CN1108189C - Catalyst for synthesizing gas by reforming methane with co2 and its preparing method - Google Patents
Catalyst for synthesizing gas by reforming methane with co2 and its preparing method Download PDFInfo
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- CN1108189C CN1108189C CN99110100A CN99110100A CN1108189C CN 1108189 C CN1108189 C CN 1108189C CN 99110100 A CN99110100 A CN 99110100A CN 99110100 A CN99110100 A CN 99110100A CN 1108189 C CN1108189 C CN 1108189C
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- carbon dioxide
- hours
- methane
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000002407 reforming Methods 0.000 title description 5
- 230000002194 synthesizing effect Effects 0.000 title description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 7
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 238000002360 preparation method Methods 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 17
- 229910052799 carbon Inorganic materials 0.000 abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 13
- 230000008021 deposition Effects 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- 238000007654 immersion Methods 0.000 abstract 1
- 229910002837 PtCo Inorganic materials 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 238000005245 sintering Methods 0.000 description 9
- 229910052763 palladium Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000010970 precious metal Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 229910021118 PdCo Inorganic materials 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000006424 Flood reaction Methods 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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
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- Catalysts (AREA)
Abstract
The present invention relates to a catalyst for producing synthetic gases by using the reformation of methane and carbon dioxide. The present invention is characterized in that a small amount of noble metals are loaded on Co/Al2O3 catalysts which are roasted in a high temperature to form a bimetallic catalyst which is composed of 2% to 12% of cobalt, 0.02% to 1% of noble metals, and the reset of Al2O3. The catalyst of the present invention adopts a step-by-step immersion method, and the preparing technology is simple. Compared with the existing catalysts, the present invention has the advantages that the catalytic activity is improved, the carbon deposition resistant performance is enhanced, and the stability of the catalyst is improved.
Description
The present invention relates to the technology of methane conversion preparing synthetic gas, be specifically related to synthesizing gas by reforming methane with co 2 a kind of be main active constituent supported bimetallic catalyst of adding the small amount of precious metals auxiliary agent and preparation method thereof with cobalt.
Methane is the main component of natural gas, and the latter is very abundant petrochemical industry fuel source.Comprehensive utilization natural gas and carbon dioxide make it to be converted into synthesis gas as hydrogen source and carbon source, have the abundant raw material cheapness, characteristic of simple process, and product C O/H
2Mol ratio can be directly synthetic as carbonyl more than or equal to 1, the raw material of F-T building-up process.
The methane carbon dioxide reformation catalyst of having reported in the patent documentation mainly is divided into two classes, and a class is a noble metal catalyst, and a class is a nickel-base catalyst, but the former costs an arm and a leg, and the latter is easy to the carbon distribution inactivation.The result of study of Lu Yong etc. shows, Al
2O
3The Co catalysts and the nickel catalyst activity that support are suitable, but continuous operation also descended because of carbon distribution is active after 9 hours (" catalysis journal " Vol.16, No.6:447～451 (1995)).The Co/Al of high-temperature roasting
2O
3Catalyst has good anti-carbon performance, but low-temperature reactivity relatively poor (" catalysis journal " Vol.19, No.3:196～200).
The objective of the invention is: provide a kind of and be applicable to synthesizing gas by reforming methane with co 2, have high catalytic activity and good anti-carbon performance, lower-cost Catalysts and its preparation method.
Synthesizing gas by reforming methane with co 2 catalyst provided by the invention is at the Co/Al of high-temperature roasting
2O
3Add small amount of precious metals Pt, Pd in the catalyst, make bimetallic catalyst, available general formula is described as MCo/Al
2O
3Catalyst component content of the present invention is (percentage by weight), and the first active constituent Co content, 2～12%, the second active constituent noble metal M content is 0.02～1%, and surplus is γ-Al
2O
3
Bimetallic catalyst of the present invention adopts the step impregnation method preparation.Preparation process is: by above-mentioned component content preparation cobalt nitrate solution and platinum acid chloride solution or palladium chloride solution, carrier floods to fry after 4 hours in cobalt nitrate solution to be done, and uniform temperature (650～1200 ℃) roasting 5 hours, makes Co/Al then
2O
3Catalyst.Co/Al after the roasting
2O
3In platinum acid chloride solution or palladium chloride solution, flood again to fry after 4 hours and do,, promptly obtain supporting the bimetallic catalyst of Co and precious metals pt or Pd in 650 ℃ of roastings 5 hours.
Bimetallic catalyst Co/Al of the present invention
2O
31200 ℃ of sintering temperatures best, Co content 5～9%, Pt or Pd content 0.02～0.6% the best.
Bimetallic catalyst of the present invention is applicable to synthesizing gas by reforming methane with co 2, directly reacts with hydrogen reducing 1 hour or without hydrogen reducing before use, and unstripped gas is formed (volume composition) CH
4/ CO
21.07～0.69, reaction temperature is at 600～800 ℃, normal pressure, suitable unstripped gas air speed 2000～20000h
-1Product C O/H
2Mol ratio is more than or equal to 1, can be directly synthetic as carbonyl, the raw material of chemical process such as F-T is synthetic.
Catalyst provided by the invention has been broken through the boundary of traditional noble metal and non-precious metal catalyst system, adopt step impregnation method to make bimetallic catalyst, preparation technology is simple, the catalytic activity height, methane and carbon dioxide conversion all reach the thermodynamic equilibrium value under the respective reaction temperature, and have anti-carbon, good stability, cost than advantages such as noble metal catalyst are low.
By the following examples the present invention is explained in detail.Embodiment 1 step impregnation method prepares bimetallic catalyst of the present invention
Raw material: cobalt nitrate Co (NO
3)
26H
2O
Chloroplatinic acid H
2PtCl
66H
2O
Palladium bichloride PdCl
2
Carrier γ-Al
2O
3, be milled to 20～40 orders
Difference by CATALYST Co content prepares certain density cobalt nitrate aqueous solution, adds a certain amount of carrier, and placed 4 hours the back that stirs, and fries and do, and in uniform temperature (650～1200 ℃) roasting 5 hours, promptly gets Co/Al in the air
2O
3Catalyst.Prepare certain density chloroplatinic acid or palladium chloride aqueous solution, add the Co/Al after a certain amount of roasting
2O
3. flood after 4 hours to fry and do, 650 ℃ of roastings are 5 hours in the air, promptly obtain bimetallic catalyst of the present invention, wherein, and Co content 2～12%, precious metals pt or Pd content 0.02～1.00%.Embodiment 2 different Co/Al
2O
3The PtCo/Al that sintering temperature makes
2O
3The catalyst reaction performance
Preparation of Catalyst:, change Co/Al with reference to the method for embodiment 1
2O
3Sintering temperature, make the PtCo/Al of Pt content 0.2%, Co content 9%
2O
3Bimetallic catalyst.
The examination condition: before the reaction, catalyst is used hydrogen reducing 1 hour down at 650 ℃.In the fixed-bed quartz reactor of continuous feed, react 700 ℃ of reaction temperatures, air speed 4090h
-1Appraisal result sees Table 1.
The different Co/Al of table 1
2O
3The PtCo/Al of sintering temperature
2O
3Catalyst reaction performance sintering temperature unstripped gas is formed conversion ratio (%) CO+H
2CO/H
2The carbon deposition quantity reaction time (℃) (CH
4/ CO
2) CH
4CO
2(%) (%) (min) 650 0.69 89.6 84.4 82.6 1.25 0.088 120
1.07 82.0 88.5 85.2 1.08 6.012 100800 0.69 89.5 82.8 85.5 1.25 0.025 120
1.07 79.2 88.0 83.4 1.09 0.067 1001200 0.69 91.1 84.2 87.1 1.25 0.016 120
1.07 the PtCo/Al of 82.6 91.5 86.4 1.11 0.081 100 embodiment, 3 different Pt content
2O
3The catalyst reaction performance
Preparation of Catalyst: with reference to the method for embodiment 1, Co/Al
2O
31200 ℃ of sintering temperatures, Co content 9% makes the PtCo/Al of different Pt content
2O
3Bimetallic catalyst.
The examination condition: the reaction procatalyst directly reacts with hydrogen reducing 1 hour or without hydrogen reducing under the temperature shown in the table 2.Unstripped gas is formed CH
4/ CO
2=1.07,700 ℃ of reaction temperatures, air speed are 4090h
-1Appraisal result sees Table 2.PtCo/Al under different Pt content of table 2 and the pretreatment condition
2O
3Catalyst reaction performance Pt content pretreatment temperature conversion ratio (%) CO+H
2CO/H
2Carbon deposition quantity
*(%) (℃) CH
4CO
2(%) (%) 0 directly react 00 0--
650 0 0 0 - -
800 76.2 90.4 83.0 1.11 2.6310.02 directly react 00 0--
650 81.6 89.1 85.1 1.07 0.0670.2 directly react 82.6 88.9 85.7 1.08 0.017
650 82.6 91.5 86.4 1.08 0.0810.6 directly react 82.1 91.5 86.4 1.08 0.035
650 83.3 90.7 86.9 1.08 0.0621.0 directly react 85.3 88.3 86.8 0.84 8.482
650 82.3 90.3 86.2 1.08 0.143
*Carbon deposition quantity is the PtCo/Al of the measurement result embodiment 4 different Co content of successive reaction after 100 minutes
2O
3The catalyst reaction performance
Preparation of Catalyst: with reference to the method for embodiment 1, Co/Al
2O
31200 ℃ of sintering temperatures, Pt content 0.2% makes the PtCo/Al of different Co content
2O
3Bimetallic catalyst.When not containing Co, carrier was in 1200 ℃ of roastings 5 hours.
The examination condition: the reaction procatalyst is used hydrogen reducing 1 hour down at 650 ℃.Unstripped gas is formed CH
4/ CO
2=1.07,700 ℃ of reaction temperatures, air speed 4090h
-1Appraisal result sees Table 3.PtCo/Al during the different Co content of table 3
2O
3Reactivity worth Co content conversion ratio (%) CO+H of catalyst
2CO/H
2Carbon deposition quantity
*(%) CH
4CO
2(%) (%) 0 51.9 69.7 60.5 1.32-2 76.3 86.3 81.1 1.06 0.0135 82.2 93.6 87.7 1.07 0.0459 82.6 91.5 86.4 1.07 0.08112 82.3 90.5 86.3 1.08 1.724
Carbon deposition quantity is the PdCo/Al of the measurement result embodiment 5 different palladium content of successive reaction after 100 minutes
2O
3The reactivity worth of catalyst
Preparation of Catalyst: with reference to the method for embodiment 1, Co/Al
2O
31200 ℃ of sintering temperatures, Co content 9% makes the PdCo/Al of different Pd content
2O
3Bimetallic catalyst.
The examination condition: the reaction procatalyst is used hydrogen reducing 1 hour under the temperature shown in the table 4.Unstripped gas is formed CH
4/ CO
2=0.69,700 ℃ of reaction temperatures, air speed 4090h
-1Appraisal result sees Table 4.PtCo/Al under the embodiment 6 differential responses temperature
2O
3The reactivity worth of catalyst
Preparation of Catalyst: with reference to the method for embodiment 1, Co/Al
2O
31200 ℃ of sintering temperatures, make Pt content 0.2%, the PtCo/Al of Co content 9%
2O
3Bimetallic catalyst.
The examination condition: the reaction procatalyst is used hydrogen reducing 1 hour down at 650 ℃.Unstripped gas is formed CH
4/ CO
2Be 0.69, air speed 4090h
-1Appraisal result sees Table 5.PdCo/Al during the different Pd content of table 4
2O
3Reactivity worth Pd content prereduction temperature inversion rate (%) CO+H of catalyst
2CO/H
2Carbon deposition quantity
*(%) (℃) CH
4CO
2(%) (%) 0 650 00 0--
800 68.9 69.5 69.2 1.41 -
900 90.3 82.9 85.9 1.18 0.0670.02 650 89.3 84.2 86.3 1.24 0.0150.20 650 91.0 84.6 87.3 1.24 0.0330.60 650 92.0 83.2 86.9 1.24 0.0371.00 650 91.0 82.7 86.2 1.23 0.074
PtCo/Al when * carbon deposition quantity is the measurement result table 5 differential responses temperature of successive reaction after 2 hours
2O
3Catalyst reaction performance reaction temperature conversion ratio (%) CO+H
2CO/H
2Carbon deposition quantity
*(℃) CH
4CO
2(%) (%) 600 59.9 59.3 59.5 1.36-650 80.1 71.9 75.3 1.32 0.013700 91.1 84.2 87.1 1.25 0.016750 96.9 87.7 91.5 1.21 0.014800 99.0 89.8 93.6 1.20 0.030
*Carbon deposition quantity is PtCo/Al under the measurement result embodiment 7 different air speeds of successive reaction after 120 minutes
2O
3The reactivity worth of catalyst
Preparation of Catalyst: with embodiment 6.
The examination condition: before the reaction, catalyst is used hydrogen reducing 1 hour down at 650 ℃.Unstripped gas is formed CH
4/ CO
2=0.69,700 ℃ of reaction temperatures.Appraisal result sees Table 5.PtCo/Al during the different air speed of table 6
2O
3Catalyst reaction performance air speed (h-1) conversion ratio (%) CO+H
2(%) CO/H
2
CH
4CO
24,090 90.4 83.1 86.0 1.2012300 90.8 81.8 85.4 1.2020000 90.2 81.8 85.2 1.2025000 87.3 80.1 83.0 1.2640000 78.3 74.1 77.8 1.31 embodiment, 8 PtCo/AL
2O
3The catalyst life experiment
Preparation of Catalyst: with embodiment 6.
The examination condition: before the reaction, catalyst is used hydrogen reducing 1 hour down at 650 ℃.Unstripped gas is formed CH
4/ CO
2=0.69,750 ℃ of reaction temperatures, air speed 4090h
-1Appraisal result sees Table 7.Table 7 PtCo/AL
2O
3Catalyst life experimental result reaction time conversion ratio (%) CO+H
2CO/H
2(hour) CH
4CO
2(%) 10 96.8 88.0 91.7 1.2120 97.4 86.5 91.0 1.2230 96.4 87.9 91.1 1.2240 96.8 90.1 92.9 1.2250 95.9 85.8 89.9 1.2060 96 6 85.5 90.2 1.22
Claims (5)
1. one kind is used for the catalyst that methane carbon dioxide reformation is produced synthesis gas, it is characterized in that at Al
20
3Last carrying bimetallic active constituent, its general formula is expressed as MCo/Al
2O
3, Co is first kind of active constituent, noble metal M is second kind of active constituent; Its component content is (percentage by weight): Co content 2～12%, and M content 0.02～1%, surplus is carrier A l
2O
3
2. methane carbon dioxide reformation according to claim 1 is produced the catalyst of synthesis gas.It is characterized in that the first component C o content is 5～9%.
3. methane carbon dioxide reformation according to claim 1 is produced the catalyst of synthesis gas.It is characterized in that the second component M is a kind of among Pt, the Pd, its content is 0.02～0.6%.
4. the described methane carbon dioxide reformation of claim 1 is produced the method for preparing catalyst of synthesis gas, it is characterized in that adopting infusion process, step is: by described Co content preparation cobalt nitrate solution, add carrier, flood to fry after 4 hours and do,, impregnated in then in the chloroplatinic acid or palladium chloride solution of described second component M content preparation 650～1200 ℃ of roastings 5 hours, flood after 4 hours to fry and do, 650 ℃ of roastings 5 hours.
5. the described catalyst of claim 1 is used to produce the purposes of synthesis gas, it is characterized in that described raw material is methane and carbon dioxide, and raw material is formed (volume composition) CH
4/ CO
2=1.07～0.69, reaction temperature is at 600～800 ℃, normal pressure, and the unstripped gas air speed is at 2000～20000h
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99110100A CN1108189C (en) | 1999-07-09 | 1999-07-09 | Catalyst for synthesizing gas by reforming methane with co2 and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99110100A CN1108189C (en) | 1999-07-09 | 1999-07-09 | Catalyst for synthesizing gas by reforming methane with co2 and its preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1280097A CN1280097A (en) | 2001-01-17 |
| CN1108189C true CN1108189C (en) | 2003-05-14 |
Family
ID=5274379
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99110100A Expired - Fee Related CN1108189C (en) | 1999-07-09 | 1999-07-09 | Catalyst for synthesizing gas by reforming methane with co2 and its preparing method |
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Cited By (1)
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|---|---|---|---|---|
| CN107282086A (en) * | 2017-07-06 | 2017-10-24 | 南京大学 | A kind of catalyst of catalytic methane dry reforming reaction and its preparation method and application |
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| CN105727972B (en) * | 2014-12-06 | 2018-02-09 | 中国石油化工股份有限公司 | A kind of method for preparing catalyst for synthesizing gas by reforming methane with co 2 |
| CN106607032A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Methane dry reforming catalyst, preparation method and application thereof and method for preparing synthesis gas through methane dry reforming |
| CN106944068B (en) * | 2016-01-07 | 2019-07-12 | 中国石油化工股份有限公司 | A kind of preparation method for methane portion oxidation synthesis gas catalyst |
| CN106944060B (en) * | 2016-01-07 | 2018-11-06 | 中国石油化工股份有限公司 | A kind of preparation method of synthesizing gas by reforming methane with co 2 catalyst |
| CN109718788B (en) * | 2017-10-31 | 2022-11-15 | 中国石油化工股份有限公司 | Methane dry reforming catalyst, preparation method and application thereof, and method for preparing synthesis gas by methane dry reforming |
| CN109718807B (en) * | 2017-10-31 | 2022-11-15 | 中国石油化工股份有限公司 | Methane dry reforming catalyst, preparation method and application thereof, and method for preparing synthesis gas by methane dry reforming |
| CN108940308B (en) * | 2018-07-18 | 2021-06-01 | 福州大学 | Preparation of platinum-cobalt composite metal photo-thermal catalyst and application of platinum-cobalt composite metal photo-thermal catalyst in methane carbon dioxide reforming |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5951982A (en) * | 1982-09-16 | 1984-03-26 | Kansai Coke & Chem Co Ltd | Preparation of gas with high calorific value from coke oven gas |
| US4579985A (en) * | 1983-11-15 | 1986-04-01 | Shell Oil Company | Process for the preparation of hydrocarbons |
| CN1044488A (en) * | 1986-09-22 | 1990-08-08 | 环球油品公司 | With the petroleum naphtha is the method for the catalytic reforming of raw material |
-
1999
- 1999-07-09 CN CN99110100A patent/CN1108189C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5951982A (en) * | 1982-09-16 | 1984-03-26 | Kansai Coke & Chem Co Ltd | Preparation of gas with high calorific value from coke oven gas |
| US4579985A (en) * | 1983-11-15 | 1986-04-01 | Shell Oil Company | Process for the preparation of hydrocarbons |
| CN1044488A (en) * | 1986-09-22 | 1990-08-08 | 环球油品公司 | With the petroleum naphtha is the method for the catalytic reforming of raw material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107282086A (en) * | 2017-07-06 | 2017-10-24 | 南京大学 | A kind of catalyst of catalytic methane dry reforming reaction and its preparation method and application |
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| Publication number | Publication date |
|---|---|
| CN1280097A (en) | 2001-01-17 |
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