技术领域technical field
本发明涉及一种低温多孔复合氧化物脱硝催化剂的制备方法及其产品和应用，适用于环境污染物NO的选择性催化还原，在环境净化领域具有应用前景。The invention relates to a preparation method of a low-temperature porous composite oxide denitrification catalyst and its product and application, which are suitable for selective catalytic reduction of environmental pollutant NO and have application prospects in the field of environmental purification.
背景技术Background technique
NOx是大气中常见的主要污染物，作为一次污染物，会对任何动植物造成多种直接危害，而且NO还可通过光化学氧化作用转化为NO2，继而形成硝酸和亚硝酸，是酸雨的主要贡献者。而NOx-SCR技术是世界上应用最广泛、最为成熟且最有效的烟气脱硝技术，其中低温SCR脱销工艺是近期国内外该领域研究的热点，由于其运行温度较低，可以将脱销反应设备置于尾气净化的尾部，烟气在经过除尘和脱硫设备之后，极大的降低了粉尘等物质对催化剂的冲蚀和毒化作用，环境相对干净，并且无需对烟气进行再加热，但是在低温温度段，可利用的催化剂种类较少，脱销活性受限，因此，开发较高低温脱销效率的低温催化剂具有重要意义。NOx is a common main pollutant in the atmosphere. As a primary pollutant, it will cause a variety of direct harm to any animal and plant, and NO can also be converted into NO2 through photochemical oxidation, and then form nitric acid and nitrous acid, which is the main cause of acid rain. contributor. The NOx-SCR technology is the most widely used, mature and effective flue gas denitrification technology in the world, and the low-temperature SCR denitrification process is a recent research hotspot in this field at home and abroad. Due to its low operating temperature, the denitrification reaction equipment can be Placed at the end of exhaust gas purification, after the flue gas passes through the dust removal and desulfurization equipment, the erosion and poisoning of the catalyst by dust and other substances are greatly reduced, the environment is relatively clean, and there is no need to reheat the flue gas, but at low temperature In the temperature range, there are fewer types of catalysts available, and the destocking activity is limited. Therefore, it is of great significance to develop low-temperature catalysts with higher low-temperature destocking efficiency.
对于低温脱硝催化剂，在诸多的活性物质中，MnOx的研究最为广泛，其表面有多种不同的表面活性氧用以完成催化循环，从而在很大程度上提高了低温催化效率，但是，一般地，Mn基催化剂在得到较高脱硝效率时，其反应温度均在100℃上，而将脱硝设备置于除尘和脱硫设备之后，为避免重复加热，反应温度需控制在100℃以下，现有的催化剂均不能满足该要求。For low-temperature denitrification catalysts, MnOx is the most widely studied among many active substances. There are many different surface active oxygen on its surface to complete the catalytic cycle, thus improving the low-temperature catalytic efficiency to a large extent. However, in general Generally speaking, when Mn-based catalysts obtain higher denitrification efficiency, the reaction temperature is above 100°C, and the denitrification equipment is placed after the dust removal and desulfurization equipment. In order to avoid repeated heating, the reaction temperature must be controlled below 100°C. None of the catalysts met this requirement.
发明内容Contents of the invention
针对目前技术中催化剂低温（<100℃）活性不佳的问题，本发明目的在于提供一种低温多孔复合氧化物脱硝催化剂的制备方法。Aiming at the problem of poor catalyst activity at low temperature (<100°C) in the current technology, the purpose of the present invention is to provide a method for preparing a low-temperature porous composite oxide denitration catalyst.
本发明的再一目的在于：提供一种上述方法制备的低温多孔复合氧化物脱硝催化剂产品。Another object of the present invention is to provide a low-temperature porous composite oxide denitration catalyst product prepared by the above method.
本发明的又一目的在于：提供一种上述产品的应用。Another object of the present invention is to provide an application of the above product.
本发明目的通过下述方案实现：一种低温多孔复合氧化物脱硝催化剂的制备方法，其特征在于，催化剂的分子式为NixMn1-x；0.3≤x≤0.9，x为摩尔数；该催化剂具有多孔结构和高比表面积，无需加致孔剂，仅以沉淀剂草酸造孔，并且无需调节pH值，无需加入乙醇等溶剂，仅以去离子水作为唯一溶剂，具体步骤如下：The object of the present invention is achieved by the following scheme: a preparation method of a low-temperature porous composite oxide denitration catalyst, characterized in that the molecular formula of the catalyst is Nix Mn1-x ; 0.3≤x≤0.9, x is the number of moles; the catalyst With porous structure and high specific surface area, no need to add porogen, only oxalic acid is used as a precipitant to make pores, and there is no need to adjust the pH value, no need to add solvents such as ethanol, only deionized water is used as the only solvent, and the specific steps are as follows:
步骤1，将镍和锰前驱体加入到去离子水中，室温搅拌至完全溶解，边搅拌边加入草酸，继续搅拌12-24小时，其中，草酸的摩尔数是金属总摩尔数的1.0-1.2倍；Step 1, add nickel and manganese precursors to deionized water, stir at room temperature until completely dissolved, add oxalic acid while stirring, and continue stirring for 12-24 hours, wherein the moles of oxalic acid are 1.0-1.2 times the total moles of metals ;
步骤2，将步骤1中的悬浮液进行抽滤与洗涤，直至滤液为中性；Step 2, suction filtering and washing the suspension in step 1 until the filtrate is neutral;
步骤3，将步骤2得到的固体放入60-100℃烘箱中，干燥12-24小时，将其研磨成粉末；Step 3, put the solid obtained in step 2 into an oven at 60-100°C, dry it for 12-24 hours, and grind it into powder;
步骤4，将步骤3的粉末在350-550℃焙烧3-6小时，得到NixMn1-x催化剂粉末。Step 4, calcining the powder in step 3 at 350-550° C. for 3-6 hours to obtain Nix Mn1-x catalyst powder.
在上述方案基础上，所述的镍前驱体为硝酸镍，硫酸镍中的一种，所述的锰前驱体为硝酸锰，醋酸锰中的一种。On the basis of the above scheme, the nickel precursor is one of nickel nitrate and nickel sulfate, and the manganese precursor is one of manganese nitrate and manganese acetate.
本发明提供一种由上述任意一项所述制备方法得到低温多孔复合氧化物脱硝催化剂产品。The invention provides a low-temperature porous composite oxide denitration catalyst product obtained by any one of the above preparation methods.
本发明还提供一种低温多孔复合氧化物脱硝催化剂产品在NH3-SCR反应中的应用。The invention also provides the application of a low-temperature porous composite oxide denitration catalyst product in NH3 -SCR reaction.
NH3-SCR反应条件如下：反应温度25-300℃，气体总流量500 mL/min，反应气组成为100-500 ppm一氧化氮，100-500 ppm氨气，3-10%氧气，其余为氮气。The NH3 -SCR reaction conditions are as follows: reaction temperature 25-300°C, total gas flow rate 500 mL/min, reaction gas composition of 100-500 ppm nitric oxide, 100-500 ppm ammonia, 3-10% oxygen, and the rest nitrogen.
或者，NH3-SCR反应条件为：反应温度25-100℃，气体总流量500 mL/min，反应气组成为100-500 ppm一氧化氮，100-500 ppm氨气，3-10%氧气，其余为氮气。Alternatively, the NH3 -SCR reaction conditions are: reaction temperature 25-100°C, total gas flow rate 500 mL/min, reaction gas composition of 100-500 ppm nitric oxide, 100-500 ppm ammonia, 3-10% oxygen, The rest is nitrogen.
本发明提供了一种合成过程简单，原料易得的制备技术，该技术对NOx-SCR脱硝在低温（<100℃）下具有较好的应用。该催化剂产品具有多孔结构和高比表面积，本发明仅采用去离子水作为唯一溶剂，无需调节pH值，无需加致孔剂，仅以沉淀剂草酸造孔，经过搅拌，抽滤，焙烧等过程即可得到低温多孔复合氧化物脱硝催化剂The invention provides a preparation technology with simple synthesis process and easy-to-obtain raw materials. The technology has better application to NOx-SCR denitrification at low temperature (<100°C). The catalyst product has a porous structure and a high specific surface area. The present invention only uses deionized water as the only solvent, without adjusting the pH value, without adding a porogen, and only uses the precipitant oxalic acid to create pores, and undergoes processes such as stirring, suction filtration, and roasting. Low-temperature porous composite oxide denitration catalyst can be obtained
本发明具有以下优点：The present invention has the following advantages:
（1）制备催化剂所用的原料易得、仅采用常规可溶性盐和沉淀剂，仅采用去离子水作为唯一溶剂。(1) The raw materials used to prepare the catalyst are readily available, only conventional soluble salts and precipitants are used, and only deionized water is used as the only solvent.
（2）制备过程中不需要通过酸碱等调节pH值，工艺较为简单。(2) During the preparation process, there is no need to adjust the pH value through acid and alkali, and the process is relatively simple.
（3）制备的催化剂具有多孔结构和高比表面积，比表面积最高可达85 m2/g，并且在较低温度（<100℃）时具有较高的脱销效果。(3) The prepared catalyst has a porous structure and a high specific surface area, the specific surface area can reach up to 85 m2 /g, and it has a high destocking effect at a low temperature (<100°C).
附图说明Description of drawings
图1为本发明实施例1~4中所述催化剂的NH3-SCR反应活性图，其中圆形为实施例1，正三角形为实施例2，倒三角形为实施例3，斜三角形为实施例4；Fig. 1 is the NH3 -SCR reaction activity diagram of the catalysts described in Examples 1 to 4 of the present invention, wherein the circle is Example 1, the regular triangle is Example 2, the inverted triangle is Example 3, and the oblique triangle is Example 4;
图2为实施例1的TEM图片。FIG. 2 is a TEM picture of Example 1.
具体实施方式Detailed ways
下面结合具体实施例进行详细说明：本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体操作过程，但本发明的保护范围不限于下述实施例。Describe in detail below in conjunction with specific embodiment: present embodiment implements under the premise of the technical solution of the present invention, has provided detailed implementation and specific operation process, but protection scope of the present invention is not limited to following embodiment.
实施例1Example 1
称取5.23克硝酸镍，15.0克硝酸锰，加入到80毫升去离子水中，室温搅拌至完全溶解，边搅拌边加入8.32克草酸，继续搅拌24小时，然后抽滤洗涤，直至滤液为中性，然后将得到的固体放入70℃烘箱中干燥12小时，将其研磨成粉末，然后将粉末在450℃焙烧4小时，得到Ni0.3Mn0.7粉末催化剂，其TEM图2所示，比表面积为85 m2/g。图2为本实施例1的TEM图片。Weigh 5.23 grams of nickel nitrate and 15.0 grams of manganese nitrate, add them to 80 milliliters of deionized water, stir at room temperature until completely dissolved, add 8.32 grams of oxalic acid while stirring, continue to stir for 24 hours, then wash with suction until the filtrate is neutral, Then the obtained solid was dried in an oven at 70°C for 12 hours, ground into powder, and then the powder was calcined at 450°C for 4 hours to obtain a Ni0.3 Mn0.7 powder catalyst, as shown in TEM Figure 2, with a specific surface area of 85 m2 /g. FIG. 2 is a TEM picture of Example 1.
实施例2Example 2
与实施例1相比较，不同的是硝酸镍的质量为8.72克，硝酸锰的质量为10.7克，其他操作条件与实施例1相同，得到Ni0.5Mn0.5粉末催化剂，比表面积为69 m2/g。Compared with Example 1, the difference is that the quality of nickel nitrate is 8.72 grams, and the quality of manganese nitrate is 10.7 grams, and other operating conditions are the same as in Example1 to obtain a Ni0.5 Mn0.5 powder catalyst with a specific surface area of 69 m / g.
实施例3Example 3
与实施例1相比较，不同的是硝酸镍的质量为12.2克，硝酸锰的质量为6.44克，其他操作条件与实施例1相同，得到Ni0.7Mn0.3粉末催化剂，比表面积为54 m2/g。Compared with Example 1, the difference is that the quality of nickel nitrate is 12.2 grams, and the quality of manganese nitrate is 6.44 grams, and other operating conditions are the same as in Example1 to obtain a Ni0.7 Mn0.3 powder catalyst with a specific surface area of 54 m / g.
实施例4Example 4
与实施例1相比较，不同的是硝酸镍的质量为15.7克，硝酸锰的质量为2.15克，其他操作条件与实施例1相同，得到Ni0.9Mn0.1粉末催化剂，比表面积为33 m2/g。Compared with Example 1, the difference is that the quality of nickel nitrate is 15.7 grams, and the quality of manganese nitrate is 2.15 grams, and other operating conditions are the same as in Example1 to obtain a Ni0.9 Mn0.1 powder catalyst with a specific surface area of 33 m / g.
测试例test case
各取新鲜制得的催化剂分别装在石英反应管中。测试温度从室温-300℃，先从室温直接升到50℃，之后每隔25℃取一个测试点，在每个测试点各保持10分钟。一氧化氮的转化率如图1本发明实施例1~4中所述催化剂的NH3-SCR反应活性图所示，从图中可以看出，当镍和锰的摩尔比为3:7时，得到的催化剂活性最佳，75-275℃时，均可达到90%以上。Each freshly prepared catalyst was packed in a quartz reaction tube. The test temperature is from room temperature to 300°C, firstly rise directly from room temperature to 50°C, then take a test point every 25°C, and keep at each test point for 10 minutes. The conversion rate of nitric oxide is shown in the NH3 -SCR reaction activity diagram of the catalyst described in the embodiments of the present invention 1 to 4 in Fig. 1, as can be seen from the figure, when the molar ratio of nickel and manganese is 3:7 , the activity of the catalyst obtained is the best, and at 75-275 °C, it can reach more than 90%.
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