JPS63222126A - Pressure oxidation coupling of methane - Google Patents
Pressure oxidation coupling of methaneInfo
- Publication number
- JPS63222126A JPS63222126A JP62054100A JP5410087A JPS63222126A JP S63222126 A JPS63222126 A JP S63222126A JP 62054100 A JP62054100 A JP 62054100A JP 5410087 A JP5410087 A JP 5410087A JP S63222126 A JPS63222126 A JP S63222126A
- Authority
- JP
- Japan
- Prior art keywords
- methane
- reaction
- catalyst
- oxidative coupling
- carbon monoxide
- 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.)
- Granted
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000005859 coupling reaction Methods 0.000 title description 4
- 238000007254 oxidation reaction Methods 0.000 title description 3
- 230000003647 oxidation Effects 0.000 title description 2
- 230000008878 coupling Effects 0.000 title 1
- 238000010168 coupling process Methods 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 10
- 238000005691 oxidative coupling reaction Methods 0.000 claims abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007789 gas Substances 0.000 abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 5
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910002090 carbon oxide Inorganic materials 0.000 description 3
- 239000013064 chemical raw material Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910001293 incoloy Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Carbon And Carbon Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はメタンの酸化的カップリング反応を加圧下で行
い炭素数２以上の炭化水素と一酸化炭素を合成する方法
に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for synthesizing a hydrocarbon having two or more carbon atoms and carbon monoxide by carrying out an oxidative coupling reaction of methane under pressure.
メタンは天然ガスの主成分として地球上に豊富に存在し
ており、現在のところ、主に燃料として使用されている
。メタンはまた所謂Ｃ１化学原料の１つとして合成ガス
を経由してアルコール製造等に用いられているが、化学
原料としての用途は石油に比べて少ない。しかし石油を
補完する炭素資源としての化学原料用途の拡大は今後に
期待される。Methane is abundant on earth as the main component of natural gas, and is currently used primarily as a fuel. Methane is also used as one of the so-called C1 chemical raw materials for alcohol production etc. via synthesis gas, but its use as a chemical raw material is less than that of petroleum. However, the use of chemical raw materials as a carbon resource that complements petroleum is expected to expand in the future.
メタンの化学原料としての用途の中、メタンを原料とす
る炭素数２以上の炭化水素の合成法は合成ガスを経由す
るフィッシャー・トロプシュ法のほかに、メタンを酸化
的に脱水素してカップＩＪングさせる方法がＵＳＰ ４
，４４３，６４７で代表される一連の特許やケラ−（Ｊ
、 Ｃａｔａｌ、 ７３ 、、９．１９８２）、ヒンセ
ン（Ｐｒｏｃ ＊ ８ ｔｈ Ｉｎｔ’ｌ ”ｆｌｇ”
Ｃａｔａｌ、 １９８４）等により報告されている。Among the uses of methane as a chemical raw material, methods for synthesizing hydrocarbons with a carbon number of 2 or more using methane as a raw material include the Fischer-Tropsch method via synthesis gas, and the cup IJ method in which methane is oxidatively dehydrogenated. The USP 4 is how to
, 443,647 and Keller (J.
, Catal, 73, 9.1982), Hinsen (Proc * 8 th Int'l "flg"
Catal, 1984) and others.
上記米国特許やケラ−は金属酸化物を触媒として開用し
、５ｉＯ１などに担持させて常圧下５００〜１０００℃
でメタンと接触させて一定時間反応させ、その後メタン
の流入をやめて分子状酸素により再び金属酸化物に再生
させた後メタンを流入する周期的反応方式を採用してお
り、メタンと酸素を共存させると目的生成物はほとんど
得られないとしている。またヒンセンはＰｂ。The above-mentioned US patent and Keller utilized metal oxides as catalysts, supported them on 5iO1, etc., and heated them at 500 to 1000°C under normal pressure.
A periodic reaction method is used in which methane is brought into contact with methane and reacted for a certain period of time, then the methane is stopped flowing and the metal oxide is regenerated by molecular oxygen, and then methane is introduced, allowing methane and oxygen to coexist. It is said that the desired product is hardly obtained. Also, Hinsen is Pb.
を触媒とし種々の担体に担持させて酸素共存下で実験し
ているが、いずれも好ましい結果は得られていない。Experiments have been carried out in the coexistence of oxygen using various carriers as catalysts, but no favorable results have been obtained in any of them.
本発明者らは、上記のように触媒による酸化的カップリ
ング反応における触媒の再生等触媒使用の煩雑さと不十
分な結果に鑑み、無触媒で酸化的カップリング反応を行
わせ、かつ反応速度を大きくするため加圧条件を採用す
ることにより、炭素数２以上の炭化水素の生成と酸化炭
素として一酸化炭素を得ることを見出し、本発明に到達
した。In view of the complexity and unsatisfactory results of using catalysts such as catalyst regeneration in catalytic oxidative coupling reactions as described above, the present inventors conducted oxidative coupling reactions without catalysts and improved the reaction rate. The present invention was achieved by discovering that by adopting pressurized conditions to increase the size, hydrocarbons having two or more carbon atoms can be produced and carbon monoxide can be obtained as carbon oxide.
すなわち本発明はメタンを分子状酸素と共に加圧下、無
触媒で６５０〜１０００℃に加熱して酸化カップリング
反応を行わせることを特徴とする炭素数２以上の炭化水
素と一酸化炭素を得る方法である。−酸化炭素がメタノ
ール合成やフィッシャｍ−トロプシュ合成の原料として
有用であることは言うまでもない。That is, the present invention provides a method for obtaining a hydrocarbon having two or more carbon atoms and carbon monoxide, which is characterized by heating methane together with molecular oxygen at 650 to 1000°C under pressure and without a catalyst to perform an oxidative coupling reaction. It is. - It goes without saying that carbon oxide is useful as a raw material for methanol synthesis and Fischer m-Tropsch synthesis.
本発明に使用するメタンは濃度が高い程有利であるが、
希釈されていても差支えない。分子状酸素は必ずしも０
．１００％である必要はなく空気のように分子状酸素を
含むガスであればよい。ただし反応ガス中のメタン１０
２のモル比か常に５以上、好ましくは１０以上であるこ
とが必要である。モル比が５未満ではそれだけ分子状酸
素が多くなり、好ましくない二酸化炭素の生成が多くな
る。The higher the concentration of methane used in the present invention, the more advantageous it is.
There is no problem even if it is diluted. Molecular oxygen is not necessarily 0
．． It does not need to be 100%, and any gas containing molecular oxygen such as air may be used. However, methane in the reaction gas
It is necessary that the molar ratio of 2 to 2 is always 5 or more, preferably 10 or more. If the molar ratio is less than 5, the amount of molecular oxygen will increase accordingly, and undesirable carbon dioxide will be produced in large quantities.
本発明のメタン酸化カップリング反応は反応温度６５０
℃〜１０００℃、好ましくは７００〜９００℃である。The methane oxidative coupling reaction of the present invention has a reaction temperature of 650
℃~1000℃, preferably 700~900℃.
反応温度が６５０℃未満ではメタンの転化速度が小さく
、一方１０００℃を超えてもそれ程向上しない。また使
用する圧力は５〜２０級個が好ましく、５ ｋｙ／−未
満では加圧の効果がほとんどなく、またｚｏｋｙ／−を
超えても収率はそれ程向上せず、高圧のための装置上の
問題があり、かつ不経済である。If the reaction temperature is less than 650°C, the conversion rate of methane will be low, while if it exceeds 1000°C, it will not improve much. In addition, the pressure used is preferably 5 to 20 class. If it is less than 5 ky/-, there is almost no effect of pressurization, and if it exceeds zoky/-, the yield will not improve much, and the It is problematic and uneconomical.
本発明のメタンの加圧酸化カップリング方法の特徴は触
媒を使用しないことである。触媒の種類を問わず、加圧
子触媒を使用すると酸化反応が進み一酸化炭素はすべて
二酸化炭素となるほか、生成した炭素数２以上の炭化水
素も酸化して二酸化炭素となってしまうので好ましくな
い。A feature of the pressure oxidative coupling method for methane of the present invention is that no catalyst is used. Regardless of the type of catalyst, if a pressurizer catalyst is used, the oxidation reaction will progress and all of the carbon monoxide will become carbon dioxide, and the generated hydrocarbons with carbon numbers of 2 or more will also be oxidized and become carbon dioxide, which is undesirable. .
本発明の加圧下で酸化カップ１１ング反ｉｆ実施するこ
とによって反応速度が大きくなるのは以下のように考察
される。すなわちエタンの生成はメタンと酸素との反応
で生成したメチルラジカル（ＣＨｓ・）のカップリング
反応に依ると考えられるが、この反応は可逆反応である
。The reason why the reaction rate is increased by carrying out the oxidation cup 11 reaction under pressure according to the present invention is considered as follows. That is, the production of ethane is thought to depend on the coupling reaction of methyl radicals (CHs.) produced by the reaction of methane and oxygen, but this reaction is a reversible reaction.
２ ＣＨｓＣ（ＣＪａ” ） ：ｊ Ｃ＊Ｈａしかもメ
チルラジカルは高いエネルギーヲ持つため、それから生
成したエタンは励起状態にある。したがって通常は容易
に分解して再びメチルラジカルとなる。しかし励起状態
のエタンが他の分子と衝突してそのエネルギーを失えば
安定なエタン分子となり、生成物となる（三体衝突理論
）。この確率は圧力の三乗に比例するから加圧下で反応
を実施することがエタン（およびエチレン）の生成に不
可欠であるものと考えられる。2 CHsC(CJa”):j C*HaMoreover, since methyl radicals have high energy, the ethane produced from them is in an excited state.Therefore, it usually decomposes easily and becomes methyl radicals again.However, ethane in an excited state If it collides with another molecule and loses its energy, it becomes a stable ethane molecule and becomes a product (three-body collision theory).Since this probability is proportional to the cube of pressure, it is possible to carry out the reaction under pressure. It is believed to be essential for the production of ethane (and ethylene).
以下に実施例を挙げて本発明を具体的に説明する。The present invention will be specifically described below with reference to Examples.
実施例１
反応は加圧流通装置を用いた。反応器は管型のインコロ
イＨ製の容器に石英管を挿入し金属表面での反応を無視
できるようにした。Example 1 A pressurized flow device was used for the reaction. The reactor was a tubular Incoloy H container with a quartz tube inserted so that reactions on the metal surface could be ignored.
反応条件は７５０℃、ＣＨａ ： ０２ ： Ｎ２ ＝
１４ ：１．６ ： ８４．４ （モル比）、ガス
光景３５０ ｍＡ／ｍｉｎを標準とし、圧力を種々変え
て行った。結果を第１表に示す。The reaction conditions were 750°C, CHa: 02: N2 =
14:1.6:84.4 (molar ratio) and a gas flow rate of 350 mA/min as standard, and the pressure was varied. The results are shown in Table 1.
第 １ 表
第１表によれば圧力の増加と共にメタン及び酸素の転化
率が上昇し、カップリング反応、燃焼反応の両者が起こ
った。反応の選択性は反応圧力の増加に伴ってカップリ
ング反応の選択性が６０係から４５％に減少し、燃焼反
応への選択性が増加した。Table 1 According to Table 1, the conversion rates of methane and oxygen increased as the pressure increased, and both a coupling reaction and a combustion reaction occurred. As the reaction pressure increased, the selectivity for the coupling reaction decreased from 60% to 45%, and the selectivity for the combustion reaction increased.
Ｃ３炭化水素の大部分はＣ５Ｈａであり、そのほかＣ８
Ｈ，、Ｃ４Ｈ８、Ｃ４Ｈ，が生成した。Most of the C3 hydrocarbons are C5Ha, and other C8
H,,C4H8,C4H, were generated.
一方圧力の上昇と共にＣＯの選択率は上昇したが、ＣＯ
２の選択率はあまり圧力に依存しないことがわかった。On the other hand, the selectivity of CO increased with increasing pressure, but CO
It was found that the selectivity of 2 does not depend much on pressure.
第１表のメタンの転化率と選択率とから生成物を収率で
あられしたのが第１図である。FIG. 1 shows the product yield calculated from the methane conversion rate and selectivity shown in Table 1.
実施例２
ＣＨ４： Ｏｘ ： Ｎｚ＝ １４ ： １．６ ：
８４．４、流量３４０ ｍｇ／ｍｔｎ、圧力１０１ｗ／
Ｊ−Ｇで温度を種々変えて実験したのが第２図である。Example 2 CH4: Ox: Nz= 14: 1.6:
84.4, flow rate 340 mg/mtn, pressure 101w/
Figure 2 shows experiments conducted at various temperatures on J-G.
８００℃を超えるとＣ，Ｈ，の収率はほぼ横ばいになる
が、Ｃ，Ｈ４、ＣＯは７５０℃以上急増する。When the temperature exceeds 800°C, the yields of C, H, and C remain almost unchanged, but the yields of C, H4, and CO rapidly increase above 750°C.
ＣＯ２は一般に少なくそれほど温度の影響を受けない。CO2 is generally small and not significantly affected by temperature.
本発明の加圧下におけるメタンの酸化カップリング反応
は温度及び圧力に最適の範囲があり、触媒を使用しなく
てもＣ１以上の炭化水素が生成し、かつ常圧触媒使用で
の反応に比ベニ酸化炭素の生成を抑えて一酸化炭素が多
く生成するため、合成原料ガスとしても有用である。The oxidative coupling reaction of methane under pressure according to the present invention has an optimal range of temperature and pressure, produces C1 or higher hydrocarbons without using a catalyst, and is superior to the reaction using a normal pressure catalyst. Since it suppresses the production of carbon oxide and produces a large amount of carbon monoxide, it is also useful as a raw material gas for synthesis.
図はメタンの加圧酸ｆヒカップリング反応における反応
条件と収率の関係を示すグラフで、第１図は圧力の影響
、第２図は温度の影響を示す。The figure is a graph showing the relationship between reaction conditions and yield in the pressurized acid f-hycoupling reaction of methane. Figure 1 shows the influence of pressure, and Figure 2 shows the influence of temperature.
Claims (2)
０〜１０００℃に加熱して酸化カップリング反応を行わ
せることを特徴とする炭素数２以上の炭化水素と一酸化
炭素を得る方法。(1) Methane with molecular oxygen under pressure without catalyst
A method for obtaining a hydrocarbon having 2 or more carbon atoms and carbon monoxide, which comprises heating to 0 to 1000°C to perform an oxidative coupling reaction.
範囲第（１）項記載の方法。(2) The method according to claim (1), wherein the pressurization is 5 to 20 kg/cm^2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62054100A JPH0788314B2 (en) | 1987-03-11 | 1987-03-11 | Method for pressurized oxidation of methane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62054100A JPH0788314B2 (en) | 1987-03-11 | 1987-03-11 | Method for pressurized oxidation of methane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63222126A true JPS63222126A (en) | 1988-09-16 |
| JPH0788314B2 JPH0788314B2 (en) | 1995-09-27 |
Family
ID=12961197
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62054100A Expired - Lifetime JPH0788314B2 (en) | 1987-03-11 | 1987-03-11 | Method for pressurized oxidation of methane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0788314B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2746396C1 (en) * | 2017-12-14 | 2021-04-13 | Мицубиси Хеви Индастриз Энджиниринг, Лтд. | Co-production unit for co-production of olefins and methanol and method for co-production of olefins and methanol |
-
1987
- 1987-03-11 JP JP62054100A patent/JPH0788314B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0788314B2 (en) | 1995-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI359131B (en) | Integrated catalytic process for converting alkane | |
| KR102061235B1 (en) | Activation method of catalyst for fischer-tropsch synthesis | |
| Choi et al. | Hydrogenation of carbon dioxide over alumina supported Fe-K catalysts | |
| Asami et al. | Synthesis of ethane and ethylene from methane and carbon dioxide over praseodymium oxide catalysts | |
| CN101624324B (en) | Hybrid autothermal catalytic process for converting alkanes to alkenes and catalysts useful for same | |
| JPH0665124A (en) | Chromia on metal oxide catalyst for oxidizing methane into methanol | |
| US7435703B2 (en) | Catalyst comprising iron oxide made by heat decomposition of an iron halide and a lanthanide | |
| KR100995792B1 (en) | Alkene separation process | |
| EA021509B1 (en) | Process for producing a mixture of aliphatic and aromatic hydrocarbons | |
| KR101816787B1 (en) | Storage method of activated catalysts for Fischer-Tropsch synthesis | |
| TWI327143B (en) | A method of manufacturing ethylene oxide | |
| JP2006502218A (en) | Rare earth metals as oxidative dehydrogenation catalysts | |
| CN113597422A (en) | By CO2Recycled methanol production process with higher carbon utilization | |
| KR101025678B1 (en) | A process for the dehydrogenation of an unsaturated hydrocarbon | |
| Chao et al. | V–Mg–O prepared via a mesoporous pathway: a low-temperature catalyst for the oxidative dehydrogenation of propane to propene | |
| EP2370379B1 (en) | Process for oxidative dehydrogenation of paraffinic lower hydrocarbons | |
| JPS63222126A (en) | Pressure oxidation coupling of methane | |
| US4826803A (en) | Process for the production of a syngas conversion catalyst | |
| Michorczyk et al. | Simultaneous propane dehydrogenation and co 2 hydrogenation overCrO x/SiO 2 catalyst | |
| JP2005519107A (en) | Process for producing alkenyl carboxylate or alkyl carboxylate | |
| Korf et al. | The development of doped Li/MgO catalyst systems for the low-temperature oxidative coupling of methane | |
| JPS6341892B2 (en) | ||
| JPS6341893B2 (en) | ||
| JPH10174871A (en) | Catalyst for production of synthesis gas and production of synthesis gas | |
| Li et al. | Oxidative coupling of methane by water as the oxidant on perovskite oxide catalysts |