CN115770587A

CN115770587A - Used for reducing SO in flue gas x With NO x Catalyst, preparation method and application thereof, and flue gas SO removal x And NO x Method (2)

Info

Publication number: CN115770587A
Application number: CN202111055118.0A
Authority: CN
Inventors: 姜秋桥; 宋海涛; 曲亚坤; 林伟; 王林
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2021-09-09
Filing date: 2021-09-09
Publication date: 2023-03-10

Abstract

The invention relates to the technical field of industrial catalysis, and discloses a method for simultaneously reducing SO in flue gas _x With NO _x Catalyst, preparation method and application thereof, and simultaneous SO removal of flue gas _x And NO _x The method of (1). For simultaneously reducing SO in flue gas _x With NO _x The catalyst of (1) contains 25 to 95 wt% of inorganic oxide based on the total weight of the catalystA substrate; 2-70 wt% rare earth metal component calculated on oxide; 1-30 wt% group IIA metal component, calculated as oxide; 1-15 wt% of one or more non-noble metal components selected from VB, VIII, IB and IIB groups calculated by oxide; 1-10 wt%, calculated as oxide, of a group VIIB non-noble metal component; 0.01 to 1.5% by weight, calculated as element, of a noble metal component. The catalyst provided by the invention is simple in preparation method, and can effectively reduce SO in flue gas _x And NO _x And (4) discharging.

Description

Used for reducing SO in flue gas x With NO x Catalyst, preparation method and application thereof, and flue gas SO removal x And NO x Method (2)

Technical Field

The invention relates to the technical field of industrial catalysis, in particular to a method for simultaneously reducing SO in flue gas _x With NO _x Catalyst, preparation method and application thereof, and simultaneous SO removal of flue gas _x And NO _x The method of (1).

Background

During the catalytic cracking reaction, coke is deposited on the catalyst due to the reaction of hydrocarbons, and the activity of the catalyst is reduced. The coke-containing catalyst is passed through a stripping section to remove hydrocarbons adsorbed on the catalyst and then passed to a regenerator. The coke-containing catalyst in the regenerator is fully contacted with air at high temperature, and the coke on the surface of the catalyst is burnt, so that the activity of the catalyst is recovered. SO is generated when the catalyst is burnt _x And NO _x And the like, which are discharged into the air to pollute the atmosphere. Along with the stricter environmental protection requirements, the emission standard of the smoke pollutants is stricter.

The main technical measures for reducing the emission of catalytic cracking regeneration flue gas pollutants at present comprise: the regenerator is optimized, and an auxiliary agent and flue gas post-treatment are used, wherein the method for adding the auxiliary agent is generally applied due to the advantages of flexible operation, no investment on facility cost and the like. At present, the desulfurization and denitrification auxiliary agent is mainly used for independently removing a smoke pollutant. For example: CN1334316A disclosesA composition containing magnesium aluminate spinel and the sulfur transfer agent of cerium/vanadium oxide for removing SO from catalytic cracking fume _x . CN101311248B provides a catalyst capable of reducing NO in catalytic cracking regeneration flue gas _x Composition for reducing NO in catalytic cracking flue gas _x 。

The above patent documents separately remove SO from the regenerated flue gas _x And NO _x When the method is used, the method has a good removal effect, but can not simultaneously remove nitrogen oxides and sulfur oxides. In addition, the total addition amount of the auxiliary agent is too large, and the cost is high.

Disclosure of Invention

The invention aims to solve the problem of overhigh cost in the prior desulfurization and denitrification technology, and provides a method for simultaneously reducing SO in flue gas _x With NO _x Catalyst, preparation method and application thereof, and simultaneous SO removal of flue gas _x And NO _x The method of (1). The catalyst provided by the invention has a simple preparation method, and can effectively reduce SO in flue gas _x And NO _x And (4) discharging.

In order to achieve the above object, the present invention provides, in a first aspect, a method for simultaneously reducing SO in flue gas _x With NO _x The catalyst of (1), comprising 25 to 95 wt% of an inorganic oxide matrix, based on the total weight of the catalyst; 2-70 wt% rare earth metal component calculated on oxide; 1-30 wt% group IIA metal component, calculated as oxide; 1-15 wt% of one or more non-noble metal components selected from VB, VIII, IB and IIB groups calculated by oxide; 1-10 wt%, calculated as oxide, of a group VIIB non-noble metal component; 0.01 to 1.5% by weight, calculated as element, of a noble metal component.

Preferably, the molar ratio of the rare earth metal component to the non-noble metal component selected from one or more of groups VB, VIII, IB and IIB is (0.4-18): 1, more preferably (0.5-12): 1, and still more preferably (1-6): 1.

The second aspect of the invention provides a method for simultaneously reducing SO in flue gas _x With NO _x The method for preparing a catalyst of (1), which comprises the steps of:

(1) Obtaining an active metal precursor by adopting a coprecipitation method or a sol-gel method;

(2) Mixing and pulping an active metal precursor, an inorganic oxide matrix and/or a precursor of the inorganic oxide matrix and optionally a precursor of a noble metal component to obtain a slurry, and drying and/or roasting the slurry to obtain a composition;

the method also optionally includes: (3) Taking a solution containing a precursor of a noble metal component as an impregnation solution, impregnating the composition obtained in the step (2) to obtain a solid product, and then drying and/or roasting the solid product;

wherein the active metal in the active metal precursor comprises rare earth metal components, IIA metal components, non-noble metal components selected from one or more of VB, VIII, IB and IIB groups and VIIB non-noble metal components;

the active metal precursor, the inorganic oxide matrix and/or the precursor of the inorganic oxide matrix and the noble metal component precursor are used in such amounts that the prepared catalyst contains 25 to 95 weight percent of the inorganic oxide matrix based on the total weight of the catalyst; 2-70 wt% rare earth metal component calculated on oxide; 1-30 wt% of a group IIA metal component, calculated as oxide; 1-15 wt% calculated by oxide of one or more non-noble metal components selected from VB, VIII, IB and IIB groups; 1-10 wt%, calculated as oxide, of a group VIIB non-noble metal component; 0.01 to 1.5% by weight, calculated as element, of a noble metal component.

The third aspect of the invention provides the catalyst of the first aspect and the catalyst prepared by the preparation method of the second aspect for removing SO while catalytically cracking the regenerated flue gas _x And NO _x Application in reactions.

The fourth aspect of the invention provides a method for simultaneously removing SO from flue gas _x And NO _x The method of (1), comprising: in the process of removing SO _x And NO _x Under the conditions of (1), SO as to contain SO _x And NO _x Is contacted with the catalyst of the first aspect and the catalyst prepared by the preparation method of the second aspect.

The invention provides a catalystCan effectively reduce NO in catalytic cracking regeneration flue gas _x And SO _x Emissions, presumably due to: the introduction of trace noble metal changes the geometric electronic structure of other metal oxide compositions in the catalyst, greatly improves the oxidation-reduction capability of the catalyst, and is beneficial to promoting SO _x Oxidation and p-NO _x Reduction of (2); on the basis, the removal of NO by the catalyst combination can be greatly improved by matching one or more non-noble metal components of VB, VIII, IB and IIB groups with the IIA group metal component _x And SO _x The ability of the cell to perform. The catalyst provided by the invention is simple in preparation method, and can effectively reduce SO in catalytic cracking regeneration flue gas _x And NO _x During which the dissociated NO is adsorbed by the catalyst _x Can promote SO _x Conversion to sulfate, thereby effecting simultaneous removal of SO _x And NO _x The purpose of (1).

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

The invention provides a method for simultaneously reducing SO in flue gas _x With NO _x The catalyst of (1), characterized in that it contains 25 to 95% by weight of an inorganic oxide matrix, based on the total weight of the catalyst; 2-70 wt% rare earth metal component calculated on oxide; 1-30 wt% group IIA metal component, calculated as oxide; 1-15 wt% calculated by oxide of one or more non-noble metal components selected from VB, VIII, IB and IIB groups; 1-10 wt%, calculated as oxide, of a group VIIB non-noble metal component; 0.01 to 1.5% by weight, calculated as element, of a noble metal component.

According to the present invention, it is preferred that the catalyst contains 40 to 90 wt% of an inorganic oxide matrix, based on the total weight of the catalyst; 4-50 wt% rare earth metal component calculated on oxide; 1-20 wt% group IIA metal component, calculated as oxide; 2-12 wt% of one or more non-noble metal components selected from VB, VIII, IB and IIB groups calculated by oxide; 1-8 wt%, calculated as oxide, of a group VIIB non-noble metal component; 0.02 to 1.2% by weight calculated as element of a noble metal component; more preferably, it contains 50-80 wt% of inorganic oxide matrix based on the total weight of the catalyst; 4-40 wt% rare earth metal component calculated on oxide; 2-15 wt% of a group IIA metal component, calculated as oxide; 2-10 wt% calculated by oxide of one or more non-noble metal components selected from VB, VIII, IB and IIB groups; 2-5 wt%, calculated as oxide, of a group VIIB non-noble metal component; 0.02 to 1.0% by weight, calculated as element, of a noble metal component; most preferably, from 50 to 80 wt% of an inorganic oxide matrix, based on the total weight of the catalyst; 7-38 wt% rare earth metal component calculated as oxide; 2-8 wt% group IIA metal component, calculated as oxide; 2-7 wt% of one or more non-noble metal components selected from VB, VIII, IB and IIB groups calculated by oxide; 2-5 wt%, calculated as oxide, of a group VIIB non-noble metal component; 0.02 to 0.05% by weight, calculated as element, of a noble metal component. In the preferred embodiment, the metal with a specific content is used in combination, so that the consumption of the noble metal can be greatly reduced, and the cost can be reduced.

According to the invention, the conventionally defined rare earth metal components can be used according to the invention in order to further increase the SO removal of the catalyst _x With NO _x Preferably, the rare earth metal component is selected from one or more of lanthanum, cerium, praseodymium and neodymium, more preferably lanthanum and/or cerium, and most preferably lanthanum.

According to the invention, the group IIA metal component is selected from one or more of beryllium, magnesium, calcium, strontium and barium, and more preferably magnesium.

The group VB non-noble metal component may be selected from at least one of vanadium, niobium and tantalum; the group VIII non-noble metal component may be selected from at least one of iron, cobalt and nickel; the group IB non-noble metal component may be copper; the group IIB non-noble metal component may be selected from at least one of zinc, cadmium, and mercury.

Preferably, said non-noble metal component of one or more of groups VB, VIII, IB, IIB is selected from one or more of iron, cobalt, nickel, copper, zinc and vanadium, more preferably cobalt and/or iron, most preferably cobalt.

Preferably, the non-noble group VIIB metal component is manganese.

Preferably, the noble metal component is selected from one or more of ruthenium, rhodium, rhenium, platinum, palladium, silver, iridium and gold, more preferably one or more of platinum, palladium and rhodium, and most preferably palladium.

According to the catalyst provided by the present invention, the inorganic oxide matrix may be various inorganic oxide matrices conventionally used in the art, for example, at least one selected from the group consisting of alumina, silica-alumina, zeolite, spinel, kaolin, diatomaceous earth, perlite, and perovskite. In the present invention, the spinel may be various commonly used spinels, and may be at least one of magnesium aluminate spinel, zinc aluminate spinel, and titanium aluminate spinel, for example.

According to a preferred embodiment of the invention, the inorganic oxide matrix is alumina.

In the present invention, the alumina may be at least one selected from the group consisting of γ -alumina, δ -alumina, η -alumina, ρ -alumina, κ -alumina and χ -alumina, and the present invention is not particularly limited thereto.

According to a preferred embodiment of the present invention, the molar ratio of the rare earth metal component to the non-noble metal component selected from one or more of groups VB, VIII, IB and IIB is (0.4-18): 1, more preferably (0.5-12): 1, and still more preferably (1-6): 1, calculated as the metal element.

According to a particularly preferred embodiment of the invention, the catalyst comprises from 50 to 80% by weight, based on the total weight of the catalyst, of alumina; 7-38% by weight, calculated as oxide, of lanthanum; 2-8% by weight, calculated as oxide, of magnesium; 2-7 wt% cobalt calculated as oxide; 2-5 wt% manganese, calculated as oxide; 0.02 to 0.05% by weight calculated as element of palladium; more preferred conditionsIn the case of the catalyst, the molar ratio of lanthanum to cobalt is (1-6): 1. The inventor of the invention finds that at least one of rare earth element La and IIA group element Mg and transition non-noble metal element containing Co and Mn and noble metal element is used as an active component in the research process, so that the NO of the catalytic cracking regeneration flue gas can be particularly effectively reduced _x And SO _x And (5) discharging. Presumably, the reason for this is probably due to: the introduction of trace noble metal changes the geometric electronic structure of the metal oxide composition, greatly improves the oxidation-reduction capability of the metal oxide composition, and is favorable for promoting SO _x Oxidation and p-NO _x Reduction of (2); on the basis of this, introduction of p-NO _x Mn and para SO with good decomposition capability _x Mg with good adsorption capacity greatly improves the NO removal of the catalyst combination _x And SO _x The ability of the cell to perform.

the method also optionally includes: (3) Taking a solution containing a precursor of a noble metal component as an impregnation liquid, impregnating the composition obtained in the step (2) to obtain a solid product, and then drying and/or roasting the solid product;

the active metal precursor, the inorganic oxide matrix and/or the precursor of the inorganic oxide matrix and the precursor of the noble metal component are used in such amounts that the prepared catalyst contains 25 to 95 weight percent of the inorganic oxide matrix based on the total weight of the catalyst; 2-70 wt% rare earth metal component calculated on oxide; 1-30 wt% group IIA metal component, calculated as oxide; 1-15 wt% of one or more non-noble metal components selected from VB, VIII, IB and IIB groups calculated by oxide; 1-10 wt%, calculated as oxide, of a group VIIB non-noble metal component; 0.01 to 1.5% by weight, calculated as element, of a noble metal component.

According to the present invention, preferably, the active metal precursor, the inorganic oxide matrix and/or the precursor of the inorganic oxide matrix and the noble metal component precursor are used in such amounts that the resulting catalyst contains 40 to 90 wt% of the inorganic oxide matrix, based on the total weight of the catalyst; 4 to 50 wt% of a rare earth metal component, calculated as oxide; 1-20 wt% group IIA metal component, calculated as oxide; 2-12 wt% of one or more non-noble metal components selected from VB, VIII, IB and IIB groups calculated by oxide; 1-8 wt%, calculated as oxide, of a group VIIB non-noble metal component; 0.02 to 1.2% by weight, calculated as element, of a noble metal component; more preferably, the active metal precursor, the inorganic oxide matrix and/or the precursor of the inorganic oxide matrix and the precursor of the noble metal component are used in such amounts that the resulting catalyst contains 5 to 80 wt% of the inorganic oxide matrix, based on the total weight of the catalyst; 4-40 wt% rare earth metal component calculated on oxide; 2-15 wt% of a group IIA metal component, calculated as oxide; 2-10 wt% calculated by oxide of one or more non-noble metal components selected from VB, VIII, IB and IIB groups; 2-5 wt%, calculated as oxide, of a group VIIB non-noble metal component; 0.02 to 1.0% by weight, calculated as element, of a noble metal component; most preferably, the catalyst comprises 50 to 80 wt% of an inorganic oxide matrix, based on the total weight of the catalyst; 7-38 wt% rare earth metal component calculated as oxide; 2-8 wt% group IIA metal component, calculated as oxide; 2-7 wt% calculated by oxide of one or more non-noble metal components selected from VB, VIII, IB and IIB groups; 2-5 wt%, calculated as oxide, of a group VIIB non-noble metal component; 0.02-0.05% by weight calculated as element of a noble metal component.

Preferably, the molar ratio of the rare earth metal component to the non-noble metal component selected from one or more of groups VB, VIII, IB and IIB in the active component precursor is (0.4-18): 1, more preferably (0.5-12): 1, and even more preferably (1-6): 1.

In the method provided by the present invention, the selection ranges of the specific types of the rare earth metal component, the IIA group metal component, one or more of the non-noble metal components of the VB, VIII, IB, IIB groups, the VIIB group non-noble metal component, the noble metal component, and the inorganic oxide matrix are as described in the first aspect above, and are not described herein again.

The method provided by the invention can adopt a coprecipitation method, also can adopt a sol-gel method, and more preferably adopts the coprecipitation method. Preferably, the active metal precursor is obtained in the step (1) by a coprecipitation method; more preferably, the co-precipitation method comprises:

(1-1) providing a first solution containing a rare earth metal component precursor, a IIA metal component precursor, one or more non-noble metal component precursors selected from VB, VIII, IB and IIB groups, and a VIIB non-noble metal component precursor;

(1-2) performing a coprecipitation reaction on the first solution and a coprecipitator;

(1-3) drying and/or roasting a solid product obtained by the coprecipitation reaction.

The method for obtaining the first solution in step (1-1) is not particularly limited in the present invention, as long as the metal component precursors are uniformly mixed. For example, each metal component precursor may be dissolved in water and sufficiently stirred to be uniform.

According to the present invention, preferably, the rare earth metal component precursor, the group IIA metal component precursor, the non-noble metal component precursor selected from one or more of groups VB, VIII, IB, IIB, and the group VIIB non-noble metal component precursor may each be independently selected from water-soluble salts of each metal component, such as nitrate, chloride, chlorate, sulfate, and the like, preferably nitrate and/or chloride. In particular, the precursor of manganese can be potassium permanganate and/or manganese chloride.

According to the present invention, the noble metal component precursor may be selected from any water-soluble compound containing the noble metal component, and preferably, the noble metal component precursor is selected from at least one of palladium nitrate, palladium chloride, chloroplatinic acid, and rhodium chloride, and further preferably, palladium nitrate and/or palladium chloride.

In the present invention, the kind and amount of the coprecipitate are not particularly limited as long as the coprecipitation reaction can be smoothly performed. The kind of the coprecipitate may be conventionally selected in the art, and preferably, the coprecipitate is a carbonate, further preferably at least one selected from ammonium carbonate, potassium carbonate, and sodium carbonate, and more preferably ammonium carbonate.

In the step (1-2), the coprecipitate may be introduced in the form of a solution, and may perform a coprecipitation reaction with the first solution. The concentrations of the first solution and the solution of the coprecipitate are not particularly limited in the present invention, as long as the solution concentration is less than the solubility at the time of preparation, thereby ensuring that the coprecipitation reaction can sufficiently occur.

Preferably, the coprecipitation reaction is carried out at a pH of 8 to 10, preferably 8.5 to 9.5. The pH of the coprecipitation reaction may be adjusted by adding an acid and/or a base, and the specific type thereof is not particularly limited, and for example, ammonia water may be used.

According to the invention, the method also comprises the step of carrying out solid-liquid separation (such as filtration or centrifugal separation) on the reaction product obtained by the coprecipitation reaction to obtain the solid product.

Preferably, the drying conditions of step (1-3) include: the temperature is 60-150 ℃ and the time is 4-12h.

Preferably, the roasting conditions in the step (1-3) include: the temperature is 300-800 ℃ and the time is 1-8h.

The noble metal component in the present invention may be introduced in step (2), or in step (3), or in part in step (2), or in part in step (3), preferably by being introduced in step (3), and this preferred embodiment is more advantageous for the dispersion of the noble metal.

The precursor of the inorganic oxide matrix is any substance that can be converted into an oxide matrix by subsequent calcination, and those skilled in the art can appropriately select the precursor by the specific kind of the specific inorganic oxide matrix, and the detailed description of the present invention is omitted here. For example, the precursor of alumina may be selected from various sols or gels of aluminum, or aluminum hydroxide. The aluminum hydroxide may be selected from at least one of gibbsite, surge dam, nordstrandite, diaspore, boehmite, and pseudoboehmite. Most preferably, the precursor of alumina is pseudo-boehmite.

According to the preparation method provided by the invention, the inorganic oxide matrix is alumina, preferably, before pulping, the inorganic oxide matrix and/or the precursor of the inorganic oxide matrix is subjected to acidification treatment, wherein the acidification treatment can be carried out according to the conventional technical means in the field, and further preferably, the acid used in the acidification treatment is hydrochloric acid.

The present invention has a wide selection range of the acidification conditions, and preferably, the acidification conditions include: the acid aluminum ratio is 0.12-0.22:1, the time is 20-40min.

In the present invention, the aluminum acid ratio refers to a mass ratio of hydrochloric acid calculated as 36% by weight of concentrated hydrochloric acid to a precursor of alumina on a dry basis, unless otherwise specified.

The specific implementation mode of the acidification peptization treatment can be as follows: adding the alumina precursor into water, pulping and dispersing.

According to the present invention, there is no particular limitation on the method of mixing and beating the active metal precursor with the inorganic oxide substrate and/or the precursor of the inorganic oxide substrate and optionally the precursor of the noble metal component, and there is no particular limitation on the order of addition of the active metal precursor with the inorganic oxide substrate and/or the precursor of the inorganic oxide substrate and optionally the precursor of the noble metal component as long as the active metal precursor is brought into contact with the inorganic oxide substrate and/or the precursor of the inorganic oxide substrate and optionally the precursor of the noble metal component and water. When the pulping process further contains a precious metal component precursor, the specific mixing and pulping process may include: adding a noble metal component precursor (which can be introduced in a solution form) into the acidified inorganic oxide matrix, mixing and pulping, adding an active metal precursor, and drying and/or roasting the slurry to obtain a catalyst finished product.

According to the present invention, preferably, the slurry of step (2) has a solid content of 5 to 40% by weight.

The drying in step (2) is preferably spray drying, and in the present invention, the spray drying may be performed according to a method generally used in the art, and the present invention is not particularly limited thereto. Those skilled in the art can select suitable spray drying conditions according to the average particle size of the target catalyst, and preferably spray drying conditions are such that the spray-dried particles have an average particle size of 60 to 80 μm and a particle size distribution mainly ranging from 20 to 100 μm.

Preferably, the roasting conditions in step (2) include: the temperature is 300-800 ℃ and the time is 1-5h.

According to the production method of the present invention, the impregnation in the step (3) is not particularly limited, and may be carried out according to a conventional technique in the art, and may be a saturated impregnation or an excess impregnation, and is preferably an excess impregnation.

According to the present invention, preferably, in step (3), the noble metal component precursor is hydrolyzed in an acid solution to provide the impregnation liquid. Specifically, it is also possible to dilute (water may be added) or concentrate (evaporation may be carried out) after the hydrolysis and then carry out the impregnation to provide a catalyst at a specific noble metal component loading.

Preferably, the acid is selected from water-soluble inorganic and/or organic acids, preferably at least one selected from hydrochloric acid, nitric acid, phosphoric acid and acetic acid.

According to the invention, the acid is preferably used in such an amount that the pH of the impregnation liquor is less than 6.0, preferably less than 5.0. The adoption of the preferred embodiment is more beneficial to uniformly dispersing the active components and improving the abrasion resistance of the finished catalyst.

The solid product can be obtained by filtering the mixture obtained after impregnation. The filtration can be carried out according to the means conventional in the art.

In the step (3) of the present invention, only the solid product may be dried, only the solid product may be calcined, or the solid product may be dried and then calcined. The conditions for the drying and calcination in the present invention are not particularly limited, and may be carried out according to the conventional techniques in the art. For example, the conditions of drying may include: the temperature is 60-150 ℃ and the time is 2-10h. The conditions of the calcination in the present invention are not particularly limited, the calcination may be performed in air or an inert atmosphere (e.g., nitrogen), and the calcination in the step (3) is preferably performed under the following conditions: the temperature is 300-800 deg.C, and the time is 0.1-5h.

The catalyst provided by the invention is suitable for any SO-containing catalyst _x And NO _x The flue gas treatment is particularly suitable for removing SO in catalytic cracking regeneration flue gas _x And NO _x . Based on the above, the third aspect of the invention provides the catalyst of the first aspect and the catalyst prepared by the preparation method of the second aspect for removing SO while catalytically cracking the regenerated flue gas _x And NO _x Application in reactions.

The fourth aspect of the invention provides a method for simultaneously removing SO from flue gas _x And NO _x The method of (1), comprising: in the removal of SO _x And NO _x Under the conditions of (1), SO as to contain SO _x And NO _x Is contacted with the catalyst of the first aspect and the catalyst prepared by the preparation method of the second aspect.

Preferably, said SO removal _x And NO _x The conditions of (a) include: the temperature is 500-800 ℃, the pressure is 0.02-4MPa, and the volume space velocity of the flue gas is 100-50000h ^-1 (ii) a Further preferably, the temperature is 550-780 ℃, the pressure is 0.03-2MPa, and the volume space velocity of the flue gas is 200-20000h ^-1 . In the present invention, the pressure is not particularly limited, and is a gauge pressure.

The invention is used for treating SO in the flue gas _x And NO _x The content of (B) is selected from a wide range as long as SO is contained _x And NO _x I.e. to facilitate removal of both. Preferably, SO is contained in the flue gas _x In an amount of 0.001-0.5 vol%, NO _x The content of (B) is 0.001-0.3 vol%; further preferably, the flue gas contains SO _x In an amount of 0.002-0.2 vol%, NO _x The content of (B) is 0.002-0.2 vol%.

Preferably, SO is contained in the flue gas _x With NO _x The volume content ratio of (A) is 1-1.4, preferably 1-1.2. This preferred embodiment is more advantageous in increasing the removal efficiency of both.

Preferably, the flue gas is catalytic cracking regeneration flue gas. The catalytic cracking regenerated flue gas contains SO _x And NO _x In addition, it may contain CO, CO ₂ 、H ₂ And (4) O component.

In the present invention, the ppm refers to a volume concentration unless otherwise specified.

The following detailed description is provided for the purpose of illustrating the invention and the resulting advantages, and is intended to help the reader clearly understand the spirit of the invention, but not to limit the scope of the invention.

In the following examples, the method is used for simultaneously reducing SO in flue gas _x With NO _x The contents of the components in the catalyst (a) are all determined by an X-ray fluorescence spectroscopy (XRF) method, which is specifically described in the compilation of petrochemical analysis methods (RIPP experimental methods), yangcui et al, published by scientific publishers in 1990. Comparative examples and raw materials used in examples: lanthanum nitrate (analytical grade, aladdin Biochemical company), magnesium nitrate (analytical grade, national drug group chemical reagents ltd.), manganese chloride (analytical grade, beijing chemical plant), cobalt nitrate (analytical grade, beijing yinocyka science and technology ltd.), ammonium carbonate (analytical grade, beijing chemical plant), ammonia (analytical grade, 25%, tianjin mao chemical plant), palladium chloride (beijing procurement and supply station, chinese pharmaceutical company), hydrochloric acid (beijing chemical plant), OX50-SiO ₂ (Zhongpetrochemical catalyst Co.).

Example 1

420mL of deionized water was weighed into a beaker, and La was added thereto with stirring ₂ O ₃ Lanthanum nitrate 30g by mass, magnesium nitrate 4g by mass of MgO, and Co ₂ O ₃ 5g of cobalt nitrate by mass and 3g of manganese chloride by mass of MnO until complete dissolution. Weighing 63g of ammonium carbonate, dissolving in 250mL of deionized water, stirring until the ammonium carbonate is fully dissolved, adding the metal nitrate mixed solution into the ammonium carbonate solution under the stirring state, and adding a certain amount of ammonia water to maintain the pH value of the solution at 9. And (3) carrying out suction filtration on the mixture with complete precipitation, leaching with deionized water, drying a filter cake mixture obtained by suction filtration at 120 ℃, roasting at 700 ℃ in air atmosphere for 6 hours, and grinding to obtain the active metal precursor.

Weighing Al ₂ O ₃ 380mL of water and 6g of 36 wt% concentrated hydrochloric acid were added to 40g of aluminum oxide in terms of mass, and the mixture was pulped. And (3) weighing 20g of active metal precursor, adding the active metal precursor into the acidified inorganic oxide matrix, mixing and stirring, drying the slurry at 200 ℃, and roasting at 700 ℃ in air atmosphere for 4 hours to obtain a catalyst microsphere semi-finished product. The mass percentage of the non-noble metal active component in the semi-finished product of the prepared microspherical catalyst is 33 percent.

Weighing palladium precursors, dissolving the precursors and dilute hydrochloric acid in a mass ratio of 1. And (2) dipping a palladium chloride solution serving as a dipping solution into the catalyst microsphere semi-finished product to obtain a solid product, drying the solid product at 120 ℃, and roasting the dried solid product at 700 ℃ in an air atmosphere for 4 hours to obtain the catalyst S-1.

Example 2

250mL of deionized water was weighed into a beaker, and La was added thereto with stirring ₂ O ₃ Lanthanum nitrate 10g by mass, magnesium nitrate 7g by mass of MgO, and Co ₂ O ₃ 5g of cobalt nitrate by mass and 3g of manganese chloride by mass of MnO until complete dissolution. Weighing 37.5g of ammonium carbonate, dissolving the ammonium carbonate in 150mL of deionized water, stirring the solution until the ammonium carbonate is fully dissolved, adding the mixed solution of the metal nitrate into the ammonium carbonate solution under the stirring state, and adding a certain amount of ammonia waterThe pH of the solution was maintained at 9. And (3) carrying out suction filtration on the mixture with complete precipitation, leaching with deionized water, drying a filter cake mixture obtained by suction filtration at 120 ℃, roasting at 700 ℃ in air atmosphere for 6 hours, and grinding to obtain the active metal precursor.

Weighing with Al ₂ O ₃ 380mL of water and 6g of 36 wt% concentrated hydrochloric acid were added to 40g of aluminum oxide in terms of mass, and the mixture was pulped. And weighing 10g of active metal precursor, adding the active metal precursor into the acidified inorganic oxide matrix, mixing and stirring, drying the slurry at 200 ℃, and roasting at 700 ℃ in air atmosphere for 4 hours to obtain a catalyst microsphere semi-finished product. The non-noble metal active component accounts for 20 percent of the mass of the prepared microsphere catalyst semi-finished product.

Weighing a palladium precursor, dissolving the palladium precursor and dilute hydrochloric acid mutually according to the mass ratio of 1. And (3) impregnating a palladium chloride solution serving as an impregnation liquid into the semi-finished product of the catalyst microsphere to obtain a solid product, drying the solid product at 120 ℃, and roasting the solid product at 700 ℃ in an air atmosphere for 4 hours to obtain the catalyst S-2.

Example 3

410mL of deionized water was weighed into a beaker, and La was added thereto with stirring ₂ O ₃ Lanthanum nitrate 30g by mass, magnesium nitrate 5g by mass of MgO, and Co ₂ O ₃ 2.6g of cobalt nitrate by mass and 3.4g of manganese chloride by mass of MnO until complete dissolution. 61.5g of ammonium carbonate is weighed and dissolved in 250mL of deionized water, the mixture is stirred until the ammonium carbonate is fully dissolved, the mixed solution of the metal nitrate is added into the ammonium carbonate solution under the stirring state, and a certain amount of ammonia water is added to maintain the pH value of the solution at 9. And (3) carrying out suction filtration on the mixture with complete precipitation, leaching with deionized water, drying a filter cake mixture obtained by suction filtration at 120 ℃, roasting at 700 ℃ in air atmosphere for 6 hours, and grinding to obtain the active metal precursor.

Weighing Al ₂ O ₃ 40g of aluminum oxide in mass, 380mL of water was addedAnd 6g of 36% by weight concentrated hydrochloric acid, followed by beating. And (3) weighing 20g of active metal precursor, adding the active metal precursor into the acidified inorganic oxide matrix, mixing and stirring, drying the slurry at 200 ℃, and roasting at 700 ℃ in air atmosphere for 4 hours to obtain a catalyst microsphere semi-finished product. The mass percentage of the non-noble metal active component in the semi-finished product of the prepared microspherical catalyst is 33 percent.

Weighing palladium precursor and dilute hydrochloric acid, dissolving the precursor and the dilute hydrochloric acid mutually according to the mass ratio of 1. And (3) dipping a palladium chloride solution serving as a dipping solution into the semi-finished product of the catalyst microsphere to obtain a solid product, drying the solid product at 120 ℃, and roasting the dried solid product at 700 ℃ in an air atmosphere for 4 hours to obtain the catalyst S-3.

Example 4

According to the method of the embodiment 1, except that the consumption of the aluminum-based metal is reduced, the mass percentage of the non-noble metal active component in the prepared microsphere catalyst semi-finished product is adjusted to 50%.

The method comprises the following specific steps: 420mL of deionized water was weighed into a beaker, and La was added thereto with stirring ₂ O ₃ Lanthanum nitrate 30g by mass, magnesium nitrate 4g by mass of MgO, and Co ₂ O ₃ 5g of cobalt nitrate by mass and 3g of manganese chloride by mass of MnO until complete dissolution. Weighing 63g of ammonium carbonate, dissolving the ammonium carbonate in 250mL of deionized water, stirring the solution until the ammonium carbonate is fully dissolved, adding the mixed solution of the metal nitrate into the ammonium carbonate solution under the stirring state, and adding a certain amount of ammonia water to maintain the pH value of the solution at 9. And (3) carrying out suction filtration on the mixture with complete precipitation, leaching with deionized water, drying a filter cake mixture obtained by suction filtration at 120 ℃, roasting at 700 ℃ in air atmosphere for 6 hours, and grinding to obtain the active metal precursor.

Weighing with Al ₂ O ₃ 20g of aluminum ore in mass was added with 240mL of water and 3g of 36 wt% concentrated hydrochloric acid, and the mixture was pulped. Weighing 20g of active metal precursor, adding the active metal precursor into the acidified inorganic oxide matrix, and mixingAnd mixing and stirring, drying the slurry at 200 ℃, and roasting for 4 hours at 700 ℃ in an air atmosphere to obtain a catalyst microsphere semi-finished product. The non-noble metal active component accounts for 50 percent of the mass of the prepared microsphere catalyst semi-finished product.

Weighing a palladium precursor, dissolving the palladium precursor and dilute hydrochloric acid mutually according to a mass ratio of 1. And (2) dipping a palladium chloride solution serving as a dipping solution into the catalyst microsphere semi-finished product to obtain a solid product, drying the solid product at 120 ℃, and roasting the dried solid product at 700 ℃ in an air atmosphere for 4 hours to obtain the catalyst S-4.

Example 5

420mL of deionized water was weighed into a beaker, and La was added thereto with stirring ₂ O ₃ 34g of lanthanum nitrate by mass, 4g of magnesium nitrate by mass of MgO, and Co by mass ₂ O ₃ 1g of cobalt nitrate by mass and 3g of manganese chloride by mass of MnO until complete dissolution. Weighing 63g of ammonium carbonate, dissolving in 250mL of deionized water, stirring until the ammonium carbonate is fully dissolved, adding the metal nitrate mixed solution into the ammonium carbonate solution under the stirring state, and adding a certain amount of ammonia water to maintain the pH value of the solution at 9. And (3) carrying out suction filtration on the mixture with complete precipitation, leaching with deionized water, drying a filter cake mixture obtained by suction filtration at 120 ℃, roasting at 700 ℃ in air atmosphere for 6 hours, and grinding to obtain the active metal precursor.

Weighing with Al ₂ O ₃ 380mL of water and 6g of 36 wt% concentrated hydrochloric acid were added to 40g of aluminum stone, and the mixture was pulped. And (3) weighing 20g of active metal precursor, adding the active metal precursor into the acidified inorganic oxide matrix, mixing and stirring, drying the slurry at 200 ℃, and roasting at 700 ℃ in air atmosphere for 4 hours to obtain a catalyst microsphere semi-finished product. The mass percentage of the non-noble metal active component in the semi-finished product of the prepared microspherical catalyst is 33 percent.

Weighing a palladium precursor, dissolving the palladium precursor and dilute hydrochloric acid mutually according to the mass ratio of 1. And (2) impregnating a palladium chloride solution serving as an impregnation liquid into the semi-finished product of the catalyst microsphere to obtain a solid product, drying the solid product at 120 ℃, and roasting for 4 hours at 700 ℃ in an air atmosphere to obtain the catalyst S-5.

Example 6

510mL of deionized water was weighed into a beaker, and La was added with stirring ₂ O ₃ Lanthanum nitrate (22 g by mass), magnesium nitrate (4 g by mass of MgO), and Co ₂ O ₃ 22g of cobalt nitrate by mass and 3g of manganese chloride by mass of MnO were dissolved completely. Weighing 76.5g of ammonium carbonate, dissolving in 300mL of deionized water, stirring until the ammonium carbonate is fully dissolved, adding the metal nitrate mixed solution into the ammonium carbonate solution under the stirring state, and adding a certain amount of ammonia water to maintain the pH value of the solution at 9. And (3) carrying out suction filtration on the mixture with complete precipitation, leaching with deionized water, drying a filter cake mixture obtained by suction filtration at 120 ℃, roasting at 700 ℃ in air atmosphere for 6 hours, and grinding to obtain the active metal precursor.

Weighing a palladium precursor, dissolving the palladium precursor and dilute hydrochloric acid mutually according to a mass ratio of 1. And (2) impregnating a palladium chloride solution serving as an impregnation liquid into the semi-finished product of the catalyst microsphere to obtain a solid product, drying the solid product at 120 ℃, and roasting the dried solid product at 700 ℃ in an air atmosphere for 4 hours to obtain the catalyst S-6.

Example 7

420mL of deionized water was weighed into a beaker, and La was added thereto with stirring ₂ O ₃ Lanthanum nitrate (30 g by mass), magnesium nitrate (4 g by mass of MgO), and Co ₂ O ₃ 5g of cobalt nitrate by mass and 3g of manganese chloride by mass of MnO until complete dissolution. Weighing 63g of ammonium carbonate, dissolving in 250mL of deionized water, stirring until the ammonium carbonate is fully dissolved, adding the metal nitrate mixed solution into the ammonium carbonate solution under the stirring state, and adding a certain amount of ammonia water to maintain the pH value of the solution at 9. And (3) carrying out suction filtration on the mixture with complete precipitation, leaching with deionized water, drying a filter cake mixture obtained by suction filtration at 120 ℃, roasting at 700 ℃ in air atmosphere for 6 hours, and grinding to obtain the active metal precursor.

Weighing with Al ₂ O ₃ 380mL of water and 6g of 36 wt% concentrated hydrochloric acid were added to 40g of aluminum stone, and the mixture was pulped. And (3) weighing 20g of active metal precursor, adding the active metal precursor into the acidified inorganic oxide matrix, mixing and stirring, drying the slurry at 200 ℃, and roasting for 4 hours at 700 ℃ in an air atmosphere to obtain a catalyst microsphere semi-finished product. The mass percentage of the non-noble metal active component in the semi-finished product of the prepared microspherical catalyst is 33 percent.

Weighing a precursor of ruthenium and dilute hydrochloric acid 1:1, dissolving mutually, diluting with deionized water to prepare a ruthenium chloride solution with the concentration of 5.6g/L, weighing 15g of a catalyst microsphere semi-finished product, and weighing a certain amount of ruthenium chloride solution with the concentration of 5.6g/L according to the mass of ruthenium-containing of 0.0045 g. And (3) impregnating the ruthenium-containing solution serving as an impregnation liquid into the semi-finished catalyst to obtain a solid product, drying the solid product at 120 ℃, and roasting the solid product at 700 ℃ in an air atmosphere for 4 hours to obtain the catalyst S-7.

Example 8

420mL of deionized water was weighed into a beaker, and CeO was added thereto with stirring ₂ 30g of cerium nitrate by mass, 4g of magnesium nitrate by mass of MgO, and Fe by mass ₂ O ₃ 5g of ferric nitrate and 3g of manganese chloride in terms of MnO mass until completely dissolved. Weighing 63g of ammonium carbonate to dissolve in 250mLStirring the mixture in ionized water until the mixture is fully dissolved, adding the mixed solution of the metal nitrate into an ammonium carbonate solution under the stirring state, and adding a certain amount of ammonia water to maintain the pH value of the solution at 9. And (3) carrying out suction filtration on the mixture with complete precipitation, leaching with deionized water, drying a filter cake mixture obtained by suction filtration at 120 ℃, roasting at 700 ℃ in air atmosphere for 6 hours, and grinding to obtain the active metal precursor.

Weighing palladium precursors, dissolving the precursors and dilute hydrochloric acid in a mass ratio of 1. And (2) dipping a palladium chloride solution serving as a dipping solution into the catalyst microsphere semi-finished product to obtain a solid product, drying the solid product at 120 ℃, and roasting the dried solid product at 700 ℃ in an air atmosphere for 4 hours to obtain the catalyst S-8.

Comparative example 1

Weighing La ₂ O ₃ Dissolving 30g of lanthanum nitrate by mass in a beaker, weighing 45g of ammonium carbonate to completely dissolve in the beaker, adding the lanthanum nitrate solution into the ammonium carbonate solution under stirring under the condition of stirring, and adding a certain amount of ammonia water to maintain the pH value of the solution at 9. And (3) carrying out suction filtration on the obtained mixture, drying the filter cake mixture obtained by suction filtration at 120 ℃, roasting for 6 hours at 700 ℃ in an air atmosphere, and grinding to obtain a catalytic precursor L.

Weighing with Co ₂ O ₃ Completely dissolving 5g of cobalt nitrate by mass in a beaker, weighing 7.5g of ammonium carbonate to completely dissolve the ammonium carbonate in the beaker, and stirring the cobalt nitrateThe solution is added into ammonium carbonate solution under stirring, and a certain amount of ammonia water is added to maintain the pH value of the solution at 9. And (3) carrying out suction filtration on the obtained mixture, drying the filter cake mixture obtained by suction filtration at 120 ℃, roasting for 6 hours at 700 ℃ in air atmosphere, and grinding to obtain the active metal precursor C.

And fully and mechanically mixing the active metal precursor L and the active metal precursor C obtained in the previous two steps to obtain a mixed precursor.

Weighing with Al ₂ O ₃ 380mL of water and 6g of 36 wt% concentrated hydrochloric acid were added to 40g of aluminum stone, and the mixture was pulped. And (3) adding 20g of mixed precursor into the acidified inorganic oxide matrix, mixing and stirring, drying the slurry at 120 ℃, and roasting at 700 ℃ in air atmosphere for 4 hours to obtain the catalyst D-1.

Comparative example 2

The catalyst was prepared as follows: weighing 15g of OX50 (SiO) ₂ ) The powder and a quantity of the palladium chloride solution prepared in example 1 was weighed out in a quantity such that the mass of the palladium contained was 0.0045 g. The palladium chloride solution was added to the OX50 powder and mixed well by constant stirring. And placing the obtained mixture in an oven at 120 ℃ until the mixture is dried, and roasting the mixture for 4 hours at 700 ℃ in an air atmosphere to obtain the catalyst D-2.

Comparative example 3

30g of La were weighed ₂ O ₃ And 5g of Co ₂ O ₃ And fully and mechanically mixing to obtain a mixed precursor.

Weighing with Al ₂ O ₃ 380mL of water and 6g of 36 wt% concentrated hydrochloric acid were added to 40g of aluminum oxide in terms of mass, and the mixture was pulped. And (3) adding 20g of mixed precursor into the acidified inorganic oxide matrix, mixing and stirring, drying the slurry at 120 ℃, and roasting at 700 ℃ in air atmosphere for 4 hours to obtain the catalyst D-3.

Comparative example 4

Comparative catalyst D-4 was prepared according to the method described in CN 1107834A. Weighing alumina, kaolin, magnesium, boron, lanthanum, platinum, titanium, alumina sol and ethyl acetate according to the proportion in the table 1, mixing, adding 5 times of water, soaking at 85 ℃ for more than 3 hours, and stirring at 85 ℃ for 3 hours after soaking to uniformly disperse the alumina, the kaolin, the magnesium, the boron, the lanthanum, the platinum, the titanium, the alumina sol and the ethyl acetate. Spray drying the slurry at the temperature of 300 ℃, and screening to obtain particles less than or equal to 200 mu m; and roasting the obtained particles at 500 ℃ for 4 hours, fully grinding the obtained active metal precursor, tabletting (15 MPa), and sieving to obtain the final catalyst, wherein the final catalyst is marked as D-4.

TABLE 1 (mass percentage)

Alumina oxide	65
		Kaolin clay	18
Magnesium alloy	2
		Boron	2
Lanthanum	3.5
		Platinum (II)	0.5
Titanium (IV)	4
		Aluminium sol	4
Ethyl acetate	1

The composition of the catalyst obtained above is shown in Table 2.

TABLE 2 composition of the catalyst

Note: in Table 2, the unit of the content of each component is "% by weight"

The evaluation criterion of the catalyst activity in the invention is SO in the reaction product _x And NO _x Change in concentration as a measure of SO in the product _x And NO _x The content is measured by an FT-IR Fourier infrared flue gas analyzer, and a fixed bed micro-reaction experimental device is adopted for evaluation. The catalyst activity evaluation results are expressed in terms of conversion.

Conversion calculation method:

wherein, C _(inlet) Refers to the inlet SO of the experimental device _x Or NO _x The concentration of (c); c _(outlet) Refers to the outlet SO of the experimental device _x Or NO _x The concentration of (2).

Test example 1

The experimental example is used for reducing NO and SO in flue gas simultaneously for the catalysts provided in the above examples and comparative examples ₂ The effect of the emissions was evaluated. The catalytic cracking reaction-regeneration evaluation is carried out on a small-sized fixed bed simulated flue gas device, the loading amount of the catalyst is 1.5g, the reaction temperature is 680 ℃, the pressure is 0.03MPa, the volume flow (standard condition) of the raw material gas is 1500mL/min, and the volume space velocity is about 15000h ^-1 . The feed gas contained 1200ppm of NO and 1200ppm of SO ₂ The balance being N ₂ . Analyzing the gas product by an on-line infrared analyzer to obtain SO after reaction ₂ And NO concentration. The results of the evaluation time of 0.5h are shown in Table 3, and the results of the evaluation time of 1.5h are shown in Table 4.

The desulfurization and denitrification performances of different catalysts within 30.5h in the table are compared

0.5h Total conversion (%)	combination-NO	combination-SO ₂	NO alone	Single SO ₂
					S-1	71	72	＜2	62
S-2	50	53	＜2	50
					S-3	57	63	＜2	60
S-4	92	78	＜2	68
					S-5	46	66	＜2	65
S-6	31	56	＜2	55
					S-7	65	70	＜2	60
S-8	59	72	＜2	65
					D-1	＜2	33	＜2	32
D-2	10	＜2	10	＜2
					D-3	5	7	＜2	7
D-4	4	24	5	23

Note: NO alone and SO alone in Table 3 ₂ Respectively means that the feed gas contains only 1200ppm NO or 1200ppm SO ₂

As can be seen from Table 3, the present invention provides a method for simultaneously reducing SO in flue gas within the first 0.5h _x With NO _x In comparison with the catalyst phase prepared according to the prior art under the same evaluation conditions, in the presence of NO and SO ₂ The removal rate of pollutants in the reaction is obviously superior to that of the method of independently feeding SO ₂ Reaction of gas with NO alone. The catalyst provided by the invention has higher catalytic conversion activity, and particularly the catalytic conversion activity of NO is greatly improved in the combined catalytic process.

TABLE 4 comparison of desulfurization and denitrification performances of different catalysts within 1.5h

Note: NO alone and SO alone in Table 4 ₂ Respectively means that the raw material gas only contains 1200ppm NO or 1200ppm SO ₂

As can be seen from Table 4, the invention provides for the simultaneous reduction of SO in flue gas within 1.5h _x With NO _x In comparison with the catalyst phase prepared according to the prior art under the same evaluation conditions, with mixing in of NO and SO ₂ The pollutant removal rate in the reaction is obviously superior to that of the single SO feeding ₂ Reaction of gas with NO alone. The total conversion at 1.5h is reduced to a small extent compared with the total conversion at 0.5h, in particular at SO ₂ The reduction amplitude is very small on the removal conversion rate, which shows that the problem of sulfur-induced inactivation can be effectively relieved by introducing the IIA group metal component, and the reaction stability of the catalyst is effectively improved.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. For simultaneously reducing SO in flue gas _x With NO _x The catalyst of (1), characterized in that it contains 25 to 95% by weight of an inorganic oxide matrix, based on the total weight of the catalyst; 2-70 wt% rare earth metal component calculated on oxide; 1-30 wt% of a group IIA metal component, calculated as oxide; 1-15 wt% of one or more non-noble metal components selected from VB, VIII, IB and IIB groups calculated by oxide; 1-10 wt%, calculated as oxide, of a group VIIB non-noble metal component; 0.01 to 1.5% by weight, calculated as element, of a noble metal component.

2. The catalyst of claim 1, wherein the inorganic oxide matrix is present in an amount of 40 to 90 wt.%, based on the total weight of the catalyst; 4-50 wt% rare earth metal component calculated on oxide; 1-20 wt% group IIA metal component, calculated as oxide; 2-12 wt% calculated by oxide of one or more non-noble metal components selected from VB, VIII, IB and IIB groups; 1-8 wt%, calculated as oxide, of a group VIIB non-noble metal component; 0.02 to 1.2% by weight, calculated as element, of a noble metal component;

preferably, the catalyst contains 50-80 wt% of inorganic oxide matrix based on the total weight of the catalyst; 4-40 wt% rare earth metal component calculated on oxide basis; 2-15 wt% group IIA metal component, calculated as oxide; 2-10 wt% calculated by oxide of one or more non-noble metal components selected from VB, VIII, IB and IIB groups; 2-5 wt%, calculated as oxide, of a group VIIB non-noble metal component; 0.02 to 1.0% by weight, calculated as element, of a noble metal component.

3. The catalyst according to claim 1, wherein the rare earth metal component is selected from one or more of lanthanum, cerium, praseodymium and neodymium, more preferably lanthanum and/or cerium;

the IIA group metal component is selected from one or more of beryllium, magnesium, calcium, strontium and barium, and is more preferably magnesium;

the non-noble metal component of one or more of VB, VIII, IB and IIB groups is one or more selected from iron, cobalt, nickel, copper, zinc and vanadium, and cobalt and/or iron are more preferably selected;

the non-noble metal component in the VIIB group is manganese;

the noble metal component is selected from one or more of ruthenium, rhodium, rhenium, platinum, palladium, silver, iridium and gold, more preferably one or more of platinum, palladium and rhodium, and most preferably palladium;

the inorganic oxide matrix is selected from at least one of alumina, silica-alumina, zeolite, spinel, kaolin, diatomaceous earth, perlite and perovskite, preferably alumina.

4. The catalyst according to any one of claims 1 to 3, wherein the molar ratio of the rare earth metal component to the non-noble metal component selected from one or more of groups VB, VIII, IB and IIB, calculated as the metal element, is (0.4-18): 1, more preferably (0.5-12): 1, still more preferably (1-6): 1.

5. For simultaneously reducing SO in flue gas _x With NO _x The method for preparing the catalyst comprises the following steps:

the active metal precursor, the inorganic oxide matrix and/or the precursor of the inorganic oxide matrix and the noble metal component precursor are used in such amounts that the prepared catalyst contains 25 to 95 weight percent of the inorganic oxide matrix based on the total weight of the catalyst; 2 to 70 wt% of a rare earth metal component, calculated as oxide; 1-30 wt% of a group IIA metal component, calculated as oxide; 1-15 wt% calculated by oxide of one or more non-noble metal components selected from VB, VIII, IB and IIB groups; 1-10 wt%, calculated as oxide, of a group VIIB non-noble metal component; 0.01 to 1.5% by weight, calculated as element, of a noble metal component.

6. The production method according to claim 5, wherein the active metal precursor, the inorganic oxide substrate and/or the precursor of the inorganic oxide substrate, and the precursor of the noble metal component are used in such amounts that the resultant catalyst contains the inorganic oxide substrate in an amount of 40 to 90% by weight, based on the total weight of the catalyst; 4 to 50 wt% of a rare earth metal component, calculated as oxide; 1-20 wt% of a group IIA metal component, calculated as oxide; 2-12 wt% of one or more non-noble metal components selected from VB, VIII, IB and IIB groups calculated by oxide; 1-8 wt%, calculated as oxide, of a group VIIB non-noble metal component; 0.02 to 1.2% by weight calculated as element of a noble metal component;

preferably, the active metal precursor, the inorganic oxide matrix and/or the precursor of the inorganic oxide matrix and the precursor of the noble metal component are used in such amounts that the resulting catalyst contains 50 to 80 wt% of the inorganic oxide matrix, based on the total weight of the catalyst; 4-40 wt% rare earth metal component calculated on oxide; 2-15 wt% group IIA metal component, calculated as oxide; 2-10 wt% calculated by oxide of one or more non-noble metal components selected from VB, VIII, IB and IIB groups; 2-5 wt%, calculated as oxide, of a group VIIB non-noble metal component; 0.02 to 1.0% by weight, calculated as element, of a noble metal component;

7. The production method according to claim 5 or 6, wherein the rare earth metal component is selected from one or more of lanthanum, cerium, praseodymium and neodymium, more preferably lanthanum and/or cerium;

the non-noble metal component in the VIIB group is manganese;

8. The production method according to any one of claims 5 to 7, wherein the active metal precursor is obtained in step (1) by a coprecipitation method; preferably, the co-precipitation method comprises:

(1-1) providing a first solution containing a rare earth metal component precursor, a group IIA metal component precursor, one or more non-noble metal component precursors selected from VB, VIII, IB and IIB groups, and a group VIIB non-noble metal component precursor;

9. The production method according to claim 8, wherein the rare earth metal component precursor, the group IIA metal component precursor, the non-noble metal component precursor selected from one or more of groups VB, VIII, IB, IIB, and the group VIIB non-noble metal component precursor may each be independently selected from nitrates and/or chlorides of each metal component;

preferably, the coprecipitate is a carbonate, and further preferably at least one selected from ammonium carbonate, potassium carbonate, and sodium carbonate;

preferably, the coprecipitation reaction is carried out at a pH of 8 to 10;

10. The production method according to any one of claims 5 to 9, wherein the slurry of step (2) has a solid content of 5 to 40% by weight;

11. The production method according to any one of claims 5 to 10, wherein in step (3), a noble metal component precursor is hydrolyzed in an acid solution to provide the impregnation liquid;

preferably, the acid is selected from water-soluble inorganic and/or organic acids, preferably at least one selected from hydrochloric acid, nitric acid, phosphoric acid and acetic acid;

preferably, the acid is used in an amount such that the pH of the impregnation solution is less than 6.0, preferably less than 5.0;

preferably, the roasting conditions in step (3) include: the temperature is 300-800 deg.C, and the time is 0.1-5h.

12. Catalyst according to any one of claims 1 to 4 or prepared according to the preparation method of any one of claims 5 to 11 for simultaneous SO removal in catalytic cracking of regenerated flue gas _x And NO _x Application in reactions.

13. SO is taken off simultaneously to flue gas _x And NO _x The method of (1), comprising: in the removal of SO _x And NO _x Under the conditions of (1), SO as to contain SO _x And NO _x Is contacted with the catalyst of any one of claims 1 to 4 or the catalyst prepared by the preparation method of any one of claims 5 to 11;

preferably, said SO removal _x And NO _x The conditions of (a) include: the temperature is 500-800 ℃, the pressure is 0.02-4MPa, and the volume space velocity of the flue gas is 100-50000h ^-1 ；

Preferably, the flue gas contains SO _x In an amount of 0.001-0.5 vol%, NO _x The content of (B) is 0.001-0.3 vol%;

preferably, the flue gas is catalytic cracking regeneration flue gas.