CN110773219A - 一种光-Fenton脱硫脱硝催化剂及其制备方法 - Google Patents
一种光-Fenton脱硫脱硝催化剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种光‑Fenton脱硫脱硝催化剂及其制备方法。所述的光‑Fenton脱硫脱硝催化剂,包括催化剂载体、通过粘结剂负载在催化剂载体上的光‑Fenton活性组分,所述光‑Fenton活性组分包括管状锰掺杂石墨相氮化碳、负载于管状锰掺杂石墨相氮化碳上的钼酸铁;其重量组分如下:催化剂载体70‑85份,粘结剂10‑30份,管状锰掺杂石墨相氮化碳0.5‑2.0份,钼酸铁0.5‑2.0份。所构建的管状Mn‑g‑C3N4/Fe2(MoO4)3具备光催化、臭氧催化、Fenton催化三种功能,不同催化体系之间能够相互依赖,相互促进,增加反应活性自由基含量,提高了真空紫外光催化协同H2O2氧化吸收体系的脱硫脱硝效率。本发明可广泛应用于各类烟气净化处理,实现SO2和NOx的超低排放,且具有成本低廉、合成简单、绿色环保等特点。
Description
技术领域
本发明涉及一种光催化剂及其制备方法,特别涉及一种真空紫外光催化协同H2O2氧化吸收脱硫脱硝的光-Fenton催化剂及其制备方法,属于烟气净化领域。
背景技术
工业锅炉燃煤所排放的SO2和NOx是造成酸雨和光化学烟雾的主要原因,严重威胁着生态环境和人类健康。2016年,环境部、国家发改委、国家能源局共同印发《全面实施燃煤电厂超低排放和节能改造工作方案》,将东部地区原计划2020年前完成的超低排放改造任务提前至2017年前总体完成,中部地区力争在2018年前基本完成,西部地区在2020年前完成。超低排放标准为烟尘、SO2和NOx排放浓度不超过10、35、50mg/m3。
目前,我国主要采用湿法脱硫(WFGD)联合选择性催化还原法(SCR)或非选择性催化还原法(SNCR)脱硝,这种组合方法可以实现很高的污染物脱除率,然而这种串联脱硫脱硝系统往往存在系统复杂,占地面积大,投资运行成本高等问题。
湿法脱硫虽然得到了市场广泛认可,但仍存在较为突出的问题:一是水耗高;二是副产物石膏含水率高,具有一定黏性,商用价值低,常抛弃填埋处理;三是腐蚀与结垢堵塞问题严重。
SCR法脱硝装置通常布置在除尘器后脱硫塔前,然而这一区间的烟气含有较高的飞灰和SO2,容易造成SCR催化剂堵塞、中毒失活。对于一些中小型火力发电厂由于不存在SCR催化剂所需的温度区间,导致SCR法脱硝难以应用于中小型发电厂。
光催化技术利用O2和H2O在催化剂表面生产超氧自由基(·O2 -)和羟基自由基(·OH)等活性自由基,将烟气中的SO2和NOx氧化成SO3和NO2,再通过洗脱液吸收,实现烟气净化。H2O2是一种经济环保型氧化剂,氧化电位为+1.78 eV,在催化剂或紫外线存在条件下,可产生活性更高的羟基自由基(·OH),,从而快速地将SO2和NOx氧化成SO4 2-和NO3 -。光催化耦合H2O2氧化吸收脱硫脱硝极具工业发展前景。李春虎等人也一直致力于在此领域的研究,已申请多项中国发明专利,如《一种烟气选择性光催化脱硫脱硝的一体化装置及工艺》(CN109046017 A)和《一种烟气光催化氧化同时脱硫脱硝的办法及装置》(CN 106621799 A)等。
g-C3N4是一种非金属有机半导体材料,具有类似石墨的层状结构,物理化学性质相对稳定,制备简单,原料廉价;但也存在着比表面积小、电子-空穴复合率高等缺点。非均相类Fenton催化剂Fe2(MoO4)3,具有多活性位点、低零点电荷、固体酸的性质及pH使用范围广等优点,但其单独使用时催化效率较低。
发明内容
本发明的目的在于提供一种比表面积大、光促Fenton协同、臭氧催化、脱硫脱硝效率高的光-Fenton脱硫脱硝催化剂及其制备方法。
本发明以γ-Al2O3、ZSM-5分子筛、活性炭纤维毡、或陶瓷等材料为催化剂载体,通过无模板法合成管状Mn-g-C3N4,进一步通过一步溶剂热法制备管状Mn-g-C3N4/ Fe2(MoO4)3复合光-Fenton活性组分,最后通过粘结剂将活性组分负载到催化剂载体上。所合成的多功能性Mn-g-C3N4/ Fe2(MoO4)3光-Fenton脱硫脱硝催化剂,通过对g-C3N4进行形貌调控和离子掺杂,同时构建 Mn-g-C3N4/ Fe2(MoO4)3复合光-Fenton催化剂,改善光催化效率,提高H2O2和O3的利用率,不仅能够发生光促Fenton反应降低电子与空穴的复合,同时也能够催化O3,因此能够大大提升光催化协同H2O2氧化吸收的脱硫脱硝性能。
本发明所述的光-Fenton脱硫脱硝催化剂,其特征在于包括催化剂载体、通过粘结剂负载在催化剂载体上的光-Fenton活性组分,所述光-Fenton活性组分包括管状锰掺杂石墨相氮化碳、负载于管状锰掺杂石墨相氮化碳上的钼酸铁(Fe2(MoO4)3);其重量组分如下:催化剂载体70-85份,粘结剂10-30份,管状锰掺杂石墨相氮化碳(Mn-g-C3N4)0.5-2.0份,钼酸铁(Fe2(MoO4)3)0.5-2.0份。
所述催化剂载体为γ-Al2O3、ZSM-5分子筛、活性炭纤维毡、陶瓷(如蜂窝陶瓷、泡沫陶瓷)等材料中的一种或几种。
所述管状锰掺杂石墨相氮化碳(Mn-g-C3N4)通过无模板法合成。
所述钼酸铁(Fe2(MoO4)3)是以硝酸铁或氯化铁为铁源,钼酸铵或钼酸钠为钼盐,通过水热法合成。
所述粘结剂为羧甲基纤维素钠、环氧树脂、硅酸钠中的一种或几种,通过超声浸渍法负载活性组分。
一种光-Fenton脱硫脱硝催化剂的制备方法,包括以下步骤:
(1)将催化剂载体洗涤、烘干备用;
(2)将三聚氰胺或尿素溶于有机溶剂中,加热搅拌使其溶解,待溶液冷却后加入一定量的稀硝酸和锰盐,将所生成的沉淀洗涤、干燥,最后置于马弗炉焙烧,得到管状Mn-g-C3N4;
(3)以硝酸铁或氯化铁为铁盐,钼酸铵或钼酸钠为钼盐,用碱液调节pH,生成钼酸铁前驱体;
(4)将步骤(2)得到的管状Mn-g-C3N4加入到钼酸铁前驱体混合液中,一步溶剂热法反应制备管状Mn-g-C3N4/ Fe2(MoO4)3光-Fenton活性组分;
(5)配制粘结剂溶液,将步骤(4)所得光-Fenton活性组分加入到粘结剂溶液中,搅拌2h,再放入步骤(1)洗涤、烘干后的载体,超声浸渍,干燥12h,即为所述光-Fenton脱硫脱硝催化剂。
所述步骤(2)中的有机溶剂为乙二醇或乙醇。
所述步骤(2)中的锰盐为乙酸锰、硝酸锰、氯化锰等锰盐中的一种。
所述步骤(2)中稀硝酸的浓度为0.1-0.2 mol/L。
所述步骤(2)中马弗炉焙烧温度为350℃~550℃,升温速率为5℃/min ~10℃/min。
所述步骤(3)中铁盐:钼盐的摩尔比为1:1.5。
所述步骤(3)中调节pH的碱液为氨水或氢氧化钠溶液。
所述步骤(4)中一步溶剂热法为将反应混合物置于聚四氟乙烯内衬的水热釜中,加热温度为140℃~180℃,反应时间为12~24h。
所述步骤(6)中干燥温度为30℃~120℃。
所述光-Fenton脱硫脱硝催化剂用于VUV/H2O2氧化脱硫脱硝涉及的主要化学反应如下:
真空紫外辐射下自由基的产生及光解SO2和NO反应过程:
管状Mn-g-C3N4/ Fe2(MoO4)3光-Fenton催化剂表面自由基产生的过程:
(Vo表示氧空位)
H2O2、O3和自由基氧化SO2的反应过程:
H2O2、O3和自由基氧化NO的反应过程:
与现有技术相比,本发明具有如下优点:
1.采用无模板法合成管状Mn-g-C3N4,方法简单环保,并且能够有效提高g-C3N4的比表面积,增加表面活性位点。
2.对g-C3N4进行Mn离子掺杂,不仅能够有效分离光生电子和空穴,同时也能催化VUV体系所产生的的O3,避免O3排放到大气中造成二次污染。
3.一步溶剂热法将钼酸铁前驱体与管状Mn-g-C3N4转化为光-Fenton催化活性组分,步骤简单。
4.构建的Mn-g-C3N4/ Fe2(MoO4)3复合体系能有效的促进光生载流子的转移,实现光-Fenton催化剂表面Fe2+和Fe3+的循环,并使Fe2+与H2O2在光催化体系中发生光促Fenton反应。
本发明可广泛应用于各类烟气净化处理,实现SO2和NOx的超低排放,且本发明具有成本低廉、合成简单、绿色环保等特点。
附图说明
图1为实施例1制备的管状g-C3N4放大45倍的形貌图。
图2为实施例1制备的光-Fenton催化剂的形貌图。
图3为实施例1制备的管状Mn-g-C3N4/Fe2(MoO4)3光-Fenton催化剂的XRD谱图。
图4为实施例1制备的管状Mn-g-C3N4/Fe2(MoO4)3光-Fenton催化剂的TEM图。
图5为实施例1制备的光-Fenton催化剂在不同H2O2浓度下的脱硫脱硝性能图。
图6为管状Mn-g-C3N4/Fe2(MoO4)3光-Fenton催化剂的光-Fenton效应机理图。
具体实施方式
下面结合附图并通过具体实施例来详细说明本发明。
实施例1:
(1)用去离子水将70 g泡沫陶瓷洗涤3次,100℃烘干待用。
(2)将1g三聚氰胺加入到30ml乙二醇溶剂中,60℃搅拌直至三聚氰胺完全溶解,待溶液冷却后加入0.05g硝酸锰和60ml 0.15mol/L稀硝酸溶液,将产生的沉淀用乙醇洗涤、抽滤、60℃烘干、520℃焙烧2h(升温速率为10℃/min),所得样品即为管状Mn-g-C3N4,其形貌如图1所示。从图1中可以看出,管状Mn-g-C3N4具有超高的长径比,且整体形貌完整,表面光滑,粗细均匀,相对于普通热缩聚合成法所得的片状g-C3N4,比表面积得到了极大的提高,使得表面活性位点增多,有利于提高光催化反应效率。
(3)称取0.30 g二水合钼酸钠溶于30ml去离子水中,再称取0.22 g六水合氯化铁溶于30ml去离子水中,在搅拌条件下将氯化铁溶液滴加到钼酸钠溶液中,滴加完毕后,用氢氧化钠溶液调节pH为5,生成钼酸铁前驱体。
(4)将管状Mn-g-C3N4加入到钼酸铁前驱体中,搅拌3h,转入100 ml水热釜中,180℃水热反应12 h,将所得样品离心洗涤,60℃烘干备用。
(5)配制20 g/100 ml硅酸钠溶液,将泡沫陶瓷放入硅酸钠溶液中浸泡1h,120℃烘干备用。
(6)将步骤(3)所得样品放入100ml去离子水中,搅拌均匀后,加入泡沫陶瓷,超声负载,然后于120℃干燥12 h,得到泡沫陶瓷负载的管状Mn-g-C3N4/Fe2(MoO4)3光-Fenton脱硫脱硝催化剂(如图2)。
图3为实施例1制备的管状Mn-g-C3N4/Fe2(MoO4)3光-Fenton催化剂的XRD谱图,从图可以明显看出g-C3N4和Fe2(MoO4)3的衍射峰。27.4°处的衍射峰对应于g-C3N4的(002)晶面,来自共轭芳族体系的层间堆叠。通过与纯单斜晶Fe2(MoO4)3标准卡片JCPDS(卡号35-0183)对比,可观察到Fe2(MoO4)3 的(200)、(112)、(220)、 (212) 、(122) 、(1(—)05)、 (2(—)24)、 (024)晶面,证明了Fe2(MoO4)3结晶较好,成功附着在管状g-C3N4上。在XRD谱图上未观察到MnOx的特征峰,这可能与Mn离子掺杂较少及g-C3N4和Fe2(MoO4)3阻碍了对表面MnOx晶相检测有关。
图4为实施例1制备的管状Mn-g-C3N4/Fe2(MoO4)3光-Fenton催化剂的TEM图,从图中可以看出g-C3N4呈规则的管状结构,并且表面附着了一层粗糙的凸起,证明了Fe2(MoO4)3和MnOX成功负载在管状g-C3N4表面。
对泡沫陶瓷负载的管状Mn-g-C3N4/Fe2(MoO4)3光-Fenton脱硫脱硝催化剂进行光催化协同H2O2氧化吸收脱硫脱硝实验测评,测评条件为:紫外光照下,进口模拟烟气SO2、NO和O2浓度分别为3000 mg/m3、550 mg/m3和8%,混合气流量为6 L/min,反应温度为50℃,空速为6000 h-1,内装100W紫外汞灯,H2O2喷淋量为0.96 L/h。
在不同H2O2浓度下,光-Fenton脱硫脱硝催化剂脱硫脱硝性能参见图5。由图5可见,H2O2浓度为0.6%时,脱硫脱硝率就能接近100%,其原因如下(反应机理如图6所示):
1.g-C3N4在VUV的激发下产生光生e-和h+,其表面吸附的O2和H2O会在光生e-和h+作用下,生成·OH、·O2 -、 H2O2等活性分子。
2.g-C3N4与Fe2(MoO4)3之间存在着光催化Fenton协同作用,首先 g-C3N4表面产生的光生e-可以把Fe3+还原为Fe2+,从而促进Fenton过程的进行,这一过程提高了光生电子利用率,同时抑制了光生载流子的复合;其次,Fe2+会与光催化反应生成的H2O2反应生成·OH,在低浓度H2O2条件下,也能够增加反应体系中的·OH含量。
3.VUV体系所产生的的O3会在MnOX的催化下产生活性更高的·OH和·O2 -。
在催化剂表面发生的光催化、Fenton催化和臭氧催化三种作用下,增加了体系活性自由基的含量,使得SO2和NO的脱除率得到了明显的提高。
实施例2:
(1)用去离子水将70 g泡沫陶瓷洗涤3次,100℃烘干待用。
(2)将1g三聚氰胺加入到30ml乙醇溶剂中,60℃搅拌直至三聚氰胺完全溶解,待溶液冷却后加入0.05g氯化锰和60ml 0.15 mol/L稀硝酸溶液,将产生的沉淀用乙醇洗涤、抽滤、60℃烘干、520℃焙烧2h(升温速率为10℃/min)。
(3)称取0.22 g四水合钼酸铵溶于30ml去离子水中,称取0.34 g九水合硝酸铁溶于30ml去离子水中,在搅拌条件下将硝酸铁溶液滴加到钼酸铵溶液中,滴加完毕后,用氨水调节pH为5,生成钼酸铁前驱体。
(4)将管状Mn-g-C3N4加入到钼酸铁前驱体中,搅拌3h,转入100 ml水热釜中,140℃水热反应12h。将所得样品离心洗涤,60℃烘干备用。
(5)将15g羧甲基纤维素钠和步骤(4)所得样品加入到90ml去离子水和10ml乙醇的混合液中,搅拌2h,形成均匀的乳浊液。
(6)将泡沫陶瓷浸入该乳浊液中,超声负载,然后于60℃下干燥12 h,得到泡沫陶瓷负载的管状Mn-g-C3N4/Fe2(MoO4)3光-Fenton脱硫脱硝催化剂。
对比例:
(1)用去离子水将70 g泡沫陶瓷洗涤3次,100℃烘干待用。
(2)采用热缩聚合法合成g-C3N4,将5g 三聚氰胺置于坩埚中,在550℃下煅烧2h,升温速率为2.3℃/min。
(3)称取0.22 g四水合钼酸铵溶于30ml去离子水中,称取0.34 g九水合硝酸铁溶于30ml去离子水中,在搅拌条件下将硝酸铁溶液滴加到钼酸铵溶液中,滴加完毕后,用氨水调节pH为5,生成钼酸铁前驱体。
(4)将g-C3N4加入到钼酸铁前驱体中,搅拌3h,转入100 ml水热釜中,140℃水热反应12h。将所得样品离心洗涤,60℃烘干备用。
(5)将15g羧甲基纤维素钠和步骤(4)所得样品加入到90ml去离子水和10ml乙醇的混合液中,搅拌2h,形成均匀的乳浊液。
(6)将泡沫陶瓷浸入该乳浊液中,超声负载,然后于60℃下干燥12 h,得到泡沫陶瓷负载的g-C3N4/Fe2(MoO4)3光-Fenton催化剂。
对实施例2和对比例制备的泡沫陶瓷负载的光-Fenton催化剂进行光催化协同H2O2氧化吸收脱硫脱硝实验测评,测评条件为:紫外光照下,进口模拟烟气SO2、NO和O2浓度分别为3000 mg/m3、550 mg/m3和8%,混合气流量为6 L/min,反应温度为50℃,空速为6000 h-1,内装100W紫外汞灯,H2O2浓度为0.6%、H2O2喷淋量为0.96 L/h,测评结果见表1。
表1 实施例2与对比例脱硫脱硝效果比较
由表1可以看出,实施例2合成的管状Mn-g-C3N4/Fe2(MoO4)3光-Fenton催化剂的脱硫脱硝性能明显高于普通g-C3N4/Fe2(MoO4)3光-Fenton催化剂,这是因为管状Mn-g-C3N4具有更大的比表面积,表面活性位点更多,对紫外光有更高的捕获率,并且能够催化O3,因此比普通热缩聚合成法的g-C3N4功能性更多,催化活性更好。
本发明的实施并不局限于上面的实施例,对本发明所做的任何形式上的变通或改变都应该涵盖在本发明保护范围内。
Claims (10)
1.一种光-Fenton脱硫脱硝催化剂,其特征在于包括催化剂载体、通过粘结剂负载在催化剂载体上的光-Fenton活性组分,所述光-Fenton活性组分包括管状锰掺杂石墨相氮化碳、负载于管状锰掺杂石墨相氮化碳上的钼酸铁;其重量组分如下:催化剂载体70-85份,粘结剂10-30份,管状锰掺杂石墨相氮化碳0.5-2.0份,钼酸铁0.5-2.0份。
2.根据权利要求1所述的光-Fenton脱硫脱硝催化剂,其特征在于所述催化剂载体为γ-Al2O3、ZSM-5分子筛、活性炭纤维毡、陶瓷中的一种或几种。
3.根据权利要求1所述的光-Fenton脱硫脱硝催化剂,其特征在于所述管状锰掺杂石墨相氮化碳为通过无模板法合成。
4.根据权利要求1所述的光-Fenton脱硫脱硝催化剂,其特征在于所述钼酸铁是以硝酸铁或氯化铁为铁源,钼酸铵或钼酸钠为钼盐,通过水热法合成。
5.一种如权利要求1所述光-Fenton脱硫脱硝催化剂的制备方法,其特征在于包括以下步骤:
(1)将催化剂载体洗涤、烘干备用;
(2)将三聚氰胺或尿素溶于有机溶剂中,加热搅拌使其溶解,待溶液冷却后加入一定量的稀硝酸和锰盐,将所生成的沉淀洗涤、干燥,最后置于马弗炉焙烧,得到管状Mn-g-C3N4;
(3)以硝酸铁或氯化铁为铁盐,钼酸铵或钼酸钠为钼盐,用碱液调节pH,生成钼酸铁前驱体;
(4)将步骤(2)得到的管状Mn-g-C3N4加入到钼酸铁前驱体混合液中,一步溶剂热法反应制备管状Mn-g-C3N4/ Fe2(MoO4)3光-Fenton活性组分;
(5)配制粘结剂溶液,将步骤(4)所得光-Fenton活性组分加入到粘结剂溶液中,搅拌2h,再放入步骤(1)洗涤、烘干后的载体,超声浸渍,干燥12h,即为所述光-Fenton脱硫脱硝催化剂。
6.根据权利要求5所述的制备方法,其特征在于所述步骤(2)中的有机溶剂为乙二醇或乙醇。
7.根据权利要求5所述的制备方法,其特征在于所述步骤(2)中的锰盐为乙酸锰、硝酸锰、氯化锰中的一种。
8.根据权利要求5所述的制备方法,其特征在于所述步骤(2)中马弗炉焙烧温度为350℃~550℃,升温速率为5℃/min ~10℃/min。
9.根据权利要求5所述的制备方法,其特征在于所述步骤(3)中铁盐:钼盐的摩尔比为1:1.5。
10.根据权利要求5所述的制备方法,其特征在于所述步骤(4)中一步溶剂热法为将反应物置于聚四氟乙烯内衬的水热釜中,加热温度为140℃~180℃,反应时间为12~24h。
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