CN1102430C - Preparation method of catalyst for methane reforming reaction by using carbon dioxide - Google Patents
Preparation method of catalyst for methane reforming reaction by using carbon dioxide Download PDFInfo
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- CN1102430C CN1102430C CN00106166A CN00106166A CN1102430C CN 1102430 C CN1102430 C CN 1102430C CN 00106166 A CN00106166 A CN 00106166A CN 00106166 A CN00106166 A CN 00106166A CN 1102430 C CN1102430 C CN 1102430C
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- zro
- alcogel
- carbon dioxide
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 19
- 238000006057 reforming reaction Methods 0.000 title claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000001376 precipitating effect Effects 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 238000000352 supercritical drying Methods 0.000 abstract description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 4
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 229910006213 ZrOCl2 Inorganic materials 0.000 abstract 1
- 239000007809 chemical reaction catalyst Substances 0.000 abstract 1
- 229910021641 deionized water Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 21
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000002407 reforming Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 235000015110 jellies Nutrition 0.000 description 3
- 239000008274 jelly Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a preparing method of a methane reaction catalyst through the reformation of carbon dioxide. Firstly, zirconium oxychloride is prepared into water solutions, ammonia water is used as precipitating agents, and prepared ZrOCl2 water solutions are dripped into the precipitating agents to be rested and aged and are washed by deionized water. Then, the washing is carried out for many times by absolute alcohol to obtain alcohol gel, the alcohol gel is dried and roasted to obtain ultra-fine ZrO2 powder, and a ZrO2 carrier is dipped into nickel nitrate to be stirred, dried and roasted to obtain the catalyst of the present invention. The present invention has the advantages of simple preparation method, easy and simple operation and simple device, and can achieve the effect that a similar catalyst which is obtained through supercritical drying is obtained.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method of preparing synthetic gas by reforming methane with carbon dioxide, belong to the chemical catalyst preparing technical field.
Background technology
Because ZrO
2Itself have acidity, alkalescence and oxidation, reducing property simultaneously and be widely used in catalysis technical field (Materials Chem.Phys., 1985,133:47).ZrO
2Both can be used as catalyst use separately (Catal.Today, 1994,20:185), can be used as catalyst carrier again.For example: Japan Patent 4613700 reports, ZrO
2Can be used as the catalyst of aromatic carboxylic acid hydrogenation preparing aldehyde, right-p t butylbenzoic acid and right-corresponding aldehyde of methyl benzoic acid hydrogenation preparing have been realized industrialization; German patent DE 9400513 reports, Pt/ZrO
2The catalyst that is used for preparing synthetic gas by reforming methane with carbon dioxide can use continuously 500 hours and keeps active constant.In addition, because nano material has high density surface lattice defect and high surface energy, has higher activity during as catalyst; The high-ratio surface that nano material had makes it be well suited for as catalyst carrier again.And nanoscale ZrO
2Both had ZrO
2Characteristic itself has the characteristic of nano material again, will inevitably embody its unique advantages during as catalyst carrier.The ultra-fine ZrO of this invention person's colloidal sol-gel of report employing once-supercritical fluid drying preparation in Chinese patent CN 1234366A
2When (～6nm) is used as the catalyst carrier of preparing synthetic gas by reforming methane with carbon dioxide, under the situation of high nickel loading, have high reaction activity and high, and catalyst is active in decline after using 600 hours, has favorable industrial application prospect.But supercritical drying need under high pressure carry out, and equipment is required harshness, has increased the cost and the technical difficulty of catalyst.Therefore, develop a kind of operating process easy, equipment is required simple ultra-fine ZrO
2The preparation method, for Ni/ZrO
2The practicability of catalyst has very important realistic meaning.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of catalyst for methane reforming reaction by using carbon dioxide, at first prepare ultra-fine ZrO
2, again with the ultra-fine ZrO of the present invention preparation
2, as the preparing carriers catalyst, and make the preparation method both easy and simple to handle, equipment is simple, can reach again and the resulting ZrO of supercritical drying
2Effect with similar supported nickel catalyst.
The preparation method of the catalyst for methane reforming reaction by using carbon dioxide that the present invention proposes comprises following each step:
The commodity zirconium oxychloride ZrOCl that 1, will contain the crystallization water
28H
2It is that the aqueous solution of 0.05～0.5mol/L is standby that O is mixed with concentration, is that 25% commodity ammoniacal liquor dilution is made precipitating reagent for 2～15 times with concentration, under the condition of continuous stirring, with the speed of 1～20ml/min with the ZrOCl for preparing
2The aqueous solution is added drop-wise in this precipitating reagent, and the final pH value of controlling solution simultaneously is between 9～13.Perhaps precipitating reagent ammoniacal liquor is added drop-wise to ZrOCl
2In the aqueous solution, the final pH value of controlling solution simultaneously is between 3～10.Dropwise the back and continue to stir 0.5～4 hour, left standstill aging 3～12 hours, obtain ZrO (OH)
2/ Zr (OH)
4The hydrosol.
2, first step gained sediment is filtered, and spend deionised water to there not being Cl
-Till, then for several times, get alcogel with absolute ethanol washing.
3, the alcogel that second step was obtained is at mobile N
2In the atmosphere, 100～800 ℃ of following drying/roastings obtain required ultra-fine ZrO
2Powder.Perhaps the second step gained alcogel is placed there-necked flask, and add certain amount of organic solvent with the ratio of 2～20ml/ (g-alcogel), 70～120 ℃ of backflow boilings 2～100 hours, suction filtration or centrifugation went out alcogel, then the N of flowing
2In the atmosphere, 100～800 ℃ of drying/roastings obtain ultra-fine ZrO
2Powder.The ultra-fine ZrO of gained under different drying/sintering temperatures
2Specific surface and particle size shown in subordinate list 1.
4, with ZrO
2Carrier impregnation is 5～10% nickel nitrates (Ni (NO in concentration
3)
26H
2O) in the solution, stirring at room is after 2 hours, and rotary evaporation is to doing.And then dry, roasting, 12～16 hours drying times, 100～200 ℃ of baking temperatures, roasting time 3～10 hours, 400～800 ℃ of sintering temperatures.
The catalyst of the present invention's preparation added an amount of α-Al before using
2O
3Make diluent, and under 700 ℃, use H
2: N
2The gaseous mixture that is 1: 9 reduced 3～13 hours, can use.
ZrO of the present invention
2Presoma can be ZrOCl
2, ZrO (NO
3)
2And various hydrates, other inorganic salts that also can be zirconium are (as ZrCl
4, Zr (NO
3)
4) etc.), the present invention preferentially uses ZrOCl
28H
2O.The precursor of active component nickel can be hydration Ni (NO
3)
2, also can be other inorganic salts or the organic salt of nickel, the present invention preferentially uses Ni (NO
3)
26H
2O.
Ni/ZrO of the present invention
2Catalyst, catalytic performance is much better than the conventional oxide nickel-loaded (as Ni/Al under identical reaction condition
2O
3Deng) catalyst, Ni/ZrO
2When catalyst is used for methane reforming reaction by using carbon dioxide, at 757 ℃, CO
2: CH
4=1: 1, under the reaction condition of WHSV=24000ml/g-cath, can be at the conversion ratio of keeping methane and carbon dioxide basically near the equilibrium conversion value, the selectivity of synthesis gas is reached more than 90%, catalyst uses continuously more than 1100 hours and does not have deactivation phenomenom, has favorable industrial application prospect.The invention will be further described below by embodiment, but embodiments of the present invention are not limited to following embodiment.
Description of drawings
Fig. 1 is Ni/ZrO of the present invention
2CH on the catalyst
4Conversion ratio is with the variation relation curve in reaction time.
The specific embodiment
Introduce embodiments of the invention below.
Embodiment 1: take by weighing 13.7g ZrOCl
2GH
2O is mixed with the aqueous solution of 0.17M, and the ammoniacal liquor dilution with 25% places beaker as precipitating reagent for 10 times, under vigorous stirring, slowly splashes into ZrOCl
2The aqueous solution, and control pH value of solution value is 10, after dropwising, continues to stir 0.5 hour, aging 2 hours then, filters, and spends deionised water to there not being Cl
-Till, use absolute ethanol washing twice again, after suction filtration or the centrifugation, alcogel is placed quartz ampoule, under 270 ℃, with the logical N of flow velocity of 30ml/min
2Dry 3 hours, make ultra-fine ZrO
2Carrier.Take by weighing a certain amount of Ni (NO
3)
26H
2O is mixed with 10% the aqueous solution, with this Ni (NO
3)
2The ultra-fine ZrO that solution impregnation 2g prepares
2Carrier, stirring at room be after 2 hours, and rotary evaporation is to doing, and 110 ℃ of dryings 12 hours.Dried sample moves into Muffle furnace 650 ℃ of roastings 5 hours, makes nickel content and be 10～15% Ni/ZrO
2Catalyst.With this catalyst α-Al
2O
3After 2: 5 dilution proportion, grind compressing tablet, be broken into 20～40 purpose particles, getting 700mg, to place internal diameter be the quartz tube reactor of 10ml, carries out the evaluation of preparing synthetic gas by reforming methane with carbon dioxide reactivity on self-built atmospheric fixed bed flow reactor.Catalyst is used H before reaction
2/ N
2The gaseous mixture of (1: 9) is warming up to 757 ℃ then in 700 ℃ of reduction 3 hours.Under normal pressure, with the flow velocity of 80ml/min with CO
2/ CH
4(1: 1) feeds reactor, air speed GHSV=2.4 * 10
4Ml/g-cath, gas chromatographic detection tail gas is formed.Reaction result shows that the initial conversion of methane and carbon dioxide is respectively 83.6% and 85.7%, and catalyst used 200 hours continuously, and is active in decline.
Embodiment 2: carrier ZrO
2Preparation, Ni/ZrO
2Preparation of catalysts and activity rating method are with embodiment 1, and different is that alcogel is at N
2Drying/sintering temperature is 650 ℃ in the atmosphere.Reaction result shows that the initial conversion of methane and carbon dioxide is respectively 84.2% and 85.9%, and catalyst used 200 hours continuously, and is active in decline.
Embodiment 3: carrier ZrO
2Preparation, Ni/ZrO
2Preparation of catalysts and activity rating method are with embodiment 1, and different is that alcogel is at N
2Drying/sintering temperature is 350 ℃ in the atmosphere.Reaction result shows, the initial conversion of methane and carbon dioxide is near equilibrium conversion, and catalyst used 1100 hours continuously, and is active in decline, and relation curve is as shown in Figure 1 over time for methane conversion.
Comparative example:
Comparative example 1:ZrO
2The preparation method of alcogel is with embodiment 1, and different is the drying employing supercritical drying of alcogel, is about to alcogel and places autoclave, adds the 15ml absolute ethyl alcohol, logical N
2To the still internal pressure be 80atm, be warming up to 270 ℃ and kept 1 hour, cooling, pressure release, logical N
2To remove ethanol in the still, obtain ultra-fine ZrO
2Powder, particle diameter 5.7nm, specific surface 160m
2/ g.Ni/ZrO
2Preparation of catalysts and activity rating method are with embodiment 1.Reaction result shows that the initial conversion of methane and carbon dioxide is near equilibrium conversion, and catalyst is active in decline after using 600 hours.
Comparative example 2: take by weighing 13.7g ZrOCl
28H
2O is mixed with the aqueous solution of 0.17M, and the ammoniacal liquor dilution with 25% places beaker as precipitating reagent for 10 times, under vigorous stirring, slowly splashes into ZrOCl
2The aqueous solution, and control pH value of solution value is 10, after dropwising, continues to stir 0.5 hour, aging 2 hours then, and spend deionised water to there not being Cl
-Till, after suction filtration or the centrifugation, put into 110 ℃ of dryings of baking oven 12 hours, obtain the conventional ZrO of particle diameter at 30～100nm
2Powder.With this ZrO
2Be catalyst carrier, nickel catalyst carried preparation and activity rating method are with embodiment 1.Reaction result shows that the initial conversion of methane is 87%, but after using 50 hours, methane conversion drops to 60%.
The baking temperature of subordinate list 1 alcogel is to ZrO
2The influence of specific surface and particle diameter
| Baking temperature (℃) | 110 270 350 420 500 650 |
| Specific surface (m 2/ g) particle diameter (nm) | 360 353 186 94 60 35 jelly jelly jelly 7-12 10-15 15-25 |
Claims (2)
1, a kind of preparation method of catalyst for methane reforming reaction by using carbon dioxide is characterized in that, this method comprises following each step:
(1) will contain the commodity zirconium oxychloride ZrOCl of the crystallization water
28H
2It is that the aqueous solution of 0.05～0.5mol/L is standby that O is mixed with concentration, is that 25% commodity ammoniacal liquor dilution is made precipitating reagent for 2～15 times with concentration, under the condition of continuous stirring, with the speed of 1～20ml/min with the ZrOCl for preparing
2The aqueous solution is added drop-wise in this precipitating reagent, and the final pH value of controlling solution simultaneously perhaps is added drop-wise to ZrOCl with precipitating reagent ammoniacal liquor between 8～11
2In the aqueous solution, the final pH value of controlling solution simultaneously dropwises the back and continues to stir 0.5～4 hour between 8～11, leaves standstill aging 3～12 hours, obtains ZrO (OH)
2/ Zr (OH)
4The hydrosol;
(2) first step gained sediment is filtered, and spend deionised water to there not being Cl
-Till, then for several times, get alcogel with absolute ethanol washing;
(3) alcogel that second step was obtained is at mobile N
2In the atmosphere, 100～800 ℃ of following drying and roastings 3 hours obtain required ultra-fine ZrO
2Powder;
(4) with ZrO
2Carrier impregnation is in 5～10% nickel nitrate solutions in concentration, after the stirring at room 2 hours, rotary evaporation is to doing, and then dry, roasting, 12～16 hours drying times, 100～200 ℃ of baking temperatures, roasting time 3～10 hours, 400～800 ℃ of sintering temperatures are catalyst for methane reforming reaction by using carbon dioxide.
2, a kind of preparation method of catalyst for methane reforming reaction by using carbon dioxide is characterized in that, this method comprises following each step:
(1) will contain the commodity zirconium oxychloride ZrOCl of the crystallization water
2GH
2It is that the aqueous solution of 0.05～0.5mol/L is standby that O is mixed with concentration, is that 25% commodity ammoniacal liquor dilution is made precipitating reagent for 2～15 times with concentration, under the condition of continuous stirring, with the speed of 1～20ml/min with the ZrOCl for preparing
2The aqueous solution is added drop-wise in this precipitating reagent, and the final pH value of controlling solution simultaneously perhaps is added drop-wise to ZrOCl with precipitating reagent ammoniacal liquor between 8～11
2In the aqueous solution, the final pH value of controlling solution simultaneously dropwises the back and continues to stir 0.5～4 hour between 8～11, leaves standstill aging 3～12 hours, obtains ZrO (OH)
2/ Zr (OH)
4The hydrosol;
(2) first step gained sediment is filtered, and spend deionised water to there not being Cl
-Till, then for several times, get alcogel with absolute ethanol washing;
(3) the second step gained alcogel is placed there-necked flask, and add a certain amount of ethanol with the ratio of 2～20ml/ (g-alcogel), 70～120 ℃ of backflow boilings 2～100 hours, suction filtration or centrifugation went out alcogel, then the N of flowing
2In the atmosphere, 100～800 ℃ of drying and roastings 3 hours obtain ultra-fine ZrO
2Powder;
(4) with ZrO
2Carrier impregnation is 5～10% nickel nitrates (Ni (NO in concentration
3)
26H
2O) in the solution, stirring at room is after 2 hours, and rotary evaporation is to doing.And then dry, roasting, 12～16 hours drying times, 100～200 ℃ of baking temperatures, roasting time 3～10 hours, 400～800 ℃ of sintering temperatures are catalyst for methane reforming reaction by using carbon dioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00106166A CN1102430C (en) | 2000-04-28 | 2000-04-28 | Preparation method of catalyst for methane reforming reaction by using carbon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00106166A CN1102430C (en) | 2000-04-28 | 2000-04-28 | Preparation method of catalyst for methane reforming reaction by using carbon dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1268394A CN1268394A (en) | 2000-10-04 |
| CN1102430C true CN1102430C (en) | 2003-03-05 |
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|---|---|---|---|
| CN00106166A Expired - Fee Related CN1102430C (en) | 2000-04-28 | 2000-04-28 | Preparation method of catalyst for methane reforming reaction by using carbon dioxide |
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| CN (1) | CN1102430C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100417597C (en) * | 2003-06-25 | 2008-09-10 | 中国科学院山西煤炭化学研究所 | Method for preparing nano ZrO2 by drying supercritical CO2 liquid |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100441293C (en) * | 2005-09-26 | 2008-12-10 | 天津大学 | Supported nickel catalyst for synthesizing chlora aniline by hydrogenation of chloronitrobenzene and its preparation method thereof |
| CN107890870B (en) * | 2017-10-25 | 2020-05-19 | 太原理工大学 | Catalyst for preparing methane from carbon dioxide and water, preparation method and application thereof |
| CN110479231A (en) * | 2019-09-05 | 2019-11-22 | 中国科学院青岛生物能源与过程研究所 | A kind of preparation method for the catalyst adding hydrogen for alpha, beta-unsaturated aldehyde selection |
| CN110586064B (en) * | 2019-09-27 | 2023-03-31 | 天津大学 | Lithium-doped zirconium oxide loaded indium oxide catalyst and preparation method and application thereof |
| CN112717939B (en) * | 2021-01-06 | 2023-02-10 | 中国船舶重工集团公司第七一九研究所 | Emulsion Ni/ZrO for catalytic hydrogenation upgrading of caprylic acid 2 Process for preparing catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5380691A (en) * | 1989-05-10 | 1995-01-10 | Rhone-Poulenc Chimie | Catalytic microporous zirconia particulates |
-
2000
- 2000-04-28 CN CN00106166A patent/CN1102430C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5380691A (en) * | 1989-05-10 | 1995-01-10 | Rhone-Poulenc Chimie | Catalytic microporous zirconia particulates |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100417597C (en) * | 2003-06-25 | 2008-09-10 | 中国科学院山西煤炭化学研究所 | Method for preparing nano ZrO2 by drying supercritical CO2 liquid |
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| CN1268394A (en) | 2000-10-04 |
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