CN110028136B - 电催化三维MnOx-CeOx/PHTS填料粒子处理废水的方法 - Google Patents
电催化三维MnOx-CeOx/PHTS填料粒子处理废水的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 27
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910016978 MnOx Inorganic materials 0.000 description 1
- 229910017278 MnxOy Inorganic materials 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
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Abstract
电催化三维MnOx‑CeOx/PHTS填料粒子处理废水的方法,属于以PHTS介孔材料为载体,锰盐、铈盐为前驱体,通过等体积浸渍法、结合干燥、焙烧工艺制备电催化MnOx‑CeOx/PHTS纳米三维填料粒子的方法,该填料可以直接用于一级、二级电催化有机废水处理,在苯酚等生产废水处理中COD去除率达到85%以上;该填料解决了传统铁炭填料在废水处理过程中易板结、污泥产生多易造成二次污染的弊病,适用于制药、化工、染料等工业生产领域废水的处理。
Description
技术领域
本发明涉及水污染控制领域,具体涉及一种工业废水处理的电催化三维MnOx-CeOx/PHTS 填料粒子的制备及处理废水的方法。MnOx指锰的多种化合价态氧化物,包括+3、+4、+5;CeOx指包括氧化铈的铈的氧化物。
背景技术
锰氧化物在自然界中广泛存在,具有优异的物理性能和化学性能,使其在环境净化中承担重要的角色。MnxOy属于变价化合物,主要表现出多样的氧化还原性。废水处理中常用的锰氧化合物主要有:三氧化二锰(Mn2O3)、二氧化锰(MnO2)、四氧化三锰(Mn3O4)方锰矿(MnO)、水锰矿(MnOOH),其反应机理主要是通过锰氧化合物与废水中的酚等有机物结合,通过锰元素的得失电子,发生氧化作用,从而去除和削弱废水中的有机物污染。但是锰氧化物在处理废水过程中,很容易造成活性高价锰价态降低,减弱甚至失去继续处理废水中有机的能力,研发高效能的活性锰处理废水材料具有重要价值。
中国科学院生态环境研究中心公开了一种高效催化臭氧氧化水中有机污染物的催化剂制备方法(申请号200710121727.5),以中孔锆为载体,制备MnxO/ZrO2催化剂,用于催化臭氧分解氧化水中有机污染物,该法选择的中孔锆必须具有高的比表面积,以减少MnxO物种的损失,但缺少对中孔锆的制备及性质的详细说明。南方化学触媒株式会社公开了一种锰化合物、其制备方法及使用方法(申请号02829370.3),使用二价锰与碱性化合物和高锰酸钾盐混合,反应沉淀获得特征锰化合物,显然,碱性条件下,由于不同锰盐理论上沉淀的条件不同,将使混合法制备均匀、稳定的锰氧化物造成困难,给专利公开的用于环境污染物气体的消除应用带来不确定性。天津化工研究设计院公开了一种臭氧分解催化剂及其制备方法(CN1785507A )。采用喷涂工艺,将以锰的氧化物为主活性组份、添加碱金属或碱土金属为助剂的活性组份负载在金属或陶瓷蜂窝载体上。仝长水等研究显示(催化学报,2010,31(9)),引入铜等组份的MnOx-CeOx催化剂在苯酚废水处理中显示良好结果,其高活性源于高价态的锰离子,而铈氧化物提供了良好的氧供体。但是其废水处理过程以Cu-MnCeOx 为催化剂,分子氧为氧源, 需要120℃、1.0 MPa的反应条件下进行,苯酚模拟废水处理量仅为4 mg/ml,在工业化应用具有一定局限性。
本发明选择贾志奇前期研发的高比表面积、大孔径的PHTS作为载体(赵永祥, 贾志奇等,一种铝掺杂PHTS介孔材料及其应用, ZL 201010130036.3),负载MnOx-CeOx活性组分,借助电催化装置,在常压、室温、低电压条件下实现较高浓度有机废水的高效处理。
发明内容
本发明提供成本低且环保的电催化三维MnOx-CeOx/PHTS 填料粒子的制备及处理有机废水的方法 ,具体可用于苯酚等有机废水的处理过程。
一种电催化三维MnOx-CeOx/PHTS 填料粒子处理有机废水的方法,其特征是加入一定量的苯酚等有机废水于电催化装置中,在电催化装置中加入三维MnOx-CeOx/PHTS 填料粒子,借助电催化作用,结合填料粒子的三维催化氧化技术,达到降解废水中苯酚等有机物,提高废水的可生化性。
电催化三维MnOx-CeOx/PHTS 填料粒子处理废水的方法,其特征是包括下述步骤:
(1)先将P123溶解到矿物酸水溶液中,P123的含量控制在1-l0Wt%,矿物酸浓度是0.01-1.6M,然后加入硅源,硅源中硅与P123摩尔比为59-65:1,同时加入掺杂铝源,掺杂铝源中铝量占硅质量的1%-15%,调节反应温度在25-45℃,反应30min-5h,加入甲苯,甲苯占P123质量的1%-20%,继续反应10-48小时,然后转入水热合成釜,反应温度控制在60-130℃,时间24-72h,过滤分离,70-120℃干燥后,在450-600℃焙烧3-15h,得到PHTS载体材料,所述PHTS载体材料比表面积是400-1200cm2/g,孔容是0. 4-1.1 cm3/g,孔径是4-18nm;
(2)称取锰盐、铈盐和葡萄糖分散到水中,所述锰盐是高锰酸钾、乙酸锰、碳酸锰中一种或几种任意组合,锰盐加入量是PHTS载体质量的5%-50%;所述铈盐是硝酸铈或硫酸铈;铈盐的加入量是PHTS载体质量的1%-10%;葡萄糖加入量是PHTS载体质量的1%-25%;采用等体积浸渍法浸渍到PHTS载体材料上,经105℃温度干燥,干燥时间3h,400-950℃高温焙烧1-3h得到MnOx-CeOx/PHTS 填料粒子;
(3)在废水电解装置中,量入100mL 有机废水,加入1-50g的MnOx-CeOx/PHTS 填料粒子,控制电解电压5-30V,电极为钛电极,长度20cm,宽度2cm,厚度0.1cm,电极间距离2cm;室温常压电解处理有机废水,空气通入量是10-100ml/min,反应时间是0.5-4h。
本发明所述催化三维MnOx-CeOx/PHTS 填料粒子处理废水的方法,其特征是所述MnOx-CeOx/PHTS 填料粒子由等体积浸渍法浸渍锰盐、铈盐和少量的葡萄糖分散液到PHTS(Plugged Hexagonal Templated Silicas ,制备详述见ZL 201010130036.3)载体材料上,经干燥、高温焙烧得到MnOx-CeOx/PHTS 填料粒子。
本发明所述MnOx-CeOx/PHTS 填料粒子制备干燥温度105℃,时长3h,焙烧温度400-950℃,优选550-850℃,焙烧1-3h。
在废水电解装置中添加一定量的MnOx-CeOx/PHTS 填料粒子,控制电解电压5-30V,电极为钛电极,长度20cm,宽度2cm,厚度0.1cm,电极间距2cm;室温常压电解处理有机废水。
MnOx-CeOx/PHTS 填料粒子的加入量是1-50g,空气通入量是10-100ml/min,优选20-50ml/min,反应时间0.5h-4h,优选1-2h。
本发明所述MnOx-CeOx/PHTS 填料粒子电催化处理的有机废水含盐量范围0-10%。盐包括氯化钠、硫酸钠。
使用本发明降解苯酚等有机废水,在有机废水CODCr为50-50000ppm范围,废水处理后CODCr去除率达到85%以上,可以直接用于一级、二级电催化有机废水处理。
本发明电催化三维MnOx-CeOx/PHTS 填料粒子的制备及处理有机废水的方法,包括如下步骤:
1)PHTS填料粒子载体制备:将非离子表面活性剂P123溶解到盐酸水溶液中,P123的含量控制在1-10 wt%,矿物酸浓度0.01-1.6 M,然后加入正硅酸乙酯,硅与P123摩尔比为59-65:1,调节反应温度在25-45℃,反应30min-5 h后,加入三甲苯介孔结构调节剂,调节剂占P123质量的 1%-20%,继续反应10-48小时,然后转入水热合成釜,反应温度控制在60-130℃,时间24-72h,过滤分离,70-120℃干燥后,在450-600℃焙烧3-15h,得到白色PHTS介孔材料,其比表面积在400-1200cm2/g,孔容0.4-1.1cm3/g,孔径4-18nm。该材料具有独特的微孔、介孔结构,有利于反应物质在孔道内的传输,适合用作载体制备负载型材料。
2)电催化三维MnOx-CeOx/PHTS 填料粒子的制备:即称取一定量的步骤1)所述的PHTS填料粒子载体,将高锰酸钾、乙酸锰、碳酸锰中一种或几种任意组合的锰盐、硝酸铈或硫酸铈盐及葡萄糖分散到等体积浸渍填料粒子载体所需的定量水中,然后浸渍所述的PHTS填料粒子载体;锰盐加入量是PHTS载体质量的5%-50%,优选10%-40%;所述铈盐加入量是PHTS载体质量的1%-10%,优选1%-5%;所述葡萄糖加入量是PHTS载体质量的1%-25%。最后将浸渍过的填料粒子于105℃干燥3h,温度400-950℃焙烧1-3h,优选550-850℃焙烧1-3h。
3) 将步骤2)所述电催化三维MnOx-CeOx/PHTS 填料粒子加入到100mL 含苯酚等废水溶液中,加入量1-50g,控制电压5-30V,空气通入量10-100ml/min,优选20-50ml/min,反应时间0.5h-4h,优选1-2h。
4)步骤3)所述含苯酚等废水溶液中盐含量范围0-10%。盐包括氯化钠、硫酸钠。
5)步骤3)所述含苯酚等废水溶液,其废水CODCr为50-50000ppm范围,废水处理后CODCr去除率达到85%以上,可以直接用于一级、二级电催化有机废水处理。
本发明提出的有机废水处理的方法,简单、成本低,有利于工业化推广,适用于制药、化工、染料等工业生产领域废水的处理。
附图说明
图1是本发明中电催化装置的结构图。
图中,1、电解桶,2、进气管,3、溢流管,4、电极,5、填料粒子。
具体实施方式
以下非限定性例子将进一步说明本发明内容,但本发明权利要求的内容并不限定于所列举的实施例。
图1所示,电催化装置包括电解桶1,电解桶1的下部设有进气2管,电解桶1的上部设有溢流管3,电解桶1内设置电极4和填料粒子5。
所述PHTS 材料是将3.0g非离子表面活性剂P123溶解到100ml酸性溶液中,控制温度35℃溶解,然后加入6.6g的正硅酸乙酯,继续保温反应,加入50mg三甲苯,继续反应22h,然后转入100℃水热合成釜,老化24h, 过滤,80℃干燥后,500℃焙烧6h,得到白色铝PHTS 。
电催化三维MnOx-CeOx/PHTS 填料粒子的制备:称取一定量的锰盐、铈盐和少量的葡萄糖分散到水中,采用等体积浸渍法浸渍到PHTS(Plugged Hexagonal TemplatedSilicas )载体材料上,经干燥、高温焙烧得到MnOx-CeOx/PHTS 填料粒子。
所述锰盐包括高锰酸钾、乙酸锰、碳酸锰中一种或几种任意组合、铈盐包括硝酸铈或硫酸铈。
实施例1
称量11.84g乙酸锰、0.83g九水硝酸铈、5g葡萄糖分散到16mL水中,浸渍30g PHTS,搅拌,于105℃干燥3h,830℃焙烧1h,制的MnOx-CeOx/PHTS 填料粒子。
图1所示的电催化装置内装有100ml COD,(为10000ppm含氯化钠2%的苯酚废水液),加入10g MnOx-CeOx/PHTS 填料粒子,控制电压15V,空气通入量20ml/min,室温常压反应时间2h,COD降至500ppm,降解率95%。
实施例2
称量2g高锰酸钾、9.1g乙酸锰、1.05g九水硝酸铈、6g葡萄糖分散到17mL水中,浸渍30g PHTS,搅拌,于105℃干燥3h,630℃焙烧1h,制的MnOx-CeOx/PHTS 填料粒子。
电催化装置内装有100ml COD,(为1500ppm含硫酸化钠2.5%的苯酚废水液),加入10g MnOx-CeOx/PHTS 填料粒子,控制电压13V,空气通入量20ml/min,室温常压反应时间2h,COD降至100ppm,降解率93.3%。
实施例3
称量9.4g乙酸锰、0.85g九水硝酸铈、5g葡萄糖分散到16.3mL水中,浸渍30g PHTS,搅拌,于105℃干燥3h,730℃焙烧1h,制的MnOx-CeOx/PHTS 填料粒子。
电催化装置内装有100ml COD(为8000ppm的苯酚废水液),加入10g MnOx-CeOx/PHTS 填料粒子,控制电压15V,空气通入量20ml/min,室温常压反应时间2h,COD降至700ppm,降解率91.2%。
本发明中P123为非离子表面活性剂。
Claims (1)
1.电催化三维MnOx-CeOx/PHTS 填料粒子处理废水的方法,其特征是包括下述步骤:
(1)先将P123溶解到矿物酸水溶液中,P123的含量控制在1-l0Wt%,矿物酸浓度是0.01-1.6M,然后加入硅源,硅源中硅与P123摩尔比为59-65:1,同时加入掺杂铝源,掺杂铝源中铝量占硅质量的1%-15%,调节反应温度在25-45℃,反应30min-5h,加入甲苯,甲苯占P123质量的1%-20%,继续反应10-48小时,然后转入水热合成釜,反应温度控制在60-130℃,时间24-72h,过滤分离,70-120℃干燥后,在450-600℃焙烧3-15h,得到PHTS载体材料,所述PHTS载体材料比表面积是400-1200cm2/g,孔容是0. 4-1.1 cm3/g,孔径是4-18nm;
(2)称取锰盐、铈盐和葡萄糖分散到水中,所述锰盐是高锰酸钾、乙酸锰、碳酸锰中一种或几种任意组合,锰盐加入量是PHTS载体质量的5%-50%;所述铈盐是硝酸铈或硫酸铈;铈盐的加入量是PHTS载体质量的1%-10%;葡萄糖加入量是PHTS载体质量的1%-25%;采用等体积浸渍法浸渍到PHTS载体材料上,经105℃温度干燥,干燥时间3h,400-950℃高温焙烧1-3h得到MnOx-CeOx/PHTS 填料粒子;
(3)在废水电解装置中,量入100mL 有机废水,加入1-50g的MnOx-CeOx/PHTS 填料粒子,控制电解电压5-30V,电极为钛电极,长度20cm,宽度2cm,厚度0.1cm,电极间距离2cm;室温常压电解处理有机废水,空气通入量是10-100ml/min,反应时间是0.5-4h。
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