技术领域technical field
本发明涉及催化剂制备技术领域，具体涉及一种一氧化碳低温催化氧化催化剂及其制备方法与应用。The invention relates to the technical field of catalyst preparation, in particular to a carbon monoxide low-temperature catalytic oxidation catalyst and its preparation method and application.
背景技术Background technique
一氧化碳是一种无色、无臭、无味的可燃性有毒气体，在空气中不易发生化学反应，性质稳定，可在大气中停留较长时间。因其具有极易与血液中运载氧的血红蛋白相结合，在极低浓度时能使人或动物遭到缺氧性伤害，轻者眩晕、头疼，重者脑细胞受到永久性损伤，甚至窒息死亡等危害，因此成为重点关注的对象。Carbon monoxide is a colorless, odorless, tasteless, flammable and toxic gas. It does not easily undergo chemical reactions in the air. It is stable in nature and can stay in the atmosphere for a long time. Because it is very easy to combine with the oxygen-carrying hemoglobin in the blood, it can cause hypoxic damage to humans or animals at extremely low concentrations. In mild cases, dizziness and headaches, in severe cases, brain cells are permanently damaged, and even suffocated to death. and other hazards, so it has become the focus of attention.
目前以贵金属(Au、Pt、Pd、Ru)为主的催化剂具有一定的一氧化碳催化氧化活性和稳定性，但是贵金属催化剂存在制备成本较高的问题。公开号CN114984940A公开了一种PGM-Au合金催化剂，具有良好的燃气热水器尾气140℃下催化氧化一氧化碳成二氧化碳的催化活性，但是Au作为一种常见的贵金属，价格高昂，实现产业化造成成本较高；公开号为CN113649025A公开了一种耐高温的负载型PdCu催化剂，在300℃以上才能达到催化剂的起活温度，耗能较高。贵金属氧化氧化催化剂成本高，过渡金属氧化物催化剂展现出更多的应用潜能；上述部分专利虽然展现出了比较优异的性能，但需要在较高温度条件下实现一氧化碳的催化氧化，消耗大量能量。At present, catalysts based on noble metals (Au, Pt, Pd, Ru) have certain catalytic oxidation activity and stability of carbon monoxide, but noble metal catalysts have the problem of high preparation cost. Publication No. CN114984940A discloses a PGM-Au alloy catalyst, which has good catalytic activity for catalyzing the oxidation of carbon monoxide into carbon dioxide at 140°C from gas water heater tail gas. However, Au, as a common noble metal, is expensive, and the industrialization results in higher costs. ; The publication number is CN113649025A, which discloses a high-temperature-resistant supported PdCu catalyst, which can only reach the activation temperature of the catalyst above 300° C., and consumes a lot of energy. The cost of noble metal oxidation catalysts is high, and transition metal oxide catalysts show more application potential; although some of the above patents show relatively excellent performance, they need to achieve catalytic oxidation of carbon monoxide at relatively high temperatures, which consumes a lot of energy.
发明内容Contents of the invention
本发明所要解决的技术问题在于如何提供一种一氧化碳低温催化氧化催化剂，能够在低温下达到较高的催化效率，并且制备成本低。The technical problem to be solved by the present invention is how to provide a low-temperature catalytic oxidation catalyst for carbon monoxide, which can achieve high catalytic efficiency at low temperature and has low preparation cost.
本发明通过以下技术手段实现解决上述技术问题的：The present invention realizes solving above-mentioned technical problem by following technical means:
本发明第一方面提出一种一氧化碳低温催化氧化催化剂，包括催化剂载体、催化剂活性组分和催化剂助剂；The first aspect of the present invention proposes a carbon monoxide low-temperature catalytic oxidation catalyst, including a catalyst carrier, a catalyst active component and a catalyst assistant;
所述催化剂载体为TiO2；The catalyst carrier is TiO2 ;
所述催化剂活性组分包括第一活性组分、第二活性组分和第三活性组分；所述第一活性组分为V2O5；第二活性组分为MoO3；第三活性组分为La2O3；The catalyst active component includes a first active component, a second active component and a third active component; the first active component is V2 O5 ; the second active component is MoO3 ; the third active component is The component is La2 O3 ;
所述催化剂助剂为纸浆棉。The catalyst auxiliary agent is pulp cotton.
有益效果：一氧化碳催化氧化催化剂以TiO2为载体，具有较高的比表面积，能够有效分散催化剂活性组分；并且没有使用过渡金属作为载体，在另一方面来说，也降低制备成本。纸浆棉在催化剂系统中起到支撑作用，能够为催化剂提供骨架、增强催化剂的强度。Beneficial effects: the carbon monoxide catalytic oxidation catalyst usesTiO2 as a carrier, has a relatively high specific surface area, and can effectively disperse catalyst active components; and does not use a transition metal as a carrier, and on the other hand, also reduces the preparation cost. Pulp cotton plays a supporting role in the catalyst system, which can provide a skeleton for the catalyst and enhance the strength of the catalyst.
第一活性组分V2O5在整个催化剂系统中起到的催化氧化一氧化碳作用，第二活性组分MoO3在整个催化剂系统中起到抗中毒的作用，第三活性组分La2O3作为稀土金属氧化物起到催化氧化一氧化碳作用。虽然单独的V2O5或La2O3都具有催化氧化的效果，但是催化氧化效率不明显，V2O5和La2O3相结合之后，V-La化合键之间紧密结合，一氧化碳催化氧化效率明显提高，在实际的使用工况环境中含有一定量的水分和SO2,在催化剂中添加一定量的MoO3提高催化剂的耐中毒能力。The first active component V2 O5 plays the role of catalytic oxidation of carbon monoxide in the whole catalyst system, the second active component MoO3 plays the role of anti-poisoning in the whole catalyst system, the third active component La2 O3 As a rare earth metal oxide, it can catalyze the oxidation of carbon monoxide. Although V2 O5 or La2O3 alone has the effect of catalytic oxidation,butthe catalytic oxidation efficiencyis not obvious. The catalytic oxidation efficiency is significantly improved. In the actual working environment, there is a certain amount of water and SO2 , and a certain amount of MoO3 is added to the catalyst to improve the poisoning resistance of the catalyst.
本发明第二方面提出上述一氧化碳低温催化氧化催化剂的制备方法，包括以下步骤：The second aspect of the present invention proposes the preparation method of above-mentioned carbon monoxide low-temperature catalytic oxidation catalyst, comprises the following steps:
(1)制备催化剂活性液前驱体：将第一活性组分催化剂盐溶解于水，得到溶液A，将第二活性组分催化剂盐溶解于水，得到溶液B；将第三活性组分催化剂盐溶解于水，得到溶液C；将溶液C倒入溶液A中混合均匀，调节pH得到混合溶液，再将溶液B倒入混合溶液中，加热搅拌，得到催化剂活性液前驱体；(1) Preparation of catalyst active liquid precursor: the first active component catalyst salt is dissolved in water to obtain solution A, the second active component catalyst salt is dissolved in water to obtain solution B; the third active component catalyst salt Dissolve in water to obtain solution C; pour solution C into solution A and mix evenly, adjust the pH to obtain a mixed solution, then pour solution B into the mixed solution, heat and stir to obtain a catalyst active liquid precursor;
(2)催化剂混炼：将催化剂活性液前驱体与TiO2以及纸浆棉混合搅拌均匀，将活性组分充分分散在载体表面，得到催化剂泥料；(2) Catalyst mixing: Mix and stir the catalyst active liquid precursor with TiO2 and pulp cotton evenly, and fully disperse the active components on the surface of the carrier to obtain catalyst sludge;
(3)催化剂干燥煅烧：将催化剂泥料放入挤出机进行挤出，挤出后进行微波干燥、梭式窑高温煅烧，使得催化剂活性液前驱体转化为催化剂活性组分,得到一氧化碳低温催化氧化催化剂。(3) Catalyst drying and calcination: put the catalyst sludge into the extruder for extrusion, then carry out microwave drying and high-temperature calcination in a shuttle kiln after extrusion, so that the catalyst active liquid precursor is converted into a catalyst active component, and carbon monoxide is catalyzed at low temperature. oxidation catalyst.
有益效果：本发明的制备方法首先将活性组分进行溶解混合得到催化剂活性液前驱体，催化剂活性液前驱体的活性组分之间紧密结合，使得所得催化剂活性效果充分发挥；其次将催化剂活性液前驱体与TiO2以及纸浆棉混合均匀，使得活性物质能够均匀的分散在载体表面，所得催化剂具有较大的比表面积，能够使得活性组分在载体表面高度分散，更有利于原料及反应产物的扩散；最后将催化剂采用微波干燥，相对于传统干燥方式时间更短，节约时间成本。Beneficial effects: the preparation method of the present invention first dissolves and mixes the active components to obtain the catalyst active liquid precursor, and the active components of the catalyst active liquid precursor are closely combined, so that the activity effect of the obtained catalyst can be fully exerted; secondly, the catalyst active liquid The precursor is evenly mixed with TiO2 and pulp cotton, so that the active material can be uniformly dispersed on the surface of the carrier, and the obtained catalyst has a large specific surface area, which can make the active component highly dispersed on the surface of the carrier, which is more conducive to the separation of raw materials and reaction products. Diffusion; Finally, the catalyst is dried by microwave, which saves time and cost compared with traditional drying methods.
优选地，所述步骤(1)中第一活性组分催化剂盐为钒盐，第二活性组分催化剂盐为钼盐，第三活性组分催化剂为镧盐；第一活性组分、第二活性组分和第三活性组分的重量份比值为(1-3):1:1。Preferably, in the step (1), the first active component catalyst salt is a vanadium salt, the second active component catalyst salt is a molybdenum salt, and the third active component catalyst is a lanthanum salt; the first active component, the second The weight ratio of the active component to the third active component is (1-3):1:1.
优选地，所述步骤(1)中采用单乙醇胺调节pH到8-10；加热温度为60-70℃；搅拌时间为20-50min。Preferably, monoethanolamine is used in the step (1) to adjust the pH to 8-10; the heating temperature is 60-70° C.; the stirring time is 20-50 min.
优选地，所述步骤(2)中TiO2与纸浆棉混合质量比为10:1；在混合搅拌机中搅拌，转速为高速搅拌转速2000-3000r/min。Preferably, in the step (2), the mixing mass ratio of TiO2 and pulp cotton is 10:1; stirring in a mixing mixer at a high-speed stirring speed of 2000-3000r/min.
更选优地，所述转速为高速搅拌转速2500r/min。More preferably, the rotational speed is a high-speed stirring rotational speed of 2500 r/min.
优选地，所述步骤(3)中挤出的形状为蜂窝状或条状；蜂窝状催化剂的孔数为10-40孔；条状催化剂的直径为1-10mm。Preferably, the shape extruded in the step (3) is honeycomb or strip; the number of holes of the honeycomb catalyst is 10-40 holes; the diameter of the strip catalyst is 1-10mm.
更优选地，蜂窝状催化剂的孔数为25孔。More preferably, the honeycomb catalyst has 25 pores.
优选地，所述步骤(3)中微波功率为200-300W，时间为20-50min。Preferably, the microwave power in the step (3) is 200-300W, and the time is 20-50min.
更优选地，所述微波干燥微波功率为250W，时间为30min。More preferably, the microwave drying power is 250W, and the time is 30min.
优选地，所述步骤(3)中煅烧温度为400-500℃，煅烧时间为3-6h。Preferably, the calcination temperature in the step (3) is 400-500°C, and the calcination time is 3-6h.
更优选地，所述煅烧温度为500℃，煅烧时间为4h。More preferably, the calcination temperature is 500° C., and the calcination time is 4 hours.
本发明第三方面提出上述一氧化碳低温催化氧化催化剂在催化氧化一氧化碳中的应用。The third aspect of the present invention proposes the application of the above-mentioned low-temperature catalytic oxidation catalyst for carbon monoxide in the catalytic oxidation of carbon monoxide.
本发明的优点在于：The advantages of the present invention are:
1、一氧化碳催化氧化催化剂以TiO2为载体，具有较高的比表面积，能够有效分散催化剂活性组分；并且没有使用过渡金属作为载体，在另一方面来说，也降低制备成本。纸浆棉在催化剂系统中起到支撑作用，能够为催化剂提供骨架、增强催化剂的强度。1. The carbon monoxide catalytic oxidation catalyst uses TiO2 as a carrier, which has a high specific surface area and can effectively disperse the active components of the catalyst; and does not use transition metals as a carrier, on the other hand, it also reduces the preparation cost. Pulp cotton plays a supporting role in the catalyst system, which can provide a skeleton for the catalyst and enhance the strength of the catalyst.
2、第一活性组分V2O5在整个催化剂系统中起到的催化氧化一氧化碳作用，第二活性组分MoO3在整个催化剂系统中起到抗中毒的作用，第三活性组分La2O3作为稀土金属氧化物起到催化氧化一氧化碳作用。虽然单独的V2O5或La2O3都具有催化氧化的效果，但是催化氧化效率不明显，V2O5和La2O3相结合之后，V-La化合键之间紧密结合，一氧化碳催化氧化效率明显提高，在实际的使用工况环境中含有一定量的水分和SO2,在催化剂中添加一定量的MoO3提高催化剂的耐中毒能力。2. The first active component V2 O5 plays a role in catalytic oxidation of carbon monoxide in the entire catalyst system, the second active component MoO3 plays an anti-poisoning role in the entire catalyst system, and the third active component La2O3 acts as a rare earth metal oxide to catalyze the oxidation of carbon monoxide. Although V2 O5 or La2O3 alone has the effect of catalytic oxidation,butthe catalytic oxidation efficiencyis not obvious. The catalytic oxidation efficiency is significantly improved. In the actual working environment, there is a certain amount of water and SO2 , and a certain amount of MoO3 is added to the catalyst to improve the poisoning resistance of the catalyst.
3、本发明的制备方法首先将活性组分进行溶解混合得到催化剂活性液前驱体，催化剂活性液前驱体的活性组分之间紧密结合，使得所得催化剂活性效果充分发挥；其次将催化剂活性液前驱体与TiO2以及纸浆棉混合均匀，使得活性物质能够均匀的分散在载体表面，所得催化剂具有较大的比表面积，能够使得活性组分在载体表面高度分散，更有利于原料及反应产物的扩散；最后将催化剂采用微波干燥，相对于传统干燥方式时间更短，节约时间成本。3. In the preparation method of the present invention, firstly, the active components are dissolved and mixed to obtain the catalyst active liquid precursor, and the active components of the catalyst active liquid precursor are closely combined, so that the activity effect of the obtained catalyst is fully exerted; secondly, the catalyst active liquid precursor is The catalyst is evenly mixed with TiO2 and pulp cotton, so that the active material can be uniformly dispersed on the surface of the carrier, and the obtained catalyst has a large specific surface area, which can make the active component highly dispersed on the surface of the carrier, which is more conducive to the diffusion of raw materials and reaction products ; Finally, the catalyst is dried by microwave, which saves time and cost compared with the traditional drying method in a shorter time.
4、本发明所得催化剂在低温80-100℃中催化氧化一氧化碳效率在90％以上。4. The catalytic oxidation efficiency of the catalyst obtained in the present invention is above 90% at a low temperature of 80-100°C.
附图说明Description of drawings
图1为本发明实施例3制备的一氧化碳低温催化氧化催化剂的SEM图；Fig. 1 is the SEM figure of the carbon monoxide low-temperature catalytic oxidation catalyst prepared in Example 3 of the present invention;
图2为实施例1-3以及对比例1-5催化剂测试结果折线图。Fig. 2 is a line chart of the catalyst test results of Examples 1-3 and Comparative Examples 1-5.
具体实施方式Detailed ways
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are part of the present invention Examples, not all examples. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
下述实施例中所用的试验材料和试剂等，如无特殊说明，均可从商业途径获得。The test materials and reagents used in the following examples can be obtained from commercial sources unless otherwise specified.
实施例中未注明具体技术或条件者，均可以按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。Those that do not indicate specific techniques or conditions in the examples can be carried out according to the techniques or conditions described in the documents in this field or according to the product instructions.
一种一氧化碳低温催化氧化催化剂，包括催化剂载体、催化剂活性组分和催化剂助剂；A low-temperature catalytic oxidation catalyst for carbon monoxide, comprising a catalyst carrier, a catalyst active component and a catalyst assistant;
所述催化剂载体为TiO2；The catalyst carrier is TiO2 ;
所述催化剂活性组分包括第一活性组分和第二活性组分；所述第一活性组分为V2O5；第二活性组分为MoO3；第三活性组分为La2O3；The catalyst active component includes a first active component and a second active component; the first active component is V2 O5 ; the second active component is MoO3 ; the third active component is La2 O3 ;
所述催化剂助剂为纸浆棉。The catalyst auxiliary agent is pulp cotton.
有益效果：一氧化碳催化氧化催化剂以TiO2为载体，具有较高的比表面积，能够有效分散催化剂活性组分；并且没有使用过渡金属作为载体，在另一方面来说，也降低制备成本。纸浆棉在催化剂系统中起到支撑作用，能够为催化剂提供骨架、增强催化剂的强度。Beneficial effects: the carbon monoxide catalytic oxidation catalyst usesTiO2 as a carrier, has a relatively high specific surface area, and can effectively disperse catalyst active components; and does not use a transition metal as a carrier, and on the other hand, also reduces the preparation cost. Pulp cotton plays a supporting role in the catalyst system, which can provide a skeleton for the catalyst and enhance the strength of the catalyst.
第一活性组分V2O5在整个催化剂系统中起到的催化氧化CO作用，第二活性组分MoO3在整个催化剂系统中起到抗中毒的作用，第三活性组分La2O3作为稀土金属氧化物起到催化氧化CO作用。虽然单独的V2O5或La2O3都具有催化氧化的效果，但是催化氧化效率不明显，V2O5和La2O3相结合之后，V-La化合键之间紧密结合，CO催化氧化效率明显提高，在实际的使用工况环境中含有一定量的水分和SO2,在催化剂中添加一定量的MoO3提高催化剂的耐中毒能力。The first active component V2 O5 plays the role of catalytic oxidation of CO in the whole catalyst system, the second active component MoO3 plays the role of anti-poisoning in the whole catalyst system, the third active component La2 O3 As a rare earth metal oxide, it can catalyze the oxidation of CO. Although V2 O5 or La2O3 alonehas the effect of catalytic oxidation,but the catalytic oxidation efficiency is notobvious . The catalytic oxidation efficiency is significantly improved. In the actual working environment, there is a certain amount of water and SO2 , and a certain amount of MoO3 is added to the catalyst to improve the poisoning resistance of the catalyst.
实施例1Example 1
本实施例第一方面提供一种一氧化碳低温催化氧化催化剂的制备方法，包括以下步骤：The first aspect of this embodiment provides a method for preparing a carbon monoxide low-temperature catalytic oxidation catalyst, comprising the following steps:
(1)制备催化剂活性液前驱体：将偏钒酸铵、七钼酸铵和六水硝酸镧重量份比值为1:1:1溶解于水，得到偏钒酸铵溶液、七钼酸铵溶液和硝酸镧溶液，将硝酸镧溶液倒入偏钒酸铵溶液中混合均匀，通过添加10mL单乙醇胺溶液将溶液pH调节到9得到混合溶液，再将七钼酸铵溶液倒入混合溶液中，于70℃加热搅拌20min，得到催化剂活性液前驱体；(1) Preparation of catalyst active liquid precursor: dissolving ammonium metavanadate, ammonium heptamolybdate and lanthanum nitrate hexahydrate in a weight ratio of 1:1:1 in water to obtain ammonium metavanadate solution and ammonium heptamolybdate solution and lanthanum nitrate solution, pour the lanthanum nitrate solution into the ammonium metavanadate solution and mix evenly, adjust the pH of the solution to 9 by adding 10mL monoethanolamine solution to obtain a mixed solution, then pour the ammonium heptamolybdate solution into the mixed solution, and Heating and stirring at 70°C for 20 minutes to obtain the catalyst active liquid precursor;
(2)催化剂混炼：将催化剂活性液前驱体与960g二氧化钛以及96g纸浆棉混合均匀，在混合搅拌机中搅拌，转速为高速搅拌转速2000r/min，将催化剂活性液前驱体充分分散在载体表面，得到催化剂泥料；(2) Catalyst mixing: Mix the catalyst active liquid precursor with 960g of titanium dioxide and 96g of pulp cotton evenly, stir in a mixing mixer at a high-speed stirring speed of 2000r/min, fully disperse the catalyst active liquid precursor on the surface of the carrier, Obtain catalyst sludge;
(3)催化剂挤出：将催化剂泥料放入挤出机进行挤出，挤出10孔数的蜂窝状催化剂；(3) Catalyst extruding: putting the catalyst sludge into the extruder to extrude, extruding the honeycomb catalyst with 10 holes;
(4)催化剂干燥煅烧：将挤出蜂窝状催化剂进行微波干燥、梭式窑高温煅烧，微波功率为200W，时间为50min；煅烧温度为400℃，煅烧时间为6h；使得催化剂活性液前驱体转化为催化剂活性组分，得到一氧化碳低温催化氧化催化剂。(4) Catalyst drying and calcination: The extruded honeycomb catalyst is subjected to microwave drying and high-temperature calcination in a shuttle kiln, the microwave power is 200W, and the time is 50min; the calcination temperature is 400°C, and the calcination time is 6h; the catalyst active liquid precursor is converted As a catalyst active component, a carbon monoxide low-temperature catalytic oxidation catalyst is obtained.
实施例2Example 2
本实施例第一方面提供一种一氧化碳低温催化氧化催化剂的制备方法，包括以下步骤：The first aspect of this embodiment provides a method for preparing a carbon monoxide low-temperature catalytic oxidation catalyst, comprising the following steps:
(1)制备催化剂活性液前驱体：将偏钒酸铵、七钼酸铵和六水硝酸镧重量份比值为2.3:1:1溶解于水，得到偏钒酸铵溶液、七钼酸铵溶液和硝酸镧溶液；将硝酸镧溶液倒入偏钒酸铵溶液中混合均匀，通过添加10mL单乙醇胺溶液将溶液pH调节到10得到混合溶液，再将七钼酸铵溶液倒入混合溶液中，于60℃加热搅拌50min，得到催化剂活性液前驱体；(1) Preparation of catalyst active liquid precursor: dissolving ammonium metavanadate, ammonium heptamolybdate and lanthanum nitrate hexahydrate in a weight ratio of 2.3:1:1 in water to obtain ammonium metavanadate solution and ammonium heptamolybdate solution and lanthanum nitrate solution; pour the lanthanum nitrate solution into the ammonium metavanadate solution and mix evenly, adjust the pH of the solution to 10 by adding 10mL of monoethanolamine solution to obtain a mixed solution, then pour the ammonium heptamolybdate solution into the mixed solution, and Heating and stirring at 60°C for 50 minutes to obtain the catalyst active liquid precursor;
(2)催化剂混炼：将催化剂活性液前驱体与900g二氧化钛以及90g纸浆棉混合均匀，混合搅拌机的转速为高速搅拌转速3000r/min，将催化剂活性液前驱体充分分散在载体表面，得到催化剂泥料；(2) Catalyst mixing: mix the catalyst active liquid precursor with 900g of titanium dioxide and 90g of pulp cotton evenly, the speed of the mixing mixer is 3000r/min at a high speed, fully disperse the catalyst active liquid precursor on the surface of the carrier, and obtain the catalyst slime material;
(3)催化剂挤出：将催化剂泥料放入挤出机进行挤出，挤出5mm直径的条状催化剂；(3) Catalyst extrusion: Catalyst sludge is put into extruder and extruded, extrude the strip catalyst of 5mm diameter;
(4)催化剂干燥煅烧：将条状催化剂进行微波干燥、梭式窑高温煅烧，微波功率为300W，时间为20min；煅烧温度为500℃，煅烧时间为5h；使得催化剂活性液前驱体进行转化为催化剂活性组分，得到一氧化碳低温催化氧化催化剂。(4) Catalyst drying and calcination: Microwave drying and high-temperature calcination of the strip catalyst in a shuttle kiln with a microwave power of 300W and a calcination time of 20 minutes; a calcination temperature of 500°C and a calcination time of 5 hours; the catalyst active liquid precursor is converted into The catalyst active component is used to obtain a low-temperature catalytic oxidation catalyst for carbon monoxide.
实施例3Example 3
本实施例第一方面提供一种一氧化碳低温催化氧化催化剂的制备方法，包括以下步骤：The first aspect of this embodiment provides a method for preparing a carbon monoxide low-temperature catalytic oxidation catalyst, comprising the following steps:
(1)制备催化剂活性液前驱体：将偏钒酸铵、七钼酸铵和六水硝酸镧重量份比值为3:1:1溶解于水，得到偏钒酸铵溶液、七钼酸铵溶液和硝酸镧溶液；将硝酸镧溶液倒入偏钒酸铵溶液中混合均匀，通过添加10mL单乙醇胺溶液将溶液pH调节到9得到混合溶液，再将七钼酸铵溶液倒入混合溶液中，于60℃加热搅拌30min，得到催化剂活性液前驱体；(1) Prepare catalyst active liquid precursor: Dissolve ammonium metavanadate, ammonium heptamolybdate and lanthanum nitrate hexahydrate in water at a weight ratio of 3:1:1 to obtain ammonium metavanadate solution and ammonium heptamolybdate solution and lanthanum nitrate solution; pour the lanthanum nitrate solution into the ammonium metavanadate solution and mix evenly, adjust the pH of the solution to 9 by adding 10mL monoethanolamine solution to obtain a mixed solution, then pour the ammonium heptamolybdate solution into the mixed solution, and Heat and stir at 60°C for 30 minutes to obtain the catalyst active liquid precursor;
(2)催化剂混炼：将催化剂活性液前驱体与920g二氧化钛以及92g纸浆棉混合均匀，混合搅拌机的转速为高速搅拌转速2500r/min，将催化剂活性液前驱体充分分散在载体表面，得到催化剂泥料；(2) Catalyst mixing: Mix the catalyst active liquid precursor with 920g of titanium dioxide and 92g of pulp cotton evenly, the speed of the mixing mixer is 2500r/min at a high speed, fully disperse the catalyst active liquid precursor on the surface of the carrier, and obtain catalyst slime material;
(3)催化剂挤出：将催化剂泥料放入挤出机进行挤出，挤出40孔蜂窝状催化剂；(3) Catalyst extrusion: Put the catalyst sludge into the extruder to extrude, and extrude the 40-hole honeycomb catalyst;
(4)催化剂干燥煅烧：将蜂窝状催化剂进行微波干燥、梭式窑高温煅烧，微波功率为250W，时间为30min；煅烧温度为500℃，煅烧时间为4h；使得催化剂活性液前驱体进行转化为催化剂活性组分，得到一氧化碳低温催化氧化催化剂。(4) Catalyst drying and calcination: The honeycomb catalyst is microwave-dried and calcined at a high temperature in a shuttle kiln, the microwave power is 250W, and the time is 30min; the calcination temperature is 500°C, and the calcination time is 4h; the catalyst active liquid precursor is transformed into The catalyst active component is used to obtain a low-temperature catalytic oxidation catalyst for carbon monoxide.
本实施例第二方面提供上述制备方法制备的一氧化碳低温催化氧化催化剂，图1为一氧化碳低温催化氧化催化剂的SEM图，从图1中可以看出，催化剂活性组分分散均匀。The second aspect of this embodiment provides the carbon monoxide low-temperature catalytic oxidation catalyst prepared by the above preparation method. FIG. 1 is an SEM image of the carbon monoxide low-temperature catalytic oxidation catalyst. It can be seen from FIG. 1 that the active components of the catalyst are evenly dispersed.
对比例1Comparative example 1
(1)制备催化剂活性液前驱体：将77g(6wt％)偏钒酸铵溶解于水，得到偏钒酸铵溶液，通过添加10mL单乙醇胺溶液将溶液pH调节到9，于60℃加热搅拌30min，得到催化剂活性液前驱体；(1) Prepare catalyst active liquid precursor: Dissolve 77g (6wt%) ammonium metavanadate in water to obtain ammonium metavanadate solution, adjust the pH of the solution to 9 by adding 10mL monoethanolamine solution, and heat and stir at 60°C for 30min , to obtain the catalyst active liquid precursor;
(2)催化剂混炼：将催化剂活性液前驱体与920g二氧化钛以及92g纸浆棉混合均匀，混合搅拌机的转速为高速搅拌转速2500r/min，将催化剂活性液前驱体充分分散在载体表面，得到催化剂泥料；(2) Catalyst mixing: Mix the catalyst active liquid precursor with 920g of titanium dioxide and 92g of pulp cotton evenly, the speed of the mixing mixer is 2500r/min at a high speed, fully disperse the catalyst active liquid precursor on the surface of the carrier, and obtain catalyst slime material;
(3)催化剂挤出：将催化剂泥料放入挤出机进行挤出，挤出40孔蜂窝状催化剂；(3) Catalyst extrusion: Put the catalyst sludge into the extruder to extrude, and extrude the 40-hole honeycomb catalyst;
(4)催化剂干燥煅烧：将蜂窝状催化剂进行微波干燥、梭式窑高温煅烧，微波功率为250W，时间为30min；煅烧温度为500℃，煅烧时间为4h，使得催化剂活性液前驱体进行转化为催化剂活性组分，得到一氧化碳低温催化氧化催化剂。(4) Catalyst drying and calcination: The honeycomb catalyst is microwave-dried and calcined at a high temperature in a shuttle kiln, the microwave power is 250W, and the time is 30min; the calcination temperature is 500°C, and the calcination time is 4h, so that the catalyst active liquid precursor is transformed The catalyst active component is used to obtain a low-temperature catalytic oxidation catalyst for carbon monoxide.
对比例2Comparative example 2
(1)制备催化剂活性液前驱体：将53g(2wt％)六水硝酸镧溶解于水，得到硝酸镧溶液；通过添加10mL单乙醇胺溶液将溶液pH调节到9，于60℃加热搅拌30min，得到催化剂活性液前驱体；(1) Prepare catalyst active liquid precursor: dissolve 53g (2wt%) lanthanum nitrate hexahydrate in water to obtain a lanthanum nitrate solution; adjust the pH of the solution to 9 by adding 10mL of monoethanolamine solution, and heat and stir at 60°C for 30min to obtain Catalyst active liquid precursor;
(2)催化剂混炼：将催化剂活性液前驱体与920g二氧化钛以及92g纸浆棉混合均匀，混合搅拌机的转速为高速搅拌转速2500r/min，将催化剂活性液前驱体充分分散在载体表面，得到催化剂泥料；(2) Catalyst mixing: Mix the catalyst active liquid precursor with 920g of titanium dioxide and 92g of pulp cotton evenly, the speed of the mixing mixer is 2500r/min at a high speed, fully disperse the catalyst active liquid precursor on the surface of the carrier, and obtain catalyst slime material;
(3)催化剂挤出：将催化剂泥料放入挤出机进行挤出，挤出40孔蜂窝状催化剂；(3) Catalyst extrusion: Put the catalyst sludge into the extruder to extrude, and extrude the 40-hole honeycomb catalyst;
(4)催化剂干燥煅烧：将蜂窝状催化剂进行微波干燥、梭式窑高温煅烧，微波功率为250W，时间为30min；煅烧温度为500℃，煅烧时间为4h，使得催化剂活性液前驱体进行转化为催化剂活性组分，得到一氧化碳低温催化氧化催化剂。(4) Catalyst drying and calcination: The honeycomb catalyst is microwave-dried and calcined at a high temperature in a shuttle kiln, the microwave power is 250W, and the time is 30min; the calcination temperature is 500°C, and the calcination time is 4h, so that the catalyst active liquid precursor is transformed The catalyst active component is used to obtain a low-temperature catalytic oxidation catalyst for carbon monoxide.
对比例3Comparative example 3
(1)制备催化剂活性液前驱体：将偏钒酸铵和六水硝酸镧重量份比值为3:1溶解于水，得到偏钒酸铵溶液和硝酸镧溶液；将硝酸镧溶液倒入偏钒酸铵溶液中混合均匀，通过添加10mL单乙醇胺溶液将溶液pH调节到9，于60℃加热搅拌30min，得到催化剂活性液前驱体；(1) Preparation of catalyst active liquid precursor: dissolving ammonium metavanadate and lanthanum nitrate hexahydrate in a weight ratio of 3:1 in water to obtain ammonium metavanadate solution and lanthanum nitrate solution; pour lanthanum nitrate solution into metavanadium Mix well in the ammonium acid solution, adjust the pH of the solution to 9 by adding 10mL monoethanolamine solution, heat and stir at 60°C for 30min, and obtain the catalyst active liquid precursor;
(2)催化剂混炼：将催化剂活性液前驱体与920g二氧化钛以及92g纸浆棉混合均匀，混合搅拌机的转速为高速搅拌转速2500r/min，将催化剂活性液前驱体充分分散在载体表面，得到催化剂泥料；(2) Catalyst mixing: Mix the catalyst active liquid precursor with 920g of titanium dioxide and 92g of pulp cotton evenly, the speed of the mixing mixer is 2500r/min at a high speed, fully disperse the catalyst active liquid precursor on the surface of the carrier, and obtain catalyst slime material;
(3)催化剂挤出：将催化剂泥料放入挤出机进行挤出，挤出40孔蜂窝状催化剂；(3) Catalyst extrusion: Put the catalyst sludge into the extruder to extrude, and extrude the 40-hole honeycomb catalyst;
(4)催化剂干燥煅烧：将蜂窝状催化剂进行微波干燥、梭式窑高温煅烧，微波功率为250W，时间为30min；煅烧温度为500℃，煅烧时间为4h，使得催化剂活性液前驱体进行转化为催化剂活性组分，得到一氧化碳低温催化氧化催化剂。(4) Catalyst drying and calcination: The honeycomb catalyst is microwave-dried and calcined at a high temperature in a shuttle kiln, the microwave power is 250W, and the time is 30min; the calcination temperature is 500°C, and the calcination time is 4h, so that the catalyst active liquid precursor is transformed The catalyst active component is used to obtain a low-temperature catalytic oxidation catalyst for carbon monoxide.
对比例4Comparative example 4
(1)制备催化剂活性液前驱体：将偏钒酸铵、偏钨酸铵和六水硝酸镧重量份比值为3:1:1溶解于水，得到偏钒酸铵溶液、偏钨酸铵溶液和硝酸镧溶液；将硝酸镧溶液倒入偏钒酸铵溶液中混合均匀，通过添加10mL单乙醇胺溶液将溶液pH调节到9得到混合溶液，再将偏钨酸铵溶液倒入混合溶液中，于60℃加热搅拌30min，得到催化剂活性液前驱体；(1) Preparation of catalyst active liquid precursor: Dissolve ammonium metavanadate, ammonium metatungstate and lanthanum nitrate hexahydrate at a weight ratio of 3:1:1 in water to obtain ammonium metavanadate solution and ammonium metatungstate solution and lanthanum nitrate solution; pour the lanthanum nitrate solution into the ammonium metavanadate solution and mix evenly, adjust the pH of the solution to 9 by adding 10mL monoethanolamine solution to obtain a mixed solution, then pour the ammonium metatungstate solution into the mixed solution, and Heat and stir at 60°C for 30 minutes to obtain the catalyst active liquid precursor;
(2)催化剂混炼：将催化剂活性液前驱体与920g二氧化钛以及92g纸浆棉混合均匀，混合搅拌机的转速为高速搅拌转速2500r/min，将催化剂活性液前驱体充分分散在载体表面，得到催化剂泥料；(2) Catalyst mixing: Mix the catalyst active liquid precursor with 920g of titanium dioxide and 92g of pulp cotton evenly, the speed of the mixing mixer is 2500r/min at a high speed, fully disperse the catalyst active liquid precursor on the surface of the carrier, and obtain catalyst slime material;
(3)催化剂挤出：将催化剂泥料放入挤出机进行挤出，挤出40孔蜂窝状催化剂；(3) Catalyst extrusion: Put the catalyst sludge into the extruder to extrude, and extrude the 40-hole honeycomb catalyst;
(4)催化剂干燥煅烧：将蜂窝状催化剂进行微波干燥、梭式窑高温煅烧，微波功率为250W，时间为30min；煅烧温度为500℃，煅烧时间为4h，使得催化剂活性液前驱体进行转化为催化剂活性组分，得到一氧化碳低温催化氧化催化剂。(4) Catalyst drying and calcination: The honeycomb catalyst is microwave-dried and calcined at a high temperature in a shuttle kiln, the microwave power is 250W, and the time is 30min; the calcination temperature is 500°C, and the calcination time is 4h, so that the catalyst active liquid precursor is transformed The catalyst active component is used to obtain a low-temperature catalytic oxidation catalyst for carbon monoxide.
对比例5Comparative example 5
(1)制备催化剂活性液前驱体：将偏钒酸铵、八水氧氯化锆和六水硝酸镧重量份比值为3:1:1溶解于水，得到偏钒酸铵溶液、氧氯化锆溶液和硝酸镧溶液；将硝酸镧溶液倒入偏钒酸铵溶液中混合均匀，通过添加10mL单乙醇胺溶液将溶液pH调节到9得到混合溶液，再将氧氯化锆溶液倒入混合溶液中，于60℃加热搅拌30min，得到催化剂活性液前驱体；(1) Preparation of catalyst active liquid precursor: dissolving ammonium metavanadate, zirconium oxychloride octahydrate and lanthanum nitrate hexahydrate in water at a weight ratio of 3:1:1 to obtain ammonium metavanadate solution, oxychloride Zirconium solution and lanthanum nitrate solution; pour the lanthanum nitrate solution into the ammonium metavanadate solution and mix evenly, adjust the pH of the solution to 9 by adding 10mL monoethanolamine solution to obtain a mixed solution, then pour the zirconium oxychloride solution into the mixed solution , heated and stirred at 60°C for 30 minutes to obtain the catalyst active liquid precursor;
(2)催化剂混炼：将催化剂活性液前驱体与920g二氧化钛以及92g纸浆棉混合均匀，混合搅拌机的转速为高速搅拌转速2500r/min，将催化剂活性液前驱体充分分散在载体表面，得到催化剂泥料；(2) Catalyst mixing: Mix the catalyst active liquid precursor with 920g of titanium dioxide and 92g of pulp cotton evenly, the speed of the mixing mixer is 2500r/min at a high speed, fully disperse the catalyst active liquid precursor on the surface of the carrier, and obtain catalyst slime material;
(3)催化剂挤出：将催化剂泥料放入挤出机进行挤出，挤出40孔蜂窝状催化剂；(3) Catalyst extrusion: Put the catalyst sludge into the extruder to extrude, and extrude the 40-hole honeycomb catalyst;
(4)催化剂干燥煅烧：将蜂窝状催化剂进行微波干燥、梭式窑高温煅烧，微波功率为250W，时间为30min；煅烧温度为500℃，煅烧时间为4h，使得催化剂活性液前驱体进行转化为催化剂活性组分，得到一氧化碳低温催化氧化催化剂。(4) Catalyst drying and calcination: The honeycomb catalyst is microwave-dried and calcined at a high temperature in a shuttle kiln, the microwave power is 250W, and the time is 30min; the calcination temperature is 500°C, and the calcination time is 4h, so that the catalyst active liquid precursor is transformed The catalyst active component is used to obtain a low-temperature catalytic oxidation catalyst for carbon monoxide.
实施例4Example 4
将实施例1-3和对比例1-5得到的催化剂经压片、破碎过筛，选取40-60目催化剂颗粒进行性能测试。将催化剂在反应管内径为10mm的固定床反应器上进行，具体测试条件如下：CO浓度8000mg/m3、SO2浓度100mg/m3、O2浓度10％、水汽含量30％，平衡气为Ar，反应温度20-100℃，催化剂装填量10mL，气时空速8000h-1，反应器出口CO浓度采用崂应3012-D烟气分析仪在线监测。The catalysts obtained in Examples 1-3 and Comparative Examples 1-5 were tabletted, crushed and sieved, and catalyst particles of 40-60 mesh were selected for performance testing. The catalyst is carried out on a fixed-bed reactor with a reaction tube inner diameter of 10 mm, and the specific test conditions are as follows: CO concentration 8000 mg/m3 , SO2 concentration 100 mg/m3 , O2 concentration 10%, water vapor content 30%, and balance gas of Ar, reaction temperature 20-100°C, catalyst loading 10mL, gas hourly space velocity 8000h-1 , CO concentration at the reactor outlet was monitored online by Laoying 3012-D flue gas analyzer.
表1为实施例1-3对比例1-5催化剂测试结果Table 1 is embodiment 1-3 comparative example 1-5 catalyst test result
从表1中看出，对比实施例1-3中看出，实施例1和实施例2的催化剂的催化氧化效果都没有实施例3的效果好，由此得出活性组分的含量增加，催化剂活性有所增加，但是，活性组分添加过多反而会有所抑制，实施例3是最佳实施例，最佳活性组分重量份比值为偏钒酸铵：七钼酸铵：六水硝酸镧＝3：1：1。As can be seen from Table 1, it can be seen from comparative examples 1-3 that the catalytic oxidation effect of the catalyst of embodiment 1 and embodiment 2 is not as good as the effect of embodiment 3, thus drawing the content of active components to increase, Catalyst activity increases to some extent, but, active component adds too much and can restrain to some extent on the contrary, embodiment 3 is best embodiment, and optimum active component weight ratio is ammonium metavanadate: ammonium heptamolybdate: hexahydrate Lanthanum nitrate = 3:1:1.
对比例1-5以实施例3为基准，对比例1相对于实施例3中活性组分中没有添加七钼酸铵和硝酸镧，对比例2相对于实施例3中活性组分中没有添加偏钒酸铵和七钼酸铵，对比例3相对于实施例3中活性组分中没有添加七钼酸铵，对比例4相对于实施例3中活性组分将七钼酸铵替换为与七钼酸铵具有同等效果的偏钨酸铵，对比例5相对于实施例3中活性组分将七钼酸铵替换为与七钼酸铵具有同等效果的八水氧氯化锆。Comparative example 1-5 is based on embodiment 3, comparative example 1 does not add ammonium heptamolybdate and lanthanum nitrate relative to the active component in embodiment 3, comparative example 2 does not add in the active component relative to embodiment 3 Ammonium metavanadate and ammonium heptamolybdate, comparative example 3 does not add ammonium heptamolybdate relative to the active component in embodiment 3, and comparative example 4 replaces ammonium heptamolybdate with respect to the active component in embodiment 3 Ammonium heptamolybdate has the same effect as ammonium metatungstate, and in comparative example 5, ammonium heptamolybdate is replaced by zirconium oxychloride octahydrate which has the same effect as ammonium heptamolybdate.
从表1和图2中可以看出，对比例1-3以及实施例3的效率排序为：对比例1＜对比例2＜对比例3＜实施例3，因此，可以认为单独添加偏钒酸铵或六水硝酸镧作为活性物质催化氧化CO具有一定的效果，但是，催化效率低于偏钒酸铵和六水硝酸镧一起的协同作用；在实施例3中还添加七钼酸铵作为活性组分，该物质的存在使得催化效率更高，七钼酸铵不仅使得催化剂效率整体提高，而且在含水含硫的工况下，耐受性更强。As can be seen from Table 1 and Figure 2, the efficiency order of Comparative Examples 1-3 and Example 3 is: Comparative Example 1<Comparative Example 2<Comparative Example 3<Example 3, therefore, it can be considered that metavanadic acid is added alone Ammonium or lanthanum nitrate hexahydrate has certain effect as active material catalytic oxidation CO, but, catalytic efficiency is lower than the synergism together of ammonium metavanadate and lanthanum nitrate hexahydrate; In embodiment 3, ammonium heptamolybdate is also added as active Components, the existence of this substance makes the catalytic efficiency higher, and the ammonium heptamolybdate not only improves the overall catalyst efficiency, but also has stronger tolerance under the conditions of water and sulfur.
从表1和图2中看出，对比例4和对比例5催化效率优于对比例3，但是低于实施例3。由此说明虽然偏钨酸铵、八水氧氯化锆也具有一定的催化氧化一氧化碳的效果，但是对比例3-5的催化效率低于偏钒酸铵、七钼酸铵以及六水硝酸镧三者之间的协同作用产生的催化效率。It can be seen from Table 1 and Fig. 2 that the catalytic efficiency of Comparative Example 4 and Comparative Example 5 is better than that of Comparative Example 3, but lower than that of Example 3. This shows that although ammonium metatungstate and zirconium oxychloride octahydrate also have a certain effect of catalytic oxidation of carbon monoxide, the catalytic efficiency of comparative examples 3-5 is lower than ammonium metavanadate, ammonium heptamolybdate and lanthanum nitrate hexahydrate The catalytic efficiency produced by the synergy between the three.
以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: it can still be described in the foregoing embodiments Modifications are made to the recorded technical solutions, or equivalent replacements are made to some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.
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| CN202310429638.6ACN116571232A (en) | 2023-04-18 | 2023-04-18 | A low-temperature catalytic oxidation catalyst for carbon monoxide and its preparation method and application |
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| CN202310429638.6ACN116571232A (en) | 2023-04-18 | 2023-04-18 | A low-temperature catalytic oxidation catalyst for carbon monoxide and its preparation method and application |
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| US20100008840A1 (en)* | 2005-11-14 | 2010-01-14 | Agency For Science, Technology And Research | Highly Dispersed Metal Catalysts |
| CN103657636A (en)* | 2013-11-21 | 2014-03-26 | 大唐南京环保科技有限责任公司 | Plate-type catalyst capable of simultaneous denitration and demercuration and preparation method thereof |
| CN103894181A (en)* | 2014-03-26 | 2014-07-02 | 北京工业大学 | A kind of low-temperature SCR catalyst and preparation method with La-doped TiO2 as carrier |
| CN105817220A (en)* | 2016-05-03 | 2016-08-03 | 展宗城 | Rare-earth modified sulfur-resisting low-temperature SCR catalyst and preparing method thereof |
| CN113996309A (en)* | 2021-11-23 | 2022-02-01 | 国能龙源催化剂江苏有限公司 | Preparation method of high-strength SCR catalyst for CO collaborative removal |
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