CN112264027B - Copper-cobalt-cerium composite oxide catalytic combustion catalyst and preparation method and application thereof - Google Patents
Copper-cobalt-cerium composite oxide catalytic combustion catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN112264027B CN112264027B CN202011162365.6A CN202011162365A CN112264027B CN 112264027 B CN112264027 B CN 112264027B CN 202011162365 A CN202011162365 A CN 202011162365A CN 112264027 B CN112264027 B CN 112264027B
- Authority
- CN
- China
- Prior art keywords
- copper
- cerium
- cobalt
- grinding
- precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalytic combustion catalyst of a copper-cobalt-cerium composite oxide, and a preparation method and application thereof, and belongs to the field of atmospheric pollution control. The invention provides a method for preparing a copper-cobalt-cerium composite oxide catalyst by a step-by-step mixing method, and the prepared composite oxide catalyst has small particle size and smaller Co3O4The particle size is beneficial to approaching active oxygen species, the catalytic oxidation reaction is more beneficial, meanwhile, the lower alpha peak position and the higher surface oxygen content mean that the catalyst has better oxidation-reduction capability, the good oxidation-reduction capability can also promote the catalytic performance, the preparation method is very simple, the cost is low, the prepared catalyst has higher VOCs removal activity, and the catalyst is particularly suitable for catalytic combustion purification treatment of organic volatile compound-containing gases (VOCs) in the industries of petrifaction, storage and transportation, spraying, printing and the like under the reaction conditions of low temperature and high space velocity.
Description
Technical Field
The invention relates to the technical field of air pollution control, in particular to a catalytic combustion catalyst of a copper-cobalt-cerium composite oxide, and a preparation method and application thereof.
Background
In recent years, Organic waste gases from petrochemical, storage and transportation, spraying, printing and other industries, mainly Volatile Organic Compounds (VOCs), have become a major pollutant in the atmosphere in some areas. VOCs and nitrogen oxides react under the irradiation of the sun to form two pollutants, namely secondary organic particulate matters and organic aerosol. VOCs are important precursors for the formation of PM2.5 and ozone, thereby accelerating the formation of urban haze and photochemical smog. In addition, some VOCs are irritating and carcinogenic to humans. Therefore, the problem of VOCs disposal is becoming a focus of increasing social attention.
The existing methods for treating VOCs include adsorption, condensation, biodegradation, direct combustion and catalytic combustion. The catalytic combustion method can convert VOCs and oxygen into carbon dioxide and water at a certain temperature, and has the characteristics of high efficiency, cleanness, no open fire, low equipment operation cost and the like.
The traditional catalyst is made of noble metals such as palladium, platinum and the like as active components, and has the problems of resource shortage, high price, poor halogen poisoning resistance and the like. In recent years, composite metal oxide catalysts have been attracting attention as noble metal alternative catalysts due to their characteristics such as low cost and good halogen resistance. Among them, transition metals such as copper, manganese, cobalt, cerium, zirconium and vanadium have received much attention, for example, chinese patent CN107519859A discloses a co-precipitation method for preparing Ce-Zr-MnO for simultaneously purifying NO and VOCs in coal-fired flue gas at low temperature2The Chinese patent CN107754809A discloses a Cu-Mn-Zr composite catalyst prepared by a sol-gel method, but the prior composite metal oxide catalyst has the problem of low activity.
Disclosure of Invention
In view of the above, the present invention aims to provide a catalytic combustion catalyst of copper-cobalt-cerium composite oxide, and a preparation method and an application thereof. The catalyst prepared by the method provided by the invention has high activity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a copper-cobalt-cerium composite oxide catalytic combustion catalyst, which comprises the following steps:
providing three precursors, wherein the three precursors comprise a cerium precursor, a cobalt precursor and a copper precursor;
carrying out first grinding on any one of the three precursors to obtain a first grinding material;
mixing any one of the two residual precursors with the first abrasive, and then carrying out second grinding to obtain a second abrasive;
mixing the rest precursor with the second grinding material, and performing third grinding to obtain a third grinding material;
and roasting the third grinding material to obtain the catalytic combustion catalyst of the copper-cobalt-cerium composite oxide.
Preferably, the cerium precursor comprises one or more of cerium sulfate, cerium acetate, cerium chloride, cerium acetate, cerium oxalate, cerium nitrate, ammonium cerium nitrate, cerium oxide and cerium oxide; the cobalt precursor comprises one or more of cobalt acetate, cobalt oxalate, cobalt nitrate, cobalt acetate, cobalt carbonate, cobalt oxide, cobaltous oxide and cobaltosic oxide; the copper precursor comprises one or more of copper carbonate, basic copper carbonate, copper acetate, copper nitrate, copper chloride, copper oxalate, copper acetate, cuprous oxide and cupric oxide.
Preferably, the cerium precursor, the cobalt precursor, and the copper precursor are added in the form of a slurry, and the solvent in the slurry independently includes one or more of water, methanol, ethanol, acetonitrile, hexane, cyclohexane, acetone, benzene, toluene, and chlorobenzene.
Preferably, the revolution rotating speed of the first grinding, the revolution rotating speed of the second grinding and the revolution rotating speed of the third grinding are respectively 50-400 r/min, the rotation rotating speed is respectively 100-800 r/min, and the time is respectively 0.05-24 h.
Preferably, the revolution rotating speed of the first grinding, the second grinding and the third grinding is independently 100-300 r/min, and the rotation rotating speed is independently 200-600 r/min.
Preferably, the particle size of the third abrasive is not greater than 5 μm.
Preferably, the roasting temperature is 300-600 ℃, and the roasting time is 10-600 min.
Preferably, the roasting temperature is 400-550 ℃ and the roasting time is 30-180 min.
The invention also provides the catalytic combustion catalyst of the copper-cobalt-cerium composite oxide prepared by the preparation method of the technical scheme.
The invention also provides the application of the copper-cobalt-cerium composite oxide catalytic combustion catalyst in the technical scheme in the catalytic combustion reaction of volatile organic compounds.
The invention provides a preparation method of a copper-cobalt-cerium composite oxide catalytic combustion catalyst, which comprises the following steps: providing three precursors, wherein the three precursors comprise a cerium precursor, a cobalt precursor and a copper precursor; carrying out first grinding on any one of the three precursors to obtain a first grinding material; mixing any one of the two residual precursors with the first abrasive, and then carrying out second grinding to obtain a second abrasive; mixing the rest precursor with the second grinding material, and performing third grinding to obtain a third grinding material; and roasting the third grinding material to obtain the catalytic combustion catalyst of the copper-cobalt-cerium composite oxide. The invention provides a method for preparing a copper-cobalt-cerium composite oxide catalyst by adopting a step-by-step mixing method, and the prepared Co composite oxide catalyst is small in particle size and smaller in Co3O4The particle size is beneficial to approaching active oxygen species, the catalytic oxidation reaction is more beneficial, meanwhile, the lower alpha peak position and the higher surface oxygen content mean that the catalyst has better oxidation-reduction capability, the good oxidation-reduction capability can also promote the catalytic performance, the preparation method is very simple, the cost is low, the prepared catalyst has higher VOCs removal activity, and the catalyst is particularly suitable for catalytic combustion purification treatment of organic volatile compound-containing gases (VOCs) in the industries of petrifaction, storage and transportation, spraying, printing and the like under the reaction conditions of low temperature and high space velocity. The data of the examples show that the T90 of toluene is 282 ℃ for the composite oxide catalyst prepared by the invention under the condition of high space velocity of 250000 mL/h/g.
Drawings
FIG. 1 is a graph showing the influence of Cu-Co-Ce composite oxide catalysts prepared by different methods on the activity of toluene catalytic combustion reaction;
FIG. 2 is a graph showing durability tests of the Cu-Co-Ce composite oxide catalyst prepared in example 1 (wherein the contents of cerium oxide and tricobalt tetraoxide are 50% and 37%, respectively, and the balance is copper oxide) in a catalytic combustion reaction of toluene.
Detailed Description
The invention provides a preparation method of a copper-cobalt-cerium composite oxide catalytic combustion catalyst, which comprises the following steps:
providing three precursors, wherein the three precursors comprise a cerium precursor, a cobalt precursor and a copper precursor;
carrying out first grinding on any one of the three precursors to obtain a first grinding material;
mixing any one of the two residual precursors with the first abrasive, and then carrying out second grinding to obtain a second abrasive;
mixing the rest precursor with the second grinding material, and performing third grinding to obtain a third grinding material;
and roasting the third grinding material to obtain the catalytic combustion catalyst of the copper-cobalt-cerium composite oxide.
The invention provides three precursors, which comprise a cerium precursor, a cobalt precursor and a copper precursor. In the present invention, the precursor is preferably a carbonate, an acetate, a bicarbonate, a nitrate or a metal oxide.
In the present invention, the cerium precursor preferably includes one or more of cerium sulfate, cerium acetate, cerium chloride, cerium acetate, cerium oxalate, cerium nitrate, cerium ammonium nitrate, cerium oxide and cerium oxide; the cobalt precursor preferably comprises one or more of cobalt acetate, cobalt oxalate, cobalt nitrate, cobalt acetate, cobalt carbonate, cobalt oxide, cobaltous oxide and cobaltosic oxide; the copper precursor preferably comprises one or more of copper carbonate, basic copper carbonate, copper acetate, copper nitrate, copper chloride, copper oxalate, copper acetate, cuprous oxide and cupric oxide.
In the present invention, the cerium precursor, the cobalt precursor, and the copper precursor are preferably added in the form of a slurry, and the solvent in the slurry preferably independently includes one or more of water, methanol, ethanol, acetonitrile, hexane, cyclohexane, acetone, benzene, toluene, and chlorobenzene. In the present invention, the solid-to-liquid ratio of the slurry is preferably less than 20: 1.
the method comprises the step of carrying out first grinding on any one of the three precursors to obtain a first grinding material.
In the invention, the revolution speed of the first grinding is preferably 50-400 r/min, more preferably 100-300 r/min, the rotation speed is preferably 100-800 r/min, more preferably 200-600 r/min, and the time is preferably 0.05-24 h. In the present invention, the first grinding is preferably carried out in a planetary ball mill.
After the first abrasive is obtained, any one of the two remaining precursors is mixed with the first abrasive and then subjected to second grinding to obtain a second abrasive. The limitation of the second grinding is consistent with the limitation range of the first grinding, and the description is omitted here.
After the second abrasive is obtained, the residual precursor and the second abrasive are mixed and then subjected to third grinding to obtain a third abrasive. The limitation of the third grinding is consistent with the limitation range of the first grinding, and the description is omitted here.
In the invention, when the cerium precursor, the cobalt precursor and the copper precursor are preferably added in a slurry form, the first grinding and the second grinding preferably sequentially comprise dewatering, drying and roasting the obtained slurry to obtain powder, adding the obtained powder into a solvent to prepare slurry, more preferably preparing cerium precursor slurry, cobalt precursor slurry and copper precursor slurry, adding the cobalt precursor slurry into the cerium precursor slurry after the first grinding, performing second grinding, dewatering, drying and roasting to obtain cerium-cobalt powder, adding the obtained cerium-cobalt powder into the solvent to prepare slurry, and then adding the copper precursor slurry into the slurry to perform third grinding.
In the present invention, the order of addition of the three precursors is preferably: the cerium precursor is added first, the cobalt precursor is added, and then the copper precursor is added.
In the present invention, the particle size of the third abrasive is preferably not more than 5 μm.
After the third grinding material is obtained, roasting the third grinding material to obtain the copper-cobalt-cerium composite oxide catalytic combustion catalyst.
In the present invention, when the cerium precursor, the cobalt precursor, and the copper precursor are preferably added in the form of a slurry, the pre-dehydration and drying are preferably further included before the firing, and the specific manner of the pre-dehydration and drying is not particularly limited in the present invention and may be a manner well known to those skilled in the art.
In the invention, the roasting temperature is preferably 300-600 ℃, more preferably 400-550 ℃, and the time is preferably 10-600 min, more preferably 30-180 min.
The invention also provides the catalytic combustion catalyst of the copper-cobalt-cerium composite oxide prepared by the preparation method of the technical scheme. In the invention, the copper-cobalt-cerium composite oxide catalytic combustion catalyst preferably comprises the following components in percentage by weight: 15-70% of cerium oxide, 25-70% of cobaltosic oxide and 5-60% of copper oxide.
The invention also provides the application of the copper-cobalt-cerium composite oxide catalytic combustion catalyst in the technical scheme in the catalytic combustion reaction of volatile organic compounds.
In order to further illustrate the present invention, the following describes in detail the copper-cobalt-cerium composite oxide catalytic combustion catalyst provided by the present invention, its preparation method and application with reference to examples, but they should not be construed as limiting the scope of the present invention.
In the following examples, the catalyst activity was tested as follows: and tabletting, grinding and screening the prepared copper-cobalt-cerium composite oxide catalyst to obtain catalyst particles of 40-60 meshes. 0.072g of the powder was weighed into a 6mm inner diameter quartz tube and placed in an electric heating furnace. The cylinder gas was used to simulate the venting of VOCs and toluene was selected as the representative VOCs component. The composition of the inlet reaction gas was: o is221%, toluene 1000ppm, N2Balancing qi. Mixing 300mL/miThe simulated gas mixture of n was passed into a quartz tube containing the catalyst, and the outlet gas was analyzed for toluene concentration by on-line chromatography. The testing temperature is 150-350 ℃; the space velocity tested was about 250000 mL/h/g. The catalyst activity index was mainly the reaction temperature T30 or T90 at which the toluene conversion reached 30% or 90% (the lower the value of T30 or T90, the better the catalyst activity).
Example 1
The preparation method of the copper-cobalt-cerium composite oxide catalyst comprises the following steps:
weighing a certain amount of cerium carbonate, adding a proper amount of water, stirring into slurry, and grinding the slurry in a planetary ball mill with revolution speed of 200r/min and rotation speed of 400r/min for 0.5 h. Then, the prepared cobalt carbonate slurry was added to the cerium carbonate slurry, and the mixed slurry was further ground for 0.5 hour in a planetary ball mill having a revolution speed of 200r/min and a rotation speed of 400 r/min. Then, adding the copper carbonate slurry, and continuously grinding the mixed slurry for 0.5h in a planetary ball mill with revolution speed of 200r/min and rotation speed of 400 r/min. After grinding, drying at 110 ℃ and calcining at 500 ℃ (180min) to obtain the copper-cobalt-cerium composite oxide catalyst.
Table 1 shows catalysts with different copper, cobalt and cerium contents and activity performance data thereof in a toluene catalytic combustion reaction, and it can be seen from table 1 that, in a process of adjusting the contents of other two components by fixing the content of a certain element in the three components (for example, the content of copper oxide is gradually increased at a certain time, or the content of cobalt oxide is gradually increased at a certain time), a better catalytic effect is obtained on a copper-cobalt-cerium composite oxide catalyst with a cerium oxide content of 30-50% and a cobaltosic oxide content of 30-50%. The optimal catalytic activity is obtained in the copper cobalt cerium composite oxide catalyst with the cerium oxide mass content of 50% and the cobaltosic oxide mass content of 37%.
TABLE 1 catalysts with different Cu, Co and Ce contents and their activity performance data in toluene catalytic combustion
Example 2
Example 2 includes the activity of the copper cobalt cerium composite oxide catalyst prepared under different calcination mixing sequences for catalytic combustion reaction of toluene. The specific preparation method is as follows:
roasting after step-by-step wet mixing: the preparation method is the same as that of example 1. In the preparation process, the mass contents of cerium oxide and cobaltosic oxide in the roasted copper-cobalt-cerium composite oxide catalyst are controlled to be 50% and 37% respectively, and the mass content of copper oxide is controlled to be 13%.
Dry mixing and roasting step by step:
s1: dry precursor powders of cerium carbonate, copper carbonate and cobalt carbonate were prepared, respectively.
S2: and (3) placing the dry material of the cerium precursor obtained in the step (S1) in a planetary ball mill with revolution speed of 200r/min and rotation speed of 400r/min for grinding for 0.5 h.
S3: and (4) adding a dry material of a cobalt precursor into the material obtained in the step S2, and grinding for 0.5h in a planetary ball mill with revolution speed of 200r/min and rotation speed of 400 r/min.
S4: and adding a dry material of a copper precursor into the material obtained in the step S3, and grinding for 0.5h in a planetary ball mill with revolution speed of 200r/min and rotation speed of 400 r/min.
S5: and (S4) roasting the material obtained in the step of 500 ℃ for 180min to obtain the copper-cobalt-cerium composite oxide catalyst. In the preparation process, the mass contents of cerium oxide and cobaltosic oxide in the roasted copper-cobalt-cerium composite oxide catalyst are controlled to be 50% and 37% respectively, and the mass content of copper oxide is controlled to be 13%.
Wet mixing step by step after roasting:
s1: dry precursor powders of cerium carbonate, copper carbonate and cobalt carbonate were prepared, respectively.
S2: and (3) respectively roasting the powder dry materials of the copper precursor, the cobalt precursor and the cerium precursor obtained in the step (S1) at 500 ℃ for 180min to obtain powder dry materials of each metal oxide, and then adding water to prepare slurry.
S3: and (3) placing the cerium oxide slurry obtained in the step (S2) into a planetary ball mill with revolution speed of 200r/min and rotation speed of 400r/min for grinding for 0.5 h.
S4: and adding the cobalt oxide slurry obtained in the step S2 into the material obtained in the step S3, and grinding for 0.5h in a planetary ball mill with revolution speed of 200r/min and rotation speed of 400 r/min.
S5: and adding the copper oxide slurry obtained in the step S2 into the material obtained in the step S3, and grinding for 0.5h in a planetary ball mill with revolution speed of 200r/min and rotation speed of 400 r/min.
S6: and (3) drying the substance obtained in the step S5 at 110 ℃ for 12h, and then roasting at 500 ℃ for 180min to obtain the copper-cobalt-cerium composite oxide catalyst. In the preparation process, the mass contents of cerium oxide and cobaltosic oxide in the roasted copper-cobalt-cerium composite oxide catalyst are controlled to be 50% and 37% respectively, and the mass content of copper oxide is controlled to be 13%.
Dry mixing step by step after roasting:
s1: dry precursor powders of cerium carbonate, copper carbonate and cobalt carbonate were prepared, respectively.
S2: and (3) respectively roasting the powder dry materials of the copper precursor, the cobalt precursor and the cerium precursor obtained in the step S1 at 500 ℃ for 180min to obtain the powder dry materials of each metal oxide.
S3: and (3) placing the dry cerium oxide obtained in the step (S2) in a planetary ball mill with revolution speed of 200r/min and rotation speed of 400r/min for grinding for 0.5 h.
S4: and (4) adding the dry material of the cobalt oxide into the material obtained in the step S3, and grinding for 0.5h in a planetary ball mill with revolution speed of 200r/min and rotation speed of 400 r/min.
S5: and adding a dry material of copper oxide into the material obtained in the step S4, and grinding for 0.5h in a planetary ball mill with revolution speed of 200r/min and rotation speed of 400 r/min.
S6: and (4) roasting the substance obtained in the step (S5) at 500 ℃ for 180min to obtain the copper-cobalt-cerium composite oxide catalyst. In the preparation process, the mass contents of cerium oxide and cobaltosic oxide in the roasted copper-cobalt-cerium composite oxide catalyst are controlled to be 50% and 37% respectively, and the mass content of copper oxide is controlled to be 13%.
FIG. 1 is a graph showing the effect of the Cu-Co-Ce composite oxide catalysts prepared by different methods on the activity of the catalytic combustion reaction of toluene, Table 2 shows the Cu-Co-Ce composite oxide catalysts prepared by different methods and their effect on the activity of toluene combustion, and Table 2 summarizes the grain size of the tricobalt tetroxide crystals (XRD analysis), H, and H on the Cu-Co-Ce composite oxide catalysts prepared by different methods2TPR minimum reduction Peak temperature (H)2TPR analysis), the proportion of chemically adsorbed oxygen on the surface and the catalytic activity for the catalytic combustion reaction of toluene. Referring to FIG. 1 and Table 2, it can be seen that the particle size of the tricobalt tetraoxide crystal on the Cu-Co-Ce composite oxide catalyst prepared by different preparation methods, H2The change rule of the properties such as the lowest reduction peak temperature (alpha peak position) of TPR, the proportion of surface chemically adsorbed oxygen and the like is basically consistent with the change rule of the catalytic combustion reaction activity of the toluene. Therefore, the preparation method has the advantages of higher dispersity, surface chemical adsorption of oxygen and H2A catalyst with reducing power and thus good catalytic activity.
TABLE 2 Cu-Co-Ce composite oxide catalyst prepared by different preparation methods and its active performance for toluene combustion
Example 3
Example 3 compares the effect of different precursors on the activity of a copper cobalt cerium composite oxide catalyst on toluene oxidation.
The specific preparation method is as follows.
The "stepwise wet mixing and then calcination" method of example 2 was used, with carbonates, nitrates, acetates and oxalates of copper, cobalt and cerium as precursors, respectively. Controlling the copper-cobalt-cerium composite oxide after roasting in the preparation processThe mass contents of cerium oxide and cobaltosic oxide in the catalyst are respectively 50% and 37%, and the balance is copper oxide. Table 3 shows the influence data of different precursors in the "wet mixing step by step and then calcination" method, and it can be seen from table 3 that the cu-co-ce composite oxide catalyst prepared by using different precursors has different properties. In sum, carbonates>Acetic acid salt>Nitrate salt>An oxalate salt. The grain size H of cobaltosic oxide2The change rule of the properties of TPR minimum reduction peak temperature (alpha peak position), surface chemical adsorption oxygen ratio and the like is basically consistent with the change rule of the catalytic combustion reaction activity of the toluene.
TABLE 3 influence of different precursors in the "Wet mix after calcination step by step" method
Example 4
Example 4 shows the durability of the catalyst prepared according to the preparation method of example 1 to the catalytic combustion reaction of toluene at 300 c, and the mass contents of cerium oxide and tricobalt tetraoxide in the copper cobalt cerium composite oxide catalyst are 50% and 37%, respectively, and the balance is copper oxide, as shown in fig. 2. The activity of the catalyst on the catalytic combustion of toluene is kept near 100% within 70h of the test, and no obvious phenomenon of catalyst activity attenuation is found, which shows that the catalyst has good durability.
Comparative example 1
Comparative example 1 is a preparation method of "one-step wet mixing and then roasting", and the specific preparation method is as follows:
weighing a certain amount of cerium carbonate, copper carbonate and cobalt carbonate respectively, adding a proper amount of water, stirring into slurry, and preparing slurry of cerium carbonate, copper carbonate and cobalt carbonate respectively. The three kinds of slurry are mixed together at the same time and ground for 1.5h in a planetary ball mill with revolution speed of 200r/min and rotation speed of 400 r/min. After grinding, drying at 110 ℃ and calcining at 500 ℃ (180min) to obtain the copper-cobalt-cerium composite oxide catalyst.
The preparation method of the sample of 'step-by-step wet mixing and then roasting' is the same as that of the example 1, and in the preparation process, the mass contents of cerium oxide and cobaltosic oxide in the roasted copper-cobalt-cerium composite oxide catalyst are controlled to be 50% and 37% respectively, and the balance is copper oxide.
The prepared copper-cobalt-cerium composite oxide catalyst is applied to the catalytic combustion reaction of toluene, the catalytic performance of the catalyst is examined, and the result is shown in table 4, and the activity of the catalyst prepared by the preparation method of 'step-by-step wet mixing and roasting' is superior to that of the preparation method of 'one-step wet mixing and roasting' shown in table 4.
TABLE 4 toluene catalytic Activity of catalysts prepared by the one-step Wet-mix-after-calcination Process
| Preparation method | Grinding time | T30(℃) | T90(℃) |
| Roasting after one-step wet mixing | 1.5h | 252 | 302 |
| Roasting after wet mixing step by step | 0.5h+0.5h+0.5h | 246 | 282 |
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (9)
1. The preparation method of the copper-cobalt-cerium composite oxide catalytic combustion catalyst is characterized by comprising the following steps of:
providing three precursors, wherein the three precursors comprise a cerium precursor, a cobalt precursor and a copper precursor;
carrying out first grinding on any one of the three precursors to obtain a first grinding material;
mixing any one of the two residual precursors with the first abrasive, and then carrying out second grinding to obtain a second abrasive;
mixing the rest precursor with the second grinding material, and performing third grinding to obtain a third grinding material; the revolution rotating speed of the first grinding, the revolution rotating speed of the second grinding and the revolution rotating speed of the third grinding are independently 50-400 r/min, the rotation rotating speed is independently 100-800 r/min, and the time is independently 0.05-24 h;
and roasting the third grinding material to obtain the catalytic combustion catalyst of the copper-cobalt-cerium composite oxide.
2. The method of claim 1, wherein the cerium precursor includes one or more of cerium sulfate, cerium acetate, cerium chloride, cerium acetate, cerium oxalate, cerium nitrate, cerium ammonium nitrate, cerium oxide and cerium oxide; the cobalt precursor comprises one or more of cobalt acetate, cobalt oxalate, cobalt nitrate, cobalt acetate, cobalt carbonate, cobalt oxide, cobaltous oxide and cobaltosic oxide; the copper precursor comprises one or more of copper carbonate, basic copper carbonate, copper acetate, copper nitrate, copper chloride, copper oxalate, copper acetate, cuprous oxide and cupric oxide.
3. The preparation method according to claim 1 or 2, wherein the cerium precursor, the cobalt precursor, and the copper precursor are added in the form of a slurry, and a solvent in the slurry independently comprises one or more of water, methanol, ethanol, acetonitrile, hexane, cyclohexane, acetone, benzene, toluene, and chlorobenzene.
4. The production method according to claim 1, wherein the revolution speed of the first grinding, the revolution speed of the second grinding, and the revolution speed of the third grinding are independently 100 to 300r/min, and the rotation speed is independently 200 to 600 r/min.
5. The method according to claim 1, wherein the particle size of the third abrasive is not more than 5 μm.
6. The method according to claim 1, wherein the roasting temperature is 300 to 600 ℃ and the roasting time is 10 to 600 min.
7. The method according to claim 1, wherein the roasting temperature is 400 to 550 ℃ and the roasting time is 30 to 180 min.
8. The catalyst for catalytic combustion of copper-cobalt-cerium composite oxide prepared by the preparation method of any one of claims 1 to 7.
9. Use of the copper cobalt cerium composite oxide catalytic combustion catalyst of claim 8 in a volatile organic compound catalytic combustion reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011162365.6A CN112264027B (en) | 2020-10-27 | 2020-10-27 | Copper-cobalt-cerium composite oxide catalytic combustion catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011162365.6A CN112264027B (en) | 2020-10-27 | 2020-10-27 | Copper-cobalt-cerium composite oxide catalytic combustion catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112264027A CN112264027A (en) | 2021-01-26 |
| CN112264027B true CN112264027B (en) | 2021-11-02 |
Family
ID=74342001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011162365.6A Active CN112264027B (en) | 2020-10-27 | 2020-10-27 | Copper-cobalt-cerium composite oxide catalytic combustion catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112264027B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115337932B (en) * | 2022-08-22 | 2023-10-27 | 广东俐峰环保科技有限公司 | Formula of cobalt-containing catalyst |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549338A (en) * | 2013-10-21 | 2015-04-29 | 上海华谊丙烯酸有限公司 | Molybdenum-containing bismuth-containing composite oxide catalyst as well as preparation method and function thereof |
| CN104549213A (en) * | 2014-08-08 | 2015-04-29 | 江西宝安新材料科技有限公司 | Methane catalytic oxidation catalyst for natural gas vehicle and preparation method of methane catalytic oxidation catalyst |
| CN104667940A (en) * | 2013-12-02 | 2015-06-03 | 中国科学院大连化学物理研究所 | Preparation method and application of deoxidization Ce-base composite oxide catalyst for coal-bed methane |
| CN106636995A (en) * | 2016-12-29 | 2017-05-10 | 柳州市凯夕贸易有限公司 | Aluminum alloy and preparation method thereof |
| CN107376896A (en) * | 2017-06-26 | 2017-11-24 | 上海理工大学 | A kind of cerium tungsten titanium composite oxide SCR denitration and preparation method thereof |
| CN107519859A (en) * | 2017-09-21 | 2017-12-29 | 北京科技大学 | Purify the Ce Zr MnO of NO and VOCs in coal-fired flue-gas simultaneously for low temperature2Method for preparing catalyst |
| CN109603835A (en) * | 2018-12-19 | 2019-04-12 | 南京工业大学 | A kind of copper cobalt and cerium compound oxide VOCs catalyst for catalytic oxidation and its preparation method and application |
| CN109731592A (en) * | 2019-01-16 | 2019-05-10 | 中国科学院过程工程研究所 | The catalyst and its preparation method and application of methacrolein selective oxidation methacrylic acid |
| WO2019211787A1 (en) * | 2018-05-02 | 2019-11-07 | Colorobbia Consulting S.R.L. | NITROGEN-DOPED TiO2 NANOPARTICLES AND THE USE THEREOF IN PHOTOCATALYSIS |
| CN110864577A (en) * | 2019-11-27 | 2020-03-06 | 天津科技大学 | Tail end heat energy utilization and emission reduction process for toluene to produce benzoic acid |
| CN110975870A (en) * | 2019-12-12 | 2020-04-10 | 重庆工商大学 | Preparation method and application of copper-cobalt composite oxide catalyst |
| CN111686804A (en) * | 2020-07-04 | 2020-09-22 | 闫英辉 | Sulfur-resistant catalyst for low-temperature catalytic combustion of VOCs (volatile organic compounds) and preparation method thereof |
-
2020
- 2020-10-27 CN CN202011162365.6A patent/CN112264027B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549338A (en) * | 2013-10-21 | 2015-04-29 | 上海华谊丙烯酸有限公司 | Molybdenum-containing bismuth-containing composite oxide catalyst as well as preparation method and function thereof |
| CN104667940A (en) * | 2013-12-02 | 2015-06-03 | 中国科学院大连化学物理研究所 | Preparation method and application of deoxidization Ce-base composite oxide catalyst for coal-bed methane |
| CN104549213A (en) * | 2014-08-08 | 2015-04-29 | 江西宝安新材料科技有限公司 | Methane catalytic oxidation catalyst for natural gas vehicle and preparation method of methane catalytic oxidation catalyst |
| CN106636995A (en) * | 2016-12-29 | 2017-05-10 | 柳州市凯夕贸易有限公司 | Aluminum alloy and preparation method thereof |
| CN107376896A (en) * | 2017-06-26 | 2017-11-24 | 上海理工大学 | A kind of cerium tungsten titanium composite oxide SCR denitration and preparation method thereof |
| CN107519859A (en) * | 2017-09-21 | 2017-12-29 | 北京科技大学 | Purify the Ce Zr MnO of NO and VOCs in coal-fired flue-gas simultaneously for low temperature2Method for preparing catalyst |
| WO2019211787A1 (en) * | 2018-05-02 | 2019-11-07 | Colorobbia Consulting S.R.L. | NITROGEN-DOPED TiO2 NANOPARTICLES AND THE USE THEREOF IN PHOTOCATALYSIS |
| CN109603835A (en) * | 2018-12-19 | 2019-04-12 | 南京工业大学 | A kind of copper cobalt and cerium compound oxide VOCs catalyst for catalytic oxidation and its preparation method and application |
| CN109731592A (en) * | 2019-01-16 | 2019-05-10 | 中国科学院过程工程研究所 | The catalyst and its preparation method and application of methacrolein selective oxidation methacrylic acid |
| CN110864577A (en) * | 2019-11-27 | 2020-03-06 | 天津科技大学 | Tail end heat energy utilization and emission reduction process for toluene to produce benzoic acid |
| CN110975870A (en) * | 2019-12-12 | 2020-04-10 | 重庆工商大学 | Preparation method and application of copper-cobalt composite oxide catalyst |
| CN111686804A (en) * | 2020-07-04 | 2020-09-22 | 闫英辉 | Sulfur-resistant catalyst for low-temperature catalytic combustion of VOCs (volatile organic compounds) and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Catalytic Combustion of Toluene over Cu-Mn Mixed Oxide Catalyst;Yi Liu et al.;《Journal of Chemical Engineering of Janpa》;20190107;第51卷(第9期);第769-777页 * |
| 掺铈的铜锰钴复合氧化物催化剂对甲苯催化燃烧的性能研究;唐伟等;《能源环境保护》;20050228;第19卷(第1期);摘要 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112264027A (en) | 2021-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104785302B (en) | Denitrifying catalyst with selective catalytic reduction and its preparation method and application | |
| CN102294248A (en) | Fe-Mn composite oxide catalyst for denitration and demercuration at the same time and preparation method thereof | |
| CN110773158B (en) | Material for room-temperature catalytic purification of VOCs (volatile organic compounds) based on metal monoatomic atoms and preparation method thereof | |
| CN107185588B (en) | A kind of low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant and preparation method thereof | |
| CN111229208B (en) | Lotus leaf-source biochar-loaded metal oxide low-temperature SCR (selective catalytic reduction) flue gas denitration catalyst and preparation method and application thereof | |
| CN108435189B (en) | Samarium-doped iron-based denitration catalyst with water resistance and sulfur resistance and preparation method thereof | |
| CN108246312A (en) | Catalyst and preparation method with low temperature active purification of volatile organic pollutant | |
| CN106964348A (en) | A kind of formaldehyde pollutants room temperature catalytic oxidation catalyst and its preparation method and application | |
| CN104174425B (en) | It is a kind of for catalyst of volatile organic matter catalysis oxidation and preparation method thereof | |
| CN112844366B (en) | Multiple poisoning resistant NH 3 -SCR catalyst and method for producing the same | |
| CN108479762A (en) | A kind of manganese oxide catalyst and its preparation method and application | |
| CN105056940A (en) | Method for preparing efficient oxidation catalyst through plasma-assisted sol gel method | |
| CN103212406B (en) | MnOx catalyst for catalytically eliminating benzene series in air and preparation method of MnOx catalyst | |
| CN112264027B (en) | Copper-cobalt-cerium composite oxide catalytic combustion catalyst and preparation method and application thereof | |
| Wu et al. | Catalytic oxidation of formaldehyde by MnCo3MOx catalyst: effect of rare earth elements and temperature | |
| Liu et al. | Simultaneous removal of NO and Hg0 from flue gas over MnSmCo/Ti catalyst at low temperature | |
| CN113210010B (en) | VOC catalyst coated in different areas and preparation method thereof | |
| CN110935470A (en) | Preparation method of exhaust gas purification catalyst | |
| CN107715858A (en) | A kind of preparation method of high temperature resistant to sulfur Ce base SCR catalysts | |
| US7223715B2 (en) | Purification catalyst, preparation process therefor and gas-purifying apparatus | |
| HAO et al. | Experimental study of Fe modified Mn/CeO2 catalyst for simultaneous removal of NO and toluene at low temperature | |
| CN110302830A (en) | VOCs purification molecular sieve based catalyst under high humidity environment and the preparation method and application thereof | |
| KR20120096171A (en) | Low temperature oxidation catalyst for removal of toxic gases and preparation method thereof | |
| CN106994341B (en) | For photocatalytic decomposition of N2Catalyst of O and preparation method and application thereof | |
| CN112755991B (en) | Modified monolithic catalyst for synergistically removing organic waste gas and NOx in coal-fired flue gas and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |