CN111545203A - Preparation method of reverse water gas spherical copper-based alumina catalyst - Google Patents
Preparation method of reverse water gas spherical copper-based alumina catalyst Download PDFInfo
- Publication number
- CN111545203A CN111545203A CN202010364015.1A CN202010364015A CN111545203A CN 111545203 A CN111545203 A CN 111545203A CN 202010364015 A CN202010364015 A CN 202010364015A CN 111545203 A CN111545203 A CN 111545203A
- Authority
- CN
- China
- Prior art keywords
- copper
- water gas
- spherical
- copper nitrate
- preparation
- 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.)
- Withdrawn
Links
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 239000010949 copper Substances 0.000 title claims abstract description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 238000010926 purge Methods 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 239000005750 Copper hydroxide Substances 0.000 claims description 4
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- -1 zinc aluminate Chemical class 0.000 description 1
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
- B01J23/72—Copper
-
- 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
-
- B01J35/51—
-
- B01J35/613—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
Abstract
The invention discloses a preparation method of a reverse water gas spherical copper-based alumina catalyst, which is used for obtaining a spherical copper-based alumina supported catalyst with uniform particle size, is safe and easily available in raw material medicament, is used for reverse water gas catalysis, shows higher catalytic reaction activity and CO at a lower temperature of 375 ℃, and is used for reverse water gas catalysis2The conversion rate reaches 68%, and the material has special value for reverse water gas reaction and water gas conversion reaction.
Description
Technical Field
The invention belongs to the field of chemical industry, and relates to a preparation method of a reverse water gas spherical copper-based alumina catalyst.
Background
The Water Gas (WGS) shift reaction has been studied for nearly a century with a relatively mature process. The reverse water gas shift Reaction (RWGS) can utilize abundant and cheap carbon dioxide as a carbon source, utilize carbon monoxide generated by the RWGS reaction as an intermediate product, and adopt an F-T synthesis method to prepare olefin; ethanol can also be produced using RWGS. The CAMERE process, which is currently widely used for the production of methanol, wherein the RWGS reaction at high temperature is the key step, the higher the carbon monoxide conversion, the more beneficial the methanol synthesis. Therefore, a high stability catalyst is critical for the CAMERE reaction.
The traditional RWGS catalyst mainly comprises zinc aluminate catalyst and Pt/CeO2Catalysts, copper-based catalysts, manganese-based catalysts, and the like. Most of the catalysts contain noble metals, so the cost is high, and the catalysts are not suitable for large-scale industrial popularization. And the iron catalyst developed recently cannot be popularized on a large scale at present because of low catalytic efficiency.
Disclosure of Invention
In order to overcome the defects, the invention aims to provide a preparation method of a reverse water gas spherical copper-based alumina catalyst, the spherical copper-based alumina supported catalyst with uniform particle size can be obtained by the method, and raw material medicaments used in the reverse water gas catalysis are safe and easily obtained, show higher catalytic reaction activity at lower temperature and have higher value in reducing the reverse water gas reaction and water gas conversion reaction temperature.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows:
a preparation method of a reverse water gas spherical copper-based alumina catalyst is characterized by comprising the following steps:
1) using copper nitrate Cu (NO)3)2Drying copper nitrate as an active component precursor for later use;
2) spherical alumina powder is used as a catalyst carrier, and nitrogen is used for purging for 0.5-2h at the temperature of 100-120 ℃;
3) adding spherical alumina powder into water, and stirring at the rotating speed of 120-160r/min for 3-6h to completely disperse the spherical alumina powder in the water;
4) preparing copper nitrate into a copper nitrate solution with the mass percentage of 3% -7%, wherein the mole ratio of the copper nitrate in the step 4) to the aluminum oxide in the step 3) is 2: 1-4: 1;
5) taking weak base with the molar weight of 100-150% of copper nitrate, pouring the weak base and the copper nitrate solution into the alumina slurry, stirring and heating to 70-110 ℃ at the speed of 60-100r/min, and reacting for 3-6 h;
the following reactions occur: cu2++2OH-→Cu(OH)2；
The generated copper hydroxide precipitate is rapidly enriched on the surface of the spherical alumina;
6) then rapidly freezing the mixed solution with liquid nitrogen, and drying in a freeze dryer at-15 deg.C to-5 deg.C for 12-24 hr; and roasting the dried powder at the temperature of 380-420 ℃ for 2-5h, converting the copper hydroxide into copper oxide, and obtaining the spherical copper-based alumina supported catalyst with catalytic activity.
The copper nitrate is dried for 12-24h at the temperature of 100-120 ℃ for standby.
The specific surface area of the spherical alumina powder is 20-32m2/g。
The mass percentage of the water added in the step 3) is 300-600% of the spherical alumina powder.
The method can obtain the following beneficial effects: the spherical copper-based alumina supported catalyst with uniform particle size is obtained, and the used raw material medicament is safe and easily available, is used for reverse water gas catalysis, shows higher catalytic reaction activity at lower temperature of 375 ℃, and contains CO2The conversion rate reaches 68%, and the material has special value for reverse water gas reaction and water gas conversion reaction.
Detailed Description
The following description is given with reference to specific examples:
example 1
1. Using copper nitrate Cu (NO)3)2As an active component precursor, 188g of copper nitrate is dried for 12 hours at 100 ℃ for standby.
2. 61g of spherical alumina powder (specific surface area 26 m)2The catalyst carrier is used as per gram), and the nitrogen is used for purging for 0.5h at 100 ℃.
3. The spherical alumina powder was added to 1L of water and stirred at a rate of 120r/min for 3 hours to completely disperse the spherical alumina powder in the water.
4. 188g of copper nitrate were prepared into a 3% copper nitrate solution.
5. 10g of urea and copper nitrate solution are poured into the alumina slurry, stirred and heated to 70 ℃ at the speed of 60r/min, and reacted for 6 h.
6. Then the mixed solution is quickly frozen by liquid nitrogen to prevent the spherical alumina from adhering, and is placed and dried in a freeze dryer (-5 ℃) for 24 hours. And roasting the dried powder at the temperature of 380 ℃ for 2h to obtain the spherical copper-based alumina supported catalyst.
The material shows higher catalytic reaction activity and CO at the lower temperature of 375 DEG C2The conversion rate reaches 68.3 percent.
Example 2
1. Using copper nitrate Cu (NO)3)2As an active component precursor, 94g of copper nitrate is dried for 18h at 100 ℃ for later use.
2. 30g of spherical alumina powder (specific surface area 28 m)2The catalyst carrier is used as per gram), and the nitrogen is used for purging for 2 hours at 100 ℃.
3. The spherical alumina powder was added to 500ml of water and stirred at 140r/min for 5 hours to completely disperse the spherical alumina powder in the water.
4. 500g of copper nitrate was prepared as a 5% copper nitrate solution.
5. 5g of sodium bicarbonate and copper nitrate solution are poured into the alumina slurry, stirred and heated to 80 ℃ at the speed of 80r/min, and reacted for 4 h.
6. Then the mixed solution is quickly frozen by liquid nitrogen to prevent the spherical alumina from adhering, and is placed and dried in a freeze dryer (-10 ℃) for 18 hours. And roasting the dried powder at the temperature of 400 ℃ for 3h to obtain the spherical copper-based alumina supported catalyst.
The material shows higher catalytic reaction activity and CO at the lower temperature of 375 DEG C2The conversion rate reaches 68.6 percent.
Example 3
1. Using copper nitrate Cu (NO)3)2As an active component precursor, 360g of copper nitrate is dried for 24 hours at 120 ℃ for standby.
2. 120g of spherical alumina powder (specific surface area 30 m) was taken2The catalyst carrier is used as per gram), and the nitrogen is used for purging for 0.5h at 120 ℃.
3. The spherical alumina powder was added to 2L of water and stirred at a rate of 160r/min for 6 hours to completely disperse the spherical alumina powder in the water.
4. 600g of copper nitrate were made up to a 7% copper nitrate solution.
5. 20g of ammonium bicarbonate and copper nitrate solution are poured into the alumina slurry, stirred and heated to 110 ℃ at the speed of 100r/min, and reacted for 6 h.
6. Then the mixed solution is quickly frozen by liquid nitrogen to prevent the spherical alumina from adhering, and is placed and dried in a freeze dryer (-15 ℃) for 24 hours. And roasting the dried powder at the temperature of 420 ℃ for 5 hours to obtain the spherical copper-based alumina supported catalyst.
The material shows higher catalytic reaction activity and CO at the lower temperature of 375 DEG C2The conversion rate reaches 68.4 percent.
Claims (4)
1. A preparation method of a reverse water gas spherical copper-based alumina catalyst is characterized by comprising the following steps:
1) using copper nitrate Cu (NO)3)2Drying copper nitrate as an active component precursor for later use;
2) spherical alumina powder is used as a catalyst carrier, and nitrogen is used for purging for 0.5-2h at the temperature of 100-120 ℃;
3) adding spherical alumina powder into water, and stirring at the rotating speed of 120-160r/min for 3-6h to completely disperse the spherical alumina powder in the water;
4) preparing copper nitrate into a copper nitrate solution with the mass percentage of 3% -7%, wherein the mole ratio of the copper nitrate in the step 4) to the aluminum oxide in the step 3) is 2: 1-4: 1;
5) taking weak base with the molar weight of 100-150% of copper nitrate, pouring the weak base and the copper nitrate solution into the alumina slurry, stirring and heating to 70-110 ℃ at the speed of 60-100r/min, and reacting for 3-6 h;
the following reactions occur: cu2++2OH-→Cu(OH)2；
The generated copper hydroxide precipitate is rapidly enriched on the surface of the spherical alumina;
6) then rapidly freezing the mixed solution with liquid nitrogen, and drying in a freeze dryer at-15 deg.C to-5 deg.C for 12-24 hr; and roasting the dried powder at the temperature of 380-420 ℃ for 2-5h, converting the copper hydroxide into copper oxide, and obtaining the spherical copper-based alumina supported catalyst with catalytic activity.
2. The preparation method of the reversed water gas ball type copper-based alumina catalyst according to claim 1, which is characterized in that: the copper nitrate is dried for 12-24h at the temperature of 100-120 ℃ for standby.
3. The preparation method of the reversed water gas ball type copper-based alumina catalyst according to claim 1, which is characterized in that: the specific surface area of the spherical alumina powder is 20-32m2/g。
4. The preparation method of the reversed water gas ball type copper-based alumina catalyst according to claim 1, which is characterized in that: the mass percentage of the water added in the step 3) is 300-600% of the spherical alumina powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010364015.1A CN111545203A (en) | 2020-04-30 | 2020-04-30 | Preparation method of reverse water gas spherical copper-based alumina catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010364015.1A CN111545203A (en) | 2020-04-30 | 2020-04-30 | Preparation method of reverse water gas spherical copper-based alumina catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111545203A true CN111545203A (en) | 2020-08-18 |
Family
ID=71996440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010364015.1A Withdrawn CN111545203A (en) | 2020-04-30 | 2020-04-30 | Preparation method of reverse water gas spherical copper-based alumina catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111545203A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115382544A (en) * | 2022-08-09 | 2022-11-25 | 中国科学院山西煤炭化学研究所 | Preparation and application of copper-aluminum catalyst for reverse water-gas shift reaction |
-
2020
- 2020-04-30 CN CN202010364015.1A patent/CN111545203A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115382544A (en) * | 2022-08-09 | 2022-11-25 | 中国科学院山西煤炭化学研究所 | Preparation and application of copper-aluminum catalyst for reverse water-gas shift reaction |
| CN115382544B (en) * | 2022-08-09 | 2024-01-05 | 中国科学院山西煤炭化学研究所 | Preparation and application of copper-aluminum catalyst for reverse water gas shift reaction |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110523424B (en) | Catalyst for hydrogen production based on Ru/NPC-CoxO and preparation method thereof | |
| CN112892610B (en) | Non-noble metal doped ZIF-67@ Co catalytic ammonia borane hydrolysis material and preparation and application thereof | |
| CN112973707A (en) | NiSn/C core-shell composite nano-catalyst and preparation method and application thereof | |
| CN112844403B (en) | Yttrium manganese nickel perovskite structure catalyst for autothermal reforming of acetic acid to produce hydrogen | |
| CN112246244B (en) | Preparation method and application of copper-copper oxide-copper cobaltate catalyst with adjustable oxygen vacancy content | |
| CN111545203A (en) | Preparation method of reverse water gas spherical copper-based alumina catalyst | |
| CN114029061B (en) | Bimetal efficient catalyst, preparation method and method for preparing ethanol/acetaldehyde by methane-carbon dioxide co-conversion | |
| CN103157475B (en) | For the Catalysts and its preparation method of coke-stove gas tri-reforming | |
| CN110548505A (en) | Core-shell type catalyst, synthesis method thereof and method for preparing gamma-valerolactone by catalyzing levulinic acid by core-shell type catalyst | |
| CN114100661A (en) | Catalyst for preparing hydrogen by decomposing molybdenum-based ammonia and preparation method thereof | |
| CN101623637A (en) | Catalyst Au/MnOx-CeO2 used for preferential oxidation of carbon monoxide and preparation method thereof | |
| CN116474811A (en) | High-efficiency bimetallic catalyst and application thereof in ammonia borane alcoholysis hydrogen production | |
| CN107043089B (en) | A kind of technique of the equipressure ammonia synthesis co-production containing carbon chemicals | |
| CN113967476B (en) | Perovskite supported cobalt high-efficiency catalyst, preparation method and method for preparing methanol by partial oxidation of methane | |
| CN114308093A (en) | High-load nickel-based carbide catalyst and preparation method and application thereof | |
| CN113441160B (en) | Nickel hydroxide/titanium carbide photo-thermal catalytic material and preparation method and application thereof | |
| CN115837275A (en) | Perovskite type high-entropy oxide and preparation method and application thereof | |
| CN112827510B (en) | Porous composite material for catalytic synthesis of propylene carbonate and preparation method thereof | |
| CN114229910A (en) | Calcium-iron dual-function composite oxygen carrier and large-scale preparation method thereof | |
| CN113731422A (en) | Preparation method of slurry bed methane synthesis catalyst | |
| CN1144773A (en) | Production technique of cobaltous oxide | |
| CN111470542A (en) | Preparation method of reverse water gas manganese oxide catalyst | |
| JPH0535017B2 (en) | ||
| CN107055571B (en) | A kind of gaseous hydrocarbon using after self-heating recapitalization is the isobaric Ammonia Process of raw material | |
| CN110694624A (en) | Cu and MgO-based bifunctional catalyst, 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 | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20200818 |