WO2017181570A1

WO2017181570A1 - Alkali (alkaline earth) metal-resistant, sulfur-resistant, and water-resistant denitrification catalyst, and manufacturing method and application thereof

Info

Publication number: WO2017181570A1
Application number: PCT/CN2016/096932
Authority: WO
Inventors: 唐幸福; 高佳逸; 黄志伟; 胡萍萍
Original assignee: 复旦大学
Priority date: 2016-04-20
Filing date: 2016-08-26
Publication date: 2017-10-26
Also published as: CN105833894B; CN105833894A

Abstract

An alkali (alkaline earth) metal-resistant, sulfur-resistant, and water-resistant denitrification catalyst, and manufacturing method thereof. The catalyst comprises: one or more carriers selected from a porous tungsten molecular sieve, titanium molecular sieve, or a manganese molecular sieve; one or more active catalytic components selected from an iron oxide, a vanadium oxide, and a molybdenum oxide; and a catalytic adjuvant of a cerium oxide. The catalyst can withstand a nitrogen oxide flue gas comprising 0-1500 μmol/g of an alkali (alkaline earth) metal ion, 0-3000 mg/m³ of SO₂ and 0-20% water vapor. Under a condition of 200-500°C and gas flow speed of 3,000-400,000 h^-1, the catalyst can achieve a NO_x conversion ratio greater than 90％ and a N₂ selectivity greater than 80%. The catalyst is specifically applicable for controlling an emission of nitrogen oxide in a flue gas from a fixed source, such as a biomass power plant, glass production plant, coking plant, and the like.

Description

兼具抗碱(土)金属和抗硫抗水功能的脱硝催化剂及其制法和应用Denitration catalyst capable of resisting alkali (earth) metal, sulfur and water resistance, preparation method and application thereof

技术领域Technical field

本发明属于催化剂技术领域，具体地涉及一种兼具抗碱(土)金属和抗硫抗水功能的脱硝催化剂及其制法和应用。The invention belongs to the technical field of catalysts, in particular to a denitration catalyst which has the functions of alkali (earth) metal resistance, sulfur resistance and water resistance, and a preparation method and application thereof.

背景技术Background technique

我国是农业大国，生物质如秸秆的拥有量位于世界前列，传统对秸秆的处理方式通常是露天焚烧和家用燃料，所排放的大气可吸入颗粒物(如PM2.5)和大气气态污染物(如NO_x)是造成灰霾天气的重要因素，对人体健康和生态环境造成巨大的危害；同时，传统化石能源的消耗带来能源匮乏和全球变暖的环境问题迫切需要人们寻求新的替代能源，生物质作为一种可再生能源得到了广泛的关注。一个能有效地同时解决上述问题的方法是将生物质集中于锅炉燃烧并使之转化为电能或热能，燃烧生成的颗粒物用除尘装置有效地收集，生成的NO_x可通过高效烟气脱硝(deNO_x)技术控制。因此，取代生物质的传统处理方式，采用生物质集中于锅炉燃烧利用技术对减少大气颗粒物和NO_x的排放量都具有非常重要的意义。China is a large agricultural country, and the amount of biomass such as straw is in the forefront of the world. The traditional treatment of straw is usually open burning and domestic fuel, atmospheric inhalable particulate matter (such as PM2.5) and atmospheric gaseous pollutants (such as NO _x) is an important factor in causing the haze, caused great harm to human health and the environment; the same time, the traditional fossil energy consumption leads to environmental problems of energy shortage and global warming is an urgent need for people to seek new alternative sources of energy, Biomass has received wide attention as a renewable energy source. Method can effectively solve the above problems simultaneously is the biomass concentration in the combustion and a boiler into electrical or thermal energy, combustion of the particulate matter efficiently collected by the dust removing device, to generate NO _x in can denitration (deNOx through efficient flue gas _x ) Technical control. Thus, instead of the traditional approach of biomass, biomass is concentrated in the use of techniques based on the reduction of combustion air and particulate matter emissions of NO _x are of great significance.

NH₃选择性催化还原NO_x技术(SelectiveCatalyticReductionofNOxbyNH3，NH₃-SCR)是目前国际上行之有效的、应用最广的火电厂烟气脱硝技术。NH₃-SCR技术就是在催化剂存在下，向烟气中喷入NH₃，将NO_x还原为N₂和H₂O。在NH₃-SCR技术的应用过程中，催化剂是核心，催化性能直接影响到NH₃-SCR***的整体脱硝效率。然而，生物质燃烧的一个显著特点是烟气中含有大量的碱金属离子和一定量的硫，碱金属离子(如K⁺)和硫氧化物(如SO₂)是NH₃-SCR反应的最典型的两类毒物，会使NH₃-SCR催化剂严重失活。尽管催化剂常常被这两类毒物同时毒害，但近年来大家所研究的解决方案都是针对其中一类毒物，原因在于有效地保护催化剂同时不受两种毒物毒害是非常困难的。因此，开发一种能够同时抗碱(土)金属中毒和抗硫中毒的NH₃-SCR催化剂才能使生物质集中燃烧利用成为现实。NH ₃ selective catalytic reduction NOx technology (Selective Catalytic Reduction of NOx _by NH3, NH ₃ -SCR) is currently the most effective and widely used thermal power plant flue gas denitration technology. NH ₃ -SCR technology is in the presence of a catalyst, is injected into the flue gas to NH _3, reducing NO _x to N ₂ and H ₂ O. In the application process of NH ₃ -SCR technology, the catalyst is the core, and the catalytic performance directly affects the overall denitration efficiency of the NH ₃ -SCR system. However, a significant feature of biomass combustion is that the flue gas contains a large amount of alkali metal ions and a certain amount of sulfur. Alkali metal ions (such as K ⁺ ) and sulfur oxides (such as SO ₂ ) are the most reactive reactions of NH ₃ -SCR. typical types of poisons, make NH ₃ -SCR serious catalyst deactivation. Although catalysts are often poisoned by both types of poisons, the solutions studied in recent years have been directed to one of the classes of poisons because it is very difficult to effectively protect the catalyst from both poisons. Therefore, the development of an NH ₃ -SCR catalyst capable of simultaneously resisting alkali (earth) metal poisoning and sulfur poisoning in order to make biomass concentrated combustion utilization become a reality.

以生物质为燃料的烟气含有大量的碱金属离子(大约是燃煤烟气的20-50倍)，尤其是含有高浓度的钾和钠离子(占金属离子的99％)，由于这些碱金属的碱性比NH₃强而优先占用催化剂的活性位，导致传统脱硝催化剂严重失活。在NH₃-SCR反应进行过程中，碱金属离子通过优先吸附占据催化活性位，阻碍催化反应的发生进而导致催化剂中毒。相对应地，如果一种催化剂具有丰富的、独立于催化活性位的碱金属捕获位，同时该碱金属捕获位具备较强的酸性和合适的尺寸，那么这种催化剂就能够抗碱金属中毒。Biomass-fueled flue gas contains a large amount of alkali metal ions (about 20-50 times that of coal-fired flue gas), especially high concentrations of potassium and sodium ions (99% of metal ions) due to these bases. The metal is more basic than NH ₃ and preferentially occupies the active site of the catalyst, resulting in severe deactivation of the conventional denitration catalyst. During the progress of the NH ₃ -SCR reaction, the alkali metal ions occupy the catalytic active sites by preferential adsorption, which hinders the occurrence of the catalytic reaction and leads to catalyst poisoning. Correspondingly, if a catalyst has a rich alkali metal capture site independent of the catalytic active site, and the alkali metal capture site has a strong acidity and a suitable size, the catalyst is resistant to alkali metal poisoning.

通常地，NH₃-SCR催化剂硫中毒主要来源于烟气中的SO₂在催化剂表面发生吸附和进一步的氧化。SO₂分子相对于NO分子酸性更强，因而SO₂能够优先吸附在催化剂表面，特别是当NH₃-SCR反应遵循Langmuir-Hinshelwood机理。更加糟糕的是，热稳定性很好的硫酸盐物种，如(NH₄)₂SO₄和M_2/nSO4(M代表催化剂中的活性金属，n代表金属离子的价态)，则会在SO₂被氧化成SO₃且与NH₃或者催化剂发生反应后生成，之后沉积在催化剂表面，占据催化活性位，导致催化剂中毒；同时，生成的SO₃和硫酸会在下游管道沉积，造成管道腐蚀。SO₂的化学吸附是由催化剂表面碱性的羟基或者O^2-所导致的，而SO₂进一步的氧化是由催化剂自身的氧化性导致的。然而，一定的氧化性是NH₃-SCR催化剂所必需的特性，因此，要想改变催化剂硫中毒，可行的策略就是研发具有酸性表面的NH₃-SCR催化剂减少SO₂的吸附。Generally, the NH ₃ -SCR catalyst sulfur poisoning is mainly derived from the adsorption and further oxidation of SO ₂ in the flue gas on the catalyst surface. The SO ₂ molecule is more acidic than the NO molecule, so SO ₂ can preferentially adsorb on the catalyst surface, especially when the NH ₃ -SCR reaction follows the Langmuir-Hinshelwood mechanism. To make matters worse, sulfated species with good thermal stability, such as (NH ₄ ) ₂ SO ₄ and M _2/n SO4 (M represents the active metal in the catalyst, and n represents the valence state of the metal ion), SO ₂ is oxidized to SO ₃ and reacted with NH ₃ or a catalyst, and then deposited on the surface of the catalyst, occupying the catalytic active site, causing catalyst poisoning; at the same time, the generated SO ₃ and sulfuric acid will deposit in the downstream pipeline, causing corrosion of the pipeline. . The chemisorption of SO ₂ is caused by a basic hydroxyl group or O ^{2 -} on the surface of the catalyst, and further oxidation of SO ₂ is caused by the oxidizing property of the catalyst itself. However, certain oxidizing properties are essential for the NH ₃ -SCR catalyst. Therefore, in order to change the catalyst sulfur poisoning, a feasible strategy is to develop an NH ₃ -SCR catalyst having an acidic surface to reduce the adsorption of SO ₂ .

综上，研制开发兼具抗碱(土)金属和抗硫抗水特性的NH₃-SCR催化剂成为研究领域的热点。In summary, the development of NH ₃ -SCR catalysts with both alkali-resistant (earth) metals and sulfur and water resistance characteristics has become a hot topic in the research field.

本发明的目的是提供一种兼具抗碱(土)金属和抗硫抗水功能的高效脱硝催化剂，该催化剂既可以抗碱(土)金属中毒，又可以抗硫抗水中毒失活。本发明是以多孔的钨分子筛、钛分子筛和锰分子筛中的一种或多种为载体，以铁氧化物、钒氧化物和钼氧化物中的一种或多种为活性组分，以铈氧化物为助剂。本发明特别适用于富碱富硫固定源烟气的氮氧化物排放控制，具有巨大的社会意义和经济价值。The object of the present invention is to provide a high-efficiency denitration catalyst which has both an alkali-resistant (earth) metal and a sulfur-resistant and water-resistant function, and is resistant to alkali (earth) metal poisoning and sulfur-resistant against water poisoning. The invention adopts one or more of porous tungsten molecular sieve, titanium molecular sieve and manganese molecular sieve as a carrier, and one or more of iron oxide, vanadium oxide and molybdenum oxide as active components, The oxide is an auxiliary. The invention is particularly suitable for the nitrogen oxide emission control of the alkali-rich sulfur-rich fixed source flue gas, and has great social significance and economic value.

发明内容Summary of the invention

本发明的第一方面提供了一种兼具抗碱(土)金属和抗硫抗水功能的脱硝催化剂，它包括：多孔分子筛载体，以及负载在载体上的活性成分和助剂；A first aspect of the present invention provides a denitration catalyst having both an alkali (earth) metal resistance and a sulfur and water resistance function, comprising: a porous molecular sieve carrier, and an active ingredient and an auxiliary agent supported on the carrier;

其中，所述活性成分选自下组：铁氧化物、钒氧化物、钼氧化物、或其组合；而所述助剂为铈氧化物；Wherein the active ingredient is selected from the group consisting of iron oxides, vanadium oxides, molybdenum oxides, or combinations thereof; and the auxiliaries are cerium oxides;

并且，以所述载体的总重量计，所述活性组分在载体上的负载量为1～10wt％，而所述助剂在载体上的负载量为0.5～10wt％；Further, the active component is supported on the carrier in an amount of from 1 to 10% by weight based on the total weight of the carrier, and the auxiliary agent is supported on the carrier in an amount of from 0.5 to 10% by weight;

以及所述活性组分和所述助剂的摩尔比为3:1～10:1。And the molar ratio of the active component to the auxiliary agent is from 3:1 to 10:1.

在另一优选例中，所述的活性组分的负载量按金属元素计。In another preferred embodiment, the active component is supported in a metal element.

在另一优选例中，所述的助剂的负载量按金属元素计。In another preferred embodiment, the loading amount of the auxiliary agent is based on the metal element.

在另一优选例中，所述活性组分和所述助剂的摩尔比按各自的金属元素摩尔数计算。In another preferred embodiment, the molar ratio of the active component to the auxiliary agent is based on the number of moles of the respective metal element. Count.

在另一优选例中，所述的多孔分子筛选自下组：钨分子筛、钛分子筛、锰分子筛、或其组合。In another preferred embodiment, the porous molecules are screened from the following group: tungsten molecular sieves, titanium molecular sieves, manganese molecular sieves, or combinations thereof.

本发明的第二方面提供了一种前驱体，该前驱体用于制备如本发明第一方面所述的兼具抗碱(土)金属和抗硫抗水功能的脱硝催化剂，并且所述的前驱体包括：多孔分子筛、用于形成活性成分的第一沉淀物和用于形成助剂的第二沉淀物；A second aspect of the present invention provides a precursor for preparing a denitration catalyst having an alkali (earth) resistance and a sulfur and water resistance function according to the first aspect of the present invention, and The precursor comprises: a porous molecular sieve, a first precipitate for forming an active ingredient, and a second precipitate for forming an auxiliary;

其中，所述的多孔分子筛选自下组：钨分子筛、钛分子筛、锰分子筛、或其组合；Wherein, the porous molecules are screened from the following group: a tungsten molecular sieve, a titanium molecular sieve, a manganese molecular sieve, or a combination thereof;

所述的第一沉淀物是含铁元素、钒元素、钼元素、或其组合的不溶性沉淀；The first precipitate is an insoluble precipitate containing iron, vanadium, molybdenum, or a combination thereof;

所述的第二沉淀物是含铈元素的不溶性沉淀；The second precipitate is an insoluble precipitate containing cerium;

并且，以所述载体的总重量计，所述第一沉淀物在载体上的负载量为1～10wt％，而所述第二沉淀物在载体上的负载量为0.5～10wt％，其中负载量按第一沉淀物和第二沉淀物各自的金属元素计；And, the first precipitate is supported on the carrier in an amount of from 1 to 10% by weight based on the total weight of the carrier, and the second precipitate is supported on the carrier in an amount of from 0.5 to 10% by weight, wherein the load is The amount is based on the respective metal elements of the first precipitate and the second precipitate;

以及所述活性组分和所述助剂的摩尔比为3:1～10:1，其中所述摩尔比按各自的金属元素摩尔数计算。And the molar ratio of the active component to the auxiliary agent is from 3:1 to 10:1, wherein the molar ratio is calculated as the number of moles of the respective metal element.

在另一优选例中，所述的多孔分子筛、用于形成活性成分的第一沉淀物和用于形成助剂的第二沉淀物形成一固态混合物。In another preferred embodiment, the porous molecular sieve, the first precipitate for forming an active ingredient, and the second precipitate for forming an auxiliary agent form a solid mixture.

在另一优选例中，所述的第一沉淀物选自下组：氢氧化物、碳酸盐或其组合。In another preferred embodiment, the first precipitate is selected from the group consisting of hydroxides, carbonates, or combinations thereof.

在另一优选例中，所述的第一沉淀物中，金属的价态选自下组：Fe(III)、Fe(II)、V(V)、Mo(VI)。In another preferred embodiment, in the first precipitate, the valence state of the metal is selected from the group consisting of Fe(III), Fe(II), V(V), and Mo(VI).

在另一优选例中，所述的第一沉淀物为不溶性沉淀。In another preferred embodiment, the first precipitate is an insoluble precipitate.

在另一优选例中，所述的第一沉淀物是可溶性的铁盐、钒盐、钼盐或其组合与沉淀剂反应形成的不溶性沉淀。In another preferred embodiment, the first precipitate is an insoluble precipitate formed by reacting a soluble iron salt, a vanadium salt, a molybdenum salt or a combination thereof with a precipitating agent.

在另一优选例中，所述的可溶性指在25℃，在水或水性溶剂的溶解度≥5g/mL。In another preferred embodiment, the solubility refers to a solubility in water or an aqueous solvent of ≥ 5 g/mL at 25 °C.

在另一优选例中，所述的不溶性指在25℃，在水或水性溶剂的溶解度≤1g/mL。In another preferred embodiment, the insoluble means that the solubility in water or an aqueous solvent is ≤ 1 g/mL at 25 °C.

在另一优选例中，所述的第二沉淀物选自下组：氢氧化物、碳酸盐或其组合。In another preferred embodiment, the second precipitate is selected from the group consisting of hydroxides, carbonates, or combinations thereof.

在另一优选例中，所述的第二沉淀物中，金属的价态选自下组：Ce(III)、Ce(IV)。In another preferred embodiment, in the second precipitate, the valence of the metal is selected from the group consisting of Ce(III), Ce(IV).

在另一优选例中，所述的第二沉淀物为不溶性沉淀。In another preferred embodiment, the second precipitate is an insoluble precipitate.

在另一优选例中，所述的第二沉淀物是可溶性的铈盐与沉淀剂反应形成的不溶性沉淀。In another preferred embodiment, the second precipitate is an insoluble precipitate formed by the reaction of a soluble cerium salt with a precipitating agent.

在另一优选例中，所述的沉淀剂选自下组：碳酸铵、氨水、尿素、或其组合。 In another preferred embodiment, the precipitating agent is selected from the group consisting of ammonium carbonate, aqueous ammonia, urea, or a combination thereof.

本发明的第三发明还提供了一种如上所述的兼具抗碱(土)金属和抗硫抗水功能的脱硝催化剂的制备方法，包括步骤：The third invention of the present invention also provides a method for preparing a denitration catalyst having both an alkali (earth) resistance and a sulfur and water resistance as described above, comprising the steps of:

(i)提供如本发明第二方面所述的前驱体；和(i) providing a precursor according to the second aspect of the invention; and

(ii)所述的前驱体在200～800℃进行焙烧，从而形成得到如本发明第一方面所述的脱硝催化剂。(ii) The precursor is calcined at 200 to 800 ° C to form a denitration catalyst according to the first aspect of the invention.

在另一优选例中，所述的前驱体是经干燥处理的前驱体。In another preferred embodiment, the precursor is a dried precursor.

在另一优选例中，所述的干燥处理包括80～130℃下干燥。In another preferred embodiment, the drying treatment comprises drying at 80 to 130 °C.

在另一优选例中，所述的干燥处理时间为2～24小时。In another preferred embodiment, the drying treatment time is 2 to 24 hours.

在另一优选例中，在步骤(ii)中，所述的焙烧的时间为1～72小时，较佳地为1～24小时，更佳地2～12小时。In another preferred embodiment, in the step (ii), the calcination time is from 1 to 72 hours, preferably from 1 to 24 hours, more preferably from 2 to 12 hours.

本发明的第四方面提供了一种制备如本发明第二方面所述的前驱体的方法，它包括步骤：A fourth aspect of the invention provides a method of preparing a precursor according to the second aspect of the invention, comprising the steps of:

(a)提供多孔分子筛载体、溶剂、活性成分原料、助剂原料和沉淀剂；(a) providing a porous molecular sieve carrier, a solvent, an active ingredient raw material, an auxiliary raw material, and a precipitating agent;

(b)将所述多孔分子筛载体、溶剂、活性成分原料、助剂原料和沉淀剂进行混合，形成第一混合物，(b) mixing the porous molecular sieve carrier, the solvent, the active ingredient raw material, the auxiliary raw material and the precipitating agent to form a first mixture,

其中，所述活性成分原料与沉淀剂反应形成用于形成活性成分的第一沉淀物；并且所述助剂原料与沉淀剂反应形成用于形成助剂的第二沉淀物，并形成含所述的多孔分子筛载体、所述第一沉淀物和所述第二沉淀物的固态沉淀物；和Wherein the active ingredient raw material reacts with a precipitating agent to form a first precipitate for forming an active ingredient; and the auxiliary raw material reacts with a precipitating agent to form a second precipitate for forming an auxiliary agent, and is formed a porous molecular sieve support, a solid precipitate of the first precipitate and the second precipitate; and

(c)从所述第一混合物中分离出所述的固态沉淀物，即为所述前体；(c) separating said solid precipitate from said first mixture, that is, said precursor;

其中，所述的活性成分原料选自下组：铁盐、钒盐、钼盐、或其组合；所述助剂原料选自下组：硫酸铈、硝酸铈、氯化铈、或其组合；所述的多孔分子筛选自下组：钨分子筛、钛分子筛、锰分子筛、或其组合；所述的沉淀剂选自下组：碱金属氢氧化物、碱土金属氢氧化物、氨水、尿素、碳酸盐、或其组合。Wherein the active ingredient raw material is selected from the group consisting of iron salt, vanadium salt, molybdenum salt, or a combination thereof; the auxiliary material is selected from the group consisting of barium sulfate, barium nitrate, barium chloride, or a combination thereof; The porous molecules are screened from the following group: tungsten molecular sieves, titanium molecular sieves, manganese molecular sieves, or a combination thereof; the precipitating agent is selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, ammonia water, urea, carbon An acid salt, or a combination thereof.

在另一优选例中，所述的前驱体制备方法中，步骤(b)还包括：In another preferred embodiment, in the method for preparing a precursor, the step (b) further comprises:

(b1)提供一液态混合物，所述液态混合物含有：溶剂、活性成分原料和助剂原料；(b1) providing a liquid mixture comprising: a solvent, an active ingredient raw material, and an auxiliary raw material;

(b2)将所述液态混合物与多孔分子筛载体和沉淀剂进行混合，从而形成所述的第一混合物。(b2) mixing the liquid mixture with a porous molecular sieve support and a precipitating agent to form the first mixture.

在另一优选例中，所述的液态混合物为溶液。In another preferred embodiment, the liquid mixture is a solution.

在另一优选例中，所述的溶剂为水。 In another preferred embodiment, the solvent is water.

在另一优选例中，在步骤(b1)中，包括：将所述活性成分原料和助剂原料溶于水中，形成溶液。In another preferred embodiment, in the step (b1), the active ingredient raw material and the auxiliary raw material are dissolved in water to form a solution.

在另一优选例中，在步骤(b2)中，包括：将多孔分子筛载体加入步骤(b1)所得的液态混合物中，搅拌下加入沉淀剂，从而形成所述的前驱体。In another preferred embodiment, in the step (b2), the porous molecular sieve support is added to the liquid mixture obtained in the step (b1), and a precipitant is added under stirring to form the precursor.

在另一优选例中，沉淀反应的时间为5分钟～4小时。In another preferred embodiment, the precipitation reaction time is from 5 minutes to 4 hours.

在另一优选例中，所述的铁盐选自下组：氯化亚铁、硫酸亚铁、氯化铁、硝酸铁、或其组合，以铁元素计，溶液中铁的浓度为0.001～5.0mol/L。In another preferred embodiment, the iron salt is selected from the group consisting of ferrous chloride, ferrous sulfate, ferric chloride, ferric nitrate, or a combination thereof, and the concentration of iron in the solution is 0.001 to 5.0 in terms of iron. Mol/L.

在另一优选例中，所述的钒盐选自下组：正钒酸盐、焦钒酸盐、偏钒酸盐、或其组合，以钒元素计，溶液中钒的浓度为0.001～5.0mol/L。In another preferred embodiment, the vanadium salt is selected from the group consisting of orthovanadate, pyrovanadate, metavanadate, or a combination thereof, and the concentration of vanadium in the solution is 0.001 to 5.0 based on the vanadium element. Mol/L.

在另一优选例中，所述为钼盐选自下组：钼酸、钼酸钠、钼酸钾、七钼酸铵、或其组合，以钼元素计，溶液中钼的浓度为0.001～5.0mol/L。In another preferred embodiment, the molybdenum salt is selected from the group consisting of molybdic acid, sodium molybdate, potassium molybdate, ammonium heptamolybdate, or a combination thereof, and the concentration of molybdenum in the solution is 0.001 in terms of molybdenum element. 5.0 mol/L.

在另一优选例中，溶液中助剂原料的浓度为0.001～5.0mol/L。In another preferred embodiment, the concentration of the auxiliary material in the solution is from 0.001 to 5.0 mol/L.

在另一优选例中，溶液中沉淀剂的浓度为0.001～5.0mol/L。In another preferred embodiment, the concentration of the precipitating agent in the solution is from 0.001 to 5.0 mol/L.

在另一优选例中，所述的前驱体制备方法中，步骤(a)之前，还包括制备多孔分子筛的步骤。In another preferred embodiment, in the precursor preparation method, before the step (a), the step of preparing the porous molecular sieve is further included.

在另一优选例中，所述的制备多孔分子筛的步骤包括：In another preferred embodiment, the step of preparing the porous molecular sieve comprises:

(a0)提供一种用于制备多孔分子筛的混合物；(a0) providing a mixture for preparing a porous molecular sieve;

其中，所述的混合液包括：钨盐、还原剂和模板剂；或钛盐、沉淀剂和模板剂；或锰盐、氧化剂和模板剂；Wherein, the mixed liquid comprises: a tungsten salt, a reducing agent and a templating agent; or a titanium salt, a precipitating agent and a templating agent; or a manganese salt, an oxidizing agent and a templating agent;

(a1)步骤(a0)中的混合物在20～220℃条件下，反应8～48小时；(a1) The mixture in the step (a0) is reacted at 20 to 220 ° C for 8 to 48 hours;

(a2)将步骤(a1)生成的产物在80～130℃干燥2～24小时；(a2) drying the product produced in the step (a1) at 80 to 130 ° C for 2 to 24 hours;

(a3)经步骤(a3)干燥后的产物在200～800℃焙烧1～12小时，得到多孔分子筛。(a3) The product dried by the step (a3) is calcined at 200 to 800 ° C for 1 to 12 hours to obtain a porous molecular sieve.

其中，所述的模板剂选自下组：碳酸铵、硫酸铵、硝酸铵、氯化铵、或其组合；所述的还原剂选自下组：柠檬酸、硫代硫酸钠、草酸、聚甲基丙烯酸钠、或其组合；所述的氧化剂选自下组：高锰酸盐、过硫酸铵、过硫酸钾、过硫酸钠、氯酸钠、过氧化氢、或其组合；所述的沉淀剂选自下组：氢氧化物、氟化物、硅酸钠、碳酸盐、或其组合。Wherein the templating agent is selected from the group consisting of ammonium carbonate, ammonium sulfate, ammonium nitrate, ammonium chloride, or a combination thereof; the reducing agent is selected from the group consisting of citric acid, sodium thiosulfate, oxalic acid, and poly Sodium methacrylate, or a combination thereof; the oxidizing agent is selected from the group consisting of permanganate, ammonium persulfate, potassium persulfate, sodium persulfate, sodium chlorate, hydrogen peroxide, or combinations thereof; The precipitant is selected from the group consisting of hydroxides, fluorides, sodium silicates, carbonates, or combinations thereof.

在另一优选例中，所述的钨盐选自下组：钨酸、钨酸钠、钨酸钾、偏钨酸铵、或其组合，以钨元素摩尔数计，钨的浓度为0.001～5.0mol/L。In another preferred embodiment, the tungsten salt is selected from the group consisting of tungstic acid, sodium tungstate, potassium tungstate, ammonium metatungstate, or a combination thereof, and the concentration of tungsten is 0.001 in terms of the number of moles of tungsten. 5.0 mol/L.

在另一优选例中，所述的钛盐选自下组：四氯化钛、硫酸钛、钛酸四丁酯、或其组合，以钛元素摩尔数计，钛的浓度为0.001～5.0mol/L。 In another preferred embodiment, the titanium salt is selected from the group consisting of titanium tetrachloride, titanium sulfate, tetrabutyl titanate, or a combination thereof, and the concentration of titanium is 0.001 to 5.0 mol based on the number of moles of titanium. /L.

在另一优选例中，所述的锰盐选自下组：硝酸锰、氯化锰、硫酸锰、乙酸锰、或其组合，以锰元素摩尔数计，锰的浓度为0.001～5.0mol/L。In another preferred embodiment, the manganese salt is selected from the group consisting of manganese nitrate, manganese chloride, manganese sulfate, manganese acetate, or a combination thereof, and the manganese concentration is 0.001 to 5.0 mol/mol in terms of the number of moles of manganese. L.

在另一优选例中，步骤(a0)混合液中还原剂的浓度为0.001～2.5mol/L。In another preferred embodiment, the concentration of the reducing agent in the mixed liquid of the step (a0) is from 0.001 to 2.5 mol/L.

在另一优选例中，步骤(a0)混合液中氧化剂的浓度为0.001～2.5mol/L。In another preferred embodiment, the concentration of the oxidizing agent in the mixed liquid in the step (a0) is from 0.001 to 2.5 mol/L.

在另一优选例中，步骤(a0)混合液中沉淀剂的浓度为0.001～5.0mol/L。In another preferred embodiment, the concentration of the precipitating agent in the mixed liquid of the step (a0) is 0.001 to 5.0 mol/L.

在另一优选例中，步骤(a0)混合液中模板剂的铵根的浓度为0.001～5.0mol/L。In another preferred embodiment, the concentration of the ammonium salt of the templating agent in the mixed liquid of the step (a0) is 0.001 to 5.0 mol/L.

本发明第五方面提供了一种脱硝方法，所述的脱硝催化剂与富碱富硫固定源烟气的氮氧化物相互接触。A fifth aspect of the present invention provides a denitration catalyst in which the denitration catalyst is in contact with the nitrogen oxides of the alkali-rich sulfur-rich fixed source flue gas.

在另一优选例中，所述的氮氧化合物包括NO、NO₂、N₂O、N₂O₃。In another preferred embodiment, the oxynitride comprises NO, NO ₂ , N ₂ O, N ₂ O ₃ .

在另一优选例中，所述的固定源包括燃煤电厂、生物质燃料电厂、玻璃厂、焦化厂。In another preferred embodiment, the fixed source includes a coal-fired power plant, a biomass fuel power plant, a glass factory, and a coking plant.

在另一优选例中，所述的脱硝催化剂用于富碱富硫固定源烟气的氮氧化物排放控制。In another preferred embodiment, the denitration catalyst is used for NOx emission control of an alkali-rich sulfur-rich stationary source flue gas.

在另一优选例中，所述的脱硝催化剂的脱硝效率在90％以上。In another preferred embodiment, the denitration catalyst has a denitration efficiency of 90% or more.

在另一优选例中，所述的脱硝催化剂的N₂选择性在85％以上。In another preferred embodiment, the denitration catalyst has a N ₂ selectivity of 85% or more.

应理解，在本发明范围内中，本发明的上述各技术特征和在下文(如实施例)中具体描述的各技术特征之间都可以互相组合，从而构成新的或优选的技术方案。限于篇幅，在此不再一一累述。It is to be understood that within the scope of the present invention, the various technical features of the present invention and the various technical features specifically described hereinafter (as in the embodiments) may be combined with each other to constitute a new or preferred technical solution. Due to space limitations, we will not repeat them here.

具体实施方式detailed description

本发明人经过广泛而深入地研究，首次意外地发现了一种兼具抗碱(土)金属和抗硫抗水功能的高效脱硝催化剂。该催化剂是以多孔的钨分子筛、钛分子筛和锰分子筛中的一种或多种为载体，以铁氧化物、钒氧化物和钼氧化物中的一种或多种为活性组分，以铈氧化物为助剂。实验表明，该催化剂既可以抗碱(土)金属中毒，又可以抗硫抗水中毒失活，特别适用于富碱富硫固定源烟气的氮氧化物排放控制。在此基础上，完成了本发明。The inventors have extensively and intensively studied, and for the first time, unexpectedly discovered a highly efficient denitration catalyst which has both alkali (earth) resistance and sulfur and water resistance. The catalyst is one or more of a porous tungsten molecular sieve, a titanium molecular sieve and a manganese molecular sieve, and one or more of iron oxide, vanadium oxide and molybdenum oxide are used as an active component. The oxide is an auxiliary. Experiments show that the catalyst can resist both alkali (earth) metal poisoning and sulfur and water poisoning, especially for nitrogen oxide emission control of alkali-rich sulfur-rich fixed source flue gas. On the basis of this, the present invention has been completed.

具体地，本发明的催化剂是以多孔的钨分子筛、钛分子筛和锰分子筛中的一种或多种为载体，以铁氧化物、钒氧化物和钼氧化物中的一种或多种为活性组分，以铈氧化物为助剂。本发明催化剂可耐受同时含有0～1500μmol/g的碱(土)金属离子、0～3000mg/m³的SO₂和0～20％水蒸气的氮氧化物烟气，在200～500℃以及3,000～400,000h^-1空速的条件下，NO_x转化率大于90％，N₂选择性大于80％。本发明特别适用于富碱富硫固定源(生物质燃料电厂、玻璃厂、焦化厂等)烟气的氮氧化物排放控制。Specifically, the catalyst of the present invention is one or more of a porous tungsten molecular sieve, a titanium molecular sieve, and a manganese molecular sieve, and is active as one or more of iron oxide, vanadium oxide, and molybdenum oxide. The component uses cerium oxide as an auxiliary. The catalyst of the present invention can withstand nitrogen oxide fumes including 0 to 1500 μmol/g of alkali metal ions, 0 to 3000 mg/m ³ of SO ₂ and 0 to 20% of water vapor at 200 to 500 ° C and under conditions of a space velocity of 3,000 ~ 400,000h ^-1, NO _x conversion is greater than 90%, N ₂ selectivity of greater than 80%. The invention is particularly suitable for the nitrogen oxide emission control of flue gas of an alkali-rich and sulfur-rich stationary source (biomass fuel power plant, glass factory, coking plant, etc.).

术语the term

如本文所用，术语“本发明催化剂”、“本发明脱硝催化剂”、“本发明的兼具抗碱(土)金属和抗硫抗水功能的脱硝催化剂”可互换使用。As used herein, the terms "catalyst of the present invention", "denitration catalyst of the present invention", "denitration catalyst of the present invention having both an alkali-resistant (earth) metal and a sulfur-resistant and water-resistant function" are used interchangeably.

如本文所用，术语“碱(土)金属”指碱金属、碱土金属、或其组合。As used herein, the term "alkali (earth) metal" refers to an alkali metal, an alkaline earth metal, or a combination thereof.

如本文所用，术语“N₂选择性”指催化产物中N₂量占含氮化合物总量的百分数。As used herein, the term "N ₂ selectivity" refers to the percentage of the amount of N ₂ in the catalytic product to the total amount of the nitrogen-containing compound.

如本文所用，术语“脱硝效率”指NH₃-SCR反应脱除的NO_x浓度与未经脱硝前烟气中NO_x浓度的百分比。As used herein, the term "denitrification efficiency" refers to the percentage of the NO _x concentration in the flue gas prior to removal of the NH ₃ -SCR reaction with _the NO _x concentration without denitration.

如本文所用，术语“包括”、“含有”、“包含”可以是开放式的或封闭式的，并且包括了“由……构成”和“基本上由……构成”。The terms "including", "comprising", and "comprising", as used herein, may be open or closed, and include "consisting of" and "consisting essentially of."

如本文所用，术语“可溶性”指在25℃，在水或水性溶剂的溶解度≥5g/ml。As used herein, the term "soluble" refers to a solubility in water or an aqueous solvent of > 5 g/ml at 25 °C.

如本文所用，术语“不溶性”指在25℃，在水或水性溶剂的溶解度≤1g/ml。As used herein, the term "insoluble" refers to a solubility in water or an aqueous solvent of < 1 g/ml at 25 °C.

多孔分子筛载体及其制法Porous molecular sieve carrier and preparation method thereof

用于制备本发明催化剂的一个主要成分是多孔分子筛。One of the main components used in the preparation of the catalyst of the present invention is a porous molecular sieve.

在本发明催化剂中，多孔分子筛被用作脱硝催化剂的载体。In the catalyst of the present invention, a porous molecular sieve is used as a carrier for the denitration catalyst.

在本发明中，对多孔分子筛没有特别限制。所述的多孔分子筛可以市售获得或用常规方法(如沉淀-焙烧法)制备。代表性的例子包括(但并不限于)：钨分子筛、钛分子筛、锰分子筛、或其组合。In the present invention, the porous molecular sieve is not particularly limited. The porous molecular sieves are commercially available or can be prepared by a conventional method such as precipitation-baking. Representative examples include, but are not limited to, tungsten molecular sieves, titanium molecular sieves, manganese molecular sieves, or combinations thereof.

在本发明中，所述的多孔分子筛载体均具有一定尺寸的孔道结构，能够容纳烟气中存在的绝大多数碱(土)金属离子。优选地，所述多孔分子筛的孔隙度为60-95％，较佳地80-90％。In the present invention, the porous molecular sieve carrier has a pore structure of a certain size and is capable of accommodating most of the alkali (earth) metal ions present in the flue gas. Preferably, the porous molecular sieve has a porosity of from 60 to 95%, preferably from 80 to 90%.

在一个优选例中，本发明提供了多孔分子筛载体的制备方法。典型地，所述方法包括：In a preferred embodiment, the invention provides a method of making a porous molecular sieve support. Typically, the method comprises:

(1)多孔钨分子筛的制备：将一定量的钨盐、还原剂和模板剂分别溶于一定量的去离子水中，各自形成溶液，然后将三种溶液依次转移至同一个反应容器中，在合适的温度(如20～220℃)条件下，反应一段时间(如8～48小时)；生成的产物经干燥(如在80～130℃，干燥2～24小时)，之后在焙烧温度(如300～500℃)焙烧一段时间(如2～8小时)，得到多孔钨分子筛。(1) Preparation of porous tungsten molecular sieve: a certain amount of tungsten salt, reducing agent and templating agent are respectively dissolved in a certain amount of deionized water to form a solution, and then the three solutions are sequentially transferred to the same reaction container, suitable At a temperature (eg, 20 to 220 ° C), the reaction is carried out for a period of time (eg, 8 to 48 hours); the resulting product is dried (eg, dried at 80 to 130 ° C for 2 to 24 hours), followed by a calcination temperature (eg, 300 °). Baking for a period of time (e.g., 2 to 8 hours) at 500 ° C to obtain a porous tungsten molecular sieve.

其中，钨盐的例子包括(但并不限于)：钨酸、钨酸钠(Na₂WO₄)、钨酸钾(K₂WO₄)、偏钨酸铵((NH₄)₁₀W₁₂O₄₁·xH₂O)的一种或多种；所述溶液中钨的浓度通常为0.001～5.0mol/L；所述的还原剂例子包括(但并不限于)：柠檬酸(C₆H₈O₇)、硫代硫酸钠(Na₂S₂O₃)、草酸(H₂C₂O₄)、聚甲基丙烯酸钠((CH₅NaO₂)n)中的一种或多种，所述溶液中还原剂的浓度为0.001～2.5mol/L；所述模板剂例子包括(但并不限于)：铵盐，如碳酸铵((NH₄)₂CO₃)、硫酸铵((NH₄)₂SO₄)、硝酸铵(NH₄NO₃)、氯化铵(NH₄Cl)中的一种或多种，所述溶液中铵根离子的浓度通常为0.001～5.0mol/L。Examples of tungsten salts include, but are not limited to, tungstic acid, sodium tungstate (Na ₂ WO ₄ ), potassium tungstate (K ₂ WO ₄ ), ammonium metatungstate ((NH ₄ ) ₁₀ W ₁₂ O One or more of ₄₁ xH ₂ O); the concentration of tungsten in the solution is usually 0.001 to 5.0 mol/L; examples of the reducing agent include (but are not limited to): citric acid (C ₆ H ₈ One or more of O ₇ ), sodium thiosulfate (Na ₂ S ₂ O ₃ ), oxalic acid (H ₂ C ₂ O ₄ ), sodium polymethacrylate ((CH ₅ NaO ₂ ) n ), The concentration of the reducing agent in the solution is 0.001 to 2.5 mol/L; examples of the template include, but are not limited to, ammonium salts such as ammonium carbonate ((NH ₄ ) ₂ CO ₃ ), ammonium sulfate ((NH _{4 )} ₂ SO ₄ ), one or more of ammonium nitrate (NH ₄ NO ₃ ), ammonium chloride (NH ₄ Cl), and the concentration of the ammonium ion in the solution is usually 0.001 to 5.0 mol/L.

(2)多孔钛分子筛的制备：将一定量的钛盐、沉淀剂和模板剂分别溶于一定量的去离子水中，各自形成溶液，然后将三种溶液依次转移至同一个反应容器中，在合适的温度(如20～220℃)条件下，反应一段时间(如8～48小时)；生成的产物经干燥(如在80～130℃，干燥2～24小时)，之后在焙烧温度(如200～800℃)焙烧一段时间(如1～12小时)，得到多孔钛分子筛。(2) Preparation of porous titanium molecular sieve: a certain amount of titanium salt, precipitant and templating agent are respectively dissolved in a certain amount of deionized water to form a solution, and then the three solutions are sequentially transferred to the same reaction container, At a suitable temperature (eg 20 to 220 ° C), the reaction is carried out for a period of time (eg 8 to 48 hours); the resulting product is dried (eg at 80-130 ° C, dried for 2 to 24 hours), then at the calcination temperature (eg 200 to 800 ° C) is calcined for a period of time (eg, 1 to 12 hours) to obtain a porous titanium molecular sieve.

其中，钛盐的例子包括(但并不限于)：四氯化钛(TiCl₄)、硫酸钛(Ti(SO₄)₂)、钛酸四丁酯(C₁₆H₃₆O₄Ti)中的一种或多种，所述溶液中钛的浓度通常为0.001～5.0mol/L；所述沉淀剂例子包括(但并不限于)：氢氧化物(如KOH、NaOH等)、氟化物(如KF、NaF等)、硅酸钠(Na₂SiO₃)、碳酸盐(如K₂CO₃、Na₂CO₃等)中的一种或多种，其溶液中沉淀剂的浓度为0.001～5.0mol/L；所述模板剂例子包括(但并不限于)：碳酸铵((NH₄)₂CO₃)、硝酸铵(NH₄NO₃)、硫酸铵((NH₄)₂SO₄)、氯化铵(NH₄Cl)中的一种或多种，所述溶液中铵根的浓度通常为0.001～5.0mol/L。Wherein, examples of titanium salts include, but are not limited to, titanium tetrachloride (TiCl ₄ ), titanium sulfate (Ti(SO ₄ ) ₂ ), tetrabutyl titanate (C ₁₆ H ₃₆ O ₄ Ti) One or more, the concentration of titanium in the solution is usually 0.001 to 5.0 mol / L; examples of the precipitating agent include (but are not limited to): hydroxide (such as KOH, NaOH, etc.), fluoride (such as One or more of KF, NaF, etc., sodium silicate (Na ₂ SiO ₃ ), carbonate (such as K ₂ CO ₃ , Na ₂ CO _{3 ,} etc.), and the concentration of the precipitant in the solution is 0.001 ～ 5.0 mol/L; examples of the templating agent include, but are not limited to, ammonium carbonate ((NH ₄ ) ₂ CO ₃ ), ammonium nitrate (NH ₄ NO ₃ ), ammonium sulfate ((NH ₄ ) ₂ SO ₄ ) And one or more of ammonium chloride (NH ₄ Cl), wherein the concentration of the ammonium in the solution is usually 0.001 to 5.0 mol/L.

(3)多孔锰分子筛的制备：将一定量的锰盐、氧化剂和模板剂分别溶于一定量的去离子水中，各自形成溶液，之后将三种溶液依次转移至同一个反应容器中，在合适的温度(如20～150℃)条件下，反应一段时间(如8～36小时)；生成的产物经干燥(如在80～130℃，干燥2～24小时)，之后在焙烧温度(如200～800℃)焙烧一段时间(如1～12小时)，得到多孔锰分子筛。(3) Preparation of porous manganese molecular sieve: a certain amount of manganese salt, oxidant and templating agent are respectively dissolved in a certain amount of deionized water to form a solution, and then the three solutions are sequentially transferred to the same reaction vessel, at appropriate Under the conditions of temperature (such as 20 ~ 150 ° C), the reaction is carried out for a period of time (such as 8 ~ 36 hours); the resulting product is dried (such as at 80 ~ 130 ° C, dried for 2 ~ 24 hours), then at the roasting temperature (such as 200 ～800 ° C) is calcined for a period of time (eg, 1 to 12 hours) to obtain a porous manganese molecular sieve.

其中，锰盐的例子包括(但并不限于)：硝酸锰(Mn(NO₃)₂)、氯化锰(MnCl₂)、硫酸锰(MnSO₄)、乙酸锰(Mn(CH₃COO)₂)中的一种或多种，所述溶液中锰的浓度通常为0.001～5.0mol/L；所述氧化剂的例子包括(但并不限于)：高锰酸盐(如KMnO₄、NaMnO₄等)、过硫酸铵((NH₄)₂S₂O₈)、过硫酸钾(K₂S₂O₈)、过硫酸钠(Na₂S₂O₈)、氯酸钠(NaClO₃)、过氧化氢(H₂O₂)中的一种或多种，所述溶液中氧化剂的浓度通常为0.001～2.5mol/L；所述模板剂的例子包括(但并不限于)：碳酸铵((NH₄)₂CO₃)、硝酸铵(NH₄NO₃)、硫酸铵((NH₄)₂SO₄)、氯化铵(NH₄Cl)中的一种或多种，所述溶液中铵根的浓度通常为0.001～5.0mol/L。Examples of the manganese salt include, but are not limited to, manganese nitrate (Mn(NO ₃ ) ₂ ), manganese chloride (MnCl ₂ ), manganese sulfate (MnSO ₄ ), manganese acetate (Mn(CH ₃ COO) ₂ One or more of the above, the concentration of manganese in the solution is usually 0.001 to 5.0 mol / L; examples of the oxidizing agent include (but are not limited to): permanganate (such as KMnO ₄ , NaMnO _4, etc.) ), ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ), potassium persulfate (K ₂ S ₂ O ₈ ), sodium persulfate (Na ₂ S ₂ O ₈ ), sodium chlorate (NaClO ₃ ), One or more of hydrogen peroxide (H ₂ O ₂ ), the concentration of the oxidizing agent in the solution is usually 0.001 to 2.5 mol/L; examples of the templating agent include, but are not limited to, ammonium carbonate (( One or more of NH ₄ ) ₂ CO ₃ ), ammonium nitrate (NH ₄ NO ₃ ), ammonium sulfate ((NH ₄ ) ₂ SO ₄ ), ammonium chloride (NH ₄ Cl), ammonium in the solution The concentration of the root is usually 0.001 to 5.0 mol/L.

活性成分、用于形成活性成分的第一沉淀物和活性成分原料Active ingredient, first precipitate and active ingredient raw material for forming active ingredient

用于制备本发明催化剂的另一主要成分是活性成分。Another major component used in the preparation of the catalyst of the invention is the active ingredient.

在本发明中，所述活性成分的例子包括(但并不限于)：铁氧化物、钒氧化物、钼氧化物、或其组合。In the present invention, examples of the active ingredient include, but are not limited to, iron oxide, vanadium oxide, molybdenum oxide, or a combination thereof.

通常，所述的活性成分是由用于形成活性成分的第一沉淀物经任选的干燥和焙烧处理形成。典型地，所述的第一沉淀物包括(但并不限于)：含铁元素、钒元素、钼元素、或其组合的不溶性沉淀，例如氢氧化物、碳酸盐或其组合。Typically, the active ingredient is formed by an optional drying and calcining treatment of the first precipitate used to form the active ingredient. Typically, the first precipitate includes, but is not limited to, an insoluble precipitate comprising an iron element, a vanadium element, a molybdenum element, or a combination thereof, such as a hydroxide, a carbonate, or a combination thereof.

通常，用可溶性的活性成分原料，经沉淀反应而形成所述的第一沉淀物。例如，将活性成分原料与沉淀剂反应形成的不溶性沉淀(第一沉淀物)，其中所述的活性成分原料包括(但并不限于)：铁盐(如氯化亚铁、硫酸亚铁、氯化铁、硝酸铁、或其组合)、钒盐(正钒酸盐、焦钒酸盐、偏钒酸盐、或其组合)、钼盐(钼酸、钼酸钠、钼酸钾、七钼酸铵、或其组合)、或其组合。Typically, the first precipitate is formed by precipitation reaction with a soluble active ingredient material. For example, an insoluble precipitate (first precipitate) formed by reacting an active ingredient raw material with a precipitating agent, wherein the active ingredient raw material includes, but is not limited to, an iron salt (such as ferrous chloride, ferrous sulfate, chlorine) Iron, ferric nitrate, or a combination thereof, vanadium salt (n-vanadate, pyrovanadate, metavanadate, or a combination thereof), molybdenum salt (molybdic acid, sodium molybdate, potassium molybdate, hepta-molybdenum) Ammonium acid, or a combination thereof, or a combination thereof.

在本发明中，所述沉淀反应、干燥处理和焙烧处理的温度和时间没有特别限制。例如，沉淀反应可以进行到大部分(如≥80％，≥90％，或≥95％)所需的产物以沉淀物方式析出。优选地，所述的干燥处理包括80～130℃下干燥。优选地，所述的干燥处理时间为2～24小时。优选地，所述的焙烧的时间为1～72小时，较佳地为1～24小时，更佳地2～12小时。In the present invention, the temperature and time of the precipitation reaction, the drying treatment, and the baking treatment are not particularly limited. For example, the precipitation reaction can proceed to a large portion (e.g., > 80%, > 90%, or > 95%) and the desired product precipitates as a precipitate. Preferably, the drying treatment comprises drying at 80 to 130 °C. Preferably, the drying treatment time is 2 to 24 hours. Preferably, the calcination time is from 1 to 72 hours, preferably from 1 to 24 hours, more preferably from 2 to 12 hours.

助剂、用于形成助剂的第二沉淀物和助剂原料Additive, second precipitate for forming auxiliaries and auxiliary materials

本发明采用的助剂为铈氧化物；所述助剂由含铈元素的不溶性沉淀，即用于形成助剂的第二沉淀物经干燥和焙烧处理所得。The auxiliaries used in the present invention are cerium oxides; the auxiliaries are obtained by insoluble precipitation of cerium-containing elements, that is, a second precipitate for forming auxiliaries, which is dried and calcined.

在另一优选例中，所述的焙烧的时间为1～72小时，较佳地为1～24小时，更佳地2～12小时。 In another preferred embodiment, the calcination time is from 1 to 72 hours, preferably from 1 to 24 hours, more preferably from 2 to 12 hours.

其中，第二沉淀物是助剂原料与沉淀剂反应形成的不溶性沉淀，所述的助剂原料选自下组：硫酸铈、硝酸铈、氯化铈、或其组合。Wherein, the second precipitate is an insoluble precipitate formed by reacting the auxiliary material with the precipitating agent, and the auxiliary material is selected from the group consisting of barium sulfate, barium nitrate, barium chloride, or a combination thereof.

催化剂及其制法Catalyst and its preparation method

本发明的脱硝催化剂包括：多孔分子筛载体，以及负载在载体上的活性成分和助剂。其中，所述活性成分选自下组：铁氧化物、钒氧化物、钼氧化物、或其组合；而所述助剂为铈氧化物；并且，以所述载体的总重量计，所述活性组分在载体上的负载量为1～10wt％，而所述助剂在载体上的负载量为0.5～10wt％；以及所述活性组分和所述助剂的摩尔比为3:1～10:1。The denitration catalyst of the present invention comprises: a porous molecular sieve support, and an active ingredient and an auxiliary agent supported on the carrier. Wherein the active ingredient is selected from the group consisting of iron oxides, vanadium oxides, molybdenum oxides, or combinations thereof; and the auxiliaries are cerium oxides; and, based on the total weight of the carrier, The active component is supported on the carrier in an amount of from 1 to 10% by weight, and the auxiliary agent is supported on the carrier in an amount of from 0.5 to 10% by weight; and the molar ratio of the active component to the auxiliary agent is 3:1 ~10:1.

此外，应理解，本发明的催化剂中还可含有对于所述载体、活性成分和助剂的结构和/或活性无影响或基本无影响的其他成分，例如少量杂质，以硅、铝镁等。优选地，所述载体、活性成分和助剂的总重量占所述催化剂总重量的80-100wt％，较佳地90-100wt％，更佳地98-100wt％。Furthermore, it is to be understood that the catalyst of the present invention may further contain other ingredients which have no or substantially no effect on the structure and/or activity of the carrier, active ingredient and adjuvant, such as small amounts of impurities, such as silicon, aluminum magnesium, and the like. Preferably, the total weight of the carrier, active ingredient and auxiliary agent is from 80 to 100% by weight, preferably from 90 to 100% by weight, more preferably from 98 to 100% by weight, based on the total weight of the catalyst.

在本发明中，所述的活性组分的负载量按金属元素计。所述的助剂的负载量按金属元素计。所述活性组分和所述助剂的摩尔比按各自的金属元素摩尔数计算。In the present invention, the active component is supported in an amount based on the metal element. The loading of the auxiliary agent is based on the metal element. The molar ratio of the active component to the adjuvant is calculated as the number of moles of the respective metal element.

一种优选的催化剂是：以多孔的钨分子筛、钛分子筛和锰分子筛中的一种或多种为载体，以铁氧化物、钒氧化物和钼氧化物中的一种或多种为活性组分，以铈氧化物为助剂，其中活性组分在载体上的负载量为1～10wt％，助剂在载体上的负载量为0.5～10wt％，活性组分和助剂的摩尔比为3:1～10:1。A preferred catalyst is one or more of a porous tungsten molecular sieve, a titanium molecular sieve and a manganese molecular sieve, and one or more of iron oxide, vanadium oxide and molybdenum oxide are used as an active group. The cerium oxide is used as an auxiliary agent, wherein the loading amount of the active component on the carrier is 1 to 10% by weight, the loading amount of the auxiliary agent on the carrier is 0.5 to 10% by weight, and the molar ratio of the active component to the auxiliary agent is 3:1 to 10:1.

本发明还提供了制备所述催化剂的方法，它包括：将本发明的前驱体在一定温度(如200～800℃)进行焙烧，从而形成所述脱硝催化剂。The present invention also provides a process for preparing the catalyst comprising: calcining a precursor of the present invention at a temperature (e.g., 200 to 800 ° C) to form the denitration catalyst.

一个优选的脱硝催化剂的制备方法是共沉淀负载法，它包括步骤：A preferred method of preparing a denitration catalyst is a coprecipitation loading process which includes the steps of:

将铁盐、钒盐、钼盐、或其组合与铈盐溶于一定量的去离子水中，超声分散，形成溶液；将多孔分子筛载体加入上述溶液，搅拌下加入一定量的沉淀剂，反应一段时间(如5分钟～4小时)，形成一固态混合物(即前驱体)。经离心、洗涤，将所述固态混合物经干燥(如在80～130℃，干燥2～24小时)，之后在焙烧温度(如200～800℃)焙烧一段时间(如1～12小时)，得到成品催化剂。Dissolving iron salt, vanadium salt, molybdenum salt, or a combination thereof and strontium salt in a certain amount of deionized water, and dispersing ultrasonically to form a solution; adding the porous molecular sieve carrier to the above solution, adding a certain amount of precipitating agent under stirring, and reacting for a period of time The time (eg, 5 minutes to 4 hours) forms a solid mixture (ie, precursor). After centrifugation and washing, the solid mixture is dried (for example, dried at 80 to 130 ° C for 2 to 24 hours), and then calcined at a calcination temperature (for example, 200 to 800 ° C) for a certain period of time (for example, 1 to 12 hours) to obtain Finished catalyst.

所述铁盐的例子包括(但并不限于)：氯化亚铁、硫酸亚铁、氯化铁、硝酸铁、或其组合，以铁元素摩尔数计，所述溶液中铁的浓度通常为0.001～5.0mol/L；所述钒盐的例子包括(但并不限于)：正钒酸盐、焦钒酸盐和偏钒酸盐或其组合，以钒元素摩尔数计，所述溶液中钒的通常浓度为0.001～5.0mol/L；所述钼盐的例子包括(但并不限于)：钼酸、钼酸钠、钼酸钾、七钼酸铵、或其组合，以钼元素摩尔数计，所述溶液中钼的浓度通常为0.001～5.0mol/L；所述铈盐的例子包括(但并不限于)：硫酸铈、硝酸铈、氯化铈、或其组合，以铈元素摩尔数计，所述溶液中铈的浓度通常为0.001～5.0mol/L；所述沉淀剂的例子包括(但并不限于)：碳酸铵、氨水、尿素、或其组合，所述溶液中沉淀剂的浓度通常为0.001～5.0mol/L。Examples of the iron salt include, but are not limited to, ferrous chloride, ferrous sulfate, ferric chloride, ferric nitrate, or a combination thereof, and the concentration of iron in the solution is usually 0.001 based on the number of moles of iron. ～5.0 mol/L; examples of the vanadium salt include, but are not limited to, orthovanadate, pyrovanadate, and metavanadate or combinations thereof, with vanadium molybdenum The usual concentration of vanadium in the solution is 0.001 to 5.0 mol/L; examples of the molybdenum salt include, but are not limited to, molybdic acid, sodium molybdate, potassium molybdate, ammonium heptamolybdate, or In combination, the concentration of molybdenum in the solution is usually 0.001 to 5.0 mol/L, and the examples of the onium salt include, but are not limited to, barium sulfate, barium nitrate, barium chloride, Or a combination thereof, the concentration of cerium in the solution is usually 0.001 to 5.0 mol/L in terms of moles of cerium element; examples of the precipitating agent include, but are not limited to, ammonium carbonate, ammonia, urea, or In combination, the concentration of the precipitating agent in the solution is usually 0.001 to 5.0 mol/L.

前驱体及其制法Precursor and its preparation

本发明还提供了用于制备脱硝催化剂的前驱体。The present invention also provides a precursor for preparing a denitration catalyst.

典型地，该前驱体包括：多孔分子筛、用于形成活性成分的第一沉淀物和用于形成助剂的第二沉淀物，其中，所述的第一沉淀物是含铁元素、钒元素、钼元素、或其组合的不溶性沉淀；所述的第二沉淀物是含铈元素的不溶性沉淀；Typically, the precursor comprises: a porous molecular sieve, a first precipitate for forming an active ingredient, and a second precipitate for forming an auxiliary, wherein the first precipitate is an iron-containing element, a vanadium element, An insoluble precipitate of molybdenum element, or a combination thereof; the second precipitate is an insoluble precipitate containing cerium;

优选地，所述的多孔分子筛、用于形成活性成分的第一沉淀物和用于形成助剂的第二沉淀物一起形成一固态混合物。Preferably, the porous molecular sieve, the first precipitate used to form the active ingredient, and the second precipitate used to form the adjuvant form a solid mixture.

通常，所述的一固态混合物是通过向溶液中加入沉淀剂而析出的。所述的沉淀剂包括(但并不限于)：碳酸铵、氨水、尿素、或其组合。Typically, the solid mixture is precipitated by the addition of a precipitant to the solution. The precipitating agent includes, but is not limited to, ammonium carbonate, aqueous ammonia, urea, or a combination thereof.

应用application

本发明的脱硝催化剂可用于富碱富硫富水蒸气固定源(生物质燃料电厂、玻璃厂、焦化厂等)烟气的氮氧化物排放控制，即用于富碱富硫富水蒸气固定源的中高温烟气的脱硝处理。The denitration catalyst of the invention can be used for nitrogen oxide emission control of flue gas of alkali-rich sulfur-rich water-saturated fixed source (biomass fuel power plant, glass factory, coking plant, etc.), that is, for the alkali-rich sulfur-rich water vapor fixed source Denitrification treatment of medium and high temperature flue gas.

本发明的主要优点包括：The main advantages of the invention include:

(a)本发明的脱硝的催化剂可同时耐受高浓度的碱(土)金属离子、SO₂和水蒸气而不失活。 (a) The denitrated catalyst of the present invention can simultaneously withstand high concentrations of alkali (earth) metal ions, SO ₂ and water vapor without being deactivated.

(b)本发明的脱硝的催化剂可以耐受较高的温度(200～500℃)而不失活，并且脱硝效率高，N₂选择性好，稳定性好。(b) The denitrated catalyst of the present invention can withstand higher temperatures (200 to 500 ° C) without deactivation, and has high denitration efficiency, good N ₂ selectivity, and good stability.

(c)本发明的脱硝催化剂可用于富碱富硫固定源(生物质燃料电厂、玻璃厂、焦化厂等)烟气的氮氧化物排放控制，应用范围较广。(c) The denitration catalyst of the invention can be used for nitrogen oxide emission control of flue gas of alkali-rich sulfur-rich stationary source (biomass fuel power plant, glass factory, coking plant, etc.), and has a wide application range.

下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法，通常按照常规条件，或按照制造厂商所建议的条件。除非另外说明，否则百分比和份数按重量计算。The invention is further illustrated below in conjunction with specific embodiments. It is to be understood that the examples are not intended to limit the scope of the invention. The experimental methods in the following examples which do not specify the specific conditions are usually in accordance with conventional conditions or according to the conditions recommended by the manufacturer. Percentages and parts are by weight unless otherwise stated.

实施例1：Example 1:

1.多孔分子筛载体的制备：将0.008mol钨酸钠(Na₂WO₄)、0.05mol碳酸铵((NH₄)₂CO₃)、和0.03mol草酸(H₂C₂O₄)分别溶于一定量去离子水中，各自形成溶液，之后将三种溶液依次转移至同一个100ml反应釜中，在160℃条件下，水热反应12小时；生成的产物抽滤洗涤至中性，在80℃干燥24小时，之后在350℃焙烧6小时得到多孔钨分子筛。1. Preparation of porous molecular sieve support: Dissolving 0.008 mol of sodium tungstate (Na ₂ WO ₄ ), 0.05 mol of ammonium carbonate ((NH ₄ ) ₂ CO ₃ ), and 0.03 mol of oxalic acid (H ₂ C ₂ O ₄ ), respectively A certain amount of deionized water was used to form a solution, and then the three solutions were sequentially transferred to the same 100 ml reaction vessel, and hydrothermally reacted at 160 ° C for 12 hours; the resulting product was washed with suction to neutrality at 80 ° C. It was dried for 24 hours and then calcined at 350 ° C for 6 hours to obtain a porous tungsten molecular sieve.

2.活性组分和助剂共沉淀负载：将一定量的偏钒酸盐和硝酸铈(Ce(NO₃)₃)一同溶于一定量的去离子水中，超声分散，形成溶液；将一定量的多孔钨分子筛载体加入上述溶液，控制质量比多孔钨分子筛：偏钒酸盐：硝酸铈＝100:10:7，搅拌下加入一定量的氨水(NH₃·H₂O)，调节pH＝8～9，反应30分钟后离心洗涤，在110℃干燥24小时，之后在450℃焙烧8小时，得到成品催化剂。2. Co-precipitation loading of active components and auxiliaries: a certain amount of metavanadate and cerium nitrate (Ce(NO ₃ ) ₃ ) are dissolved together in a certain amount of deionized water, ultrasonically dispersed to form a solution; The porous tungsten molecular sieve carrier is added to the above solution to control the mass ratio of the porous tungsten molecular sieve: metavanadate: cerium nitrate = 100:10:7, and a certain amount of ammonia water (NH ₃ ·H ₂ O) is added under stirring to adjust the pH=8 ～9, after 30 minutes of reaction, the mixture was centrifuged, dried at 110 ° C for 24 hours, and then calcined at 450 ° C for 8 hours to obtain a finished catalyst.

3.催化剂的性能测试：取0.5g已制备的催化剂放入固定床石英管反应器，石英管内径＝8mm，模拟烟气由NO、NH₃、O₂和N₂组成，其中NO 500ppm、NH₃500ppm、O₂3％，空速400,000h^-1，反应温度200～500℃，反应尾气用NO-NO₂-NO_x分析仪(Thermo42i-HL)在线检测。在该测试条件下，催化剂的脱硝效率稳定在95％以上，N₂选择性在92％以上。3. Performance test of the catalyst: 0.5 g of the prepared catalyst was placed in a fixed bed quartz tube reactor, the inner diameter of the quartz tube was 8 mm, and the simulated flue gas was composed of NO, NH ₃ , O ₂ and N ₂ , wherein NO 500 ppm, NH ₃ 500 ppm, O ₂ 3%, airspeed 400,000 h ^-1 , reaction temperature 200-500 ° C, reaction tail gas was detected on-line with NO-NO ₂ -NO _x analyzer (Thermo42i-HL). Under the test conditions, the denitration efficiency of the catalyst was stabilized above 95%, and the N ₂ selectivity was above 92%.

4.同时抗碱(土)金属和抗硫抗水性能测试：将一定量的碱金属盐氯化钾(KCl)，采用浸渍法高浓度负载到一定质量的催化剂上，K⁺负载浓度为400μmol/g，在350℃焙烧4小时；同时，模拟烟气中额外加入SO₂和水蒸气，使得SO₂浓度为1300mg/m³，水蒸气体积比为10％，其他测试条件不变。在该测试条件下，催化剂的脱硝效率依然稳定在92％以上，SO₂氧化率低于1％，N₂选择性在85％以上，证明催化剂活性未受到高浓度K⁺、SO₂和水蒸气的影响。4. Simultaneous resistance to alkali (earth) metal and sulfur and water resistance test: a certain amount of alkali metal salt potassium chloride (KCl) is loaded onto a certain mass of catalyst by impregnation method, and the K ⁺ loading concentration is 400 μmol. /g, calcined at 350 ° C for 4 hours; at the same time, SO ₂ and water vapor were additionally added to the simulated flue gas so that the SO ₂ concentration was 1300 mg/m ³ and the water vapor volume ratio was 10%, and other test conditions were unchanged. Under the test conditions, the denitration efficiency of the catalyst remained stable above 92%, the SO ₂ oxidation rate was less than 1%, and the N ₂ selectivity was above 85%, demonstrating that the catalyst activity was not affected by high concentrations of K ⁺ , SO ₂ and water vapor. Impact.

实施例2：Example 2:

1.多孔分子筛载体的制备：将0.01mol钨酸钾(K₂WO₄)、0.06mol硝酸铵(NH₄NO₃)和0.025mol柠檬酸(C₆H₈O₇)分别溶于一定量的去离子水中，各自形成溶液，之后将三种溶液依次转移至同一个100ml反应釜中，在180℃条件下，水热反应6小时；生成的产物抽滤洗涤至中性，在105℃干燥12小时，之后在400℃焙烧4小时得到多孔钨分子筛。1. Preparation of porous molecular sieve support: 0.01 mol of potassium tungstate (K ₂ WO ₄ ), 0.06 mol of ammonium nitrate (NH ₄ NO ₃ ) and 0.025 mol of citric acid (C ₆ H ₈ O ₇ ) are respectively dissolved in a certain amount In deionized water, each solution was formed, and then the three solutions were sequentially transferred to the same 100 ml reaction vessel, and hydrothermally reacted at 180 ° C for 6 hours; the resulting product was washed with suction to neutrality and dried at 105 ° C. After hours, it was calcined at 400 ° C for 4 hours to obtain a porous tungsten molecular sieve.

2.活性组分和助剂共沉淀负载：将一定量的氯化亚铁(FeCl₂)、氯化铁(FeCl₃)和氯化铈(CeCl₃)一同溶于一定量的去离子水中，超声分散，形成溶液；将一定量的多孔钨分子筛载体加入上述溶液，控制质量比多孔钨分子筛：氯化亚铁：氯化铁：氯化铈＝100:3:6:4，搅拌下加入一定量的氨水(NH₃·H₂O)，调节pH＝8～9，反应10分钟后离心洗涤，在110℃干燥24小时，之后在350℃焙烧4小时，得到成品催化剂。2. Active component and auxiliary co-precipitation load: a certain amount of ferrous chloride (FeCl ₂ ), ferric chloride (FeCl ₃ ) and cesium chloride (CeCl ₃ ) are dissolved together in a certain amount of deionized water, Ultrasonic dispersion, forming a solution; adding a certain amount of porous tungsten molecular sieve carrier to the above solution, controlling the mass ratio of porous tungsten molecular sieve: ferrous chloride: ferric chloride: cesium chloride = 100:3:6:4, adding a certain amount of stirring The amount of ammonia water (NH ₃ ·H ₂ O) was adjusted to pH=8 to 9, and after 10 minutes of reaction, it was centrifuged and washed, dried at 110 ° C for 24 hours, and then calcined at 350 ° C for 4 hours to obtain a finished catalyst.

3.催化剂的性能测试：取0.5g已制备的催化剂放入固定床石英管反应器，石英管内径＝8mm，模拟烟气由NO、NH₃、O₂和N₂组成，其中NO1000ppm、NH₃1000ppm、O₂3％，空速200,000h^-1，反应温度200～500℃，反应尾气用NO-NO₂-NO_x分析仪(Thermo42i-HL)在线检测。在该测试条件下，催化剂的脱硝效率稳定在95％以上，N₂选择性在92％以上。3. Performance test of the catalyst: 0.5 g of the prepared catalyst was placed in a fixed bed quartz tube reactor, the inner diameter of the quartz tube was 8 mm, and the simulated flue gas was composed of NO, NH ₃ , O ₂ and N ₂ , wherein NO 1000 ppm, NH ₃ 1000 ppm, O ₂ 3%, space velocity 200,000 h ^-1 , reaction temperature 200-500 ° C, reaction tail gas was detected on-line with a NO-NO ₂ -NO _x analyzer (Thermo42i-HL). Under the test conditions, the denitration efficiency of the catalyst was stabilized above 95%, and the N ₂ selectivity was above 92%.

4.同时抗碱(土)金属和抗硫抗水性能测试：将一定量的碱金属盐氯化钾(KCl)，采用浸渍法高浓度负载到一定质量的催化剂上，K⁺负载浓度为700μmol/g，在400℃焙烧8小时；同时，模拟烟气中额外加入SO₂和水蒸气，使得SO₂浓度为1300mg/m³，水蒸气体积比为20％，其他测试条件不变。在该测试条件下，催化剂的脱硝效率依然稳定在90％以上，SO₂氧化率低于1％，N₂选择性在88％以上，证明催化剂活性未受到高浓度K⁺、SO₂和水蒸气的影响。4. Simultaneous resistance to alkali (earth) metal and sulfur and water resistance test: a certain amount of alkali metal salt potassium chloride (KCl) is loaded onto a certain mass of catalyst by impregnation method, and the K ⁺ loading concentration is 700 μmol. /g, calcined at 400 ° C for 8 hours; at the same time, SO ₂ and water vapor were additionally added to the simulated flue gas so that the SO ₂ concentration was 1300 mg/m ³ and the water vapor volume ratio was 20%, and other test conditions were unchanged. Under the test conditions, the denitration efficiency of the catalyst is still stable above 90%, the SO ₂ oxidation rate is less than 1%, and the N ₂ selectivity is above 88%, which proves that the catalyst activity is not affected by high concentrations of K ⁺ , SO ₂ and water vapor. Impact.

实施例3：Example 3:

1.多孔分子筛载体的制备：将0.015mol硫酸钛(Ti(SO₄)₂)、0.08mol氢氧化钠(NaOH)、0.09mol硅酸钠(Na₂SiO₃)和0.03mol硫酸铵((NH₄)₂SO₄)分别溶于一定量的去离子水中，各自形成溶液，之后将三种溶液依次转移至同一个100ml反应釜中，在190℃条件下，水热反应36小时；生成的产物抽滤洗涤至中性，在105℃干燥12小时，得到多孔钛分子筛。 1. Preparation of porous molecular sieve support: 0.015 mol of titanium sulfate (Ti(SO ₄ ) ₂ ), 0.08 mol of sodium hydroxide (NaOH), 0.09 mol of sodium silicate (Na ₂ SiO ₃ ) and 0.03 mol of ammonium sulfate ((NH) ₄ ) ₂ SO ₄ ) are respectively dissolved in a certain amount of deionized water to form a solution, and then the three solutions are sequentially transferred to the same 100 ml reaction kettle, and hydrothermally reacted at 190 ° C for 36 hours; It was washed with suction to neutrality, and dried at 105 ° C for 12 hours to obtain a porous titanium molecular sieve.

2.活性组分和助剂共沉淀负载：将一定量的偏钒酸盐和硝酸铈(Ce(NO₃)₃)一同溶于一定量的去离子水中，超声分散，形成溶液；将一定量的多孔钛分子筛载体加入上述溶液，控制质量比多孔钛分子筛：偏钒酸盐：硝酸铈＝100:8:5，搅拌下加入一定量的氨水(NH₃·H₂O)，调节pH＝8～9，反应1小时后离心洗涤，在110℃干燥24小时，之后在450℃焙烧8小时，得到成品催化剂。2. Co-precipitation loading of active components and auxiliaries: a certain amount of metavanadate and cerium nitrate (Ce(NO ₃ ) ₃ ) are dissolved together in a certain amount of deionized water, ultrasonically dispersed to form a solution; The porous titanium molecular sieve carrier is added to the above solution to control the mass ratio of the porous titanium molecular sieve: metavanadate: cerium nitrate = 100:8:5, and a certain amount of ammonia water (NH ₃ ·H ₂ O) is added under stirring to adjust the pH=8 ～9, the reaction was centrifuged for 1 hour, dried at 110 ° C for 24 hours, and then calcined at 450 ° C for 8 hours to obtain a finished catalyst.

3.催化剂的性能测试：取0.5g已制备的催化剂放入固定床石英管反应器，石英管内径＝8mm，模拟烟气由NO、NH₃、O₂和N₂组成，其中NO500ppm、NH₃500ppm、O₂3％，空速400,000h^-1，反应温度200～500℃，反应尾气用NO-NO₂-NO_x分析仪(Thermo42i-HL)在线检测。在该测试条件下，催化剂的脱硝效率稳定在90％以上，N₂选择性在80％以上。3. Performance test of the catalyst: 0.5 g of the prepared catalyst was placed in a fixed bed quartz tube reactor, the inner diameter of the quartz tube was 8 mm, and the simulated flue gas was composed of NO, NH ₃ , O ₂ and N ₂ , wherein NO 500 ppm, NH ₃ 500 ppm, O ₂ 3%, airspeed 400,000 h ^-1 , reaction temperature 200-500 ° C, reaction tail gas was detected on-line with a NO-NO ₂ -NO _x analyzer (Thermo42i-HL). Under the test conditions, the denitration efficiency of the catalyst was stabilized above 90%, and the N ₂ selectivity was above 80%.

4.同时抗碱(土)金属和抗硫抗水性能测试：将一定量的碱金属盐氯化钾(KCl)，采用浸渍法高浓度负载到一定质量的催化剂上，K⁺负载浓度为400μmol/g，在600℃焙烧6小时；同时，模拟烟气中额外加入SO₂和水蒸气，使得SO₂浓度为2700mg/m³，水蒸气体积比为10％，其他测试条件不变。在该测试条件下，催化剂的脱硝效率依然稳定在90％以上，SO₂氧化率低于1％，N₂选择性在85％以上，证明催化剂活性未受到高浓度K⁺、SO₂和水蒸气的影响。4. Simultaneous resistance to alkali (earth) metal and sulfur and water resistance test: a certain amount of alkali metal salt potassium chloride (KCl) is loaded onto a certain mass of catalyst by impregnation method, and the K ⁺ loading concentration is 400 μmol. /g, calcined at 600 ° C for 6 hours; at the same time, SO ₂ and water vapor were additionally added to the simulated flue gas so that the SO ₂ concentration was 2700 mg/m ³ and the water vapor volume ratio was 10%, and other test conditions were unchanged. Under the test conditions, the denitration efficiency of the catalyst is still stable above 90%, the SO ₂ oxidation rate is less than 1%, and the N ₂ selectivity is above 85%, which proves that the catalyst activity is not affected by high concentrations of K ⁺ , SO ₂ and water vapor. Impact.

实施例4：Example 4:

1.多孔分子筛载体的制备：将0.008mol钨酸钠(Na₂WO₄)、0.05mol硫酸铵((NH₄)₂SO₄)和0.03mol草酸(H₂C₂O₄)分别溶于一定量的去离子水中，各自形成溶液，之后将三种溶液依次转移至同一个100ml反应釜中，在180℃条件下，水热反应3小时；生成的产物抽滤洗涤至中性，在105℃干燥12小时，得到多孔钨分子筛。1. Preparation of porous molecular sieve carrier: respectively dissolve 0.008 mol of sodium tungstate (Na ₂ WO ₄ ), 0.05 mol of ammonium sulfate ((NH ₄ ) ₂ SO ₄ ) and 0.03 mol of oxalic acid (H ₂ C ₂ O ₄ ) The amount of deionized water was each formed into a solution, and then the three solutions were sequentially transferred to the same 100 ml reaction vessel, and hydrothermally reacted at 180 ° C for 3 hours; the resulting product was washed with suction to neutrality at 105 ° C. After drying for 12 hours, a porous tungsten molecular sieve was obtained.

2.活性组分和助剂共沉淀负载：将一定量的七钼酸铵((NH₄)₆Mo₇O₂₄·4H₂O)和氯化铈(CeCl₃)一同溶于一定量的去离子水中，超声分散，形成溶液；将一定量的多孔钨分子筛载体加入上述溶液，控制质量比多孔钨分子筛：七钼酸铵：氯化铈＝100:10:5，搅拌下加入一定量的碳酸铵((NH₄)₂CO₃)，调节pH＝8～9，反应2小时后离心洗涤，在110℃干燥24小时，之后在400℃焙烧12小时，得到成品催化剂。2. Active component and auxiliary co-precipitation load: a certain amount of ammonium heptamolybdate ((NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O) and cesium chloride (CeCl ₃ ) are dissolved together in a certain amount In ionic water, ultrasonically dispersed to form a solution; a certain amount of porous tungsten molecular sieve carrier is added to the above solution to control the mass ratio of porous tungsten molecular sieve: ammonium heptamolybdate: cesium chloride = 100:10:5, and a certain amount of carbonic acid is added under stirring Ammonium ((NH ₄ ) ₂ CO ₃ ), adjusted pH = 8 to 9, after 2 hours of reaction, centrifugally washed, dried at 110 ° C for 24 hours, and then calcined at 400 ° C for 12 hours to obtain a finished catalyst.

3.催化剂的性能测试：取0.5g已制备的催化剂放入固定床石英管反应器，石英管内径＝8mm，模拟烟气由NO、NH₃、O₂和N₂组成，其中NO1000ppm、NH₃1000ppm、O₂3％，空速400,000h^-1，反应温度200～500℃，反应尾气用NO-NO₂-NO_x分析仪(Thermo42i-HL)在线检测。在该测试条件下，催化剂的脱硝效率稳定在93％以上，N₂ 选择性在87％以上。3. Performance test of the catalyst: 0.5 g of the prepared catalyst was placed in a fixed bed quartz tube reactor, the inner diameter of the quartz tube was 8 mm, and the simulated flue gas was composed of NO, NH ₃ , O ₂ and N ₂ , wherein NO 1000 ppm, NH ₃ 1000 ppm, O ₂ 3%, space velocity 400,000 h ^-1 , reaction temperature 200-500 ° C, reaction tail gas was detected on-line with a NO-NO ₂ -NO _x analyzer (Thermo42i-HL). Under the test conditions, the denitration efficiency of the catalyst was stabilized above 93%, and the N ₂ selectivity was above 87%.

4.同时抗碱(土)金属和抗硫抗水性能测试：将一定量的碱金属盐氯化钾(KCl)，采用浸渍法高浓度负载到一定质量的催化剂上，K⁺负载浓度为400μmol/g，在500℃焙烧12小时；同时，模拟烟气中额外加入SO₂和水蒸气，使得SO₂浓度为1300mg/m³，水蒸气体积比为10％，其他测试条件不变。在该测试条件下，催化剂的脱硝效率依然稳定在90％以上，SO₂氧化率低于1％，N₂选择性在83％以上，证明催化剂活性未受到高浓度K⁺、SO₂和水蒸气的影响。4. Simultaneous resistance to alkali (earth) metal and sulfur and water resistance test: a certain amount of alkali metal salt potassium chloride (KCl) is loaded onto a certain mass of catalyst by impregnation method, and the K ⁺ loading concentration is 400 μmol. /g, calcined at 500 ° C for 12 hours; at the same time, SO ₂ and water vapor were additionally added to the simulated flue gas so that the SO ₂ concentration was 1300 mg/m ³ and the water vapor volume ratio was 10%, and other test conditions were unchanged. Under the test conditions, the denitration efficiency of the catalyst is still stable above 90%, the SO ₂ oxidation rate is less than 1%, and the N ₂ selectivity is above 83%, which proves that the catalyst activity is not affected by high concentrations of K ⁺ , SO ₂ and water vapor. Impact.

实施例5：Example 5:

1.多孔分子筛载体的制备：将0.0007mol偏钨酸铵((NH₄)₁₀W₁₂O₄₁·xH₂O)、0.1mol氯化铵(NH₄Cl)和0.02mol聚甲基丙烯酸钠((CH₅NaO₂)n)分别溶于一定量的去离子水中，各自形成溶液，之后将三种溶液依次转移至同一个100ml反应釜中，在160℃条件下，水热反应12小时；生成的产物抽滤洗涤至中性，在105℃干燥12小时，得到多孔钨分子筛。1. Preparation of porous molecular sieve support: 0.0007 mol of ammonium metatungstate ((NH ₄ ) ₁₀ W ₁₂ O ₄₁ · xH ₂ O), 0.1 mol of ammonium chloride (NH ₄ Cl) and 0.02 mol of sodium polymethacrylate ( (CH ₅ NaO ₂ )n) are respectively dissolved in a certain amount of deionized water to form a solution, and then the three solutions are sequentially transferred to the same 100 ml reactor, and hydrothermally reacted at 160 ° C for 12 hours; The product was washed with suction to neutrality and dried at 105 ° C for 12 hours to obtain a porous tungsten molecular sieve.

2.活性组分和助剂共沉淀负载：将一定量的偏钒酸盐和硝酸铈(Ce(NO₃)₃)一同溶于一定量的去离子水中，超声分散，形成溶液；将一定量的多孔钨分子筛载体加入上述溶液，控制质量比多孔钨分子筛：偏钒酸盐：硝酸铈＝100:11:8，搅拌下加入一定量的尿素(CO(NH₂)₂)，调节pH＝8～9，反应30分钟后离心洗涤，在110℃干燥12小时，之后在500℃焙烧8小时，得到成品催化剂。2. Co-precipitation loading of active components and auxiliaries: a certain amount of metavanadate and cerium nitrate (Ce(NO ₃ ) ₃ ) are dissolved together in a certain amount of deionized water, ultrasonically dispersed to form a solution; The porous tungsten molecular sieve carrier is added to the above solution to control the mass ratio of the porous tungsten molecular sieve: metavanadate: cerium nitrate = 100:11:8, and a certain amount of urea (CO(NH ₂ ) ₂ ) is added under stirring to adjust the pH=8 ～9, the reaction was centrifuged for 30 minutes, dried at 110 ° C for 12 hours, and then calcined at 500 ° C for 8 hours to obtain a finished catalyst.

3.催化剂的性能测试：取0.5g已制备的催化剂放入固定床石英管反应器，石英管内径＝8mm，模拟烟气由NO、NH₃、O₂和N₂组成，其中NO500ppm、NH₃500ppm、O₂3％，空速400,000h^-1，反应温度200～500℃，反应尾气用NO-NO₂-NO_x分析仪(Thermo42i-HL)在线检测。在该测试条件下，催化剂的脱硝效率稳定在95％以上，N₂选择性在90％以上。3. Performance test of the catalyst: 0.5 g of the prepared catalyst was placed in a fixed bed quartz tube reactor, the inner diameter of the quartz tube was 8 mm, and the simulated flue gas was composed of NO, NH ₃ , O ₂ and N ₂ , wherein NO 500 ppm, NH ₃ 500 ppm, O ₂ 3%, airspeed 400,000 h ^-1 , reaction temperature 200-500 ° C, reaction tail gas was detected on-line with a NO-NO ₂ -NO _x analyzer (Thermo42i-HL). Under the test conditions, the denitration efficiency of the catalyst was stabilized above 95%, and the N ₂ selectivity was above 90%.

4.同时抗碱(土)金属和抗硫抗水性能测试：将一定量的碱金属盐氯化钙(CaCl₂)，采用浸渍法高浓度负载到一定质量的催化剂上，Ca²⁺负载浓度为400μmol/g，在350℃焙烧12小时；同时，模拟烟气中额外加入SO₂和水蒸气，使得SO₂浓度为2700mg/m³，水蒸气体积比为20％，其他测试条件不变。在该测试条件下，催化剂的脱硝效率依然稳定在91％以上，SO₂氧化率低于1％，N₂选择性在83％以上，证明催化剂活性未受到高浓度Ca²⁺、SO₂和水蒸气的影响。 4. Simultaneous resistance to alkali (earth) metal and sulfur and water resistance test: a certain amount of alkali metal salt calcium chloride (CaCl ₂ ) is loaded onto a certain mass of catalyst by impregnation method, Ca ²⁺ loading concentration It was calcined at 400 ° C for 12 hours at 400 μmol/g; at the same time, SO ₂ and water vapor were additionally added to the simulated flue gas so that the SO ₂ concentration was 2700 mg/m ³ and the water vapor volume ratio was 20%, and other test conditions were unchanged. Under the test conditions, the denitration efficiency of the catalyst is still stable above 91%, the SO ₂ oxidation rate is less than 1%, and the N ₂ selectivity is above 83%, which proves that the catalyst activity is not affected by high concentration of Ca ²⁺ , SO ₂ and water. The effect of steam.

实施例6：Example 6

1.多孔分子筛载体的制备：将0.09mol硫酸锰(MnSO₄)、0.25mol硫酸铵((NH₄)₂SO₄)和0.06mol高锰酸钾(KMnO₄)分别溶于一定量的去离子水中，各自形成溶液，之后将三种溶液依次转移至同一个100ml反应釜中，在140℃条件下，水热反应18小时；生成的产物抽滤洗涤至中性，在105℃干燥10小时，得到多孔锰分子筛。1. Preparation of porous molecular sieve support: 0.09 mol of manganese sulfate (MnSO ₄ ), 0.25 mol of ammonium sulfate ((NH ₄ ) ₂ SO ₄ ) and 0.06 mol of potassium permanganate (KMnO ₄ ) were respectively dissolved in a certain amount of deionized In water, each formed a solution, and then the three solutions were sequentially transferred to the same 100 ml reaction kettle, and hydrothermally reacted at 140 ° C for 18 hours; the resulting product was washed with suction to neutrality, and dried at 105 ° C for 10 hours. A porous manganese molecular sieve was obtained.

2.活性组分和助剂共沉淀负载：将一定量的偏钒酸盐和硝酸铈(Ce(NO₃)₃)一同溶于一定量的去离子水中，超声分散，形成溶液；将一定量的多孔锰分子筛载体加入上述溶液，控制质量比多孔锰分子筛：偏钒酸盐：硝酸铈＝100:5:3，搅拌下加入一定量的氨水(NH₃·H₂O)，调节pH＝8～9，反应1小时后离心洗涤，在110℃干燥12小时，之后在400℃焙烧12小时，得到成品催化剂。2. Co-precipitation loading of active components and auxiliaries: a certain amount of metavanadate and cerium nitrate (Ce(NO ₃ ) ₃ ) are dissolved together in a certain amount of deionized water, ultrasonically dispersed to form a solution; The porous manganese molecular sieve carrier is added to the above solution to control the mass ratio of porous manganese molecular sieve: metavanadate: cerium nitrate = 100:5:3, and a certain amount of ammonia water (NH ₃ ·H ₂ O) is added under stirring to adjust pH=8 ～9, the reaction was centrifuged for 1 hour, dried at 110 ° C for 12 hours, and then calcined at 400 ° C for 12 hours to obtain a finished catalyst.

3.催化剂的性能测试：取0.5g已制备的催化剂放入固定床石英管反应器，石英管内径＝8mm，模拟烟气由NO、NH₃、O₂和N₂组成，其中NO1000ppm、NH₃1000ppm、O₂3％，空速400,000h^-1，反应温度200～500℃，反应尾气用NO-NO₂-NO_x分析仪(Thermo42i-HL)在线检测。在该测试条件下，催化剂的脱硝效率稳定在95％以上，N₂选择性在85％以上。3. Performance test of the catalyst: 0.5 g of the prepared catalyst was placed in a fixed bed quartz tube reactor, the inner diameter of the quartz tube was 8 mm, and the simulated flue gas was composed of NO, NH ₃ , O ₂ and N ₂ , wherein NO 1000 ppm, NH ₃ 1000 ppm, O ₂ 3%, space velocity 400,000 h ^-1 , reaction temperature 200-500 ° C, reaction tail gas was detected on-line with a NO-NO ₂ -NO _x analyzer (Thermo42i-HL). Under the test conditions, the denitration efficiency of the catalyst was stabilized at 95% or more and the N ₂ selectivity was above 85%.

4.同时抗碱(土)金属和抗硫抗水性能测试：将一定量的碱金属盐氯化钾(KCl)，采用浸渍法高浓度负载到一定质量的催化剂上，K⁺负载浓度为1000μmol/g，在400℃焙烧12小时；同时，模拟烟气中额外加入SO₂和水蒸气，使得SO₂浓度为1000mg/m³，水蒸气体积比为20％，其他测试条件不变。在该测试条件下，催化剂的脱硝效率依然稳定在90％以上，SO₂氧化率低于1％，N₂选择性在85％以上，证明催化剂活性未受到高浓度K⁺、SO₂和水蒸气的影响。4. Simultaneous resistance to alkali (earth) metal and sulfur and water resistance test: a certain amount of alkali metal salt potassium chloride (KCl) is applied to a certain mass of catalyst by impregnation method, and the K ⁺ loading concentration is 1000 μmol. /g, calcined at 400 ° C for 12 hours; at the same time, SO ₂ and water vapor were additionally added to the simulated flue gas so that the SO ₂ concentration was 1000 mg/m ³ and the water vapor volume ratio was 20%, and other test conditions were unchanged. Under the test conditions, the denitration efficiency of the catalyst is still stable above 90%, the SO ₂ oxidation rate is less than 1%, and the N ₂ selectivity is above 85%, which proves that the catalyst activity is not affected by high concentrations of K ⁺ , SO ₂ and water vapor. Impact.

在本发明提及的所有文献都在本申请中引用作为参考，就如同每一篇文献被单独引用作为参考那样。此外应理解，在阅读了本发明的上述讲授内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。 All documents mentioned in the present application are hereby incorporated by reference in their entirety in their entireties in the the the the the the the the In addition, it should be understood that various modifications and changes may be made by those skilled in the art in the form of the appended claims.

Claims

一种兼具抗碱(土)金属和抗硫抗水功能的脱硝催化剂，其特征在于，所述的脱硝催化剂包括：多孔分子筛载体，以及负载在载体上的活性成分和助剂；A denitration catalyst having both an alkali (earth) resistance and a sulfur and water resistance function, wherein the denitration catalyst comprises: a porous molecular sieve carrier, and an active ingredient and an auxiliary agent supported on the carrier;

其中，所述活性成分选自下组：铁氧化物、钒氧化物、钼氧化物、或其组合；而所述助剂为铈氧化物；Wherein the active ingredient is selected from the group consisting of iron oxides, vanadium oxides, molybdenum oxides, or combinations thereof; and the auxiliaries are cerium oxides;

并且，以所述载体的总重量计，所述活性组分在载体上的负载量为1～10wt％，而所述助剂在载体上的负载量为0.5～10wt％；Further, the active component is supported on the carrier in an amount of from 1 to 10% by weight based on the total weight of the carrier, and the auxiliary agent is supported on the carrier in an amount of from 0.5 to 10% by weight;

以及所述活性组分和所述助剂的摩尔比为3:1～10:1。And the molar ratio of the active component to the auxiliary agent is from 3:1 to 10:1.
如权利要求1所述的脱硝催化剂，其特征在于，所述的多孔分子筛选自下组：钨分子筛、钛分子筛、锰分子筛、或其组合。The denitration catalyst of claim 1 wherein said porous molecules are selected from the group consisting of tungsten molecular sieves, titanium molecular sieves, manganese molecular sieves, or combinations thereof.
一种前驱体，其特征在于，所述前驱体用于制备权利要求1所述的兼具抗碱(土)金属和抗硫抗水功能的脱硝催化剂，并且所述的前驱体包括：多孔分子筛、用于形成活性成分的第一沉淀物和用于形成助剂的第二沉淀物；A precursor characterized in that the precursor is used for preparing the denitration catalyst having the alkali-resistant (earth) metal and sulfur and water resistance functions according to claim 1, and the precursor comprises: a porous molecular sieve a first precipitate for forming an active ingredient and a second precipitate for forming an auxiliary;

其中，所述的多孔分子筛选自下组：钨分子筛、钛分子筛、锰分子筛、或其组合；Wherein, the porous molecules are screened from the following group: a tungsten molecular sieve, a titanium molecular sieve, a manganese molecular sieve, or a combination thereof;

所述的第一沉淀物是含铁元素、钒元素、钼元素、或其组合的不溶性沉淀；The first precipitate is an insoluble precipitate containing iron, vanadium, molybdenum, or a combination thereof;

所述的第二沉淀物是含铈元素的不溶性沉淀；The second precipitate is an insoluble precipitate containing cerium;

并且，以所述载体的总重量计，所述第一沉淀物在载体上的负载量为1～10wt％，而所述第二沉淀物在载体上的负载量为0.5～10wt％，其中负载量按第一沉淀物和第二沉淀物各自的金属元素计；And, the first precipitate is supported on the carrier in an amount of from 1 to 10% by weight based on the total weight of the carrier, and the second precipitate is supported on the carrier in an amount of from 0.5 to 10% by weight, wherein the load is The amount is based on the respective metal elements of the first precipitate and the second precipitate;

以及所述活性组分和所述助剂的摩尔比为3:1～10:1，其中所述摩尔比按各自的金属元素摩尔数计算。And the molar ratio of the active component to the auxiliary agent is from 3:1 to 10:1, wherein the molar ratio is calculated as the number of moles of the respective metal element.
如权利要求3所述的前驱体，其特征在于，所述的多孔分子筛、用于形成活性成分的第一沉淀物和用于形成助剂的第二沉淀物形成一固态混合物。The precursor according to claim 3, wherein said porous molecular sieve, a first precipitate for forming an active ingredient, and a second precipitate for forming an auxiliary agent form a solid mixture.
一种权利要求1所述的兼具抗碱(土)金属和抗硫抗水功能的脱硝催化剂的制备方法，其特征在于，包括步骤：A method for preparing a denitration catalyst having the function of resisting alkali (earth) metal and sulfur and water resistance according to claim 1, characterized in that it comprises the steps of:

(i)提供如权利要求3所述的前驱体；和(i) providing the precursor of claim 3;

(ii)所述的前驱体在200～800℃进行焙烧，从而形成得到如权利要求1所述的脱硝催化剂。(ii) The precursor is calcined at 200 to 800 ° C to form the denitration catalyst according to claim 1.
一种制备权利要求3所述的前驱体的制备方法，其特征在于，包括步骤：A method for preparing a precursor according to claim 3, comprising the steps of:

(a)提供多孔分子筛载体、溶剂、活性成分原料、助剂原料和沉淀剂；(a) providing a porous molecular sieve carrier, a solvent, an active ingredient raw material, an auxiliary raw material, and a precipitating agent;

(b)将所述多孔分子筛载体、溶剂、活性成分原料、助剂原料和沉淀剂进行混合，形成第一混合物，(b) mixing the porous molecular sieve carrier, the solvent, the active ingredient raw material, the auxiliary raw material and the precipitating agent to form a first mixture,

其中，所述活性成分原料与沉淀剂反应形成用于形成活性成分的第一沉淀物；并且所述助剂原料与沉淀剂反应形成用于形成助剂的第二沉淀物，并形成含所述的多孔分子筛载体、所述第一沉淀物和所述第二沉淀物的固态沉淀物；和Wherein the active ingredient raw material reacts with a precipitating agent to form a first precipitate for forming an active ingredient; and the auxiliary raw material reacts with a precipitating agent to form a second precipitate for forming an auxiliary agent, and is formed a porous molecular sieve support, a solid precipitate of the first precipitate and the second precipitate; and

(c)从所述第一混合物中分离出所述的固态沉淀物，即为所述前体；(c) separating said solid precipitate from said first mixture, that is, said precursor;

其中，所述的活性成分原料选自下组：铁盐、钒盐、钼盐、或其组合；所述助剂原料选自下组：硫酸铈、硝酸铈、氯化铈、或其组合；所述的多孔分子筛选自下组：钨分子筛、钛分子筛、锰分子筛、或其组合；所述的沉淀剂选自下组：碱金属氢氧化物、碱土金属氢氧化物、氨水、尿素、碳酸盐、或其组合。Wherein the active ingredient raw material is selected from the group consisting of iron salt, vanadium salt, molybdenum salt, or a combination thereof; the auxiliary material is selected from the group consisting of barium sulfate, barium nitrate, barium chloride, or a combination thereof; The porous molecules are screened from the following group: tungsten molecular sieves, titanium molecular sieves, manganese molecular sieves, or a combination thereof; the precipitating agent is selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, ammonia water, urea, carbon An acid salt, or a combination thereof.
如权利要求5所述的前驱体制备方法，其特征在于，在步骤(b)中，包括：The method of preparing a precursor according to claim 5, wherein in the step (b), the method comprises:

(b1)提供一液态混合物，所述液态混合物含有：溶剂、活性成分原料和助剂原料；(b1) providing a liquid mixture comprising: a solvent, an active ingredient raw material, and an auxiliary raw material;

(b2)将所述液态混合物与多孔分子筛载体和沉淀剂进行混合，从而形成所述的第一混合物。(b2) mixing the liquid mixture with a porous molecular sieve support and a precipitating agent to form the first mixture.
如权利要求5所述的前驱体制备方法，其特征在于，所述方法还包括：在步骤(a)之前，制备多孔分子筛的步骤。The method of preparing a precursor according to claim 5, wherein the method further comprises the step of preparing a porous molecular sieve before the step (a).
一种脱硝方法，其特征在于，如权利要求1所述的脱硝催化剂与富碱富硫固定源烟气的氮氧化物相互接触。A denitration method characterized in that the denitration catalyst according to claim 1 is in contact with the nitrogen oxides of the alkali-rich sulfur-rich fixed source flue gas.
一种如权利要求1所述的脱硝催化剂的用途，其特征在于，所述的脱硝催化剂用于富碱富硫固定源烟气的氮氧化物排放控制。 Use of a denitration catalyst according to claim 1 wherein said denitration catalyst is used for NOx emission control of an alkali-rich sulfur-rich stationary source flue gas.