CN114797841A - Mn (manganese) 4+ And Ce 3+ Preparation method of enhanced Mn-M-Ti-O ultralow-temperature denitration catalyst - Google Patents

Mn (manganese) 4+ And Ce 3+ Preparation method of enhanced Mn-M-Ti-O ultralow-temperature denitration catalyst Download PDF

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CN114797841A
CN114797841A CN202210295908.4A CN202210295908A CN114797841A CN 114797841 A CN114797841 A CN 114797841A CN 202210295908 A CN202210295908 A CN 202210295908A CN 114797841 A CN114797841 A CN 114797841A
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王阳慧
金璐瑶
蒋鹏
刘雪松
宋佳丹
徐鑫涛
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Abstract

Mn (manganese) 4+ And Ce 3+ The preparation method of the enhanced Mn-M-Ti-O ultralow temperature denitration catalyst is characterized in that the Mn-M-Ti-O (M ═ Ce, La and Gd) ultralow temperature denitration catalyst is TiO 2 Loading denitration active component and auxiliary agent as carrier and oxidizing Mn with ozone x+ And hydrogen peroxide reduction of Ce 4+ Thus obtaining the product. The catalyst obtained by the invention has appropriate specific surface area (70-90 m) 2 Per g), uniform particle size (1-5 μm), surface Mn 4+ High proportion (47-50%), surface Ce 3+ High ratio (19-25%), high surface activityThe method has the characteristics of large number of sexual oxygen species (45-50%), small average pore diameter (less than 13nm), high hydrothermal stability, wide low-temperature active temperature window (125-400 ℃), good denitration performance and the like, meets the requirements of the high-efficiency denitration SCR catalyst, has controllable product components, simple operation flow, low cost and good stability, and is easy to realize large-scale industrial production.

Description

一种Mn4+和Ce3+增强型Mn-M-Ti-O超低温脱硝催化剂的制备 方法A kind of preparation method of Mn4+ and Ce3+ enhanced Mn-M-Ti-O ultra-low temperature denitration catalyst

技术领域technical field

本发明属于环境保护技术领域,具体是涉及一种Mn4+和Ce3+增强型 Mn-M-Ti-O超低温脱硝催化剂的制备方法。The invention belongs to the technical field of environmental protection, in particular to a preparation method of a Mn 4+ and Ce 3+ enhanced Mn-M-Ti-O ultra-low temperature denitration catalyst.

背景技术Background technique

如今占据发电总量60-70%的煤电机组,计划将在2060年全部退出,太阳能、 风能、生物质能主要占据主导地位。垃圾焚烧、生物质能等行业,是整个环保行 业变废为宝的出路,但其产生的烟气具有含酸性物质且温度低等特殊性,而目前 国内催化剂难以满足超低温的温度需求,尾气必须经升温处理,导致温室效应严 重,且各类超低温催化剂一直被国外所垄断,因此急需开发高效、抗中毒能力强 的超低温脱硝催化剂。Today, coal-fired power units, which account for 60-70% of the total power generation, are all planned to be withdrawn in 2060, and solar energy, wind energy, and biomass energy are mainly in the dominant position. Waste incineration, biomass energy and other industries are the way out for the entire environmental protection industry to turn waste into treasure, but the flue gas produced by it has the particularity of containing acidic substances and low temperature. At present, domestic catalysts are difficult to meet the temperature requirements of ultra-low temperature, and the exhaust gas must be After heating, the greenhouse effect is serious, and all kinds of ultra-low temperature catalysts have been monopolized by foreign countries. Therefore, it is urgent to develop ultra-low temperature denitration catalysts with high efficiency and strong anti-poisoning ability.

近年来在各项研究中已证明过渡金属氧化物对SCR反应具有活性,尤其是 Mn基的氧化物催化剂因其出色的催化性能而被广泛研究用于低温NH3-SCR反 应。其具体优点为:稳定性突出、比表面积大。锰氧化物容易形成一个氧化还原 循环,从而体现良好的低温SCR脱硝性能。Mn具有MnO、Mn2O3、Mn3O4、Mn5O8、 MnO2五种常见价态,其中MnO2的氧转移能力优于其他,具有最佳催化效能。但 单MnOx催化剂存在N2选择性差、容易失活等缺点。因此需通过掺杂其他金属氧 化物对其进行改性,使其具有较高的氧化还原能力和酸性位点,从而具有较好的 SCR性能。In recent years, transition metal oxides have been proved to be active for SCR reaction in various studies, especially Mn-based oxide catalysts have been widely studied for low-temperature NH3 -SCR reaction due to their excellent catalytic performance. Its specific advantages are: outstanding stability and large specific surface area. Manganese oxides easily form a redox cycle, which reflects good low-temperature SCR denitration performance. Mn has five common valence states: MnO, Mn 2 O 3 , Mn 3 O 4 , Mn 5 O 8 , and MnO 2 . Among them, MnO 2 has better oxygen transfer ability than others and has the best catalytic performance. However, single MnOx catalysts have disadvantages such as poor N2 selectivity and easy deactivation. Therefore, it needs to be modified by doping other metal oxides to make it have higher redox ability and acid sites, so as to have better SCR performance.

本发明脱硝催化剂中稀土金属元素(M=Ce、La、Gd)主要以助催化剂形式 存在,其主要起如下作用:引起催化剂的表面电子不平衡,形成不饱和的化学键 和氧空位,增加表面吸附氧的浓度,提高催化剂的氧化能力;另外,能够提供更 多的NH3吸附位点,增加催化剂的活性;同时,还可以降低硫酸盐的热稳定性, 促进其分解,从而提高催化剂的抗硫中毒能力。Mn与稀土元素协同作用以Ce为 例:The rare earth metal elements (M=Ce, La, Gd) in the denitration catalyst of the present invention mainly exist in the form of promoters, which mainly play the following roles: cause the surface electron imbalance of the catalyst, form unsaturated chemical bonds and oxygen vacancies, increase surface adsorption The concentration of oxygen can improve the oxidation capacity of the catalyst; in addition, it can provide more NH 3 adsorption sites and increase the activity of the catalyst; at the same time, it can also reduce the thermal stability of sulfate and promote its decomposition, thereby improving the sulfur resistance of the catalyst. Poisoning ability. The synergistic effect of Mn and rare earth elements takes Ce as an example:

1、在Ce4+与Ce3+之间发生氧化还原位移,从而增强MnOx的低温活性,而 Ce4+/Ce3+比值越高,Ce4+与Ce3+之间的氧储存和释放越强,SCR活性越高。1. A redox shift occurs between Ce 4+ and Ce 3+ , which enhances the low-temperature activity of MnO x , and the higher the Ce 4+ /Ce 3+ ratio, the better the oxygen storage between Ce 4+ and Ce 3+ . The stronger the release, the higher the SCR activity.

2、提供更多的NH3吸附位点,Mn-Ce样品具有较高的还原性且可以在Lewis 酸性位上提供更多的氨气吸附位点。2. Provide more NH 3 adsorption sites. The Mn-Ce sample has higher reducibility and can provide more NH 3 adsorption sites on Lewis acid sites.

3、Ce提高了Mn基催化剂结构的稳定性,使其具有较大的比表面积。3. Ce improves the stability of the Mn-based catalyst structure and makes it have a larger specific surface area.

为了进一步提高Mn4+的浓度从而提升其氧化还原性能,可通过添加氧化剂的 形式,Mn-Ce催化剂采用过氧化氢改性能够提高催化剂表面Ce3+/(Ce3++Ce4+)的摩 尔比,表明过氧化氢改性后可以提高表面氧空位的浓度。同时,过氧化氢改性后 的催化剂表面的Ce物种分散增强,有助于提高其NH3-SCR活性。In order to further increase the concentration of Mn 4+ to improve its redox performance, the Mn-Ce catalyst can be modified with hydrogen peroxide in the form of adding an oxidant, which can improve the surface Ce 3+ /(Ce 3+ +Ce 4+ ) of the catalyst surface. molar ratio, indicating that the hydrogen peroxide modification can increase the concentration of surface oxygen vacancies. At the same time, the dispersion of Ce species on the surface of the hydrogen peroxide-modified catalyst is enhanced, which helps to improve its NH 3 -SCR activity.

因此,本发明采用稀土金属与Mn基协同作用并以新型氧化还原形式改性催 化剂,开发出超低温Mn基脱硝催化剂,有望解决比表面积大、温度窗口窄、活 性氧物种少等问题,实现垃圾焚烧、生物质能领域超低排放。Therefore, the present invention adopts the synergistic effect of rare earth metals and Mn groups and modifies the catalyst in a new redox form, and develops an ultra-low temperature Mn-based denitration catalyst, which is expected to solve the problems of large specific surface area, narrow temperature window, and few active oxygen species, and realize waste incineration. , Ultra-low emissions in the field of biomass energy.

发明内容SUMMARY OF THE INVENTION

本发明的目的在于合成一种Mn4+和Ce3+增强型Mn-M-Ti-O(M=Ce、La、Gd) 超低温脱硝催化剂。The purpose of the present invention is to synthesize a Mn 4+ and Ce 3+ enhanced Mn-M-Ti-O (M=Ce, La, Gd) ultra-low temperature denitration catalyst.

为了实现上述目的,本发明采用如下技术方案:In order to achieve the above object, the present invention adopts the following technical solutions:

一种Mn4+和Ce3+增强型Mn-M-Ti-O超低温脱硝催化剂的制备方法,该脱硝 催化剂是以TiO2为载体,负载脱硝活性成分和稀土金属元素助剂,并经臭氧氧化、 双氧水还原、煅烧制得。经氧化后活性组分表面Mn4+比例提高,催化氧化性能增 强;双氧水还原能够促进Ce4+还原为Ce3+,提高活性组分表面Ce3+比例及表面活 性氧物种数量,增加氧缺位,促进电子传递。A preparation method of a Mn 4+ and Ce 3+ enhanced Mn-M-Ti-O ultra-low temperature denitration catalyst, the denitration catalyst uses TiO 2 as a carrier, supports denitration active components and rare earth metal auxiliaries, and is oxidized by ozone , hydrogen peroxide reduction, calcination obtained. After oxidation, the proportion of Mn 4+ on the surface of the active component increases, and the catalytic oxidation performance is enhanced; the reduction of hydrogen peroxide can promote the reduction of Ce 4+ to Ce 3+ , increase the proportion of Ce 3+ on the surface of the active component and the number of surface active oxygen species, and increase the oxygen deficiency. bit to facilitate electron transfer.

所述活性成分为过渡金属元素锰;所述助剂为稀土金属元素铈、镧、钆中的 一种,优选为铈。The active component is the transition metal element manganese; the auxiliary agent is one of the rare earth metal elements cerium, lanthanum and gadolinium, preferably cerium.

所述脱硝催化剂比表面积为70-90m2/g,粒度为1-5μm,表面Mn4+比例为 47-50%,表面Ce3+比例为19-25%,表面活性氧物种数量为45-50%,平均孔径小 于13nm;脱硝效率达97%以上的催化活性温度窗口为125-400℃。The denitration catalyst has a specific surface area of 70-90 m 2 /g, a particle size of 1-5 μm, a surface Mn 4+ ratio of 47-50%, a surface Ce 3+ ratio of 19-25%, and the number of surface active oxygen species 45- 50%, the average pore diameter is less than 13nm; the catalytic activity temperature window with denitration efficiency over 97% is 125-400℃.

具体包括如下步骤:Specifically include the following steps:

(1)将硝酸锰溶液与M(NO3)x固体加入蒸馏水中搅拌溶解,得到混合溶液; 式中M为Ce、La或Gd;(1) adding manganese nitrate solution and M(NO 3 ) x solid in distilled water and stirring to dissolve to obtain a mixed solution; M in the formula is Ce, La or Gd;

(2)将催化剂载体TiO2加入混合溶液中,搅拌均匀,得到混合浆液;(2) adding the catalyst carrier TiO 2 into the mixed solution, stirring evenly, to obtain a mixed slurry;

(3)调节混合浆液pH值,继续常温搅拌,得到悬浊液;(3) adjust the pH value of the mixed slurry, continue stirring at room temperature to obtain a suspension;

(4)采用气动搅拌机边搅拌边向悬浊液中通入臭氧,使其充分氧化;(4) Pneumatic mixer is used to introduce ozone into the suspension while stirring to make it fully oxidized;

(5)通入完毕后,滴加双氧水至臭氧氧化后的浆液中;(5) after passing through, add hydrogen peroxide dropwise to the slurry after ozonation;

(6)继续搅拌一段时间后,离心洗涤数次;(6) after continuing to stir for a period of time, centrifugal washing several times;

(7)将洗涤完毕后的催化剂干燥;(7) drying the catalyst after washing;

(8)将干燥出来的产物进行程序升温煅烧;(8) temperature-programmed calcination is carried out to the dried product;

(9)将煅烧产品磨成粉体,得到符合要求的材料。(9) Grind the calcined product into powder to obtain the required material.

硝酸锰溶液的浓度为50wt%,硝酸锰溶液、M(NO3)x、蒸馏水、TiO2的质量 比为(5.94-6.31):(6.04-7.64):100:3.53。The concentration of manganese nitrate solution is 50wt%, and the mass ratio of manganese nitrate solution, M(NO 3 ) x , distilled water and TiO 2 is (5.94-6.31):(6.04-7.64):100:3.53.

步骤(3)中,采用浓度为20~30wt%的氨水调节pH至8~10。In step (3), the pH is adjusted to 8-10 by using ammonia water with a concentration of 20-30 wt%.

步骤(4)中,臭氧氧化的具体方法为:采用具有凸型或凹型螺旋桨的气动搅 拌机并在螺旋桨轴上设置通气孔,将悬浊液置于气动搅拌机中,边搅拌边通过通 气孔向悬浊液中通入臭氧;螺旋桨转速为10-15r/min,臭氧通气量500mL/min。In step (4), the concrete method of ozone oxidation is: adopt a pneumatic mixer with a convex or concave propeller and set a ventilation hole on the propeller shaft, place the suspension in the pneumatic mixer, and pass the ventilation hole to the suspension while stirring. Ozone is introduced into the turbid liquid; the speed of the propeller is 10-15r/min, and the ozone ventilation volume is 500mL/min.

步骤(5)中,滴加双氧水的具体方法为:将滴管伸入浆液底部逐滴滴加双氧 水,滴速控制在10秒/滴。In step (5), the concrete method of dripping hydrogen peroxide is: the dropper is stretched into the bottom of slurry and drip hydrogen peroxide, and the dripping speed is controlled at 10 seconds/drip.

步骤(7)中,干燥方法选择负压力干燥或喷雾蒸干法:负压力干燥法是以真 空泵形成负压力状态,经干燥炉、加热室、搅拌、驱动、蒸汽、过滤、冷凝等装 置进行干燥;喷雾蒸干法是将催化剂泵入喷雾干燥器内,经喷头雾化后由喷雾干 燥器底部喷出。In step (7), the drying method selects negative pressure drying or spray evaporation drying method: the negative pressure drying method is to form a negative pressure state with a vacuum pump, and dry through devices such as drying furnace, heating chamber, stirring, driving, steam, filtration, and condensation. ; The spray evaporation method is to pump the catalyst into the spray dryer, and spray it out from the bottom of the spray dryer after being atomized by the nozzle.

步骤(8)中,程序升温的速率为10℃/min,煅烧温度为500-550℃,煅烧时 间为4小时。In step (8), the temperature-programmed rate is 10°C/min, the calcination temperature is 500-550°C, and the calcination time is 4 hours.

本发明的有益效果是:The beneficial effects of the present invention are:

本发明采用的是将Mn(NO3)2与M(NO3)x(M=Ce、La、Gd)的前驱体溶液混合, 再通过氨水调节溶液的pH值,得到混合溶液,经臭氧氧化、双氧水还原后再通 过负压力干燥或喷雾蒸干法将溶液进行干燥,然后通过煅烧和球磨得到符合要求 粒度的材料。本发明的制备方法具有操作简单、设备要求简便等优点。In the present invention, Mn(NO 3 ) 2 is mixed with the precursor solution of M(NO 3 ) x ( M=Ce, La, Gd), and then the pH value of the solution is adjusted by ammonia water to obtain a mixed solution, which is oxidized by ozone , The hydrogen peroxide is reduced, and then the solution is dried by negative pressure drying or spray evaporation, and then the material with the required particle size is obtained by calcination and ball milling. The preparation method of the invention has the advantages of simple operation, convenient equipment requirements and the like.

本发明制备的Mn4+和Ce3+增强型Mn-M-Ti-O(M=Ce、La、Gd)超低温脱硝催 化剂中,硝酸锰溶液的质量分数调节范围20%-30%,硝酸铈(镧、钆)的质量分 数调节范围20%-30%。该复合粉体具有适中比表面积(70-90m2/g),粒度均一(1-5μm),表面Mn4+比例高(47-50%),表面Ce3+比例高(19-25%),表面活性氧 物种数量多(45-50%),平均孔径小(小于13nm),水热稳定性高,低温活性温度 窗口宽(125-400℃)、脱硝性能好等优点,符合SCR催化剂载体的需求。In the Mn 4+ and Ce 3+ enhanced Mn-M-Ti-O (M=Ce, La, Gd) ultra-low temperature denitration catalyst prepared by the invention, the mass fraction of manganese nitrate solution is adjusted in the range of 20%-30%, cerium nitrate The adjustment range of the mass fraction of (lanthanum, gadolinium) is 20%-30%. The composite powder has moderate specific surface area (70-90m 2 /g), uniform particle size (1-5μm), high proportion of surface Mn 4+ (47-50%), and high proportion of surface Ce 3+ (19-25%). , the number of surface active oxygen species is large (45-50%), the average pore size is small (less than 13nm), the hydrothermal stability is high, the low temperature active temperature window is wide (125-400℃), and the denitration performance is good. demand.

经大量研究表明,铈等稀土金属元素即可提供酸性位保证SCR催化活性又可 降低硫酸盐的稳定性,促进其分解,提升催化剂的抗SO2中毒的能力。此外,铈 等稀土金属元素还可以带来大量晶格氧的缺陷,起到提高氧储存的能力增强催化 剂还原性的作用。因此添加铈等稀土金属元素可提高催化剂结构的稳定性,使其 具有较大的比表面积,为SCR反应提供了大量的活性中心。A large number of studies have shown that rare earth metal elements such as cerium can provide acid sites to ensure SCR catalytic activity, but also reduce the stability of sulfate, promote its decomposition, and improve the ability of the catalyst to resist SO 2 poisoning. In addition, rare-earth metal elements such as cerium can also bring a large number of lattice oxygen defects, which play a role in improving the oxygen storage ability and enhancing the reducibility of the catalyst. Therefore, the addition of rare earth metal elements such as cerium can improve the stability of the catalyst structure, make it have a larger specific surface area, and provide a large number of active centers for the SCR reaction.

具体实施方式Detailed ways

以下通过实施例来对本发明予以进一步的说明(实施例中所用试剂为化学 纯),需要注意的是下面的实施例仅用作举例说明,本发明内容并不局限于此。The present invention is further illustrated by the following examples (reagents used in the examples are chemically pure), it should be noted that the following examples are only used for illustration, and the content of the present invention is not limited thereto.

实施例1:锰元素含量为24wt%、铈元素含量为24wt%的MnCeTi-O超低温 脱硝催化剂的制备。Example 1: Preparation of MnCeTi-O ultra-low temperature denitration catalyst with manganese content of 24wt% and cerium content of 24wt%.

步骤1:将6.31g硝酸锰溶液与7.64g硝酸铈固体溶于100g蒸馏水中,搅拌 30分钟,得到混合溶液。Step 1: Dissolve 6.31 g of manganese nitrate solution and 7.64 g of solid cerium nitrate in 100 g of distilled water, and stir for 30 minutes to obtain a mixed solution.

步骤2:将3.53g催化剂载体二氧化钛加入步骤1的混合溶液中,继续搅拌1 小时,得到硝酸锰、硝酸铈、二氧化钛的混合浆液。Step 2: Add 3.53 g of catalyst carrier titanium dioxide into the mixed solution of step 1, and continue to stir for 1 hour to obtain a mixed slurry of manganese nitrate, cerium nitrate and titanium dioxide.

步骤3:向步骤2中的混合浆液中慢慢滴加氨水溶液(分析纯,浓度为 20~30wt%),调节溶液pH至10,继续常温搅拌半小时,得到锰铈钛悬浊液。Step 3: Slowly add aqueous ammonia solution (analytical purity, concentration 20-30wt%) to the mixed slurry in Step 2, adjust the pH of the solution to 10, and continue stirring at room temperature for half an hour to obtain a manganese-cerium-titanium suspension.

步骤4:采用具有凸型或凹型螺旋桨的气动搅拌机并在螺旋桨上设置通气孔; 将搅拌完成的锰铈钛悬浊液放置于气动搅拌机中,在进行螺旋充分搅拌的同时, 通过通气孔向悬浊液中通入臭氧,使其充分氧化,螺旋桨转速为10-15r/min,通 气量500mL/min。Step 4: Use a pneumatic mixer with a convex or concave propeller and set a ventilation hole on the propeller; place the stirred manganese-cerium-titanium suspension in the pneumatic mixer, and while fully stirring the screw, pass the ventilation hole to the suspension. Ozone is introduced into the turbid liquid to make it fully oxidized, the speed of the propeller is 10-15r/min, and the ventilation rate is 500mL/min.

步骤5:将双氧水滴加至氧化完成的浆液中,滴加方式为将滴管伸入浆液底 部逐滴滴加,控制滴加速度在10秒/滴。Step 5: Add hydrogen peroxide dropwise to the oxidized slurry in a dropwise manner by inserting a dropper into the bottom of the slurry and drop by dropwise, and control the dripping speed at 10 seconds/drop.

步骤6:继续搅拌一段时间后,将氧化、还原完成后的浆液离心洗涤数次, 得到较湿润的催化剂固体。Step 6: After continuing to stir for a period of time, the slurry after oxidation and reduction is centrifuged and washed several times to obtain a relatively wet catalyst solid.

步骤7:将得到的催化剂固体采用喷雾蒸干法(即将催化剂泵入喷雾干燥器 内,经喷头雾化后由喷雾干燥器底部喷出),引入浆液粒度为10-20μm,喷雾温度 控制在250-300℃,有效减少干燥时间。Step 7: The obtained catalyst solid is sprayed to dryness (that is, the catalyst is pumped into the spray dryer, and sprayed from the bottom of the spray dryer after being atomized by the nozzle), the particle size of the introduced slurry is 10-20 μm, and the spray temperature is controlled at 250 -300℃, effectively reduce drying time.

步骤8:将得到的干燥材料放入马弗炉中进行程序升温煅烧。煅烧温度为 550℃,升温速度为10℃/min,煅烧时间为4小时。Step 8: Put the obtained dry material into a muffle furnace for temperature-programmed calcination. The calcination temperature was 550°C, the heating rate was 10°C/min, and the calcination time was 4 hours.

步骤9:将煅烧得到的材料放到球磨机中进行球磨,得到粒度为1-5μm的 MnCeTi-O超低温脱硝催化剂。Step 9: put the calcined material into a ball mill for ball milling to obtain a MnCeTi-O ultra-low temperature denitration catalyst with a particle size of 1-5 μm.

对比例1Comparative Example 1

按实施例1的方法制备MnCeTi脱硝催化剂,不同之处在于省去臭氧氧化、 双氧水还原步骤。The MnCeTi denitration catalyst was prepared by the method of Example 1, except that the steps of ozone oxidation and hydrogen peroxide reduction were omitted.

MnCeTi-O超低温脱硝催化剂的NH3-SCR反应活性如表1所示,该催化剂在 125-350℃温度范围内脱硝转化率保持在100%,400℃以下始终保持在98%以上, 具备良好的脱硝性能。The NH 3 -SCR reaction activity of the MnCeTi-O ultra-low temperature denitration catalyst is shown in Table 1. The denitration conversion rate of the catalyst is maintained at 100% in the temperature range of 125-350 °C, and it is always maintained at more than 98% below 400 °C. Denitrification performance.

表1 MnCeTi-O超低温脱硝催化剂表征活性Table 1 Characterization activity of MnCeTi-O catalyst for ultra-low temperature denitration

Figure BDA0003563299550000051
Figure BDA0003563299550000051

实施例1、对比例1所制备脱硝催化剂的XPS离子种类比例如表2所示,可 知经臭氧氧化、双氧水还原后Mn4+、Ce3+、活性氧物种比例显著提升,有利于低 温还原。The XPS ion species ratio of the denitration catalyst prepared in Example 1 and Comparative Example 1 is shown in Table 2. It can be seen that the ratio of Mn 4+ , Ce 3+ , and active oxygen species is significantly increased after ozone oxidation and hydrogen peroxide reduction, which is conducive to low-temperature reduction.

表2脱硝催化剂的XPS离子种类比例Table 2 XPS ion species ratio of denitration catalyst

Figure BDA0003563299550000052
Figure BDA0003563299550000052

MnCeTi-O超低温脱硝催化剂的程序升温还原(H2-TPR)耗氢量如表3所示, 可以看出经臭氧氧化、双氧水还原的催化剂使得MnO2、表面CeO2低温还原峰面 积增加,说明臭氧氧化使得Mn4+增多、双氧水还原使得Ce3+增多,有利于低温还 原。The hydrogen consumption of temperature-programmed reduction (H 2 -TPR) of the MnCeTi-O ultra-low temperature denitration catalyst is shown in Table 3. It can be seen that the catalysts reduced by ozone oxidation and hydrogen peroxide increase the area of the low temperature reduction peaks of MnO 2 and surface CeO 2 , indicating that Ozone oxidation increases Mn 4+ , and hydrogen peroxide reduction increases Ce 3+ , which is beneficial to low temperature reduction.

表3 MnCeTi-O超低温脱硝催化剂的程序升温还原(H2-TPR)耗氢量Table 3 Temperature-programmed reduction (H 2 -TPR) hydrogen consumption of MnCeTi-O ultra-low temperature denitration catalysts

Figure BDA0003563299550000053
Figure BDA0003563299550000053

Figure BDA0003563299550000061
Figure BDA0003563299550000061

实施例2:锰元素含量为24wt%、铈元素含量为24wt%的MnCeTi-O超低温 脱硝催化剂的制备。Example 2: Preparation of MnCeTi-O ultra-low temperature denitration catalyst with manganese content of 24wt% and cerium content of 24wt%.

步骤1:将6.31g硝酸锰溶液与7.64g硝酸铈固体溶于100g蒸馏水中,搅拌 30分钟,得到混合溶液。Step 1: Dissolve 6.31 g of manganese nitrate solution and 7.64 g of solid cerium nitrate in 100 g of distilled water, and stir for 30 minutes to obtain a mixed solution.

步骤2:将3.53g催化剂载体二氧化钛加入步骤1的混合溶液中,继续搅拌1 小时,得到硝酸锰、硝酸铈、二氧化钛的混合浆液。Step 2: Add 3.53 g of catalyst carrier titanium dioxide into the mixed solution of step 1, and continue to stir for 1 hour to obtain a mixed slurry of manganese nitrate, cerium nitrate and titanium dioxide.

步骤3:向步骤2的混合浆液中慢慢滴加氨水溶液(分析纯,浓度为 20~30wt%),调节溶液pH至8,继续常温搅拌半小时,得到锰铈钛悬浊液。Step 3: Slowly add aqueous ammonia solution (analytical purity, concentration 20-30wt%) to the mixed slurry in step 2, adjust the pH of the solution to 8, and continue stirring at room temperature for half an hour to obtain a manganese-cerium-titanium suspension.

步骤4:采用具有凸型或凹型螺旋桨的气动搅拌机并在螺旋桨上设置通气孔; 将搅拌完成的锰铈钛悬浊液放置于气动搅拌机中,在进行螺旋充分搅拌的同时, 通过通气孔向悬浊液中通入臭氧,使其充分氧化,螺旋桨转速为10-15r/min,通 气量500mL/min。Step 4: Use a pneumatic mixer with a convex or concave propeller and set a ventilation hole on the propeller; place the stirred manganese-cerium-titanium suspension in the pneumatic mixer, and while fully stirring the screw, pass the ventilation hole to the suspension. Ozone is introduced into the turbid liquid to make it fully oxidized, the speed of the propeller is 10-15r/min, and the ventilation rate is 500mL/min.

步骤5:将双氧水滴加至氧化完成的浆液中,滴加方式为将滴管伸入浆液底 部逐滴滴加,控制滴加速度在10秒/滴。Step 5: Add hydrogen peroxide dropwise to the oxidized slurry in a dropwise manner by inserting a dropper into the bottom of the slurry and drop by dropwise, and control the dripping speed at 10 seconds/drop.

步骤6:继续搅拌一段时间后,将氧化、还原完成后的浆液离心洗涤数次, 得到较湿润的催化剂固体。Step 6: After continuing to stir for a period of time, the slurry after oxidation and reduction is centrifuged and washed several times to obtain a relatively wet catalyst solid.

步骤7:将得到的催化剂固体采用喷雾蒸干法干燥,引入浆液粒度为10-20μm, 喷雾温度控制在250-300℃,有效减少干燥时间。Step 7: The obtained catalyst solid is dried by spray evaporation method, the particle size of the introduced slurry is 10-20 μm, and the spray temperature is controlled at 250-300° C. to effectively reduce the drying time.

步骤8:将得到的干燥材料放入马弗炉中进行程序升温煅烧。煅烧温度为 550℃,升温速度为10℃/min,煅烧时间为4小时。Step 8: Put the obtained dry material into a muffle furnace for temperature-programmed calcination. The calcination temperature was 550°C, the heating rate was 10°C/min, and the calcination time was 4 hours.

步骤9:将煅烧得到的材料放到球磨机中进行球磨,得到粒度为1-5μm的 MnCeTi-O超低温脱硝催化剂。Step 9: put the calcined material into a ball mill for ball milling to obtain a MnCeTi-O ultra-low temperature denitration catalyst with a particle size of 1-5 μm.

MnCeTi-O超低温脱硝催化剂的NH3-SCR反应活性如表4所示,该催化剂在 125-275℃温度范围内脱硝转化率保持在100%,400℃以下始终保持在97%以上, 具备良好的脱硝性能。The NH 3 -SCR reaction activity of the MnCeTi-O ultra-low temperature denitration catalyst is shown in Table 4. The denitration conversion rate of the catalyst is maintained at 100% in the temperature range of 125-275 °C, and it is always maintained at more than 97% below 400 °C. Denitrification performance.

表4 MnCeTi-O超低温脱硝催化剂表征活性Table 4 Characterization activity of MnCeTi-O ultra-low temperature denitration catalyst

Figure BDA0003563299550000062
Figure BDA0003563299550000062

Figure BDA0003563299550000071
Figure BDA0003563299550000071

MnCeTi-O超低温脱硝催化剂的XPS离子种类比例如表5所示,对比对比例1、 实施例1,可知经臭氧氧化、双氧水还原后的Mn4+、Ce3+、活性氧物种比例提升, 且相比于pH=10时制备的催化剂要低,说明pH=10为最佳pH值。The XPS ion species ratio of the MnCeTi-O ultra-low temperature denitration catalyst is shown in Table 5. Comparing Comparative Example 1 and Example 1, it can be seen that the ratio of Mn 4+ , Ce 3+ , and active oxygen species after ozone oxidation and hydrogen peroxide reduction is increased, and Compared with the catalyst prepared at pH=10, it is lower, indicating that pH=10 is the optimal pH value.

表5 MnCeTi-O超低温脱硝催化剂的XPS离子种类及活性氧物种数量比例Table 5 XPS ion species and active oxygen species ratio of MnCeTi-O ultra-low temperature denitration catalyst

Figure BDA0003563299550000072
Figure BDA0003563299550000072

实施例3:锰元素含量为24wt%、铈元素含量为24wt%的MnCeTi-O超低温 脱硝催化剂的制备。Example 3: Preparation of MnCeTi-O ultra-low temperature denitration catalyst with manganese content of 24wt% and cerium content of 24wt%.

步骤1:将6.31g硝酸锰溶液与7.64g硝酸铈固体溶于100g蒸馏水中,搅拌 30分钟,得到混合溶液。Step 1: Dissolve 6.31 g of manganese nitrate solution and 7.64 g of solid cerium nitrate in 100 g of distilled water, and stir for 30 minutes to obtain a mixed solution.

步骤2:将3.53g催化剂载体二氧化钛加入步骤1的混合溶液中,继续搅拌1 小时,得到硝酸锰、硝酸铈、二氧化钛的混合浆液。Step 2: Add 3.53 g of catalyst carrier titanium dioxide into the mixed solution of step 1, and continue to stir for 1 hour to obtain a mixed slurry of manganese nitrate, cerium nitrate and titanium dioxide.

步骤3:向步骤2中的混合浆液中慢慢滴加氨水溶液(分析纯,浓度为 20~30wt%),调节溶液pH至10,继续常温搅拌半小时,得到锰铈钛悬浊液。Step 3: Slowly add aqueous ammonia solution (analytical purity, concentration 20-30wt%) to the mixed slurry in Step 2, adjust the pH of the solution to 10, and continue stirring at room temperature for half an hour to obtain a manganese-cerium-titanium suspension.

步骤4:采用具有凸型或凹型螺旋桨的气动搅拌机并在螺旋桨上设置通气孔; 将搅拌完成的锰铈钛悬浊液放置于气动搅拌机中,在进行螺旋充分搅拌的同时, 通过通气孔向悬浊液中通入臭氧,使其充分氧化,螺旋桨转速为10-15r/min,通 气量300mL/min;氧化过程中发现溶液颜色未快速变深,可能是由于较低的通气 速度下Mn2+不能快速完全氧化成Mn4+,因此通气时间需适当延长。Step 4: Use a pneumatic mixer with a convex or concave propeller and set a ventilation hole on the propeller; place the stirred manganese-cerium-titanium suspension in the pneumatic mixer, and while fully stirring the screw, pass the ventilation hole to the suspension. Ozone was introduced into the turbid liquid to make it fully oxidized. The speed of the propeller was 10-15r/min, and the ventilation rate was 300mL/min. During the oxidation process, it was found that the color of the solution did not become darker rapidly, which may be due to the fact that Mn 2+ It cannot be rapidly and completely oxidized to Mn 4+ , so the ventilation time should be appropriately prolonged.

步骤5:将双氧水滴加至氧化完成的浆液中,滴加方式为将滴管伸入浆液底 部逐滴滴加,控制滴加速度在10秒/滴。Step 5: Add hydrogen peroxide dropwise to the oxidized slurry in a dropwise manner by inserting a dropper into the bottom of the slurry and drop by dropwise, and control the dripping speed at 10 seconds/drop.

步骤6:继续搅拌一段时间后,将氧化、还原完成后的浆液离心洗涤数次, 得到较湿润的催化剂固体。Step 6: After continuing to stir for a period of time, the slurry after oxidation and reduction is centrifuged and washed several times to obtain a relatively wet catalyst solid.

步骤7:将得到的催化剂固体采用喷雾蒸干法干燥(即将催化剂泵入喷雾干 燥器内,经喷头雾化后由喷雾干燥器底部喷出),引入浆液粒度为10-20μm,喷雾 温度控制在250-300℃,有效减少干燥时间。Step 7: The obtained catalyst solid is dried by spray evaporation (that is, the catalyst is pumped into the spray dryer, and sprayed from the bottom of the spray dryer after being atomized by the nozzle), the particle size of the introduced slurry is 10-20 μm, and the spray temperature is controlled at 250-300℃, effectively reduce drying time.

步骤8:将得到的干燥材料放入马弗炉中进行程序升温煅烧。煅烧温度为 550℃,升温速度为10℃/min,煅烧时间为4小时。Step 8: Put the obtained dry material into a muffle furnace for temperature-programmed calcination. The calcination temperature was 550°C, the heating rate was 10°C/min, and the calcination time was 4 hours.

步骤9:将煅烧得到的材料放到球磨机中进行球磨,得到粒度为1-5μm的 MnCeTi-O超低温脱硝催化剂。Step 9: put the calcined material into a ball mill for ball milling to obtain a MnCeTi-O ultra-low temperature denitration catalyst with a particle size of 1-5 μm.

MnCeTi-O超低温脱硝催化剂的NH3-SCR反应活性如表6所示,该催化剂在 125-275℃温度范围内脱硝转化率保持在100%,400℃以下始终保持在96%以上, 具备良好的脱硝性能。The NH 3 -SCR reaction activity of the MnCeTi-O ultra-low temperature denitration catalyst is shown in Table 6. The denitration conversion rate of the catalyst is maintained at 100% in the temperature range of 125-275 °C, and it is always maintained at more than 96% below 400 °C. Denitrification performance.

表6 MnCeTi-O超低温脱硝催化剂表征活性Table 6 Characterization activity of MnCeTi-O ultra-low temperature denitration catalyst

Figure BDA0003563299550000081
Figure BDA0003563299550000081

MnCeTi-O超低温脱硝催化剂的XPS离子种类比例如表7所示,对比对比例1、 实施例1,可知臭氧氧化、双氧水还原后Mn4+、Ce3+、活性氧物种比例提升,且 相较于500mL/min的臭氧通气量有所减少。The XPS ion species ratio of the MnCeTi-O ultra-low temperature denitration catalyst is shown in Table 7. Comparing Comparative Example 1 and Example 1, it can be seen that the ratio of Mn 4+ , Ce 3+ and active oxygen species after ozone oxidation and hydrogen peroxide reduction is increased, and compared to Ozone ventilation was reduced at 500 mL/min.

表7 MnCeTi-O超低温脱硝催化剂的XPS离子种类比例Table 7 XPS ion species ratio of MnCeTi-O ultra-low temperature denitration catalyst

Figure BDA0003563299550000082
Figure BDA0003563299550000082

实施例4:锰元素含量为24wt%、铈元素含量为24wt%的MnCeTi-O超低温 脱硝催化剂的制备。Example 4: Preparation of MnCeTi-O ultra-low temperature denitration catalyst with manganese content of 24wt% and cerium content of 24wt%.

步骤1:将6.31g硝酸锰溶液与7.64g硝酸铈固体溶于100g蒸馏水中,搅拌 30分钟,得到混合溶液。Step 1: Dissolve 6.31 g of manganese nitrate solution and 7.64 g of solid cerium nitrate in 100 g of distilled water, and stir for 30 minutes to obtain a mixed solution.

步骤2:将3.53g催化剂载体二氧化钛加入步骤1的混合溶液中,继续搅拌1 小时,得到硝酸锰、硝酸铈、二氧化钛的混合浆液。Step 2: Add 3.53 g of catalyst carrier titanium dioxide into the mixed solution of step 1, and continue to stir for 1 hour to obtain a mixed slurry of manganese nitrate, cerium nitrate and titanium dioxide.

步骤3:向步骤2中的混合浆液中慢慢滴加氨水溶液(分析纯,浓度为 20~30wt%),调节溶液pH至10,继续常温搅拌半小时,得到锰铈钛悬浊液。Step 3: Slowly add aqueous ammonia solution (analytical purity, concentration 20-30wt%) to the mixed slurry in Step 2, adjust the pH of the solution to 10, and continue stirring at room temperature for half an hour to obtain a manganese-cerium-titanium suspension.

步骤4:采用具有凸型或凹型螺旋桨的气动搅拌机并在螺旋桨上设置通气孔; 将搅拌完成的锰铈钛悬浊液放置于气动搅拌机中,在进行螺旋充分搅拌的同时, 通过通气孔向悬浊液中通入臭氧,使其充分氧化,螺旋桨转速为10-15r/min,通 气量500mL/min。Step 4: Use a pneumatic mixer with a convex or concave propeller and set a ventilation hole on the propeller; place the stirred manganese-cerium-titanium suspension in the pneumatic mixer, and while fully stirring the screw, pass the ventilation hole to the suspension. Ozone is introduced into the turbid liquid to make it fully oxidized, the speed of the propeller is 10-15r/min, and the ventilation rate is 500mL/min.

步骤5:将双氧水滴加至氧化完成的浆液中,滴加方式为将滴管伸入浆液底 部逐滴滴加,控制滴加速度在10秒/滴。Step 5: Add hydrogen peroxide dropwise to the oxidized slurry in a dropwise manner by inserting a dropper into the bottom of the slurry and drop by dropwise, and control the dripping speed at 10 seconds/drop.

步骤6:继续搅拌一段时间后,将氧化、还原完成后的浆液离心洗涤数次, 得到较湿润的催化剂固体。Step 6: After continuing to stir for a period of time, the slurry after oxidation and reduction is centrifuged and washed several times to obtain a relatively wet catalyst solid.

步骤7:将得到的催化剂固体采用负压力干燥法(即以真空泵形成负压力状 态,经干燥炉、加热室、搅拌、驱动、蒸汽、过滤、冷凝等装置进行干燥),负压 力中内部温度控制在160-180℃的范围内。Step 7: The obtained catalyst solid is dried by a negative pressure (that is, a negative pressure state is formed by a vacuum pump, and dried through devices such as a drying furnace, a heating chamber, stirring, driving, steam, filtration, and condensation), and the internal temperature is controlled in the negative pressure. in the range of 160-180°C.

步骤8:将得到的干燥材料放入马弗炉中进行程序升温煅烧。煅烧温度为 550℃,升温速度为10℃/min,煅烧时间为4小时。Step 8: Put the obtained dry material into a muffle furnace for temperature-programmed calcination. The calcination temperature was 550°C, the heating rate was 10°C/min, and the calcination time was 4 hours.

步骤9:将煅烧得到的材料放到球磨机中进行球磨,得到粒度为1-5μm的 MnCeTi-O超低温脱硝催化剂。Step 9: put the calcined material into a ball mill for ball milling to obtain a MnCeTi-O ultra-low temperature denitration catalyst with a particle size of 1-5 μm.

MnCeTi-O超低温脱硝催化剂的NH3-SCR反应活性如表8所示,该催化剂在 125-350℃温度范围内脱硝转化率保持在100%,400℃以下始终保持在96%以上, 具备良好的脱硝性能。The NH 3 -SCR reaction activity of the MnCeTi-O ultra-low temperature denitration catalyst is shown in Table 8. The denitration conversion rate of the catalyst is maintained at 100% in the temperature range of 125-350 °C, and it is always maintained at more than 96% below 400 °C. Denitrification performance.

表8 MnCeTi-O超低温脱硝催化剂表征活性Table 8 Characterization activity of MnCeTi-O ultra-low temperature denitration catalyst

Figure BDA0003563299550000091
Figure BDA0003563299550000091

MnCeTi-O超低温脱硝催化剂的XPS离子种类比例如表9所示,对比对比例 1可知,经臭氧氧化、双氧水还原后Mn4+、Ce3+比例有所提升,有利于低温还原。The XPS ion species ratio of the MnCeTi-O ultra-low temperature denitration catalyst is shown in Table 9. Compared with Comparative Example 1, it can be seen that the ratio of Mn 4+ and Ce 3+ has increased after ozone oxidation and hydrogen peroxide reduction, which is conducive to low temperature reduction.

表9 MnCeTi-O超低温脱硝催化剂的XPS离子种类比例Table 9 XPS ion species ratio of MnCeTi-O ultra-low temperature denitration catalyst

Figure BDA0003563299550000092
Figure BDA0003563299550000092

实施例5:锰元素含量为24wt%、铈元素含量为24wt%的MnCeTi-O超低温 脱硝催化剂的制备。Example 5: Preparation of MnCeTi-O ultra-low temperature denitration catalyst with manganese content of 24wt% and cerium content of 24wt%.

步骤1:将6.31g硝酸锰溶液与7.64g硝酸铈固体溶于100g蒸馏水中,搅拌 30分钟,得到混合溶液。Step 1: Dissolve 6.31 g of manganese nitrate solution and 7.64 g of solid cerium nitrate in 100 g of distilled water, and stir for 30 minutes to obtain a mixed solution.

步骤2:将3.53g催化剂载体二氧化钛加入步骤1的混合溶液中,继续搅拌1 小时,得到硝酸锰、硝酸铈、二氧化钛的混合浆液。Step 2: Add 3.53 g of catalyst carrier titanium dioxide into the mixed solution of step 1, and continue to stir for 1 hour to obtain a mixed slurry of manganese nitrate, cerium nitrate and titanium dioxide.

步骤3:向步骤2中的混合浆液中慢慢滴加氨水溶液(分析纯,浓度为 20~30wt%),调节溶液pH至10,继续常温搅拌半小时,得到锰铈钛悬浊液。Step 3: Slowly add aqueous ammonia solution (analytical purity, concentration 20-30wt%) to the mixed slurry in Step 2, adjust the pH of the solution to 10, and continue stirring at room temperature for half an hour to obtain a manganese-cerium-titanium suspension.

步骤4:采用具有凸型或凹型螺旋桨的气动搅拌机并在螺旋桨上设置通气孔; 将搅拌完成的锰铈钛悬浊液放置于气动搅拌机中,在进行螺旋充分搅拌的同时, 通过通气孔向悬浊液中通入臭氧,使其充分氧化,螺旋桨转速为10-15r/min,通 气量500mL/min。Step 4: Use a pneumatic mixer with a convex or concave propeller and set a ventilation hole on the propeller; place the stirred manganese-cerium-titanium suspension in the pneumatic mixer, and while fully stirring the screw, pass the ventilation hole to the suspension. Ozone is introduced into the turbid liquid to make it fully oxidized, the speed of the propeller is 10-15r/min, and the ventilation rate is 500mL/min.

步骤5:将双氧水滴加至氧化完成的浆液中,滴加方式为将滴管伸入浆液底 部逐滴滴加,控制滴加速度在10秒/滴。Step 5: Add hydrogen peroxide dropwise to the oxidized slurry in a dropwise manner by inserting a dropper into the bottom of the slurry and drop by dropwise, and control the dripping speed at 10 seconds/drop.

步骤6:继续搅拌一段时间后,将氧化、还原完成后的浆液离心洗涤数次, 得到较湿润的催化剂固体。Step 6: After continuing to stir for a period of time, the slurry after oxidation and reduction is centrifuged and washed several times to obtain a relatively wet catalyst solid.

步骤7:将得到的催化剂固体采用喷雾蒸干法,引入浆液粒度为10-20μm, 喷雾温度控制在250-300℃,有效减少干燥时间。Step 7: The obtained catalyst solid is evaporated to dryness by spray method, the particle size of the introduced slurry is 10-20 μm, and the spray temperature is controlled at 250-300° C. to effectively reduce the drying time.

步骤8:将得到的干燥材料放入马弗炉中进行程序升温煅烧。煅烧温度为 500℃,升温速度为10℃/min,煅烧时间为4小时。Step 8: Put the obtained dry material into a muffle furnace for temperature-programmed calcination. The calcination temperature was 500°C, the heating rate was 10°C/min, and the calcination time was 4 hours.

步骤9:将煅烧得到的材料放到球磨机中进行球磨,得到粒度为1-5μm的 MnCeTi-O超低温脱硝催化剂。Step 9: put the calcined material into a ball mill for ball milling to obtain a MnCeTi-O ultra-low temperature denitration catalyst with a particle size of 1-5 μm.

MnCeTi-O超低温脱硝催化剂的NH3-SCR反应活性如表10所示,该催化剂在 125-275℃温度范围内脱硝转化率保持在100%,400℃以下始终保持在95%以上, 具备良好的脱硝性能。The NH 3 -SCR reaction activity of the MnCeTi-O ultra-low temperature denitration catalyst is shown in Table 10. The denitration conversion rate of the catalyst is maintained at 100% in the temperature range of 125-275 °C, and it is always maintained above 95% below 400 °C. Denitrification performance.

表10 MnCeTi-O超低温脱硝催化剂表征活性Table 10 Characterization activity of MnCeTi-O ultra-low temperature denitration catalyst

Figure BDA0003563299550000101
Figure BDA0003563299550000101

MnCeTi-O超低温脱硝催化剂的XPS离子种类比例表11所示,对比对比例1、 实施例1,可知经臭氧氧化、双氧水还原后Mn4+、Ce3+比例提升,且相较于550℃ 制备的催化剂有所下降,说明温度对催化剂的脱硝性能有所影响。The XPS ion species ratio of the MnCeTi-O ultra-low temperature denitration catalyst is shown in Table 11. Comparing Comparative Example 1 and Example 1, it can be seen that the ratio of Mn 4+ and Ce 3+ increases after ozone oxidation and hydrogen peroxide reduction, and compared with 550 ℃ preparation The catalyst has decreased, indicating that the temperature has an influence on the denitration performance of the catalyst.

表11 MnCeTi-O超低温脱硝催化剂的XPS离子种类比例Table 11 Species ratio of XPS ions of MnCeTi-O ultra-low temperature denitration catalysts

Figure BDA0003563299550000111
Figure BDA0003563299550000111

实施例6:锰元素含量为24wt%、镧元素含量为24wt%的MnLaTi-O超低温 脱硝催化剂的制备。Example 6: Preparation of MnLaTi-O ultra-low temperature denitration catalyst with manganese content of 24wt% and lanthanum content of 24wt%.

步骤1:将5.94g硝酸锰溶液与7.62g硝酸铈固体溶于100g蒸馏水中,搅拌 30分钟,得到混合溶液。Step 1: Dissolve 5.94 g of manganese nitrate solution and 7.62 g of solid cerium nitrate in 100 g of distilled water, and stir for 30 minutes to obtain a mixed solution.

步骤2:将3.53g催化剂载体二氧化钛加入步骤1的混合溶液中,继续搅拌1 小时,得到硝酸锰、硝酸镧、二氧化钛的混合浆液。Step 2: Add 3.53 g of catalyst carrier titanium dioxide to the mixed solution of step 1, and continue to stir for 1 hour to obtain a mixed slurry of manganese nitrate, lanthanum nitrate and titanium dioxide.

步骤3:向步骤2中的混合浆液中慢慢滴加氨水溶液(分析纯,浓度为 20~30wt%),调节溶液pH至10,继续常温搅拌半小时,得到锰镧钛悬浊液。Step 3: Slowly add aqueous ammonia solution (analytical purity, concentration 20-30wt%) to the mixed slurry in step 2, adjust the pH of the solution to 10, and continue stirring at room temperature for half an hour to obtain a manganese-lanthanum-titanium suspension.

步骤4:采用具有凸型或凹型螺旋桨的气动搅拌机并在螺旋桨上设置通气孔; 将搅拌完成的锰镧钛悬浊液放置于气动搅拌机中,在进行螺旋充分搅拌的同时, 通过通气孔向悬浊液中通入臭氧,使其充分氧化,螺旋桨转速为10-15r/min,通 气量500mL/min。Step 4: Use a pneumatic mixer with a convex or concave propeller and set ventilation holes on the propeller; place the stirred manganese-lanthanum-titanium suspension in the pneumatic mixer, while fully stirring the screw, pass the ventilation hole to the suspension. Ozone is introduced into the turbid liquid to make it fully oxidized, the speed of the propeller is 10-15r/min, and the ventilation rate is 500mL/min.

步骤5:将双氧水滴加至氧化完成的浆液中,滴加方式为将滴管伸入浆液底 部逐滴滴加,控制滴加速度在10秒/滴。Step 5: Add hydrogen peroxide dropwise to the oxidized slurry in a dropwise manner by inserting a dropper into the bottom of the slurry and drop by dropwise, and control the dripping speed at 10 seconds/drop.

步骤6:继续搅拌一段时间后,将氧化、还原完成后的浆液离心洗涤数次, 得到较湿润的催化剂固体。Step 6: After continuing to stir for a period of time, the slurry after oxidation and reduction is centrifuged and washed several times to obtain a relatively wet catalyst solid.

步骤7:将得到的催化剂固体采用喷雾蒸干法干燥(即将催化剂泵入喷雾干 燥器内,经喷头雾化后由喷雾干燥器底部喷出),引入浆液粒度为10-20μm,喷雾 温度控制在250-300℃,有效减少干燥时间。Step 7: The obtained catalyst solid is dried by spray evaporation (that is, the catalyst is pumped into the spray dryer, and sprayed from the bottom of the spray dryer after being atomized by the nozzle), the particle size of the introduced slurry is 10-20 μm, and the spray temperature is controlled at 250-300℃, effectively reducing drying time.

步骤8:将得到的干燥材料放入马弗炉中进行程序升温煅烧。煅烧温度为550 ℃,升温速度为10℃/min,煅烧时间为4小时。Step 8: Put the obtained dry material into a muffle furnace for temperature-programmed calcination. The calcination temperature was 550°C, the heating rate was 10°C/min, and the calcination time was 4 hours.

步骤9:将煅烧得到的材料放到球磨机中进行球磨,得到粒度为1-5μm的 MnLaTi-O超低温脱硝催化剂。Step 9: put the calcined material into a ball mill for ball milling to obtain a MnLaTi-O ultra-low temperature denitration catalyst with a particle size of 1-5 μm.

对比例2Comparative Example 2

按照实施例6的方法制备脱硝催化剂,不同之处在于,省去臭氧氧化、双氧 水还原步骤。The denitration catalyst was prepared according to the method of Example 6, except that the steps of ozone oxidation and hydrogen peroxide reduction were omitted.

MnLaTi-O超低温脱硝催化剂的NH3-SCR反应活性如表12所示,该催化剂在 100-350℃温度范围内脱硝转化率保持在100%,400℃以下始终保持在97%以上, 具备良好的脱硝性能。The NH 3 -SCR reaction activity of the MnLaTi-O ultra-low temperature denitration catalyst is shown in Table 12. The denitration conversion rate of the catalyst is maintained at 100% in the temperature range of 100-350 °C, and it is always maintained above 97% below 400 °C. Denitrification performance.

表12 MnLaTi-O超低温脱硝催化剂表征活性Table 12 Characterization activity of MnLaTi-O ultra-low temperature denitration catalyst

Figure BDA0003563299550000121
Figure BDA0003563299550000121

对比实施例6、对比例1所制备脱硝催化剂的XPS离子种类比例如表13所 示,可知经臭氧氧化、双氧水还原后Mn4+、La3+比例提升,有利于低温还原。The ratios of XPS ions of the denitration catalysts prepared in Comparative Example 6 and Comparative Example 1 are shown in Table 13. It can be seen that the ratio of Mn 4+ and La 3+ increases after ozone oxidation and hydrogen peroxide reduction, which is beneficial to low-temperature reduction.

表13 1MnLaTi-O超低温脱硝催化剂的XPS离子种类比例Table 13 Species ratio of XPS ions of 1MnLaTi-O ultra-low temperature denitration catalyst

Figure BDA0003563299550000122
Figure BDA0003563299550000122

实施例7:锰元素含量为24wt%、钆元素含量为24wt%的MnGdTi-O超低温 脱硝催化剂的制备。Example 7: Preparation of MnGdTi-O ultra-low temperature denitration catalyst with manganese content of 24wt% and gadolinium content of 24wt%.

步骤1:将5.94g硝酸锰与6.04g硝酸钆固体溶于100g蒸馏水中,搅拌30分 钟,得到混合溶液。Step 1: Dissolve 5.94g of manganese nitrate and 6.04g of gadolinium nitrate solid in 100g of distilled water, and stir for 30 minutes to obtain a mixed solution.

步骤2:将3.53g催化剂载体二氧化钛加入步骤1的混合溶液中,继续搅拌1 小时得到硝酸锰、硝酸钆、二氧化钛的混合浆液。Step 2: Add 3.53 g of catalyst carrier titanium dioxide to the mixed solution of step 1, and continue stirring for 1 hour to obtain a mixed slurry of manganese nitrate, gadolinium nitrate and titanium dioxide.

步骤3:向步骤2中的混合浆液中慢慢滴加氨水溶液(分析纯,浓度为 20~30wt%),调节溶液pH至10,继续常温搅拌半小时,得到锰钆钛悬浊液。Step 3: Slowly add aqueous ammonia solution (analytical purity, concentration 20-30wt%) to the mixed slurry in step 2, adjust the pH of the solution to 10, and continue stirring at room temperature for half an hour to obtain a manganese-gadolinium-titanium suspension.

步骤4:采用具有凸型或凹型螺旋桨的气动搅拌机并在螺旋桨上设置通气孔; 将搅拌完成的锰钆钛悬浊液放置于气动搅拌机中,在进行螺旋充分搅拌的同时, 通过通气孔向悬浊液中通入臭氧,使其充分氧化,螺旋桨转速为10-15r/min,通 气量500mL/min。Step 4: Use a pneumatic mixer with a convex or concave propeller and set a ventilation hole on the propeller; place the stirred manganese-gadolinium-titanium suspension in the pneumatic mixer, and while fully stirring the screw, pass the ventilation hole to the suspension. Ozone is introduced into the turbid liquid to make it fully oxidized, the speed of the propeller is 10-15r/min, and the ventilation rate is 500mL/min.

步骤5:将双氧水滴加至氧化完成的浆液中,滴加方式为将滴管伸入浆液底 部逐滴滴加,控制滴加速度在10秒/滴。Step 5: Add hydrogen peroxide dropwise to the oxidized slurry in a dropwise manner by inserting a dropper into the bottom of the slurry and drop by dropwise, and control the dripping speed at 10 seconds/drop.

步骤6:继续搅拌一段时间后,将氧化、还原完成后的浆液离心洗涤数次, 得到较湿润的催化剂固体。Step 6: After continuing to stir for a period of time, the slurry after oxidation and reduction is centrifuged and washed several times to obtain a relatively wet catalyst solid.

步骤7:将得到的催化剂固体采用喷雾蒸干法干燥(即将催化剂泵入喷雾干 燥器内,经喷头雾化后由喷雾干燥器底部喷出),引入浆液粒度为10-20μm,喷雾 温度控制在250-300℃,有效减少干燥时间。Step 7: The obtained catalyst solid is dried by spray evaporation (that is, the catalyst is pumped into the spray dryer, and sprayed from the bottom of the spray dryer after being atomized by the nozzle), the particle size of the introduced slurry is 10-20 μm, and the spray temperature is controlled at 250-300℃, effectively reduce drying time.

步骤8:将得到的干燥材料放入马弗炉中进行程序升温煅烧。煅烧温度为550 ℃,升温速度为10℃/min,煅烧时间为4小时。Step 8: Put the obtained dry material into a muffle furnace for temperature-programmed calcination. The calcination temperature was 550°C, the heating rate was 10°C/min, and the calcination time was 4 hours.

步骤9:将煅烧得到的材料放到球磨机中进行球磨,得到粒度为1-5μm的 MnGdTi-O超低温脱硝催化剂。Step 9: put the calcined material into a ball mill for ball milling to obtain a MnGdTi-O ultra-low temperature denitration catalyst with a particle size of 1-5 μm.

对比例3Comparative Example 3

按照实施例7的方法制备脱硝催化剂,不同之处在于,省去臭氧氧化、双氧 水还原步骤。The denitration catalyst was prepared according to the method of Example 7, except that the steps of ozone oxidation and hydrogen peroxide reduction were omitted.

MnGdTi-O超低温脱硝催化剂的NH3-SCR反应活性如表14所示,该催化剂 在100-350℃温度范围内脱硝转化率保持在100%,400℃以下始终保持在97%以 上,具备良好的脱硝性能。The NH 3 -SCR reaction activity of the MnGdTi-O ultra-low temperature denitration catalyst is shown in Table 14. The denitration conversion rate of the catalyst is maintained at 100% in the temperature range of 100-350 °C, and it is always maintained at more than 97% below 400 °C, with good performance. Denitrification performance.

表14 MnGdTi-O超低温脱硝催化剂表征活性Table 14 Characterization activity of MnGdTi-O ultra-low temperature denitration catalyst

Figure BDA0003563299550000131
Figure BDA0003563299550000131

对比实施例6、对比例1所制备脱硝催化剂的XPS离子种类比例如表15所 示,可知经臭氧氧化、双氧水还原后Mn4+、Gd3+比例提升,有利于低温还原。The XPS ion species ratios of the denitration catalysts prepared in Comparative Example 6 and Comparative Example 1 are shown in Table 15. It can be seen that the ratio of Mn 4+ and Gd 3+ increases after ozone oxidation and hydrogen peroxide reduction, which is beneficial to low-temperature reduction.

表15 MnCeTi-O超低温脱硝催化剂的XPS离子种类比例Table 15 Species ratio of XPS ions of MnCeTi-O ultra-low temperature denitration catalysts

Figure BDA0003563299550000132
Figure BDA0003563299550000132

实施例1-7所制备的MGdTi-O超低温脱硝催化剂的比表面积及孔径如表16 所示。The specific surface area and pore size of the MGdTi-O ultra-low temperature denitration catalysts prepared in Examples 1-7 are shown in Table 16.

表16 MGdTi-O超低温脱硝催化剂的比表面积及孔径Table 16 Specific surface area and pore size of MGdTi-O ultra-low temperature denitration catalysts

实施例1Example 1 实施例2Example 2 实施例3Example 3 实施例4Example 4 实施例5Example 5 实施例6Example 6 实施例7Example 7 比表面积specific surface area 8888 8080 7979 8585 7575 8383 8080 孔径Aperture 11.4311.43 12.212.2 10.610.6 12.3212.32 12.9412.94 12.1412.14 12.08 12.08

以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精 神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护 范围之内。The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection of the present invention. within the range.

Claims (10)

1. Mn (manganese) 4+ And Ce 3+ The preparation method of the enhanced Mn-M-Ti-O ultralow temperature denitration catalyst is characterized in that the denitration catalyst is TiO 2 The carrier is loaded with denitration active ingredients and rare earth metal element auxiliaries, and is prepared by ozone oxidation, hydrogen peroxide reduction and calcination.
2. A Mn as claimed in claim 1 4+ And Ce 3+ Enhanced Mn-M-Ti-O ultralow temperature denitrationThe preparation method of the catalyst is characterized in that the active component is transition metal element manganese; the auxiliary agent is one of rare earth metal elements of cerium, lanthanum and gadolinium.
3. A Mn as claimed in claim 1 4+ And Ce 3+ The preparation method of the enhanced Mn-M-Ti-O ultralow-temperature denitration catalyst is characterized in that the specific surface area of the denitration catalyst is 70-90M 2 Per g, particle size 1-5 μm, surface Mn 4+ 47-50% of surface Ce 3+ The proportion is 19-25%, the number of surface active oxygen species is 45-50%, and the average pore diameter is less than 13 nm; the temperature window of catalytic activity for denitration efficiency reaching more than 97 percent is 125-400 ℃.
4. A Mn as set forth in any one of claims 1 to 3 4+ And Ce 3+ The preparation method of the enhanced Mn-M-Ti-O ultralow-temperature denitration catalyst is characterized by comprising the following steps:
(1) mixing manganese nitrate solution with M (NO) 3 ) x Adding the solid into distilled water, stirring and dissolving to obtain a mixed solution; wherein M is Ce, La or Gd;
(2) making the catalyst carrier TiO 2 Adding the mixture into the mixed solution, and uniformly stirring to obtain mixed slurry;
(3) adjusting the pH value of the mixed slurry, and continuously stirring at normal temperature to obtain a suspension;
(4) introducing ozone into the suspension while stirring by using a pneumatic stirrer to fully oxidize the suspension;
(5) after the introduction is finished, adding hydrogen peroxide dropwise into the slurry after the ozone oxidation;
(6) after continuously stirring for a period of time, centrifugally washing for a plurality of times;
(7) drying the washed catalyst;
(8) carrying out temperature programming calcination on the dried product;
(9) grinding the calcined product into powder to obtain the material meeting the requirement.
5. A compound of claim 4n 4+ And Ce 3+ The preparation method of the enhanced Mn-M-Ti-O ultralow-temperature denitration catalyst is characterized in that the concentration of a manganese nitrate solution is 50 wt%, and the manganese nitrate solution and M (NO) are 3 ) x Distilled water, TiO 2 The mass ratio of (5.94-6.31): (6.04-7.64): 100: 3.53.
6. a Mn according to claim 4 4+ And Ce 3+ The preparation method of the enhanced Mn-M-Ti-O ultralow-temperature denitration catalyst is characterized in that in the step (3), ammonia water with the concentration of 20-30 wt% is adopted to adjust the pH value to 8-10.
7. A Mn according to claim 4 4+ And Ce 3+ The preparation method of the enhanced Mn-M-Ti-O ultralow temperature denitration catalyst is characterized in that in the step (4), the specific method of ozone oxidation is as follows: adopting a pneumatic stirrer with a convex or concave propeller, arranging a vent hole on a propeller shaft, placing the suspension in the pneumatic stirrer, and introducing ozone into the suspension through the vent hole while stirring; the rotating speed of the propeller is 10-15r/min, and the ozone ventilation volume is 500 mL/min.
8. A Mn according to claim 4 4+ And Ce 3+ The preparation method of the enhanced Mn-M-Ti-O ultralow-temperature denitration catalyst is characterized in that in the step (5), the specific method for dropwise adding hydrogen peroxide is as follows: and (4) extending a dropper into the bottom of the slurry, and dropwise adding hydrogen peroxide, wherein the dropping speed is controlled to be 10 seconds per drop.
9. A Mn according to claim 4 4+ And Ce 3+ The preparation method of the enhanced Mn-M-Ti-O ultralow temperature denitration catalyst is characterized in that in the step (7), the drying method is negative pressure drying or spray evaporation: the negative pressure drying method is that a vacuum pump forms a negative pressure state, and the drying is carried out by a drying furnace, a heating chamber, stirring, driving, steam, filtering, condensing and other devices; the spray evaporation method is to pump the catalyst into a spray dryer, atomize the catalyst by a nozzle and spray the atomized catalyst out of the bottom of the spray dryer.
10. A Mn according to claim 4 4+ And Ce 3+ The preparation method of the enhanced Mn-M-Ti-O ultralow temperature denitration catalyst is characterized in that in the step (8), the temperature programming rate is 10 ℃/min, the calcination temperature is 500-.
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