CN106215932B - 一种新型臭氧催化剂及其制备方法 - Google Patents
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Abstract
本发明涉及臭氧催化氧化使用的一种新型复合型催化剂及其制备方法，其目的在于制备一种高效、稳定的用于废水深度处理的臭氧催化氧化催化剂。本发明所述的催化剂为在活性炭或其他多孔载体上负载锰、镁双金属氧化物活性物质，其制备方法包括选择多孔载体材料并进行预处理；将多孔材料载体置于金属盐溶液中，使金属离子深入到多孔材料内部；加入氢氧化钠等易溶强碱溶液形成金属氢氧化物沉淀，并附着于载体上；将负载完成的多孔型催化剂进行干燥、焙烧获得催化剂成品。本发明的催化剂较单一催化剂提高了催化效率，克服了锰系催化剂易流失和镁系催化剂催化活性不高的缺点，将锰系催化剂的高催化活性与镁系催化剂的高稳定性优点相结合，加强了催化剂的稳定性和复用性。
Description
技术领域
本发明涉及一种废水的臭氧催化氧化处理的方法，具体涉及一种臭氧催化氧化中应用的催化剂及其制备方法。
背景技术
臭氧催化氧化是高级氧化技术中技术较为成熟、处理效果较好且稳定的一种。臭氧催化氧化是利用臭氧在水中产生无选择性氧化的高活性羟基自由基来实现对难降解物质的降解的。从臭氧催化氧化的机理来看，显然羟基自由基的生成是对该种方法处理的处理效果起决定性作用的影响因素。
由于过渡金属原子结构的特殊性，使得过渡金属可作为优良的催化剂。目前已有大量研究聚焦于过渡金属，尤其是对于锰、铁、钛、铈等金属及其氧化物作为臭氧催化氧化剂的研究已经很深入。陈春茂等研究了MnOx/AC对的负载量对高浓度炼油废水的臭氧催化氧化处理过程的催化作用，结果显示最佳处理效果时COD去除率77%，但随着使用次数的增加，锰的流失量加大，第六次使用后去除率降到了50%左右，复用性和稳定性欠佳。陈俊等人研究了MgO对4-氯苯酚的臭氧催化氧化降解，结果显示4-氯苯酚降解率为98%，TOC去除率达到了65%，且催化剂催化效果较锰系稳定。
专利CN105381804A以软锰矿石粉为原料制备了用以臭氧催化氧化处理焦化废水的催化剂，该专利制备的催化剂在运行20天后，对催化剂的平均去除率仍达30%，相比未添加催化剂时提高了10%。
专利CN104646020A以改性活性炭为载体，利用浸渍法制备了一种锰铁共载臭氧催化剂。该催化剂在臭氧质量浓度为1.5mg/L,气体流量为2L/min的条件下，60min内可使酚氰混合液中的苯酚和CN的去除率达到90%以上，COD去除率达到81.89%。
专利CN104437546A以水渣微粉、氧化镁、六水合氯化镁与催化活性物质（主要是铁氧化物）等制备了一种铁镁共载催化剂。
发明内容
本发明的目的在于发明一种高效、稳定的用于废水深度处理的臭氧催化氧化催化剂。
为实现上述发明目的，本发明提供了一种臭氧催化剂的制备方法，包括如下步骤：选择多孔载体材料，用酸碱和去离子水将多孔材料内部堵塞的孔疏通，并清洗使其显中性；将多孔材料载体置于金属盐溶液中，使金属离子深入到多孔材料内部；加入氢氧化钠等易溶强碱溶液形成金属氢氧化物沉淀，并附着于载体上；将负载完成的多孔型催化剂进行干燥、焙烧获得催化剂成品。
本发明催化剂制备所用的金属盐溶液中，金属离子为锰离子和镁离子，实验结果表明，投加的镁锰离子之比在2:5 ~ 5:2之间为最佳。在将多孔载体材料置于上述金属盐溶液后，需搅拌2~6小时使金属离子深入到载体内部。之后加入强碱溶液，形成金属离子的氢氧化物胶体沉淀，并保持载体处于被沉淀淹没状态2~24小时。将上述载有金属离子氢氧化物胶体沉淀的载体材料取出，清洗1~3次，在100~120℃下干燥2~12小时，然后于400~600℃下焙烧1~6小时，即完成本发明的催化剂的制备。
作为本发明的进一步改进，催化剂的多孔载体为稳定、高比表面积的活性载体，如颗粒活性炭（GAC）、活性炭纤维丝（ACF）、γ-Al2O3、Al2O3-TiO2等。多孔载体在经酸碱溶液清洗后，要用去离子水将其冲洗至pH=7。
作为本发明的进一步改进，催化剂制备过程中在加入强碱溶液前可投加高锰酸钾，使得焙烧后形成MgO/MnOx复合金属氧化物，所投加的高锰酸钾与锰离子之比在2:1~1:6之间。
本发明的有益效果如下：本发明所涉及的复合金属氧化物臭氧催化剂，相较于传统的单金属氧化物催化剂，具有催化效率高、稳定性高、制备简便等优点，能显著降低臭氧法的处理成本。另外，催化剂载体使用的多孔材料具有较高的比表面积和较大的孔容积，具有很好的吸附能力，将污染物富集在催化剂表面，可以显著辅助催化氧化反应的进行。
附图说明
图1 催化剂COD与色度去除性能；
图2 催化剂COD与色度去除性能。
具体实施方式
为了使本发明的目的、技术方案与优点更加清楚，下面将结合具体实施案例对本发明进行详细叙述。
实施例1
以颗粒活性炭为载体的催化剂制作方法。
将商用椰壳颗粒活性炭置于浓度为1-4mol/L的硫酸溶液中搅拌1-5小时。
将清洗后的活性炭颗粒置于浓度为1-4mol/L的氢氧化钠溶液中，搅拌1-5小时，然后过滤留下活性炭颗粒，将过滤后的活性炭用去离子水反复冲洗直至pH在7左右。
将清洗完毕的活性炭颗粒置于0.5-2.0mol/L的硝酸锰溶液中，然后加入与硝酸锰等物质的量的硝酸镁后，于120转/min的转速搅拌5小时后静置3-5小时。
往静置后的活性炭颗粒中加入氢氧化钠溶液，加入氢氧化钠的量以使生成的沉淀将活性炭颗粒完全浸没为宜，静置12小时后，将过滤后的活性炭颗粒用去离子水冲洗1-2次后置于恒温干燥箱内于100℃下烘干12小时。
将烘干的活性炭颗粒置于马弗炉内于450℃下灼烧3小时，至此臭氧催化剂（MnOx&MgO/GAC）制备完毕。
当反应条件为臭氧浓度30mg/L，气体流量0.8L/min，催化剂用量1g/L时，本实施例制备的催化剂处理印染废水二沉池出水的效果如图1所示。
从图1可以看出，本专利制备的镁锰共载催化剂对色度和COD的去除具有很好的效果，10min时COD去除率能达到50%以上，对色度的去除率能达到近90%，在25min时，对COD的去除率达到80%左右，色度去除率达到92%。
实施例2
改进的以颗粒活性炭为载体的催化剂制作方法。
本实施例与实施例1步骤基本相同，但在步骤三完成后增加如下步骤：根据高锰酸钾与硝酸锰反应生成二氧化锰的化学反应方程式，边搅拌边加入稍过量的高锰酸钾溶液，于120转/min的转速搅拌5小时后静置3-5小时。之后进行实施例1所述后续步骤直至完成。
当反应条件为臭氧浓度30mg/L，气体流量0.8L/min，催化剂用量1g/L时，本实施例制备的催化剂处理印染废水二沉池出水的效果如图2所示。
由图2可知，实施例2制备的催化剂对印染废水二级出水的处理效果好于实施例1制备的催化剂。
Claims (3)
1.一种用于废水深度处理的臭氧催化氧化催化剂制备方法，其特征在于：该催化剂为在多孔载体上负载锰、镁双金属氧化物活性物质；所述多孔载体为颗粒活性炭、活性炭纤维丝，多孔载体首先用酸、碱将多孔载体内部堵塞的孔疏通，然后用去离子水清洗使其显中性；催化剂的制备方法为：首先将多孔载体置于金属盐溶液中，使金属离子深入到多孔材料内部，然后加入氢氧化钠易溶强碱溶液形成金属氢氧化物凝胶沉淀，并附着于载体上，最后将负载完成的多孔型催化剂进行干燥、焙烧获得催化剂成品；催化剂制备所用的金属离子为锰离子和镁离子，投加的镁锰离子之比在2:5～5:2之间；催化剂制备过程中在加入强碱溶液前投加高锰酸钾，使得焙烧后形成MgO/MnOx复合金属氧化物，投加的高锰酸钾与锰离子之比在2:1～1:6之间。
2.根据权利要求1中所述的用于废水深度处理的臭氧催化氧化催化剂制备方法，其特征在于：催化剂在焙烧前在80～140℃下干燥6～10小时。
3.根据权利要求1中所述的用于废水深度处理的臭氧催化氧化催化剂制备方法，其特征在于：催化剂干燥后于400～700℃下焙烧1～5小时。
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