CN112958163A - Porous ceramic carrier catalyst coating method - Google Patents
Porous ceramic carrier catalyst coating method Download PDFInfo
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- CN112958163A CN112958163A CN202110219015.7A CN202110219015A CN112958163A CN 112958163 A CN112958163 A CN 112958163A CN 202110219015 A CN202110219015 A CN 202110219015A CN 112958163 A CN112958163 A CN 112958163A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 239000000919 ceramic Substances 0.000 title claims abstract description 41
- 238000000576 coating method Methods 0.000 title claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000010926 purge Methods 0.000 claims abstract description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 24
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 14
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 12
- 239000005751 Copper oxide Substances 0.000 claims description 12
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 12
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 12
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 12
- 229910000431 copper oxide Inorganic materials 0.000 claims description 12
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 12
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 12
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 description 7
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
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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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The application discloses a porous ceramic carrier catalyst coating method. The method comprises the following steps: step (1) SiO with the mass fraction of 65-70 percent215-20% of Al by mass2O3And MeO with the mass fraction of 10-15%XAfter mixing, calcining at the temperature of 1200-1300 ℃ until the mixture is molten to obtain mixed molten slurry; step (2) immersing the porous ceramic carrier in the mixed molten slurry obtained in the step (1) for 1-3min, and then taking out to obtain a primary carrier; step (3) purging the primary carrier in the step (2) for 1-3min by using gas with the pressure of 10-20Mpa, and then transferring the primary carrier to water for standing for 10-15min to obtain a secondary carrier; and (4) curing the secondary carrier in the step (3) for 12-16h to obtain the porous ceramic carrier coated with the catalyst. The catalyst prepared by the method can improve the water content in the temperature of 350-450 DEG CWhen gas with the amount of 35-50% is used for catalysis, the catalytic performance of the catalyst is reduced.
Description
Technical Field
The application relates to the technical field of catalysts, in particular to a porous ceramic carrier catalyst coating method.
Background
The catalyst can change the chemical reaction rate of reactants in a chemical reaction without changing the chemical balance, and the property of the catalyst is not changed. However, when the catalyst catalyzes a gas having a high water content, water molecules occupy active components on the catalyst, and inhibit catalytic binding of the catalyst to chemical reactants, thereby inhibiting the activity of the catalyst. The catalytic performance of the existing catalyst is reduced when the existing catalyst is catalyzed by gas with higher temperature and more moisture content.
Disclosure of Invention
In order to solve the problem that the catalytic performance of the catalyst is reduced when the catalyst is catalyzed by gas with the temperature of 350-450 ℃ and the moisture volume content of 35-50 percent, the application provides a coating method of a porous ceramic carrier catalyst.
The application provides a porous ceramic carrier catalyst coating method which adopts the following technical scheme:
a porous ceramic support catalyst coating method, comprising the steps of:
step (1) SiO with the mass fraction of 65-70 percent215-20% of Al by mass2O3And MeO with the mass fraction of 10-15%XAfter mixing, calcining at the temperature of 1200-1300 ℃ until the mixture is molten to obtain mixed molten slurry;
step (2) immersing the porous ceramic carrier in the mixed molten slurry obtained in the step (1) for 1-3min, and then taking out to obtain a primary carrier;
step (3) purging the primary carrier in the step (2) for 1-3min by using gas with the pressure of 10-20Mpa, and then transferring the primary carrier to water for standing for 10-15min to obtain a secondary carrier;
and (4) curing the secondary carrier in the step (3) for 12-16h to obtain the porous ceramic carrier coated with the catalyst.
By adopting the technical scheme, in the step (1), SiO is added2、Al2O3And MeOXMixing and heating to melt to make SiO2、Al2O3And MeOXMutually blending; the porous ceramic carrier has a porous structure and further has a large specific surface area, and in the step (2), the porous ceramic carrier is immersed in the mixed molten slurry, so that the surface of the porous ceramic carrier can be coated with more mixed molten slurry; in the step (3), the surface is coated with a mixture of the molten slurryBlowing the porous carrier by using gas to quickly cool and solidify the mixed molten slurry, solidifying the mixed molten slurry on the surface of the porous carrier, and then placing the porous carrier in water for standing to obtain a secondary carrier; and (4) curing the secondary carrier to obtain the porous ceramic carrier coated with the catalyst.
Preferably, in the step (1), the MeOXIs one or more of manganese oxide, copper oxide, cerium oxide, chromium oxide, nickel oxide and iron oxide.
Preferably, in the step (3), the gas contains 15-20% of oxygen component by volume fraction.
Preferably, in the step (4), the secondary carrier is maintained in an environment with the temperature of 800-.
In summary, the porous ceramic catalyst carrier prepared by the method of the present application has a structure with silane groups surrounding the catalyst core, and when the gas with the temperature of 350-.
Detailed Description
The present application will be described in further detail with reference to examples and comparative examples.
Examples
Example 1
In this example 1, a method for coating a porous ceramic supported catalyst includes the following steps:
step (1) preparing SiO with the mass fraction of 65%220% by mass of Al2O3And 15% by mass of MeOXAfter mixing, calcining at 1250 ℃ until the mixture is molten to obtain mixed molten slurry; the MeOXThe composite material is a composition of manganese oxide, copper oxide, cerium oxide, chromium oxide, nickel oxide and iron oxide, and the mass fraction ratio of the manganese oxide, the copper oxide, the cerium oxide, the chromium oxide, the nickel oxide and the iron oxide is 1: 1: 1: 1: 1: 1;
step (2) immersing the porous ceramic carrier in the mixed molten slurry obtained in the step (1) for 2min, and then taking out to obtain a primary carrier;
using gas with the pressure of 15MPa and the oxygen content of 17% by volume in the step (3), purging the primary carrier in the step (2) for 2min, and then transferring the primary carrier to water at room temperature for standing for 12min to obtain a secondary carrier;
and (4) curing the secondary carrier in the step (3) for 14 hours in an environment with the temperature of 850 ℃ and the moisture content of 25% to obtain the porous ceramic carrier coated with the catalyst.
Example 2
In this example 2, a method for coating a porous ceramic supported catalyst includes the following steps:
step (1) adding 70% of SiO by mass215% by mass of Al2O3And 15% by mass of MeOXAfter mixing, calcining at 1300 ℃ until the mixture is molten to obtain mixed molten slurry; the MeOXThe composite material is a composition of manganese oxide, copper oxide, cerium oxide, chromium oxide, nickel oxide and iron oxide, and the mass fraction ratio of the manganese oxide, the copper oxide, the cerium oxide, the chromium oxide, the nickel oxide and the iron oxide is 1: 1: 1: 1: 1: 1;
step (2) immersing the porous ceramic carrier in the mixed molten slurry obtained in the step (1) for 3min, and then taking out to obtain a primary carrier;
using gas with the pressure of 10MPa and the oxygen content of 20% by volume in the step (3), purging the primary carrier in the step (2) for 3min, and then transferring the primary carrier to water at room temperature for standing for 10min to obtain a secondary carrier;
and (4) curing the secondary carrier in the step (3) for 16 hours in an environment with the temperature of 900 ℃ and the moisture content of 30% to obtain the porous ceramic carrier coated with the catalyst.
Example 3
In this example 3, a method for coating a porous ceramic supported catalyst includes the following steps:
step (1) adding 70% of SiO by mass220% by mass of Al2O3And 10% by mass of MeOXMixing, calcining at 1200 deg.C to melt to obtainMixing the molten slurry; the MeOXThe composite material is a composition of manganese oxide, copper oxide, cerium oxide, chromium oxide, nickel oxide and iron oxide, and the mass fraction ratio of the manganese oxide, the copper oxide, the cerium oxide, the chromium oxide, the nickel oxide and the iron oxide is 1: 1: 1: 1: 1: 1;
step (2) immersing the porous ceramic carrier in the mixed molten slurry obtained in the step (1) for 1min, and then taking out to obtain a primary carrier;
using gas with the pressure of 20MPa and the oxygen content of 15% by volume in the step (3), purging the primary carrier in the step (2) for 1min, and then transferring the primary carrier to water at room temperature for standing for 15min to obtain a secondary carrier;
and (4) curing the secondary carrier in the step (3) for 12 hours in an environment with the temperature of 800 ℃ and the moisture content of 20 percent to obtain the porous ceramic carrier coated with the catalyst.
Example 4
In this example 4, a method for coating a porous ceramic supported catalyst includes the following steps:
step (1) adding 67% of SiO by mass218% by mass of Al2O3And 15% by mass of MeOXAfter mixing, calcining at 1260 ℃ until the mixture is molten to obtain mixed molten slurry; the MeOXThe composite material is a composition of manganese oxide, copper oxide, cerium oxide, chromium oxide, nickel oxide and iron oxide, and the mass fraction ratio of the manganese oxide, the copper oxide, the cerium oxide, the chromium oxide, the nickel oxide and the iron oxide is 1: 1: 1: 1: 1: 1;
step (2) immersing the porous ceramic carrier in the mixed molten slurry obtained in the step (1) for 2min, and then taking out to obtain a primary carrier;
using gas with the pressure of 17MPa and the oxygen content of 15% by volume in the step (3), purging the primary carrier in the step (2) for 2min, and then transferring the primary carrier to water at room temperature for standing for 13min to obtain a secondary carrier;
and (4) curing the secondary carrier in the step (3) for 12 hours in an environment with the temperature of 870 ℃ and the moisture content of 23 percent to obtain the porous ceramic carrier coated with the catalyst.
Example 5
In this example 5, a method for coating a porous ceramic supported catalyst includes the following steps:
step (1) adding 68% of SiO by mass219% by mass of Al2O3And 13% by mass of MeOXAfter mixing, calcining at 1270 ℃ until the mixture is molten to obtain mixed molten slurry; the MeOXThe composite material is a composition of manganese oxide, copper oxide, cerium oxide, chromium oxide, nickel oxide and iron oxide, and the mass fraction ratio of the manganese oxide, the copper oxide, the cerium oxide, the chromium oxide, the nickel oxide and the iron oxide is 1: 1: 1: 1: 1: 1;
step (2) immersing the porous ceramic carrier in the mixed molten slurry obtained in the step (1) for 2min, and then taking out to obtain a primary carrier;
using gas with the pressure of 20MPa and the oxygen content of 15% by volume in the step (3), purging the primary carrier in the step (2) for 2min, and then transferring the primary carrier to water at room temperature for standing for 15min to obtain a secondary carrier;
and (4) curing the secondary carrier in the step (3) for 15 hours in an environment with the temperature of 840 ℃ and the moisture content of 24 percent to obtain the porous ceramic carrier coated with the catalyst.
Performance test
Test method
The catalyst-coated porous ceramic supports obtained in examples 1 to 5 were placed at temperatures of 350 ℃, 400 ℃ and 450 ℃ at a mass concentration of 100ng/Nm of gas-phase dioxin3The mass concentration of gas-phase dioxin after 5 hours of reaction was detected in an environment of 40% moisture content and an airspeed of 20000h-1, and the catalytic performance of the porous ceramic carrier coated with the catalyst was calculated, and the results are shown in table 1.
Catalytic performance ═ mass concentration of dioxin before reaction-mass concentration of dioxin after reaction ÷ concentration of dioxin before reaction × 100%
TABLE 1 catalytic Properties of catalyst-coated porous ceramic Supports in examples 1-5 of the present application
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Catalytic performance at 350% | 92.31 | 92.78 | 91.34 | 92.45 | 91.89 |
| Catalytic performance at 400% | 93.28 | 93.17 | 91.76 | 92.79 | 92.14 |
| Catalytic performance at 450% | 93.49 | 93.41 | 92.04 | 93.14 | 92.35 |
In combination with examples 1-5, and in combination with Table 1, it can be seen that the catalyst coated porous ceramic supports prepared herein have good catalytic properties.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (4)
1. A method of coating a porous ceramic supported catalyst, the method comprising the steps of:
step (1) SiO with the mass fraction of 65-70 percent215-20% of Al by mass2O3And MeO with the mass fraction of 10-15%XAfter mixing, calcining at the temperature of 1200-1300 ℃ until the mixture is molten to obtain mixed molten slurry;
step (2) immersing the porous ceramic carrier in the mixed molten slurry obtained in the step (1) for 1-3min, and then taking out to obtain a primary carrier;
step (3) purging the primary carrier in the step (2) for 1-3min by using gas with the pressure of 10-20Mpa, and then transferring the primary carrier to water for standing for 10-15min to obtain a secondary carrier;
and (4) curing the secondary carrier in the step (3) for 12-16h to obtain the porous ceramic carrier coated with the catalyst.
2. The method of claim 1, wherein the step of coating the porous ceramic support catalyst comprises: in the step (1), the MeOXIs one or more of manganese oxide, copper oxide, cerium oxide, chromium oxide, nickel oxide and iron oxide.
3. The method of claim 1, wherein the step of coating the porous ceramic support catalyst comprises: in the step (3), the gas contains 15-20% of oxygen component by volume fraction.
4. The method of claim 1, wherein the step of coating the porous ceramic support catalyst comprises: in the step (4), the secondary carrier is maintained in an environment with the temperature of 800-.
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| CN202110219015.7A CN112958163A (en) | 2021-02-26 | 2021-02-26 | Porous ceramic carrier catalyst coating method |
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| CN202110219015.7A CN112958163A (en) | 2021-02-26 | 2021-02-26 | Porous ceramic carrier catalyst coating method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112958109A (en) * | 2021-02-26 | 2021-06-15 | 上海大学材料基因组工程(萍乡)研究院 | Preparation and application method of high-efficiency catalytic carrier |
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| CN112958109A (en) * | 2021-02-26 | 2021-06-15 | 上海大学材料基因组工程(萍乡)研究院 | Preparation and application method of high-efficiency catalytic carrier |
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Application publication date: 20210615 |