CN1090588C - Nickel-base catalyst for preparing synthetic gas by reforming methane with carbon dioxide and preparation method thereof - Google Patents
Nickel-base catalyst for preparing synthetic gas by reforming methane with carbon dioxide and preparation method thereof Download PDFInfo
- Publication number
- CN1090588C CN1090588C CN99107321A CN99107321A CN1090588C CN 1090588 C CN1090588 C CN 1090588C CN 99107321 A CN99107321 A CN 99107321A CN 99107321 A CN99107321 A CN 99107321A CN 1090588 C CN1090588 C CN 1090588C
- Authority
- CN
- China
- Prior art keywords
- nickel
- catalyst
- hours
- preparation
- base catalyst
- 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.)
- Expired - Fee Related
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 32
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 title claims abstract description 23
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000002407 reforming Methods 0.000 title claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 229960004756 ethanol Drugs 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 239000000017 hydrogel Substances 0.000 claims description 4
- 241000370738 Chlorion Species 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 claims description 2
- 239000000499 gel Substances 0.000 claims description 2
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 23
- 239000007789 gas Substances 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 229910052759 nickel Inorganic materials 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 abstract description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 8
- 238000007654 immersion Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 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
- 238000001833 catalytic reforming Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a nickel base catalyst for producing synthetic gases by using carbon dioxide to reform methane. The present invention is characterized in that a carrier of the catalyst is ZrO2, wherein the weight percentage of Ni is from 5% to 50%; the weight percentage of the ZrO2 is from 50% to 95%. The preparation of the catalyst adopts an immersion method, namely, ZrO2 powder is dipped into commercialized nickel nitrate with the concentration of 5% to 10% and with crystallized water to react fully, and the ZrO2 powder is evaporated, dried and roasted to obtain the catalyst of the present invention. The catalyst of the present invention can cause the conversion rate of the methane and the selectivity of the synthetic gases to reach more than 90%, and the activity of the catalyst can be stably maintained for 600 hours for a long time and can not be devitalized.
Description
The present invention relates to a kind of nickel-base catalyst and preparation method who is used for preparing synthetic gas by reforming methane with carbon dioxide, belong to chemical technology field.
Raising along with people's environmental consciousness, the utilization of greenhouse gases and control more and more receive publicity, carbonic acid gas catalytic reforming methane preparing synthetic gas can be converted into important chemical material with carbonic acid gas and these two kinds of main greenhouse gases of methane effectively, and reforming methane with carbon dioxide can make CO/H
2=1: 1 synthetic gas is compared with steam reforming methane, and the synthetic gas of this ratio is unlikely the waste that causes hydrogen source when being used for oxo process etc.Over 20 years, domestic and international investigator has dropped into great amount of manpower and material resources are studied this catalyzed reaction, but up to now, this process still differs greatly with industrialization demands.Studies show that, with precious metal Ru, Rh, the Pd even load all has high reaction activity and high and anti-carbon performance on suitable carriers the time, for example, German patent DE 9400513 reports, Pd/ZrO
2Catalyzer uses after 500 hours continuously, and reactive behavior remains unchanged substantially.But the noble metal catalyst shortcoming is to cost an arm and a leg, and does not have magnetism economically during industrialization.In base metal, nickel catalyzator has high reaction activity and high, but the carbon distribution phenomenon is serious, and carbon distribution both can cover catalyst surface and cause catalyst deactivation, also can cause reactor plugs that the catalyst bed stressor layer is risen.
The present invention seeks to develop the high and strong long lifetime nickel-base catalyst of carbon accumulation resisting ability of a kind of reactive behavior, make it when being used for preparing synthetic gas by reforming methane with carbon dioxide, can satisfy the requirement of industrialization catalyst activity and work-ing life.The high reactivity of this catalyzer not only can make carbonic acid gas and methane conversion near thermodynamic equilibrium value, and catalyzer using no obvious carbon distribution more than 600 hours, and catalyzer is still kept its initial activity at this moment.
The nickel-base catalyst that is used for preparing synthetic gas by reforming methane with carbon dioxide of the present invention's development, its carrier is ZrO
2, wherein the weight percent of Ni is 5%～50%, ZrO
2Weight percent be 50%～95%.
The preparation method who is used for the nickel-base catalyst of preparing synthetic gas by reforming methane with carbon dioxide of the present invention, be made up of the following step:
(1) will contain the commercialization zirconium oxychloride ZrOCl of crystal water
28H
2It is that the aqueous solution of 0.05～0.5mol/L is standby that O is mixed with concentration, with concentration is that the dilution of 25% commodity ammoniacal liquor is made precipitation agent for 2～15 times, in the container of above-mentioned precipitation agent is housed, under the condition of continuously stirring, with the speed of 5～20ml/min with the above-mentioned ZrOCl for preparing
2The aqueous solution is added drop-wise in the precipitation agent, and the pH value of control solution is 9～13; Dropwise the back and continue to stir 0.5～4 hour, left standstill aging 2～4 hours;
(2) (resistance is not less than 10 till having chlorion with deionized water wash with (1) gained hydrogel
-5Ω);
(3) with the water in dehydrated alcohol displacement (2) gained hydrogel, the gained gel is called alcogel;
(4) (3) gained alcogel is placed autoclave, additional proportion is: add 10～20ml dehydrated alcohol in every gram alcogel, feed exsiccant N in autoclave
2, to pressure be 60～80atm, be warming up to 260C and kept 0.5～4 hour, cooling, pressure release, logical exsiccant N
2To remove ethanol remaining in the still, obtain ultra-fine Zr0
2Powder;
(5) with above-mentioned ZrO
2It is 5～10% to have the commercialization nitric acid nickel (NO of crystal water that powder impregnated in concentration
3)
26H
2In the O solution, continuously stirring, be heated to the water distilled-to-dryness, and then 100～200 ℃ dry 12～16 hours down, at last 400～800 ℃ of following roastings 3～10 hours, be nickel-base catalyst of the present invention.
Catalyzer of the present invention in reduction with before using with quartz sand or α-Al
2O
3Oxide compound etc. inertia, thermostability is made thinner.Under 700 ℃, lead to H before using
2: N
2The gas mixture that is 1: 9 reduced 3～13 hours.
The presoma of catalyst activity component nickel of the present invention can be the inorganic salt of nickel, as nickelous nitrate etc., can be the organic salt of nickel, as nickel acetate etc.ZrO
2Presoma can be ZrOCl
2, also can be other inorganic salt of zirconium.
Ni/ZrO of the present invention
2Catalyzer is under identical reaction conditions, and catalytic performance is much better than traditional Ni/Al
2O
3Deng catalyzer, Ni/ZrO
2When catalyzer is used for methane reforming reaction by using carbon dioxide, at 750 ℃, CO
2: CH
4=1: 1, under the reaction conditions of WHSV=24000ml/g.h, the selectivity of methane conversion and synthetic gas is all reached more than 90%, catalyst activity can be steady in a long-term, keeps more than 600 hours and do not have a deactivation phenomenom.The invention will be further described below by embodiment, but embodiments of the present invention are not limited to following embodiment.
Description of drawings;
CH when Fig. 1 is to use catalyzer of the present invention
4Transformation efficiency.
Introduce embodiments of the invention below:
Embodiment 1: 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 precipitation agent for 10 times, under vigorous stirring, slowly splashes into ZrOCl
2The aqueous solution, and the control solution PH is 10, after dropwising, continue to stir 0.5 hour, aging 2 hours then, the gained throw out is filtered, and with deionized water wash to there not being Cl
-Till, use twice of absolute ethanol washing again.Alcogel is placed autoclave, add the 40ml dehydrated alcohol, logical N
2To the still internal pressure be 80atm, be warming up to 260 ℃ 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.Take by weighing Ni (NO
3)
26H
2O 2.96g is mixed with 10% the aqueous solution, with this Ni (NO
3)
2The ultra-fine ZrO that solution impregnation 2g prepares
2Carrier, 110 ℃ of dryings 12 hours, dried sample moves in the retort furnace, and 650 ℃ of roastings 5 hours make catalyzer No. 1.
Embodiment 2: take by weighing 6.5g ZrOCl
28H
2O is mixed with the aqueous solution of 0.1M, and the ammoniacal liquor dilution with 25% places beaker as precipitation agent for 10 times, under vigorous stirring, slowly splashes into ZrOCl
2The aqueous solution, and the control solution PH is 9, after dropwising, continue to stir 0.5 hour, aging 4 hours then, the gained throw out is filtered, and with deionized water wash to there not being Cl
-Till, use twice of absolute ethanol washing again.Alcogel is placed autoclave, add the 20ml dehydrated alcohol, logical N
2To the still internal pressure be 70atm, be warming up to 260 ℃ and kept 1 hour, cooling, pressure release, logical N
2To remove ethanol in the still, obtain ultra-fine ZrO
2Powder.Take by weighing Ni (NO
3)
26H
2O 1.48g is mixed with 10% the aqueous solution, with this Ni (NO
3)
2The ultra-fine ZrO that solution impregnation 1g prepares
2Carrier, 110 ℃ of dryings 12 hours, dried sample moves in the retort furnace, and 650 ℃ of roastings 5 hours make catalyzer No. 2.
Embodiment 3: 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 precipitation agent for 10 times, under vigorous stirring, slowly splashes into ZrOCl
2The aqueous solution, and the control solution PH is 10, after dropwising, continue to stir 0.5 hour, aging 2 hours then, the gained throw out is filtered, and with deionized water wash to there not being Cl
-Till, use twice of absolute ethanol washing again.Alcogel is placed autoclave, add the 40ml dehydrated alcohol, logical N
2To the still internal pressure be 80atm, be warming up to 260 ℃ 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.Take by weighing Ni (NO
3)
26H
2O 1g is mixed with 5% the aqueous solution, with this Ni (NO
3)
2The ultra-fine ZrO that solution impregnation 1g prepares
2Carrier, 110 ℃ of dryings 12 hours, dried sample moves in the retort furnace, and 650 ℃ of roastings 5 hours make catalyzer No. 3.
The evaluating catalyst method:
Take by weighing above-mentioned three kinds of each 200mg of catalyzer, add 500mg α-Al
2O
3Make thinner, grind compressing tablet and be placed in the quartz tube reactor that internal diameter is 15mm, feed H
2/ N
2(1: 10), 700 ℃ were reduced 3 hours down.Be warming up to 800 ℃ then, under the normal pressure, with the flow velocity of 80ml/min with CO
2/ CH
4(1: 1) feeds reactor, and gas chromatographic detection tail gas is formed.The result shows, uses 1,2, No. 3 catalyzer all can make CH
4And CO
2Transformation efficiency and the selectivity of synthetic gas all reach more than 90%, No. 1 catalyzer is no obvious carbon distribution after using 600 hours, activity is without any decline, CH when using No. 1 catalyzer
4Transformation efficiency as shown in Figure 1.
Comparative example:
Take by weighing Ni (NO
3)
26H
2O 2.35g is mixed with 10% the aqueous solution, with this Ni (NO
3)
2Solution impregnation 5g γ-Al
2O
3Carrier, then 110 ℃ dry 12 hours down, dried sample moves in the retort furnace, 650 ℃ of roastings 3 hours.Take by weighing the 500mg catalyzer and put into quartz tube reactor, feed H
2/ N
2(1: 10), 650 ℃ were reduced 3 hours down.Be warming up to 800 ℃ then, under the normal pressure, with the flow velocity of 40ml/min with CO
2/ CH
4(1: 1) feeds reactor, and gas chromatographic detection tail gas is formed.The result shows that the catalyzer initial activity also can reach the initial activity of the described catalyzer of this patent, but this catalyzer can be because of the carbon distribution inactivation after using 60 hours.
Claims (1)
1, a kind of preparation method who is used for the nickel-base catalyst of preparing synthetic gas by reforming methane with carbon dioxide is characterized in that this preparation method is made up of the following step:
(1) will contain the commercialization zirconium oxychloride ZrOCl of crystal water
28H
20 to be mixed with concentration be that the aqueous solution of 0.05～0.5mol/L is standby, with concentration is that the dilution of 25% commodity ammoniacal liquor is made precipitation agent for 2～15 times, in the container of above-mentioned precipitation agent is housed, under the condition of continuously stirring, with the speed of 5～20ml/min with the above-mentioned ZrOCl for preparing
2The aqueous solution is added drop-wise in the precipitation agent, and the pH value of control solution is 9～13; Dropwise the back and continue to stir 0.5～4 hour, left standstill aging 2～4 hours;
(2) with (1) gained hydrogel with deionized water wash till do not have a chlorion;
(3) with the water in dehydrated alcohol displacement (2) gained hydrogel, the gained gel is called alcogel;
(4) (3) gained alcogel is placed autoclave, additional proportion is: add 10～20ml dehydrated alcohol in every gram alcogel, feed exsiccant N in autoclave
2, to pressure be 60～80atm, be warming up to 260 ℃ and kept 0.5～4 hour, cooling, pressure release, logical exsiccant N
2To remove ethanol remaining in the still, obtain ultra-fine ZrO
2Powder;
(5) with above-mentioned ZrO
2It is 5～10% to have the commercialization nitric acid nickel (NO of crystal water that powder impregnated in concentration
3)
26H
2In the O solution, continuously stirring, be heated to the water distilled-to-dryness, and then 100～200 ℃ dry 12～16 hours down, at last 400～800 ℃ of following roastings 3～10 hours, be nickel-base catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99107321A CN1090588C (en) | 1999-05-14 | 1999-05-14 | Nickel-base catalyst for preparing synthetic gas by reforming methane with carbon dioxide and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99107321A CN1090588C (en) | 1999-05-14 | 1999-05-14 | Nickel-base catalyst for preparing synthetic gas by reforming methane with carbon dioxide and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1234366A CN1234366A (en) | 1999-11-10 |
| CN1090588C true CN1090588C (en) | 2002-09-11 |
Family
ID=5272706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99107321A Expired - Fee Related CN1090588C (en) | 1999-05-14 | 1999-05-14 | Nickel-base catalyst for preparing synthetic gas by reforming methane with carbon dioxide and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1090588C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100388975C (en) * | 2005-09-29 | 2008-05-21 | 北京化工大学 | Metal carrier catalyst for producing synthetic gas by methane carbon dioxide reformation and its production |
| CN101462058B (en) * | 2007-12-20 | 2013-01-09 | 上海焦化有限公司 | Catalyst for producing synthesis gas by reforming natural gas-carbon dioxide for industry |
| CN104801333B (en) * | 2015-03-03 | 2017-12-19 | 新奥科技发展有限公司 | A kind of preparation method of loading type nickel-based catalyst |
| CN105056951A (en) * | 2015-08-11 | 2015-11-18 | 雅本化学股份有限公司 | Heterogeneously catalyzed and ozonized nano-composite catalyst and preparation method thereof |
| CN106944071B (en) * | 2016-01-07 | 2019-07-12 | 中国石油化工股份有限公司 | The preparation method of methane portion oxidation synthesis gas catalyst |
| CN106391021A (en) * | 2016-08-19 | 2017-02-15 | 内蒙古大学 | Preparation method and use of high dispersion supported catalyst for methane reforming with carbon dioxide |
| 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 |
| CN113145123B (en) * | 2021-04-26 | 2022-11-25 | 清华大学 | Low-temperature high-activity Ni-based catalyst and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053596A (en) * | 1990-01-26 | 1991-08-07 | 斯南普罗吉蒂联合股票公司 | Use CO 2Transform light hydrocarbon and make the catalysis system and the method for synthetic gas |
| CN1090254A (en) * | 1992-12-21 | 1994-08-03 | 阿莫科公司 | With nickel is the method for making of the synthetic gas of catalyzer |
| CN1120469A (en) * | 1995-06-15 | 1996-04-17 | 华南理工大学 | Catalyst for producing synthetic gas by methane selectively oxidizing |
-
1999
- 1999-05-14 CN CN99107321A patent/CN1090588C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053596A (en) * | 1990-01-26 | 1991-08-07 | 斯南普罗吉蒂联合股票公司 | Use CO 2Transform light hydrocarbon and make the catalysis system and the method for synthetic gas |
| CN1090254A (en) * | 1992-12-21 | 1994-08-03 | 阿莫科公司 | With nickel is the method for making of the synthetic gas of catalyzer |
| CN1120469A (en) * | 1995-06-15 | 1996-04-17 | 华南理工大学 | Catalyst for producing synthetic gas by methane selectively oxidizing |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1234366A (en) | 1999-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0414573B1 (en) | Steam reforming catalyst for hydrocarbon and method for manufacturing the same | |
| US5874381A (en) | Cobalt on alumina catalysts | |
| CN110327933B (en) | Catalyst for preparing methanol by carbon dioxide hydrogenation, preparation method and application thereof | |
| CN102441393A (en) | Fischer-Tropsch synthesis catalyst by taking modified alumina as carrier and application thereof | |
| CN101698152A (en) | Cobalt-based compounded catalyst and preparing method and application thereof | |
| CN108380218A (en) | A kind of uniform nickel cobalt (alloy) catalyst of support type and preparation method thereof | |
| CN103611540B (en) | A kind of Catalysts and its preparation method for CO hydrogenation and application | |
| CN101081362B (en) | Carrier containing magnalium complexes and method for preparing the same | |
| CN103599788A (en) | Cobalt-based catalyst for CO hydrogenation and preparation method and application thereof | |
| CN102441402A (en) | Fischer-Tropsch synthesis catalyst and application thereof | |
| CN110787789A (en) | Preparation and application of catalyst for preparing methanol by carbon dioxide hydrogenation | |
| CN1090588C (en) | Nickel-base catalyst for preparing synthetic gas by reforming methane with carbon dioxide and preparation method thereof | |
| CN105148930A (en) | Modified Co-Ce core-shell structure catalyst for carbon monoxide (CO) low-temperature oxidation | |
| CN114029063B (en) | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof | |
| CN103589446B (en) | A kind of method of iron-based liquid hydrocarbon | |
| CN110433815A (en) | A kind of carbon dioxide methanation nickel-base catalyst and its preparation method and application | |
| CN100471562C (en) | Hydrogen-enriched CO slective oxidation catalyst, its production and use | |
| CN1046099C (en) | Producing synthetic gas reaction by methane partial oxidation and its catalyst | |
| CN111036199A (en) | Application of rutile type titanium oxide supported catalyst in carbon dioxide hydrogenation reaction | |
| CN1039478C (en) | Catalyst for carbon dioxide hydrogenation-methanation and its preparation method | |
| JP4016100B2 (en) | Catalyst for water gas shift reaction | |
| CN104588022B (en) | Reduction method of Fischer-Tropsch synthesis catalyst | |
| CN115138359B (en) | Supported single-atom synergistic nanoparticle bimetallic catalyst and preparation and application thereof | |
| CN1102430C (en) | Preparation method of catalyst for methane reforming reaction by using carbon dioxide | |
| CN102284296B (en) | CO selective oxidation catalyst in hydrogen-enriched atmosphere, as well as preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |