CN112337460A - 一种络合酸液制备Mn基尖晶石低温脱硝催化剂的方法 - Google Patents
一种络合酸液制备Mn基尖晶石低温脱硝催化剂的方法 Download PDFInfo
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Abstract
本发明公开了一种低温高效锰基尖晶石脱硝催化剂的制备方法,其特征在于,包括如下步骤:将锰盐与金属盐溶于蒸馏水中,在20‑90℃条件下搅拌1‑12h,在搅拌的同时缓慢加入络合酸液,所述锰盐、金属盐、蒸馏水和络合酸液的摩尔比为:0.1‑1.0:0.025‑0.05:6.5‑10.5:0.05‑1.0;室温下搅拌1‑2h,溶液呈透明胶状,放置于90‑140℃的烘箱中烘干发酵至蓬松多孔的尖晶石前躯体;将制得的尖晶石前躯体,研磨并过50‑200目筛,于空气氛围下,以2‑10℃min‑1的升温速度,设置升温程序从室温升至400‑750℃的马弗炉中焙烧3‑6h,待炉温冷却至室温,得到锰基尖晶石相脱硝催化剂。本发明方法制出的尖晶石脱硝催化剂粒径大小适中分布均匀,低温活性高,在100‑150℃脱硝活性保持在90%以上,具有良好的抗硫抗水能力。
Description
技术领域
本发明属于工业尾气烟气脱硝处理和环保材料催化剂的制备领域,具体涉及尖晶石脱硝催化剂的合成方法。
背景技术
氮氧化合物(NOx)是形成酸雨、光化学烟雾、臭氧消耗和水资源富营养化等一系列问题的大气重要污染物之一,对人类的健康和自然环境造成了严重的危害。目前高效去除氮氧化合物的方法,是利用催化材料对氮氧化合物进行催化还原转化氮气。其中,NH3选择性催化还原NOx(NH3-SCR)的反应,以其较高的NOx去除率而得到了广泛的应用。
然而,工业窑炉排放的烟气温度低于300℃,甚至有些垃圾焚烧炉、水泥窑炉、陶瓷窑炉、玻璃窑炉等会低于150℃,因此要求NH3-SCR催化剂须在低温下(100~300℃)保持良好的催化活性。目前已经商业化的NH3-SCR催化剂V2O5-WO3(MoO3)/TiO2是一种典型的中温NH3-SCR催化剂。但该催化剂存在着工作温度窗口窄且温度高(350-400℃)、氮气选择率低、催化剂元素污染性大回收处理麻烦等不足。因此,更多的研究人员将研发方向集中在开发低温高活、性能稳定、成本低环境友好的NH3-SCR催化剂。
目前,低温脱硝催化剂的制备主要以浸渍法为主,中国专利CN109647502A一种新型低碳环保催化剂的制备方法及应用中,以经过处理的H-β分子筛为载体,通过浸渍的方式与活性组分结合,但H-β分子筛载体前处理较复杂需要300-600℃煅烧3-6小时,浸渍阶段与活性组分离子交换的时间较长,相比于氧化铝或钛白粉做载体,分子筛载体的成本较高,不适合大范围工业应用;专利CN110787807A低温脱硝催化剂及其制备方法和烟气脱硝的方法中,采用自制介孔TiO2作为载体与含有过渡金属盐溶液和铁助剂进行煅烧制备得到,但介孔TiO2前期制备需要经过酸解、还原、结晶、成胶、煅烧,表面氢化还原等工艺,制备过程复杂不易操作,也不适合工业化生产应用。专利CN109603815A采用沉淀法制备的高选择性低温锰基脱硝催化剂;专利CN110743561A采用混合挤出成型煅烧晶化法制备低温脱硝催化剂;专利CN107983354A阐述了一种抗碱中毒铜基尖晶石低温脱硝催化剂的制备方法,专利重点阐述了尖晶石相的低温脱硝催化剂增强了铜基尖晶石催化剂的抗碱中毒能力,并未报道脱硝性能和抗硫抗水性;以上专利均未提及催化剂形貌对脱硝性能的是否有影响。
发明内容
本发明要解决的问题是克服现有技术的不足,通过溶液络合法制备出外形呈规则立方体的Mn基尖晶石低温脱硝催化剂,因其外观结构规则、比表面积大、活性位点多和电子交互能力强而表现出较优的低温脱硝活性及抗硫抗水性能。
本发明实现上述目标采用如下技术方案予以实现:
本发明提供一种络合酸液制备Mn基尖晶石低温脱硝催化剂的制备方法,包括以下步骤:
1)将锰盐与金属盐溶于蒸馏水中,在20-90℃条件下搅拌1-12h,在搅拌的同时缓慢加入络合酸液,所述锰盐、金属盐、蒸馏水和络合酸液的摩尔比为:0.1-1.0:0.025-0.05:6.5-10.5:0.05-1.0;金属盐为M的醋酸盐或硝酸盐中的一种或多种混合物,所述金属M为Ni、Cr、Co、Fe中的一种;继续在室温下搅拌1-2h,得到透明胶状溶液;
2)将步骤1)得到透明胶状溶液放置于90-140℃的烘箱中烘干发酵至蓬松多孔的尖晶石前躯体;
3)将制得的蓬松多孔的尖晶石前躯体,研磨并过50-200目筛,于空气氛围下,以2-10℃min-1的升温速度,设置升温程序从室温升至400-750℃的马弗炉中焙烧3-6h,待炉温冷却至室温,得到Mn基尖晶石低温脱硝催化剂活性组分;
4)以直径为5mm的硅铝球为载体,对Mn基尖晶石相脱硝催化剂活性组分进行滚涂成型,烘干焙烧之后,获得络合酸液制备的Mn基尖晶石相低温脱硝催化剂成品。
本发明上述制备方法中,步骤(1)中锰盐优选为醋酸锰、硝酸锰、氯化锰中的一种或几种的混合物。
所述络合酸液优选为体积比为2-20:80-98的0.05mol/L的盐酸与0.5mol/L柠檬酸的混酸,体积比为2-20:80-98的0.05mol/L的盐酸与0.5mol/L乙二胺四乙酸(EDTA)的混酸,体积比为2-20:80-98的0.05mol/L的醋酸与0.5mol/L柠檬酸的混酸,或体积比为2-20: 80-98的0.05mol/L的醋酸与0.5mol/L乙二胺四乙酸(EDTA)的混酸中的一种。
与现有技术相比,本发明的有益效果是:
1.本发明方法利用尖晶石结构相对稳定,组分、物相、价态和形貌均可调控,制备出的样品比表面积大、活性位点多和离子之间的电子交互能力强,表现出较优的低温脱硝活性及抗水抗硫性能。
2.本发明方法通过络合酸液将金属盐溶液形成均匀的络合物溶液,制备出的Mn基尖晶石低温脱硝催化剂粒径大小适中分布均匀,低温活性高,在100-150℃脱硝活性保持在90%以上。
3.本发明方法合成的Mn基尖晶石低温脱硝催化剂具有良好的抗硫抗水能力,为工业废气低温净化提供了新的思路。
附图说明
图1为本发明实施例1络合酸液制备的Mn基尖晶石低温脱硝催化剂的XRD谱图;
图2为本发明实施例1络合酸液制备的Mn基尖晶石低温脱硝催化剂的扫描电镜图;
图3为本发明实施例1-4络合酸液制备的Mn基尖晶石低温脱硝催化剂的脱硝准率与温度的变化图;
图4为本发明实施例1-4络合酸液制备的Mn基尖晶石低温脱硝催化剂的抗水抗硫性测试图。
具体实施方式
下面结合附图及具体实施方式来进一步详细描述本发明技术方案及技术效果。
下面的实施例可以使本专业的专业技术人员更全面地理解本发明,但不以任何方式限制本发明。
实施例1
(1)将36.75g醋酸锰((CH3COO)2Mn·4H2O)缓慢加入到120ml的50℃的蒸馏水中,至全部溶解;
(2)将40g硝酸铬(Cr(NO3)2·9H2O)加入到已溶解的醋酸锰溶液中,搅拌3h。
(3)将配制体积比为8:92的0.05mol/L的盐酸与0.5mol/L的柠檬酸的450ml络合酸液,缓慢加入到醋酸锰溶液中,搅拌1h;
(4)将所得溶液放入烘箱中,在120℃条件下烘干6h,得到发酵至蓬松多孔的尖晶石前躯体,将其研磨并过100目筛;
(5)在空气氛围中,以2-10℃/min的升温速度,升温至500℃焙烧5h,待炉温冷却至室温,得到Mn基尖晶石相低温脱硝催化剂活性组分;
(6)以直径为5mm的硅铝球为载体,对锰基尖晶石活性组分进行滚涂成型,烘干焙烧之后,获得络合酸液制备的Mn基尖晶石相低温脱硝催化剂成品。
实施例2
(1)将29g硝酸镍(Ni(NO3)2·6H2O)溶解在70ml的50℃的蒸馏水中,搅拌至全部溶解。
(2)将53.7g质量分数为50%的硝酸锰(Mn(NO3)2)溶液缓慢加入到硝酸镍的溶液中,搅拌3h;
(3)将配置体积比为12:88的0.05mol/L的盐酸与0.5mol/L的柠檬酸的450ml络合酸液,缓慢加入到金属盐溶液中,搅拌1h;
(4)将所得溶液放入烘箱中,在120℃条件下烘干6h,得到发酵至蓬松干燥的固体,将固体研磨并过100目筛;
(5)在空气氛围中,以2-10℃/min的升温速度,升温至500℃焙烧5h,待炉温冷却至室温,得到络合酸液制备的锰基尖晶石相低温脱硝催化剂活性组分;
(6)以直径为5mm的硅铝球为载体,对Mn基尖晶石活性组分进行滚涂成型,烘干焙烧之后,制得催化剂成品。
实施例3
(1)将36.75g醋酸锰((CH3COO)2Mn·4H2O)缓慢加入到120ml的50℃的蒸馏水中,至全部溶解;
(2)将29g硝酸铬(Co(NO3)2·9H2O)加入到已溶解的醋酸锰溶液中,搅拌2h。
(3)将配置体积比为8:92的0.05mol/L的盐酸与0.5mol/L的EDTA溶液的450ml络合酸液,缓慢加入到金属盐溶液中,搅拌1h;
(4)将所得溶液放入烘箱中,在120℃条件下烘干6h,得到发酵至蓬松干燥的固体,将固体研磨并过100目筛;
(5)在空气氛围中,以2-10℃/min的升温速度,升温至500℃焙烧5h,待炉温冷却至室温,得到锰基尖晶石相低温脱硝催化剂活性组分;
(6)以直径为5mm的硅铝球为载体,对锰基尖晶石活性组分进行滚涂成型,烘干焙烧之后,制得催化剂成品。
实施例4
(1)将40g硝酸铬(Cr(NO3)2·9H2O)缓慢加入70ml的50℃的蒸馏水中,至全部溶解。
(2)将53.7g质量分数为50%的硝酸锰溶液(Mn(NO3)2)缓慢加入到硝酸铬溶液中,搅拌3h。
(3)将配置体积比为12:88的0.05mol/L的盐酸与0.5mol/L的EDTA的450ml络合酸液,缓慢加入到金属盐溶液中,搅拌1h;
(4)将所得溶液放入烘箱中,在120℃条件下烘干6h,得到发酵至蓬松干燥的固体,将固体研磨并过100目筛;
(5)在空气氛围中,以2-10℃/min的升温速度,升温至500℃焙烧5h,待炉温冷却至室温,得到锰基尖晶石低温脱硝催化剂活性组分;
(6)以直径为5mm的硅铝球为载体,对锰基尖晶石活性组分进行滚涂成型,烘干焙烧之后,制得催化剂成品。
锰基尖晶石相低温脱硝催化剂的氮氧化合物脱除率测试
将实施例1-4制备的球形锰基尖晶石低温脱硝催化剂量取20ml,置于固定床圆柱形反应装置中,反应系统的温度窗口为80-180℃,模拟烟气由600ppmNO、650ppmNH3、5Vol.%O2其余为N2组成,总流量为200L/h,空速为10000h-1,气体组分采用德国testo-350烟气分析仪。不同实施例在不同温度下的NOx脱除率,见图3。由图3的数据可以看出,温度在100℃时,NOx脱除率已达到90%以上,继续升温至120℃,NOx脱除率接近100%,低温脱硝活性优异。
锰基尖晶石相低温脱硝催化剂的抗硫抗水性测试
锰基尖晶石相低温脱硝催化剂在脱硝实验中,在120℃条件下,通入200ppm的SO2和5Vol.%H2O,NOx的脱除率图,见图4。由图4中数据可知,通入SO2和水蒸气后,NOx 脱除率迅速降至到90%,且脱硝性能维持在90%左右,停止通入SO2和水蒸气后,NOx 脱除率最终恢复到95%,
通过实验检测发现,利用本发明方法的实施例2-4络合酸液制备的锰基尖晶石低温脱硝催化剂,其XRD谱图和SEM谱图结果均得到类似的结论,因此,此后不再赘述,不再一一给出结构测试图。仅对制备得到的产品进行NOx脱除性能测试和抗水抗硫性测试。
申请人声明,以上所述仅是本发明中的几种实施案例而已,并非对本发明做任何形式上的限制,本发明并不局限于上述详细方法。任何熟悉本专业的技术人员,在不脱离本发明技术方案范围内,对本发明的任何改进,或利用上述揭示的结构或技术内容做出些许更改或修饰,视为等效案例。凡是对本发明技术和原料在未脱离本发明技术方案内容,进行任何简单修改、等同变化与修饰,均人属本发明技术方案范围内。
Claims (3)
1.一种络合酸液制备Mn基尖晶石相低温脱硝催化剂的方法,其特征在于,包括如下步骤:
1)将锰盐与金属盐溶于蒸馏水中,在20-90℃条件下搅拌1-12h;在搅拌的同时缓慢加入络合酸液,所述锰盐、金属盐、蒸馏水和络合酸液的摩尔比为:0.1-1.0:0.025-0.05:6.5-10.5:0.05-1.0;金属盐为M的醋酸盐或硝酸盐中的一种或多种混合物,所述金属M为Ni、Cr、Co、Fe中的一种,继续在室温下搅拌1-2h,得到透明胶状溶液;
2)将步骤1)得到透明胶状溶液放置于90-140℃的烘箱中烘干发酵至蓬松多孔的尖晶石前躯体;
3)将制得的蓬松多孔的尖晶石前躯体研磨并过50-200目筛后,于空气氛围下,以2-10℃min-1的升温速度,设置升温程序从室温升至400-750℃的马弗炉中焙烧3-6h,待炉温冷却至室温,得到络合酸液制备的Mn基尖晶石相脱硝催化剂活性组分;
4)以直径为5mm的硅铝球为载体,对Mn基尖晶石相脱硝催化剂活性组分进行滚涂成型,烘干焙烧之后,获得络合酸液制备的Mn基尖晶石相低温脱硝催化剂成品。
2.根据权利要求1所述的方法,其特征在于,步骤1)中所述的锰盐为醋酸锰、硝酸锰、氯化锰中的一种或几种的混合物。
3.根据权利要求1所述的方法,其特征在于,步骤1)中,所述络合酸液为体积比为2-20:80-98的0.05mol/L的盐酸与0.5mol/L柠檬酸的混酸、体积比为2-20:80-98的0.05mol/L的盐酸与0.5mol/L乙二胺四乙酸的混酸、体积比为2-20:80-98的0.05mol/L的醋酸与0.5mol/L柠檬酸的混酸,或体积比为2-20:80-98的0.05mol/L的醋酸与0.5mol/L乙二胺四乙酸的混酸中的一种。
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