CN105478155B - 一种可再生非均相芬顿型催化剂及其制备方法和应用 - Google Patents
一种可再生非均相芬顿型催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于工业催化剂技术领域,具体为一种可再生非均相芬顿型催化剂及其制备方法和应用。本发明催化剂以商用沸石为载体,以高分子对载体进行表面修饰,再以Fe或Co为活性组分进行负载,最后经焙烧在沸石表面形成铁或钴复合价态氧化物。该催化剂对工业中难处理的含酚类或染料等有机废水具有高效降解能作用,在室温(<30℃)和接近中性条件(pH=6~8)下对废水中有机物降解率可达90%以上,且催化剂再生性能良好。本发明利用非均相芬顿催化剂进行氧化去除废水中酚类和染料等有机物,成本低、不产生二次污染,是一项非常具有应用前景的有机废水处理工艺。
Description
技术领域
本发明属于工业催化剂技术领域,具体涉及一种非均相芬顿(Fenton)催化剂及其制备方法,还涉及该催化剂在降解工业有机废水中的应用。
背景技术
随着社会发展和人口增长,由此造成的环境污染日益加剧,去除水中难降解污染物、减少水体污染已经引起了人们的广泛关注[BabuponnusamiA.,et. al., Journal of EnvironmentalChemical Engineering. 2014,2,557]。随着废水水质日趋复杂和国家对环境保护的重视,传统处理方式已经越来越难以满足难降解废水的处理需求。
高级氧化技术(AOPs)基于体系中产生的强氧化活性的羟基自由基(HO·),可以无选择的去除和降解常规方法无法分解的有机污染物,已经广泛应用于酚类、药物、农药和垃圾渗滤液等废水的处理中[Pouran S.R.,et. al.,Journal of Cleaner Production.2014,64,24]。与其他高级氧化技术相比,芬顿体系有较长的研究历史和较广阔的应用空间。
芬顿体系在使用过程中具有试剂无毒性,均相体系没有传输阻碍,操作简单,投资相对较小等优点,所以一直广泛用于有毒有害废水的处理中。但传统芬顿法仍存在缺点,如H2O2利用率低,反应所需pH较低,产生的Fe2+和Fe3+影响出水色度等。因此类芬顿体系逐渐受到人们的关注,如通过引入光照(可见光、紫外光)、电流等诱导HO·产生;研究应用于芬顿体系的新型催化剂,提高芬顿体系处理能力并尽量消除其负面影响。
芬顿催化剂早期研究主要集中在均相方面,具有催化反应迅速,无传质阻力,反应条件更温和等优点,常用催化剂为过渡金属,如Co、Fe、Mn、Cu、Ni等盐类,研究表明硫酸铜[宋天顺等,水处理技术,2007,33,22]、硫酸铁[Ramirez J.H.,et. al., Catalysis Today2005,107,68]催化染料废水的效果均非常显著。随着芬顿体系中催化剂研究的深入,均相催化剂存在适用pH范围较窄、催化剂难以回收利用、化学污泥产量大且难处理等问题,因此,非均相催化剂逐渐成为芬顿体系的研究重点。非均相催化剂与废水的分离较简便,处理流程大大简化,常用非均相催化剂主要分为三类:贵金属(如Pd、Pt、Au、Ag等)、过渡金属(主要为Fe和Co)及稀土金属等。大量研究表明,贵金属和稀土金属具有较高的催化活性和催化稳定性,过渡金属虽然活性相对一般,但价格较低,在非均相芬顿体系催化剂开发上具有显著的发展优势和潜在的发展前景。
沸石是一种无机硅酸盐类多孔材料,作为催化剂载体具有较高的稳定性、较大的比表面积以及较高的酸性位。我们所选用的沸石(Y型沸石、β沸石、丝光沸石、ZSM-5、镁碱沸石等)具有12员环或10员环孔道结构,均已实现工业生产,成本较低,来源广泛,因此本发明采用一系列商用沸石作为芬顿催化剂载体。
苯酚是最常见的有毒性、强腐蚀性的难降解有机物之一。苯酚主要用于合成材料、酚醛树脂、油漆、炸药、煤气、炼油、纺织等工业。含酚废水来源广、水量多、危害大。苯酚作为一种典型难降解物质,当使用的催化剂对其有显著降解效果时,则可认为催化剂效果良好。
本发明以一系列商用沸石作为载体,通过高分子对其表面进行修饰后负载Fe或Co的氧化物,从而制备高稳定性类芬顿催化剂。该催化剂在室温和接近中性pH条件下能高效降解酚类废水和染料废水,具有非常重要的工业应用价值。
发明内容
本发明的目的在于提出一种室温与中性pH条件下具有优异低温催化活性的高稳定性可再生非均相芬顿型催化剂及其制备方法,以及在降解酚类和染料等工业有机废水中的应用。
本发明提出的可再生非均相芬顿型催化剂,以沸石为载体、以过渡金属Fe、Co为活性组分、通过引入高分子来调节Fe、Co在载体表面分布而制备得到;活性组分在催化剂中的负载量为5~25wt.%。该催化剂在室温(<30℃)和接近中性条件(pH=6~8)下与H2O2共同作用,表现出具有强的氧化能力,有机物(以苯酚和罗丹明B为例)在2h内的降解率均可超过90%,适合处理各种浓度的酚类和染料废水,且催化剂稳定性和再生性能良好。
本发明提出的芬顿型催化剂的制备方法,具体步骤如下:
(1)将高分子聚合物溶于一定量甲醇溶液,再将作为载体的商用沸石分子筛浸渍于上述溶液中;室温下搅拌1-12h,用旋转蒸发仪去除溶剂,30-100℃干燥1-12h,然后高温(110—130℃,优选120℃)活化;
(2)将活性组分Fe或Co的前驱体配置成前驱体盐溶液;
(3)将活性组分的前驱体盐溶液采用常压浸渍到沸石载体上,浸渍温度为10-25℃,浸渍时间0.5h~12h;以金属元素计,控制催化剂中最终活性组分负载量为5~25wt.%;
(4)将浸渍后的固体在25~120℃下干燥1~5h,然后置于马弗炉中300~700℃下焙烧2~7h,即得到所需的沸石负载型催化剂。
本发明催化剂使用回收后经干燥处理,再置于马弗炉中焙烧,得到可再生的催化剂。
上述方法中,所述高分子聚合物为聚醚酰亚胺、聚乙烯亚胺伙聚甲亚胺等;所用载体为商用Y型沸石、β沸石、丝光沸石、镁碱沸石、ZSM-5沸石等,其硅铝比为2-∞,晶粒尺寸为0.1~2μm。
上述方法中,所用铁源(金属Fe活性组分的前驱体)为硝酸铁(Fe(NO3)3·9H2O)、硫酸亚铁铵((NH4)2Fe(SO4)2.6H2O)、氯化铁(FeCl3)、硫酸铁(Fe2(SO4)3)等,钴源(金属Co活性组分的前驱体)为硝酸钴(Co(NO3)2·6H2O)、氯化钴(CoCl2·6H2O)、硫酸钴(CoSO4·7H2O)等。配制的盐溶液浓度为0.18-0.9mol/L。
本发明催化剂经回收后,干燥处理的温度为25-120℃,时间为1-5 h,置于马弗炉中焙烧,温度为300~700℃,时间为2~7h,得到可再生的催化剂。
本发明制备的催化剂,可用于高效降解酚类废水和染料废水。
具体来说,在酚类和染料废水中投加少量双氧水和上述非均相催化剂构成类芬顿反应体系进行反应。
其中,所述的酚类为苯酚或萘酚中的一种或一种以上,浓度为1-2000ml/L;所述的染料废水为罗丹明B和酸性红1中的一种或一种以上,染料浓度为1-1000ml/L。
其中,反应体系的pH=6-8,反应温度为10-30℃。
本发明以商用沸石为载体的类芬顿催化剂的设计原理及催化作用机理如下:
在催化剂材料的体系设计上,采用商用沸石作为载体,用聚乙烯亚胺等高分子对载体进行修饰,不仅增强了活性组分在载体上的分散性,也调节了活性组分的化学价态,进而能有效提高芬顿反应的催化效率。
首先是过氧化氢和有机物分子通过扩散吸附到催化剂表面的活性中心上,过氧化氢分子在铁元素催化作用下生成羟基自由基,通过自由基反应氧化降解有机物,最后完全降解产物CO2从催化剂表面发生脱附反应逃逸。
附图说明
图1分别是Y型分子筛负载前和负载后的XRD图谱,均是典型的FAU沸石拓扑结构。负载焙烧后,衍射峰强度降低,但其晶体结构未被破坏,仍保持Y型沸石的结构类型,且没有氧化铁的衍射峰,说明氧化铁颗粒尺寸很小并且被均匀负载在催化剂表面。
图2分别是Y型分子筛负载前和负载后的低温氮吸附-脱附图,均呈现典型的I类微孔吸附曲线类型。负载后材料比表面积、孔体积、微孔比表面积和微孔体积均有一定程度下降,这说明微孔被部分堵塞。负载前比表面积为499.1 m2/g,孔容积为0.306 cm3/g,微孔比表面积355.2m2/g,微孔体积0.198 cm3/g。负载后比表面积为367.7 m2/g,孔容积为0.275cm3/g,微孔比表面积239.3 m2/g,微孔体积0.131 cm3/g。
图3是负载铁后催化剂的扫描电镜图片,图片显示负载后催化剂表面较粗糙,且形貌不均一,说明催化剂表面表面被氧化铁粒子所覆盖。
图4是苯酚降解率随时间变化曲线,催化剂在降解苯酚的实验中起到吸附和降解双重作用,反应前10min内,Y型分子筛吸附苯酚,之后随着催化活性位的产生,苯酚降解率逐渐增加,1h后由于苯酚浓度减少,反应缓慢进行。
图5是苯酚紫外吸收光谱随时间变化的降解曲线。
图6是罗丹明B降解率随时间变化曲线。
具体实施方式
下面结合实施例对本发明作进一步说明。
催化剂的制备:
(I)称取0.1g聚乙烯亚胺,溶于10g甲醇中,将1g Y型沸石加入上述溶液中,在室温下搅拌12h,用旋转蒸发仪除去甲醇,固体粉末在100℃下干燥过夜;再高温活化;
(II)称取一定量硝酸铁,溶于10g去离子水中,将I得到的粉末投入硝酸铁溶液中,在室温下搅拌12h,所得混合物在70℃下干燥5h,得到块状固体;调节Fe3+的浓度范围分别为0.18mol/L、0.36 mol/L、0.54 mol/L、0.72 mol/L和0.90mol/L,分别制备出催化剂A、B、C、D、E;
(Ⅲ)在600℃煅烧5h,得到比表面为367.6 m2/g的芬顿固体催化剂。
参照以上催化剂制备方法,以不同类型沸石、活性组分、高分子聚合物和负载量的催化剂制备如表1所示。
催化剂的芬顿反应性能测试条件:催化反应在装有所制催化剂的烧杯中进行,催化剂装填0.5g,以1g/L的苯酚溶液为试验水样,取10ml试验水样于催化剂装填烧杯中;试验水样加入30% 浓度的双氧水0.14ml,反应在室温下进行,反应时间为2h。催化剂的芬顿氧化反应性能测试结果见表2。
催化剂制备均在室温(10-30℃)下,具体实施例如下(表1):
表1
。
芬顿反应实施例:实验均在在室温(10-30℃)、中性pH下实施,以硝酸铁为无机盐,以聚乙烯亚胺为高分子聚合物制备催化剂。催化剂的芬顿氧化反应性能测试结果如下表(表2):
表2
。
本发明所提供的新型负载型催化剂的特征可用如下方法进行表征:
1. 粉末X-射线衍射(XRD)。在粉末X-射线衍射中,参照沸石标准图谱,确定负载后催化剂结构是否被破坏,且活性组分是否被均匀负载在催化剂上;
2. 低温氮吸附;
3.扫描电镜;
4.苯酚降解率随时间的变化曲线;
5.苯酚紫外吸收光谱随时间变化的降解曲线;
6.罗丹明B降解率随时间变化曲线。
Claims (7)
1.一种可再生非均相芬顿型催化剂的制备方法,该催化剂以沸石为载体、以过渡金属Fe或Co为活性组分、通过引入高分子来调节Fe、Co在载体表面分布而制备得到;活性组分在催化剂中的负载量为5~25wt.%;
其特征在于,具体步骤为:
(1)将高分子聚合物溶于一定量甲醇溶液,再将作为载体的商用沸石分子筛浸渍于上述溶液中;室温下搅拌1-12h,用旋转蒸发仪去除溶剂,30-100℃干燥1-12h,然后高温活化,活化温度为110—130℃;
(2)将活性组分Fe或Co的前驱体配置成前驱体盐溶液;
(3)将活性组分的前驱体盐溶液采用常压浸渍到沸石载体上,浸渍温度为10-25℃,浸渍时间0.5h~12h;以金属元素计,控制催化剂中最终活性组分负载量为5~25wt.%;
(4)将浸渍后的固体在25~120℃下干燥1~5h,然后置于马弗炉中300~700℃下焙烧2~7h,即得到所需的沸石负载型催化剂;
所述高分子聚合物为聚醚酰亚胺或聚乙烯亚胺或聚甲亚胺。
2.按照权利要求1所述的制备方法,其特征在于,所述载体为商用Y型沸石、β沸石、丝光沸石、镁碱沸石或ZSM-5沸石,其硅铝比为2-∞,晶粒尺寸为0.1~2μm。
3.按照权利要求1所述的制备方法,其特征在于,所述活性组分前驱体为九水合硝酸铁、硫酸亚铁铵、氯化铁或硫酸铁,或六水合硝酸钴、氯化钴或硫酸钴。
4.按照权利要求1所述的制备方法,其特征在于,所述前驱体盐溶液浓度为0.18-0.9mol/L。
5.采用权利要求1所述制备方法制备得到的可再生非均相芬顿型催化剂在处理酚类和染料废水的用途,其特征在于:在酚类和染料废水中投加少量双氧水和所述催化剂构成类芬顿反应体系进行反应。
6.根据权利要求5所述的用途,其特征在于:所述的酚类为苯酚或萘酚中的一种或一种以上,浓度为1-2000ml/L;所述的染料废水为罗丹明B和酸性红1中的一种或一种以上,染料浓度为1-1000ml/L。
7.根据权利要求5所述的用途,其特征在于:所述反应体系pH=6-8,反应温度为10-30℃。
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