CN106799233B - 一种用于去除水中痕量难降解有机物的中空纳米铜/稀土催化剂及其制备方法和应用 - Google Patents
一种用于去除水中痕量难降解有机物的中空纳米铜/稀土催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于水处理技术领域,具体涉及一种用于去除废水中痕量难降解有机物的催化剂的制备方法及应用。该催化剂是通过铜和稀土金属对于中空磁性纳米材料进行改性制得的。我们发现其在废水处理净化工艺中可以高效地选择性催化氧化废水中的痕量难降解有机物。本方法制备的催化剂具有能和反应液充分接触、选择性高、活性高、性能稳定、使用寿命长、易于回收重复利用的特点。
Description
技术领域
本发明属于水处理技术领域,具体涉及一种用于去除废水中痕量难降解有机物的催化剂的制备方法及应用。
背景技术
痕量难降解有机物,容易在生物体内富集,也容易成为水体的潜在污染源。这类污染物多包括多环芳烃、卤代烃、抗生素表面活性剂、有机染料等。它们的共同特点是毒性大、成分复杂、化学耗氧量高,因而一般处理技术对其降解效果很差。如果这些物质不加处理的排放到环境中,势必会造成其在环境中的富集,从而产生严重的污染环境并威胁人类的身体健康。随着工农业的发展,人们制造出了很多难降解有机物,传统的生物处理法在处理这类难降解有毒有机废水尤其是含残留微量难降解有机物的废水时显得力不从心,由此各种高级氧化技术应运而生,并且发展迅速。因此痕量难降解有机物的治理已成为了目前水污染防治研究中的热点和难点。
催化臭氧氧化技术在难降解有机物的污染治理中显示出很好的应用前景。其将臭氧的强氧化性、催化剂的吸附和催化特性相结合,能够在常温常压下高效地氧化甚至矿化那些传统臭氧氧化工艺难以氧化的有机污染物。然而,臭氧催化氧化过程中用到的均相催化剂通常为一些贵金属催化剂,价格昂贵。同时,这种均相催化剂的分离、回收及再生仍存在较大问题,催化氧化后催化剂的损耗较大。而非均相催化氧化因为催化剂制备工艺简单、易于回收处理、水处理成本较低等优点而成为了非常可行的方案。非均相催化剂主要包括金属氧化物(MnO2、Al2O3等)及负载于载体上的金属或金属氧化物(Cu-Al2O3,Mn-Al2O3,Mn-ZSM-5等)。然而,我们在试验过程中发现这些催化剂虽然价格十分便宜,但是通常存在单组分催化活性低,机械强度不够大,易粉碎,比表面积小,表面活性组分团聚或流失,不能很好的和反应液接触等问题。因此,基于本申请人课题组对于非均相催化氧化的研究,我们认为寻找一种同时具有均相和非均相催化体系优点的改性纳米催化剂是解决以上问题的有效方法,这种方法也逐步成为人们当下在相关领域研究的重点和难点。
发明内容
本发明目的在于解决上述现有技术存在的缺陷,提供一种用于去除水中痕量难降解有机物的催化剂及其制备方法和应用。
为了实现上述目的,本发明采用的技术方案为:
选用低密度,机械性能好,具有磁性的中空磁性纳米材料作为催化剂的载体。这种载体可通过催化剂悬浮使反应液充分接触,并且在回收过程可通过磁铁吸取省去离心或过滤等过程。鉴于传统单一金属活性组分催化剂的催化活性较差,本发明采用铜/稀土双金属改性上述的中空磁性纳米催化剂,我们发现这种双金属改性能高效地选择性催化氧化废水中的痕量难降解有机物。这对于降解有机物废水,减少污染物的排放,具有显著的实际应用意义。
本发明采用以下技术予以实现:
将铜和稀土金属溶液按一定的物质的量比例混合,用浸渍法将其负载到中空磁性纳米介孔载体上,从而制备铜/稀土改性中空磁性纳米介孔催化剂,本方法制备的催化剂选择性和活性高,性质稳定,使用寿命长,易于回收,可重复利用,可以有效地选择性催化氧化废水中的痕量抗生素。
这种制备方法具体包括以下步骤:
一种用于去除水中痕量难降解有机物的中空纳米铜/稀土催化剂的制备方法,包括以下步骤:
(a)将聚苯乙烯微球分散于水中,按照1:1-2的质量比向上述分散液中加入粒径5-15nm的四氧化三铁颗粒,在常温下调节pH值至2-3,使四氧化三铁通过静电吸附作用负载在聚苯乙烯微球表面,然后在上述溶液中滴加正硅酸乙酯和十八烷基三甲基硅烷的混合物,在常温常压下进行水解反应,待水解完全后将反应液过滤,经过焙烧,去除聚苯乙烯微球,得到中空磁性介孔纳米载体;
(b)将铜和稀土金属的可溶性盐按一定物质的量比例混合,形成浸渍液,并按照1wt%-50wt%的浸渍量,采用浸渍法负载到步骤(a)得到的中空磁性介孔纳米载体上,浸渍20-28小时后,将溶液过滤得到催化剂前驱体,将上述前驱体阴干20-28h,然后550-650℃下焙烧2-4h,即得到铜/稀土改性的中空纳米催化剂。
进一步地,在步骤(b)中,所述的稀土金属为镧、铈、钐、钇中的一种。
进一步地,在步骤(b)中,所述的铜和稀土金属的物质的量比例为1:1~1:4。
进一步地,在步骤(b)所述的浸渍过程中,浸渍液的质量分数为1%~50%。
进一步地,在步骤(a)中正硅酸乙酯和十八烷基三甲基硅烷的体积比为1-2:1。
进一步地,步骤(a)中的焙烧温度为550-650℃。
一种上述方法制备得到的中空纳米铜/稀土催化剂。
一种上述催化剂的用途,将其用于去除水中痕量难降解有机物。
进一步地,将中空纳米铜/稀土催化剂在25-35℃的条件下通入臭氧,催化氧化含有浓度为10-6-10-9mg/l难降解有机物的废水。
本发明的优点和有益效果:
本发明选用低密度,机械性能好,具有磁性的中空磁性纳米材料作为催化剂的载体。这种载体可通过催化剂悬浮使反应液充分接触,并且在回收过程可通过磁铁吸取省去离心或过滤等过程;
本发明开发了采用铜和稀土金属负载改性中空磁性纳米介孔材料制备催化剂,与传统催化剂相比,此催化剂为双组份协同催化剂,可以和反应液充分混合,选择性和活性高,性质稳定,使用寿命长,易于回收并且在重复利用阶段仍然可以保持很高的活性和稳定性(如图2所示)。同时测试结果表明,此催化剂可以有效地去催化氧化水中痕量的难降解有机物,因而在废水处理领域具有非常好的应用前景。
附图说明
图1 磁性纳米中空材料TEM图;
图2 催化剂的循环使用性能。
具体实施方式
为了使本发明的目的,技术方案和优点更加清晰,下面将结合本发明中的附图和实例对本发明作进一步的说明。以下实例只是本发明只是本发明的一些实例,并不是全部。基于本发明的实例,本领域其他人员在没有做出创造性劳动的前提下所获得其他实例,都属于本发明的保护范围之内。
下面结合实施例对本发明作进一步的说明。
实施例 1
将粒径为10nm的四氧化三铁与聚苯乙烯微球混合,质量比例为1:1.5,在常温下调节pH值至2.3使其充分反应,然后与正硅酸乙酯和十八烷基三甲基硅烷在常温常压下进行水解反应,其体积比为1.5:1,将正硅酸乙酯水解产生的二氧化硅负载到聚苯乙烯微球,过滤,600℃高温焙烧,去除中心的聚苯乙烯微球,得到中空磁性介孔球;
将硝酸铜和硝酸钇按物质的量之比为1:1,硝酸盐质量分数为10%,采用浸渍法负载到上述步骤得到的中空磁性介孔球上,过滤,阴干24h,600℃下焙烧3h,即得到铜、稀土钇改性中空磁性介孔球催化剂;
将铜、稀土钇改性中空磁性介孔球催化剂在30℃的条件下通入4.26mg/min的臭氧,催化氧化含浓度为10-7mol/L的抗生素废水,反应20min后,经液相色谱测定,抗生素的初期效率为99.35%。
实施例 2
将粒径为5nm的四氧化三铁与聚苯乙烯微球混合,质量比例为1:2,在常温下调节pH值至2使其充分反应,然后与正硅酸乙酯和十八烷基三甲基硅烷在常温常压下进行水解反应,其体积比为2:1,将正硅酸乙酯水解产生的二氧化硅负载到聚苯乙烯微球,过滤,550℃高温焙烧,去除中心的聚苯乙烯微球,得到中空磁性介孔球;
将硝酸铜和硝酸钇按物质的量之比为1:2,硝酸盐质量分数为1%,采用浸渍法负载到上述步骤得到的中空磁性介孔球上,过滤,阴干20h,550℃下焙烧4h,即得到铜、钇改性中空磁性介孔球催化剂;
将铜、钇改性中空磁性介孔球催化剂在35℃的条件下通入4.26mg/min的臭氧,催化氧化含浓度为10-7mol/L的罗丹明B废水,反应20min后,经液相色谱测定,罗丹明B的初期效率为91.92%。
实施例 3
将粒径为15nm的四氧化三铁与聚苯乙烯微球混合,质量比例为1:1,在常温下调节pH值至2.3使其充分反应,然后与正硅酸乙酯和十八烷基三甲基硅烷在常温常压下进行水解反应,其体积比为1:1,将正硅酸乙酯水解产生的二氧化硅负载到聚苯乙烯微球,过滤,650℃高温焙烧,去除中心的聚苯乙烯微球,得到中空磁性介孔球;
将硝酸铜和硝酸铈按物质的量之比为1:1配置成溶液,硝酸盐质量分数为50%,采用浸渍法负载到上述步骤得到的中空磁性介孔球上,过滤,阴干28h,650℃下焙烧2h,即得到铜、铈改性中空磁性介孔球催化剂;
将铜、铈改性中空磁性介孔球催化剂在30℃的条件下通入4.26mg/min的臭氧,催化氧化含浓度为10-9mol/L的亚甲基蓝废水,反应20min后,经液相色谱测定,亚甲基蓝的初期效率为88.91%。
实施例 4
催化剂载体制备如实例1所述;
将硝酸铜和硝酸钐按物质的量之比为1:1,质量分数为10%,采用浸渍法负载到上述步骤得到的中空磁性介孔球上,过滤,阴干24h,600℃下焙烧3h,即得到铜、钐改性中空磁性介孔球催化剂;
将铜、钐改性中空磁性介孔球催化剂在30℃的条件下通入4.26mg/min的臭氧,催化氧化含浓度为10-7mol/L的邻苯二甲酸二甲酯(DMP)废水,反应20min后,经液相色谱测定,DMP的初期效率为90.68%。
实施例 5
催化剂载体制备如实例1所述;
将硝酸铜和硝酸镧按物质的量之比为1:1,质量分数为10%,采用浸渍法负载到上述步骤得到的中空磁性介孔球上,过滤,阴干24h,600℃下焙烧3h,即得到铜、镧改性中空磁性介孔球催化剂;
将铜、镧改性中空磁性介孔球催化剂在30℃的条件下通入4.26mg/min的臭氧,催化氧化含浓度为10-6mol/L的苯酚废水,反应20min后,经液相色谱测定,苯酚的初期效率为92.56%。
实施例 6
催化剂载体制备如实例1所述;
将硝酸铜和硝酸钇按物质的量之比为1:1,质量分数为10%,采用浸渍法负载到上述步骤得到的中空磁性介孔球上,过滤,阴干24h,600℃下焙烧3h,即得到铜、钇改性中空磁性介孔球催化剂;
将铜、钇改性中空磁性介孔球催化剂在30℃的条件下通入6.48mg/min的臭氧,催化氧化含浓度为10-7mol/L的抗生素废水,反应20min后,经液相色谱测定,抗生素的初期效率为99.58%。
实施例 7
催化剂载体制备如实例1所述;
将硝酸铜和硝酸钇按物质的量之比为1:4,质量分数为30%,采用浸渍法负载到上述步骤得到的中空磁性介孔球上,过滤,阴干24h,600℃下焙烧3h,即得到铜、钇改性中空磁性介孔球催化剂;
将铜、钇改性中空磁性介孔球催化剂在30℃的条件下通入6.48mL/min的臭氧,催化氧化含浓度为10-7的4-氯苯酚废水,反应20min后,经液相色谱测定,4-氯苯酚的初期效率为87.31%。
图1、图2为实施例1得到催化剂的表征结果,如图1所示,磁性纳米中空材料的球形度比较好,分散较均匀,催化剂尺寸约为300nm,壁厚约为15nm。其表面有明显的黑点说明活性组分与磁性纳米中空材料结合,分散在载体的表面。从图2中可以看出,催化剂循环使用6次后催化剂降解率还在85%以上。实施例2-6得到催化剂的表征结果与实施例1相近,不在一一赘述。
Claims (6)
1.一种用于去除水中痕量难降解有机物的中空纳米铜/稀土催化剂的制备方法,其特征在于,包括以下步骤:
(a)将聚苯乙烯微球分散于水中,按照1:1-2的质量比向上述分散液中加入粒径5-15nm的四氧化三铁颗粒,在常温下调节pH值至2-3,使四氧化三铁通过静电吸附作用负载在聚苯乙烯微球表面,然后在上述溶液中滴加正硅酸乙酯和十八烷基三甲基硅烷的混合物,在常温常压下进行水解反应,待水解完全后将反应液过滤,经过焙烧,去除聚苯乙烯微球,得到中空磁性介孔纳米载体;
(b)将铜和稀土金属的可溶性盐按一定物质的量比例混合,形成浸渍液,并按照1wt%-50wt%的浸渍量,采用浸渍法负载到步骤(a)得到的中空磁性介孔纳米载体上,浸渍20-28小时后,将溶液过滤得到催化剂前驱体,将上述前驱体阴干20-28h,然后550-650℃下焙烧2-4h,即得到铜/稀土改性的中空纳米催化剂;
所述的稀土金属为镧、铈、钐、钇中的一种;
所述的铜和稀土金属的物质的量比例为1:1~1:4;
在步骤(b)所述的浸渍过程中,浸渍液的质量浓度为1%~50%。
2.根据权利要求1所述方法,其特征在于,在步骤(a)中正硅酸乙酯和十八烷基三甲基硅烷的体积比为1-2:1。
3.根据权利要求1所述方法,其特征在于,步骤(a)中的焙烧温度为550-650℃。
4.一种根据权利要求1~3任一项所述方法制备得到的中空纳米铜/稀土催化剂。
5.一种权利要求4所述催化剂的用途,其特征在于,用于去除水中痕量难降解有机物。
6.根据权利要求5所述的用途,其特征在于,将中空纳米铜/稀土催化剂在25-35℃的条件下通入臭氧,催化氧化含有浓度为10-6-10-9mg/L难降解有机物的废水。
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