技术领域Technical field
本发明属于大气污染控制技术领域，尤其涉及一种用于协同脱除甲苯和NOx的催化剂及其制备方法和应用。The invention belongs to the technical field of air pollution control, and in particular relates to a catalyst for collaborative removal of toluene and NOx and its preparation method and application.
背景技术Background technique
近年来，大气污染问题日益严重，环境问题也频频出现。氮氧化物(NOx)和挥发性有机物(VOCs)是造成大气污染的主要污染物，会引发雾霾、酸雨、光化学烟雾等多种环境问题并对人体健康产生较大危害。因此，减少NOx和VOCs的排放迫在眉睫，对我国空气质量和环境的改善具有重大意义。In recent years, air pollution has become increasingly serious, and environmental problems have also appeared frequently. Nitrogen oxides (NOx) and volatile organic compounds (VOCs) are the main pollutants causing air pollution, causing haze, acid rain, photochemical smog and other environmental problems and causing great harm to human health. Therefore, it is urgent to reduce the emissions of NOx and VOCs, which is of great significance to the improvement of my country's air quality and environment.
氨催化氧化(NH3-SCR)是目前最为成熟的脱硝技术。而在众多VOCs中，对甲苯的研究较为深入，且VOCs的主要排放源，如：燃煤电厂、钢铁工业、印刷行业、皮革生产等排放的VOCs均含有甲苯，催化氧化技术目前被认为是脱除甲苯的最优技术。由于NH3-SCR与甲苯催化氧化的活性温度窗口接近，且NH3-SCR催化剂对甲苯的催化氧化也显示出活性，因此将甲苯和NOx协同脱除是一个经济性与实用性并存的选择。Ammonia catalytic oxidation (NH3 -SCR) is currently the most mature denitrification technology. Among the many VOCs, toluene has been studied in depth, and the VOCs emitted by the main emission sources of VOCs, such as coal-fired power plants, steel industry, printing industry, leather production, etc., all contain toluene. Catalytic oxidation technology is currently considered to be the most effective way to remove VOCs. Optimal technology for toluene removal. Since the activity temperature windows of NH3 -SCR and toluene catalytic oxidation are close, and the NH3 -SCR catalyst also shows activity in the catalytic oxidation of toluene, the coordinated removal of toluene and NOx is an economical and practical option.
用于协同脱除甲苯和NOx的催化剂主要分为贵金属催化剂和金属氧化物催化剂两大类。贵金属催化剂虽催化活性优异，但资源有限，价格昂贵，且易烧结易中毒。而金属氧化物催化剂尤其是Mn基催化剂热稳定性好，且价格低廉，其表面具有多种氧化态金属离子和晶格氧，表面活性位点丰富，是协同脱除甲苯和NOx的较好选择。Catalysts used for the collaborative removal of toluene and NOx are mainly divided into two categories: precious metal catalysts and metal oxide catalysts. Although noble metal catalysts have excellent catalytic activity, they have limited resources, are expensive, and are prone to sintering and poisoning. Metal oxide catalysts, especially Mn-based catalysts, have good thermal stability and low price. Their surfaces contain various oxidation states of metal ions and lattice oxygen, and are rich in surface active sites. They are a good choice for the collaborative removal of toluene and NOx. .
有鉴于此，特提出本发明。In view of this, the present invention is proposed.
发明内容Contents of the invention
本发明的目的在于提供一种用于协同脱除甲苯和NOx的催化剂及其制备方法和应用，以解决上述问题。The object of the present invention is to provide a catalyst for collaborative removal of toluene and NOx and its preparation method and application to solve the above problems.
为实现以上目的，本发明特采用以下技术方案：In order to achieve the above objects, the present invention adopts the following technical solutions:
本发明提供一种用于协同脱除甲苯和NOx的催化剂，所述催化剂包括MnCuTi混合氧化物，粒径为250-380μm，比表面积为155.10-164.25m2/g，孔体积为0.270-0.281cm3/g，平均孔径为6.672-6.951mm。The invention provides a catalyst for collaborative removal of toluene and NOx. The catalyst includes MnCuTi mixed oxide, with a particle size of 250-380 μm, a specific surface area of 155.10-164.25m2/ g, and a pore volume of 0.270-0.281cm.3 /g, the average pore diameter is 6.672-6.951mm.
本发明还提供一种所述的催化剂的制备方法：将硝酸铜、硝酸锰溶液、去离子水和冰醋酸与乙醇混合，得到溶液A；The invention also provides a method for preparing the catalyst: mixing copper nitrate, manganese nitrate solution, deionized water, glacial acetic acid and ethanol to obtain solution A;
将钛酸丁酯溶于乙醇得到溶液B；Dissolve butyl titanate in ethanol to obtain solution B;
搅拌下将溶液B加入溶液A中形成溶胶并继续搅拌，经过老化、干燥、研磨、煅烧，经压片和过筛后，即得。Add solution B to solution A under stirring to form a sol and continue stirring. After aging, drying, grinding, calcining, tableting and sieving, it is obtained.
进一步地，所述压片为将所述煅烧后的产物置于模具中，在15-25MPa压力下保持5-10min后，随后取至40-60目筛子中研磨、过筛，得到40-60目的颗粒催化剂。Further, the tableting process is to place the calcined product in a mold, hold it under a pressure of 15-25MPa for 5-10 minutes, and then take it to a 40-60 mesh sieve for grinding and sieving to obtain 40-60 mesh. Target particle catalyst.
所得催化剂充分发挥了Mn、Cu、Ti三种金属间的协同作用，形成了丰富的氧空位和活性位点，有利于活性氧的吸附和低温协同反应活性的提高。The obtained catalyst fully exerts the synergistic effect between Mn, Cu, and Ti metals, forming abundant oxygen vacancies and active sites, which is beneficial to the adsorption of active oxygen and the improvement of low-temperature synergistic reaction activity.
作为另一种技术方案，进一步地，所述研磨后分别过40目筛和过100目筛；所述压片为将所述过40目筛的产物和所述过100目筛的产物依次间隔置于模具中，在15-25MPa压力下保持5-10min，随后取至40-60目筛中研磨、过筛，得到40-60目的颗粒催化剂，此过程可以最大化地保持催化剂成型颗粒和催化活性的平衡，同时，其催化活性和选择性也更优。As another technical solution, further, after grinding, the products are passed through a 40-mesh sieve and the 100-mesh sieve respectively; the tableting process is to separate the product that passes through the 40-mesh sieve and the product that passes through the 100-mesh sieve in sequence. Place it in the mold and keep it under a pressure of 15-25MPa for 5-10 minutes, then grind and sieve it into a 40-60 mesh sieve to obtain a 40-60 mesh granular catalyst. This process can maximize the retention of the catalyst particles and catalytic The balance of activity, at the same time, its catalytic activity and selectivity are also better.
进一步地，所述溶液A中Mn与Cu的原子摩尔比为2-4:1，Mn、Cu之和与Ti的原子摩尔比为1:3-4。Further, the atomic molar ratio of Mn to Cu in the solution A is 2-4:1, and the atomic molar ratio of the sum of Mn, Cu and Ti is 1:3-4.
进一步地，所述溶液A中冰醋酸、去离子水与乙醇的加入体积比为1:1:2.5-3。Further, the added volume ratio of glacial acetic acid, deionized water and ethanol in the solution A is 1:1:2.5-3.
进一步地，所述溶液B中钛酸丁酯与乙醇的体积比为1:1-1.5。Further, the volume ratio of butyl titanate to ethanol in solution B is 1:1-1.5.
进一步地，所述干燥的温度为70-90℃，干燥的时间为12-20h。Further, the drying temperature is 70-90°C, and the drying time is 12-20 hours.
进一步地，所述煅烧的温度为430-470℃，煅烧的时间为4-5h。Further, the calcination temperature is 430-470°C, and the calcination time is 4-5 hours.
优选地，所述煅烧的升温速率为5-10℃/min；Preferably, the heating rate of the calcination is 5-10°C/min;
优选地，所述煅烧在空气氛围下进行。Preferably, the calcination is performed in an air atmosphere.
本发明还提供一种所述的催化剂的应用，即在固定床反应器中进行，气相包括NO、NH3、O2、C7H8和N2，烟气空速为40000-60000mL/(g·h)，反应温度为180-300℃。The invention also provides an application of the catalyst, which is carried out in a fixed bed reactor. The gas phase includes NO, NH3 , O2 , C7 H8 and N2 , and the flue gas space velocity is 40000-60000mL/( g·h), the reaction temperature is 180-300°C.
相比现有技术，本发明提供的用于协同脱除甲苯和NOx的催化剂，所用的原料成本低，制备工艺简单可控，可重复性强。该催化剂具有氧化还原性能优异、活性中心均匀分散、比表面积、平均孔径及孔容较大等优势，并且是一种环境友好型催化剂，在协同脱除甲苯和NOx的反应中表现出良好的催化活性和较高的选择性。同时，催化剂应用条件广泛，操作简单，具有良好的工业应用潜力。Compared with the existing technology, the catalyst provided by the present invention for collaborative removal of toluene and NOx has low raw material cost, simple and controllable preparation process, and strong repeatability. The catalyst has the advantages of excellent redox performance, uniformly dispersed active centers, large specific surface area, average pore diameter and pore volume. It is an environmentally friendly catalyst and shows good catalysis in the reaction of collaborative removal of toluene and NOx. activity and higher selectivity. At the same time, the catalyst has a wide range of application conditions, is simple to operate, and has good industrial application potential.
附图说明Description of the drawings
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly explain the specific embodiments of the present invention or the technical solutions in the prior art, the accompanying drawings that need to be used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings in the following description The drawings illustrate some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without exerting any creative effort.
图1为实施例1-4所得催化剂脱除甲苯的活性评价图；Figure 1 is an activity evaluation chart for toluene removal by the catalyst obtained in Examples 1-4;
图2为实施例1-4所得催化剂脱除NOx的活性评价图；Figure 2 is an evaluation diagram of the NOx removal activity of the catalyst obtained in Examples 1-4;
图3为实施例1-4所得催化剂的N2选择性评价图；Figure 3 is an N2 selectivity evaluation diagram of the catalyst obtained in Examples 1-4;
图4为实施例1-4所得催化剂的CO2选择性评价图。Figure 4 is a CO2 selectivity evaluation diagram of the catalyst obtained in Examples 1-4.
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中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例只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 drawings in the embodiments of the present invention. Obviously, the described embodiments These are only some embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.
实施例中未标明物质的比例关系之处，应当理解为可以以任意比例进行匹配。未标明物质的比例单位之处，应当理解为质量比的关系。Where the proportional relationship of substances is not indicated in the examples, it should be understood that matching can be carried out in any proportion. Where the proportional unit of a substance is not indicated, it should be understood that the relationship is based on mass ratio.
实施例1Example 1
一种用于协同脱除甲苯和NOx的催化剂，所述催化剂为Mn1.25Cu0.75/TiO2，粒径为345μm，比表面积为164.247m2/g，孔体积为0.2739cm3/g，平均孔径为6.672mm。其制备方法如下：A catalyst for the collaborative removal of toluene and NOx. The catalyst is Mn1.25 Cu0.75 /TiO2 , with a particle size of 345 μm, a specific surface area of 164.247m2 /g, a pore volume of 0.2739cm3 /g, and an average pore diameter. is 6.672mm. Its preparation method is as follows:
S1：取1.14g三水合硝酸铜、2.79g质量分数为50％的硝酸锰溶液、8mL去离子水、8mL冰醋酸加入23mL乙醇中，常温搅拌至完全溶解形成溶液A。S1: Add 1.14g copper nitrate trihydrate, 2.79g manganese nitrate solution with a mass fraction of 50%, 8mL deionized water, and 8mL glacial acetic acid into 23mL ethanol, and stir at room temperature until completely dissolved to form solution A.
S2：取17mL钛酸丁酯，加入23mL乙醇中，常温搅拌至混合均匀形成溶液B。S2: Take 17 mL of butyl titanate, add 23 mL of ethanol, and stir at room temperature until evenly mixed to form solution B.
S3：在剧烈搅拌下，将溶液B逐滴加入溶液A中，常温搅拌3h，之后老化2h，得到溶胶。将溶胶置于70℃烘箱中干燥20h，研磨成粉。S3: Under vigorous stirring, add solution B dropwise to solution A, stir at room temperature for 3 hours, and then age for 2 hours to obtain a sol. The sol was dried in a 70°C oven for 20 h and ground into powder.
S4：在空气气氛下，将S3产物放入管式炉中，从室温程序升温到450℃下煅烧5h，升温速率为5℃/min。最后降至室温下得到MnCuTi混合氧化物催化剂。S4: In an air atmosphere, put the S3 product into a tube furnace and calcine it in a programmed temperature rise from room temperature to 450°C for 5 hours at a temperature rise rate of 5°C/min. Finally, it was lowered to room temperature to obtain the MnCuTi mixed oxide catalyst.
S5：将S4所制得的催化剂置于模具中，在15MPa压力下保持10min后，将压好的样品缓慢取至40-60目筛子中研磨、过筛，得到40-60目的催化剂颗粒，命名为Mn1.25Cu0.75/TiO2。S5: Place the catalyst prepared in S4 into the mold, and after holding it under 15MPa pressure for 10 minutes, slowly take the pressed sample to a 40-60 mesh sieve, grind and sieve to obtain 40-60 mesh catalyst particles, which are named It is Mn1.25 Cu0.75 /TiO2 .
将S5所得的催化剂颗粒装入固定床连续流动石英反应器中，通入常压下的模拟烟气，NO浓度为500ppm，NH3浓度为500ppm，O2含量为10.0vol.％，C7H8浓度为100ppm，N2作为平衡气，反应温度为180-300℃，反应空速控制在60000mL/(g·h)。The catalyst particles obtained in S5 are loaded into a fixed-bed continuous flow quartz reactor, and simulated flue gas under normal pressure is introduced. The NO concentration is 500 ppm, the NH3 concentration is 500 ppm, the O2 content is 10.0 vol.%, and C7 H8 The concentration is 100ppm, N2 is used as the balance gas, the reaction temperature is 180-300°C, and the reaction space velocity is controlled at 60000mL/(g·h).
测试结果：稳态时240℃下，甲苯的转化率为99.29％，NOx的转化率为66.48％。Test results: At steady state at 240°C, the conversion rate of toluene is 99.29% and the conversion rate of NOx is 66.48%.
实施例2Example 2
一种用于协同脱除甲苯和NOx的催化剂，所述催化剂为Mn1.5Cu0.5/TiO2，粒径为291μm，比表面积为163.477m2/g，孔体积为0.2808cm3/g，平均孔径为6.8719mm。其制备方法如下：A catalyst for the collaborative removal of toluene and NOx. The catalyst is Mn1.5 Cu0.5 /TiO2 , with a particle size of 291 μm, a specific surface area of 163.477m2 /g, a pore volume of 0.2808cm3 /g, and an average pore diameter. is 6.8719mm. Its preparation method is as follows:
S1：取0.75g三水合硝酸铜、3.36g质量分数为50％的硝酸锰溶液、8mL去离子水、8mL冰醋酸加入23mL乙醇中，常温搅拌至完全溶解形成溶液A。S1: Add 0.75g copper nitrate trihydrate, 3.36g manganese nitrate solution with a mass fraction of 50%, 8mL deionized water, and 8mL glacial acetic acid into 23mL ethanol, and stir at room temperature until completely dissolved to form solution A.
S2：取17mL钛酸丁酯，加入23mL乙醇中，常温搅拌至混合均匀形成溶液B。S2: Take 17 mL of butyl titanate, add 23 mL of ethanol, and stir at room temperature until evenly mixed to form solution B.
S3：在剧烈搅拌下，将溶液B逐滴加入溶液A中，常温搅拌3h，之后老化2h，得到溶胶。将溶胶置于70℃烘箱中干燥20h，研磨成粉。S3: Under vigorous stirring, add solution B dropwise to solution A, stir at room temperature for 3 hours, and then age for 2 hours to obtain a sol. The sol was dried in a 70°C oven for 20 h and ground into powder.
S4：在空气气氛下，将S3产物放入管式炉中，从室温程序升温到450℃下煅烧5h，升温速率为5℃/min。最后降至室温下得到MnCuTi混合氧化物催化剂。S4: In an air atmosphere, put the S3 product into a tube furnace and calcine it in a programmed temperature rise from room temperature to 450°C for 5 hours at a temperature rise rate of 5°C/min. Finally, it was lowered to room temperature to obtain the MnCuTi mixed oxide catalyst.
S5：将S4所制得的催化剂置于模具中，在15MPa压力下保持10min后，将压好的样品缓慢取至40-60目筛子中研磨、过筛，得到40-60目的催化剂颗粒，命名为Mn1.5Cu0.5/TiO2。S5: Place the catalyst prepared in S4 into the mold, and after holding it under 15MPa pressure for 10 minutes, slowly take the pressed sample to a 40-60 mesh sieve, grind and sieve to obtain 40-60 mesh catalyst particles, which are named It is Mn1.5 Cu0.5 /TiO2 .
将S5所得的催化剂颗粒装入固定床连续流动石英反应器中，通入常压下的模拟烟气，NO浓度为500ppm，NH3浓度为500ppm，O2含量为10.0vol.％，C7H8浓度为100ppm，N2作为平衡气，反应温度为180-300℃，反应空速控制在60000mL/(g·h)。The catalyst particles obtained in S5 are loaded into a fixed-bed continuous flow quartz reactor, and simulated flue gas under normal pressure is introduced. The NO concentration is 500 ppm, the NH3 concentration is 500 ppm, the O2 content is 10.0 vol.%, and C7 H8 The concentration is 100ppm, N2 is used as the balance gas, the reaction temperature is 180-300°C, and the reaction space velocity is controlled at 60000mL/(g·h).
测试结果：稳态时240℃下，甲苯的转化率为99.83％，NOx的转化率为87.29％。Test results: At steady state at 240°C, the conversion rate of toluene is 99.83% and the conversion rate of NOx is 87.29%.
实施例3Example 3
一种用于协同脱除甲苯和NOx的催化剂，所述催化剂为Mn1.75Cu0.25/TiO2，粒径为367μm，比表面积为155.098m2/g，孔体积为0.2695cm3/g，平均孔径为6.9509mm。其制备方法如下：A catalyst for the collaborative removal of toluene and NOx. The catalyst is Mn1.75 Cu0.25 /TiO2 , with a particle size of 367 μm, a specific surface area of 155.098m2 /g, a pore volume of 0.2695cm3 /g, and an average pore diameter. is 6.9509mm. Its preparation method is as follows:
S1：取0.38g三水合硝酸铜、3.91g质量分数为50％的硝酸锰溶液、8mL去离子水、8mL冰醋酸加入23mL乙醇中，常温搅拌至完全溶解形成溶液A。S1: Add 0.38g copper nitrate trihydrate, 3.91g 50% manganese nitrate solution, 8mL deionized water, and 8mL glacial acetic acid into 23mL ethanol, and stir at room temperature until completely dissolved to form solution A.
S2：取17mL钛酸丁酯，加入23mL乙醇中，常温搅拌至混合均匀形成溶液B。S2: Take 17 mL of butyl titanate, add 23 mL of ethanol, and stir at room temperature until evenly mixed to form solution B.
S3：在剧烈搅拌下，将溶液B逐滴加入溶液A中，常温搅拌3h，之后老化2h，得到溶胶。将溶胶置于70℃烘箱中干燥20h，研磨成粉。S3: Under vigorous stirring, add solution B dropwise to solution A, stir at room temperature for 3 hours, and then age for 2 hours to obtain a sol. The sol was dried in a 70°C oven for 20 h and ground into powder.
S4：在空气气氛下，将S3产物放入管式炉中，从室温程序升温到450℃下煅烧5h，升温速率为5℃/min。最后降至室温下得到MnCuTi混合氧化物催化剂。S4: In an air atmosphere, put the S3 product into a tube furnace and calcine it in a programmed temperature rise from room temperature to 450°C for 5 hours at a temperature rise rate of 5°C/min. Finally, it was lowered to room temperature to obtain the MnCuTi mixed oxide catalyst.
S5：将S4所制得的催化剂置于模具中，在15MPa压力下保持10min后，将压好的样品缓慢取至40-60目筛子中研磨、过筛，得到40-60目的催化剂颗粒，命名为Mn1.75Cu0.25/TiO2。S5: Place the catalyst prepared in S4 into the mold, and after holding it under 15MPa pressure for 10 minutes, slowly take the pressed sample to a 40-60 mesh sieve, grind and sieve to obtain 40-60 mesh catalyst particles, which are named It is Mn1.75 Cu0.25 /TiO2 .
将S5所得的催化剂颗粒装入固定床连续流动石英反应器中，通入常压下的模拟烟气，NO浓度为500ppm，NH3浓度为500ppm，O2含量为10.0vol.％，C7H8浓度为100ppm，N2作为平衡气，反应温度为180-300℃，反应空速控制在60000mL/(g·h)。The catalyst particles obtained in S5 are loaded into a fixed-bed continuous flow quartz reactor, and simulated flue gas under normal pressure is introduced. The NO concentration is 500 ppm, the NH3 concentration is 500 ppm, the O2 content is 10.0 vol.%, and C7 H8 The concentration is 100ppm, N2 is used as the balance gas, the reaction temperature is 180-300°C, and the reaction space velocity is controlled at 60000mL/(g·h).
测试结果：稳态时240℃下，甲苯的转化率为98.24％，NOx的转化率为85.05％。Test results: At steady state at 240°C, the conversion rate of toluene is 98.24% and the conversion rate of NOx is 85.05%.
实施例4Example 4
一种用于协同脱除甲苯和NOx的催化剂，所述催化剂为Mn1.5Cu0.5/TiO2-γ，粒径为278μm，比表面积为165.328m2/g，孔体积为0.2845cm3/g，平均孔径为6.8392mm。其制备方法如下：A catalyst for the collaborative removal of toluene and NOx. The catalyst is Mn1.5 Cu0.5 /TiO2 -γ, with a particle size of 278 μm, a specific surface area of 165.328m2 /g, and a pore volume of 0.2845cm3 /g. The average hole diameter is 6.8392mm. Its preparation method is as follows:
S1：取0.75g三水合硝酸铜、3.36g质量分数为50％的硝酸锰溶液、8mL去离子水、8mL冰醋酸加入23mL乙醇中，常温搅拌至完全溶解形成溶液A。S1: Add 0.75g copper nitrate trihydrate, 3.36g manganese nitrate solution with a mass fraction of 50%, 8mL deionized water, and 8mL glacial acetic acid into 23mL ethanol, and stir at room temperature until completely dissolved to form solution A.
S2：取17mL钛酸丁酯，加入23mL乙醇中，常温搅拌至混合均匀形成溶液B。S2: Take 17 mL of butyl titanate, add 23 mL of ethanol, and stir at room temperature until evenly mixed to form solution B.
S3：在剧烈搅拌下，将溶液B逐滴加入溶液A中，常温搅拌3h，之后老化2h，得到溶胶。将溶胶置于70℃烘箱中干燥20h，研磨成粉，分别过40目筛和过100目筛。S3: Under vigorous stirring, add solution B dropwise to solution A, stir at room temperature for 3 hours, and then age for 2 hours to obtain a sol. The sol was dried in an oven at 70°C for 20 hours, ground into powder, and passed through a 40-mesh sieve and a 100-mesh sieve respectively.
S4：在空气气氛下，将S3的两种不同目数的产物放入管式炉中，从室温程序升温到450℃下煅烧5h，升温速率为5℃/min。最后降至室温下得到两种不同目数的MnCuTi混合氧化物催化剂。S4: In an air atmosphere, put two products of S3 with different mesh numbers into a tube furnace and calcine them from room temperature to 450°C for 5 hours at a heating rate of 5°C/min. Finally, it was lowered to room temperature to obtain two MnCuTi mixed oxide catalysts with different mesh sizes.
S5：将S4所制得的两种不同目数的MnCuTi混合氧化物催化剂依次间隔置于模具中，在15MPa压力下保持10min后，将压好的样品缓慢取至40-60目筛子中研磨，得到40-60目的催化剂颗粒，命名为Mn1.5Cu0.5/TiO2-γ。S5: Place the two MnCuTi mixed oxide catalysts of different mesh sizes prepared in S4 sequentially into the mold. After maintaining for 10 minutes under a pressure of 15MPa, slowly take the pressed sample to a 40-60 mesh sieve and grind it. Catalyst particles of 40-60 mesh were obtained, named Mn1.5 Cu0.5 /TiO2 -γ.
将S5所得的催化剂颗粒装入固定床连续流动石英反应器中，通入常压下的模拟烟气，NO浓度为500ppm，NH3浓度为500ppm，O2含量为10.0vol.％，C7H8浓度为100ppm，N2作为平衡气，反应温度为180-300℃，反应空速控制在60000mL/(g·h)。The catalyst particles obtained in S5 are loaded into a fixed-bed continuous flow quartz reactor, and simulated flue gas under normal pressure is introduced. The NO concentration is 500 ppm, the NH3 concentration is 500 ppm, the O2 content is 10.0 vol.%, and C7 H8 The concentration is 100ppm, N2 is used as the balance gas, the reaction temperature is 180-300°C, and the reaction space velocity is controlled at 60000mL/(g·h).
测试结果：稳态时240℃下，甲苯的转化率为100％，NOx的转化率为90.21％。Test results: At steady state at 240°C, the conversion rate of toluene is 100% and the conversion rate of NOx is 90.21%.
表1实施例1-4所得催化剂的孔结构对比Table 1 Comparison of pore structures of catalysts obtained in Examples 1-4
实施例1-4所制得的MnCuTi混合氧化物催化剂即Mn1.25Cu0.75/TiO2、Mn1.5Cu0.5/TiO2、Mn1.75Cu0.25/TiO2、Mn1.5Cu0.5/TiO2-γ的性能参数如表1所示，可以看出，本发明提供的制备方法所制得的催化剂，均具有较高的比表面积和孔体积。Performance of the MnCuTi mixed oxide catalysts prepared in Examples 1-4, namely Mn1.25 Cu0.75 /TiO2 , Mn1.5 Cu0.5 /TiO2 , Mn1.75 Cu0.25 /TiO2 , and Mn1.5 Cu0.5 /TiO2 -γ The parameters are shown in Table 1. It can be seen that the catalysts prepared by the preparation method provided by the present invention have high specific surface area and pore volume.
其活性评价测试结果如图1和图2所示，其选择性如图3和图4所示。Its activity evaluation test results are shown in Figures 1 and 2, and its selectivity is shown in Figures 3 and 4.
由图1-2可知，本发明提供的制备方法所制得的催化剂，在240℃条件下，可实现甲苯的完全转化，同时，NOx的转化率也较高，尤其是实施例4超过了90％。且当MnCu比例为1.5:0.5时，即催化剂为Mn1.5Cu0.5/TiO2和Mn1.5Cu0.5/TiO2-γ时，催化剂的整体活性最佳。As can be seen from Figures 1-2, the catalyst prepared by the preparation method provided by the present invention can achieve complete conversion of toluene at 240°C. At the same time, the conversion rate of NOx is also high, especially in Example 4, which exceeds 90 %. And when the MnCu ratio is 1.5:0.5, that is, when the catalyst is Mn1.5 Cu0.5 /TiO2 and Mn1.5 Cu0.5 /TiO2 -γ, the overall activity of the catalyst is optimal.
由图3-4可知，本发明提供的制备方法所制得的催化剂，尤以实施例4为最佳，在240℃条件下，N2选择性可达80％左右，同时，CO2选择性可达73％，实施例2次之。It can be seen from Figures 3-4 that the catalyst prepared by the preparation method provided by the present invention, especially Example 4, is the best. Under the condition of 240°C, the N2 selectivity can reach about 80%. At the same time, the CO2 selectivity It can reach 73%, followed by Example 2.
请注意，以上实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。以上实施例仅表达了本申请的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。因此，本申请专利的保护范围应以所附权利要求为准。Please note that the technical features of the above embodiments can be combined in any way. To simplify the description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features , should be considered to be within the scope of this manual. The above embodiments only express several implementation modes of the present application, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the invention patent. It should be noted that, for those of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present application, and these all fall within the protection scope of the present application. Therefore, the scope of protection of this patent application should be determined by the appended claims.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311067481.3ACN116920873A (en) | 2023-08-23 | 2023-08-23 | A catalyst for collaborative removal of toluene and NOx and its preparation method and application |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311067481.3ACN116920873A (en) | 2023-08-23 | 2023-08-23 | A catalyst for collaborative removal of toluene and NOx and its preparation method and application |
| Publication Number | Publication Date |
|---|---|
| CN116920873Atrue CN116920873A (en) | 2023-10-24 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311067481.3APendingCN116920873A (en) | 2023-08-23 | 2023-08-23 | A catalyst for collaborative removal of toluene and NOx and its preparation method and application |
| Country | Link |
|---|---|
| CN (1) | CN116920873A (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117463356A (en)* | 2023-10-27 | 2024-01-30 | 中国科学院山西煤炭化学研究所 | A composite functional coating catalyst and its preparation method |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000016603A (en)* | 1996-06-12 | 2000-03-25 | 브라이언 이. 케프너 | Absorbent, catalyst, and/or binder system reinforced by contacting with acid |
| CN103055889A (en)* | 2012-12-31 | 2013-04-24 | 上海电气石川岛电站环保工程有限公司 | A kind of low-temperature denitrification MnOx-CuO-TiO2 catalyst and its preparation method and application |
| CN114160147A (en)* | 2021-11-29 | 2022-03-11 | 华南理工大学 | Composite oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas and preparation method and application thereof |
| CN114768794A (en)* | 2022-04-27 | 2022-07-22 | 华南理工大学 | Composite manganese oxide catalyst for synchronously removing VOCs and NOx in medium-low temperature flue gas and preparation method and application thereof |
| CN115888749A (en)* | 2022-11-04 | 2023-04-04 | 中国科学院山西煤炭化学研究所 | Synergistic denitration and demercuration catalyst and preparation method and application thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000016603A (en)* | 1996-06-12 | 2000-03-25 | 브라이언 이. 케프너 | Absorbent, catalyst, and/or binder system reinforced by contacting with acid |
| CN103055889A (en)* | 2012-12-31 | 2013-04-24 | 上海电气石川岛电站环保工程有限公司 | A kind of low-temperature denitrification MnOx-CuO-TiO2 catalyst and its preparation method and application |
| CN114160147A (en)* | 2021-11-29 | 2022-03-11 | 华南理工大学 | Composite oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas and preparation method and application thereof |
| CN114768794A (en)* | 2022-04-27 | 2022-07-22 | 华南理工大学 | Composite manganese oxide catalyst for synchronously removing VOCs and NOx in medium-low temperature flue gas and preparation method and application thereof |
| CN115888749A (en)* | 2022-11-04 | 2023-04-04 | 中国科学院山西煤炭化学研究所 | Synergistic denitration and demercuration catalyst and preparation method and application thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117463356A (en)* | 2023-10-27 | 2024-01-30 | 中国科学院山西煤炭化学研究所 | A composite functional coating catalyst and its preparation method |
| Publication | Publication Date | Title |
|---|---|---|
| CN110787840B (en) | Bimetallic MOFs catalyst and preparation method and application thereof | |
| WO2015149499A1 (en) | Low-temperature and highly efficient denitration catalyst and preparation method therefor | |
| CN110368991B (en) | SCR low-temperature denitration catalyst based on ZIF-67 porous carbon skeleton modification and preparation method thereof | |
| CN102513123B (en) | Rare earth perovskite type catalyst for treating industrial waste gas and preparation method and application thereof | |
| CN113413904B (en) | A g-C3N4 loaded manganese-cerium composite oxide low-temperature NH3-SCR catalyst and its preparation method and application | |
| CN106732581B (en) | Ru/CeTiO for low-temperature SCR reactionxProcess for preparing catalyst | |
| CN102000582B (en) | Preparation and application of sulfur-resistant La0.7Sr0.3Co1-xFexO3 perovskite catalyst | |
| CN104289227A (en) | Mn, Co, Ce and Ti four-component NH3-SCR supported catalyst for low-temperature flue gas denitrification | |
| CN109772463B (en) | A kind of CO reduction low temperature denitration catalyst ZIF-67-Me/CuOx and its preparation method and application | |
| CN105833901A (en) | A PrOx-MnOx/SAPO-34 low-temperature SCR flue gas denitrification catalyst and its preparation method and application | |
| CN112547045A (en) | Preparation method of photocatalytic denitration catalyst with porous titanium dioxide as carrier | |
| CN106179329A (en) | A kind of low temperature manganio denitrating catalyst with active carbocoal as carrier and preparation method and application | |
| CN110538656B (en) | A kind of catalyst for photocatalyst degrading formaldehyde and preparation method and use thereof | |
| CN104815671A (en) | Selective catalytic reduction low-temperature denitration catalyst and preparation method thereof | |
| CN110252317A (en) | A Ce-Fe-Based Catalyst for Nitrogen Oxide Removal at Low Temperature and High Efficiency | |
| CN105771967A (en) | Metal oxide-vanadate/attapulgite catalyst | |
| CN107649121A (en) | The method of modifying and modified manganese based denitration catalyst and preparation method of a kind of manganese based denitration catalyst | |
| CN107413350A (en) | Mischmetal denitrating catalyst and preparation method thereof | |
| CN116212853B (en) | δ-MnO2 catalytic material and its preparation method and its application in the preparation of formaldehyde-degradable filters | |
| CN116920873A (en) | A catalyst for collaborative removal of toluene and NOx and its preparation method and application | |
| CN116618085A (en) | Preparation method and application of three-way catalyst for cooperatively removing multiple pollutants | |
| CN104084213B (en) | For the method for making of ferrimanganic titanium catalyst and the catalyst of preparation thereof of the denitration of stationary source flue gas low-temperature | |
| CN109954514A (en) | Molecular sieve-supported modified manganese-based catalyst for denitrification of diesel vehicle exhaust, preparation method and application | |
| CN113663667B (en) | Manganese-based composite catalyst based on transition metal modification and preparation method and application thereof | |
| CN115400745A (en) | Cerium-based catalyst for efficiently degrading CVOCs (chemical vapor deposition) |
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |