WO2020151577A1 - 磷酸修饰的氧化铈催化剂及其制备方法和应用 - Google Patents

磷酸修饰的氧化铈催化剂及其制备方法和应用 Download PDF

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WO2020151577A1
WO2020151577A1 PCT/CN2020/072585 CN2020072585W WO2020151577A1 WO 2020151577 A1 WO2020151577 A1 WO 2020151577A1 CN 2020072585 W CN2020072585 W CN 2020072585W WO 2020151577 A1 WO2020151577 A1 WO 2020151577A1
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cerium oxide
phosphoric acid
catalyst
oxide catalyst
chlorine
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French (fr)
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吴忠标
翁小乐
戴晓霞
刘越
王海强
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Zhejiang University
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Zhejiang University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B01J27/1804—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8659—Removing halogens or halogen compounds
    • B01D53/8662—Organic halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/206—Organic halogen compounds
    • B01D2257/2064—Chlorine

Definitions

  • the invention relates to the technical field of air pollution control, in particular to a phosphoric acid modified cerium oxide catalyst and a preparation method and application thereof.
  • Chlorine-containing volatile organic compounds are a type of organic matter, such as chlorobenzene, dichlorobenzene, trichloroethylene, etc., which are commonly used reagents in industrial production processes and are discharged into the environment in the form of waste water or exhaust gas. Most of the chlorinated volatile organic compounds are environmentally persistent and highly toxic. They can exist for a long time in the atmosphere or water environment, and accumulate in organisms through the food chain, causing "carcinogenic, teratogenic, and mutagenic" effects. Chlorine-containing organic compounds are generally toxic. The U.S.
  • Environmental Protection Agency screened out 65 categories and 129 priority control "blacklists" from more than 70,000 compounds based on the toxicity of the compounds, the possibility of natural degradation, and the probability of occurrence in water. , Of which there are 7 kinds of PCBs and related compounds.
  • the most serious pollutants to my country's environment include one type of polychlorinated biphenyls, four types of chlorinated benzenes, and ten types of halogenated hydrocarbons. It can be seen that the pollution of organic chlorides is quite common and serious, so the treatment of organic chlorides is currently an important part of environmental protection.
  • Chlorine-containing volatile organic compounds can be roughly divided into two categories: one is low molecular weight organic chlorides, mainly including chloroform, carbon tetrachloride, dichloroethane, trichloroethylene, trichloroethane, and tetrachloride Ethylene, chlorobenzene, etc.; the second is polychlorinated compounds, including polychlorinated biphenyl furans and dioxins. Most of these compounds come from organic solvents in industrial applications, fire extinguishing agents, thermal conductive fluids, intermediates of chemical products, and by-products of the power industry. Their concentration in industrial waste gas or incineration plants varies greatly.
  • the former is typically between 200 and 2000 ppm, while the latter is usually less than 1 ng/m 3 .
  • Organized emission of chlorine-containing volatile organic compounds can generally be collected and processed to effectively reduce the content in the exhaust gas.
  • the development and application of high-efficiency terminal processing technology is the focus of current research work.
  • low-temperature plasma technology and membrane separation technology have gradually emerged in the treatment of low-concentration organic waste gas, and photocatalytic technology has also been further developed.
  • the commonly used control technologies mainly include thermal combustion, catalytic combustion, adsorption, absorption, condensation, etc.
  • the removal efficiency is usually related to the inlet concentration.
  • Catalytic combustion technology has become one of the most promising technologies due to its high processing efficiency, low energy consumption, heat recovery and no secondary pollution.
  • the key problem to be solved in the development of catalysts in the catalytic combustion of chlorinated volatile organic pollutants is to increase the service life of the catalyst.
  • transition metal oxides such as manganese oxide and cerium oxide show good activity in the catalytic combustion of chlorine-containing organic substances, these transition metal oxides can even achieve the same catalytic activity as noble metals, but they cannot avoid catalyst chlorination.
  • the problem of poisoning The chlorine adsorbed on the surface of the catalyst can form oxychloride or chloride with metal ions, thereby reducing the number of active centers of the catalyst or affecting the redox performance of the active centers, and inhibiting the activity of the catalyst.
  • this process also increases the environmental risk of producing highly toxic polychlorinated by-products, especially dioxins.
  • the Chinese patent document with the publication number CN108295852A discloses a Ce-Zr catalyst for the catalytic oxidation of chlorine-containing volatile organic compounds, especially a Ru/CeZrO x type catalyst, which can maintain a relatively high temperature at a lower temperature. Good activity and conversion rate. Due to the use of Ru, the catalyst cost is higher.
  • the Chinese patent document with publication number CN103962134A discloses a method for the combustion and elimination of chlorinated aromatic hydrocarbons, using cerium oxide nanorods, nanocubes and nano-octahedrons as carriers to support precious metal (Ru) ruthenium as a catalyst, and the reaction is absorbed by dilute alkali solution exhaust.
  • the method has high catalytic activity and no secondary pollutants are generated in the reaction. Also, due to the use of Ru, the catalyst cost is relatively high.
  • the Chinese patent document with publication number CN10389425A discloses a catalyst for the combustion of polychlorinated aromatic hydrocarbons, which is Fe, Ni, Cr, Bi or Mn doped with cobalt tetroxide.
  • the catalyst has high catalytic activity and strong resistance to chlorine poisoning, but its structure is fragile and cannot be suitable for exhaust gas treatment at high airspeed.
  • the Chinese patent document with the publication number CN103962127A discloses a catalyst for the combustion of chlorinated aromatic hydrocarbons, which is Sr, Ce, Mg, Al, Fe, Co, Ni, Cu doped perovskite structure LaMnO 3 .
  • the catalyst has the advantages of simple preparation, low cost, good thermal stability, but low catalytic activity and easy low-temperature chlorine poisoning.
  • the existing catalysts for catalytic oxidation of chlorine-containing volatile organic compounds have poor water resistance and sulfur resistance, and have higher requirements for the moisture content and sulfur content of the flue gas of chlorine-containing volatile organic compounds.
  • the flue gas needs to be dehydrated and desulfurized first.
  • the invention provides a phosphoric acid-modified cerium oxide catalyst and a preparation method thereof.
  • the prepared catalyst can be used for the catalytic oxidation and degradation of chlorine-containing volatile organic compounds.
  • the catalyst has high catalytic activity, and has strong resistance to chlorine poisoning, sulfur poisoning and water resistance. , Catalytic life is long, and it is not easy to produce toxic by-products during the catalytic oxidation of chlorine-containing volatile organic compounds, and there is no secondary pollution.
  • a preparation method of phosphoric acid modified cerium oxide catalyst includes the following steps:
  • cerium oxide is immersed in a phosphoric acid solution to introduce characteristic phosphoric acid groups on the surface of the catalyst (it will be converted into trihydroxyphosphate in the presence of water vapor), which can be effectively used in the presence of oxygen and water
  • the chlorine-containing volatile organic compounds are dechlorinated to promote the desorption of chlorine on the catalyst surface and prevent chlorine poisoning of the catalyst.
  • the water in the flue gas promotes the catalytic oxidation process.
  • the experimental data shows that the catalyst also has good resistance. Sulfur performance.
  • the loading of phosphorus in the catalyst has an important effect on the catalytic activity of the catalyst.
  • the loading of phosphorus When the loading of phosphorus is low, it has little effect on the chlorine resistance, sulfur resistance and water resistance of the catalyst, and the increase in catalytic activity is not obvious. A higher loading will reduce the catalytic activity of the catalyst, so the phosphorus loading needs to be controlled.
  • the phosphorus loading in the cerium oxide catalyst is 0.1-5%.
  • the phosphorus loading in the cerium oxide catalyst is 0.3 to 1%.
  • the catalyst When the phosphorus loading is controlled at 0.3 to 1%, the catalyst not only has higher catalytic activity, but also has excellent resistance to chlorine, sulfur and water.
  • the concentration of the phosphoric acid solution is 10 to 200 g/L, and the molar ratio of cerium oxide to phosphoric acid is 1:0.05 to 1. More preferably, the molar ratio of cerium oxide to phosphoric acid is 1. :0.05 ⁇ 0.2.
  • the soaking temperature of cerium oxide is 10 to 80°C, and the soaking time is 0.5 to 3h; more preferably, in step (1), the soaking temperature of cerium oxide is 10 to 40°C, and the soaking time For 0.5 ⁇ 1h.
  • Step (1) After soaking, cooling, filtering and washing, a light yellow precipitate is obtained.
  • step (2) calcination can be performed under nitrogen or air atmosphere.
  • the calcination temperature of the catalyst is too high to obtain a form with good catalytic performance and the catalytic efficiency is reduced; the calcination temperature is too low to obtain a catalyst of the target composition.
  • the calcination temperature is 200-300°C.
  • the catalyst calcination time is not easy to be too long, and the calcination time is too long, which causes the catalyst lattice to collapse and the specific surface area decreases.
  • the calcination time is 1 to 2 hours.
  • the present invention also provides the application of the phosphoric acid-modified cerium oxide catalyst in the catalytic oxidation and degradation of chlorine-containing volatile organic substances, including:
  • the volume fraction of water vapor in the flue gas is 0.1 to 5%
  • the reaction temperature is 100 to 300°C.
  • the mass fraction of water vapor in the flue gas is 0.5-2%.
  • the catalyst's catalytic oxidation efficiency of chlorinated volatile organic compounds is improved.
  • the content of water vapor is 0.5-2%
  • the catalyst shows the best removal efficiency of chlorobenzene, increasing water
  • the catalyst still exhibits better catalytic activity.
  • the reaction temperature is 200-300°C.
  • the cerium oxide catalyst has better oxidation efficiency for chlorine-containing volatile organic compounds in the medium and low temperature zone of 100-300°C, and the catalytic efficiency is the best when the temperature zone is 200-300°C.
  • the present invention has simple preparation process, low cost, and is suitable for large-scale production
  • the CeO 2 catalyst treated by phosphoric acid of the present invention makes full use of CeO 2 due to the reversible conversion of Ce 4+ /Ce 3+ , which has good oxygen storage and release performance and oxygen fluidity, and the effect of phosphate on the water of chlorine-containing organic matter
  • the dechlorination ability enables the catalyst of the present invention to stably convert chlorine-containing volatile organic pollutants into H 2 O, CO 2 and HCl for a long time in the environment of industrial waste gas and flue gas. Better chlorine performance;
  • the catalyst of the present invention uses cheap cerium oxide as the active material and uses phosphoric acid treatment, which greatly increases the life of the catalyst, inhibits the generation of toxic by-products during the catalytic reaction, and avoids secondary pollution.
  • Figure 1 is the SS NMR characterization result diagram of the catalyst prepared in Example 1;
  • Fig. 2 is a graph showing the in-situ infrared characterization results of the catalyst prepared in Example 1.
  • the phosphorus loading of the prepared catalyst is 0.7%.
  • the phosphorus loading of the prepared catalyst is 0.4%.
  • the phosphorus loading of the prepared catalyst is 0.7%.
  • the phosphorus loading of the prepared catalyst is 1.2%.
  • the phosphorus loading of the prepared catalyst is 1.2%.
  • the cerium oxide powder was directly calcined at 300° C. for 2 hours in an air atmosphere to obtain a catalyst.
  • Catalytic oxidation of chlorobenzene with the catalyst prepared in the above 5 examples is as follows:
  • the activity experiment was carried out on a fixed bed reactor, the catalyst loading was 1.0g, and the particle size was 40-60 mesh.
  • the test reaction temperature is 100°C, 150°C, 200°C, 225°C, 250°C, 300°C, and the test data for 1 hour reaction is shown in Table 1.
  • the catalyst prepared by the method of the present invention has better oxidation efficiency for chlorobenzene in the medium and low temperature zone of 150-300°C, especially the catalysts prepared in Examples 1 and 3
  • the catalytic efficiency of 300°C temperature zone is above 90%. It can be seen that the catalyst of the present invention is very suitable for the catalytic oxidation of chlorobenzene in flue gas at medium and low temperature.
  • the following experiments were carried out on a fixed bed reactor with a catalyst loading of 1g and a particle size of 40-60 mesh.
  • the test reaction temperature is 100°C, 150°C, 200°C, 225°C, 250°C, 300°C, and the test data for 1 hour reaction is shown in Table 2.
  • the following experiments were carried out on a fixed bed reactor with a catalyst loading of 1g and a particle size of 40-60 mesh.
  • the specific test reaction temperature is 100°C, 150°C, 200°C, 225°C, 250°C, 300°C, and the test data for 1 hour reaction is shown in Table 3.
  • the following experiments were carried out on a fixed bed reactor with a catalyst loading of 1g and a particle size of 40-60 mesh.
  • the test reaction temperature is 100°C, 150°C, 200°C, 225°C, 250°C, 300°C, and the test data for 1 hour reaction is shown in Table 4.
  • the following experiments were carried out on a fixed bed reactor with a catalyst loading of 1g and a particle size of 40-60 mesh.
  • the test reaction temperature is specifically set at 300°C, N 2 is the carrier gas, and the test data is shown in Table 5.
  • the catalyst of Comparative Example 1 without phosphoric acid modification has poor stability and is prone to chlorine poisoning and loses catalytic activity.
  • the following experiments were carried out on a fixed bed reactor with a catalyst loading of 1g and a particle size of 40-60 mesh.
  • the test reaction temperature is specifically 300°C, N 2 is the carrier gas, and the test data is shown in Table 6.
  • the catalyst of the present invention is highly adaptable to flue gas components and is suitable for various compositions. Used in flue gas.

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Abstract

本发明涉及大气污染控制技术领域，公开了一种磷酸修饰的氧化铈催化剂及其制备方法和应用。所述制备方法包括以下步骤：(1)将氧化铈在磷酸溶液中浸泡，之后过滤出氧化铈并洗涤至中性，烘干；(2)将烘干后的氧化铈于100～400℃下锻烧1～4小时，得到磷酸修饰的氧化铈催化剂。本发明制备方法制得的催化剂可用于含氯挥发性有机物的催化氧化降解，其催化活性高，抗氯中毒、抗硫中毒和抗水能力强，催化寿命较长，并且在催化氧化含氯挥发性有机物时不易产生有毒副产物，无二次污染。

Description

磷酸修饰的氧化铈催化剂及其制备方法和应用 技术领域
本发明涉及大气污染控制技术领域，尤其涉及一种磷酸修饰的氧化铈催化剂及其制备方法和应用。
背景技术
含氯挥发性有机物是有机物的一种，如氯苯、二氯苯、三氯乙烯等，都是工业生产过程中常用的试剂，以废水或废气的形式排放至环境中。大部含氯挥发性有机物具有环境持久性、高毒性，可在大气环境或水环境中长期存在，并通过食物链在生物体内富集，造成“致癌、致畸、致突变”效应。含氯有机化合物普遍具有毒性，美国环保局基于化合物的毒性、自然降解的可能性及在水中出现的概率等因素从7万余种化合物中筛选出65类、129种优先控制的“黑名单”，其中就有7种多氯联苯及有关化合物。在“黑名单”上，对我国环境污染最严重的污染物包括1种多氯联苯、4种氯代苯类、10种卤代烃类。由此可见，有机氯化物的污染相当普遍和严重，因此对有机氯化物的处理是目前环境保护的一项重要工作内容。
含氯挥发性有机化合物大致上可以分为两大类：一是低分子量有机氯化物，主要包括三氯甲烷、四氯化碳、二氯乙烷、三氯乙烯、三氯乙烷、四氯乙烯、氯苯等；二是聚合氯化物，包括多氯联苯呋喃、二噁英等。这些化合物大多数来自于工业应用中的有机溶剂、灭火剂、热导液和化工产品的中间体以及电力工业的副产物。它们在工业废气或焚烧厂中的浓度相差甚大，前者典型浓度在200～2000ppm之间，而后者通常低于1ng/m 3。有组织排放的含氯挥发性有机物一般可经收集和处理有效减少尾气中的含量。作为最后一道防线，高效末端处理技术的开发与应用是目前研究工作重点。近年来，低温等离子体技术、膜分离技术在低浓度有机废气处理中逐渐崭露头角，光催化技术也在进一步的发展中。目前常用的控制技术主要有热力燃烧法、催化燃烧法、吸附法、吸收法、冷凝法等，其去除效率通常与进口浓度相关。在保证去除效率的基础上，结合投资成本、适用工 况与操作安全等方面，现行技术各有优缺点。催化燃烧技术凭借其处理效率高、能耗低、热力可回收和无二次污染的特点成为最具应用前景的技术之一。
含氯挥发性有机污染物催化燃烧中催化剂的开发首要解决的关键问题是提高催化剂的使用寿命。虽然，部分过渡金属氧化物如氧化锰、氧化铈等在催化燃烧含氯有机物中表现出较好的活性，这些过渡金属氧化物甚至可以达到与贵金属一样的催化活性，但是都无法避免催化剂氯化中毒的问题。催化剂表面吸附的氯可与金属离子形成氯氧化合物或氯化物，从而减少催化剂的活性中心数量或影响活性中心的氧化还原性能，并抑制了催化剂的活性。此外，这一过程还增加了生成高毒性多氯副产物，特别是二噁英的环境风险。
公开号为CN108295852A的中国专利文献公开了一种针对含氯挥发性有机物催化氧化反应的Ce-Zr类催化剂，尤其是一种Ru/CeZrO x型催化剂，可以实现在较低的温度下仍保持较好的活性和转化率。由于Ru的使用，催化剂成本较高。
公开号为CN103962134A的中国专利文献公开了一种氯代芳烃燃烧消除的方法，以氧化铈纳米棒、纳米立方体和纳米正八面体为载体负载贵金属(Ru)钌作为催化剂，并通过稀碱溶液吸收反应尾气。该方法催化活性高，反应无二次污染物产生，同样由于Ru的使用，催化剂成本较高。
公开号为CN10389425A的中国专利文献公开了一种用于多氯代芳香烃燃烧的催化剂，其为Fe、Ni、Cr、Bi或Mn掺杂四氧化三钴。该催化剂催化活性高，抗氯中毒能力强，但结构脆弱，无法适用于高空速下的废气处理。
公开号为CN103962127A的中国专利文献公开了一种用于氯代芳烃燃烧的催化剂，其为Sr、Ce、Mg、Al、Fe、Co、Ni、Cu掺杂的钙钛矿结构的LaMnO 3。该催化剂制备简单，成本低廉，热稳定性好，但催化活性低，且易低温氯中毒。
并且现有的含氯挥发性有机物催化氧化的催化剂抗水性和抗硫性较差，对含氯挥发性有机物烟气的含水量和含硫量有较高的要求，在进行催化氧化降解之前，需要先对烟气进行脱水和脱硫。
发明内容
本发明提供了一种磷酸修饰的氧化铈催化剂及其制备方法，制得的催化剂可用于含氯挥发性有机物的催化氧化降解，其催化活性高，抗氯中毒、抗硫中毒和抗水能力强，催化寿命较长，并且在催化氧化含氯挥发性有机物时不易产生有毒副产物，无二次污染。
具体技术方案如下：
一种磷酸修饰的氧化铈催化剂的制备方法，包括以下步骤：
(1)将氧化铈在磷酸溶液中浸泡，之后过滤出氧化铈并洗涤至中性，烘干；
(2)将烘干后的氧化铈于100～400℃下锻烧1～4小时，得到磷酸修饰的氧化铈催化剂。
本发明的制备方法通过将氧化铈于磷酸溶液中浸泡，在催化剂表面引入特征磷酸基团(在有水汽存在的情况下会转化成三羟基磷酸根)，在氧气和水的存在下可以有效地对含氯挥发性有机物进行脱氯处理，从而促进催化剂表面氯的解吸，防止催化剂氯中毒，同时烟气中的水对催化氧化过程有促进作用，实验数据表面，该催化剂同时具有较好的抗硫性能。
催化剂中磷的负载量对催化剂的催化活性具有重要的影响，磷负载量较低时其对催化剂的抗氯、抗硫和抗水性能影响较小，并且催化活性增量不明显，而当磷负载量较高时反而会降低催化剂的催化活性，所以需要控制磷负载量。
优选的，以磷元素的质量百分比计，所述的氧化铈催化剂中磷负载量为0.1～5％。
进一步优选的，以磷元素的质量百分比计，所述的氧化铈催化剂中磷负载量为0.3～1％。
磷负载量控制在0.3～1％时，催化剂不仅具有较高的催化活性，其抗氯、抗硫和抗水性能也比较优异。
优选的，步骤(1)中，所述的磷酸溶液的浓度为10～200g/L，氧化铈与磷酸的摩尔比为1∶0.05～1；进一步优选的，氧化铈与磷酸的摩尔比为1∶0.05～0.2。
优选的，步骤(1)中，氧化铈的浸泡温度为10～80℃，浸泡时间为 0.5～3h；进一步优选的，步骤(1)中，氧化铈的浸泡温度为10～40℃，浸泡时间为0.5～1h。
步骤(1)经过浸泡、冷却、过滤和洗涤后，得到淡黄色沉淀。
步骤(2)中，可在氮气或空气氛围下进行煅烧。
催化剂的煅烧温度太高，得不到具有良好催化性能的形态，催化效率降低；煅烧温度过低，得不到目的组成的催化剂。
优选的，步骤(2)中，煅烧温度为200～300℃。
催化剂煅烧时间也不易太长，煅烧时间太长，导致催化剂晶格塌陷，比表面积降低。
优选的，步骤(2)中，煅烧时间为1～2h。
本发明还提供了所述磷酸修饰的氧化铈催化剂在催化氧化降解含氯挥发性有机物中的应用，包括：
将含有含氯挥发性有机物和水蒸气的烟气在所述氧化铈催化剂的作用下进行反应；
所述烟气中，水蒸气的体积分数为0.1～5％；
反应温度为100～300℃。
优选的，所述烟气中，水蒸气的质量分数为0.5～2％。
适当提高烟气中水蒸气的含量，催化剂对含氯挥发性有机物的催化氧化效率所提高，当水蒸气的含量为0.5～2％时，催化剂表现出最佳的氯苯脱除效率，增加水蒸气的含量增至5％时，催化剂仍表现出较好的催化活性。
优选的，反应温度为200～300℃。
所述的氧化铈催化剂在100～300℃的中低温区对含氯挥发性有机物的氧化效率均较好，特别在200～300℃温区时，其催化效率最佳。
与现有技术相比，本发明的有益效果为：
(1)本发明制备工艺简单，成本低，适合大规模生产；
(2)本发明的磷酸处理的CeO 2催化剂，充分利用CeO 2因Ce 4+/Ce 3+的可逆转换而具有良好的储放氧性能及氧流动性，以及磷酸根对含氯有机物的水解脱氯能力，使得本发明催化剂可以在工业废气及烟气环境中，长时间稳定地将含氯挥发性有机污染物转化为H 2O、CO 2和HCl，实现低温 脱氯，抗水、抗氯性能较好；
(3)实验数据表明，本发明的催化剂具有较好的抗硫性能；
(4)本发明的催化剂以价格低廉的氧化铈为活性材料，使用磷酸处理，极大提高了催化剂的寿命，并抑制了催化反应过程中生成有毒副产物，避免二次污染。
附图说明
图1为实施例1制得的催化剂的SS NMR表征结果图；
图2为实施例1制得的催化剂的原位红外表征结果图。
具体实施方式
实施例1
催化剂制备：
(1)将氧化铈粉末与磷酸(磷酸溶液的浓度1mol/L)以1∶0.05摩尔比混合，在30℃下反应0.5h，将所得混合物冷却、静置、洗涤后得到黄色氧化铈沉淀。
(2)将所得的混合物洗涤至中性，烘干后，在空气气氛下于200℃锻烧1h得到催化剂。
所制得催化剂的磷负载量为0.7％。
如图1所示，经过SS NMR表征，证明了氧化铈表面磷酸根基团的存在。后续的原位红外表征如图2所示，也证明了磷酸处理后的氧化铈表面存在P-O和P＝O。经过试验表征，磷酸处理后的催化剂表面，磷酸的主要存在形式为双羟基磷酸根。
实施例2
催化剂制备：
(1)将氧化铈粉末与磷酸以1∶0.05摩尔比混合，在80℃下反应0.5h，将所得混合物冷却、静置、洗涤后得到黄色氧化铈沉淀。
(2)将所得的混合物洗涤至中性，烘干后，在空气气氛下于200℃锻烧1h得到催化剂。
所制得催化剂的磷负载量为0.4％。
实施例3
催化剂制备：
(1)将氧化铈粉末与磷酸以1∶0.05摩尔比混合，在30℃下反应0.5h，将所得混合物冷却、静置、洗涤后得到黄色氧化铈沉淀。
(2)将所得的混合物洗涤至中性，烘干后，在空气气氛下于300℃锻烧2h得到催化剂。
所制得催化剂的磷负载量为0.7％。
实施例4
催化剂制备：
(1)将氧化铈粉末与磷酸以1∶0.2摩尔比混合，在30℃下反应1h，将所得混合物冷却、静置、洗涤后得到黄色氧化铈沉淀。
(2)将所得的混合物洗涤至中性，烘干后，在空气气氛下于200℃锻烧1h得到催化剂。
所制得催化剂的磷负载量为1.2％。
实施例5
催化剂制备：
(1)将氧化铈粉末与磷酸以1∶0.2摩尔比混合，在30℃下反应1h，将所得混合物冷却、静置、洗涤后得到黄色氧化铈沉淀。
(2)将所得的混合物洗涤至中性，烘干后，在空气气氛下于300℃锻烧2h得到催化剂。
所制得催化剂的磷负载量为1.2％。
对比例1
将氧化铈粉末直接在空气气氛下于300℃锻烧2h得到催化剂。
应用例1
将以上5个实施例制得的催化剂催化氧化氯苯，具体如下：
活性实验在固定床反应器上进行，催化剂装填量为1.0g，颗粒度为40～60目。初始气体浓度为：氯苯＝1000ppm，[O 2]＝10％，[H 2O]＝0.2％，N 2为载气，GHSV(气体空速)＝10000h -1。测试反应温度具体取100℃、150℃、200℃、225℃、250℃、300℃，反应1h时的测试数据详见表1。
表1催化剂对氯苯的催化氧化效率/％
Figure PCTCN2020072585-appb-000001
Figure PCTCN2020072585-appb-000002
由表1的实验结果可知，采用本发明的方法制备得到的催化剂在150～300℃的中低温区对氯苯的氧化效率均较好，特别是实施例1和3制得的催化剂在200～300℃温区催化效率在90％以上。由此可知，本发明的催化剂非常适于中低温烟气下催化氧化氯苯。
应用例2
以下实验在固定床反应器上进行，催化剂装填量为1g，颗粒度为40～60目。初始气体浓度为：氯苯＝1000ppm，[O 2]＝10％，[H 2O]＝0.5％，N 2为载气，GHSV(气体空速)＝10000h -1。测试反应温度具体取100℃、150℃、200℃、225℃、250℃、300℃，反应1h时的测试数据详见表2。
表2H 2O(0.5％)对氯苯的催化氧化效率的影响/％
Figure PCTCN2020072585-appb-000003
应用例3
以下实验在固定床反应器上进行，催化剂装填量为1g，颗粒度为40～60目。初始气体浓度为：氯苯＝1000ppm，[O 2]＝10％，[H 2O]＝2％，N 2为载气，GHSV(气体空速)＝10000h -1。测试反应温度具体取100℃、150℃、200℃、225℃、250℃、300℃，反应1h时的测试数据详见表3。
表3H 2O(2％)对氯苯的催化氧化效率的影响/％
Figure PCTCN2020072585-appb-000004
应用例4
以下实验在固定床反应器上进行，催化剂装填量为1g，颗粒度为40～60目。初始气体浓度为：氯苯＝1000ppm，[O 2]＝10％，[H 2O]＝5％，N 2为载气，GHSV(气体空速)＝10000h -1。测试反应温度具体取100℃、150℃、200℃、225℃、250℃、300℃，反应1h时的测试数据详见表4。
表4H 2O(5％)对氯苯的催化氧化效率的影响/％
Figure PCTCN2020072585-appb-000005
由表1～4实验结果可知，适当提高烟气中H 2O的含量，本发明的催化剂对氯苯的催化氧化效率仍有所提高，当通水量为0.2～2％时，表现出最佳的氯苯脱除效率。增加含水量至5％时，本发明的催化剂仍表现出较好的活性，在300℃时，催化效率均在85％以上。由此可知，本催化剂可以充分利用烟气中的H 2O，极大地促进氯苯的催化氧化。
而对比例1未经磷酸修饰的催化剂在200～300℃、烟气中含水率较低时对氯苯的催化氧化效率还算较好，但是随着烟气中含水率的增加，其对氯苯的催化氧化效率迅速下降，说明未经磷酸修饰的氧化铈催化剂的抗水 性能较差。
应用例5
催化剂催化氧化氯苯稳定性测试
以下实验在固定床反应器上进行，催化剂装填量为1g，颗粒度为40～60目。初始气体浓度为：氯苯＝1000ppm，[O 2]＝10％，[H 2O]＝0.5％，N 2为载气，GHSV(气体空速)＝10000h -1。测试反应温度具体取300℃，N 2为载气，测试数据详见表5。
表5催化剂的稳定性/％(测试温度为300℃)
Figure PCTCN2020072585-appb-000006
由表5可知，本发明的催化剂在氯苯对催化剂处理数小时后(含有一定的水蒸气)，其氯苯氧化活性几乎不受影响，本发明的催化剂具有良好的抗氯中毒性能，能够长时间稳定运行。
而对比例1未经磷酸修饰的催化剂稳定性很差，容易氯中毒而失去催化活性。
应用例6
催化剂催化氧化氯苯抗硫性测试
以下实验在固定床反应器上进行，催化剂装填量为1g，颗粒度为40～60目。初始气体浓度为：氯苯＝1000ppm，[O 2]＝10％，[H 2O]＝0.5％，[SO 2]＝50ppm，N 2为载气，GHSV(气体空速)＝10000h -1。测试反应温度具体取300℃，N 2为载气，测试数据详见表6。
表6催化剂的抗硫活性/％(测试温度为300℃)
Figure PCTCN2020072585-appb-000007
Figure PCTCN2020072585-appb-000008
由表6可知，本发明的催化剂在SO 2对催化剂处理数小时后，其氯苯氧化活性几乎不受影响，本发明的催化剂对烟气组分的适应性较强，适于各种组成的烟气中使用。
而对比例1未经磷酸修饰的催化剂稳定性很差，容易氯中毒和硫中毒而失去催化活性。
以上所述的实施例对本发明的技术方案和有益效果进行了详细说明，应理解的是以上所述仅为本发明的具体实施例，并不用于限制本发明，凡在本发明的原则范围内所做的任何修改、补充和等同替换等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种磷酸修饰的氧化铈催化剂的制备方法，其特征在于，包括以下步骤：
    (1)将氧化铈在磷酸溶液中浸泡，之后过滤出氧化铈并洗涤至中性，烘干；
    (2)将烘干后的氧化铈于100～400℃下锻烧1～4小时，得到磷酸修饰的氧化铈催化剂。
  2. 根据权利要求1所述的磷酸修饰的氧化铈催化剂的制备方法，其特征在于，以磷元素的质量百分比计，所述的氧化铈催化剂中磷负载量为0.1～5％。
  3. 根据权利要求1所述的磷酸修饰的氧化铈催化剂的制备方法，其特征在于，步骤(1)中，所述的磷酸溶液的浓度为10～200g/L，氧化铈与磷酸的摩尔比为1 ∶0.05～1。
  4. 根据权利要求1或3所述的磷酸修饰的氧化铈催化剂的制备方法，其特征在于，步骤(1)中，氧化铈的浸泡温度为10～80℃，浸泡时间为0.5～3h。
  5. 根据权利要求1所述的磷酸修饰的氧化铈催化剂的制备方法，其特征在于，步骤(2)中，煅烧温度为200～300℃。
  6. 根据权利要求5所述的磷酸修饰的氧化铈催化剂的制备方法，其特征在于，步骤(2)中，煅烧时间为1～2h。
  7. 一种磷酸修饰的氧化铈催化剂，其特征在于，根据权利要求1～6任一项所述的制备方法制得。
  8. 一种根据权利要求7所述的磷酸修饰的氧化铈催化剂在催化氧化降解含氯挥发性有机物中的应用，其特征在于，包括：
    将含有含氯挥发性有机物和水蒸气的烟气在所述氧化铈催化剂的作用下进行反应；
    所述烟气中，水蒸气的体积分数为0.1～5％；
    反应温度为100～300℃。
  9. 根据权利要求8所述的应用，其特征在于，所述烟气中，水蒸气 的质量分数为0.5～2％。
  10. 根据权利要求8所述的应用，其特征在于，反应温度为200～300℃。
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