CN111686802A - 一种环保型甲醛净化催化剂及其制备方法 - Google Patents
一种环保型甲醛净化催化剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种环保型甲醛净化催化剂及其制备方法,以TiO2纳米管与Ce基固态离子液体为复合载体,以贵金属Pd为活性组分,且催化剂中Pd的质量分数为2.0~8.0wt%;所述Ce基固态离子液体为Ce0.66[BMIM]PMo12O40、Ce0.33[BMIM]2PMo12O40、Ce0.33[BMIM]HPMo12O40中的一种;所述催化剂通过TiO2纳米管的制备,TiO2纳米管与Ce基固态离子液体复合载体的合成,活性组分Pd的负载三步最终得到甲醛净化用的Pd基催化剂。本发明所制备的催化剂在保持较高催化效率的前提下,具有优异的抗湿性能以及稳定性。
Description
技术领域
本发明属于环境保护技术领域,涉及一种甲醛净化技术,特别是涉及一种环保型甲醛室温净化催化剂及其制备方法。
背景技术
甲醛是人民最熟悉的室内主要空气污染物之一,不仅是室内装修的产物,而且已经无处不在地渗透到我们的日常生活中,如抽油烟机排气、二手烟雾、汽车材料、油漆涂料、水产品等均会释放出甲醛。游离的甲醛分子充斥在我们生活环境中,危害着人们的身体健康。据有关报道称,长时间居住在含有甲醛的环境内会引起嗓子不舒服、眼睛酸痛等症状,并且容易诱发白血病等癌症,严重时甚至会引起死亡。有关部门对装修住宅区的空气质量进行检测,报告结果表明,70%甲醛含量超过国家规定标准。由此可见,甲醛潜在的影响已经不可忽视,针对它的治理已引起大家的高度重视,如何在短时间内高效脱除甲醛已经成为人们迫切需要解决的难题,探寻有效去除甲醛的方法具有重要意义,进而为人类提供一个绿色健康的生活环境。
目前消除甲醛污染的方法主要由通风法、植物净化法、物理吸附法、光降解法、生物法和催化氧化法等。目前应用比较广泛的技术主要由吸附法和催化氧化法,吸附法虽然简单易行,但是存在易受其他组分竞争吸附、吸附时间短且吸附剂再生困难等问题。催化氧化法是将甲醛和氧气在催化剂作用下发生反应生成水和二氧化碳的反应,其具有效率高、操作易控制、无二次污染等优点,具有较大的潜在能力。但对于催化氧化法而言,不同类型的催化剂对于甲醛的转化率有着较大的差异,提高催化剂的脱除效率是催化氧化技术应用的关键步骤。
中国专利CN105854594A将银负载在二氧化钛上制得一种空气中去除甲醛的催化剂,其可以将空气中的甲醛氧化成二氧化碳;美国专利US 5585083发明看了一种Pt/SnO2催化剂去除空气中甲醛的方法,催化剂在没有额外输入能量的条件下在-5~25℃下可以将甲醛完全降解为二氧化碳和水。中国CN102941111A公开了一种用于室温甲醛净化的金属载体负载的催化剂,所述催化剂由金属载体、负载于金属载体上的多孔无机材料、负载于多孔无机材料上的贵金属活性组分和助剂组成,所述金属载体为铁铬铝合金,所述贵金属选自铂、铑、钯、金或银中的任意一种或者至少两种的混合物,所述助剂为碱金属单质、碱金属化合物、碱土金属单质或碱土金属化合物中的任意一种或者至少两种的混合物。上述发明中的催化剂抗湿性能和稳定性都较差。
发明内容
为了解决现有甲醛净化技术中存在的问题,本发明公开了一种环保型甲醛净化催化剂及其制备方法,以TiO2纳米管与Ce基固态离子液体为复合载体,以贵金属Pd为活性组分,所述催化剂在保持较高催化效率的前提下,具有优异的抗湿性能以及稳定性。
本发明是通过如下技术方案实现的:
一方面,本发明公开了一种环保型甲醛净化催化剂,以TiO2纳米管与Ce基固态离子液体为复合载体,以Pd为活性组分,负载活性组分Pd所采用的方法为NaBH4还原手段,且催化剂中Pd的质量分数为2.0~8.0wt%;所述Ce基固态离子液体为Ce0.66[BMIM]PMo12O40、Ce0.33[BMIM]2PMo12O40、Ce0.33[BMIM]HPMo12O40中的一种。
另一方面,本发明还公开了一种环保型甲醛净化催化剂的制备方法,具体是通过如下步骤实现的:
(1)TiO2纳米管的制备
将 P25加入到物质的量为10mol/L的氢氧化钠溶液中混合均匀,然后转移至水热反应釜中在130-160℃下反应18-30h,将所得产物经离心、洗涤、干燥后于400-600℃焙烧处理4-6h,即可得到TiO2纳米管;
(2)TiO2纳米管与Ce基固态离子液体复合载体的合成
将TiO2纳米管、磷钼酸、硝酸铈、 1-丁基-3-甲基咪唑(BMIM)加入到去离子水中得到混合物A,在室温下搅拌15min后转移至超声反应釜中,同时通入氮气25-35min以去除反应釜中的空气,随后在室温条件下于150W~300W反应3h~6h,然后进行离心,所得固体产物在70-90℃干燥3-5h,所得固体即为TiO2纳米管与Ce基固态离子液体的复合载体;磷钼酸、硝酸铈和 1-丁基-3-甲基咪唑在该反应过程中形成Ce基固态离子液体;
(3)活性组分Pd的负载
在室温条件下配置PdCl2溶液,然后向其中加入PVP(平均分子量10000)搅拌30min,接着向其中加入新鲜配置的NaBH4溶液并继续搅拌30min,将步骤(2)制备的TiO2纳米管与Ce基固态离子液体复合载体加入到其中并继续搅拌1h,依次经离心、洗涤、干燥得到Pd基催化剂。
作为一种优选实施方式,步骤(1)中,在150℃的水热反应釜中反应24h,将所得产物经离心、洗涤、干燥后于500℃焙烧处理5h,即可得到TiO2纳米管。
作为一种优选实施方式,步骤(2)中,向超声反应釜中通入氮气30min,随后在室温条件下于200W反应5h,然后进行离心,所得固体产物在80℃干燥4h,所得固体即为TiO2纳米管与Ce基固态离子液体的复合载体;进一步地,混合物A中TiO2纳米管的质量浓度为10~20g/100mL;磷钼酸、硝酸铈、 1-丁基-3-甲基咪唑的摩尔比为1:(1~2):(0.33~0.66);混合物A中1-丁基-3-甲基咪唑的摩尔浓度为0.1mol/L。
作为一种优选实施方式,步骤(3)中,PVP与元素Pd的质量比为(0.5~0.8):1;NaBH4与元素Pd的摩尔比为(5~10):1。
与现有技术相比,本发明具有如下有益效果。
1)本发明将金属阳离子和有机阳离子掺杂,共同作为杂多酸根的反荷离子,从而成功的将Lewis酸性引入杂化材料的阳离子部分,制备出无机-有机杂化的同时具有Brönsted-Lewis双酸性的类离子液体催化剂;这种引入Lewis酸性的方式有效避免了水不稳定性,从而为甲醛在较高湿度下进行完全转化反应提供了良好的保障。
2)Ce基固态离子液体在催化剂表面形成的独特微环境,其可以有效避免反应过程中水气对催化活性的抑制,而且还可以强化TiO2纳米管与Pd之间的协同效应,从而在室温下将甲醛完全催化转化为二氧化碳和水。
3)本发明采用TiO2纳米管和Ce基固态离子液体作为复合载体,其不仅具
有高比表面积而且表面还具有丰富的氧空位,一方面有利于活性组分Pd获得均匀分散;另一方面Ce以离子液体形态和TiO2之间形成的强相互作用会进一步强化活性氧物种的迁移从而强化催化氧化效果。
具体实施方式
下面结合具体实施方式对本发明作进一步的说明,需要注意的是本发明并不局限于以下的实施例,在本发明所述的所有实验条件范围内对本发明所做的任何变动均属于本发明的保护范围。
实施例1
1)TiO2纳米管的制备:称取4g P25(TiO2) 加入到40mL 10mol/L的氢氧化钠溶液中,然后将混合溶液转移至水热反应釜中在150℃下反应24h,将所得产物经离心、洗涤、干燥后于500℃焙烧处理5h,即可得到TiO2纳米管。
2)TiO2纳米管与Ce基固态离子液体复合载体的合成
将TiO2纳米管、磷钼酸、硝酸铈、 1-丁基-3-甲基咪唑(BMIM)加入到去离子水中得到混合物A,在室温下搅拌15min后转移至超声反应釜中,同时通入氮气30min以驱除反应釜中的空气,随后在室温条件下于220W反应5h,反应结束中将混合物进行离心,所得固体产物在80℃干燥4 h,所得固体即为TiO2纳米管与Ce基固态离子液体Ce0.66[BMIM]PMo12O40复合载体。其中混合物A中TiO2纳米管的质量浓度为15g/100mL;磷钼酸、硝酸铈、 1-丁基-3-甲基咪唑的摩尔比为1:1:0.66;混合物A中BMIM的摩尔浓度为0.1mol/L。
3)活性组分Pd的负载
在室温条件下配置一定浓度的PdCl2溶液,然后向其中加入一定量的PVP(平均分子量10000)搅拌30min,接着向其中加入一定量新鲜配置的NaBH4溶液并继续搅拌30min,将制备的复合载体加入到其中并继续搅拌1h,最后将所得混合物经离心、洗涤、干燥后获得最终Pd含量为8 wt%的催化剂。其中PVP与元素Pd的质量比为0.65:1; NaBH4与元素Pd的摩尔比为8:1。该催化剂标记为A。
取0.1g催化剂A,放置于固定床反应器中进行试验,试验条件如下:氧气20%,氮气80%,甲醛气体由甲醛气体发生器产生,控制甲醛含量为600 ppm,空气湿度为50%,反应空速为50000 h-1,温度为25℃,反应6h后经气相色谱对尾气检测后计算所得甲醛转化率为99.98%。
实施例2。
1)TiO2纳米管的制备:称取4g P25(TiO2) 加入到40mL 10mol/L的氢氧化钠溶液中,然后将混合溶液转移至水热反应釜中在130℃下反应30h,将所得产物经离心、洗涤、干燥后于400℃焙烧处理6h,即可得到TiO2纳米管。
2)TiO2纳米管与Ce基固态离子液体复合载体的合成
将TiO2纳米管、磷钼酸、硝酸铈、 1-丁基-3-甲基咪唑(BMIM)加入到去离子水中得到混合物A,在室温下搅拌15min后转移至超声反应釜中,同时通入氮气25min以驱除反应釜中的空气,随后在室温条件下于150W反应6h,反应结束中将混合物进行离心,所得固体产物在70℃干燥5 h,所得固体即为TiO2纳米管与Ce基固态离子液体Ce0.33[BMIM]2PMo12O40的复合载体。其中混合物A中TiO2纳米管的质量浓度为10g/100mL;磷钼酸、硝酸铈、 1-丁基-3-甲基咪唑的摩尔比为1:2:0.33;混合物A中BMIM的摩尔浓度为0.1mol/L。
3)活性组分Pd的负载
在室温条件下配置一定浓度的PdCl2溶液,然后向其中加入一定量的PVP(平均分子量10000)搅拌30min,接着向其中加入一定量新鲜配置的NaBH4溶液并继续搅拌30min,将制备的复合载体加入到其中并继续搅拌1h,最后将所得混合物经离心、洗涤、干燥后获得Pd含量为5 wt%的催化剂。其中PVP与元素Pd的质量比为0.5:1; NaBH4与元素Pd的摩尔比为5:1。该催化剂标记为B。
取0.1g催化剂B,放置于固定床反应器中进行试验,试验条件如下:氧气20%,氮气80%,甲醛气体由甲醛气体发生器产生,控制甲醛含量为600 ppm,空气湿度为90%,反应空速为50000 h-1,温度为25℃,反应6h后经气相色谱对尾气检测后计算所得甲醛转化率为99.61%。
实施例3
1)TiO2纳米管的制备:称取4g P25(TiO2) 加入到40mL 10mol/L的氢氧化钠溶液中,然后将混合溶液转移至水热反应釜中在160℃下反应18h,将所得产物经离心、洗涤、干燥后于600℃焙烧处理4h,即可得到TiO2纳米管。
2)TiO2纳米管与Ce基固态离子液体复合载体的合成
将TiO2纳米管、磷钼酸、硝酸铈、 1-丁基-3-甲基咪唑(BMIM)加入到去离子水中得到混合物A,在室温下搅拌15min后转移至超声反应釜中,同时通入氮气35min以驱除反应釜中的空气,随后在室温条件下于300W反应3h,反应结束中将混合物进行离心,所得固体产物在90℃干燥3 h,所得固体即为TiO2纳米管与Ce基固态离子液体Ce0.33[BMIM]HPMo12O40的复合载体。其中混合物A中TiO2纳米管的质量浓度为20g/100mL;磷钼酸、硝酸铈、 1-丁基-3-甲基咪唑的摩尔比为1:1:0.33;混合物A中BMIM的摩尔浓度为0.1mol/L。
3)活性组分Pd的负载
在室温条件下配置一定浓度的PdCl2溶液,然后向其中加入一定量的PVP(平均分子量10000)搅拌30min,接着向其中加入一定量新鲜配置的NaBH4溶液并继续搅拌30min,将制备的复合载体加入到其中并继续搅拌1h,最后将所得混合物经离心、洗涤、干燥后获得最终Pd含量为2.0 wt%的催化剂。其中PVP与元素Pd的质量比为0.65:1; NaBH4与元素Pd的摩尔比为7.5:1。该催化剂标记为C。
取0.1g催化剂C,放置于固定床反应器中进行试验,试验条件如下:氧气20%,氮气80%,甲醛气体由甲醛气体发生器产生,控制甲醛含量为600 ppm,空气湿度为70%,反应空速为50000 h-1,,温度为25℃,反应6h后经气相色谱对尾气检测后计算所得甲醛转化率为99.46%。
实施例4。
取0.1g催化剂A,放置于固定床反应器中进行试验,试验条件如下:氧气20%,氮气80%,甲醛气体由甲醛气体发生器产生,控制甲醛含量为600 ppm,空气湿度为70%,反应空速为50000 h-1,温度为25℃,反应120h后经气相色谱对尾气检测后计算所得甲醛转化率由最初的99.98仅下降到99.85%。
对比实施例1。
1)TiO2纳米管的制备:称取4g P25(TiO2) 加入到40mL 10mol/L的氢氧化钠溶液中,然后将混合溶液转移至水热反应釜中在150℃下反应24h,将所得产物经离心、洗涤、干燥后于500℃焙烧处理5h,即可得到TiO2纳米管。
2)活性组分Pd的负载
在室温条件下配置一定浓度的PdCl2溶液,然后向其中加入一定量的PVP(平均分子量10000)搅拌30min,接着向其中加入一定量新鲜配置的NaBH4溶液并继续搅拌30min,将制备的TiO2纳米管加入其中并继续搅拌1h,最后将所得混合物经离心、洗涤、干燥后获得最终Pd含量为8 wt%的催化剂。其中PVP与元素Pd的质量比为0.65:1; NaBH4与元素Pd的摩尔比为8:1。该催化剂标记为D。
取0.1g催化剂D,放置于固定床反应器中进行试验,试验条件如下:氧气20%,氮气80%,甲醛气体由甲醛气体发生器产生,控制甲醛含量为600 ppm,空气湿度为50%,反应空速为50000 h-1,温度为25℃,反应6h后经气相色谱对尾气检测后计算所得甲醛转化率为88.45%,当继续反应到120h后甲醛转化率下降为73.43%。
对比实施例2。
1)Ce基固态离子液体的合成
将磷钼酸、硝酸铈、 1-丁基-3-甲基咪唑(BMIM)加入到去离子水中得到混合物A,在室温下搅拌15min后转移至超声反应釜中,同时通入氮气30min以驱除反应釜中的空气,随后在室温条件下于220W反应5h,反应结束中将混合物进行离心,所得固体产物在80℃干燥4h,所得固体即为Ce基固态离子液体Ce0.66[BMIM]PMo12O40。其中磷钼酸、硝酸铈、1-丁基-3-甲基咪唑的摩尔比为1:1:0.66;混合物A中BMIM的摩尔浓度为0.1mol/L。
2)活性组分Pd的负载
在室温条件下配置一定浓度的PdCl2溶液,然后向其中加入一定量的PVP(平均分子量10000)搅拌30min,接着向其中加入一定量新鲜配置的NaBH4溶液并继续搅拌30min,将制备的Ce0.66[BMIM]PMo12O40加入其中并继续搅拌1h,最后将所得混合物经离心、洗涤、干燥后获得最终Pd含量为8 wt%的催化剂。其中PVP与元素Pd的质量比为0.65:1; NaBH4与元素Pd的摩尔比为8:1。该催化剂标记为E。
取0.1g催化剂E,放置于固定床反应器中进行试验,试验条件如下:氧气20%,氮气80%,甲醛气体由甲醛气体发生器产生,控制甲醛含量为600 ppm,空气湿度为50%,反应空速为50000 h-1,温度为25℃,反应6h后经气相色谱对尾气检测后计算所得甲醛转化率为93.24%,当继续反应到120h后甲醛转化率下降为89.57%。
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是本发明的原理,在不脱离本发明精神和范围的前提下本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明的范围内。本发明要求的保护范围由所附的权利要求书及其等同物界定。
Claims (6)
1.一种环保型甲醛净化催化剂,其特征在于:以TiO2纳米管与Ce基固态离子液体为复合载体,以Pd为活性组分,且催化剂中Pd的质量分数为2.0~8.0wt%;所述Ce基固态离子液体为Ce0.66[BMIM]PMo12O40、Ce0.33[BMIM]2PMo12O40、Ce0.33[BMIM]HPMo12O40中的一种。
2.一种环保型甲醛净化催化剂的制备方法,其特征在于:是通过如下步骤实现的:
(1)TiO2纳米管的制备
将 P25加入到物质的量为10mol/L的氢氧化钠溶液中混合均匀,然后转移至水热反应釜中在130-160℃下反应18-30h,将所得产物经离心、洗涤、干燥后于400-600℃焙烧处理4-6h,即可得到TiO2纳米管;
(2)TiO2纳米管与Ce基固态离子液体复合载体的合成
将TiO2纳米管、磷钼酸、硝酸铈、 1-丁基-3-甲基咪唑加入到去离子水中得到混合物A,在室温下搅拌15min后转移至超声反应釜中,同时通入氮气25-35min以去除反应釜中的空气,随后在室温条件下于150W~300W反应3h~6h,然后进行离心,所得固体产物在70-90℃干燥3-5h,所得固体即为TiO2纳米管与Ce基固态离子液体的复合载体;磷钼酸、硝酸铈和 1-丁基-3-甲基咪唑在该反应过程中形成Ce基固态离子液体;
(3)活性组分Pd的负载
在室温条件下配置PdCl2溶液,然后向其中加入PVP(平均分子量10000)搅拌30min,接着向其中加入新鲜配置的NaBH4溶液并继续搅拌30min,将步骤(2)制备的TiO2纳米管与Ce基固态离子液体的复合载体加入到其中并继续搅拌1h,依次经离心、洗涤、干燥得到Pd基催化剂。
3.如权利要求2所述的环保型甲醛净化催化剂的制备方法,其特征在于:步骤(1)中,在150℃的水热反应釜中反应24h,将所得产物经离心、洗涤、干燥后于500℃焙烧处理5h,即可得到TiO2纳米管。
4.如权利要求2所述的环保型甲醛净化催化剂的制备方法,其特征在于:步骤(2)中,向超声反应釜中通入氮气30min,随后在室温条件下于200W反应5h,然后进行离心,所得固体产物在80℃干燥4h,所得固体即为TiO2纳米管与Ce基固态离子液体的复合载体。
5.如权利要求4所述的环保型甲醛净化催化剂的制备方法,其特征在于:步骤(2)中,混合物A中TiO2纳米管的质量浓度为10~20g/100mL;磷钼酸、硝酸铈、 1-丁基-3-甲基咪唑的摩尔比为1:(1~2):(0.33~0.66);混合物A中1-丁基-3-甲基咪唑的摩尔浓度为0.1mol/L。
6.如权利要求2所述的环保型甲醛净化催化剂的制备方法,其特征在于:步骤(3)中,PVP与元素Pd的质量比为(0.5~0.8):1; NaBH4与元素Pd的摩尔比为(5~10):1。
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CN115624975A (zh) * | 2022-10-28 | 2023-01-20 | 华侨大学 | 一种适用于室温高效脱除甲醛的非贵金属催化剂及其制备方法 |
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