CN101164864B - Catalytic methane cracking hydrogen production and two-step method for making synthesized gas - Google Patents
Catalytic methane cracking hydrogen production and two-step method for making synthesized gas Download PDFInfo
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- CN101164864B CN101164864B CN200710066247A CN200710066247A CN101164864B CN 101164864 B CN101164864 B CN 101164864B CN 200710066247 A CN200710066247 A CN 200710066247A CN 200710066247 A CN200710066247 A CN 200710066247A CN 101164864 B CN101164864 B CN 101164864B
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- gas
- methane
- hydrogen
- cerium
- carbon monoxide
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000007789 gas Substances 0.000 title claims abstract description 46
- 239000001257 hydrogen Substances 0.000 title claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 title description 4
- 238000005336 cracking Methods 0.000 title description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 230000008929 regeneration Effects 0.000 claims abstract description 19
- 238000011069 regeneration method Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000011084 recovery Methods 0.000 claims abstract description 8
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims description 11
- 238000007233 catalytic pyrolysis Methods 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 235000011089 carbon dioxide Nutrition 0.000 claims description 6
- 238000003421 catalytic decomposition reaction Methods 0.000 claims description 6
- 239000003610 charcoal Substances 0.000 claims description 5
- 229910001268 Ferrocerium Inorganic materials 0.000 claims description 3
- KFVLFWWLSIOANK-UHFFFAOYSA-N cerium cobalt Chemical compound [Co].[Co].[Co].[Co].[Co].[Ce] KFVLFWWLSIOANK-UHFFFAOYSA-N 0.000 claims description 3
- WITQLILIVJASEQ-UHFFFAOYSA-N cerium nickel Chemical compound [Ni].[Ce] WITQLILIVJASEQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 2
- 229910052799 carbon Inorganic materials 0.000 abstract 2
- 238000004523 catalytic cracking Methods 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 description 8
- 239000003345 natural gas Substances 0.000 description 7
- 235000009508 confectionery Nutrition 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 235000007926 Craterellus fallax Nutrition 0.000 description 1
- 240000007175 Datura inoxia Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Classifications
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- 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
- Y02P20/584—Recycling of catalysts
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- Hydrogen, Water And Hydrids (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This invention discloses a method for catalytic cracking methane to produce hydrogen and two-step method for producing synthetic gas. In this invention, cerium base oxide composition is used as catalyst, fist to crack methane into hydrogen and carbon, and then the carbon is oxidized to produce carbon monoxide, and at the same time, the regeneration of the catalyst is realized. The collection of hydrogen and carbon monoxide are proceeded separately by respective recovery systems, and then mixing them. This invention has advantages of: short process, low reaction temperature, simple operation, low production cost, the mixture can be made according the need of the down-stream products, such as liquid hydrocarbons.
Description
Technical field
The invention belongs to the chemical preparation field, particularly utilize catalyst methane, a step produces hydrogen and two and goes on foot the method for producing synthetic gas.
Background technology
Along with the exhaustion day by day of petroleum resources and constantly increasing the weight of of environmental pollution, Sweet natural gas is abundant as a kind of reserves, the energy of cleaning has become the focus of research.Scholarly forecast, to 1920's, in the energy structure in the world, Sweet natural gas will rise to 40% from present 25%, become the global topmost energy thereby substitute oil, and also will substitute oil simultaneously becomes topmost industrial chemicals.Exploration shows that the China's natural gas prospective reserves reaches 43,000,000,000,000 m
3, account for 10% of world's Sweet natural gas total reserves, about 35,000,000,000,000 m of the reserves of coal-seam gas
3, and methane (CH
4) be the main component of Sweet natural gas, coal-seam gas, therefore, in the face of Sweet natural gas and coal bed gas resource than horn of plenty, China has great strategic importance to catalytic conversion technique research of methane.
In many methyl hydride catalyzed technology, utilize methane to produce synthetic gas, again with the synthetic gas separating and preparing hydrogen or be converted into chemical or liquid hydrocarbon is the field of enlivening of conversion of natural gas utilization always.Usually, methane preparing synthetic gas method comprises the steam reforming and the CO 2 reformation of methane, has risen catalyzing part oxidation method (POM) afterwards again.Steam reforming reaction is a strong endothermic process, though there is the energy consumption height in industrialization, and equipment bulky complex, the deficiency of process cost costliness; CO 2 reformation technology also is among the research; Partial oxidation reaction temperature height, and methane (CH
4) and oxygen (O
2) gas mixture has the potentially dangerous of blast, is difficult to realize that industry amplifies.More than the common deficiency of these processes be to have generated carbon monoxide (CO), carbonic acid gas (CO
2) and hydrogen (H
2) mixed gas, as utilizing hydrogen (H wherein separately
2) or carbon monoxide (CO), just certainly will increase separation costs.
Therefore, rationally adopt a kind of catalyzer, separately prepare two kinds of gases that synthetic gas is formed by methane, promptly hydrogen and carbon monoxide could solve the deficiency that above-mentioned prior art exists preferably, are reducing hydrogen (H
2), carbon monoxide (CO) and synthetic gas production cost the time, expand three's purposes greatly.
Summary of the invention
Technical problem to be solved by this invention provides the method for a kind of catalytic methane cracking hydrogen production and two-step method making synthesized gas, whole process flow is short, its temperature of reaction reduces than traditional hydrogen production process, simple to operate, can reduce production costs, can carry out the mixing of different ratios, the expanded application scope according to downstream chemical product or liquid hydrocarbon preparation technology needs.
The scheme that technical problem adopted that solves invention is: with cerium-based composite oxides as catalyzer, with methane elder generation catalytic pyrolysis is hydrogen and charcoal, be carbon monoxide with char combustion again, realize catalyst regeneration simultaneously, collect respectively through hydrogen recovery system and carbon monoxide recovery system, be mixed into synthetic gas.
Of the present inventionly also comprise following technical scheme: when the cerium-based composite oxides catalyst consumption was 0.5g～3g, the flow of methane was 10Ncm
3Min
-1～55Ncm
3Min
-1, the entire reaction temperature is 673K～1073K, and the time of catalytic pyrolysis preparing hydrogen is 70 minutes～150 minutes, and the time of catalyst regeneration system carbon monoxide is 60 minutes～90 minutes.The regeneration gas that catalyst regeneration adopts is carbonic acid gas or oxygen-rich air.
The invention has the beneficial effects as follows:
1. the synthesis gas preparation process is divided into independently two steps, promptly earlier by catalyst cracking methane (CH
4) prepare hydrogen (H
2), regenerated catalyst is prepared carbon monoxide (CO) afterwards.Hydrogen (H in the product gas
2) realize separating automatically through two reaction process of catalysis and regeneration with carbon monoxide (CO), temperature of reaction has bigger reduction than traditional hydrogen production process simultaneously.
2. hydrogen (H
2) and carbon monoxide (CO) can carry out the mixing of different ratios according to downstream chemical product or liquid hydrocarbon preparation technology needs, can obtain the synthetic gas of different purposes.
3. this method is reducing hydrogen (H
2) and carbon monoxide (CO) and synthetic gas production cost the time, expanded three's range of application greatly, both can utilize pure hydrogen (H separately
2) and carbon monoxide (CO), also the two suitably can be mixed forming the synthetic gas comprehensive utilization.
4. whole process flow is short, and is simple to operate, can realize a step hydrogen manufacturing two steps preparing synthetic gas.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
Embodiment 1
A) implementation condition
The employing mol ratio is that the composite oxides of 2: 1 cerium cobalt are catalyzer, and industrial methane is reactor feed gas, and oxygen is resurgent gases, and quartz fixed bed reactor is of a size of Φ 1000mm * 10mm, and catalyst levels is 1.6g, and the methane gas flow is 50Ncm
3Min
-1, catalytic pyrolysis and catalyst regeneration temperature are 873K, and the catalytic pyrolysis time is 280 minutes, regeneration of oxygen flow 40Ncm
3Min
-1, with the hydrogen (H that collects
2) and carbon monoxide (CO) adopt suitable ratio to mix in purposes.
B) result of implementation
Do not detect carbon monoxide (CO) or carbonic acid gas (CO in the product gas that obtains after the methane catalytic decomposition reaction
2) existence, hydrogen (H
2) volumn concentration in product gas reached 97%; The high reactivity of catalyzer has kept 100 minutes.Detected carbon monoxide (CO) volumn concentration has reached 98% in catalyzer disappears charcoal regenerative process product gas, and the whole recovery time is 65 minutes, and the regeneration rear catalyst carries out 20 circulation experiment tests, and activity is not seen obvious reduction.
Embodiment 2
A) implementation condition
The employing mol ratio is that the composite oxides of 4: 1 cerium nickel are catalyzer, and industrial methane is reactor feed gas, and oxygen is resurgent gases, and quartz fixed bed reactor is of a size of Φ 1000mm * 10mm, and catalyst levels is 0.6g, and the methane gas flow is 35Ncm
3Min
-1, catalytic pyrolysis and catalyst regeneration temperature are 973K, and the catalytic pyrolysis time is 235 minutes, regeneration of oxygen flow 30Ncm
3Min
-1, with the hydrogen (H that collects
2) and carbon monoxide (CO) adopt suitable ratio to mix in purposes.
B) result of implementation
Do not detect carbon monoxide (CO) or carbonic acid gas (CO equally in the product gas that obtains after the methane catalytic decomposition reaction
2), hydrogen (H
2) volumn concentration in product gas is 95%; The high reactivity of catalyzer has kept 90 minutes.Catalyzer disappears, and carbon monoxide (CO) volumn concentration reaches 97% in the charcoal regenerative process product gas, and the whole recovery time continues 70 minutes, and the regeneration rear catalyst carries out 20 circulation experiments tests, and activity is not also seen obvious reduction.
Embodiment 3
A) implementation condition
The employing mol ratio is that the composite oxides of 7: 3 ferrocerium are catalyzer, and industrial methane is reactor feed gas, and carbonic acid gas is a resurgent gases, and quartz fixed bed reactor is of a size of Φ 1000mm * 10mm, and catalyst levels is 0.6g, and the methane gas flow is 60Ncm
3Min
-1, catalytic pyrolysis and catalyst regeneration temperature are 1073K, and the catalytic pyrolysis time is 265 minutes, regeneration of oxygen flow 50Ncm
3Min
-1With the hydrogen (H that collects
2) and carbon monoxide (CO) adopt suitable ratio to mix in purposes.
B) result of implementation
Hydrogen (H in the product gas that obtains after the methane catalytic decomposition reaction
2) volumn concentration reach 94%; The high reactivity of catalyzer has kept 85 minutes.Detected carbon monoxide (CO) volumn concentration reaches 95% in catalyzer disappears charcoal regenerative process product gas, and the whole recovery time continues 75 minutes, and the regeneration rear catalyst carries out 15 circulation experiment tests, and activity is not seen obvious reduction.
Claims (3)
1. the method for methane catalytic decomposition hydrogen manufacturing and two-step method making synthesized gas, it is characterized in that: with cerium-based composite oxides as catalyzer, with methane elder generation catalytic pyrolysis is hydrogen and charcoal, be carbon monoxide with char combustion again, realize catalyst regeneration simultaneously, collect respectively through hydrogen recovery system and carbon monoxide recovery system, be mixed into synthetic gas, described cerium-based composite oxides is the cerium cobalt, cerium nickel or ferrocerium composite oxides, and the mol ratio of cerium cobalt composite oxide is 2: 1, the mol ratio of cerium ni compound oxide is 4: 1, and the mol ratio of ferrocerium composite oxides is 7: 3.
2. the method for methane catalytic decomposition hydrogen manufacturing according to claim 1 and two-step method making synthesized gas is characterized in that: when the cerium-based composite oxides catalyst consumption was 0.5g～3g, the flow of methane was 10Ncm
3Min
-1～55Ncm
3Min
-1, the entire reaction temperature is 673K～1073K, and the time of catalytic pyrolysis preparing hydrogen is 70 minutes～150 minutes, and the time of catalyst regeneration system carbon monoxide is 60 minutes～90 minutes.
3. the method for methane catalytic decomposition hydrogen manufacturing according to claim 2 and two-step method making synthesized gas is characterized in that: the regeneration gas that catalyst regeneration adopts is carbonic acid gas or oxygen-rich air.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710066247A CN101164864B (en) | 2007-09-28 | 2007-09-28 | Catalytic methane cracking hydrogen production and two-step method for making synthesized gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710066247A CN101164864B (en) | 2007-09-28 | 2007-09-28 | Catalytic methane cracking hydrogen production and two-step method for making synthesized gas |
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| Publication Number | Publication Date |
|---|---|
| CN101164864A CN101164864A (en) | 2008-04-23 |
| CN101164864B true CN101164864B (en) | 2010-05-26 |
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|---|---|---|---|
| CN200710066247A Expired - Fee Related CN101164864B (en) | 2007-09-28 | 2007-09-28 | Catalytic methane cracking hydrogen production and two-step method for making synthesized gas |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086324B (en) * | 2013-01-23 | 2014-10-15 | 大连理工大学 | Device and method for carrying out atomization and catalytic reforming on organic liquid fuels |
| CN103332650B (en) * | 2013-06-04 | 2014-12-17 | 东南大学 | System and method for simultaneous dry-method hydrogen production from catalytic methane decomposition and carbon dioxide separation |
| CN105013506B (en) * | 2015-06-25 | 2017-12-12 | 中国石油天然气集团公司 | Bifunctional catalyst and its preparation method and hydrogen production process for methane catalytic decomposition |
| CN104986729B (en) * | 2015-06-29 | 2017-05-10 | 昆明理工大学 | Preparation method for hydrogen and carbon dioxide through static bed |
| CN109519158A (en) * | 2018-10-25 | 2019-03-26 | 安蔓页岩技术有限公司 | A method of shale and neighbouring oil-bearing reservoir of the one exploitation containing organic matter |
| WO2020185107A1 (en) * | 2019-03-13 | 2020-09-17 | Qatar Foundation | Regeneration and activation of catalysts for carbon and syngas production |
| CN111153385A (en) * | 2019-12-31 | 2020-05-15 | 四川天采科技有限责任公司 | Full-efficient natural gas medium-low temperature direct cracking circulation hydrogen production method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1468800A (en) * | 2003-06-20 | 2004-01-21 | 中国科学院广州能源研究所 | Autothermal catalytic marsh gas reforming process of preparing synthetic gas |
| US20040142815A1 (en) * | 2002-12-30 | 2004-07-22 | Conocophillips Company | Use of nonmicroporous support for syngas catalyst |
| US20050069485A1 (en) * | 2003-09-26 | 2005-03-31 | Korea Institute Of Energy Research | Compact partial oxidation reactor assemblage with fast start-up capability |
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- 2007-09-28 CN CN200710066247A patent/CN101164864B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040142815A1 (en) * | 2002-12-30 | 2004-07-22 | Conocophillips Company | Use of nonmicroporous support for syngas catalyst |
| CN1468800A (en) * | 2003-06-20 | 2004-01-21 | 中国科学院广州能源研究所 | Autothermal catalytic marsh gas reforming process of preparing synthetic gas |
| US20050069485A1 (en) * | 2003-09-26 | 2005-03-31 | Korea Institute Of Energy Research | Compact partial oxidation reactor assemblage with fast start-up capability |
Non-Patent Citations (2)
| Title |
|---|
| 莫若飞等.催化裂解甲烷制氢研究进展.天然气化工27 3.2002,27(3),43-48. |
| 莫若飞等.催化裂解甲烷制氢研究进展.天然气化工27 3.2002,27(3),43-48. * |
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| CN101164864A (en) | 2008-04-23 |
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