CN1696084A - Method for preparing C-2 hydrocarbon through catalyzing oxidative coupling of methane hydrocarbon - Google Patents
Method for preparing C-2 hydrocarbon through catalyzing oxidative coupling of methane hydrocarbon Download PDFInfo
- Publication number
- CN1696084A CN1696084A CN 200410042178 CN200410042178A CN1696084A CN 1696084 A CN1696084 A CN 1696084A CN 200410042178 CN200410042178 CN 200410042178 CN 200410042178 A CN200410042178 A CN 200410042178A CN 1696084 A CN1696084 A CN 1696084A
- Authority
- CN
- China
- Prior art keywords
- methane
- hydrocarbon
- silver
- preparing
- time
- 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.)
- Pending
Links
Abstract
A process for preparing C2 hydrocarbon from methane by catalytc oxidizing and coupling at lower temp features that its catalyst is prepared from Ag and carrier chosen from SiO2, Al2O3, MCM-41, SBA-15, HZSM-5 and HMCM-22 through ultrasonic dipping or chemical drawing.
Description
Technical field
The present invention relates to a kind of method of preparing carbon dihydrocarbon.
Background technology
Along with the minimizing day by day of petroleum resources, the Sweet natural gas that reserves are abundant and effective utilization of coal bed gas resource more and more come into one's own. and methane is the main component (＞90%) of Sweet natural gas and coal-seam gas, it is predicted that China's reserves that can tap natural gas are 12-16 trillion m
3, the coal-seam gas reserves are about 100,000,000,000,000 m
3(wherein depth of burial be no more than 2000 meters 30-35 trillion m are arranged
3, account for global reserves 13%), amounting to into crude oil has 1,200 hundred million ton; Compare with coal, the hydrogen-carbon ratio height of Sweet natural gas pollutes for a short time, is a kind of energy of cleaning.But the most attractive potential application approach of Sweet natural gas (or methane) is to pass through preparing carbon dihydrocarbon.
Research is under alap temperature, realize methane oxidation coupling, important scientific meaning and practical value are arranged, it also is the problem of a very challenging property, traditional methane oxidative coupling catalyst, AU-8654352 and US-4777313 patent disclosure the promoted single or mixed metal oxide catalyst of a kind of basic metal, AU-A-42806-89 and EP418071 patent disclosure a kind of basic metal or the promoted metal oxide catalyst of alkaline earth metal chloride; Patent disclosures such as US4914252, AU8652925 and EP418971 a kind of metal halide load on Al
2O
3, SiO
2, the catalysis profit on the inert support such as float stone, the disclosed BaF of CN1100669A
2The Sm that/LaOF catalysis profit and CN1145824A are disclosed
2O
3-LiMgO catalyzer, methane conversion and C
2The selectivity of hydrocarbon is higher, is catalysis profit preferably in reporting at present.But all there is temperature of reaction height (being higher than 750 ℃) in above-mentioned catalyzer, reactionless active weakness under the low temperature,
Support silver catalyst and the reaction of ethylene epoxidizing epoxy ethane is had active high, the characteristics that selectivity is good, wherein the inferior top layer oxygen on the silver has the ability of selective oxidation, and top layer oxygen species cause complete oxidation.But bibliographical information silver, silver suboxide and support silver catalyst oxidative coupling of methane is not had activity, nano metal particles is because nanometer size effect has some unique catalytic performances, therefore the size that reduces silver particles can make top layer oxygen species become easily to the migration on inferior top layer, is used for methane oxidation coupling and still lacks the most basic understanding supporting nanometer silver.
Summary of the invention
The object of the present invention is to provide a kind of method of methane oxidation coupling, used catalyzer just has methane oxidation coupling activity preferably at low temperatures.
The active constituent that catalyzer of the present invention uses is silver, and carrier is mainly the silica-alumina material of silicon-dioxide, aluminium sesquioxide, MCM-41, SBA-15, HZSM-5, HMCM-22, and the loading of silver on catalyzer is 0.5-20%.
Support of the catalyst of the present invention can be from commercially available or synthetic voluntarily, the synthetic method reference literature.Silver can be from salt or metal, as: AgNO
3With silver etc.
The preparation method of catalyst system therefor of the present invention can be the ultrasonic immersing method.
Used silver salt concentration is 0.5 * 10 when flooding among the present invention
-4-5 * 10
-4MolAg/ml, dipping time are 5-10h, and drying temperature is 50-200 ℃, time of drying 5-24h, maturing temperature is 200-600 ℃, roasting time is 2-8h.
The dipping preparation process of catalyzer is: carrier joined in an amount of silver salt solution, and ultrasonic immersing, drying, roasting, processing can obtain required catalyzer.
The evaluation of catalyzer under normal pressure, is used CH in fixed-bed reactor
4: O
2=80: 1-2: 1 unstripped gas, air speed are 10,000h
-1Condition under carry out.Temperature of reaction is 400-800 ℃.
Methane oxidization catalyzing coupling method of the present invention can be realized preparing carbon dihydrocarbon under lower temperature, realized the active breakthrough of no methane oxidation coupling under the low temperature, not only to using research but also fundamental research all being had important directive significance.
Embodiment
The present invention is further illustrated by implementation example below.
Embodiment 1:
Take by weighing silica supports 20 grams, drop in the room temperature silver nitrate solution of 45ml 0.2mol/l, ultrasonic immersing 10h, 100 ℃ of dry 12h, 500 ℃ of roasting 5h obtain required catalyzer.Got by tem analysis, the mean diameter of silver particles is 4-5nm.Consist of CH at unstripped gas
4: O
2=50: 1, He balance (volume percent), gas volume air speed are 1.0 * 10
4h
-1Situation under, the space-time yield of the carbon two in the time of 550 ℃ is 22mmol/kgh; Space-time yield in the time of 700 ℃ is 700mmol/kgh.
Embodiment 2:
Step is with embodiment 1, but with SBA-15 carrier replacement silica supports, other is constant, obtains required catalyzer.Got by tem analysis, the mean diameter of silver particles is 4-5nm.Consist of CH at unstripped gas
4: O
2=80: 1, He balance (volume percent), gas volume air speed are 1.0 * 10
4h
-1Situation under, the space-time yield of the carbon two in the time of 550 ℃ is 134mmol/kgh; Carbon two space-time yields in the time of 700 ℃ are 1405mmol/kgh.
Embodiment 3:
Step is with embodiment 1, but with HZSM-5 carrier replacement silica supports, other is constant, obtains required catalyzer.Got by tem analysis, the mean diameter of silver particles is 2-3nm.Consist of CH at unstripped gas
4/ O
2=50: 1, He balance (volume percent), gas volume air speed are 1.0 * 10
4h
-1Situation under, the space-time yield of the carbon two in the time of 400 ℃ is 5mmol/kgh.
Embodiment 4:
Step is with embodiment 3, but replaces the silver nitrate solution of 0.2mol/l with the silver nitrate solution of 0.4mol/l, and other is constant, obtains required catalyzer.Consist of CH at unstripped gas
4/ O
2=50: 1, He balance (volume percent), gas volume air speed are 1.0 * 10
4h
-1Situation under, the space-time yield of the carbon two in the time of 400 ℃ is 40mmol/kgh.
Embodiment 5:
Preparation of Catalyst obtains required catalyzer with embodiment 2.Consist of CH at unstripped gas
4/ O
2=3: 1, He balance (volume percent), gas volume air speed are 1.0 * 10
4h
-1Situation under, the space-time yield of the carbon two in the time of 550 ℃ is 84mmol/kgh; Carbon two space-time yields in the time of 700 ℃ are 2032mmol/kgh.
Claims (3)
1. the method for a preparing carbon dihydrocarbon, the catalyst activity component of using is silver, and carrier is silicon-dioxide, aluminium sesquioxide, MCM-41, SBA-15, HZSM-5 or HMCM-22, and the loading of silver is 0.5-20%; Reaction conditions is: temperature 400-800 ℃, and air speed 1.0 * 10
4h
-1
2. methane oxidization catalyzing coupling method as claimed in claim 1 is characterized in that described silver particles is 1-20nm.
3. methane oxidization catalyzing coupling method as claimed in claim 1 is characterized in that the methane and the ratio of oxygen are 80: 1-2: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410042178 CN1696084A (en) | 2004-05-10 | 2004-05-10 | Method for preparing C-2 hydrocarbon through catalyzing oxidative coupling of methane hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410042178 CN1696084A (en) | 2004-05-10 | 2004-05-10 | Method for preparing C-2 hydrocarbon through catalyzing oxidative coupling of methane hydrocarbon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1696084A true CN1696084A (en) | 2005-11-16 |
Family
ID=35348998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410042178 Pending CN1696084A (en) | 2004-05-10 | 2004-05-10 | Method for preparing C-2 hydrocarbon through catalyzing oxidative coupling of methane hydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1696084A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101385982B (en) * | 2007-09-14 | 2010-11-24 | 北京化工大学 | Meso mol sieve catalyst for producing ethylene by oxidation coupling of methane and preparation method thereof |
| CN105170138A (en) * | 2014-05-29 | 2015-12-23 | 中国石油化工股份有限公司 | Methane oxidative coupling reaction catalyst and preparation method thereof |
| CN105330501A (en) * | 2015-11-13 | 2016-02-17 | 厦门中科易工化学科技有限公司 | Method for chlorinating and coupling methanol |
| CN105451874A (en) * | 2013-08-23 | 2016-03-30 | 沙特基础工业公司 | Reactor comprising a plasma source and a catalyst comprising a mesoporous support material for the preparation of ethene from methane |
| CN105658605A (en) * | 2013-11-11 | 2016-06-08 | 沙特基础工业公司 | Process for the conversion of methane to c2+ hydrocarbons |
| CN108136370A (en) * | 2015-07-15 | 2018-06-08 | 沙特基础工业全球技术公司 | Promote catalyst for the silver of methane oxidation coupling |
| CN111203285A (en) * | 2018-11-22 | 2020-05-29 | 中国石油化工股份有限公司 | Supported catalyst, preparation method thereof and method for preparing olefin by oxidative coupling of methane |
| CN111790369A (en) * | 2020-07-14 | 2020-10-20 | 福州大学 | Silver-loaded black indium-based composite photothermal catalytic material for methane coupling and preparation method and application thereof |
| CN115487853A (en) * | 2021-06-18 | 2022-12-20 | 中国石油化工股份有限公司 | Mixed catalyst containing lanthanum oxycarbonate and silver loaded molecular sieve and preparation method and application thereof |
-
2004
- 2004-05-10 CN CN 200410042178 patent/CN1696084A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101385982B (en) * | 2007-09-14 | 2010-11-24 | 北京化工大学 | Meso mol sieve catalyst for producing ethylene by oxidation coupling of methane and preparation method thereof |
| US9770700B2 (en) * | 2013-08-23 | 2017-09-26 | Saudi Basic Industries Corporation | Reactor comprising a plasma source and a catalyst comprising a mesoporous support material for the preparation of ethene from methane |
| CN105451874A (en) * | 2013-08-23 | 2016-03-30 | 沙特基础工业公司 | Reactor comprising a plasma source and a catalyst comprising a mesoporous support material for the preparation of ethene from methane |
| US20160199806A1 (en) * | 2013-08-23 | 2016-07-14 | Saudi Basic Industries Corporation | Reactor comprising a plasma source and a catalyst comprising a mesoporous support material for the preparation of ethene from methane |
| CN105658605A (en) * | 2013-11-11 | 2016-06-08 | 沙特基础工业公司 | Process for the conversion of methane to c2+ hydrocarbons |
| CN105170138A (en) * | 2014-05-29 | 2015-12-23 | 中国石油化工股份有限公司 | Methane oxidative coupling reaction catalyst and preparation method thereof |
| CN108136370A (en) * | 2015-07-15 | 2018-06-08 | 沙特基础工业全球技术公司 | Promote catalyst for the silver of methane oxidation coupling |
| CN105330501A (en) * | 2015-11-13 | 2016-02-17 | 厦门中科易工化学科技有限公司 | Method for chlorinating and coupling methanol |
| CN111203285A (en) * | 2018-11-22 | 2020-05-29 | 中国石油化工股份有限公司 | Supported catalyst, preparation method thereof and method for preparing olefin by oxidative coupling of methane |
| CN111790369A (en) * | 2020-07-14 | 2020-10-20 | 福州大学 | Silver-loaded black indium-based composite photothermal catalytic material for methane coupling and preparation method and application thereof |
| CN111790369B (en) * | 2020-07-14 | 2021-07-13 | 福州大学 | Silver-loaded black indium-based composite photothermal catalytic material for methane coupling and preparation method and application thereof |
| CN115487853A (en) * | 2021-06-18 | 2022-12-20 | 中国石油化工股份有限公司 | Mixed catalyst containing lanthanum oxycarbonate and silver loaded molecular sieve and preparation method and application thereof |
| CN115487853B (en) * | 2021-06-18 | 2023-11-10 | 中国石油化工股份有限公司 | Mixed catalyst containing lanthanum oxide carbonate and silver loaded molecular sieve, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100428991C (en) | Catalyst for preparing heavy hydrocarbon with synthetic gas and its prepn process | |
| CN101224425A (en) | Co catalyst with controllable Fischer-Tropsch product distribution, preparing and applications thereof | |
| CN101898131B (en) | Dehydrogenation catalyst taking Sn-containing alumina as carrier and preparation method thereof | |
| CN109865516A (en) | A kind of ferrum-based catalyst and its preparation method and application | |
| CN1696084A (en) | Method for preparing C-2 hydrocarbon through catalyzing oxidative coupling of methane hydrocarbon | |
| CN104971717B (en) | The ZnO/Al of Pt modifications2O3Catalyst and its preparation method and application | |
| CN104588011B (en) | Alkane dehydrogenation catalyst and preparation method thereof | |
| CN106607043B (en) | Ferrum-based catalyst and its preparation method and application | |
| CN101380587A (en) | Propane dehydrogenation catalyst to produce propylene and preparation method thereof | |
| CN105032503A (en) | Regeneration method of noble metal catalyst | |
| CN102649079A (en) | Method for converting synthetic gas into low-carbon alkene with ferro-manganese base catalyst | |
| CN110548499A (en) | Composite carrier catalyst for acetylene hydrochlorination and application thereof | |
| CN102553632B (en) | A kind of catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof and application | |
| CN103418442B (en) | Preparation method of precious metal-containing low-carbon alkane dehydrogenation catalyst carrier | |
| CN101890361A (en) | Catalyst for use in highly selective preparation of gasoline fractions from synthesis gas and preparation method thereof | |
| CN107626317A (en) | A kind of Ce base oxide catalysts and its preparation and application | |
| CN104923258A (en) | Catalyst regeneration method | |
| CN103589446A (en) | Fe-based preparation method of liquid hydrocarbon | |
| CN107199049A (en) | Amido modified mesopore molecular sieve, the nickel-base catalyst based on the molecular sieve and its preparation and application | |
| CN1176746C (en) | Fischer-Tropsch catalyst and its preparing process | |
| CN103586066B (en) | The method of benzaldehyde prepared by bimetallic-modified SBA-15 catalyst low-temperature gaseous phase selective catalytic oxidation phenmethylol | |
| CN106607047A (en) | Iron-based catalyst for preparing low-carbon olefins from synthesis gas and application of iron-based catalyst | |
| CN101524644B (en) | Cobalt-based catalyst for the oil-wax co-production of synthetic natural gas, preparation method and application thereof | |
| CN101274277B (en) | Catalyst for synthesizing intermediate distillate oil used for slurry bed and preparation and application | |
| CN1057321C (en) | Catalyst for preparing heavy hydrocarbon from synthesized gas and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |