CN102125825A - 一种ZrO2纳米管负载B2O3催化剂的制备方法 - Google Patents

一种ZrO2纳米管负载B2O3催化剂的制备方法 Download PDF

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CN102125825A
CN102125825A CN 201010571056 CN201010571056A CN102125825A CN 102125825 A CN102125825 A CN 102125825A CN 201010571056 CN201010571056 CN 201010571056 CN 201010571056 A CN201010571056 A CN 201010571056A CN 102125825 A CN102125825 A CN 102125825A
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CN102125825B (zh
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王西新
赵建玲
侯晓蕊
赵靓
唐成春
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Hebei University of Technology
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Abstract

本发明为一种ZrO2纳米管负载B2O3催化剂的制备方法。该方法包括以下步骤：配制含有浓度为0.5-1.0％NH4F、0.1-6％硼化物和5-12％(NH4)2SO4的水溶液，以其作为反应介质，锆片作阳极，铂片作阴极，阳极与阴极间距离为1.5cm，采用10-30V直流电室温进行阳极氧化，反应3-5小时，停止反应，将氧化物干燥、焙烧即制得催化剂；所述的浓度百分比均为质量百分比。本发明所制备B2O3/ZrO2催化剂同时具有较大的比表面积和体积，当比表面积与纳米粉体相同时，体积是纳米粉体的上万倍，解决了粉体载体比表面积与体积之间的矛盾，可克服粉体ZrO2负载B2O3催化剂所存在的缺陷。

Description

一种ZrO<sub>2</sub>纳米管负载B<sub>2</sub>O<sub>3</sub>催化剂的制备方法
技术领域
本发明属于纳米功能材料制备技术领域，特别涉及一种ZrO2纳米管负载B2O3催化剂的制备方法。
技术背景
氧化锆同时具有酸性、碱性、氧化性和还原性，是一种性能优异的催化剂载体。ZrO2负载B2O3催化剂对烷烃异构化、酚的烷基化、Friedel-Crafts酰基化、酯交换、Beckmann重排等反应都具有很好的催化性能。
目前，ZrO2负载B2O3催化剂的制备方法主要分为两个步骤，首先采用沉淀法、溶胶-凝胶法等方法制备ZrO2载体，然后以硼酸等为硼源制备催化剂。
《Journal of Molecular Catalysis A》(2004，212，P337-344)报导一种制备B2O3/ZrO2催化剂的方法，该方法采用沉淀法制备载体，将氨水滴入ZrOCl2·8H2O溶液中生成沉淀物，沉淀物经过滤、洗涤、干燥制得氢氧化氧锆，然后把氢氧化氧锆加入硼酸水溶液中，搅拌、浓缩，干燥、煅烧制得催化剂。
《Catalysis Communications》(2002，3，P411-416)报导一种制备B2O3/ZrO2催化剂的方法，该方法以ZrO(NO3)2·2H2O为锆源，具体步骤与前述方法相同。
《Applied Catalysis A》(2004，263，P83-89)报导一种制备B2O3/TiO2-ZrO2催化剂的方法，该方法采用溶胶-凝胶法制备载体，分别配置TiCl4和ZrOCl2·8H2O的无水甲醇溶液，冰浴冷却，在0℃温度下搅拌混合，在搅拌条件下将氨水的无水乙醇溶液加入TiCl4和ZrOCl2·8H2O的无水甲醇混合溶液中，水解形成凝胶，经老化、过滤、洗涤、干燥，得到TiO2-ZrO2复合氧化物载体，然后以硼酸为硼源、采用浸渍法制得催化剂。
上述方法制得的ZrO2载体负载B2O3催化剂都是粉体，存在制备工艺过程复杂、废液量大等缺点。众所周知，载体的结构、形貌、比表面积等对催化剂的性能有显著影响。常用的粉体载体比表面积较小，限制了其应用；纳米粉体载体虽可提高催化剂的比表面积和催化活性，但颗粒太小，存在不易与反应介质分离、流失严重、介质流动阻力大等缺陷。
发明内容
本发明所要解决的技术问题是：提供一种阳极氧化法制备B2O3/ZrO2纳米管负载催化剂的方法，以解决现有粉体载体负载B2O3催化剂所存在的缺陷以及制备工艺过程复杂、废液量大等缺点。
本发明解决该技术问题所采用的技术方案是：
一种ZrO2纳米管负载B2O3催化剂的制备方法，包括以下步骤：
配制含有浓度为0.5-1.0％NH4F、0.1-6％硼化物和5-12％(NH4)2SO4的水溶液，以其作为反应介质，锆片作阳极，铂片作阴极，阳极与阴极间距离为1.5cm，采用10-30V直流电室温进行阳极氧化，反应3-5小时，停止反应，将氧化物干燥、焙烧即制得催化剂；
所述的浓度百分比均为质量百分比。
按上述方法所制B2O3/ZrO2纳米管负载催化剂的长度20-60μm、管径50-150nm。
上述制备方法中所述的硼化物为硼酸、硼酸铵中的一种或两种的混合物。
本发明的有益效果是：
(1)本发明的突出特点是，在电解液中加入0.1-6％(wt)的硼化物，采用阳极氧化法直接制备ZrO2纳米管负载B2O3催化剂。所用硼化物为硼酸、硼酸铵中的一种或两种的混合物，硼酸或硼酸根在阳极氧化过程中会进入ZrO2纳米管结构中。
(2)本发明的显著特点是，所制备B2O3/ZrO2催化剂的载体是氧化锆纳米管，同时具有较大的比表面积和体积，当比表面积与纳米粉体相同时，体积是纳米粉体的上万倍，解决了粉体载体比表面积与体积之间的矛盾，可克服粉体ZrO2负载B2O3催化剂所存在的缺陷。另外，氧化锆纳米管载体高的长径比和内部中空的管状结构有利于催化剂性能的提高。
(3)本发明的显著特点是，制备工艺简单，操作方便，成本低，催化剂的管径和管长可控，易于工业化生产。所用电解液基本无毒，可回收、循环使用。
(4)本发明合适的阳极氧化电压为10-30V，电压升高，反应速度加快，管径增大；电压降低，反应速度减慢，管径缩小。
通过调整电解液组成、阳极氧化电压和反应时间，能够制备长度20-60μm、管径50-150nm的ZrO2纳米管负载B2O3催化剂。
附图说明：
图1为本发明实施例1所制备的ZrO2纳米管负载B2O3催化剂实物图。
下面结合附图和实施例对本发明进一步说明。
具体实施方式
实施例1
配制含1.0％(wt)NH4F、2％(wt)硼酸、10％(wt)(NH4)2SO4的水溶液为反应介质，锆片作阳极，铂片作阴极，阳极与阴极间距离为1.5cm，采用20V直流电室温进行阳极氧化反应4小时，在锆片表面生成氧化物。反应结束后，将氧化物120℃干燥、500℃焙烧即制得催化剂。
从附图1中可以看出：该催化剂管径120nm，长度达到50μm，比表面积为24.3m2/g，与直径42nm粉体的比表面积相似，体积是粉体的1.46万倍。
实施例2
配制含0.5％(wt)NH4F、6％(wt)硼酸铵、5％(wt)(NH4)2SO4的水溶液为反应介质，锆片作阳极，铂片作阴极，阳极与阴极间距离为1.5cm，采用30V直流电室温进行阳极氧化反应3小时，在锆片表面生成氧化物。反应结束后，将氧化物120℃干燥、400℃焙烧即制得催化剂。
实施例3
配制含1.0％(wt)NH4F、0.1％(wt)硼酸、12％(wt)(NH4)2SO4的水溶液为反应介质，锆片作阳极，铂片作阴极，阳极与阴极间距离为1.5cm，采用10V直流电室温进行阳极氧化反应5小时，在锆片表面生成氧化物。反应结束后，将氧化物120℃干燥、600℃焙烧即制得催化剂。
实施例4
配制含0.5％(wt)NH4F、4％(wt)硼酸铵、12％(wt)(NH4)2SO4的水溶液为反应介质，锆片作阳极，铂片作阴极，阳极与阴极间距离为1.5cm，采用20V直流电室温进行阳极氧化反应5小时，在锆片表面生成氧化物。反应结束后，将氧化物120℃干燥、400℃焙烧即制得催化剂。
实施例5
配制含0.6％(wt)NH4F、3％(wt)硼酸、8％(wt)(NH4)2SO4的水溶液为反应介质，锆片作阳极，铂片作阴极，阳极与阴极间距离为1.5cm，采用15V直流电室温进行阳极氧化反应4小时，在锆片表面生成氧化物。反应结束后，将氧化物120℃干燥、400℃焙烧即制得催化剂。
实施例6
配制含0.5％(wt)NH4F、1％(wt)硼酸、4％(wt)硼酸铵、12％(wt)(NH4)2SO4的水溶液为反应介质，锆片作阳极，铂片作阴极，阳极与阴极间距离为1.5cm，采用10V直流电室温进行阳极氧化反应3小时，在锆片表面生成氧化物。反应结束后，将氧化物120℃干燥、600℃焙烧即制得催化剂。
实施例7
配制含0.8％(wt)NH4F、2％(wt)硼酸、2％(wt)硼酸铵、8％(wt)(NH4)2SO4的水溶液为反应介质，锆片作阳极，铂片作阴极，阳极与阴极间距离为1.5cm，采用20V直流电室温进行阳极氧化反应3小时，在锆片表面生成氧化物。反应结束后，将氧化物120℃干燥、600℃焙烧即制得催化剂。
实施例8
配制含1.0％(wt)NH4F、4％(wt)硼酸、2％(wt)硼酸铵、5％(wt)(NH4)2SO4的水溶液为反应介质，锆片作阳极，铂片作阴极，阳极与阴极间距离为1.5cm，采用30V直流电室温进行阳极氧化反应5小时，在锆片表面生成氧化物。反应结束后，将氧化物120℃干燥、600℃焙烧即制得催化剂。

Claims (3)

1.一种ZrO2纳米管负载B2O3催化剂的制备方法，其特征为包括以下步骤：
配制含有浓度为0.5-1.0％NH4F、0.1-6％硼化物和5-12％(NH4)2SO4的水溶液，以其作为反应介质，锆片作阳极，铂片作阴极，阳极与阴极间距离为1.5cm，采用10-30V直流电室温进行阳极氧化，反应3-5小时，停止反应，将氧化物干燥、焙烧即制得催化剂；
所述的浓度百分比均为质量百分比。
2.如权利要求1所述的ZrO2纳米管负载B2O3催化剂的制备方法，其特征为按上述方法所制催化剂的长度20-60μm、管径50-150nm。
3.如权利要求1所述的ZrO2纳米管负载B2O3催化剂的制备方法，其特征为所述的硼化物为硼酸、硼酸铵中的一种或两种的混合物。
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