CN111054352B - Integral non-noble metal catalyst for purifying PTA oxidized tail gas and preparation method thereof - Google Patents

Integral non-noble metal catalyst for purifying PTA oxidized tail gas and preparation method thereof Download PDF

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CN111054352B
CN111054352B CN201811201384.8A CN201811201384A CN111054352B CN 111054352 B CN111054352 B CN 111054352B CN 201811201384 A CN201811201384 A CN 201811201384A CN 111054352 B CN111054352 B CN 111054352B
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honeycomb ceramic
coating
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drying
catalyst
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CN111054352A (en
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卢媛娇
缪长喜
蒋见
张磊
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/843—Arsenic, antimony or bismuth
    • B01J23/8437—Bismuth
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
    • F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2209/00—Specific waste
    • F23G2209/14—Gaseous waste or fumes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention mainly relates to an integral non-noble metal catalyst for purifying PTA oxidized tail gas and a preparation method thereof. The perovskite catalyst and the cerium-aluminum composite oxide carrier are synthesized by adopting a coprecipitation method, then the cerium-aluminum composite oxide carrier is coated on the honeycomb ceramic, and the perovskite powder is coated on the honeycomb ceramic of the load carrier to obtain the monolithic catalyst. The catalyst prepared by the invention has the characteristics of low cost, high activity and good toxicity resistance, and can realize high-efficiency catalytic combustion removal on PTA and other industrial waste gases.

Description

Integral non-noble metal catalyst for purifying PTA oxidized tail gas and preparation method thereof
Technical Field
The invention relates to an integral non-noble metal catalyst for purifying PTA oxidized tail gas and a preparation method thereof, belonging to the technical field of catalytic combustion environmental protection.
Background
Purified Terephthalic Acid (PTA) oxidation waste gas is organic waste gas containing various pollutants discharged by an oxidation reactor and is the largest harmful gas discharged by a PTA device. The main component N of the gas2The volume fraction of the organic matter is about 94 percent, and the total mass concentration of the organic matter is more than 1000mg/m3The mass concentration of bromide is about 100mg/m3The mass concentration of CO is about 5000mg/m3All of them are seriously over the national emission standard.
Although various measures are taken by various PTA manufacturers in China in the past to treat the oxidized tail gas, the treatment effect is not ideal. With the continuous enhancement of the environmental protection consciousness of human beings and the continuous perfection of environmental protection laws and regulations, the requirement for thoroughly treating the oxidized tail gas is more and more strong. Driven by this requirement, in recent years, class 2 technologies have appeared with relatively remarkable effects and have been used industrially for treating PTA oxidation tail gas, wherein one class is called Thermal oxidation (Thermal oxidation) technology, and the other class is called Catalytic oxidation (Catalytic oxidation) technology, or Catalytic Combustion (Catalytic Combustion) technology. The thermal oxidation technology is characterized in that harmful substances in the tail gas are cracked at high temperature, and the temperature of the thermal cracking is as high as 800-900 ℃. The catalytic oxidation technology reduces the operation temperature to 280-450 ℃ by means of the action of the catalyst.
The thermal oxidation technology can remove pollutants such as methyl acetate, p-xylene, carbon monoxide and the like in PTA waste gas, but the removal rate of bromide in the PTA waste gas is low and is only 57%, the incineration temperature is as high as 800 ℃, a large amount of fuel oil needs to be consumed, the operation cost is high, potential safety hazards exist due to improper operation, and NO can be generated simultaneouslyx. The catalytic combustion is carried out at a low temperature (250-400 ℃), and the organic matters are subjected to flameless combustion oxidation by using the catalyst and are converted into carbon dioxide and water. The operation is safe and stable, no large valve bank is frequently switched, the operation cost is low, and no secondary pollution is generated. Therefore, catalytic combustion is the most popular technology for controlling PTA exhaust emissions among manufacturers.
The catalyst for catalytic combustion mainly comprises noble metal catalysts such as Pt, Pd, Rh and the like, which have high activity and good selectivity, but have rare resources and high price, the current industrial catalytic combustion catalyst is mainly the noble metal catalyst, and the industrial catalytic combustion catalyst in China is imported, and the main suppliers are Engelhard, Johnson Matthey and other companies; single metal oxide catalysts, such as copper, manganese, cobalt and other metal oxides, are relatively low in cost but generally active; the composite oxide catalyst is easy to obtain, has higher catalytic activity than a corresponding single oxide, can reach the activity of a noble metal catalyst under certain conditions, and is a hotspot of research in the field of catalytic combustion catalysts at present, for example, patent CN103252242B discloses a catalytic combustion catalyst of a composite oxide of copper, manganese and cerium. Compared with noble metal catalysts, the composite metal oxide catalyst has the advantages of low price, halogen poisoning resistance and reliable stability, so the development of the non-noble metal composite oxide catalytic combustion catalyst has wide application prospect.
Disclosure of Invention
The invention aims to solve the problems of high price, poor toxicity resistance and the like of a PTA tail gas catalytic combustion noble metal catalyst in the prior art, and provides a novel integral non-noble metal catalyst for purifying PTA tail gas and a preparation method thereof.
The technical scheme adopted by the invention is as follows: an integral non-noble metal catalyst for purifying PTA oxidized tail gas comprises an active component, a carrier coating and a honeycomb ceramic skeleton, wherein the active component is a vacancy type perovskite catalyst AxBO3Wherein x is 0.6-0.95, A is at least one of La, Ce and Bi, B is transition metal Co, and the carrier coating is cerium-aluminum composite oxide.
In the technical scheme, the perovskite catalyst A with the defect type active componentxBO3Wherein x is 0.75 to 0.86.
In the technical scheme, the perovskite catalyst A with the defect type active componentxBO3Wherein x is 0.78-0.82.
In the technical scheme, A is at least two of La, Ce and Bi; the preferable scheme is that A is La and Bi or Ce and Bi. In the technical scheme, the molar ratio of the two elements at the A position is 9: 1-1: 9.
The most preferable technical scheme is that A is a mixture of La, Ce and Bi, wherein the molar ratio of lanthanide to Bi is 7: 3-8: 2, and the molar ratio of lanthanide La to Ce is 7: 1-1: 7.
The invention relates to a preparation method of an integral catalyst for purifying PTA oxidized tail gas, which comprises the following steps: 1) preparing vacancy type perovskite catalyst powder; 2) preparing carrier composite oxide coating powder; 3) pretreating the honeycomb ceramic; 4) coating of a carrier coating; 5) and (3) coating the active component.
The preparation method comprises the following steps of: precipitating a salt solution of a metal A, B component and an alkaline precipitator to a pH value of 10-11, filtering and washing until the pH value is 7-8, drying at 100-120 ℃ for 10-12 h, and roasting at 600-800 ℃ for 3-5 h to obtain the perovskite powder catalyst.
The above preparation method, wherein the preparation of the washcoat: precipitating with a cerium-aluminum metal salt solution and an alkaline precipitator to a pH value of 9-11, filtering and washing until the pH value is 7-8, drying at 100-120 ℃ for 10-12 h, and roasting at 400-600 ℃ for 2-5 h to obtain the composite oxide catalyst powder.
The preparation method comprises the following steps of pretreatment of the honeycomb ceramic: drying the honeycomb ceramic at 100-120 ℃ for 4-8 h, and roasting at 300-500 ℃ for 2-5 h.
The above preparation method, wherein the application of the washcoat: firstly dispersing carrier composite oxide coating powder into water to prepare a coating liquid I, dipping the honeycomb ceramic in the coating liquid I for 3-8 hours, taking out slurry remained in a blow-drying duct, drying at 100-120 ℃ for 10-12 hours, roasting at 400-600 ℃ for 2-5 hours, weighing, repeating the coating process for at least 3 times until the coating amount on a honeycomb ceramic framework in unit volume is 180-240 g/L, and the mass ratio of solids in the coating liquid I is 30-50%.
The above preparation method, wherein the coating of the active ingredient: firstly dispersing vacancy type perovskite catalyst powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier in the step 4) into the coating liquid II for 3-8 hours, then taking out, blow-drying residual slurry in a pore channel, drying at 100-120 ℃ for 10-12 hours, roasting at 400-600 ℃ for 2-5 hours, then dry-weighing, repeating the coating process for at least 3 times until the coating amount on a honeycomb ceramic framework in unit volume is 50-100 g/L, and preparing the integral non-noble metal catalyst, wherein the solid mass ratio of the coating liquid II is 30-50%.
The invention relates to a method for catalytic combustion of PTA oxidized tail gas, which comprises the following steps: the required amount of catalyst is put into a constant temperature area of a fixed bed reactor, and the upper part and the lower part of the catalyst are filled with porcelain rings. The main components of the oxidation tail gas of the PTA device are methyl acetate, paraxylene and methyl bromide. Under the set temperature and pressure, the waste gas is sent to a preheater by a flowmeter, mixed and gasified with oxygen and nitrogen, then enters the upper end of a reactor, flows through a catalyst bed layer for catalytic reaction, and the reaction product is directly injected into a gas chromatograph by a valve and is analyzed on line for the conversion rate of the waste gas and the selectivity of the product. And each gram of catalyst is used for treating tail gas containing 500-25000 ppm to be 5-50L per hour. Reactivity of the catalyst toThe level of the reaction temperature at which the oxidation tail gas component is completely converted is used as an evaluation criterion, and the lower the temperature at which the component is completely converted is, the better the performance of the catalyst is. Wherein T is99The reaction temperature at which the purification rate of the component in the off-gas was 99% was shown. T of the Mixed sample99Expressed as the reaction temperature at which the purification of all components reached 99%. T of Mixed samplenThe purification rate of dibromomethane at 400 ℃ is represented as n%, and the purification rates of methyl acetate and p-xylene at this time are 99% or more.
Compared with the prior art, the invention adopts non-noble metal with lower price as the active component, achieves better elimination effect, and has high activity and stability. The catalyst prepared by the method is used for PTA tail gas treatment reaction, the purification rate of the oxidized tail gas is more than 99% at the reaction temperature of 200-400 ℃, and the reaction product is CO2，H2O, HBr and Br2The selectivity of the final product carbon dioxide is more than 99 percent. Wherein HBr and Br2Can be completely absorbed by the alkali solution, has good elimination effect, keeps the performance of the catalyst stable, and obtains better technical effect.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Preparation of the washcoat: a solution of 43.41g of cerium nitrate and 750.26g of aluminum nitrate was prepared, and 20 wt% aqueous ammonia was added thereto with stirring to adjust the pH to 10.5, followed by filtration, drying at 110 ℃ and calcination at 450 ℃ for 4 hours to obtain cerium-aluminum oxide powder. The examples and comparative examples herein each use the cerium-aluminum composite oxide prepared by this method.
Preparation of active ingredients: lanthanum nitrate 22.21g and cobalt nitrate 29.10g are prepared into a solution, a mixed solution of sodium hydroxide and sodium carbonate is added to the solution under the condition of stirring until the pH value is 10.5, then the solution is filtered and washed, dried at 110 ℃, and roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
[ example 2 ]
Preparation of active ingredients: lanthanum nitrate 35.17g and cobalt nitrate 29.10g are prepared into a solution, a mixed solution of sodium hydroxide and sodium carbonate is added to the solution under the condition of stirring until the pH value is 10.5, then the solution is filtered and washed, dried at 110 ℃, and roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly dispersing perovskite powder into water to prepare a coating liquid II, soaking the honeycomb ceramic loaded with the carrier in the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then carrying out dry weighing, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
[ example 3 ]
Preparation of active ingredients: a solution is prepared by 27.77g of lanthanum nitrate and 29.10g of cobalt nitrate, a mixed solution of sodium hydroxide and sodium carbonate is added to the solution under the condition of stirring until the pH value is 10.5, then the solution is filtered and washed, dried at 110 ℃, and roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, soaking the honeycomb ceramic in the coating solution I for 4 hours, taking out residual slurry in a blow-dried pore channel, drying at 110 ℃ for 12 hours, roasting at 500 ℃ for 3 hours, weighing, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
[ example 4 ] A method for producing a polycarbonate
Preparation of active ingredients: a solution was prepared from 31.84g of lanthanum nitrate and 29.10g of cobalt nitrate, and a mixed solution of sodium hydroxide and sodium carbonate was added thereto with stirring to a pH of 10.5, followed by filtration washing, drying at 110 ℃ and calcination at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly dispersing perovskite powder into water to prepare a coating liquid II, soaking the honeycomb ceramic loaded with the carrier in the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then carrying out dry weighing, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
[ example 5 ]
Preparation of active ingredients: 28.88g of lanthanum nitrate and 29.10g of cobalt nitrate are prepared into a solution, a mixed solution of sodium hydroxide and sodium carbonate is added into the solution under the condition of stirring until the pH value is 10.5, then the solution is filtered, washed, dried at 110 ℃, and roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, soaking the honeycomb ceramic in the coating solution I for 4 hours, taking out residual slurry in a blow-dried pore channel, drying at 110 ℃ for 12 hours, roasting at 500 ℃ for 3 hours, weighing, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
[ example 6 ]
Preparation of active ingredients: lanthanum nitrate 30.36g and cobalt nitrate 29.10g are prepared into a solution, a mixed solution of sodium hydroxide and sodium carbonate is added into the solution under the condition of stirring until the pH value is 10.5, then the solution is filtered and washed, dried at 110 ℃, and roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly dispersing perovskite powder into water to prepare a coating liquid II, soaking the honeycomb ceramic loaded with the carrier in the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then carrying out dry weighing, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
[ example 7 ]
Preparation of active ingredients: 33.86g of cerium nitrate and 29.10g of cobalt nitrate are prepared into a solution, a mixed solution of sodium hydroxide and sodium carbonate is added to the solution under the condition of stirring until the pH value is 10.5, then the solution is filtered, washed, dried at 110 ℃ and roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
[ example 8 ]
Preparation of active ingredients: preparing a solution from 37.84g of bismuth nitrate and 29.10g of cobalt nitrate, adding a mixed solution of sodium hydroxide and sodium carbonate to the solution under the condition of stirring until the pH value is 10.5, filtering and washing, drying at 110 ℃, and roasting at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
[ example 9 ]
Preparation of active ingredients: lanthanum nitrate 25.99g, bismuth nitrate 3.78g and cobalt nitrate 29.10g are prepared into a solution, a mixed solution of sodium hydroxide and sodium carbonate is added into the solution under the condition of stirring until the pH value is 10.5, then the solution is filtered, washed, dried at 110 ℃ and roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
[ example 10 ]
Preparation of active ingredients: lanthanum nitrate 23.10g, bismuth nitrate 7.57g and cobalt nitrate 29.10g are prepared into a solution, a mixed solution of sodium hydroxide and sodium carbonate is added into the solution under the condition of stirring until the pH value is 10.5, then the solution is filtered, washed, dried at 110 ℃ and roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
[ example 11 ]
Preparation of active ingredients: lanthanum nitrate 20.21g, bismuth nitrate 11.35g and cobalt nitrate 29.10g are prepared into a solution, a mixed solution of sodium hydroxide and sodium carbonate is added into the solution under the condition of stirring until the pH value is 10.5, then the solution is filtered, washed, dried at 110 ℃ and roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, soaking the honeycomb ceramic in the coating solution I for 4 hours, taking out residual slurry in a blow-dried pore channel, drying at 110 ℃ for 12 hours, roasting at 500 ℃ for 3 hours, weighing, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
[ example 12 ] A method for producing a polycarbonate
Preparation of active ingredients: lanthanum nitrate 17.32g, bismuth nitrate 15.13g and cobalt nitrate 29.10g are prepared into a solution, a mixed solution of sodium hydroxide and sodium carbonate is added into the solution under the condition of stirring until the pH value is 10.5, then the solution is filtered, washed, dried at 110 ℃ and roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, soaking the honeycomb ceramic in the coating solution I for 4 hours, taking out residual slurry in a blow-dried pore channel, drying at 110 ℃ for 12 hours, roasting at 500 ℃ for 3 hours, weighing, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
[ example 13 ]
Preparation of active ingredients: 14.44g of lanthanum nitrate, 18.92g of bismuth nitrate and 29.10g of cobalt nitrate are prepared into a solution, a mixed solution of sodium hydroxide and sodium carbonate is added into the solution under the condition of stirring until the pH value is 10.5, then the solution is filtered, washed, dried at 110 ℃ and roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
[ example 14 ]
Preparation of active ingredients: lanthanum nitrate 11.55g, bismuth nitrate 22.70g and cobalt nitrate 29.10g are prepared into a solution, a mixed solution of sodium hydroxide and sodium carbonate is added into the solution under the condition of stirring until the pH value is 10.5, then the solution is filtered, washed, dried at 110 ℃ and roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, soaking the honeycomb ceramic in the coating solution I for 4 hours, taking out residual slurry in a blow-dried pore channel, drying at 110 ℃ for 12 hours, roasting at 500 ℃ for 3 hours, weighing, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
[ example 15 ]
Preparation of active ingredients: lanthanum nitrate 8.66g, bismuth nitrate 26.48g and cobalt nitrate 29.10g are prepared into a solution, a mixed solution of sodium hydroxide and sodium carbonate is added into the solution under the condition of stirring until the pH value is 10.5, then the solution is filtered, washed, dried at 110 ℃ and roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
[ example 16 ]
Preparation of active ingredients: lanthanum nitrate 5.78g, bismuth nitrate 30.27g and cobalt nitrate 29.10g are prepared into a solution, a mixed solution of sodium hydroxide and sodium carbonate is added into the solution under the condition of stirring until the pH value is 10.5, then the solution is filtered, washed, dried at 110 ℃ and roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
[ example 17 ]
Preparation of active ingredients: lanthanum nitrate 2.89g, bismuth nitrate 34.05g and cobalt nitrate 29.10g are prepared into a solution, a mixed solution of sodium hydroxide and sodium carbonate is added to the solution under the condition of stirring until the pH value is 10.5, then the solution is filtered, washed, dried at 110 ℃ and roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
[ example 18 ]
Preparation of active ingredients: lanthanum nitrate 25.99g, cerium nitrate 3.39g and cobalt nitrate 29.10g are prepared into a solution, a mixed solution of sodium hydroxide and sodium carbonate is added into the solution under the condition of stirring until the pH value is 10.5, then the solution is filtered, washed, dried at 110 ℃ and roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
[ example 19 ]
Preparation of active ingredients: 30.48g of cerium nitrate, 3.78g of bismuth nitrate and 29.10g of cobalt nitrate are prepared into a solution, a mixed solution of sodium hydroxide and sodium carbonate is added into the solution under the condition of stirring until the pH value is 10.5, then the solution is filtered, washed, dried at 110 ℃ and roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
[ example 20 ]
Preparation of active ingredients: preparing a solution from 17.33g of lanthanum nitrate, 3.39g of cerium nitrate, 11.35g of bismuth nitrate and 29.10g of cobalt nitrate, adding a mixed solution of sodium hydroxide and sodium carbonate to the solution under the condition of stirring until the pH value is 10.5, filtering and washing, drying at 110 ℃, and roasting at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
[ example 21 ]
Preparation of active ingredients: lanthanum nitrate 2.89g, cerium nitrate 20.32g, bismuth nitrate 11.35g and cobalt nitrate 29.10g are prepared into a solution, under the condition of stirring, a mixed solution of sodium hydroxide and sodium carbonate is added into the solution until the pH value is 10.5, then the solution is filtered, washed, dried at 110 ℃, and roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
[ example 22 ]
Preparation of active ingredients: lanthanum nitrate 20.21g, cerium nitrate 3.39g, bismuth nitrate 7.57g and cobalt nitrate 29.10g are prepared into a solution, under the condition of stirring, a mixed solution of sodium hydroxide and sodium carbonate is added to the solution until the pH value is 10.5, then the solution is filtered, washed, dried at 110 ℃, and roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
[ example 23 ]
Preparation of active ingredients: lanthanum nitrate 2.89g, cerium nitrate 23.70g, bismuth nitrate 7.57g and cobalt nitrate 29.10g are prepared into a solution, under the condition of stirring, a mixed solution of sodium hydroxide and sodium carbonate is added into the solution until the pH value is 10.5, then the solution is filtered and washed, dried at 110 ℃, and then roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
Comparative example 1
Preparation of active ingredients: 37.02g of lanthanum nitrate and 29.10g of cobalt nitrate are prepared into a solution, a mixed solution of sodium hydroxide and sodium carbonate is added into the solution under the condition of stirring until the pH value is 10.5, then the solution is filtered, washed, dried at 110 ℃, and roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly dispersing perovskite powder into water to prepare a coating liquid II, soaking the honeycomb ceramic loaded with the carrier in the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then carrying out dry weighing, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
Comparative example 2
Preparation of active ingredients: a solution was prepared from 43.41g of cerium nitrate and 29.10g of cobalt nitrate, and a mixed solution of sodium hydroxide and sodium carbonate was added thereto with stirring to a pH of 10.5, followed by filtration and washing, drying at 110 ℃ and then calcination at 650 ℃ for 4 hours to obtain a perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
Comparative example 3
Preparation of active ingredients: 48.51g of bismuth nitrate and 29.10g of cobalt nitrate are prepared into a solution, a mixed solution of sodium hydroxide and sodium carbonate is added to the solution under the condition of stirring until the pH value is 10.5, then the solution is filtered, washed, dried at 110 ℃ and roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly dispersing perovskite powder into water to prepare a coating liquid II, soaking the honeycomb ceramic loaded with the carrier in the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then carrying out dry weighing, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
Comparative example 4
Preparation of active ingredients: lanthanum nitrate 18.51g and cobalt nitrate 29.10g are prepared into a solution, a mixed solution of sodium hydroxide and sodium carbonate is added to the solution under the condition of stirring until the pH value is 10.5, then the solution is filtered and washed, dried at 110 ℃, and then roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, soaking the honeycomb ceramic in the coating solution I for 4 hours, taking out residual slurry in a blow-dried pore channel, drying at 110 ℃ for 12 hours, roasting at 500 ℃ for 3 hours, weighing, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
Comparative example 5
Preparation of active ingredients: lanthanum nitrate 29.62g, bismuth nitrate 9.70g and cobalt nitrate 29.10g were mixed to prepare a solution, and a mixed solution of sodium hydroxide and sodium carbonate was added thereto with stirring to a pH of 10.5, followed by filtration, washing, drying at 110 ℃, and then baking at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
Comparative example 6
Preparation of active ingredients: lanthanum nitrate 33.32g, cerium nitrate 4.34g and cobalt nitrate 29.10g are prepared into a solution, a mixed solution of sodium hydroxide and sodium carbonate is added to the solution under the condition of stirring until the pH value is 10.5, then the solution is filtered, washed, dried at 110 ℃ and roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
Comparative example 7
Preparation of active ingredients: a solution is prepared by 39.07g of cerium nitrate, 4.85g of bismuth nitrate and 29.10g of cobalt nitrate, a mixed solution of sodium hydroxide and sodium carbonate is added to the solution under the condition of stirring until the pH value is 10.5, then the solution is filtered, washed, dried at 110 ℃ and roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly dispersing perovskite powder into water to prepare a coating liquid II, soaking the honeycomb ceramic loaded with the carrier in the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then carrying out dry weighing, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
Comparative example 8
Preparation of active ingredients: lanthanum nitrate 25.92g, cerium nitrate 4.34g, bismuth nitrate 9.70g and cobalt nitrate 29.10g are prepared into a solution, under the condition of stirring, a mixed solution of sodium hydroxide and sodium carbonate is added into the solution until the pH value is 10.5, then the solution is filtered and washed, dried at 110 ℃, and then roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
Comparative example 9
Preparation of active ingredients: 16.50g of strontium nitrate and 29.10g of cobalt nitrate are prepared into a solution, a mixed solution of sodium hydroxide and sodium carbonate is added into the solution under the condition of stirring until the pH value is 10.5, then the solution is filtered and washed, dried at 110 ℃, and then roasted at 650 ℃ for 4 hours to obtain perovskite powder.
Coating of the carrier coating: firstly, dispersing cerium-aluminum composite oxide powder into water to prepare a coating solution I, dipping the honeycomb ceramic into the coating solution I for 4 hours, taking out the honeycomb ceramic to blow dry the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, weighing the honeycomb ceramic, and repeating the coating process for 3 times.
Coating of active ingredients: firstly, dispersing perovskite powder into water to prepare a coating liquid II, dipping the honeycomb ceramic loaded with the carrier into the coating liquid II for 4 hours, then taking out the honeycomb ceramic, blow-drying the slurry remained in a pore channel, drying the honeycomb ceramic at 110 ℃ for 12 hours, roasting the honeycomb ceramic at 500 ℃ for 3 hours, then weighing the honeycomb ceramic in a drying way, and repeating the coating process for 3 times to obtain the monolithic non-noble metal catalyst, wherein the component content of the catalyst is shown in Table 1.
[ example 24 ]
The fresh catalysts of examples 1 to 23 and comparative examples 1 to 9 were subjected to the evaluation of catalytic reaction performance under the same conditions on a fixed bed reactor catalytic reaction apparatus, and the reaction results are shown in Table 1. In this experiment, the single evaluation concentrations of the main components of the exhaust gas were respectively: 15000ppm methyl acetate, 4000ppm p-xylene, 500ppm methyl bromide, the concentrations of the three components in the mixed sample are respectively: 10000ppm of methyl acetate, 2000ppm of p-xylene and 300ppm of methyl bromide. The process conditions evaluated were: the reaction pressure is 0.05 MPa-0.10 MPa, the amount of the waste gas treated by each gram of catalyst is 25L per hour, and the temperature is programmed to the reaction temperature until the conversion is completed. Wherein T is99The reaction temperature at which the purification rate of the component in the exhaust gas was 99% was indicated. T of Mixed sample99Expressed as the reaction temperature at which the purification of all components reached 99%. T of Mixed samplenIt was found that the purification rate of dibromomethane at 400 ℃ was n%, and that the purification rates of methyl acetate and p-xylene were 99% or more.
TABLE 1
Figure BDA0001830090910000161
Figure BDA0001830090910000171
[ example 25 ]
Fresh catalysts of examples 5, 10 and 22 and comparative example 8 were subjected to catalytic reaction performance evaluation under the same conditions on a fixed bed reactor catalytic reaction apparatus, and the reaction results are shown in table 2. In this experiment, the single evaluation concentrations of the main components of the exhaust gas were respectively: 15000ppm methyl acetate, 4000ppm p-xylene, 500ppm methyl bromide, and the concentrations of the three components in the mixed sample are respectively: 10000ppm of methyl acetate, 2000ppm of p-xylene and 300ppm of methyl bromide. The process conditions evaluated were: the reaction pressure is 0.05MPa to 0.10MPa, the amount of the waste gas treated by each gram of the catalyst is 50L per hour,the temperature was programmed to the reaction temperature until complete conversion. Wherein T is99The reaction temperature at which the purification rate of the component in the exhaust gas was 99% was indicated. T of Mixed sample99Expressed as the reaction temperature at which the purification of all components reached 99%. T of the Mixed samplenThe results show that the purification rate of dibromomethane at 400 ℃ is n%, and the purification rates of methyl acetate and p-xylene are more than 99%.
TABLE 2
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION A element component x Acetic acid methyl ester T99 Para-xylene T99 Bromomethane T99 Mixed sample T99
Example 5 La 0.78 250 280 315 340
Example 10 La:Bi＝8:2 0.78 220 260 285 320
Example 22 La:Ce:Bi＝7:1:2 0.78 200 230 275 295
Comparative example 8 La:Ce:Bi＝7:1:2 1 340 355 390 400(T85)

Claims (9)

1. An integral non-noble metal catalyst for purifying PTA oxidized tail gas comprises an active component, a carrier coating and a honeycomb ceramic skeleton, wherein the active component is a vacancy type perovskite catalyst AxBO3Wherein x is 0.75-0.86, A is at least one of La, Ce and Bi, B is transition metal Co, and the carrier coating is cerium-aluminum composite oxide.
2. The monolithic non-noble metal catalyst of claim 1, wherein a is at least two of La, Ce, Bi.
3. The monolithic non-noble metal catalyst of claim 2, wherein the molar ratio of the two elements in A is 9:1 to 1: 9.
4. A method of preparing the monolithic catalyst for PTA oxidation exhaust gas purification as recited in any one of claims 1-3, comprising the steps of: 1) preparing vacancy type perovskite catalyst powder; 2) preparing carrier composite oxide coating powder; 3) pretreating the honeycomb ceramic; 4) coating of a carrier coating; 5) coating of the active ingredient.
5. The production method according to claim 4, wherein the perovskite catalyst of the active component-deficient type is produced by: precipitating a salt solution of a metal A, B component and an alkaline precipitator to a pH value of 10-11, filtering, washing, drying and roasting to obtain the active component vacancy type perovskite catalyst powder.
6. The production method according to claim 4, wherein the production of the washcoat: precipitating with a cerium-aluminum metal salt solution and an alkaline precipitator until the pH value is 9-11, filtering, washing, drying and roasting to obtain composite oxide coating powder.
7. The production method according to claim 4, wherein the pretreatment of the honeycomb ceramic: drying the honeycomb ceramic at 100-120 ℃ for 4-8 h, and roasting at 300-500 ℃ for 2-5 h.
8. The method of claim 4, wherein the step 4) of applying the washcoat: firstly, dispersing carrier composite oxide coating powder into water to prepare a coating liquid I, dipping the honeycomb ceramic in the coating liquid I for 3-8 hours, taking out slurry remained in a blow-drying duct, drying, roasting, weighing, repeating the coating process for at least 3 times until the coating amount on a honeycomb ceramic framework in unit volume is 180-240 g/L, wherein the mass ratio of solids in the coating liquid I is 30-50%; coating of the active component in the step 5): firstly, dispersing vacancy type perovskite catalyst powder into water to prepare a coating liquid II, soaking the honeycomb ceramic loaded with the carrier in the step 4) in the coating liquid II for 3-8 hours, then taking out, blow-drying residual slurry in a pore channel, then drying, roasting, weighing, and repeating the coating process for at least 3 times until the coating amount on a honeycomb ceramic framework in unit volume is 50-100 g/L to prepare the integral non-noble metal catalyst, wherein the solid mass ratio of the coating liquid II is 30-50%.
9. A catalytic combustion method for PTA oxidized tail gas is characterized in that the PTA oxidized tail gas is contacted with the catalyst of claims 1-3, a mixture of nitrogen and oxygen or air is introduced at the temperature of 200-400 ℃, and methyl acetate, xylene and dibromomethane volatile organic compounds in the PTA oxidized tail gas are catalytically combusted to generate carbon dioxide, water, hydrogen bromide and bromine elementary substances; wherein each gram of catalyst is 5-50L per hour for treating tail gas containing 500-25000 ppm.
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