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CN110743569A - Process furnace flue gas CO deep purification method, catalyst composition, preparation method and application - Google Patents

Process furnace flue gas CO deep purification method, catalyst composition, preparation method and application Download PDF

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Publication number
CN110743569A
CN110743569A CN201911092211.1A CN201911092211A CN110743569A CN 110743569 A CN110743569 A CN 110743569A CN 201911092211 A CN201911092211 A CN 201911092211A CN 110743569 A CN110743569 A CN 110743569A
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China
Prior art keywords
catalyst composition
mixture
hours
baking
flue gas
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CN201911092211.1A
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Chinese (zh)
Inventor
齐文义
郝代军
李小苗
陈千惠
左世伟
黄延召
孟学峰
邓向军
邹颖
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China Petroleum and Chemical Corp
China Petrochemical Corp
Sinopec Engineering Group Co Ltd
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China Petrochemical Corp
Sinopec Engineering Group Co Ltd
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Priority to CN201911092211.1A priority Critical patent/CN110743569A/en
Publication of CN110743569A publication Critical patent/CN110743569A/en
Pending legal-status Critical Current

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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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/864—Removing carbon monoxide or hydrocarbons
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2065—Cerium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20707—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D2255/20715—Zirconium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/00—Catalysts
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    • B01D2255/2073—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/00—Catalysts
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    • B01D2255/20746—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D2255/20—Metals or compounds thereof
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    • B01D2255/20761—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/20776—Tungsten
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
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    • B01D2258/0283—Flue gases
    • 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
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    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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Abstract

The invention discloses a process furnace flue gas CO deep purification method, a catalyst composition, a preparation method and application. The catalyst composition comprises the following components in percentage by weight of the composition: 4 to 25 weight percent of a compound of the general formula LaMn1－xCoxO3X is 0.1 to 0.8; 2 to 10 wt% of WO3(ii) a 1-7 wt% of CuO; 2-15 wt% of cerium-zirconium mixed oxide; 55-85 wt% of TiO2(ii) a 50 mu g/g-1000 mu g/g of noble metal. The catalyst composition provided by the invention is placed near the burnout zone of the heating furnace or at the rear part of the flue, so that CO in the process furnace flue gas can be deeply removed and converted into carbon dioxide, and the catalyst composition has higher CO removal efficiency.

Description

Process furnace flue gas CO deep purification method, catalyst composition, preparation method and application
Technical Field
The invention relates to the technical field of flue gas purification, in particular to a process furnace flue gas CO deep purification method, a catalyst composition, a preparation method and application.
Background
In the industrial production process, a high-temperature smelting facility, such as an anode furnace of a process furnace, is involved, the furnace generates high-temperature and dust-containing harmful flue gas, and the like, and the process furnace, such as the process furnace in an oil refinery, is a main single-point emission source of NOx and has important contribution to the total NOx emission of the refinery, so that the NOx control faces a great challenge. With the implementation of new "oil refining industry pollutant emission standards", NOx emissions from most enterprises are under greater pressure. In recent years, in order to reduce the emission of NOx in the flue gas of a heating furnace in an oil refinery process, the technology of a low NOx burner is widely applied, and the content of CO in the flue gas is generally increased while the content of NOx in the flue gas is reduced, wherein the content of CO in the flue gas is even as high as 1000mg/m3The above. Although there is no clear limit to CO emission, CO is an atmospheric pollutant with a wider influence range, is colorless, odorless, inflammable and explosive, can enter human blood through a respiratory system and then is combined with hemoglobin, so that the combination of the hemoglobin and oxygen is prevented, oxygen deficiency of body tissues is caused, and severe people can suffocate and die. Meanwhile, due to the excessively high CO content and the relatively low combustion temperature, the combustion nozzle of the heating furnace has the possibility of flameout, and the safety operation risk of the heating furnace is aggravated. The CO content of the process furnace can be reduced by increasing O2The content or the combustion temperature of a hearth is solved, but no matter the oxygen content or the combustion temperature of the hearth is increased, the content of NOx in the flue gas can be causedRising, losing the meaning of low NOx combustion.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a process furnace flue gas CO deep purification method, a catalyst composition, a preparation method and application.
The invention is realized by the following steps:
in a first aspect, the embodiments of the present invention provide a catalyst composition for deep purification of CO in flue gas of a process furnace, the catalyst composition contains the following components by weight of the composition: 4 to 25 weight percent of a compound of the general formula LaMn1－xCoxO3X is 0.1 to 0.8; 2 to 10 wt% of WO3(ii) a 1-7 wt% of CuO; 2-15 wt% of cerium-zirconium mixed oxide; 55-85 wt% of TiO2(ii) a 50 mu g/g-1000 mu g/g of noble metal.
The embodiment of the invention provides a catalyst composition for deeply purifying CO in process furnace flue gas, wherein the catalyst composition is LaMn combined according to a certain proportion1－xCoxO3Perovskite component of, WO3Anatase type TiO2Cerium-zirconium mixed oxide and noble metal, LaMn1－xCoxO3Perovskite component of, WO3CuO, a mixed oxide of cerium and zirconium and an active component of noble metal having good catalytic oxidation capability for CO, wherein the active component is loaded on TiO2The active component particles can be mutually blocked and separated to prevent the active component particles from moving and forming clusters, so that the action area of the active component in the catalytic oxidation process is increased, and the catalytic oxidation capacity of CO is effectively improved. The obtained catalyst composition has the capability of deeply purifying CO in flue gas, and the existing method for improving O is relieved2The content or the combustion temperature of a hearth is solved to reduce the content of CO, but the increase of the oxygen content or the combustion temperature of the hearth can cause the increase of the content of NOx in flue gas, namely, the catalyst composition with the increased content in the embodiment of the invention can remove CO deeply and simultaneously remove COAnd the NOx content is effectively reduced.
In an alternative embodiment, the catalyst composition comprises, by weight, the following ingredients, based on the weight of the composition:
5 wt% to 15 wt% of a compound of the formula LaMn1－xCoxO30.1 to 0.8, 3wt to 6 wt% of WO32 to 6 weight percent of CuO, 5 to 10 weight percent of cerium-zirconium mixed oxide and 60 to 80 weight percent of TiO2And 200-1000 mug/g of noble metal.
In an alternative embodiment, the TiO is2Is anatase type TiO2；
Preferably, the noble metal includes at least one of Pt, Pd, Au, and Ru;
preferably, the cerium-zirconium molar ratio in the cerium-zirconium mixed oxide is 0.5 to 2.0: 0.5-1.0.
the embodiment of the invention provides a catalyst composition, TiO, for deeply purifying CO in process furnace flue gas2Preferably anatase TiO2Anatase type TiO2The catalyst has high specific surface area and large pore volume, can load more active components, increases the interaction between the active components and a carrier, has good catalytic oxidation capacity on CO by noble metals including Pt, Pd, Au and Ru, and can reduce the energy barrier of CO so as to oxidize CO into CO2The cerium-zirconium molar ratio is 0.5-2.0: the zirconium mixed oxide of 0.5-1.0 can exert the catalytic oxidation capability of the zirconium mixed oxide to the maximum extent, and CuO is helpful for the reaction of CO and NOx and reduces the content of NOx.
In a second aspect, the embodiment of the present invention further provides a preparation method of the above catalyst composition, including the following steps: the method comprises the following steps: and mixing and roasting corresponding raw materials according to the component proportion of the catalyst composition to obtain the catalyst composition.
In an alternative embodiment, the preparation of the catalyst composition comprises the steps of: according to the formula, the perovskite component and anatase TiO are taken2And a forming agent, mixing to obtain a first mixture; mixing the first mixture with a solution of tungstate and a solution of cupric saltMixing, baking and roasting to obtain a second mixture; and mixing the second mixture with noble metal, and baking and roasting to obtain the catalyst composition.
The embodiment of the invention also provides a preparation method of the catalyst composition, in the preparation process of the catalyst composition, the forming agent is used as a carrier to compound all the components in the catalyst composition, and according to the formula, the perovskite component and anatase TiO are taken2And a forming agent, mixing to obtain a first mixture; mixing the first mixture with a tungstate and copper salt solution, and baking and roasting to obtain a second mixture; on the premise of not introducing other solvents, the rest components are mixed by utilizing the components contained in the composition, then the second mixture is mixed with the noble metal, the mixture is roasted and roasted, the second mixture is mixed with the noble metal and roasted, and the second mixture is used as a dispersing agent, so that the noble metal can be uniformly dispersed to obtain the catalyst composition.
In an alternative embodiment, the preparation of the second mixture comprises the steps of: perovskite component, anatase type TiO according to the formula2The cerium-zirconium mixed oxide and the forming agent are ground and mixed into uniform mixed powder, and the tungstate aqueous solution, the copper salt solution and the mixed powder are mixed into blocks again under the stirring state, repeatedly extruded, baked and roasted;
preferably, the forming agent comprises at least one of polyoxyethylene, carboxymethyl cellulose and corn starch, and the amount of the forming agent is 0.5 wt% to 5 wt%, and more preferably, the amount of the forming agent is 1 wt% to 4 wt%;
more preferably, the repeated pressing comprises the steps of: repeatedly squeezing the mixed blocks into fine blocks, keeping moisture, standing for 16-24 hr, squeezing into strips, and drying in the shade for 36-48 hr;
more preferably, the baking and roasting comprises the following steps: the dried in the shade strip was baked at 140 ℃ for 6-12 hours at 120 ℃ and then baked at 750 ℃ for 6-12 hours at 650 ℃.
The embodiment of the invention also provides a preparation method of the catalyst composition, in the preparation process of the catalyst composition, the forming agent is used as a carrier to compound all the components in the catalyst composition, and the preparation method specifically comprises the following steps:
firstly, weighing a proper amount of a compound with the general formula of LaMn1－xCoxO3Perovskite component, anatase type TiO2Cerium-zirconium mixed oxide, forming agent (forming agent such as one or mixture of polyoxyethylene, carboxymethyl cellulose and corn starch) in container; mechanically mixing the components uniformly, and grinding for 2-3 hours to obtain uniform powder; weighing a proper amount of tungstate, putting the tungstate into a beaker, and adding a proper amount of distilled water to completely dissolve the tungstate; weighing a proper amount of copper salt, putting the copper salt into a beaker, and adding a proper amount of distilled water to completely dissolve salts; sequentially adding tungstate solution and copper salt under stirring, slowly adding appropriate amount of LaMn1－xCoxO3Perovskite component, anatase type TiO2Mixing the cerium-zirconium mixed oxide and a forming agent to form a block, repeatedly extruding the block into fine blocks in an extruder, moisturizing and standing for 16-24 hours, extruding the fine blocks into strips, and drying the strips in the shade for 36-48 hours;
in the step, tungstate solution and copper salt solution are slowly added into the LaMn1－xCoxO3Perovskite component, anatase type TiO2Cerium zirconium mixed oxide and forming agent powder, and the addition sequence can ensure that all the components in the mixed solution are fully impregnated into TiO2The inner and outer surfaces of the carrier micropores improve the removal activity of the product, and the long-time standing can enable salt ions to more fully impregnate the inner and outer surfaces of the carrier micropores, thereby improving the removal activity of the product. The mixture is dried in the shade before roasting so as to reduce the moisture content, so that the high-temperature roasting is prevented from generating thermal collapse under the condition that the moisture content of the salt solution is too high, and the product yield is reduced. Tungsten trioxide and copper oxide are respectively introduced into the catalyst in the form of raw materials of tungstate and copper salt, so that tungstate and copper salt elements are favorably distributed on the inner surface and the outer surface of the micropore, and the activity of the catalytic assistant is higher. Finally, converting tungstate and copper salt into tungsten oxide by roastingAnd copper oxide.
Then baking the strips obtained by drying in the shade for 6-12 hours at the temperature of 120-140 ℃ in an oven, and then baking the strips for 6-12 hours at the temperature of 650-750 ℃ in a muffle furnace; the primary roasting can make tungstate and copper salt decompose quickly to generate corresponding oxides, and can also ensure that other four components do not deteriorate.
In an alternative embodiment, the preparation of the catalyst composition comprises the steps of: the solution of the noble metal is dipped into the second mixture by adopting an equal volume method, then the second mixture is placed in an oven for baking for 4 to 8 hours at the temperature of 120 ℃ and 140 ℃, and then the second mixture is baked for 4 to 8 hours in a muffle furnace at the temperature of 600 ℃ and 650 ℃.
Soaking and mixing by an equal-volume soaking method, then roasting, and carrying out LaMn treatment in the early stage1－xCoxO3Perovskite component, anatase type TiO2、WO3And cerium zirconium mixed oxide to TiO2On the basis, the noble metal particles are arranged on the surface of the catalyst, and the noble metal can reduce the energy barrier of CO, so that the catalytic effect of the catalyst composition is effectively enhanced, and the prepared catalyst composition preferably comprises but is not limited to honeycomb shapes, plate shapes, corrugated shapes and the like.
In a third aspect, the embodiment of the present invention also provides a method for deeply purifying CO in flue gas of a process furnace by using the above catalyst composition, the method comprising the following steps: catalytic oxidation of CO in process furnace flue gas to CO using catalyst composition2。
The embodiment of the invention also provides a method for deeply purifying CO in the flue gas of the process furnace by using the catalyst composition, which comprises the following steps: catalytic oxidation of CO in process furnace flue gas to CO using catalyst composition2. The catalyst composition provided by the embodiment of the invention has good catalytic effect on catalytic oxidation of CO, so that CO in flue gas is catalytically oxidized into CO2。
In an alternative embodiment, during the catalytic oxidation: firstly, placing the catalyst composition near an ember zone of a heating furnace or at the rear part of a flue, or placing the catalyst composition in an externally-connected reactor, and then carrying out catalytic oxidation reaction;
preferably, the space velocity of the catalytic oxidation is 500-－1Preferably 1000-15000 h－1。
In an alternative embodiment, the temperature of CO in the flue gas of the catalytic oxidation process furnace by the catalyst composition is 120-900 ℃, preferably 150-850 ℃;
preferably, the catalyst composition is placed near the burnout zone of the heating furnace, and the temperature of the burnout zone of the heating furnace is controlled to be 600-900 ℃, preferably 650-850 ℃;
preferably, the catalyst composition is placed at the rear part of the flue of the heating furnace, and the temperature at the rear part of the flue of the heating furnace is controlled to be 120-600 ℃, preferably 150-550 ℃.
In a fourth aspect, the embodiment of the invention also provides an application of the method for deeply purifying the CO in the process furnace flue gas by using the catalyst composition in deeply purifying the CO in the process furnace flue gas.
The invention has the following beneficial effects:
the invention provides a process furnace flue gas CO deep purification method, a catalyst composition, a preparation method and application. The catalyst composition comprises a catalyst of the general formula Lamn1－xCoxO3Perovskite component of (A), TiO2、WO3CuO, a mixed oxide of cerium and zirconium, and a noble metal, the catalyst composition being formed of TiO2As a carrier, loading the general formula of LaMn on the carrier1－xCoxO3Perovskite component of, WO3The catalyst composition comprises CuO, a mixed oxide of cerium and zirconium and active components of noble metals, wherein due to mutual separation among active component particles, agglomeration among the active component particles is reduced, the energy barrier of carbon monoxide is reduced due to the use of the noble metals, the capability of different active components for catalyzing and oxidizing the carbon monoxide is synergistic, the carbon monoxide is oxidized into carbon dioxide in the presence of oxygen, the CO in the process furnace flue gas can be deeply purified by utilizing the catalyst composition, and the content of NOx in the flue gas is effectively reduced while the CO in the flue gas is deeply purified.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
Respectively weighing LaMn as a general formula0.4Co0.6O310.0g (100 parts on a dry basis), 16.8g of cerium-zirconium mixed oxide (cerium-zirconium molar ratio 1: 1, 95 parts on a dry basis), and anatase TiO2171.7g (dry basis 95 parts) and 6.0g (dry basis 100 parts) of carboxymethyl cellulose are put into a container 1 with the volume of 1000ml, mechanically and uniformly stirred and ground for 3 hours; 9.8g of a compound of the formula (NH)4)6W7O24·6H2O(WO382 parts of dry base), putting the mixture into a beaker 1 with the volume of 500ml, adding 105g of distilled water, and stirring the mixture to completely dissolve the mixture; weighing 5.8g of Cu (NO) with a chemical general formula3)2·2.5H2O (34 parts of CuO dry basis) is put into a beaker 2 with the volume of 500ml, 35g of distilled water is added, and the mixture is stirred to be completely dissolved; then under the condition of stirring, slowly adding the solutions in the beakers 1 and 2 into the container 1 in sequence, stirring for 30 minutes after adding, repeatedly extruding the mixture into fine blocks in an extruder, preserving moisture and standing for 18 hours; extruding into strips, and drying in the shade for 48 hours; baking the mixture in an oven for 7 hours at 120 ℃, and then baking the mixture for 8 hours in a muffle furnace at 680 ℃; soaking the strip with noble metal such as Pt solution to obtain Pt content of 200 μ g/g; baking the mixture in an oven at 120 ℃ for 4 hours, and baking the mixture in a muffle furnace at 620 ℃ for 6 hours to obtain the target catalyst composition 1.
Example 2
Respectively weighing LaMn as a general formula0.4Co0.6O316.0g of perovskite (dry basis is 100 portions), 16.8g of cerium-zirconium mixed oxide (cerium-zirconium molar ratio is 0.5: 0.8, dry basis is95 parts) of anatase type TiO2157.6g (dry basis 95 parts), corn starch and carboxymethyl cellulose each 3.0g (dry basis 100 parts) were put in a container 1 having a volume of 1000ml, mechanically stirred uniformly, and ground for 3 hours; weighing 12.2g of (NH)4)6W7O24·6H2O(WO382 parts of dry base), putting the mixture into a beaker 1 with the volume of 500ml, adding 105g of distilled water, and stirring the mixture to completely dissolve the mixture; weighing 11.8g of Cu (NO) with a chemical general formula3)2·2.5H2O (34 parts of CuO dry basis) is put into a beaker 2 with the volume of 500ml, and 45g of distilled water is added and stirred to be completely dissolved; then under the condition of stirring, slowly adding the solutions in the beakers 1 and 2 into the container 1 in sequence, stirring for 30 minutes after adding, repeatedly extruding the mixture into a fine block in an extruder, preserving moisture and standing for 24 hours; extruding into strips, and drying in the shade for 42 hours; baking for 6 hours in an oven at 130 ℃, and then baking for 7 hours in a muffle furnace at 700 ℃; impregnating the obtained strip with a noble metal such as Pd solution by an isometric method to make the Pd content of the strip 500 mug/g; baking the mixture in an oven at 130 ℃ for 5 hours and baking the mixture in a muffle furnace at 630 ℃ for 7 hours to obtain the target catalyst composition 2.
Example 3
Respectively weighing LaMn as a general formula0.4Co0.6O330.0g (100 parts on a dry basis), 21.1g of cerium-zirconium mixed oxide (cerium-zirconium molar ratio 1.5: 0.6, 95 parts on a dry basis), and anatase-type TiO2137.6g (95 parts on a dry basis) and 6.0g (100 parts on a dry basis) of carboxymethyl cellulose are put into a container 1 with the volume of 1000ml, mechanically and uniformly stirred and ground for 3 hours; 14.6g of a compound of the formula (NH)4)6W7O24·6H2O(WO382 parts of dry base), putting the mixture into a beaker 1 with the volume of 500ml, adding 105g of distilled water, and stirring the mixture to completely dissolve the mixture; weighing 10.8g of CuCl2·2H2O (46 parts of CuO dry basis) is put into a beaker 2 with the volume of 500ml, 45g of distilled water is added, and the mixture is stirred to be completely dissolved; then under the condition of stirring, the solutions in the beakers 1 and 2 are added into the container 1 slowly in sequence, stirred for 30 minutes after the addition is finished, and then the mixture is placed into an extruder to be repeatedly extruded into fine block shapesKeeping moisture and standing for 24 hours; extruding into strips, and drying in the shade for 40 hours; baking for 6 hours at 120 ℃ in an oven, and then baking for 8 hours at 690 ℃ in a muffle furnace; soaking the obtained strip-shaped object with noble metal such as Ru solution by an isometric method to make the Ru content be 1000 mug/g; baking the mixture in an oven at 140 ℃ for 4 hours and in a muffle furnace at 650 ℃ for 6 hours to obtain the target catalyst composition 3 of the invention.
Example 4
Respectively weighing LaMn as a general formula0.4Co0.6O320.0g (100 parts on a dry basis), 12.6g of cerium-zirconium mixed oxide (cerium-zirconium molar ratio 2: 0.8, 95 parts on a dry basis), and anatase TiO2149.3g (dry basis 95 parts), polyoxyethylene and carboxymethyl cellulose each 3.0g (dry basis 100 parts) are put into a container 1 with the volume of 1000ml, mechanically stirred evenly and ground for 3 hours; weighing 12.2g of (NH)4)6W7O24·6H2O(WO382 parts of dry base), putting the mixture into a beaker 1 with the volume of 500ml, adding 110g of distilled water, and stirring the mixture to completely dissolve the mixture; 14.1g of CuCl of the formula2·2H2O (46 parts of CuO dry basis) is put into a beaker 2 with the volume of 500ml, 45g of distilled water is added, and the mixture is stirred to be completely dissolved; then under the condition of stirring, slowly adding the solutions in the beakers 1 and 2 into the container 1 in sequence, stirring for 30 minutes after adding, repeatedly extruding the mixture into a fine block in an extruder, preserving moisture and standing for 24 hours; extruding into strips, and drying in the shade for 48 hours; baking for 6 hours in an oven at 120 ℃, and then baking for 6 hours in a muffle furnace at 750 ℃; impregnating the obtained strip with a noble metal such as Au solution by an isometric method to make the Au content of the strip 800 mug/g; baking the mixture in an oven at 120 ℃ for 6 hours and in a muffle furnace at 650 ℃ for 5 hours to obtain the target catalyst composition 4 of the invention.
Example 5
Respectively weighing LaMn as a general formula0.3Co0.7O324.0g (100 parts on a dry basis), 10.5g of cerium-zirconium mixed oxide (cerium-zirconium molar ratio 1.2: 0.8, 95 parts on a dry basis), and anatase TiO2160.6g (95 parts on a dry basis) and 6.0g (100 parts on a dry basis) of corn starch were placed in a container1, mechanically stirring uniformly in a 1000ml container, and grinding for 3 hours; weighing 7.3g of (NH)4)6W7O24·6H2O(WO382 parts of dry base), putting the mixture into a beaker 1 with the volume of 500ml, adding 105g of distilled water, and stirring the mixture to completely dissolve the mixture; 21.7g of CuCl of the formula2·2H2O (46 parts of CuO dry basis) is put into a beaker 2 with the volume of 500ml, 50g of distilled water is added, and the mixture is stirred to be completely dissolved; then under the condition of stirring, slowly adding the solutions in the beakers 1 and 2 into the container 1 in sequence, stirring for 30 minutes after adding, repeatedly extruding the mixture into a fine block in an extruder, preserving moisture and standing for 24 hours; extruding into strips, and drying in the shade for 48 hours; baking for 6 hours in an oven at 130 ℃, and then baking for 7 hours in a muffle furnace at 720 ℃; soaking the strip with noble metal such as Pt solution in an equal volume method to make Pt content at 400 μ g/g; baking the mixture for 6 hours at 130 ℃ in an oven and baking the mixture for 6 hours at 610 ℃ in a muffle furnace to obtain the target catalyst composition 5 of the invention.
Example 6
Respectively weighing LaMn as a general formula0.3Co0.7O318.0g (100 parts on a dry basis), 14.7g (cerium-zirconium molar ratio 1.5: 0.4, 95 parts on a dry basis) of a cerium-zirconium mixed oxide, and anatase-type TiO2150.3g (95 parts of dry basis) and 4.0g (100 parts of dry basis) of corn starch are put into a container 1 with the volume of 1000ml, mechanically and uniformly stirred and ground for 3 hours; 14.6g of a compound of the formula (NH)4)6W7O24·6H2O(WO382 parts of dry base), putting the mixture into a beaker 1 with the volume of 500ml, adding 105g of distilled water, and stirring the mixture to completely dissolve the mixture; 38.2g of Cu (NO) are weighed out3)2·2.5H2O (34 parts of CuO dry basis) is put into a beaker 2 with the volume of 500ml, and 45g of distilled water is added and stirred to be completely dissolved; then under the condition of stirring, slowly adding the solutions in the beakers 1 and 2 into the container 1 in sequence, stirring for 30 minutes after adding, repeatedly extruding the mixture into a fine block in an extruder, preserving moisture and standing for 24 hours; extruding into strips, and drying in the shade for 48 hours; baking at 140 deg.C for 6 hr in oven, and baking at 730 deg.C in muffle furnaceBurning for 7 hours; impregnating the obtained strip with a noble metal such as Au solution by an equal volume method to make the Au content of the strip 600 mug/g; the mixture is baked in an oven at 130 ℃ for 6 hours and baked in a muffle furnace at 650 ℃ for 5 hours to obtain the target catalyst composition 6 of the invention.
Example 7
Respectively weighing LaMn as a general formula0.4Co0.6O312.0g (100 parts on a dry basis), 18.9g of cerium-zirconium mixed oxide (cerium-zirconium molar ratio 1: 1, 95 parts on a dry basis), and anatase TiO2158.5g (95 parts on a dry basis) and 6.0g (100 parts on a dry basis) of carboxymethyl cellulose are put into a container 1 with the volume of 1000ml, mechanically and uniformly stirred and ground for 3 hours; 9.8g of a compound of the formula (NH)4)6W7O24·6H2O(WO382 parts of dry base), putting the mixture into a beaker 1 with the volume of 500ml, adding 105g of distilled water, and stirring the mixture to completely dissolve the mixture; 26.4g of Cu (NO) of the formula3)2·2.5H2O (34 parts of CuO dry basis) is put into a beaker 2 with the volume of 500ml, and 45g of distilled water is added and stirred to be completely dissolved; then under the condition of stirring, slowly adding the solutions in the beakers 1 and 2 into the container 1 in sequence, stirring for 30 minutes after adding, repeatedly extruding the mixture into a fine block in an extruder, preserving moisture and standing for 24 hours; extruding into strips, and drying in the shade for 48 hours; baking for 6 hours in an oven at 130 ℃, and then baking for 7 hours in a muffle furnace at 700 ℃; impregnating the obtained strip with a noble metal such as Pd solution by an isometric method to make the Pd content of the strip 300 mug/g; baking the mixture for 6 hours at 140 ℃ in an oven and baking the mixture for 6 hours at 650 ℃ in a muffle furnace to obtain the target catalyst composition 7 of the invention.
Example 8
Respectively weighing LaMn as a general formula0.5Co0.5O314.0g (100 parts on a dry basis), 16.8g of cerium-zirconium mixed oxide (cerium-zirconium molar ratio 1: 1, 95 parts on a dry basis), and anatase TiO2164.6g (95 parts on a dry basis) and 6.0g (100 parts on a dry basis) of corn starch are put into a container 1 with the volume of 1000ml, mechanically and uniformly stirred and ground for 3 hours; weighing 7.3g of (NH)4)6W7O24·6H2O(WO382 parts of dry base), putting the mixture into a beaker 1 with the volume of 500ml, adding 105g of distilled water, and stirring the mixture to completely dissolve the mixture; weighing 20.6g of Cu (NO) with a chemical general formula3)2·2.5H2O (34 parts of CuO dry basis) is put into a beaker 2 with the volume of 500ml, and 45g of distilled water is added and stirred to be completely dissolved; then under the condition of stirring, slowly adding the solutions in the beakers 1 and 2 into the container 1 in sequence, stirring for 30 minutes after adding, repeatedly extruding the mixture into a fine block in an extruder, preserving moisture and standing for 24 hours; extruding into strips, and drying in the shade for 48 hours; baking for 7 hours in an oven at 130 ℃, and then baking for 7 hours in a muffle furnace at 720 ℃; soaking the obtained strip with noble metal such as Ru solution by an isometric method to make its Ru content be 700 mug/g; baking the mixture in an oven at 140 ℃ for 5 hours and in a muffle furnace at 620 ℃ for 6 hours to obtain the target catalyst composition 8.
The results of the performance tests on the catalyst compositions of examples 1-8 above are as follows:
the noble metal content of the catalytic oxidation catalyst composition for deeply purifying CO in process furnace flue gas is measured by an X-ray diffraction (XRD) method; with N2The specific surface area and pore volume of the composition were determined by adsorption-desorption method. The noble metal content, specific surface area and pore volume of the CO deep purification catalytic oxidation catalyst compositions of examples 1-8 are shown in table 1.
TABLE 1 analysis results of CO deep purification catalytic oxidation catalyst composition
The following examples 9 to 18 are methods for deep purification of CO from process furnace flue gas using the catalyst compositions of examples 1 to 8, and since examples 9 to 18 are tests conducted in a laboratory, the catalyst compositions were placed in a removal device reactor, a simulated process furnace flue gas having a certain ratio was introduced, and after the reaction, the removal rate of CO in the flue gas was tested, wherein the removal rate of CO in the flue gas was conducted according to the following steps:
a catalytic oxidation catalyst composition for deeply purifying process furnace flue gas CO, in particular to a catalytic oxidation catalyst composition for deeply purifying process furnace flue gas CO in an oil refinery, which has the following performance tests:
on a small CO catalytic oxidation removal device, the flue gas condition of a process furnace is simulated, and the CO removal performance of the CO deep purification catalytic oxidation catalyst is tested. The flue gas is composed of SO2、N2、CO、H2O and O2Mixed gas prepared according to a certain proportion. Wherein SO2Is 1000mg/m3，CO 2000mg/m3，H2O 10(v)％，O23.5 (v)%, and the balance of N2. And analyzing by a CO online flue gas analyzer. Weighing 5.0g of the discharged composition, loading the composition into a reactor, heating the composition to a set value under a nitrogen flow, stopping the nitrogen flow, introducing mixed gas, wherein the gas flow is 2000ml/min, sampling and analyzing the composition once every 30 minutes, reacting for 36 hours, and taking the average value of the CO removal rate in 36 hours as the comparison of the performance of the composition.
The CO removal rate of the composition is defined as:
in the formula: x is the CO removal rate (%) of the composition; c1Is the content of CO in the reacted gas mg/m3；C2The content of CO in the mixed gas before reaction is mg/m3。
Example 9
5.0g of the special catalyst composition prepared in example 1 was weighed into a reactor of a CO catalytic oxidation removal unit, heated to 680 ℃ under a nitrogen flow, then the nitrogen was stopped, and SO was introduced2、N2、CO、H2O and O2Mixed gas prepared according to a certain proportion. Wherein SO2Is 1000mg/m3，CO2000mg/m3，H2O 10(v)％，O23.5 (v)%, and the balance of N2. The gas flow is 2000ml/min, sampling and analyzing are carried out every 30 minutes, the reaction is carried out for 36 hours, and the CO removal rate is 100 percent.
Example 10
Weighing 5.0gThe special catalyst composition prepared in example 5 was placed in a reactor of a CO catalytic oxidation removal unit, heated to 830 ℃ under a nitrogen flow, then the nitrogen was stopped, and SO was introduced2、N2、CO、H2O and O2Mixed gas prepared according to a certain proportion. Wherein SO2Is 1000mg/m3，CO 2000mg/m3，H2O 10(v)％，O23.5 (v)%, and the balance of N2. The gas flow is 2000ml/min, sampling and analyzing are carried out every 30 minutes, the reaction is carried out for 36 hours, and the CO removal rate is 100 percent.
Example 11
5.0g of the special catalyst composition prepared in example 1 was weighed into a reactor of a CO catalytic oxidation removal device, heated to 300 ℃ under a nitrogen flow, and then the nitrogen was stopped and SO was introduced2、N2、CO、H2O and O2Mixed gas prepared according to a certain proportion. Wherein SO2Is 1000mg/m3，CO 2000mg/m3，H2O 10(v)％，O23.5 (v)%, and the balance of N2. The gas flow is 2000ml/min, sampling and analyzing are carried out every 30 minutes, the reaction is carried out for 36 hours, and the CO removal rate is 99.0 percent.
Example 12
5.0g of the special catalyst composition prepared in example 2 was weighed into a reactor of a CO catalytic oxidation removal unit, heated to 300 ℃ under a nitrogen flow, then the nitrogen was stopped, and SO was introduced2、N2、CO、H2O and O2Mixed gas prepared according to a certain proportion. Wherein SO2Is 1000mg/m3，CO 2000mg/m3，H2O 10(v)％，O23.5 (v)%, and the balance of N2. The gas flow is 2000ml/min, sampling and analyzing are carried out every 30 minutes, the reaction is carried out for 36 hours, and the CO removal rate is 99.5 percent.
Example 13
5.0g of the special catalyst composition prepared in example 3 was weighed into a reactor of a CO catalytic oxidation removal unit, heated to 300 ℃ under a nitrogen flow, then the nitrogen was stopped, and SO was introduced2、N2、CO、H2O and O2Mixing at a certain proportionA gas. Wherein SO2Is 1000mg/m3，CO 2000mg/m3，H2O 10(v)％，O23.5 (v)%, and the balance of N2. The gas flow is 2000ml/min, sampling and analyzing are carried out every 30 minutes, the reaction is carried out for 36 hours, and the CO removal rate is 99.3 percent.
Example 14
5.0g of the special catalyst composition prepared in example 4 was weighed into a reactor of a CO catalytic oxidation removal unit, heated to 300 ℃ under a nitrogen flow, then the nitrogen was stopped, and SO was introduced2、N2、CO、H2O and O2Mixed gas prepared according to a certain proportion. Wherein SO2Is 1000mg/m3，CO 2000mg/m3，H2O 10(v)％，O23.5 (v)%, and the balance of N2. The gas flow is 2000ml/min, sampling and analyzing are carried out every 30 minutes, the reaction is carried out for 36 hours, and the CO removal rate is 99.8 percent.
Example 15
5.0g of the special catalyst composition prepared in example 5 was weighed into a reactor of a CO catalytic oxidation removal unit, heated to 300 ℃ under a nitrogen flow, then the nitrogen was stopped, and SO was introduced2、N2、CO、H2O and O2Mixed gas prepared according to a certain proportion. Wherein SO2Is 1000mg/m3，CO 2000mg/m3，H2O 10(v)％，O23.5 (v)%, and the balance of N2. The gas flow is 2000ml/min, sampling and analyzing are carried out every 30 minutes, the reaction is carried out for 36 hours, and the CO removal rate is 99.5 percent.
Example 16
5.0g of the special catalyst composition prepared in example 6 was weighed into a reactor of a CO catalytic oxidation removal unit, heated to 300 ℃ under a nitrogen flow, then the nitrogen was stopped, and SO was introduced2、N2、CO、H2O and O2Mixed gas prepared according to a certain proportion. Wherein SO2Is 1000mg/m3，CO 2000mg/m3，H2O 10(v)％，O23.5 (v)%, and the balance of N2. The gas flow is 2000ml/min, sampling and analyzing are carried out every 30 minutes, the reaction is carried out for 36 hours, and CO is removedThe removal rate was 99.2%.
Example 17
5.0g of the special catalyst composition prepared in example 7 was weighed into a reactor of a CO catalytic oxidation removal unit, heated to 300 ℃ under a nitrogen flow, then the nitrogen was stopped, and SO was introduced2、N2、CO、H2O and O2Mixed gas prepared according to a certain proportion. Wherein SO2Is 1000mg/m3，CO 2000mg/m3，H2O 10(v)％，O23.5 (v)%, and the balance of N2. The gas flow is 2000ml/min, sampling and analyzing are carried out every 30 minutes, the reaction is carried out for 36 hours, and the CO removal rate is 99.7 percent.
Example 18
5.0g of the special catalyst composition prepared in example 8 was weighed into a reactor of a CO catalytic oxidation removal unit, heated to 300 ℃ under a nitrogen flow, then the nitrogen was stopped, and SO was introduced2、N2、CO、H2O and O2Mixed gas prepared according to a certain proportion. Wherein SO2Is 1000mg/m3，CO 2000mg/m3，H2O 10(v)％，O23.5 (v)%, and the balance of N2. The gas flow is 2000ml/min, sampling and analyzing are carried out every 30 minutes, the reaction is carried out for 36 hours, and the CO removal rate is 99.4 percent.
Comparative example 1
5.0g of the perovskite of example 4 of the formula LaMn was weighed out0.4Co0.6O3Change to LaMn0.9Co0.2O3The rest of the catalyst composition prepared in the same manner as in example 4 was charged into a reactor of a CO catalytic oxidation removal apparatus, heated to 300 ℃ under a nitrogen stream, and then the nitrogen was stopped and SO was introduced thereinto2、N2、CO、H2O and O2Mixed gas prepared according to a certain proportion. Wherein SO2Is 1000mg/m3，CO 2000mg/m3，H2O 10(v)％，O23.5 (v)%, and the balance of N2. The gas flow is 2000ml/min, sampling and analyzing are carried out every 30 minutes, the reaction is carried out for 36 hours, and the CO removal rate is 81.4 percent.
Comparative example 2
5.0g of the tungstate of example 4 was replaced with distilled water, and the catalyst composition prepared in the same manner as in example 4 was charged into a reactor of a CO catalytic oxidation removal apparatus, heated to 300 ℃ under a nitrogen stream, and then the nitrogen was stopped, and SO was introduced thereinto2、N2、CO、H2O and O2Mixed gas prepared according to a certain proportion. Wherein SO2Is 1000mg/m3，CO2000mg/m3，H2O 10(v)％，O23.5 (v)%, and the balance of N2. The gas flow is 2000ml/min, sampling and analyzing are carried out every 30 minutes, the reaction is carried out for 36 hours, and the CO removal rate is 84.2 percent.
Comparative example 3
5.0g of the catalyst composition prepared in example 4 was weighed out and the calcination temperature of the second mixture in example 4 was raised to 650 ℃ to 850 ℃ and the rest was charged into a reactor of a CO catalytic oxidation removal apparatus, heated to 300 ℃ under a nitrogen stream, and then the nitrogen was stopped and supplied with SO2、N2、CO、H2O and O2Mixed gas prepared according to a certain proportion. Wherein SO2Is 1000mg/m3，CO2000mg/m3，H2O 10(v)％，O23.5 (v)%, and the balance of N2. The gas flow is 2000ml/min, sampling and analyzing are carried out every 30 minutes, the reaction is carried out for 36 hours, and the CO removal rate is 88.5 percent.
As can be seen from the above comparative examples, by replacing the components in the catalyst composition provided in the examples of the present invention with other components or changing the parameters in the preparation process, the resulting catalyst composition has a significantly reduced CO removal rate.
In summary, the embodiment of the invention provides a process furnace flue gas CO deep purification method, a catalyst composition, a preparation method and an application. The catalyst composition comprises the following components in parts by weight: 4 to 25 weight percent of a compound of the general formula LaMn1－xCoxO3X is 0.1 to 0.8; 2 to 10 wt% of WO3(ii) a 1-7 wt% of CuO; 2-15 wt% of cerium-zirconium mixed oxide; 55-85 wt% of TiO2(ii) a 50 mu g/g-1000 mu g/g of noble metal. For the practice of the inventionThe catalytic ability of the catalyst composition provided in the example is tested, and it can be seen that the catalytic oxidation ability of the catalyst composition in the example of the invention to the CO in the process furnace flue gas is very high, substantially close to 100%, even if the CO in the process furnace flue gas can be catalytically oxidized into CO by using the catalyst composition in the example of the invention2Therefore, the problem that the risk of extinguishing or explosion of the furnace fire caused by too high CO content or too low hearth temperature due to low NOx combustion can be solved, the operation safety of the heating furnace is greatly improved, and the high CO removal efficiency is achieved.
Compared with the prior art, the embodiment of the invention has the following beneficial effects:
1) the reduction of the CO content in the flue gas in the embodiment of the invention is carried out by using the catalyst composition without increasing the combustion temperature and O content of the heating furnace2And the content of the component B is higher than that of the component B, so that the advantage of reducing NOx emission of low NOx combustion is fully exerted, and the low NOx emission is realized.
2) The catalyst composition in the embodiment of the invention is placed in a heating furnace, so that the risk of extinguishing or explosion of furnace fire caused by too high CO content or too low temperature of a hearth due to low NOx combustion can be eliminated, and the operation safety of the heating furnace is greatly improved.
3) The method for deep purification in the embodiment of the invention can provide a larger operation space for the heating furnace to implement low NOx emission.
4) The catalyst composition provided by the embodiment of the invention has higher CO removal efficiency.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A catalyst composition for deeply purifying CO in flue gas of a process furnace, which is characterized by comprising the following components in percentage by weight of the composition:
4 to 25 weight percent of a compound of the general formula LaMn1－xCoxO3X is 0.1 to 0.8;
2 to 10 wt% of WO3；
1wt％－7wt％CuO；
2-15 wt% of cerium-zirconium mixed oxide;
55-85 wt% of TiO2(ii) a And
50 mu g/g-1000 mu g/g of noble metal.
2. The catalyst composition of claim 1, wherein the TiO2Is anatase type TiO2；
Preferably, the noble metal includes at least one of Pt, Pd, Au, and Ru;
preferably, the cerium-zirconium molar ratio in the cerium-zirconium mixed oxide is 0.5 to 2.0: 0.5-1.0.
3. a process for preparing a catalyst composition according to claim 1 or 2, comprising the steps of: and mixing and roasting corresponding raw materials according to the component proportion of the catalyst composition to obtain the catalyst composition.
4. The method of claim 3, comprising the steps of: proportionally mixing tungstate solution, copper salt solution, perovskite component and anatase TiO2Mixing the cerium-zirconium mixed oxide with a forming agent, and then carrying out extrusion forming to obtain a first mixture; baking and roasting the first mixture to obtain a second mixture; and mixing the second mixture with a noble metal, and baking and roasting to obtain the catalyst composition.
5. The method of claim 4, wherein the preparing of the second mixture comprises the steps of: perovskite component, anatase type TiO according to the formula2The cerium-zirconium mixed oxide and the forming agent are ground and mixed into uniform mixed powder,under the stirring state, mixing the tungstate aqueous solution, the copper salt solution and the mixed powder into blocks again, repeatedly extruding, baking and roasting;
preferably, the forming agent comprises at least one of polyoxyethylene, carboxymethyl cellulose and corn starch, and the amount of the forming agent is 0.5 wt% to 5 wt%, and more preferably, the amount of the forming agent is 1 wt% to 4 wt%;
more preferably, the repeated pressing comprises the steps of: repeatedly squeezing the mixed blocks into fine blocks, keeping moisture, standing for 16-24 hr, squeezing into strips, and drying in the shade for 36-48 hr;
more preferably, the baking and roasting comprises the following steps: the dried in the shade strip was baked at 140 ℃ for 6-12 hours at 120 ℃ and then baked at 750 ℃ for 6-12 hours at 650 ℃.
6. The method of claim 4, wherein the preparation of the catalyst composition comprises the steps of: dipping the second mixture in a noble metal solution by adopting an isometric method, and then baking and roasting;
preferably, the baking and roasting comprises the following steps: baking at 140 ℃ for 4-8 hours at 120 ℃ and then baking at 650 ℃ for 4-8 hours at 600 ℃.
7. A method for deeply purifying CO in flue gas of a process furnace by using the catalyst composition of any one of claims 1 to 2 or the catalyst composition prepared by the preparation method of any one of claims 3 to 6, which is characterized by comprising the following steps: catalytic oxidation of CO in process furnace flue gas to CO using catalyst composition2。
8. The method according to claim 7, characterized in that during the catalytic oxidation: placing the catalyst composition near an after-burning zone of a heating furnace or at the rear part of a flue, or placing the catalyst composition in an externally-connected reactor, and then carrying out catalytic oxidation reaction;
preference is given toThe space velocity of the catalytic oxidation is 500-－1Preferably 1000-15000 h－1。
9. The method as claimed in claim 7, wherein the temperature of CO in the flue gas of the catalytic oxidation process furnace by the catalyst composition is 120-900 ℃, preferably 150-850 ℃;
preferably, the catalyst composition is placed near the burnout zone of the heating furnace, and the temperature of the burnout zone of the heating furnace is controlled to be 600-900 ℃, preferably 650-850 ℃;
preferably, the catalyst composition is placed at the rear part of the flue of the heating furnace, and the temperature at the rear part of the flue of the heating furnace is controlled to be 120-600 ℃, preferably 150-550 ℃.
10. Use of a catalyst composition according to any one of claims 7 to 9 for the deep purification of CO from process furnace flue gas.
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CN111549198A (en) * 2020-04-30 2020-08-18 中国科学院力学研究所 Method for self-sustaining combustion of converter diffused gas based on perovskite type catalyst

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