CN113171774A - Alkali metal poisoning resistant VOCs catalytic combustion catalyst and preparation method thereof - Google Patents
Alkali metal poisoning resistant VOCs catalytic combustion catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 35
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 34
- 206010027439 Metal poisoning Diseases 0.000 title claims abstract description 24
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 23
- 238000007084 catalytic combustion reaction Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 17
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 230000000694 effects Effects 0.000 claims abstract description 13
- 230000007062 hydrolysis Effects 0.000 claims abstract description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 13
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 10
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000003763 carbonization Methods 0.000 claims abstract description 7
- 230000005587 bubbling Effects 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 14
- 239000012621 metal-organic framework Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 7
- 238000010000 carbonizing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000001939 inductive effect Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000013114 Co-MOF-74 Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- KJFVITRRNTVAPC-UHFFFAOYSA-L tetramethylazanium;sulfate Chemical compound C[N+](C)(C)C.C[N+](C)(C)C.[O-]S([O-])(=O)=O KJFVITRRNTVAPC-UHFFFAOYSA-L 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 3
- 238000005266 casting Methods 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000001294 propane Substances 0.000 description 11
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 10
- 230000000607 poisoning effect Effects 0.000 description 8
- 231100000572 poisoning Toxicity 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000012922 MOF pore Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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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
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/398—Egg yolk like
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- 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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
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Abstract
The invention belongs to the technical field of chemical catalysts, and particularly relates to an alkali metal poisoning resistant VOCs catalytic combustion catalyst and a preparation method thereof. The catalyst of the invention is formed by encapsulating cobalt oxide with catalytic activity in silicon dioxide, and the shell layer of the silicon dioxide provides a confinement effect and a protection function. According to the invention, a nano-casting method of MOF is adopted, siloxane precursor salt is filled into the pore channels of the MOF, the hydrolysis of the siloxane precursor salt is promoted by using an inert gas bubbling method, and a one-dimensional cowpea-shaped catalyst is prepared through carbonization and calcination; the silica shell enables the cobalt oxide with high loading capacity to be well dispersed, has smaller particle size, effectively improves the catalytic activity of the catalyst, enables the cobalt oxide to be free from the influence of alkali metal, and improves the alkali metal poisoning resistance. The catalyst has high activity, good stability and strong alkali metal poisoning resistance, and completely meets the actual requirements.
Description
Technical Field
The invention belongs to the technical field of chemical catalysts, and particularly relates to an alkali metal poisoning resistant VOCs catalytic combustion catalyst and a preparation method thereof.
Background
Volatile Organic Compounds (VOCs) are a major atmospheric pollutant. The VOCs discharged from automobile exhaust and industrial production process not only cause serious pollution to the environment, but also seriously threaten the health of human beings. Over the past several decades, catalytic combustion processes have become one of the most effective and most widely used techniques for the abatement of various VOCs pollutants. In the VOCs catalytic combustion catalyst, the noble metal-based catalyst has stronger oxidation performance and shows excellent VOCs conversion capability. But the disadvantages of high price, easy poisoning, easy sintering and the like limit the large-scale application of the material. Therefore, it is necessary to develop a high-efficiency catalyst for catalytic combustion of VOCs without noble metals. Among many transition metal oxide catalysts, cobalt-based oxide catalysts have received much attention from researchers because of their environmental friendliness, high cost performance, and good catalytic performance in various redox reactions.
In the practical application process, alkali metals exist in fly ash of coal-fired power plants and diesel vehicles, which can cause serious catalyst poisoning. Alkali metals, a common material from biomass coal and fuel/petroleum additives, are a significant problem that cannot be ignored in the application of VOCs catalytic combustion catalysts (e.g., cobalt-based catalysts). In addition to plugging catalyst channels, alkali metals can also affect adsorption-desorption behavior and normal redox cycling by changing the acid-base properties of the catalyst and binding with active components. Pu-Xian Gao et al (W. Tang, J. Weng, X. Lu, L. Wen, A. Subramanian, C. -Y. Nam, P. -X. Gao. appl. Catl. B: Environ., 2019, 256, 117859-3O4The poisoning effect of alkali metals during the oxidation of propane on the catalyst. They found that alkali metals can reduce the mobility of oxygen by a "blocking effect". In addition, as the reaction proceeds, the alkali metal forms a stable surface carbonate species, thereby sequestering the CO2Desorption of the product had a significant effect. Therefore, after the alkali metal poisoning, the catalyst activity is drastically decreased. Therefore, it is important to improve the alkali metal poisoning resistance of VOCs catalytic combustion catalysts (e.g., cobalt oxide catalysts), but the methods so farThe method yield is not obvious, and the requirement of alkali metal poisoning resistance in the practical application of the VOCs catalytic combustion catalyst cannot be completely met.
Disclosure of Invention
The invention aims to provide a VOCs catalytic combustion catalyst with high activity, good stability and strong alkali metal poisoning resistance and a preparation method thereof aiming at the defects of the existing VOCs catalytic combustion catalyst.
The alkali metal poisoning resistant VOCs catalytic combustion catalyst provided by the invention is of a one-dimensional cowpea-shaped structure, and is formed by encapsulating cobalt oxide with catalytic activity in silicon dioxide, and a silicon dioxide shell layer provides a confinement effect and a protection function. The limiting function can ensure that the cobalt oxide with high load capacity is well dispersed, has smaller particle size and effectively improves the catalytic activity of the catalyst; the protection effect can prevent the cobalt oxide from being influenced by alkali metal, and the alkali metal poisoning resistance is obviously improved.
The molar ratio of the cobalt oxide to the silicon dioxide in the catalyst is 0.2-0.35.
The invention also provides a preparation method of the alkali metal poisoning resistant VOCs catalytic combustion catalyst, siloxane precursor salt is filled into the pore channel of the MOF by adopting a nano-casting method of the MOF, the hydrolysis of the MOF is promoted by utilizing an inert gas bubbling method, and the one-dimensional cowpea-shaped catalyst is prepared by carbonization and calcination; the method comprises the following specific steps:
(1) immersing a certain amount of MOF sample into a certain amount of siloxane precursor salt, and keeping the MOF sample at the temperature of 50-70 ℃ for 12-15 hours; then washing the wet sample for several times by using methanol to remove redundant siloxane precursor salt, and placing the sample in a quartz tube after washing;
(2) bubbling 10-30 mL/min inert gas flow in 0.01-0.1 mol/L solution for hydrolysis, and inducing hydrolysis of siloxane precursor for 24-48 h at 50-70 ℃ by using generated wet gas flow;
(3) after drying for 5-12 h, carbonizing the sample at 600-700 ℃ for 3-5 h in an inert gas flow environment of 150-200 mL/min; and calcining the carbonized sample in an air atmosphere at 500-600 ℃ for 2-5 h to obtain the alkali metal poisoning resistant VOCs catalytic combustion catalyst.
In the step (1), the MOF is MOF of Co metal centers such as Co-CAT-1, Co-ZIF-67 or Co-MOF-74.
In the step (1), the siloxane precursor salt is Tetramethylsiloxane (TMOS) or Tetraethylsiloxane (TEOS).
In the step (2), the inert gas is nitrogen or helium, and the like.
The solution is deionized water, or acid solution or alkali solution, such as HCl.
In the preparation process, the time for immersing the MOF in the siloxane precursor salt is different, the amount of the precursor salt entering the MOF pore channel is different, and the catalytic activity of the finally obtained catalyst is greatly changed.
In the preparation process, the different concentrations of the HCl solution and the different time for inducing the hydrolysis of the siloxane precursor can cause the great change of the shape structure of the finally obtained catalyst, thereby causing the great change of the catalytic activity and the alkali metal poisoning resistance of the catalyst.
In the preparation process, the morphology and the structure of the finally obtained catalyst are greatly changed due to different carbonization temperatures and different carbonization times, so that the catalytic activity and the alkali metal poisoning resistance of the catalyst are greatly changed.
In the preparation process, the concentration of the solution HC is not too high during bubbling hydrolysis, and is kept between 0.01 and 0.1 mol/L. The hydrolysis temperature is not too low or too high and is kept between 50 and 70 ℃; the hydrolysis time is not suitable to be too short or too long and is kept between 24 and 48 hours; otherwise, the framework structure of the MOF is damaged, so that the active components of the catalyst are not dispersed well, and the activity and alkali metal poisoning resistance of the catalyst are affected.
The temperature rising rate of the carbonization and calcination is 1-3 ℃/min, the carbonization time of the sample under the inert gas flow is 3-5 h, the calcination time of the sample under the air atmosphere is 2-5 h, if the temperature rising rate and the temperature rising time exceed the range, the catalyst can be sintered, so that the structure and the surface appearance of the catalyst are damaged, the specific surface area of the catalyst is reduced, and the catalytic activity and the alkali metal poisoning resistance of the calcined catalyst are not facilitated.
Compared with the prior art, the invention has the following advantages:
(1) the catalyst has a special shape structure, and the outer silicon dioxide shell layer provides a complex diffusion migration path for alkali metal, so that the alkali metal is difficult to contact with an active site, and the alkali metal poisoning resistance of the catalyst is obviously improved.
(2) The catalyst has good confinement effect, and can still realize good dispersion of the active component under the condition of high active component loading capacity, so as to obtain nanoparticles with relatively small particle size.
(3) Compared with the traditional supported catalyst, the catalyst has the advantages of high catalytic activity, strong alkali metal poisoning resistance, good stability and the like, the preparation process is relatively simple and stable, and the catalyst can be applied to VOCs catalytic combustion scenes under the condition of alkali metals on a large scale.
Drawings
Fig. 1 is a graph showing the comparison of propane conversion efficiency between the one-dimensional cowpea-like silica encapsulated cobaltosic oxide catalyst obtained in example 1 of the present invention before and after potassium poisoning and the one-dimensional cowpea-like silica supported cobaltosic oxide catalyst before and after potassium poisoning.
Detailed Description
In order to more clearly illustrate the present invention, the following examples are given, but the present invention is not limited to the scope of the examples.
Example 1:
a0.8 g sample of prepared Co-CAT-1 was immersed in 8 mL of Tetramethylsiloxane (TMOS) and held at 60 ℃ for 12 h. The wetted sample was then washed several times with methanol to remove excess TMOS, and after washing was complete the sample was placed in a quartz tube. Using 15 mL/min N2The gas stream was bubbled through a 0.1M HCl solution, and the resulting humidified gas stream induced hydrolysis of TMOS at 50 ℃ for 30 h. After drying for 5 h, the sample was at 150 mL/min N2Carbonizing at 600 deg.C for 4 h in gas flow environment. The obtained sample was calcined at 500 ℃ for 2 hours in an air atmosphere (heating rate 1 ℃/min). Finally obtaining the one-dimensional cowpea-shaped silicon dioxide packaged cobaltosic oxide catalystAn oxidizing agent.
The catalysts described above were tested for catalytic activity and resistance to alkali metal poisoning: taking 0.3 g of the prepared catalyst, putting the catalyst into a fixed bed reactor for activity test, and simulating the composition of reaction gas as follows: 0.2 vol% propane, 2.5 vol% oxygen and nitrogen balance the carrier gas. The total flow rate of the gas is 100 mL/min, and the corresponding test space velocity (GHSV) is 25000 h-1. The catalyst can maintain over 95 percent of propane conversion rate at the reaction temperature of over 240 ℃. After 1 wt% potassium poisoning, the catalyst can maintain a propane conversion of 95% or more at a reaction temperature of 270 ℃ or more.
Example 2:
a0.8 g sample of prepared Co-CAT-1 was immersed in 8 mL of Tetramethylsiloxane (TMOS) and held at 60 ℃ for 12 h. The wetted sample was then washed several times with methanol to remove excess TMOS, and after washing was complete the sample was placed in a quartz tube. Using 15 mL/min N2The gas stream was bubbled through deionized water, and the resulting humidified gas stream induced hydrolysis of TMOS for 30 h at 60 ℃. After drying for 5 h, the sample was at 150 mL/min N2Carbonizing at 600 deg.C for 4 h in gas flow environment. The obtained sample was calcined at 500 ℃ for 2 hours in an air atmosphere (heating rate 1 ℃/min). Finally obtaining the one-dimensional cowpea-shaped silicon dioxide packaged cobaltosic oxide catalyst.
The catalysts described above were tested for catalytic activity and resistance to alkali metal poisoning: taking 0.3 g of the prepared catalyst, putting the catalyst into a fixed bed reactor for activity test, and simulating the composition of reaction gas as follows: 0.2 vol% propane, 2.5 vol% oxygen and nitrogen balance the carrier gas. The total flow rate of the gas is 100 mL/min, and the corresponding test space velocity (GHSV) is 25000 h-1. The catalyst can maintain over 95 percent of propane conversion rate at the reaction temperature of over 250 ℃. After 1 wt% potassium poisoning, the catalyst can maintain a propane conversion of 95% or more at a reaction temperature of 285 ℃ or more.
Example 3:
a0.8 g sample of prepared Co-CAT-1 was immersed in 8 mL of Tetramethylsiloxane (TMOS) and held at 60 ℃ for 12 h. The wet sample was then washed several times with methanolExcess TMOS was removed and after washing the sample was placed in a quartz tube. Using 15 mL/min N2The gas stream was bubbled through a 0.05M HCl solution, and the resulting humidified gas stream induced hydrolysis of TMOS at 50 ℃ for 30 h. After drying for 5 h, the sample was at 150 mL/min N2Carbonizing at 600 deg.C for 3 h in gas flow environment. The obtained sample was calcined at 500 ℃ for 2 hours in an air atmosphere (heating rate 1 ℃/min). Finally obtaining the one-dimensional cowpea-shaped silicon dioxide packaged cobaltosic oxide catalyst.
The catalysts described above were tested for catalytic activity and resistance to alkali metal poisoning: taking 0.3 g of the prepared catalyst, putting the catalyst into a fixed bed reactor for activity test, and simulating the composition of reaction gas as follows: 0.2 vol% propane, 2.5 vol% oxygen and nitrogen balance the carrier gas. The total flow rate of the gas is 100 mL/min, and the corresponding test space velocity (GHSV) is 25000 h-1. The catalyst can maintain over 95 percent of propane conversion rate at the reaction temperature of over 245 ℃. After 1 wt% potassium poisoning, the catalyst can maintain a propane conversion of 95% or more at a reaction temperature of 275 ℃ or more.
Claims (9)
1. The catalyst is characterized by being of a one-dimensional cowpea-shaped structure, and formed by encapsulating cobalt oxide with catalytic activity in silicon dioxide, wherein a silicon dioxide shell layer provides a confinement effect and a protection function.
2. The VOCs catalytic combustion catalyst of claim 1, wherein the molar ratio of cobalt oxide to silica is in the range of 0.2 to 0.35.
3. A method for preparing a catalyst for catalytic combustion of VOCs according to claim 1 or 2, comprising the steps of:
(1) immersing an MOF sample into siloxane precursor salt, and keeping the MOF sample at the temperature of 50-70 ℃ for 12-15 h; then washing the wet sample for several times by using methanol to remove redundant siloxane precursor salt, and placing the sample in a quartz tube after washing;
(2) bubbling 10-30 mL/min inert gas flow in 0.01-0.1 mol/L solution for hydrolysis, and inducing TMOS (tetramethylammonium sulfate) to hydrolyze for 24-48 h at 50-70 ℃ by using generated humid gas flow;
(3) drying the hydrolyzed product for 5-12 h, then placing the product in an inert gas flow environment of 150-200 mL/min, and carbonizing the product for 3-5 h at 600-700 ℃; and calcining the carbonized sample in an air atmosphere at 500-600 ℃ for 2-5 h to obtain the alkali metal poisoning resistant VOCs catalytic combustion catalyst.
4. The method according to claim 3, wherein the MOF in step (1) is a Co-metal-centered MOF selected from the group consisting of Co-CAT-1, Co-ZIF-67 and Co-MOF-74.
5. The method according to claim 3, wherein the siloxane precursor salt in step (1) is Tetramethylsiloxane (TMOS) or Tetraethylsiloxane (TEOS).
6. The method according to claim 3, wherein the inert gas in the step (2) is nitrogen or helium.
7. The method according to claim 3, wherein the solution in the step (2) is deionized water, or an acid solution or an alkali solution.
8. The method according to claim 3, wherein the solution in the bubble hydrolysis in the step (2) is HCl with a concentration of 0.01 to 0.1 mol/L.
9. The method according to claim 3, wherein in the step (3), the temperature increase rate is 1 to 3 ℃/min during the carbonization and calcination.
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Cited By (2)
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| CN113270599A (en) * | 2021-05-25 | 2021-08-17 | 西安交通大学 | Electrode catalyst, composite electrode and preparation process thereof |
| CN116422363A (en) * | 2022-12-06 | 2023-07-14 | 有研资源环境技术研究院(北京)有限公司 | Preparation method of hydrophobic Pd-based catalyst and hydrophobic Pd-based catalyst |
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