CN113877604B

CN113877604B - Catalyst for purifying exhaust gas containing bromine-containing organic matter, method for producing the same, and method for purifying exhaust gas containing bromine-containing organic matter

Info

Publication number: CN113877604B
Application number: CN202010628921.8A
Authority: CN
Inventors: 蒋见; 缪长喜; 卢媛娇; 孙清; 张磊; 张新玉
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2020-07-01
Filing date: 2020-07-01
Publication date: 2024-03-26
Anticipated expiration: 2040-07-01
Also published as: CN113877604A

Abstract

The invention relates to the technical field of catalytic combustion and environmental protection, and discloses a catalyst for purifying waste gas containing bromine-containing organic matters, a preparation method thereof and a method for purifying waste gas containing bromine-containing organic matters, wherein the catalyst comprises an integral carrier containing an alumina coating, and a noble metal active component and a non-noble metal active component which are loaded on the integral carrier; wherein the non-noble metal active component is a composite oxide containing cobalt oxide, manganese oxide and/or titanium oxide; the mole ratio of Co to Mn in the composite oxide is 3-15:1, and/or the molar ratio of Co to Ti is 1-8:1. the catalyst prepared by the invention has higher halogen toxicity resistance and stability, is used for purifying waste gas containing bromine-containing organic matters, and still has higher catalytic activity and selectivity at lower reaction temperature.

Description

Catalyst for purifying exhaust gas containing bromine-containing organic matter, method for producing the same, and method for purifying exhaust gas containing bromine-containing organic matter

Technical Field

The invention relates to the technical field of catalytic combustion environment protection, in particular to a catalyst for purifying waste gas containing bromine-containing organic matters, a preparation method thereof and a method for purifying waste gas containing bromine-containing organic matters.

Background

Waste gases containing volatile organic compounds are often generated in petrochemical production processes, and if the waste gases are directly discharged into the atmosphere, the waste gases can cause great harm to the atmospheric environment. Most volatile organic compounds have peculiar smell, and generate lesions and even cancerogenesis to human bodies; in particular, the volatile organic waste gas containing halogen has high toxicity, and can generate photochemical reaction with ozone to generate photochemical smog, thereby greatly damaging the global environment.

The treatment method of volatile organic compounds at home and abroad is mainly divided into a physical method and a chemical method. The physical method comprises an adsorption method, a condensation method, a membrane separation method and the like, and has the advantages that volatile organic compounds can be recycled, but the treatment is not thorough, and secondary pollution is easy to cause. The chemical method mainly comprises a direct thermal combustion method, a catalytic combustion method and the like, and is characterized in that the treatment is thorough; however, the thermal combustion method is to crack harmful substances in the tail gas at high temperature, the temperature of thermal cracking is up to 800-900 ℃, a large amount of fuel oil is required to be consumed, the operation cost is high, the energy consumption is high, the removal rate of halogen-containing organic matters is low, and meanwhile, nitrogen oxides can be generated. The catalytic combustion method can reduce the operation temperature by means of the catalyst, greatly reduce the energy consumption, ensure safe and stable operation, reduce the operation cost, and not produce nitrogen oxides, thereby not producing secondary pollution. Therefore, catalytic combustion is an ideal method for treating petrochemical organic waste gas.

The catalysts used in the current catalytic combustion method mainly comprise: noble metal catalysts, such as Pt, pd, rh and the like, have high activity, but have poor halogen resistance, are easy to poison, have poor stability, and have rare resources and high price; single metal oxide catalysts, such as copper, manganese, cobalt, etc., which are relatively low cost but generally active; the catalytic activity of the composite oxide catalyst is higher than that of the corresponding single oxide, for example, CN103252242B discloses a catalytic combustion catalyst of composite oxides of copper, manganese and cerium, but the reaction temperature is still higher, and the catalytic activity is still to be improved.

Disclosure of Invention

The invention aims to solve the problems of poor toxicity resistance and low catalytic activity of the catalyst in the prior art, and provides a catalyst for purifying waste gas containing bromine-containing organic matters, a preparation method thereof and a method for purifying waste gas containing bromine-containing organic matters.

In order to achieve the above object, an aspect of the present invention provides a catalyst for purifying exhaust gas containing bromine-containing organic matter, the catalyst comprising a monolith support comprising an alumina coating layer and a noble metal active component and a non-noble metal active component supported on the monolith support;

wherein the non-noble metal active component is a composite oxide containing cobalt oxide, manganese oxide and/or titanium oxide;

the mole ratio of Co to Mn in the composite oxide is 3-15:1, and/or the molar ratio of Co to Ti is 1-8:1.

in a second aspect, the present invention provides a method for producing a catalyst for purifying exhaust gas containing bromine-containing organic matter, the method comprising:

(1) Coating slurry containing alumina and/or alumina precursor on a monolithic carrier, and then drying and/or roasting to obtain the monolithic carrier containing alumina coating;

(2) Loading a composite oxide containing cobalt oxide, manganese oxide and/or titanium oxide and a noble metal active component on a monolithic carrier containing an alumina coating;

wherein the mole ratio of Co to Mn in the composite oxide is 3-15:1, and/or the molar ratio of Co to Ti is 1-8:1.

In a third aspect, the present invention provides a catalyst prepared by the preparation method of the second aspect.

In a fourth aspect, the present invention provides a method for purifying an exhaust gas containing a bromine-containing organic substance, comprising bringing the exhaust gas containing a bromine-containing organic substance into contact with the catalyst of the first aspect or the third aspect in an oxygen-containing atmosphere to perform catalytic combustion.

The catalyst prepared by adopting the technical scheme of the invention catalyzes waste gas containing bromine-containing organic matters to carry out catalytic combustion reaction at a lower reaction temperature, and can still obtain higher conversion rate and CO ₂ The selectivity shows that the catalyst has higher catalytic activity and selectivity, and still has higher catalytic activity and selectivity when the catalytic combustion reaction is carried out for 1000h, thus showing that the catalyst has higher stability and higher halogen toxicity resistance.

Drawings

FIG. 1 is a Raman spectrum of the composite oxide prepared in example 2;

FIG. 2 is a Raman spectrum of the composite oxide prepared in example 5;

FIG. 3 is a Raman spectrum of the composite oxide prepared in example 7;

FIG. 4 is a Raman spectrum of the composite oxide prepared in comparative example 5;

fig. 5 is a raman spectrum of the composite oxide prepared in comparative example 6.

Detailed Description

The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.

The inventor of the present invention found through research that in the catalyst, under the condition that Co and Mn and/or Ti exist in a specific proportion in the composite oxide, the composite oxide containing cobalt oxide and manganese oxide and/or titanium oxide, the noble metal active component and the monolithic carrier containing the alumina coating can generate synergistic action, the halogen toxicity resistance and the stability of the catalyst can be significantly improved, and the catalyst still has excellent catalytic activity and selectivity under the lower reaction temperature in the treatment of waste gas containing bromine-containing organic matters.

In a first aspect, the present invention provides a catalyst for purifying exhaust gas containing bromine-containing organic matter, the catalyst comprising a monolith support comprising an alumina coating and a noble metal active component and a non-noble metal active component supported on the monolith support;

the composite oxide may contain cobalt oxide and manganese oxide, may contain cobalt oxide and titanium oxide, and may contain cobalt oxide, manganese oxide and titanium oxide at the same time. According to the present invention, preferably, the non-noble metal active component is a composite oxide containing cobalt oxide, manganese oxide and titanium oxide. The use of this preferred embodiment is further advantageous in further improving the halogen poisoning resistance, catalytic activity, selectivity and stability of the catalyst.

In the invention, the mole ratio of Co to Mn in the composite oxide is 3-15:1, and/or the molar ratio of Co to Ti is 1-8: 1' indicates that when Mn is contained in the composite oxide, the molar ratio of Co to Mn is 3 to 15:1, a step of; when Ti is contained in the composite oxide, the molar ratio of Co to Ti is 1-8:1 does not mean that Mn and Ti are necessarily contained in the composite oxide at the same time.

According to the present invention, in order to further improve the halogen poisoning resistance, catalytic activity, selectivity, and stability of the catalyst, it is preferable that the molar ratio of Co to Mn in the composite oxide is 3.5 to 14.5:1, preferably 6-12:1.

According to the present invention, preferably, the molar ratio of Co to Ti in the composite oxide is 1.5 to 7.5:1, preferably 3-6:1.

according to the present invention, it is preferable that the loading amount of the non-noble metal active component is 30 to 150g (for example, may be 30g, 40g, 50g, 60g, 70g, 80g, 90g, 100g, 110g, 120g, 130g, 140g and 150g, or any value between any two values), more preferably 35 to 140g, still more preferably 60 to 120g, in terms of oxide, with respect to 1L of the monolith support.

Preferably, according to the present invention, 615-725cm in the Raman spectrum of the composite oxide in the catalyst ^-1 Peak intensity at the position is higher than 175-230cm ^-1 Peak intensity at position, 175-230cm ^-1 The peak intensity at the position is higher than 450-475cm ^-1 Peak intensity at position and 475-525cm ^-1 Peak intensity at the location. The catalyst with the preferred raman spectrum peak intensity has better catalytic performance and halogen toxicity resistance. Co in the prior art ₃ O ₄ Respectively at 689cm in Raman spectrum of (C) ^-1 ，619cm ^-1 ，521cm ^-1 And 481cm ^-1 Peak appears at position and 689cm ^-1 Peak intensity at position higher than 521cm ^-1 And 481cm ^-1 Peak intensity at position, 521cm ^-1 And 481cm ^-1 Peak intensity at position higher than 619cm ^-1 Peak intensity at the location.

According to the present invention, the loading amount of the noble metal active component may be selected in a wide range, and in order to further improve the halogen poisoning resistance, catalytic activity, selectivity and stability of the catalyst, it is preferable that the loading amount of the noble metal active component is 100 to 2000mg (for example, may be 100mg, 200mg, 400mg, 600mg, 800mg, 1000mg, 1200mg, 1400mg, 1600mg, 1800mg, 2000mg, or any value between any two values) in terms of metal element, more preferably 400 to 800mg, with respect to 1L of the monolith support.

According to the present invention, preferably, the noble metal is selected from at least one of Au, ag, pt, pd, ru, rh, os and Ir.

More preferably, the noble metal is Pt and/or Pd.

More preferably, the noble metals are Pt and Pd.

Further preferably, the noble metal active component has a molar ratio of Pt to Pd, calculated as metal element, of 0.01 to 10:1, more preferably 0.05 to 5:1, further preferably 0.1 to 0.5:1. the use of Pt and Pd in the preferred ratio is more advantageous for improving the catalytic performance of the catalyst.

According to the present invention, in order to further increase the number of cells and the specific surface area of the monolith support, thereby further increasing the catalytic activity and selectivity of the catalyst, it is preferable that the content of the alumina coating layer in the monolith support is 5 to 20 wt%, preferably 7 to 15 wt%.

According to the present invention, the monolith support has a conventional schematic in the art, and preferably, the monolith support is selected from monolith supports having a parallel cell structure with two open ends.

According to the invention, the porosity of the cross section of the monolithic support can be chosen within a wide range, preferably the porosity of the cross section of the monolithic support is between 30 and 90%, preferably between 45 and 75%. The porosity of the cross section of the monolithic support refers to the ratio of the pore area of the cross section of the monolithic support to the total cross-sectional area.

The cross-sectional area of the channels of the monolithic support according to the invention can be selected within a wide range, preferably the cross-sectional area of each channel is 0.5-1.5 μm ² More preferably 0.7-1.3 μm ² 。

According to the present invention, the kind of monolithic support may be selected in a wide range, and preferably, the monolithic support is a ceramic monolithic support.

More preferably, the ceramic monolith support is at least one selected from the group consisting of a cordierite monolith support, a mullite monolith support, a zirconia monolith support and an alumina monolith support, and further preferably a cordierite monolith support and/or a mullite monolith support.

In a second aspect, the present invention provides a method for preparing a catalyst for purifying exhaust gas containing bromine-containing organic matter, the method comprising:

according to the present invention, preferably, the method further comprises: in the step (1), the slurry containing the alumina and/or the alumina precursor is stirred and colloid-milled before being coated on the monolithic carrier. Preferably, the stirring conditions include: the stirring time is 0.1-5 hours, and the rotating speed is 200-1500rpm. Preferably, the conditions of the colloid mill include: the colloid milling time is 0.1-5 hours, and the size of the tooth gap of the colloid mill is 0.01-1mm.

According to the present invention, the slurry containing alumina and/or alumina precursor and the monolith support are preferably used in such an amount that the content of the alumina coating layer in the monolith support containing the alumina coating layer obtained in step (1) is 5 to 20% by weight, more preferably 7 to 15% by weight.

According to the present invention, preferably the slurry containing alumina and/or alumina precursor contains alumina and/or alumina precursor, water and optionally a pore-forming agent, optionally an acid.

According to the invention, preferably the weight ratio of alumina and/or alumina precursor to water, calculated as alumina, is between 0.05 and 0.8:1, more preferably 0.3 to 0.7:1.

The slurry may or may not contain a pore-forming agent, and preferably contains a pore-forming agent. The existence of the pore-forming agent improves the specific surface area of the alumina coating, and is more beneficial to improving the catalytic reaction efficiency of the catalyst.

According to the present invention, preferably, the weight ratio of alumina and/or alumina precursor to pore-forming agent, calculated as alumina, is 1:0.3 to 2.5, more preferably 1:0.35-1.5.

The slurry may or may not contain an acid, and more preferably contains an acid. The presence of the acid is more advantageous for optimizing the coating effect of the alumina-containing slurry.

According to the invention, preferably the weight ratio of alumina and/or alumina precursor to acid, calculated as alumina, is 1:0.01 to 0.2, more preferably 1:0.05-0.15.

According to the present invention, the coating method in the step (1) is not particularly limited as long as the alumina-containing slurry can be uniformly adhered to the monolith support, and is preferably a positive pressure coating method or a negative pressure coating method, and more preferably a negative pressure coating method. The negative pressure coating is carried out in a coating machine and specifically comprises the following steps: the alumina-containing slurry at one end of the monolith support is coated onto the monolith support by forming a low pressure environment in a coater. Preferably, the pressure in the coater is 0-5kPa. The negative pressure coating employed in the examples of the present invention.

The pressures described in the present invention are absolute pressures.

According to the present invention, the number of coating steps (1) is not particularly limited, and may be one-time or multiple-time, as long as a desired amount of load is obtained, and the number of coating steps may be specifically selected according to the actual situation by those skilled in the art.

According to the present invention, the kind of the alumina precursor is not particularly limited, and preferably the alumina precursor is selected from pseudo-boehmite and/or alumina sol, more preferably pseudo-boehmite.

According to the present invention, the kind of the pore-forming agent is not particularly limited as long as it can cause pores to be formed in the alumina coating layer without damaging the overall structure of the alumina coating layer, and preferably, the pore-forming agent is at least one selected from urea, carboxymethyl cellulose and polyvinyl alcohol, and more preferably, urea.

According to the present invention, the kind of the acid is not particularly limited as long as the viscosity of the slurry containing alumina can be increased to improve the coating efficiencyIt is also preferable that the acid is selected from HNO ₃ 、H ₂ SO ₄ 、HCl、CH ₃ COOH (acetic acid) and H ₂ C ₂ O ₄ At least one of (oxalic acid), more preferably HNO ₃ 。

According to the present invention, the conditions for the drying in the step (1) are not particularly limited, and preferably the conditions for the drying include: the drying temperature is 80-130 ℃, preferably 100-125 ℃; the drying time is 1-25h, preferably 2-10h.

More preferably, the drying conditions of step (1) include: heating from room temperature to drying temperature at a rate of 0.3-0.8deg.C/min.

According to the present invention, preferably, the method further comprises: before the drying in the step (1), the monolithic carrier coated with the slurry containing alumina and/or alumina precursor is purged to remove residual liquid, and then the monolithic carrier is left at room temperature for 5-15h. The kind of the gas used for the purge is not particularly limited, and may be, for example, air, nitrogen, helium, and other inert gases. The purging is usually performed by high-pressure purging, and the pressure is not particularly limited as long as the residual liquid can be purged.

According to the present invention, the conditions of the firing in step (1) are not particularly limited, and preferably, the conditions of the firing in step (1) include: roasting in an oxygen-containing atmosphere at a roasting temperature of 300-600 ℃, preferably 450-550 ℃; the calcination time is 3 to 10 hours, preferably 5 to 8 hours.

More preferably, the roasting conditions of step (1) include: and after the drying is finished, heating to a roasting temperature at a speed of 0.3-0.8 ℃/min for roasting.

According to the present invention, the oxygen content in the oxygen-containing atmosphere may be selected in a wide range, and preferably the oxygen content in the oxygen-containing atmosphere is 5 to 25% by volume.

According to the invention, preferably, the oxygen-containing atmosphere contains oxygen and optionally an inert gas.

According to the present invention, preferably, the inert gas is selected from at least one of nitrogen, helium, neon and argon. It is understood that the inert gas according to the present invention refers to a gas that does not participate in the reaction under the firing conditions in the present invention. From an economic point of view, the oxygen-containing atmosphere may be air.

In the step (2) of the present invention, the composite oxide may be first supported on the monolithic support containing the alumina coating, and then the noble metal active component may be supported, or the noble metal active component may be first supported on the monolithic support containing the alumina coating, and then the composite oxide may be supported, or the composite oxide and the noble metal active component may be jointly supported on the noble metal active component. In order to further improve the catalytic performance of the catalyst prepared, preferably, step (2) comprises the steps of:

(2-1) supporting a composite oxide containing cobalt oxide and manganese oxide and/or titanium oxide on a monolithic support containing an alumina coating to obtain a semi-finished catalyst;

(2-2) supporting the noble metal active component on the semi-finished catalyst.

According to a particularly preferred embodiment of the present invention, step (2-1) supports a composite oxide comprising cobalt oxide, manganese oxide and titanium oxide on a monolithic support comprising an alumina coating.

According to the present invention, preferably, the step (2-1) includes: coating slurry containing the composite oxide on a monolithic carrier containing an alumina coating, and then drying and/or roasting to obtain a semi-finished catalyst; and/or the number of the groups of groups,

step (2-2) comprises: a slurry containing a noble metal source is coated on the semi-finished catalyst and then calcined.

According to the present invention, the coating in step (2-1) is performed in the manner described above, and will not be described here.

According to the present invention, the number of coating steps (2-1) is not particularly limited, and may be one-time or multiple-time, as long as the required load is obtained, and the number of coating steps may be specifically selected according to the actual situation by those skilled in the art.

According to the present invention, the solid content of the composite oxide-containing slurry may be selected in a wide range so as to be able to satisfy the coating, and preferably the solid content of the composite oxide-containing slurry is 10 to 35% by weight, preferably 20 to 30% by weight.

According to the present invention, it is preferable that the slurry containing the composite oxide and the monolithic support containing the alumina coating are used in amounts such that the loading of the composite oxide is 30 to 150g, more preferably 35 to 140g, still more preferably 60 to 120g, in terms of oxide, relative to 1L of the monolithic support containing the alumina coating in the resulting semi-finished catalyst.

According to the present invention, preferably, the drying conditions of step (2-1) include: the drying temperature is 80-130 ℃, more preferably 100-125 ℃; the drying time is 1 to 25 hours, more preferably 2 to 10 hours.

According to the invention, the method further comprises: before the drying in the step (2-1), the monolith support coated with the slurry containing the composite oxide is purged to remove the residual liquid. The purpose and specific operation of the purge may be as described above and will not be described in detail herein.

According to the present invention, the conditions for the firing in step (2-1) may be selected in a wide range, and preferably, the conditions for the firing in step (2-1) include: in an oxygen-containing atmosphere, the roasting temperature is 300-600 ℃, more preferably 450-550 ℃; the calcination time is 3 to 10 hours, more preferably 3.5 to 7 hours.

According to the present invention, the molar ratio of Co to Mn and the molar ratio of Co to Ti in the composite oxide are selected in the ranges described above, and are not described herein.

According to the present invention, the method for producing the composite oxide of step (2) is not particularly limited, and preferably, the composite oxide of step (2) is produced by a coprecipitation method.

According to the present invention, preferably, the preparation method of the composite oxide of step (2) includes: mixing a precursor solution containing cobalt precursor, a manganese precursor and/or a titanium precursor with a precipitant to carry out precipitation reaction to obtain a precipitation product, and then drying and roasting the precipitation product.

According to the present invention, in order to enhance the effect of the precipitation reaction, preferably, the preparation method of the composite oxide of step (2) includes: and (3) adding a cobalt-containing precursor, a manganese-containing precursor and/or a titanium-containing precursor solution and a precipitant into the reactor in parallel flow for precipitation reaction, and controlling the pH value of the reaction system in the parallel flow adding process.

According to the present invention, in order to enhance the effect of the precipitation reaction, preferably, the preparation method of the composite oxide of step (2) further comprises: before mixing the cobalt-containing precursor and the manganese-containing precursor and/or the titanium-containing precursor solution with the precipitant, the cobalt-containing precursor and the manganese-containing precursor and/or the titanium-containing precursor solution are subjected to colloid milling. Preferably, the conditions of the colloid mill include: the colloid milling time is 10-50min, and the size of colloid mill tooth gap is 0.01-1mm.

According to the present invention, preferably, the precursor solution contains a cobalt precursor, a manganese precursor, and a titanium precursor. The catalytic performance of the catalyst can be further improved by adopting the preferred embodiment.

According to the present invention, the kind of the cobalt precursor and the manganese precursor is not particularly limited as long as free cobalt ions and manganese ions can be provided, and preferably, the cobalt precursor and the manganese precursor are each independently selected from at least one of nitrate, acetate, sulfate, oxalate and halide of a metal, and more preferably nitrate.

According to the present invention, the type of the titanium precursor is not particularly limited, and the titanium precursor is preferably titanate and/or titanium tetrachloride, more preferably tetraethyl titanate and/or titanium tetrachloride, and still more preferably tetraethyl titanate.

According to the present invention, the kind of the precipitant is not particularly limited as long as it can react with cobalt ions, manganese ions and titanium ions to produce precipitation, and preferably the precipitant is selected from at least one of carbonates, bicarbonates and hydroxides of alkali metals, and more preferably from at least one of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and lithium hydroxide.

According to the present invention, preferably, the conditions of the precipitation reaction include: the reaction temperature is 10 to 90 ℃ (for example, it may be 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, or any value between any two values), more preferably 50 to 80 ℃; the pH is 8.5 to 11 (e.g., may be 8.5, 9, 9.5, 10, 10.5, 11, 11.5, or any value therebetween), more preferably 9 to 10.

According to the present invention, preferably, stirring may be further performed during the precipitation reaction. The stirring is beneficial to improving the effect of the precipitation reaction. The rate of agitation may be selected in a wide range, preferably the agitation rate is 200-1500rpm.

According to the present invention, the conditions under which the precipitated product is dried are not particularly limited, and preferably the conditions under which the precipitated product is dried include: the drying temperature is 100-120 ℃, and the drying time is 2-8h.

According to the present invention, the conditions under which the precipitated product is calcined are not particularly limited, and preferably the conditions under which the precipitated product is calcined include: in an oxygen-containing atmosphere, the roasting temperature is 400-600 ℃, more preferably 450-550 ℃; the calcination time is 3 to 8 hours, more preferably 3.5 to 7 hours.

According to the present invention, there is no particular limitation on the method of coating in step (2-2), and preferably, the method of coating is selected from a spray coating method, a dip coating method, or a spin coating method, and more preferably, a dip coating method.

According to the present invention, preferably, the method of coating the slurry containing the noble metal source on the semi-finished catalyst in step (2-2) employs an equivalent impregnation method. The adoption of the optimized equivalent impregnation method is more beneficial to improving the coating effect and reducing the loss of noble metals.

According to the present invention, the content of the noble metal in the noble metal-containing slurry is not particularly limited, and preferably the noble metal content of the noble metal-containing slurry is 0.05 to 0.5% by weight, preferably 0.1 to 0.35% by weight, in terms of metal element.

According to the present invention, the amount of the slurry containing the noble metal source and the amount of the semi-finished catalyst to be used may be selected in a wide range, so that the amount of the noble metal supported in the catalyst to be produced is 100 to 2000mg, more preferably 400 to 800mg, in terms of metal element, relative to 1L of the alumina-coated monolith support.

According to the present invention, preferably, the noble metal source is selected from a precursor of at least one of Au, ag, pt, pd, ru, rh, os and Ir, more preferably a precursor of Pt and/or a precursor of Pd, and still more preferably a precursor of Pt and a precursor of Pd.

Preferably, the precursors of Pt and Pd are used in amounts such that the molar ratio of Pt and Pd supported on the surface of the monolithic support containing the alumina coating is 0.01 to 10, calculated as metal element: 1, more preferably 0.05 to 5:1, further preferably 0.1 to 0.5:1.

according to the present invention, the amounts of the Pt precursor and the Pd precursor may be selected in a wide range, and preferably, the Pt precursor and the Pd precursor are each independently a soluble acid and/or a soluble salt of a metal.

According to the present invention, the precursor of Pt is preferably at least one selected from chloroplatinic acid, platinum nitrate and platinum chloride, and further preferably chloroplatinic acid.

According to the present invention, preferably, the precursor of Pd is selected from at least one of palladium nitrate, tetraaminopalladium nitrate and palladium chloride, and further preferably palladium chloride.

According to the present invention, the conditions for the firing in step (2-2) may be selected in a wide range, and preferably, the conditions for the firing in step (2-2) include: in an oxygen-containing atmosphere, the roasting temperature is 300-600 ℃, more preferably 450-550 ℃; the calcination time is 3 to 10 hours, more preferably 4 to 8 hours.

According to the present invention, preferably, the method further comprises: in step (2-2), a slurry containing a noble metal source is coated on the semi-finished catalyst before calcination, and then dried. The drying conditions may be selected in a wide range, and preferably include: the drying temperature is 80-130 ℃, more preferably 100-125 ℃; the drying time is 1 to 25 hours, more preferably 3.5 to 7 hours.

In a third aspect, the present invention provides a catalyst for purifying exhaust gas containing bromine-containing organic matters prepared by the preparation method described in the second aspect. The catalyst has higher halogen toxicity resistance and still has higher catalytic activity and selectivity at lower reaction temperature. The structural composition and component content of the catalyst are as described in the first aspect, and are not described in detail herein.

In a fourth aspect, the present invention provides a method for purifying an exhaust gas containing a bromine-containing organic matter, comprising bringing the exhaust gas containing the bromine-containing organic matter into contact with the catalyst of the first aspect or the third aspect in an oxygen-containing atmosphere to perform catalytic combustion.

Specifically, in the presence of oxygen-containing atmosphere, waste gas containing bromine-containing organic matters contacts with a catalyst to perform catalytic combustion to generate carbon dioxide and water, and the waste gas also contains the bromine-containing organic matters, so that hydrogen bromide and/or bromine simple substances are generated.

According to the present invention, preferably, the conditions of the catalytic combustion include: the temperature is 200-450 ℃, preferably 250-400 ℃; volume space velocity of 3000-30000h ^-1 Preferably 5000-25000h ^-1 The method comprises the steps of carrying out a first treatment on the surface of the The pressure is 0-3MPa, preferably 0-2MPa. The use of the preferable conditions can further enhance the effect of purifying the exhaust gas containing the bromine-containing organic matter.

In the present invention, the exhaust gas containing the bromine-containing organic matter may be any exhaust gas which can be treated by a catalytic combustion method in industry. The composition of the waste gas containing the bromine-containing organic matters and the content selection range of the bromine-containing organic matters are wider. The inventor of the present invention found in the research process that the catalyst provided by the present invention is particularly suitable for treating waste gas containing bromine-containing organic matters, and is particularly suitable for treating PTA oxidation tail gas.

According to the present invention, the bromine-containing organic matter is preferably contained in the exhaust gas in an amount of 0.1 to 150ppm, more preferably 0.1 to 100ppm, in terms of Br element.

According to the present invention, preferably, the bromine-containing organic matter includes, but is not limited to, at least one of monobromomethane, dibromomethane, monobromoethane, dibromoethane, monobromoethylene, and dibromoethylene, and more preferably, dibromomethane.

According to a preferred embodiment of the present invention, the exhaust gas containing bromine-containing organic matter further comprises aromatic hydrocarbon and/or ester compounds. The aromatic hydrocarbon includes, but is not limited to, at least one of benzene, toluene, ethylbenzene, diethylbenzene, xylene, n-propylbenzene and isopropylbenzene, preferably xylene, more preferably para-xylene; the ester compounds include, but are not limited to, methyl acetate, ethyl acetate, preferably methyl acetate.

In the embodiments of the present invention, methyl acetate, paraxylene and dibromomethane are exemplified as the exhaust gas containing the bromine-containing organic matter, and the present invention is not limited thereto.

According to the present invention, the oxygen content in the oxygen-containing atmosphere may be selected in a wide range as long as the exhaust gas containing the bromine-containing organic matter can be catalytically combusted, and in order to further enhance the purification effect, the oxygen content in the oxygen-containing atmosphere is preferably 3 to 100% by volume.

According to the present invention, preferably, the inert gas is selected from at least one of nitrogen, helium, neon and argon. It is understood that the inert gas according to the present invention refers to a gas which does not participate in the reaction under the reaction conditions in the present invention.

It will be appreciated by those skilled in the art that the catalyst may also be reduced prior to the catalytic reaction, and the method of reduction is not particularly limited and may be a reduction method conventionally used in the art, for example, the method of reduction includes: and (3) in a mixed atmosphere of hydrogen and inert gas, carrying out reduction treatment on the catalyst for 3-10h at the temperature of 250-350 ℃. Preferably, the hydrogen content in the mixture of hydrogen and inert gas is 1-10% by volume. Preferably, the inert gas is selected from at least one of nitrogen, helium, neon and argon. It is understood that the inert gas according to the present invention refers to a gas that does not participate in the reaction under the reducing conditions in the present invention.

The present invention will be described in detail by examples. In the following examples of the present invention,

methyl acetate conversion = amount of reacted methyl acetate species/(amount of unreacted methyl acetate species + amount of reacted methyl acetate species);

para-xylene conversion = amount of para-xylene reacted/(amount of para-xylene unreacted + amount of para-xylene reacted);

dibromomethane conversion = amount of reacted dibromomethane material +.f (amount of unreacted dibromomethane material + amount of reacted dibromomethane material);

CO ₂ the selectivity of (1) = the amount of material of the reactant converted to carbon dioxide +.a-);

pseudo-boehmite is a commercial product of Susan agent Utility Co., ltd, and the content of alumina is 72% by weight.

The firing in the following examples and comparative examples was carried out under an air atmosphere without particular limitation.

Example 1

(1) Mixing 50g of alumina, 25g of urea and 5g of concentrated nitric acid (the mass fraction is 68%, the same applies hereinafter) with 100g of water, stirring for 30 minutes at a rotation speed of 500rpm, and then colloid milling for 30 minutes by using a colloid mill (the width of tooth gaps of the colloid mill is 0.05 mm) to obtain alumina slurry;

The slurry containing alumina was applied to a cordierite monolith type carrier (having a parallel cell structure with both ends open, a porosity of 60%, and a cross-sectional area of each cell of 1 mm) in a coater under a condition of 3kPa ² ) Blowing out residual liquid in the cordierite monolithic carrier by adopting high-pressure nitrogen after coating, standing for 10 hours at room temperature, keeping for 10 hours at a heating rate of 0.5 ℃/min from 20 ℃ to 110 ℃, drying, and then heating at a heating rate of 0.5 ℃/min from 110 ℃ to 55 DEG CThe mixture was calcined at 0℃for 6 hours to obtain a cordierite monolith carrier having an alumina coating. The alumina coating layer accounts for 10% of the total mass of the alumina coating layer and the cordierite monolithic carrier by multiple impregnation, drying and firing.

(2) Preparing cobalt nitrate hexahydrate and manganese nitrate into aqueous solution according to the mol ratio shown in table 1, adding sodium carbonate solution and the aqueous solution into a reaction vessel in parallel flow under the condition of stirring at 60 ℃ (300 rpm), controlling the pH value of the reaction system to be 9.5, filtering, drying the obtained precipitate at 110 ℃ for 5 hours, and roasting at 500 ℃ for 6 hours to obtain composite oxide particles;

dispersing the obtained composite oxide particles into water, then using a colloid mill (colloid mill tooth peak size is 0.05 mm) for 30min to obtain slurry containing the composite oxide, coating the slurry containing the composite oxide on a cordierite integral carrier containing an alumina coating in a coating machine under the condition of 3kPa, drying the slurry remained in a pore channel by adopting high-pressure nitrogen after the coating is completed, drying at 110 ℃ for 5h and roasting at 550 ℃ for 6h, and carrying out multiple dipping, drying and roasting to obtain a semi-finished catalyst, wherein the loading amount of the composite oxide is 90g/L relative to 1L of integral carrier containing the alumina coating in terms of oxide.

Preparing chloroplatinic acid and palladium chloride into an aqueous solution containing platinum element and palladium element (the total content of the platinum element and the palladium element is 0.1 percent by weight based on metal element), immersing the semi-finished catalyst in the aqueous solution containing the platinum element and the palladium element in an equivalent way, drying at 110 ℃ for 5 hours, and roasting at 550 ℃ for 6 hours to obtain the catalyst, wherein the loading of the platinum and the palladium is 400mg/L based on metal element relative to 1L of monolithic carrier containing an alumina coating, and the molar ratio of the platinum element to the palladium element is 0.25:1.

(3) The catalyst obtained in the step (2) is subjected to reduction treatment, and the method specifically comprises the following steps: the catalyst was subjected to reduction treatment at 300℃for 6 hours in a mixed atmosphere of hydrogen and nitrogen (containing 5% by volume of hydrogen). Then in a mixed atmosphere of oxygen and nitrogen (oxygen content is 10 vol%) under the pressure of 0.1MPa and volume space velocity of 20000 hr ^-1 Under the condition of (2)Catalytic combustion reaction of PTA-simulated oxidation tail gas (the rest is nitrogen) containing 1000ppm of methyl acetate, 500ppm of paraxylene and 100ppm of dibromomethane with the catalyst after reduction treatment, gradually increasing the reaction temperature from 200 ℃ at a speed of 0.1 ℃/min, recording the lowest reaction temperature T1 when the methyl acetate conversion is 99%, the lowest reaction temperature T2 when the paraxylene conversion is 99% and the lowest reaction temperature T3 when the dibromomethane conversion is 99%, respectively, and calculating CO when the reaction is carried out to 20h ₂ Is selected from the group consisting of (1). The content of each component of the obtained catalyst is shown in table 1; t1, T2 and T3 and CO ₂ The selectivities of (2) are shown in Table 2.

(4) Under the condition that the temperature T3 and other catalytic combustion conditions are unchanged, the catalytic combustion reaction is carried out, and the conversion rate of methyl acetate, paraxylene and dibromomethane and the CO are carried out until 1000h ₂ The selectivities of (2) are shown in Table 2.

Example 2

A catalyst was prepared and a catalytic combustion reaction was carried out by catalyzing an exhaust gas containing a bromine-containing organic matter in accordance with the method of example 1, except that 50g of alumina was replaced with 50g of pseudo-boehmite, and cobalt nitrate hexahydrate and manganese nitrate were formulated into an aqueous solution in accordance with the molar ratios shown in Table 1. The raman spectrum of the composite oxide in the obtained catalyst is shown in fig. 1, and the peak positions and the relative intensities of the peaks obtained by the raman spectrum are shown in table 3.

The content of each component of the obtained catalyst is shown in table 1; t1, T2 and T3 and CO ₂ The selectivities of (2) are shown in Table 2.

When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO ₂ The selectivities of (2) are shown in Table 2.

Example 3

A catalyst was prepared and a catalytic combustion reaction was carried out by catalyzing an exhaust gas containing a bromine-containing organic matter in accordance with the method of example 1, except that cobalt nitrate hexahydrate and manganese nitrate were formulated into an aqueous solution in the molar ratio shown in Table 1.

Run to 1000hConversion of methyl acetate, para-xylene and dibromomethane and CO ₂ The selectivities of (2) are shown in Table 2.

Example 4

A catalyst was prepared and a catalytic combustion reaction was carried out by catalyzing an exhaust gas containing a bromine-containing organic matter in accordance with the method of example 1, except that in step (2), manganese nitrate was replaced with tetraethyl titanate, cobalt nitrate hexahydrate and tetraethyl titanate were prepared into an aqueous ethanol solution in accordance with the molar ratio shown in Table 1, and a sodium carbonate solution and the aqueous solution were added to a reaction vessel in parallel flow with stirring at 20 ℃.

Example 5

A catalyst was prepared and a catalytic combustion reaction was carried out by catalyzing an exhaust gas containing a bromine-containing organic matter in accordance with the method of example 4, except that 50g of alumina was replaced with 50g of pseudo-boehmite, and cobalt nitrate hexahydrate and tetraethyltitanate were prepared into an aqueous ethanol solution in accordance with the molar ratio shown in Table 1 in step (2). The raman spectrum of the obtained composite oxide is shown in fig. 2, and the peak positions and the relative intensities of the peaks of the raman spectrum are shown in table 3.

Example 6

A catalyst was prepared and a catalytic combustion reaction was carried out by catalyzing an exhaust gas containing a bromine-containing organic matter in accordance with the method of example 4, except that 50g of alumina was replaced with 50g of pseudo-boehmite, and cobalt nitrate hexahydrate and tetraethyltitanate were prepared into an aqueous ethanol solution in accordance with the molar ratio shown in Table 1.

Example 7

A catalyst was prepared and a catalytic combustion reaction was carried out by catalyzing an exhaust gas containing a bromine-containing organic matter in accordance with the method of example 4, except that 50g of alumina was replaced with 50g of pseudo-boehmite, cobalt nitrate hexahydrate and tetraethyltitanate were replaced with cobalt nitrate hexahydrate, manganese nitrate and tetraethyltitanate, and cobalt nitrate hexahydrate, manganese nitrate and tetraethyltitanate were prepared into an aqueous ethanol solution in accordance with the molar ratios shown in Table 1 (volume ratio of ethanol to water: 1:5). The raman spectrum of the obtained composite oxide is shown in fig. 3, and the peak positions and the relative intensities of the peaks of the raman spectrum are shown in table 3.

Example 8

A catalyst was prepared and a catalytic combustion reaction was carried out by catalyzing an exhaust gas containing a bromine-containing organic matter in accordance with the method of example 7, except that cobalt nitrate hexahydrate, manganese nitrate and tetraethyl titanate were prepared into an aqueous ethanol solution in accordance with the molar ratios shown in Table 1, and the aqueous ethanol solution and sodium carbonate solution were added to a reaction vessel in parallel with stirring at 20℃to control the pH of the reaction system to 8.5.

Example 9

A catalyst was prepared and a catalytic combustion reaction was carried out by catalyzing an exhaust gas containing a bromine-containing organic matter in accordance with the method of example 7, except that cobalt nitrate hexahydrate, manganese nitrate and tetraethyl titanate were prepared into an aqueous ethanol solution in accordance with the molar ratios shown in Table 1, and the aqueous ethanol solution and sodium carbonate solution were added to a reaction vessel in parallel with stirring at 20℃to control the pH of the reaction system to 9.

Example 10

A catalyst was prepared and a catalytic combustion reaction was carried out by catalyzing an exhaust gas containing a bromine-containing organic matter in accordance with the method of example 7, except that cobalt nitrate hexahydrate, manganese nitrate and tetraethyl titanate were prepared into an aqueous ethanol solution in accordance with the molar ratios shown in Table 1, and the aqueous ethanol solution and sodium carbonate solution were added to a reaction vessel in parallel with stirring at 20℃to control the pH of the reaction system to 10.

Example 11

A catalyst was prepared and catalytic combustion reactions were carried out on exhaust gas containing bromine-containing organics as in example 7, except that 50g of pseudo-boehmite was replaced with 50g of alumina; the composite oxide loading was 35g/L in terms of oxide relative to 1L of monolithic support containing alumina coating.

Example 12

A catalyst was prepared and catalytic combustion reactions were carried out on exhaust gas containing bromine-containing organics as in example 7, except that 50g of pseudo-boehmite was replaced with 50g of alumina; the composite oxide loading was 140g/L in terms of oxide relative to 1L of monolithic support containing alumina coating.

Example 13

A catalyst was prepared and catalytic combustion reactions were carried out on exhaust gas containing bromine-containing organics as in example 7, except that 50g of pseudo-boehmite was replaced with 50g of alumina; in the step (2), the molar ratio of the platinum element to the palladium element in the obtained catalyst is 0.1:1.

Example 14

A catalyst was prepared and a catalytic combustion reaction was carried out by the method of example 13, except that in step (2), the molar ratio of the platinum element to the palladium element in the obtained catalyst was 0.5:1.

Example 15

A catalyst was prepared and catalytic combustion reactions were carried out on exhaust gas containing bromine-containing organics as in example 7, except that 50g of pseudo-boehmite was replaced with 50g of alumina; in the step (2), the loading amount of platinum and palladium in terms of metal element was 800mg/L with respect to 1L of the monolithic support containing the alumina coating.

The content of each component of the obtained catalystSee table 1; t1, T2 and T3 and CO ₂ The selectivities of (2) are shown in Table 2.

Example 16

A catalyst was prepared and catalytic combustion reactions were carried out on exhaust gas containing bromine-containing organics as in example 7, except that 50g of pseudo-boehmite was replaced with 50g of alumina; the PTA simulated oxidation tail gas (the rest gas is nitrogen) containing 2000ppm of methyl acetate, 700ppm of paraxylene and 200ppm of dibromomethane is contacted with the catalyst after the reduction treatment to carry out catalytic combustion reaction.

Example 17

A catalyst was prepared and a catalytic combustion reaction was carried out by catalyzing an exhaust gas containing a bromine-containing organic matter in the same manner as in example 7, except that in step (3), a PTA pseudo-oxidation off-gas (the balance being nitrogen) containing 3000ppm of methyl acetate, 1000ppm of p-xylene and 300ppm of dibromomethane was brought into contact with the catalyst after the reduction treatment to carry out the catalytic combustion reaction.

Example 18

A catalyst was prepared and used to catalyze the catalytic combustion of exhaust gases containing bromine-containing organics as in example 7, except that the alumina coating was 15% of the total mass of the alumina coating and cordierite monolith support.

The content of each component of the obtained catalyst is shown in table 1; t1, T2 and T3 and CO ₂ The selectivity of (2) is shown in the table2。

Example 19

A catalyst was prepared and used to catalyze the catalytic combustion of exhaust gases containing bromine-containing organics as in example 7, except that the alumina coating was 7% of the total mass of the alumina coating and cordierite monolith support.

Example 20

A catalyst was prepared and a catalytic combustion reaction was carried out by catalyzing an exhaust gas containing a bromine-containing organic matter in accordance with the method of example 7, except that the composite oxide was supported in an amount of 60g in terms of oxide relative to 1L of the monolith support.

Example 21

A catalyst was prepared and a catalytic combustion reaction was carried out by catalyzing an exhaust gas containing a bromine-containing organic matter in accordance with the method of example 7, except that the composite oxide was supported at 120g in terms of oxide relative to 1L of the monolith support.

Example 22

A catalyst was prepared and a catalytic combustion reaction was carried out by the method of example 7, except that in step (2), the molar ratio of the platinum element to the palladium element in the obtained catalyst was 10:1.

Example 23

A catalyst was prepared and a catalytic combustion reaction was performed by catalyzing an exhaust gas containing a bromine-containing organic matter in accordance with the method of example 7, except that cobalt nitrate hexahydrate, manganese nitrate and tetraethyl titanate were prepared into an aqueous ethanol solution in accordance with the molar ratios shown in Table 1.

Example 24

Comparative example 1

A catalyst was prepared and a catalytic combustion reaction was carried out by catalyzing an exhaust gas containing a bromine-containing organic matter in the same manner as in example 7, except that in step (2), the alumina-coated cordierite monolith support was impregnated with an aqueous solution containing a platinum element and a palladium element directly without carrying out the loading of the composite oxide.

Comparative example 2

A catalyst was prepared and a catalytic combustion reaction was carried out by catalyzing an exhaust gas containing a bromine-containing organic matter in accordance with the method of example 7, except that cobalt nitrate hexahydrate, manganese nitrate and tetraethyl titanate were replaced with cobalt nitrate hexahydrate, and cobalt nitrate hexahydrate was formulated into an aqueous solution.

Comparative example 3

A catalyst was prepared and a catalytic combustion reaction was carried out by catalyzing an exhaust gas containing a bromine-containing organic matter in accordance with the method of example 7, except that cobalt nitrate hexahydrate, manganese nitrate and tetraethyl titanate were replaced with manganese nitrate, and manganese nitrate was formulated into an aqueous solution.

Comparative example 4

A catalyst was prepared and a catalytic combustion reaction was carried out by catalyzing an exhaust gas containing a bromine-containing organic matter in accordance with the method of example 7, except that cobalt nitrate hexahydrate, manganese nitrate and tetraethyl titanate were replaced with tetraethyl titanate, and tetraethyl titanate was formulated into an aqueous ethanol solution.

Comparative example 5

A catalyst was prepared and a catalytic combustion reaction was carried out by catalyzing an exhaust gas containing a bromine-containing organic matter in accordance with the method of example 7, except that cobalt nitrate hexahydrate, manganese nitrate and tetraethyl titanate were replaced with cobalt nitrate hexahydrate and manganese nitrate, and aqueous solutions were prepared in accordance with the molar ratios shown in Table 1. The raman spectrum of the obtained composite oxide is shown in fig. 4, and the peak positions and the relative intensities of the peaks of the raman spectrum are shown in table 4.

Comparative example 6

A catalyst was prepared and a catalytic combustion reaction was carried out by catalyzing an exhaust gas containing a bromine-containing organic matter in accordance with the method of example 7, except that cobalt nitrate hexahydrate, manganese nitrate and tetraethyl titanate were replaced with cobalt nitrate hexahydrate and manganese nitrate, and aqueous solutions were prepared in accordance with the molar ratios shown in Table 1. The raman spectrum of the obtained composite oxide is shown in fig. 5, and the peak positions and the relative intensities of the peaks of the raman spectrum are shown in table 4.

Comparative example 7

A catalyst was prepared and a catalytic combustion reaction was performed by catalyzing an exhaust gas containing a bromine-containing organic matter according to the method of example 7, except that cobalt nitrate hexahydrate, manganese nitrate and tetraethyl titanate were replaced with cobalt nitrate hexahydrate and tetraethyl titanate, and an aqueous ethanol solution was prepared in accordance with the molar ratios shown in Table 1.

Run to the firstAt 1000h, the conversion of methyl acetate, para-xylene and dibromomethane and CO ₂ The selectivities of (2) are shown in Table 2.

TABLE 1

TABLE 2

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TABLE 3 Table 3

Raman shift (cm) ^-1 )	175-230	450-475	475-525	615-725
					Relative intensity	M	W	W	VS

Note that: w, M, S, VS represents peak intensity in Raman spectrum, W is less than 20 represents weak, M is 20-40 represents medium, S is 40-70 represents strong, VS is more than 70 represents very strong, and the same is true.

TABLE 4 Table 4

Raman shift (cm) ^-1 )	150-175	450-475	475-525	550-650
					Relative intensity	M	W	W	VS

As can be seen from tables 1 and 2, the catalyst prepared by the embodiment of the invention catalyzes the mixed gas of methyl acetate, paraxylene and dibromomethane to perform catalytic combustion reaction at a lower reaction temperature, can still ensure that the conversion rate of methyl acetate, paraxylene and dibromomethane reaches more than 99%, and the CO is generated when the reaction is performed for 20h ₂ The selectivity of the catalyst can reach 99 percent, which shows that the catalyst has higher catalytic activity and selectivity, and still has higher catalytic activity and selectivity when the catalytic combustion reaction is carried out for 1000h at the temperature of T3, which shows that the catalyst has the advantages of high catalytic activity, low cost, high catalyst activity and high catalyst selectivityThe chemical agent has better stability and higher halogen toxicity resistance.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims

1. A catalyst for purifying exhaust gas containing bromine-containing organic matter, characterized in that the catalyst comprises a monolith support comprising an alumina coating layer and a noble metal active component and a non-noble metal active component supported on the monolith support;

wherein the non-noble metal active component is a composite oxide containing cobalt oxide, manganese oxide and titanium oxide; the mole ratio of Co to Mn in the composite oxide is 3-15:1, the mole ratio of Co to Ti is 1-8:1, a step of;

the loading amount of the noble metal active component is 100-2000mg calculated by metal element relative to 1L of integral carrier; the loading of the non-noble metal active component is 30-150g calculated by oxide.

2. The catalyst according to claim 1, wherein the molar ratio of Co to Mn in the composite oxide is 3.5-14.5:1.

3. the catalyst according to claim 2, wherein the molar ratio of Co to Mn in the composite oxide is 6-12:1.

4. the catalyst according to claim 1, wherein the molar ratio of Co to Ti in the composite oxide is 1.5-7.5:1.

5. the catalyst according to claim 1, wherein the molar ratio of Co to Ti in the composite oxide is 3-6:1.

6. The catalyst according to claim 1, wherein the loading amount of the non-noble metal active component is 35 to 140g in terms of oxide with respect to 1L of the monolith support.

7. The catalyst according to claim 6, wherein the loading amount of the non-noble metal active component is 60 to 120g in terms of oxide with respect to 1L of the monolith support.

8. The catalyst according to claim 1, wherein the composite oxide in the catalyst has a raman spectrum of 615-725cm ^-1 Peak intensity at the position is higher than 175-230cm ^-1 Peak intensity at position, 175-230cm ^-1 The peak intensity at the position is higher than 450-475cm ^-1 Peak intensity at position and 475-525cm ^-1 Peak intensity at the location.

9. The catalyst according to claim 1, wherein the loading amount of the noble metal active component is 400 to 800mg in terms of metal element with respect to 1L of the monolith support.

10. The catalyst of claim 1, wherein the noble metal is selected from at least one of Au, ag, pt, pd, ru, rh, os and Ir.

11. The catalyst of claim 10, wherein the noble metal is Pt and/or Pd.

12. The catalyst of claim 11, wherein the noble metals are Pt and Pd.

13. The catalyst according to claim 12, wherein the noble metal active component has a molar ratio of Pt to Pd, calculated as metal element, of 0.01 to 10:1.

14. the catalyst according to claim 13, wherein the noble metal active component has a molar ratio of Pt to Pd, calculated as metal element, of 0.05 to 5:1.

15. the catalyst according to claim 14, wherein the noble metal active component has a molar ratio of Pt to Pd, calculated as metal element, of 0.1 to 0.5:1.

16. the catalyst of claim 1, wherein the alumina coating is present in the monolith support in an amount of from 5 to 20 wt.%.

17. The catalyst of claim 16, wherein the alumina coating is present in the monolith support in an amount of from 7 to 15 wt%.

18. The catalyst of claim 1, wherein the monolithic support has a porosity of 30-90% in cross section.

19. The catalyst of claim 1, wherein the monolith support is a ceramic monolith support.

20. The catalyst according to claim 19, wherein the ceramic monolith support is selected from at least one of a cordierite monolith support, a mullite monolith support, a zirconia monolith support and an alumina monolith support.

21. A method for preparing a catalyst for purifying exhaust gas containing bromine-containing organic matter, the method comprising:

(2) Loading a composite oxide containing cobalt oxide, manganese oxide and titanium oxide and a noble metal active component on a monolithic carrier containing an alumina coating;

wherein the mole ratio of Co to Mn in the composite oxide is 3-15:1, the mole ratio of Co to Ti is 1-8:1, a step of; the loading of the noble metal is 100-2000mg in terms of metal element and the loading of the composite oxide is 30-150g in terms of oxide relative to 1L of monolithic carrier containing the alumina coating.

22. The production method according to claim 21, wherein the slurry containing alumina and/or an alumina precursor and the monolith support are used in such an amount that the alumina coating layer is contained in an amount of 5 to 20% by weight in the monolith support containing the alumina coating layer obtained in step (1).

23. The production method according to claim 22, wherein the slurry containing alumina and/or an alumina precursor and the monolith support are used in such an amount that the alumina coating layer is contained in an amount of 7 to 15% by weight in the monolith support containing the alumina coating layer obtained in step (1).

24. The method of claim 21, wherein the slurry comprising alumina and/or alumina precursor comprises alumina and/or alumina precursor, water, and optionally a pore-forming agent, optionally an acid.

25. The process according to claim 24, wherein the weight ratio of alumina and/or alumina precursor to water calculated as alumina is 0.05-0.8:1.

26. the method of claim 25, wherein the weight ratio of alumina and/or alumina precursor to water calculated as alumina is 0.3-0.7:1.

27. the method of claim 24, wherein the weight ratio of alumina and/or alumina precursor to pore former is 1:0.3-2.5.

28. The method of claim 27, wherein the weight ratio of alumina and/or alumina precursor to pore former is 1:0.35-1.5.

29. The method of claim 24, wherein the weight ratio of alumina and/or alumina precursor to acid, calculated as alumina, is 1:0.01-0.2.

30. The method of claim 29, wherein the weight ratio of alumina and/or alumina precursor to acid, calculated as alumina, is 1:0.05-0.15.

31. The method of claim 21, wherein the alumina precursor is pseudo-boehmite and/or an alumina sol.

32. The method of claim 24, wherein the pore-forming agent is selected from at least one of urea, carboxymethyl cellulose, and polyvinyl alcohol.

33. The process according to claim 24, wherein the acid is selected from HNO ₃ 、H ₂ SO ₄ 、HCl、CH ₃ COOH and H ₂ C ₂ O ₄ At least one of them.

34. The method of claim 21, wherein the drying conditions of step (1) comprise: the drying temperature is 80-130; the drying time is 1-25h.

35. The method of claim 34, wherein the drying conditions of step (1) comprise: the drying temperature is 100-125 ℃; the drying time is 2-10h.

36. The method of claim 21, wherein the firing conditions of step (1) comprise: roasting in an oxygen-containing atmosphere at a roasting temperature of 300-600 ℃; the roasting time is 3-10h.

37. The method of claim 36, wherein the firing conditions of step (1) comprise: roasting in an oxygen-containing atmosphere at a roasting temperature of 450-550 ℃; the roasting time is 5-8h.

38. The preparation method of claim 21, wherein the step (2) comprises the steps of:

(2-1) supporting a composite oxide containing cobalt oxide, manganese oxide and titanium oxide on an integral carrier containing an alumina coating to obtain a semi-finished catalyst;

39. The production method according to claim 38, wherein step (2-1) comprises: coating slurry containing the composite oxide on a monolithic carrier containing an alumina coating, and then drying and/or roasting to obtain a semi-finished catalyst; and/or the number of the groups of groups,

40. The process according to claim 39, wherein the slurry containing the composite oxide has a solid content of 10 to 35% by weight.

41. The process according to claim 40, wherein the slurry containing the composite oxide has a solid content of 20 to 30% by weight.

42. The process according to claim 39, wherein the slurry containing the composite oxide and the monolithic support containing the alumina coating are used in amounts such that the amount of the composite oxide supported on the oxide is 35 to 140g relative to 1L of the monolithic support containing the alumina coating in the semi-finished catalyst.

43. The process according to claim 42, wherein the slurry containing the composite oxide and the monolithic support containing the alumina coating are used in amounts such that the amount of the composite oxide supported on the oxide is 60 to 120g relative to 1L of the monolithic support containing the alumina coating in the semi-finished catalyst.

44. The method according to claim 39, wherein the drying conditions of step (2-1) include: the drying temperature is 80-130 ℃, and the drying time is 1-25h.

45. The process of claim 44, wherein the drying conditions of step (2-1) comprise: the drying temperature is 100-125 ℃; the drying time is 2-10h.

46. The process of claim 39, wherein the conditions of the firing of step (2-1) comprise: in an oxygen-containing atmosphere, the roasting temperature is 300-600 ℃; the roasting time is 3-10h.

47. The process of claim 46, wherein the conditions of the firing of step (2-1) comprise: in an oxygen-containing atmosphere, the roasting temperature is 450-550 ℃; the roasting time is 3.5-7h.

48. The production method according to claim 21, wherein a molar ratio of Co and Mn in the composite oxide is 3.5 to 14.5:1.

49. The process according to claim 48, wherein the molar ratio of Co to Mn in the composite oxide is from 6 to 12:1.

50. the production method according to claim 21, wherein a molar ratio of Co and Ti in the composite oxide is 1.5 to 7.5:1.

51. the process according to claim 50, wherein the molar ratio of Co to Ti in the composite oxide is 3 to 6:1.

52. the production method according to claim 21, wherein the composite oxide of step (2) is produced by a coprecipitation method.

53. The process according to claim 52, wherein the process for producing the composite oxide of step (2) comprises: mixing a precursor solution containing a cobalt precursor, a manganese precursor and a titanium precursor with a precipitant to perform precipitation reaction to obtain a precipitate, and drying and roasting the precipitate.

54. The method of claim 53, wherein the cobalt precursor and the manganese precursor are each independently selected from at least one of a nitrate, acetate, sulfate, oxalate, and halide of a metal.

55. The process of claim 53 wherein the precursor of titanium is a titanate and/or titanium tetrachloride.

56. The process of claim 53 wherein the precipitating agent is selected from at least one of alkali metal carbonates, bicarbonates, and hydroxides.

57. The process of claim 53 wherein the precipitating agent is at least one of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and lithium hydroxide.

58. The process of claim 53 wherein the precipitation reaction conditions comprise: the reaction temperature is 10-90 ℃; the pH value is 8.5-11.

59. The process of claim 58, wherein the precipitation reaction conditions comprise: the reaction temperature is 50-80 ℃; the pH value is 9-10.

60. The process of claim 53 wherein the conditions for drying the precipitated product comprise: the drying temperature is 100-120 ℃, and the drying time is 2-8h.

61. The process of claim 53 wherein the conditions for calcining the precipitated product comprise: in an oxygen-containing atmosphere, the roasting temperature is 400-600 ℃; the roasting time is 3-8h.

62. The process of claim 61, wherein the conditions for calcining the precipitated product comprise: in an oxygen-containing atmosphere, the roasting temperature is 450-550 ℃; the roasting time is 3.5-7h.

63. The process according to claim 39, wherein the slurry containing the noble metal source and the semi-finished catalyst are used in amounts such that the catalyst is produced with a noble metal loading of 400 to 800mg in terms of metal element relative to 1L of the alumina-coated monolith support.

64. The process according to claim 39, wherein the noble metal source is selected from precursors of at least one of Au, ag, pt, pd, ru, rh, os and Ir.

65. The process of claim 64, wherein the noble metal source is selected from a precursor of Pt and/or a precursor of Pd.

66. The method of claim 65, wherein the noble metal source is a precursor of Pt and a precursor of Pd.

67. The process of claim 66 wherein the precursors of Pt and Pd are used in amounts such that the molar ratio of Pt and Pd supported on the surface of the monolithic support comprising the alumina coating is 0.01-10, calculated as metal element: 1.

68. the process according to claim 67, wherein the precursor of Pt and the precursor of Pd are used in such an amount that the molar ratio of Pt to Pd supported on the surface of the monolithic support having an alumina coating is 0.05 to 5 in terms of metal element: 1.

69. The method of claim 68, wherein the precursors of Pt and Pd are used in amounts such that the molar ratio of Pt and Pd supported on the surface of the monolithic support comprising the alumina coating is 0.1 to 0.5, calculated as metal element: 1.

70. the method of claim 66, wherein the Pt precursor and the Pd precursor are each independently a soluble acid and/or a soluble salt of a metal.

71. The method of claim 70, wherein the precursor of Pt is selected from at least one of chloroplatinic acid, platinum nitrate, and platinum chloride.

72. The process according to claim 70, wherein the precursor of Pd is at least one selected from the group consisting of palladium nitrate, tetraaminopalladium nitrate and palladium chloride.

73. The method according to claim 39, wherein the conditions of the firing in step (2-2) include: in an oxygen-containing atmosphere, the roasting temperature is 300-600 ℃; the roasting time is 3-10h.

74. The method according to claim 73, wherein the conditions of the firing of step (2-2) include: in an oxygen-containing atmosphere, the roasting temperature is 450-550 ℃; the roasting time is 5-8h.

75. A catalyst for purifying exhaust gas containing bromine-containing organic matters prepared by the production method as claimed in any one of claims 21 to 74.

76. A method for purifying an exhaust gas containing a bromine-containing organic matter, characterized in that the exhaust gas containing a bromine-containing organic matter is contacted with the catalyst according to any one of claims 1 to 20 and claim 75 in an oxygen-containing atmosphere to perform catalytic combustion.

77. The method of claim 76, wherein the conditions of catalytic combustion comprise: the temperature is 200-450 ℃, and the volume airspeed is 3000-30000h ^-1 The pressure is 0-3MPa.

78. The method of claim 77, wherein said catalytic combustion conditions include: the temperature is 250-400 ℃; volume space velocity of 5000-25000h ^-1 The method comprises the steps of carrying out a first treatment on the surface of the The pressure is 0-2MPa.

79. The process recited in any one of claims 76-78, wherein in said offgas comprising bromine-containing organics, the content of bromine-containing organics is from 0 to 100ppm as elemental Br.

80. The method of any of claims 76-78, wherein the bromine-containing organic is selected from at least one of dibromomethane, monobromomethane, monobromoethane, and dibromoethane.