2N(CH3)2CH2CH(OH)CH2OH]+ Cl-对孔道的相互连通和表面活化作用，有机物完全碳化强化了多孔载体的微孔结构，通过水热反应均匀掺杂与高温灼烧制备的多孔载体负载稀土金属氧化物、过渡金属氧化物和贵金属形成的多元金属催化活性中心的臭氧非均相氧化固体催化剂具有更强的吸附选择性和更高的吸附容量，多元金属的协同效应、特别是掺杂贵金属的稳定性和高活性，可以抑制金属的熔析出，增强了催化剂的抗毒性，提高了催化活性，具有良好的环境效益和经济效益。
具体实施方式
实施例1:1.35g次氯酸锂，1.65g双(乙酰丙酮)铍，140ml去离子水，加入到容积为500ml的可密闭反应器中搅拌混合均匀，该水溶液的重量浓度为2.1%，次氯酸锂:双(乙酰丙酮)铍的重量之比=1:1.2；加入洗涤过筛-200目～+400目标准筛的2.75g活性炭、3.75g光卤石、4.75g伊利石、5.75g钠硼解石、6.75g氢氧化铝、7.75g天青石，次氯酸锂和双(乙酰丙酮)铍的重量（3g）:多孔矿物材料的重量（31.5g）=1:9.5，升温至36℃，继续搅拌反应3.2h，洗涤过滤，干燥恒重后得到扩孔改性载体31g；在500ml超声波反应器中，投入扩孔改性载体31g，再加入3.25g二甲基十六烷基乙基硫酸乙酯铵溶于100ml去离子水的水溶液，该水溶液的重量浓度为3.1%，搅拌混合均匀，二甲基十六烷基乙基硫酸乙酯铵（3.25g）:扩孔改性载体（31g ）=1:9.5；控制超声功率密度为0.4W/m3、超声波频率21kHz、温度41℃，超声振荡2.2h；超声活化完成后，把超声波反应器中的超声表面活化载体混合液转移至500ml水热反应釜中，再加入由2.1g硼砂、3.05g硫酸钾、1.6g乙酰丙酮钐、2.05g三(4,4,4-三氟-1-(2-噻吩)-1,3-丁二酮)铕、2.6g三氟甲烷磺酸铥(III)、3. 05g碳酸镥水合物、5.05g葡萄糖酸钴、6.1gL -天门冬氨基酸钼、2. 05g四氯金钾、3.1g六亚硝基铑三钠、3.05g十二酰胺丙基二甲基二羟丙基氯化铵和50ml去离子水配制的水溶液，该水溶液的重量浓度为40.3%，该水溶液的重量:超声表面活化载体混合液的重量=83.8g:134.25g=1:1.6，控制温度125℃，水热反应时间为8.3h，然后进行冷却，烘干得细粉粒物；细粉粒物在马弗炉内，620℃，灼烧3.2h，降温冷却后，得到臭氧非均相氧化固体催化剂，该臭氧非均相氧化固体催化剂为细粉颗粒状。
实施例2:0.24g次氯酸锂，0.36g双(乙酰丙酮)铍，10ml去离子水，加入到容积为100ml的可密闭反应器中搅拌混合均匀，该水溶液的重量浓度为5.7%，次氯酸锂:双(乙酰丙酮)铍的重量之比=1:1.5；加入洗涤过筛-200目～+400目标准筛的1.45g活性炭、1.65g光卤石、1.85g伊利石、2.05g钠硼解石、2.25g氢氧化铝、2.45g天青石，次氯酸锂和双(乙酰丙酮)铍的重量（0.6g）:多孔矿物材料的重量（11.7g）=1:19.5，升温至48℃，继续搅拌反应5.8h，洗涤过滤，干燥恒重后得到扩孔改性载体11.5g；在100ml超声波反应器中，投入扩孔改性载体11.5g，再加入2.2g二甲基十六烷基乙基硫酸乙酯铵溶于26ml去离子水的水溶液，该水溶液的重量浓度为7.8%，搅拌混合均匀，二甲基十六烷基乙基硫酸乙酯铵（2.2g）:扩孔改性载体（11.5g ）=1:5.2；控制超声功率密度为0.7W/m3、超声波频率29kHz、温度54℃，超声振荡4.7h；超声活化完成后，把超声波反应器中的超声表面活化载体混合液转移至100ml水热反应釜中，再加入由0.78g硼砂、0.97g硫酸钾、0.58g乙酰丙酮钐、0.67g三(4,4,4-三氟-1-(2-噻吩)-1,3-丁二酮)铕、0.78g三氟甲烷磺酸铥(III)、0.87g碳酸镥水合物、1.48g葡萄糖酸钴、1.77gL -天门冬氨基酸钼、0.68g四氯金钾、0.87g六亚硝基铑三钠、1.98g十二酰胺丙基二甲基二羟丙基氯化铵和10ml去离子水配制的水溶液，该水溶液的重量浓度为53.3%，该水溶液的重量:超声表面活化载体混合液的重量=21.43g:39.7g=1:1.9，控制温度175℃，水热反应时间为15.5h，然后进行冷却，烘干得细粉粒物；细粉粒物在马弗炉内，930℃，灼烧7.5h，降温冷却后，得到臭氧非均相氧化固体催化剂，该臭氧非均相氧化固体催化剂为细粉颗粒状。
比较例1: 制备过程不加次氯酸锂、双(乙酰丙酮)铍、二甲基十六烷基乙基硫酸乙酯铵、十二酰胺丙基二甲基二羟丙基氯化铵、硼砂和硫酸钾外，整个制备过程、制备条件和实施例1完全相同。
实施例1、实施例2和比较例1制备的臭氧非均相氧化固体催化剂的参数列入表1。
表1实施例和比较例制备臭氧非均相氧化固体催化剂参数
项目 平均孔径(nm) 孔体积(cm3/g) BET比表面(m2/g)
实施例1 4.723 0.6246 758.77
实施例2 4.226 0.5739 641.39
比较例1 2.393 0.3385 454.49

Claims (2)

1.一种臭氧非均相氧化固体催化剂的制备方法，其特征是在可密闭反应器中加入A组分和去离子水搅拌制备水溶液，控制A组分的重量浓度为2%～6%，溶液制备完成后，在搅拌下加入B组分，升温至35℃～50℃，继续搅拌反应3h～6h，洗涤过滤，干燥恒重后得到扩孔改性载体，扩孔改性载体投入超声波反应器，加入由C组分和去离子水配制的水溶液，C组分的重量浓度为3%～8%，搅拌混合均匀，控制超声功率密度为0.3～0.8W/m3、频率20kHz～30kHz、40℃～55℃，超声振荡2h～5h，得到超声表面活化载体混合液，转移至水热反应釜中，再加入D组分和去离子水配制的水溶液，D组分的重量浓度为40%～55%，按重量计，D组分去离子水溶液:超声表面活化载体混合液的重量比=1:（1.5～2），控制温度120℃～180℃，水热反应时间为8h～16h，然后进行冷却，烘干得细粉粒物，细粉粒物在马弗炉内，600℃～950℃，灼烧3h～8h，得到臭氧非均相氧化固体催化剂；所述A组分由次氯酸锂、双(乙酰丙酮)铍组成，按重量计，次氯酸锂:双(乙酰丙酮)铍的重量之比=1:（1～1.6），B组分由活性炭、光卤石、伊利石、钠硼解石、氢氧化铝、天青石组成，按重量计，活性炭:光卤石:伊利石:钠硼解石:氢氧化铝:天青石的重量之比=（5～15）:（7～17）:（9～19）:（11～21）:（13～23）:（15～25），按重量计，A组分:B组分的重量之比=1:（10～20），C组分是二甲基十六烷基乙基硫酸乙酯铵，按重量计，C组分:扩孔改性载体的重量之比=1:（5～10），D组分由硼砂、硫酸钾、乙酰丙酮钐、三(4,4,4-三氟-1-(2-噻吩)-1,3-丁二酮)铕、三氟甲烷磺酸铥(III)、碳酸镥水合物稀土金属化合物催化活性助剂，葡萄糖酸钴、L -天门冬氨基酸钼、四氯金钾、六亚硝基铑三钠、十二酰胺丙基二甲基二羟丙基氯化铵组成，按重量计，硼砂:硫酸钾: 乙酰丙酮钐:三(4,4,4-三氟-1-(2-噻吩)-1,3-丁二酮)铕:三氟甲烷磺酸铥(III):碳酸镥水合物:葡萄糖酸钴:L -天门冬氨基酸钼:四氯金钾:六亚硝基铑三钠:十二酰胺丙基二甲基二羟丙基氯化铵的重量之比=（4～8）:（6～10）:（3～6）:（4～7）:（5～8）:（6～9）:（10～15）:（12～18）:（4～7）:（6～9）:（6～20）。
2.根据权利要求1所述B组分由活性炭、光卤石、伊利石、钠硼解石、氢氧化铝、天青石组成，活性炭、光卤石、伊利石、钠硼解石、氢氧化铝、天青石分别进行粉碎，去离子水洗涤干燥除去水分后，经标准筛进行筛分，控制粒径为0.0370mm～0.0750mm。
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Application publication date: 20170804