技术领域Technical field
本发明属于工业废气处理技术领域，尤其涉及一种复合功能涂层催化剂及其制备方法。The invention belongs to the technical field of industrial waste gas treatment, and in particular relates to a composite functional coating catalyst and a preparation method thereof.
背景技术Background technique
在钢铁、石化、焦化、橡胶、涂料等生产过程中，不可避免地产生大量的废气。在这大量的废气中，氮氧化物(NOx)会导致酸雨、光化学烟雾等环境问题，挥发性有机污染物(VOCs)具有多重环境效应，是形成臭氧和诱发雾霾的重要前体物，给人类健康和生存环境带来严重危害。因此，如何高效脱除废气中的NOx和VOCs是目前环保领域的重要课题。其中，对NOx的脱除，目前已有较为成熟的(V-W/TiO2 NH3-SCR技术等)应用技术。对较低浓度VOCs的脱除，催化氧化法具有低能耗、低操作温度、无二次污染、适用范围广等优点，是最具前景的VOCs消除技术。此外，针对废气中的NOx和VOCs的脱除，一般需要两个操作单元独立完成，若能使用单一催化剂实现二者的协同脱除，则可节省设备空间、简化工艺流程、节约成本，具有显著的社会效益。In the production processes of steel, petrochemicals, coking, rubber, coatings, etc., a large amount of waste gas is inevitably produced. In this large amount of exhaust gas, nitrogen oxides (NOx) can cause environmental problems such as acid rain and photochemical smog. Volatile organic pollutants (VOCs) have multiple environmental effects and are important precursors for the formation of ozone and inducing haze. It brings serious harm to human health and living environment. Therefore, how to efficiently remove NOx and VOCs from exhaust gas is an important issue in the current environmental protection field. Among them, for the removal of NOx, there are currently relatively mature application technologies (VW/TiO2 NH3 -SCR technology, etc.). For the removal of lower concentration VOCs, the catalytic oxidation method has the advantages of low energy consumption, low operating temperature, no secondary pollution, and wide application range, and is the most promising VOCs elimination technology. In addition, the removal of NOx and VOCs in exhaust gas generally requires two operating units to be completed independently. If a single catalyst can be used to achieve the coordinated removal of the two, it can save equipment space, simplify the process, and save costs, which has significant social benefits.
在诸多脱硝、脱VOCs催化剂中，锰基催化剂价格低廉、同时具有良好的VOCs催化氧化活性和SCR脱硝活性，且活性温度窗口重叠度高，极具潜力作为协同脱除催化剂。不足之处是，在SCR过程中，存在氨的过度氧化生成氧化亚氮(N2O)的问题，导致氮气选择性降低，制约了其推广使用。Among many denitration and VOCs removal catalysts, manganese-based catalysts are low-priced, have good VOCs catalytic oxidation activity and SCR denitration activity, and have high overlapping activity temperature windows. They have great potential as synergistic removal catalysts. The disadvantage is that during the SCR process, there is a problem of excessive oxidation of ammonia to generate nitrous oxide (N2 O), which leads to a reduction in nitrogen selectivity and restricts its promotion and use.
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复合功能涂层催化剂及其制备方法，采取多次涂覆、依次赋能的设计思路，制备一种新的协同脱除工业尾气中的NOx和苯系物VOCs的催化剂，实现高氮气选择性。The purpose of the present invention is to provide a composite functional coating catalyst and its preparation method, adopting the design idea of multiple coatings and sequential energization, to prepare a new synergistic removal of NOx and benzene series VOCs in industrial exhaust gas. Catalyst to achieve high nitrogen selectivity.
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:
本发明提供一种复合功能涂层催化剂的制备方法，至少依次包括：制备涂覆钛酸的载体，负载催化氧化活性组分，包覆第二活性组分。The invention provides a method for preparing a composite functional coating catalyst, which at least sequentially includes: preparing a carrier coated with titanic acid, loading a catalytic oxidation active component, and coating a second active component.
进一步地，所述制备涂覆钛酸的载体是将载体置于钛醇盐液中浸泡0.5～3小时，取出沥干后，通入过热蒸汽反应0.5～3小时，得到涂覆钛酸的载体。其中，所述浸泡时间优选为1小时，所述通入过热蒸汽的时间优选为1.5小时。Further, the method of preparing a titanic acid-coated carrier is to soak the carrier in a titanium alkoxide solution for 0.5 to 3 hours, take it out and drain it, and then add superheated steam to react for 0.5 to 3 hours to obtain a titanic acid-coated carrier. . Wherein, the soaking time is preferably 1 hour, and the time for passing superheated steam is preferably 1.5 hours.
优选地，所述载体包括制备成型的板式、蜂窝或特定几何结构的载体。Preferably, the carrier includes a prepared shaped plate, honeycomb or carrier with a specific geometric structure.
优选地，所述载体的原料包括分子筛、二氧化钛或多孔陶瓷中的一种或多种。Preferably, the raw material of the carrier includes one or more of molecular sieves, titanium dioxide or porous ceramics.
优选地，所述载体置于钛醇盐液中之前，先进行预处理；优选地，所述预处理为对所述载体进行除灰、清洗和烘干。Preferably, the carrier is pre-treated before being placed in the titanium alkoxide solution; preferably, the pre-treatment includes dust removal, cleaning and drying of the carrier.
进一步地，所述过热蒸汽的通入量为化学消耗量的1.05～10倍。Further, the amount of superheated steam introduced is 1.05 to 10 times the chemical consumption.
优选地，所述过热蒸汽的通入量为化学消耗量的3～5倍。Preferably, the amount of superheated steam introduced is 3 to 5 times the chemical consumption.
进一步地，所述反应的温度为80～180℃。Further, the temperature of the reaction is 80-180°C.
优选地，所述反应的温度不低于反应生成醇类操作压力下的沸点温度，可以加快反应进程。Preferably, the temperature of the reaction is not lower than the boiling point temperature of the alcohol produced by the reaction under the operating pressure, which can speed up the reaction process.
所述制备涂覆钛酸的载体，在提供活性载体的同时，利用自身羟基的强键合力，使其与结构载体牢固结合，同时为所述负载催化氧化活性组分的步骤操作提供丰富的活性组分键合位点。The preparation of a titanic acid-coated carrier not only provides an active carrier, but also utilizes the strong bonding force of its own hydroxyl groups to firmly combine with the structural carrier, and at the same time provides abundant activity for the step of loading the catalytic oxidation active component. Component bonding sites.
进一步地，所述负载催化氧化活性组分是将所述涂覆钛酸的载体置于催化氧化活性组分的溶液A中浸泡0.5～2小时，在55～90℃烘干6～24小时，随后在310～380℃煅烧2～6小时。Further, the method of loading the catalytic oxidation active component is to place the titanic acid-coated carrier in the solution A of the catalytic oxidation active component, soak it for 0.5 to 2 hours, and dry it at 55 to 90°C for 6 to 24 hours. It is then calcined at 310-380°C for 2-6 hours.
优选的，所述煅烧温度为350±5℃，煅烧时间为3小时。Preferably, the calcination temperature is 350±5°C and the calcination time is 3 hours.
优选地，所述溶液A包括醋酸铜、醋酸锰、醋酸钠和柠檬酸中一种或多种的混合溶液。Preferably, the solution A includes a mixed solution of one or more of copper acetate, manganese acetate, sodium acetate and citric acid.
优选地，所述混合溶液中，醋酸铜、醋酸锰、醋酸钠和柠檬酸的摩尔比为5～7：10～12：0.5～1.5：11～18；更优选地，所述醋酸铜、醋酸锰、醋酸钠、柠檬酸的摩尔比为6：12：1：11～18。Preferably, in the mixed solution, the molar ratio of copper acetate, manganese acetate, sodium acetate and citric acid is 5-7:10-12:0.5-1.5:11-18; more preferably, the molar ratio of copper acetate, acetic acid The molar ratio of manganese, sodium acetate and citric acid is 6:12:1:11~18.
优选地，所述混合溶液的温度控制在40～50℃，总溶质浓度280～350g/L。升高所述混合液体温度可加快溶质的溶解，提高溶解度，同时降低了液体的粘度，提高浸润效果。液体温度过高则会加快酸性气体的挥发，导致溶质组分的提前析出。而液体温度过低，溶质难以溶解。因此，在40～50℃的温度区间液体综合状态达到最佳。Preferably, the temperature of the mixed solution is controlled at 40-50°C, and the total solute concentration is 280-350g/L. Increasing the temperature of the mixed liquid can accelerate the dissolution of the solute, increase the solubility, and at the same time reduce the viscosity of the liquid and improve the infiltration effect. If the liquid temperature is too high, the volatilization of acidic gases will be accelerated, leading to early precipitation of solute components. If the liquid temperature is too low, the solute is difficult to dissolve. Therefore, the comprehensive state of the liquid reaches its optimum in the temperature range of 40 to 50°C.
优选的，所述烘干温度为65～80℃，所述烘干时间为16～20小时。Preferably, the drying temperature is 65-80°C, and the drying time is 16-20 hours.
在烘干过程中，随着酸性气体的挥发，活性组分Cu、Mn、Na以柠檬酸盐的形态沉积并均匀分散在载体表面和内部孔隙。During the drying process, as the acidic gas volatilizes, the active components Cu, Mn, and Na are deposited in the form of citrate and evenly dispersed on the surface and internal pores of the carrier.
制备涂覆钛酸的载体和负载催化氧化活性组分两步骤充分利用钛酸丰富的羟基与铜、锰离子的强键合力，使其高度分散并与钛原子紧密键合，经上述处理过程后，得到高活性的VOCs脱除催化剂，同时具有较好的NOx脱除效率，但SCR氮气选择性较差。The two steps of preparing the carrier coated with titanic acid and loading the catalytic oxidation active component make full use of the strong bonding force between the abundant hydroxyl groups of titanic acid and copper and manganese ions, making it highly dispersed and tightly bonded with titanium atoms. After the above treatment process , a highly active VOCs removal catalyst is obtained with good NOx removal efficiency, but the SCR nitrogen selectivity is poor.
进一步地，所述包覆第二活性组分是将所述负载催化氧化活性组分的产物置入混合液体B中浸泡0.5～2小时，取出沥干后，在80～150℃烘干1～6小时，随后在310～420℃煅烧2～6小时。Further, the method of coating the second active component is to put the product loaded with the catalytic oxidation active component into the mixed liquid B and soak it for 0.5 to 2 hours, take it out and drain it, and then dry it at 80 to 150°C for 1 to 6 hours, and then calcined at 310~420℃ for 2~6 hours.
优选地，所述混合液体B包括醋酸铁和钒的草酸盐混合溶液。Preferably, the mixed liquid B includes an oxalate mixed solution of iron acetate and vanadium.
优选地，所述醋酸铁、钒的草酸盐的摩尔比为1：15～20。Preferably, the molar ratio of iron acetate and vanadium oxalate is 1:15-20.
优选地，所述混合液体B的总溶质浓度55～165g/L。Preferably, the total solute concentration of the mixed liquid B is 55 to 165 g/L.
申请人发现加入铁可以抑制活性组分钒的团聚并减小团簇尺度，从而改善包覆效果，增强低温段NH3-SCR活性。The applicant found that adding iron can inhibit the agglomeration of the active component vanadium and reduce the cluster size, thereby improving the coating effect and enhancing the NH3 -SCR activity in the low temperature section.
优选的，所述煅烧温度为380～400℃，煅烧时间为5小时。Preferably, the calcination temperature is 380-400°C, and the calcination time is 5 hours.
所述包覆第二活性组分的设计原理，是利用其对NH3的强吸附作用，使气体中绝大部分的NH3优先吸附于催化剂的外包覆层参与SCR反应，从而避免了被内层活性组分铜锰过度氧化生成氧化亚氮，氮气选择性因此显著提高。The design principle of the second active component coating is to utilize its strong adsorption effect on NH3 so that most of the NH3 in the gas is preferentially adsorbed on the outer coating layer of the catalyst to participate in the SCR reaction, thereby avoiding being The active component copper and manganese in the inner layer is over-oxidized to generate nitrous oxide, so the nitrogen selectivity is significantly improved.
所述包覆结构的设计，不仅显著提高了催化剂的氮气选择性，同时也消除了NH3对VOCs催化氧化过程的抑制作用。这一增益效果与外包覆层对传质过程的不利影响相互抵消，催化剂的VOCs脱除活性保持不变。The design of the coating structure not only significantly improves the nitrogen selectivity of the catalyst, but also eliminates the inhibitory effect of NH3 on the catalytic oxidation process of VOCs. This gain effect is offset by the adverse effect of the outer coating on the mass transfer process, and the VOCs removal activity of the catalyst remains unchanged.
本发明还提供一种所述的制备方法制得的复合功能涂层催化剂，用于协同脱除NOx和苯系物VOCs。The invention also provides a composite functional coating catalyst prepared by the preparation method, which is used to collaboratively remove NOx and benzene series VOCs.
相比现有技术，本发明的催化剂结构设计上采用涂覆工艺，利用钛酸羟基的强键合力，实现了结构载体与活性载体以及活性组分牢固结合。在活性组分涂层的设计上采取分别赋能的方法，依次涂覆以VOC脱除为主的铜锰催化氧化功能层、以NOx脱除为主的NH3-SCR包覆层，得到了复合功能涂层催化剂。所得催化剂的催化氧化温度T90低至195℃，该温度下NOx的转化率和N2选择性分别高达95％和98％。Compared with the existing technology, the catalyst structure design of the present invention adopts a coating process and utilizes the strong bonding force of the titanate hydroxyl group to achieve a firm combination of the structural carrier, the active carrier and the active components. In the design of the active component coating, the method of separate empowerment is adopted, and the copper-manganese catalytic oxidation functional layer mainly for VOC removal and the NH3 -SCR coating layer mainly for NOx removal are sequentially coated to obtain Composite functional coating catalyst. The catalytic oxidation temperature T of the resulting catalyst is as low as195 °C, and the NOx conversion rate and Nselectivity at this temperature are as high as 95% and 98%, respectively.
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5所得催化剂不同温度下NOx和甲苯转化率曲线图。Figure 1 is a graph showing the NOx and toluene conversion rates of the catalyst obtained in Example 5 at different temperatures.
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.
催化剂NOx脱除活性测试条件：反应温度150～300℃，催化剂装填体积5L，模拟气流速25Nm3/h，NO浓度500ppm，氨氮摩尔比＝1.0，氧浓度6.0％，水含量8.0％，氮气为平衡气。Catalyst NOx removal activity test conditions: reaction temperature 150~300℃, catalyst filling volume 5L, simulated gas flow rate25Nm3 /h, NO concentration 500ppm, ammonia nitrogen molar ratio = 1.0, oxygen concentration 6.0%, water content 8.0%, nitrogen Balance Qi.
催化剂VOCs脱除活性检测以甲苯为模型化合物的测试条件：反应温度150～300℃，催化剂装填体积5L，模拟气流速25Nm3/h，VOCs模型化合物甲苯浓度1000ppm，氧浓度6.0％，水含量8.0％，氮气为平衡气。Test conditions for catalyst VOCs removal activity using toluene as the model compound: reaction temperature 150-300°C, catalyst filling volume 5L, simulated gas flow rate25Nm3 /h, VOCs model compound toluene concentration 1000ppm, oxygen concentration 6.0%, water content 8.0 %, nitrogen is the balance gas.
实施例1Example 1
一种复合功能涂层催化剂的制备方法：A method for preparing a composite functional coating catalyst:
(1)将除灰、清洗和烘干后的蜂窝陶瓷载体置于正丁醇钛溶液中浸泡3小时，取出沥干后，通入化学消耗量10倍的过热蒸汽在80℃反应3小时，得到涂覆钛酸的载体。(1) Soak the honeycomb ceramic carrier after dust removal, cleaning and drying in titanium n-butoxide solution for 3 hours. After taking it out and draining it, add superheated steam with 10 times the chemical consumption to react at 80°C for 3 hours. A titanate-coated support was obtained.
(2)将步骤(1)所得载体在摩尔比6：12：1：18的醋酸铜、醋酸锰、醋酸钠、柠檬酸的混合溶液浸泡2小时。控制混合液的温度为50℃，总溶质浓度350g/L，取出沥干后在90℃烘干6小时，将烘干后的产物在310℃煅烧6小时。(2) Soak the carrier obtained in step (1) in a mixed solution of copper acetate, manganese acetate, sodium acetate, and citric acid in a molar ratio of 6:12:1:18 for 2 hours. Control the temperature of the mixed solution to 50°C and the total solute concentration to 350g/L. Take it out and drain it, dry it at 90°C for 6 hours, and calcine the dried product at 310°C for 6 hours.
(3)将步骤(2)所得产物在摩尔比1：20的醋酸铁、草酸氧钒混合溶液中浸泡2小时，混合液总溶质浓度165g/L，取出沥干后，在150℃烘干1小时，将烘干后的产物在420℃煅烧2小时。(3) Soak the product obtained in step (2) in a mixed solution of iron acetate and vanadyl oxalate with a molar ratio of 1:20 for 2 hours. The total solute concentration of the mixed solution is 165g/L. Take it out and drain it, and dry it at 150°C for 1 hour. hours, and the dried product was calcined at 420°C for 2 hours.
煅烧后即得协同脱除NOx和苯系物VOCs的复合功能涂层催化剂。所得催化剂性能见表1。After calcination, a composite functional coating catalyst that can synergistically remove NOx and benzene series VOCs is obtained. The obtained catalyst properties are shown in Table 1.
实施例2Example 2
一种复合功能涂层催化剂的制备方法：A method for preparing a composite functional coating catalyst:
(1)将除灰、清洗和烘干后的蜂窝陶瓷载体置于异丙醇钛溶液中浸泡0.5小时，取出沥干后，通入化学消耗量1.05倍的过热蒸汽在180℃反应0.5小时，得到涂覆钛酸的载体。(1) Soak the honeycomb ceramic carrier after dust removal, cleaning and drying in titanium isopropoxide solution for 0.5 hours. After taking it out and draining it, add superheated steam with 1.05 times the chemical consumption to react at 180°C for 0.5 hours. A titanate-coated support was obtained.
(2)将步骤(1)所得载体在摩尔比6：12：1：11的醋酸铜、醋酸锰、醋酸钠、柠檬酸的混合溶液浸泡0.5小时。控制混合液的温度为40℃，总溶质浓度350g/L，取出沥干后在55℃烘干24小时，将烘干后的产物在380℃煅烧2小时。(2) Soak the carrier obtained in step (1) in a mixed solution of copper acetate, manganese acetate, sodium acetate, and citric acid in a molar ratio of 6:12:1:11 for 0.5 hours. Control the temperature of the mixed solution to 40°C and the total solute concentration to 350g/L. Take it out and drain it, dry it at 55°C for 24 hours, and calcine the dried product at 380°C for 2 hours.
(3)将步骤(2)所得产物在摩尔比1：15的醋酸铁、草酸钒混合溶液中浸泡0.5小时，混合液总溶质浓度55g/L，取出沥干后，在80℃烘干6小时，将烘干后的载体在310℃煅烧6小时。(3) Soak the product obtained in step (2) in a mixed solution of iron acetate and vanadium oxalate with a molar ratio of 1:15 for 0.5 hours. The total solute concentration of the mixed solution is 55g/L. Take it out and drain it, and dry it at 80°C for 6 hours. , calcine the dried carrier at 310°C for 6 hours.
煅烧后即得协同脱除NOx和苯系物VOCs的复合功能涂层催化剂。所得催化剂性能见表1。After calcination, a composite functional coating catalyst that can synergistically remove NOx and benzene series VOCs is obtained. The obtained catalyst properties are shown in Table 1.
实施例3Example 3
一种复合功能涂层催化剂的制备方法：A method for preparing a composite functional coating catalyst:
(1)将除灰、清洗和烘干后的蜂窝陶瓷载体置于正丁醇钛溶液中浸泡1小时，取出沥干后，通入化学消耗量3倍的过热蒸汽在170℃反应1.5小时，得到涂覆钛酸的载体。(1) Soak the honeycomb ceramic carrier after dust removal, cleaning and drying in titanium n-butoxide solution for 1 hour. After taking it out and draining it, add superheated steam with 3 times the chemical consumption to react at 170°C for 1.5 hours. A titanate-coated support was obtained.
(2)将步骤(1)所得载体在摩尔比6：12：1：16的醋酸铜、醋酸锰、醋酸钠、柠檬酸的混合溶液浸泡1小时。控制混合液的温度为45℃，总溶质浓度350g/L，取出沥干后在65℃烘干16小时，将烘干后的产物在350℃煅烧3小时。(2) Soak the carrier obtained in step (1) in a mixed solution of copper acetate, manganese acetate, sodium acetate, and citric acid in a molar ratio of 6:12:1:16 for 1 hour. Control the temperature of the mixed solution to 45°C and the total solute concentration to 350g/L. Take it out and drain it, dry it at 65°C for 16 hours, and calcine the dried product at 350°C for 3 hours.
(3)将步骤(2)所得产物在摩尔比1：18的醋酸铁、草酸氧钒混合溶液中浸泡1.5小时，混合液总溶质浓度155g/L，取出沥干后，在100℃烘干3小时，将烘干后的载体在380℃煅烧5小时。(3) Soak the product obtained in step (2) in a mixed solution of iron acetate and vanadyl oxalate with a molar ratio of 1:18 for 1.5 hours. The total solute concentration of the mixed solution is 155g/L. Take it out and drain it, and dry it at 100°C for 3 hours, the dried carrier was calcined at 380°C for 5 hours.
煅烧后即得协同脱除NOx和苯系物VOCs的复合功能涂层催化剂。所得催化剂性能见表1。After calcination, a composite functional coating catalyst that can synergistically remove NOx and benzene series VOCs is obtained. The obtained catalyst properties are shown in Table 1.
实施例4Example 4
一种复合功能涂层催化剂的制备方法：A method for preparing a composite functional coating catalyst:
(1)将除灰、清洗和烘干后的板式二氧化钛载体置于正丁醇钛溶液中浸泡1小时，取出沥干后，通入化学消耗量5倍的过热蒸汽在170℃反应1.5小时，得到涂覆钛酸的载体。(1) Soak the plate-type titanium dioxide carrier after dust removal, cleaning and drying in titanium n-butoxide solution for 1 hour. After taking it out and draining it, add superheated steam with 5 times the chemical consumption and react at 170°C for 1.5 hours. A titanate-coated support was obtained.
(2)将步骤(1)所得载体在摩尔比6：12：1：16的醋酸铜、醋酸锰、醋酸钠、柠檬酸的混合溶液浸泡1小时。控制混合液的温度为45℃，总溶质浓度350g/L，取出沥干后在80℃烘干20小时，将烘干后的产物在355℃煅烧3小时。(2) Soak the carrier obtained in step (1) in a mixed solution of copper acetate, manganese acetate, sodium acetate, and citric acid in a molar ratio of 6:12:1:16 for 1 hour. Control the temperature of the mixed solution to 45°C and the total solute concentration to 350g/L. Take it out and drain it, dry it at 80°C for 20 hours, and calcine the dried product at 355°C for 3 hours.
(3)将步骤(2)所得产物在摩尔比1：18的醋酸铁、草酸氧钒混合溶液中浸泡1.5小时，混合液总溶质浓度155g/L，取出沥干后，在120℃烘干3小时，将烘干后的载体在420℃煅烧5小时。(3) Soak the product obtained in step (2) in a mixed solution of iron acetate and vanadyl oxalate with a molar ratio of 1:18 for 1.5 hours. The total solute concentration of the mixed solution is 155g/L. Take it out and drain it, and dry it at 120°C for 3 hours, the dried carrier was calcined at 420°C for 5 hours.
煅烧后即得协同脱除NOx和苯系物VOCs的复合功能涂层催化剂。所得催化剂性能见表1。After calcination, a composite functional coating catalyst that can synergistically remove NOx and benzene series VOCs is obtained. The obtained catalyst properties are shown in Table 1.
实施例5Example 5
一种复合功能涂层催化剂的制备方法：A method for preparing a composite functional coating catalyst:
(1)将除灰、清洗和烘干后的蜂窝陶瓷载体置于正丁醇钛溶液中浸泡1小时，取出沥干后，通入化学消耗量5倍的过热蒸汽在生成醇沸点温度下反应2.5小时，得到涂覆钛酸的载体。(1) Soak the honeycomb ceramic carrier after dust removal, cleaning and drying in titanium n-butoxide solution for 1 hour. After taking it out and draining it, add superheated steam with 5 times the chemical consumption to react at the boiling point temperature of alcohol. After 2.5 hours, a titanate-coated carrier was obtained.
(2)将步骤(1)所得载体在摩尔比6：12：1：17的醋酸铜、醋酸锰、醋酸钠、柠檬酸的混合溶液浸泡1小时。控制混合液的温度为50℃，总溶质浓度350g/L，取出沥干后在80℃烘干18小时，将烘干后的产物在350℃煅烧3小时。(2) Soak the carrier obtained in step (1) in a mixed solution of copper acetate, manganese acetate, sodium acetate, and citric acid in a molar ratio of 6:12:1:17 for 1 hour. Control the temperature of the mixed solution to 50°C and the total solute concentration to 350g/L. Take it out and drain it, dry it at 80°C for 18 hours, and calcine the dried product at 350°C for 3 hours.
(3)将步骤(2)所得产物在摩尔比1：18的醋酸铁、草酸氧钒混合溶液中浸泡1小时，混合液总溶质浓度155g/L，取出沥干后，在120℃烘干3小时，将烘干后的载体在420℃煅烧3小时。(3) Soak the product obtained in step (2) in a mixed solution of iron acetate and vanadyl oxalate with a molar ratio of 1:18 for 1 hour. The total solute concentration of the mixed solution is 155g/L. Take it out and drain it, and dry it at 120°C for 3 seconds. hours, the dried carrier was calcined at 420°C for 3 hours.
煅烧后即得协同脱除NOx和苯系物VOCs的复合功能涂层催化剂。所得催化剂性能见图1和表1。After calcination, a composite functional coating catalyst that can synergistically remove NOx and benzene series VOCs is obtained. The obtained catalyst properties are shown in Figure 1 and Table 1.
实施例6Example 6
一种复合功能涂层催化剂的制备方法：A method for preparing a composite functional coating catalyst:
(1)将除灰、清洗和烘干后的蜂窝陶瓷载体置于正丁醇钛溶液中浸泡1小时，取出沥干后，通入化学消耗量5倍的过热蒸汽在不低于生成醇沸点温度下反应2.5小时，得到涂覆钛酸的载体。(1) Soak the honeycomb ceramic carrier after dust removal, cleaning and drying in titanium n-butoxide solution for 1 hour. After taking it out and draining it, introduce superheated steam with 5 times the chemical consumption at no less than the boiling point of the generated alcohol. The reaction was carried out for 2.5 hours at room temperature to obtain a titanate-coated carrier.
(2)将步骤(1)所得载体在摩尔比5：11：1.5：15的醋酸铜、醋酸锰、醋酸钠、柠檬酸的混合溶液浸泡2小时。控制混合液的温度为50℃，总溶质浓度350g/L，取出沥干后在80℃烘干16小时，将烘干后的产物在350℃煅烧3小时。(2) Soak the carrier obtained in step (1) in a mixed solution of copper acetate, manganese acetate, sodium acetate, and citric acid in a molar ratio of 5:11:1.5:15 for 2 hours. Control the temperature of the mixed solution to 50°C and the total solute concentration to 350g/L. Take it out and drain it, dry it at 80°C for 16 hours, and calcine the dried product at 350°C for 3 hours.
(3)将步骤(2)所得产物在摩尔比1：18的醋酸铁、草酸氧钒混合溶液中浸泡1小时，混合液总溶质浓度155g/L，取出沥干后，在120℃烘干3小时，将烘干后的载体在400℃煅烧5小时。(3) Soak the product obtained in step (2) in a mixed solution of iron acetate and vanadyl oxalate with a molar ratio of 1:18 for 1 hour. The total solute concentration of the mixed solution is 155g/L. Take it out and drain it, and dry it at 120°C for 3 seconds. hours, the dried carrier was calcined at 400°C for 5 hours.
煅烧后即得协同脱除NOx和苯系物VOCs的复合功能涂层催化剂。所得催化剂性能见表1。After calcination, a composite functional coating catalyst that can synergistically remove NOx and benzene series VOCs is obtained. The obtained catalyst properties are shown in Table 1.
对比例1Comparative example 1
一种协同脱除NOx和苯系物VOCs的催化剂的制备方法：A preparation method for a catalyst that synergistically removes NOx and benzene VOCs:
(1)将除灰、清洗和烘干后的蜂窝陶瓷载体置于正丁醇钛溶液中浸泡1小时，取出沥干后，通入化学消耗量5倍的过热蒸汽在170℃反应1.5小时，得到涂覆钛酸的载体。(1) Soak the honeycomb ceramic carrier after dust removal, cleaning and drying in titanium n-butoxide solution for 1 hour. After taking it out and draining it, add superheated steam with 5 times the chemical consumption and react at 170°C for 1.5 hours. A titanate-coated support was obtained.
(2)将步骤(1)所得载体在摩尔比6：12：1：16的醋酸铜、醋酸锰、醋酸钠、柠檬酸的混合溶液浸泡1小时。控制混合液的温度为45℃，总溶质浓度350g/L，取出沥干后在80℃烘干20小时，将烘干后的载体在355℃煅烧3小时。(2) Soak the carrier obtained in step (1) in a mixed solution of copper acetate, manganese acetate, sodium acetate, and citric acid in a molar ratio of 6:12:1:16 for 1 hour. Control the temperature of the mixed solution to 45°C and the total solute concentration to 350g/L. Take it out and drain it, dry it at 80°C for 20 hours, and calcine the dried carrier at 355°C for 3 hours.
煅烧后即得该催化剂。所得催化剂性能见表1。The catalyst is obtained after calcination. The obtained catalyst properties are shown in Table 1.
对比例2Comparative example 2
一种协同脱除NOx和苯系物VOCs的催化剂的制备方法：A preparation method for a catalyst that synergistically removes NOx and benzene VOCs:
(1)将除灰、清洗和烘干后的蜂窝陶瓷置于正丁醇钛溶液中浸泡1小时，取出沥干后，通入化学消耗量5倍的过热蒸汽在170℃反应1.5小时，得到涂覆钛酸的载体。(1) Soak the honeycomb ceramics after dust removal, cleaning and drying in titanium n-butoxide solution for 1 hour. After taking it out and draining it, add superheated steam with 5 times the chemical consumption and react at 170°C for 1.5 hours to obtain Titanic acid coated carrier.
(2)将步骤(1)所得载体在摩尔比1：18的醋酸铁、草酸氧钒混合溶液中浸泡1.5小时，混合液总溶质浓度155g/L，取出沥干后，在120℃烘干3小时，将烘干后的载体在420℃煅烧5小时。(2) Soak the carrier obtained in step (1) in a mixed solution of iron acetate and vanadyl oxalate with a molar ratio of 1:18 for 1.5 hours. The total solute concentration of the mixed solution is 155g/L. Take it out and drain it, and dry it at 120°C for 3 seconds. hours, the dried carrier was calcined at 420°C for 5 hours.
煅烧后即得该催化剂。所得催化剂性能见表1。The catalyst is obtained after calcination. The obtained catalyst properties are shown in Table 1.
对比例3Comparative example 3
一种协同脱除NOx和苯系物VOCs的催化剂的制备方法：A preparation method for a catalyst that synergistically removes NOx and benzene VOCs:
(1)将除灰、清洗和烘干后的蜂窝陶瓷载体在摩尔比6：12：1：16的醋酸铜、醋酸锰、醋酸钠、柠檬酸的混合溶液浸泡1小时。控制混合液的温度为45℃，总溶质浓度350g/L，取出沥干后在80℃烘干20小时。将烘干后的产物在355℃煅烧3小时。(1) Soak the honeycomb ceramic carrier after dust removal, cleaning and drying in a mixed solution of copper acetate, manganese acetate, sodium acetate and citric acid in a molar ratio of 6:12:1:16 for 1 hour. Control the temperature of the mixed solution to 45°C and the total solute concentration to 350g/L. Take it out and drain it and dry it at 80°C for 20 hours. The dried product was calcined at 355°C for 3 hours.
(2)将步骤(1)所得产物在摩尔比1：18的醋酸铁、草酸氧钒混合溶液中浸泡1.5小时，混合液总溶质浓度155g/L，取出沥干后，在120℃烘干3小时，将烘干后的载体在420℃煅烧5小时。(2) Soak the product obtained in step (1) in a mixed solution of iron acetate and vanadyl oxalate with a molar ratio of 1:18 for 1.5 hours. The total solute concentration of the mixed solution is 155g/L. Take it out and drain it, and dry it at 120°C for 3 seconds. hours, the dried carrier was calcined at 420°C for 5 hours.
煅烧后即得该催化剂。所得催化剂性能见表1。The catalyst is obtained after calcination. The obtained catalyst properties are shown in Table 1.
表1实施例1～6及对比例1～3的催化剂240℃性能检测结果Table 1 240°C performance test results of catalysts of Examples 1 to 6 and Comparative Examples 1 to 3
由图1和表1中可以看出，本发明实施例1～6所得的催化剂具有较低VOCs催化氧化脱除温度，同时表现出优异的NOx脱除率和N2选择性。As can be seen from Figure 1 and Table 1, the catalysts obtained in Examples 1 to 6 of the present invention have lower VOCs catalytic oxidation removal temperatures, and at the same time exhibit excellent NOx removal rate and N2 selectivity.
对比例1～3的结果表明，催化剂制备过程中，活性载体层、VOCs催化氧化层、NH3-SCR包覆层缺一不可，三者之间紧密配合、分工协作方可实现NOx和VOCs的高效脱除和高N2选择性。The results of Comparative Examples 1 to 3 show that during the catalyst preparation process, the active carrier layer, VOCs catalytic oxidation layer, and NH3 -SCR coating layer are indispensable. Only by close cooperation and division of labor between the three can the reduction of NOx and VOCs be achieved. Efficient removal and highN selectivity.
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 protection scope of this patent application should be determined by the appended claims.
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| CN202311409946.9ACN117463356B (en) | 2023-10-27 | 2023-10-27 | Composite functional coating catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07155599A (en)* | 1993-12-10 | 1995-06-20 | Babcock Hitachi Kk | Catalyst for removal of nox in water gas and its production |
| CN103933971A (en)* | 2014-04-23 | 2014-07-23 | 中国科学院山西煤炭化学研究所 | Low-temperature denitration catalyst as well as preparation method and application thereof |
| CN104383926A (en)* | 2014-11-14 | 2015-03-04 | 浙江工业大学 | Flue gas denitration catalyst as well as preparing method and application thereof |
| BR102018015844A2 (en)* | 2018-08-02 | 2020-02-11 | Instituto De Tecnologia E Pesquisa | IMMOBILIZATION OF TIO2 NANOPARTICLES IN POLYMERIC FIBERS AND PRODUCT OBTAINED |
| CN116920873A (en)* | 2023-08-23 | 2023-10-24 | 中国科学院山西煤炭化学研究所 | A catalyst for collaborative removal of toluene and NOx and its preparation method and application |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07155599A (en)* | 1993-12-10 | 1995-06-20 | Babcock Hitachi Kk | Catalyst for removal of nox in water gas and its production |
| CN103933971A (en)* | 2014-04-23 | 2014-07-23 | 中国科学院山西煤炭化学研究所 | Low-temperature denitration catalyst as well as preparation method and application thereof |
| CN104383926A (en)* | 2014-11-14 | 2015-03-04 | 浙江工业大学 | Flue gas denitration catalyst as well as preparing method and application thereof |
| BR102018015844A2 (en)* | 2018-08-02 | 2020-02-11 | Instituto De Tecnologia E Pesquisa | IMMOBILIZATION OF TIO2 NANOPARTICLES IN POLYMERIC FIBERS AND PRODUCT OBTAINED |
| CN116920873A (en)* | 2023-08-23 | 2023-10-24 | 中国科学院山西煤炭化学研究所 | A catalyst for collaborative removal of toluene and NOx and its preparation method and application |
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| CN117463356B (en) | 2025-09-05 |
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