CN111054376B - Non-noble metal catalyst for catalytic combustion of PTA (pure terephthalic acid) oxidized tail gas and application thereof - Google Patents

Non-noble metal catalyst for catalytic combustion of PTA (pure terephthalic acid) oxidized tail gas and application thereof Download PDF

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CN111054376B
CN111054376B CN201811201431.9A CN201811201431A CN111054376B CN 111054376 B CN111054376 B CN 111054376B CN 201811201431 A CN201811201431 A CN 201811201431A CN 111054376 B CN111054376 B CN 111054376B
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cobalt
manganese
gallium
catalyst
indium
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CN111054376A (en
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蒋见
缪长喜
卢媛娇
孙清
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • B01J23/84—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
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0234—Impregnation and coating simultaneously
    • 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
    • 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 a non-noble metal catalyst for catalytic combustion of PTA (pure terephthalic acid) oxidized tail gas, which is a honeycomb ceramic monolithic catalyst loaded with cobalt, manganese, gallium and/or indium composite oxides. The catalyst is synthesized by adopting a coprecipitation method, namely alkaline precipitants such as sodium carbonate, sodium bicarbonate, sodium hydroxide and ammonia water are added into a salt solution of cobalt, manganese, gallium and/or indium, then the mixture is filtered and roasted to obtain cobalt, manganese, gallium and/or indium composite oxides, and then the cobalt, manganese, gallium and/or indium composite oxides are loaded on honeycomb ceramics 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

Non-noble metal catalyst for catalytic combustion of PTA oxidized tail gas and application thereof
Technical Field
The invention relates to a non-noble metal catalyst for catalytic combustion of PTA oxidized tail gas, 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 gas 2 The volume fraction of the organic matter is about 94 percent, and the total mass concentration of the organic matter is more than 1000mg/m 3 The mass concentration of bromide is about 100mg/m 3 The mass concentration of CO is about 5000mg/m 3 All 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 demand, class 2 technologies have emerged in recent years, and have been used industrially as PTA oxidation tail gas treatment technologies, one of which is called Thermal oxidation (Thermal oxidation) technology, and the other 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 thermal cracking temperature is as high as 800-900 ℃. And the catalytic oxidation technology reduces the operation temperature to 280-450 ℃ by the action of the catalyst.
The thermal oxidation technology can remove pollutants such as methyl acetate, paraxylene, 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 percent, the burning temperature is up to 800 ℃, a large amount of fuel oil needs to be consumed, the operation cost is high, the potential safety hazard exists when the operation is not carried out, and NO can be generated x . The catalytic combustion is carried out at a low temperature (250-400 ℃), and the organic matters are oxidized by the catalyst in a flameless combustion mode and are converted into carbon dioxide and water. The operation is safe and stable, a large valve group which is frequently switched is not needed, the operation cost is low, and secondary pollution is not 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 catalysts in China are imported, and the main suppliers include 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 that of a corresponding single oxide, can reach the activity of a noble metal catalyst under certain conditions, and is a hot point of research in the field of catalytic combustion catalysts at present, for example, a catalytic combustion catalyst of a composite oxide of copper, manganese and cerium is disclosed in patent CN 103252242B. 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
One of the technical problems to be solved by the invention is that the PTA tail gas catalytic combustion noble metal catalyst in the prior art is expensive and poor in toxicity resistance, and the like, and provides a new integral non-noble metal catalyst for PTA tail gas catalytic combustion and a new integral non-noble metal catalyst for PTA tail gas catalytic combustion. The prepared catalyst has the advantages of low raw material cost, high activity, good toxicity resistance and the like. The second technical problem to be solved by the present invention is a method for preparing a catalyst corresponding to the first technical problem. The third technical problem to be solved by the invention is the application of the catalyst corresponding to the first technical problem in the catalytic combustion reaction of PTA tail gas.
In order to solve one of the technical problems, the technical scheme adopted by the invention is as follows: a non-noble metal catalyst for catalytic combustion of PTA oxidized tail gas features that its carrier is honeycomb ceramic and is loaded with Co, mn, ga and/or in metal composite oxide.
In the scheme, the molar ratio of the cobalt to the manganese in the cobalt, manganese, gallium and/or indium metal composite oxide is 1 (0.1-10), and the molar ratio of the cobalt to the gallium/indium is 1 (0.1-1).
In the above scheme, preferably, the metal composite oxide loaded on the honeycomb ceramic is a cobalt, manganese, gallium and indium composite oxide, and the four metal elements are used cooperatively, so that the conversion rate of dibromomethane is improved when the PTA oxidation tail gas is treated.
The molar ratio range of the cobalt and the manganese elements in the cobalt, manganese, gallium and/or indium metal composite oxide is 1 (0.1-1), the molar ratio range of the cobalt and the gallium elements is 1 (0.1-0.5), and the molar ratio range of the cobalt and the indium elements is 1 (0.1-0.5).
In the scheme, the coating amount of the cobalt, manganese, gallium and/or indium metal composite oxide on the honeycomb ceramic framework of the catalyst is 50-200 g/L.
In the scheme, the coating amount of the cobalt, manganese, gallium and/or indium metal composite oxide on the honeycomb ceramic framework of the catalyst is 100-170 g/L.
To solve the second technical problem, the invention adopts the following technical scheme: a preparation method of a non-noble metal catalyst for catalytic combustion of PTA oxidized tail gas comprises the following steps: uniformly dispersing cobalt, manganese, gallium and/or indium metal composite oxide particles in an aqueous phase, carrying out colloid milling to prepare coating liquid, and then coating the coating liquid on honeycomb ceramics to prepare an integral catalyst; the preparation method of the cobalt, manganese, gallium and/or indium metal composite oxide particles comprises the steps of preparing metal cobalt salt, metal manganese salt, metal gallium salt and/or indium metal salt into an aqueous solution according to a certain proportion, adding sodium carbonate, sodium bicarbonate, sodium hydroxide and an ammonia alkaline precipitator into the aqueous solution to a certain pH value, and then obtaining cobalt, manganese, gallium and/or indium metal composite oxide powder.
In the above scheme, the cobalt salt and manganese salt used for preparing the cobalt, manganese, gallium and/or indium metal composite oxide powder are selected from nitrate, acetate and halide.
In the scheme, the stirring temperature for preparing the cobalt, manganese, gallium and/or indium metal composite oxide powder is between 10 and 90 ℃; when preparing the cobalt-manganese metal composite oxide powder, precipitator is added to a certain pH value range of 9-11.
In the scheme, when the cobalt, manganese, gallium and/or indium composite oxide particles are uniformly dispersed in the aqueous phase and are colloid-milled to prepare the coating liquid, the weight percentage of the cobalt, manganese, gallium and/or indium composite oxide in the coating liquid accounts for 10-35% of the coating liquid.
In the scheme, the drying temperature is 100-125 ℃, the drying time is 1-25 hours, the roasting temperature is 300-600 ℃, and the roasting time is 3-10 hours when the cobalt, manganese, gallium and/or indium metal composite oxide coating liquid is coated and dipped on the honeycomb ceramic.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: a catalytic combustion method for PTA oxidized tail gas is characterized in that the PTA oxidized tail gas is contacted with the catalyst, a mixture of nitrogen and oxygen or air is introduced at the temperature of 200-450 ℃, and illegal organic matters such as methyl acetate, dimethylbenzene and dibromomethane in the PTA oxidized tail gas can be catalytically combusted to generate carbon dioxide, water, hydrogen bromide and bromine elementary substances.
The catalyst prepared by the invention has high activity, under the conditions that the concentration of methyl acetate in PTA oxidized tail gas component is 7500ppm, the concentration of paraxylene is 1500ppm and the concentration of dibromomethane is 250ppm, the conversion rates of methyl acetate, paraxylene and dibromomethane are above 99% at the temperature of a catalyst bed layer inlet of more than 345 ℃, and the selectivity of a final product carbon dioxide is above 99%.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Cobalt nitrate hexahydrate, manganese nitrate and nitric acid are prepared into aqueous solution according to the mole ratio shown in the table 1, sodium carbonate solution is added into the aqueous solution under the condition of stirring at 40 ℃ until the pH value reaches 9.5, then the aqueous solution is filtered, dried at 110 ℃ and roasted at 500 ℃ for 4 hours to obtain cobalt-manganese metal composite oxide powder. Dispersing the obtained cobalt-manganese-gallium metal composite oxide powder into water, carrying out colloid milling to obtain a coating solution, wherein the solid content of the coating solution is 30%, soaking the honeycomb ceramic in the coating solution for 4 hours, then taking out, drying residual slurry in a pore channel, then drying at 110 ℃, roasting at 500 ℃ to obtain the integral non-noble metal catalyst, and coating for multiple times, wherein the coating amount on the honeycomb ceramic framework in unit volume is 110g/L.
Under the condition that the PTA simulated oxidation tail gas contains 1500ppm of methyl acetate, 300ppm of p-xylene and 50ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 1.
[ example 2 ]
Cobalt nitrate hexahydrate, manganese nitrate and nitric acid are prepared into aqueous solution according to the mole ratio shown in the table 1, sodium carbonate solution is added into the aqueous solution under the condition of stirring at 40 ℃ until the pH value reaches 9.5, then the aqueous solution is filtered, dried at 110 ℃ and roasted at 500 ℃ for 4 hours to obtain cobalt-manganese metal composite oxide powder. Dispersing the obtained cobalt-manganese-gallium metal composite oxide powder into water, carrying out colloid milling to obtain a coating liquid, wherein the solid content of the coating liquid is 30%, soaking the honeycomb ceramic in the coating liquid for 4 hours, taking out the honeycomb ceramic, blow-drying the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃, roasting the honeycomb ceramic at 500 ℃ to obtain the integral non-noble metal catalyst, and coating the honeycomb ceramic on a honeycomb ceramic framework in unit volume for multiple times, wherein the coating amount on the honeycomb ceramic framework in unit volume is 110g/L.
Under the condition that PTA simulated oxidation tail gas contains 1500ppm of methyl acetate, 300ppm of paraxylene and 50ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 1.
[ example 3 ]
Cobalt nitrate hexahydrate, manganese nitrate and nitric acid are prepared into aqueous solution according to the mole ratio shown in the table 1, sodium carbonate solution is added into the aqueous solution under the condition of stirring at 40 ℃ until the pH value reaches 9.5, then the aqueous solution is filtered, dried at 110 ℃ and roasted at 500 ℃ for 4 hours to obtain cobalt-manganese metal composite oxide powder. Dispersing the obtained cobalt-manganese-gallium metal composite oxide powder into water, carrying out colloid milling to obtain a coating solution, wherein the solid content of the coating solution is 30%, soaking the honeycomb ceramic in the coating solution for 4 hours, then taking out, drying residual slurry in a pore channel, then drying at 110 ℃, roasting at 500 ℃ to obtain the integral non-noble metal catalyst, and coating for multiple times, wherein the coating amount on the honeycomb ceramic framework in unit volume is 110g/L.
Under the condition that the PTA simulated oxidation tail gas contains 1500ppm of methyl acetate, 300ppm of p-xylene and 50ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 1.
[ example 4 ]
Cobalt nitrate hexahydrate, manganese nitrate and indium nitrate are prepared into aqueous solution according to the mol ratio shown in the table 1, sodium carbonate solution is added into the aqueous solution under the condition of stirring at 40 ℃ until certain pH value is 9.5, then filtering, drying at 110 ℃ and roasting at 500 ℃ for 4 hours are carried out to obtain cobalt manganese metal composite oxide powder. Dispersing the obtained cobalt-manganese-indium metal composite oxide powder into water, carrying out colloid milling to obtain a coating liquid, wherein the solid content of the coating liquid is 30%, soaking the honeycomb ceramic in the coating liquid for 4 hours, taking out the honeycomb ceramic, blow-drying the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃, roasting the honeycomb ceramic at 500 ℃ to obtain the integral non-noble metal catalyst, and coating the honeycomb ceramic for multiple times, wherein the coating amount on a honeycomb ceramic framework in unit volume is 110g/L.
Under the condition that the PTA simulated oxidation tail gas contains 1500ppm of methyl acetate, 300ppm of p-xylene and 50ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 1.
[ example 5 ]
Cobalt nitrate hexahydrate, manganese nitrate and indium nitrate are prepared into aqueous solution according to the mol ratio shown in the table 1, sodium carbonate solution is added into the aqueous solution under the condition of stirring at the temperature of 40 ℃ until certain pH value is 9.5, then the aqueous solution is filtered, dried at the temperature of 110 ℃ and roasted at the temperature of 500 ℃ for 4 hours to obtain cobalt-manganese metal composite oxide powder. Dispersing the obtained cobalt-manganese-indium metal composite oxide powder into water, carrying out colloid milling to obtain a coating liquid, wherein the solid content of the coating liquid is 30%, soaking the honeycomb ceramic in the coating liquid for 4 hours, taking out the honeycomb ceramic, blow-drying the residual slurry in a pore channel, drying the honeycomb ceramic at 110 ℃, roasting the honeycomb ceramic at 500 ℃ to obtain the integral non-noble metal catalyst, and coating the honeycomb ceramic for multiple times, wherein the coating amount on a honeycomb ceramic framework in unit volume is 110g/L.
Under the condition that PTA simulated oxidation tail gas contains 1500ppm of methyl acetate, 300ppm of paraxylene and 50ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 1.
[ example 6 ] A method for producing a polycarbonate
Cobalt nitrate hexahydrate, manganese nitrate and indium nitrate are prepared into aqueous solution according to the mol ratio shown in the table 1, sodium carbonate solution is added into the aqueous solution under the condition of stirring at the temperature of 40 ℃ until certain pH value is 9.5, then the aqueous solution is filtered, dried at the temperature of 110 ℃ and roasted at the temperature of 500 ℃ for 4 hours to obtain cobalt-manganese metal composite oxide powder. Dispersing the obtained cobalt-manganese-indium metal composite oxide powder into water, carrying out colloid milling to obtain a coating solution, wherein the solid content of the coating solution is 30%, soaking the honeycomb ceramic in the coating solution for 4 hours, then taking out, drying residual slurry in a pore channel, then drying at 110 ℃, roasting at 500 ℃ to obtain the integral non-noble metal catalyst, and coating for multiple times, wherein the coating amount on the honeycomb ceramic framework in unit volume is 110g/L.
Under the condition that PTA simulated oxidation tail gas contains 1500ppm of methyl acetate, 300ppm of paraxylene and 50ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 1.
[ example 7 ]
Cobalt nitrate hexahydrate, manganese nitrate, gallium nitrate and indium nitrate are prepared into aqueous solution according to the molar ratio shown in the table 1, sodium carbonate solution is added into the aqueous solution under the condition of stirring at 40 ℃ until the pH value reaches 9.5, and then the aqueous solution is filtered, dried at 110 ℃ and roasted at 500 ℃ for 4 hours to obtain cobalt-manganese metal composite oxide powder. Dispersing the obtained cobalt-manganese-gallium-indium metal composite oxide powder into water, carrying out colloid milling to obtain a coating liquid, wherein the solid content of the coating liquid is 30%, soaking the honeycomb ceramic in the coating liquid for 4 hours, taking out the honeycomb ceramic, blow-drying the honeycomb ceramic, drying the honeycomb ceramic at 110 ℃, roasting the honeycomb ceramic at 500 ℃ to obtain the integral non-noble metal catalyst, and coating for multiple times, wherein the coating amount on the honeycomb ceramic framework in unit volume is 110g/L.
Under the condition that the PTA simulated oxidation tail gas contains 1500ppm of methyl acetate, 300ppm of p-xylene and 50ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 1.
[ example 8 ]
Cobalt nitrate hexahydrate, manganese nitrate, gallium nitrate and indium nitrate are prepared into aqueous solution according to the molar ratio shown in the table 1, sodium carbonate solution is added into the aqueous solution under the condition of stirring at 40 ℃ until the pH value reaches 9.5, and then the aqueous solution is filtered, dried at 110 ℃ and roasted at 500 ℃ for 4 hours to obtain cobalt-manganese metal composite oxide powder. Dispersing the obtained cobalt-manganese-gallium-indium metal composite oxide powder into water, carrying out colloid milling to obtain a coating solution, wherein the solid content of the coating solution is 30%, soaking the honeycomb ceramic in the coating solution for 4 hours, then taking out, drying residual slurry in a pore channel, then drying at 110 ℃, roasting at 500 ℃ to obtain the integral non-noble metal catalyst, and coating for multiple times, wherein the coating amount on the honeycomb ceramic framework in unit volume is 110g/L.
Under the condition that the PTA simulated oxidation tail gas contains 1500ppm of methyl acetate, 300ppm of p-xylene and 50ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 1.
[ example 9 ] A method for producing a polycarbonate
Cobalt nitrate hexahydrate, manganese nitrate, gallium nitrate and indium nitrate are prepared into aqueous solution according to the molar ratio shown in the table 1, sodium carbonate solution is added into the aqueous solution under the condition of stirring at 40 ℃ until the pH value reaches 9.5, and then the aqueous solution is filtered, dried at 110 ℃ and roasted at 500 ℃ for 4 hours to obtain cobalt-manganese metal composite oxide powder. Dispersing the obtained cobalt-manganese-gallium-indium metal composite oxide powder into water, carrying out colloid milling to obtain a coating liquid, wherein the solid content of the coating liquid is 30%, soaking the honeycomb ceramic in the coating liquid for 4 hours, taking out the honeycomb ceramic, blow-drying the honeycomb ceramic, drying the honeycomb ceramic at 110 ℃, roasting the honeycomb ceramic at 500 ℃ to obtain the integral non-noble metal catalyst, and coating for multiple times, wherein the coating amount on the honeycomb ceramic framework in unit volume is 110g/L.
Under the condition that the PTA simulated oxidation tail gas contains 1500ppm of methyl acetate, 300ppm of p-xylene and 50ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 1.
[ example 10 ] A method for producing a polycarbonate
Cobalt nitrate hexahydrate, manganese nitrate, gallium nitrate and indium nitrate are prepared into aqueous solution according to the molar ratio shown in the table 1, sodium carbonate solution is added into the aqueous solution under the condition of stirring at 40 ℃ until certain pH value is 9.5, and then the aqueous solution is filtered, dried at 110 ℃ and roasted at 500 ℃ for 4 hours to obtain cobalt-manganese metal composite oxide powder. Dispersing the obtained cobalt-manganese-gallium-indium metal composite oxide powder into water, carrying out colloid milling to obtain a coating liquid, wherein the solid content of the coating liquid is 20%, soaking the honeycomb ceramic in the coating liquid for 3 hours, then taking out, blow-drying residual slurry in a pore channel, drying at 110 ℃, roasting at 500 ℃ to obtain the integral non-noble metal catalyst, and coating for multiple times, wherein the coating amount on a honeycomb ceramic framework in unit volume is 50g/L.
Under the condition that the PTA simulated oxidation tail gas contains 1500ppm of methyl acetate, 300ppm of p-xylene and 50ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 1.
[ example 11 ]
Cobalt nitrate hexahydrate, manganese nitrate, gallium nitrate and indium nitrate are prepared into aqueous solution according to the molar ratio shown in the table 1, sodium carbonate solution is added into the aqueous solution under the condition of stirring at 40 ℃ until certain pH value is 9.5, and then the aqueous solution is filtered, dried at 110 ℃ and roasted at 500 ℃ for 4 hours to obtain cobalt-manganese metal composite oxide powder. Dispersing the obtained cobalt-manganese-gallium-indium metal composite oxide powder into water, carrying out colloid milling to obtain a coating liquid, wherein the solid content of the coating liquid is 25%, soaking the honeycomb ceramic in the coating liquid for 4 hours, then taking out, blow-drying residual slurry in a pore channel, drying at 110 ℃, roasting at 500 ℃ to obtain the integral non-noble metal catalyst, and coating for multiple times, wherein the coating amount on a honeycomb ceramic framework in unit volume is 100g/L.
Under the condition that the PTA simulated oxidation tail gas contains 1500ppm of methyl acetate, 300ppm of p-xylene and 50ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 1.
[ example 12 ]
Cobalt nitrate hexahydrate, manganese nitrate, gallium nitrate and indium nitrate are prepared into aqueous solution according to the molar ratio shown in the table 1, sodium carbonate solution is added into the aqueous solution under the condition of stirring at 40 ℃ until certain pH value is 9.5, and then the aqueous solution is filtered, dried at 110 ℃ and roasted at 500 ℃ for 4 hours to obtain cobalt-manganese metal composite oxide powder. Dispersing the obtained cobalt-manganese-gallium-indium metal composite oxide powder into water, carrying out colloid milling to obtain a coating liquid, wherein the solid content of the coating liquid is 35%, soaking the honeycomb ceramic in the coating liquid for 4 hours, taking out the honeycomb ceramic, blow-drying the honeycomb ceramic, drying the honeycomb ceramic at 110 ℃, roasting the honeycomb ceramic at 500 ℃ to obtain the integral non-noble metal catalyst, and coating the honeycomb ceramic for multiple times, wherein the coating amount on a honeycomb ceramic framework in unit volume is 150g/L.
Under the condition that PTA simulated oxidation tail gas contains 1500ppm of methyl acetate, 300ppm of paraxylene and 50ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 1.
[ example 13 ]
Cobalt nitrate hexahydrate, manganese nitrate, gallium nitrate and indium nitrate are prepared into aqueous solution according to the molar ratio shown in the table 1, sodium carbonate solution is added into the aqueous solution under the condition of stirring at 40 ℃ until certain pH value is 9.5, and then the aqueous solution is filtered, dried at 110 ℃ and roasted at 500 ℃ for 4 hours to obtain cobalt-manganese metal composite oxide powder. Dispersing the obtained cobalt-manganese-gallium-indium metal composite oxide powder into water, carrying out colloid milling to obtain a coating liquid, wherein the solid content of the coating liquid is 25%, soaking the honeycomb ceramic in the coating liquid for 4 hours, then taking out, blow-drying residual slurry in a pore channel, drying at 110 ℃, roasting at 500 ℃ to obtain the integral non-noble metal catalyst, and coating for multiple times, wherein the coating amount on a honeycomb ceramic framework in unit volume is 180g/L.
Under the condition that PTA simulated oxidation tail gas contains 1500ppm of methyl acetate, 300ppm of paraxylene and 50ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 1.
[ example 14 ]
Cobalt nitrate hexahydrate, manganese nitrate, gallium nitrate and indium nitrate are prepared into aqueous solution according to the molar ratio shown in the table 1, sodium carbonate solution is added into the aqueous solution under the condition of stirring at 40 ℃ until certain pH value is 9.5, and then the aqueous solution is filtered, dried at 110 ℃ and roasted at 500 ℃ for 4 hours to obtain cobalt-manganese metal composite oxide powder. Dispersing the obtained cobalt-manganese-gallium-indium metal composite oxide powder into water, carrying out colloid milling to obtain a coating liquid, wherein the solid content of the coating liquid is 25%, soaking the honeycomb ceramic in the coating liquid for 4 hours, then taking out, blow-drying residual slurry in a pore channel, drying at 110 ℃, roasting at 500 ℃ to obtain the integral non-noble metal catalyst, and coating for multiple times, wherein the coating amount on a honeycomb ceramic framework in unit volume is 200g/L.
Under the condition that the PTA simulated oxidation tail gas contains 1500ppm of methyl acetate, 300ppm of p-xylene and 50ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 1.
[ example 15 ]
Cobalt nitrate hexahydrate, manganese nitrate, gallium nitrate and indium nitrate are prepared into aqueous solution according to the molar ratio shown in the table 1, sodium carbonate solution is added into the aqueous solution under the condition of stirring at 40 ℃ until the pH value is 8.5, and then the aqueous solution is filtered, dried at 110 ℃ and roasted at 500 ℃ for 4 hours to obtain cobalt-manganese metal composite oxide powder. Dispersing the obtained cobalt-manganese-gallium-indium metal composite oxide powder into water, carrying out colloid milling to obtain a coating solution, wherein the solid content of the coating solution is 30%, soaking the honeycomb ceramic in the coating solution for 4 hours, then taking out, drying residual slurry in a pore channel, drying at 110 ℃, roasting at 500 ℃ to obtain the integral non-noble metal catalyst, and the coating amount on the honeycomb ceramic framework in unit volume is 110g/L.
Under the condition that the PTA simulated oxidation tail gas contains 1500ppm of methyl acetate, 300ppm of p-xylene and 50ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 1.
[ example 16 ]
Cobalt nitrate hexahydrate, manganese nitrate, gallium nitrate and indium nitrate are prepared into aqueous solution according to the molar ratio shown in the table 1, sodium carbonate solution is added into the aqueous solution under the condition of stirring at 40 ℃ until certain pH is 9.0, and then the aqueous solution is filtered, dried at 110 ℃ and roasted at 500 ℃ for 4 hours to obtain cobalt-manganese metal composite oxide powder. Dispersing the obtained cobalt-manganese-gallium-indium metal composite oxide powder into water, carrying out colloid milling to obtain a coating liquid, wherein the solid content of the coating liquid is 30%, soaking the honeycomb ceramic in the coating liquid for 4 hours, taking out the honeycomb ceramic, blow-drying the honeycomb ceramic, drying the honeycomb ceramic at 110 ℃, and roasting the honeycomb ceramic at 500 ℃ to obtain the integral non-noble metal catalyst, wherein the coating amount on the honeycomb ceramic framework in unit volume is 110g/L.
Under the condition that PTA simulated oxidation tail gas contains 1500ppm of methyl acetate, 300ppm of paraxylene and 50ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 1.
[ example 17 ] to provide
Cobalt nitrate hexahydrate, manganese nitrate, gallium nitrate and indium nitrate are prepared into aqueous solution according to the molar ratio shown in the table 1, sodium carbonate solution is added into the aqueous solution under the condition of stirring at 40 ℃ until certain pH value is 10.0, and then the aqueous solution is filtered, dried at 110 ℃ and roasted at 500 ℃ for 4 hours to obtain cobalt-manganese metal composite oxide powder. Dispersing the obtained cobalt-manganese-gallium-indium metal composite oxide powder into water, carrying out colloid milling to obtain a coating liquid, wherein the solid content of the coating liquid is 30%, soaking the honeycomb ceramic in the coating liquid for 4 hours, taking out the honeycomb ceramic, blow-drying the honeycomb ceramic, drying the honeycomb ceramic at 110 ℃, and roasting the honeycomb ceramic at 500 ℃ to obtain the integral non-noble metal catalyst, wherein the coating amount on the honeycomb ceramic framework in unit volume is 110g/L.
Under the condition that PTA simulated oxidation tail gas contains 1500ppm of methyl acetate, 300ppm of paraxylene and 50ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 1.
[ example 18 ] A method for producing a polycarbonate
Cobalt nitrate hexahydrate, manganese nitrate, gallium nitrate and indium nitrate are prepared into aqueous solution according to the molar ratio shown in the table 1, sodium carbonate solution is added into the aqueous solution under the condition of stirring at 40 ℃ until certain pH is 9.0, and then the aqueous solution is filtered, dried at 110 ℃ and roasted at 500 ℃ for 4 hours to obtain cobalt-manganese metal composite oxide powder. Dispersing the obtained cobalt-manganese-gallium-indium metal composite oxide powder into water, carrying out colloid milling to obtain a coating liquid, wherein the solid content of the coating liquid is 30%, soaking the honeycomb ceramic in the coating liquid for 4 hours, taking out the honeycomb ceramic, blow-drying the honeycomb ceramic, drying the honeycomb ceramic at 110 ℃, and roasting the honeycomb ceramic at 500 ℃ to obtain the integral non-noble metal catalyst, wherein the coating amount on the honeycomb ceramic framework in unit volume is 110g/L.
Under the condition that the PTA simulated oxidation tail gas contains 3000ppm of methyl acetate, 600ppm of p-xylene and 100ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 1.
[ example 19 ]
Cobalt nitrate hexahydrate, manganese nitrate, gallium nitrate and indium nitrate are prepared into aqueous solution according to the molar ratio shown in the table 1, sodium carbonate solution is added into the aqueous solution under the condition of stirring at 40 ℃ until certain pH value is 9.0, and then the aqueous solution is filtered, dried at 110 ℃ and roasted at 500 ℃ for 4 hours to obtain cobalt-manganese metal composite oxide powder. Dispersing the obtained cobalt-manganese-gallium-indium metal composite oxide powder into water, carrying out colloid milling to obtain a coating liquid, wherein the solid content of the coating liquid is 30%, soaking the honeycomb ceramic in the coating liquid for 4 hours, taking out the honeycomb ceramic, blow-drying the honeycomb ceramic, drying the honeycomb ceramic at 110 ℃, and roasting the honeycomb ceramic at 500 ℃ to obtain the integral non-noble metal catalyst, wherein the coating amount on the honeycomb ceramic framework in unit volume is 110g/L.
Under the condition that the PTA simulated oxidation tail gas contains 7500ppm of methyl acetate, 1500ppm of paraxylene and 250ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 1.
Comparative example 1
Palladium chloride (PdCl) 2 ) And chloroplatinic acid (H) 2 PtCl 6 ) Preparing a solution of a certain concentration as an impregnation solution, loading palladium and platinum on the honeycomb ceramic by an impregnation method, drying at 110 ℃, calcining at 500 ℃, and then introducing hydrogen at 450 ℃ for 3 hours to obtain a catalyst, the catalyst active component loading being 0.25% pd (mass%) and 0.5% pt (mass%).
Under the condition that the PTA simulated oxidation tail gas contains 1500ppm of methyl acetate, 300ppm of paraxylene and 50ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 2.
Comparative example 2
Preparing cobalt nitrate hexahydrate into an aqueous solution, adding a sodium carbonate solution into the aqueous solution under the condition of stirring at 40 ℃ until the pH value is 9.0, filtering, drying at 110 ℃, and roasting at 500 ℃ for 4 hours to obtain cobalt oxide powder. Dispersing the obtained cobalt oxide powder into water to prepare a coating liquid, wherein the solid content of the coating liquid is 30%, soaking the honeycomb ceramic in the coating liquid for 4 hours, taking out the honeycomb ceramic, blow-drying the residual slurry in a pore channel, drying at 110 ℃, and roasting at 500 ℃ to prepare the integral non-noble metal catalyst, wherein the coating amount on the honeycomb ceramic framework in unit volume is 110g/L.
Under the condition that the PTA simulated oxidation tail gas contains 1500ppm of methyl acetate, 300ppm of p-xylene and 50ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 2.
Comparative example 3
Manganese nitrate is prepared into aqueous solution, sodium carbonate solution is added into the aqueous solution under the condition of stirring at 40 ℃ until certain pH value is 9.0, then the aqueous solution is filtered, dried at 110 ℃ and roasted at 500 ℃ for 4 hours to obtain manganese oxide powder. Dispersing the obtained manganese oxide powder into water to obtain a coating solution, wherein the solid content of the coating solution is 30%, dipping the honeycomb ceramic in the coating solution for 4 hours, taking out the honeycomb ceramic, drying slurry remained in pore channels by blowing, drying at 110 ℃, and roasting at 500 ℃ to obtain the integral non-noble metal catalyst, wherein the coating amount on the honeycomb ceramic framework in unit volume is 110g/L.
Under the condition that the PTA simulated oxidation tail gas contains 1500ppm of methyl acetate, 300ppm of paraxylene and 50ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 2.
Comparative example 4
Preparing gallium nitrate into water solution, adding sodium carbonate solution to the water solution under the condition of stirring at 40 ℃ until the pH value is 9.0, then filtering, drying at 110 ℃, and roasting at 500 ℃ for 4 hours to obtain gallium oxide powder. Dispersing the obtained gallium oxide powder into water to prepare a coating liquid, wherein the solid content of the coating liquid is 30%, soaking the honeycomb ceramic in the coating liquid for 4 hours, taking out the honeycomb ceramic, blow-drying the residual slurry in a pore channel, drying at 110 ℃, and roasting at 500 ℃ to prepare the integral non-noble metal catalyst, wherein the coating amount on the honeycomb ceramic framework in unit volume is 110g/L.
Under the condition that the PTA simulated oxidation tail gas contains 1500ppm of methyl acetate, 300ppm of paraxylene and 50ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 2.
[ COMPARATIVE EXAMPLE 5 ]
Preparing indium nitrate into an aqueous solution, adding a sodium carbonate solution into the aqueous solution under the condition of stirring at 40 ℃ until the pH value is 9.0, filtering, drying at 110 ℃, and roasting at 500 ℃ for 4 hours to obtain manganese oxide powder. And dispersing the obtained indium oxide powder into water to prepare a coating solution, wherein the solid content of the coating solution is 30%, soaking the honeycomb ceramic in the coating solution for 4 hours, taking out the honeycomb ceramic, blow-drying residual slurry in a pore channel, drying at 110 ℃ and roasting at 500 ℃ to prepare the integral non-noble metal catalyst, and the coating amount on the honeycomb ceramic framework in unit volume is 110g/L.
Under the condition that the PTA simulated oxidation tail gas contains 1500ppm of methyl acetate, 300ppm of paraxylene and 50ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 2.
Comparative example 6
Copper nitrate, manganese nitrate and cerium nitrate are prepared into an aqueous solution according to the molar ratio of Cu/Mn/Ce =1/4/2, a sodium carbonate solution is added into the aqueous solution under the condition of stirring at 40 ℃ until the pH value reaches 9.0, and then the aqueous solution is filtered, dried at 110 ℃ and roasted at 500 ℃ for 4 hours to obtain metal composite oxide powder. Dispersing the obtained metal composite oxide powder into water to prepare a coating solution, wherein the solid content of the coating solution is 30%, soaking the honeycomb ceramic in the coating solution for 4 hours, taking out the honeycomb ceramic, drying slurry remained in pore channels by blowing, drying at 110 ℃, and roasting at 500 ℃ to prepare the integral non-noble metal catalyst, wherein the coating amount on the honeycomb ceramic framework in unit volume is 110g/L.
Under the condition that PTA simulated oxidation tail gas contains 1500ppm of methyl acetate, 300ppm of paraxylene and 50ppm of dibromomethane at the space velocity of 20000h < -1 >, catalytic combustion reaction is carried out under the catalysis of the catalyst, and the reaction results are shown in Table 1.
TABLE 1
Figure BDA0001830091960000121
The substrate concentrations in examples 1 to 17 were: methyl acetate (1500 ppm), p-xylene (300 ppm), dibromomethane (50 ppm);
the substrate concentrations in example 18 were: methyl acetate (3000 ppm), p-xylene (600 ppm), dibromomethane (100 ppm);
the substrate concentrations in example 19 were: methyl acetate (7500 ppm), p-xylene (1500 ppm), dibromomethane (250 ppm)
TABLE 2
Comparative example Active component of catalyst T1(℃) T2(℃) T3(℃) CO2 Selectivity
1 0.25％pd+0.5％pt 320 375 395 99％
2 Co 305 330 355 99％
3 Mn 340 370 400 99％
4 Ga 342 373 403 99％
5 In 345 376 405 99％
6 Cu,Mn,Ce 310 335 360 99％
In Table 2, the substrate concentrations were methyl acetate (1500 ppm), p-xylene (300 ppm) and dibromomethane (50 ppm).
In table 1 and table 2, T1 is the lowest inlet temperature at which the conversion of methyl acetate is 99% or more, T2 is the lowest inlet temperature at which the conversion of p-xylene is 99% or more, and T3 is the lowest inlet temperature at which the conversion of dibromomethane is 99% or more.

Claims (10)

1. A non-noble metal catalyst for catalytic combustion of PTA oxidized tail gas is characterized in that a carrier is honeycomb ceramic and loads cobalt, manganese, gallium and indium metal composite oxides;
the molar ratio of cobalt to manganese in the cobalt, manganese, gallium and indium metal composite oxide is 1 (0.1-10), the molar ratio of cobalt to gallium is 1 (0.1-1), and the molar ratio of cobalt to indium is 1 (0.1-1).
2. The catalyst of claim 1, which is used for catalytic combustion of non-noble metal in PTA oxidation tail gas, and is characterized in that the molar ratio of the cobalt to the gallium is 1 (0.1-0.5), and the molar ratio of the cobalt to the indium is 1 (0.1-0.5).
3. The catalyst for catalytic combustion of non-noble metal for PTA oxidation tail gas according to claim 1, wherein the coating amount of the cobalt, manganese, gallium and indium metal composite oxide on the honeycomb ceramic skeleton of the catalyst is 50-200 g/L.
4. The non-noble metal catalyst for catalytic combustion of PTA oxidized tail gas as claimed in claim 3, wherein the coating amount of the cobalt, manganese, gallium and indium metal composite oxide on the honeycomb ceramic skeleton of the catalyst is 100-170 g/L.
5. The method for preparing the non-noble metal catalyst for catalytic combustion of PTA oxidized tail gas in any one of claims 1-4 comprises the following steps: uniformly dispersing cobalt, manganese, gallium and indium metal composite oxide particles in a water phase, carrying out colloid milling to prepare coating liquid, and then coating the coating liquid on honeycomb ceramics to prepare an integral catalyst; the cobalt, manganese, gallium and indium metal composite oxide particles are prepared by preparing metal cobalt salt, metal manganese salt, metal gallium salt and metal indium salt into an aqueous solution according to a certain proportion, adding sodium carbonate, sodium bicarbonate, sodium hydroxide and an ammonia alkaline precipitator into the aqueous solution to a certain pH value, and then obtaining cobalt, manganese, gallium and indium metal composite oxide powder.
6. The method as claimed in claim 5, wherein the cobalt salt and manganese salt used for preparing the cobalt, manganese, gallium and indium composite oxide powder are selected from nitrate, acetate and halide.
7. The method of claim 5, wherein the stirring temperature for preparing the cobalt, manganese, gallium and indium composite oxide powder is between 10-90 ℃; when preparing the cobalt, manganese, gallium and indium metal composite oxide powder, adding a precipitator until the pH value is within a range of 9-11.
8. The method of claim 5, wherein when the particles of the cobalt, manganese, gallium, and indium composite oxides are uniformly dispersed in the aqueous phase and colloid-milled to form the coating solution, the weight percentage of the cobalt, manganese, gallium, and indium composite oxides in the coating solution is 10-35%.
9. The method of claim 5, wherein the coating solution of the composite oxides of Co, mn, ga and in is applied to the honeycomb ceramic at a drying temperature of 100-125 ℃ for 1-25 hours, at a calcination temperature of 300-600 ℃ for 3-10 hours.
10. A catalytic combustion method for PTA oxidation tail gas is characterized in that the PTA oxidation tail gas is contacted with the catalyst in any one of claims 1 to 4 or the catalyst obtained by the preparation method in any one of claims 5 to 9, and a mixture of nitrogen and oxygen or air is introduced at the temperature of 200-450 ℃, so that methyl acetate, xylene and dibromomethane in the PTA oxidation tail gas are catalytically combusted to generate carbon dioxide, water, hydrogen bromide and bromine.
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