JPH01168626A - Oxidative conversion of methane - Google Patents
Oxidative conversion of methaneInfo
- Publication number
- JPH01168626A JPH01168626A JP62328208A JP32820887A JPH01168626A JP H01168626 A JPH01168626 A JP H01168626A JP 62328208 A JP62328208 A JP 62328208A JP 32820887 A JP32820887 A JP 32820887A JP H01168626 A JPH01168626 A JP H01168626A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- methane
- oxide
- rare earth
- reaction
- 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000006243 chemical reaction Methods 0.000 title claims description 35
- 230000001590 oxidative effect Effects 0.000 title claims description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 20
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 11
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 10
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005977 Ethylene Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 29
- 239000002131 composite material Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 11
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 abstract description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract description 2
- 230000009918 complex formation Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- -1 rare earth compound Chemical class 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- 229910002761 BaCeO3 Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910002248 LaBO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 101100389125 Rattus norvegicus Egln3 gene Proteins 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (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脱水素三量化反応によって、主と
してエタン、エチレン等の炭化水素類を合成する方法に
関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for synthesizing hydrocarbons, mainly ethane, ethylene, etc., by an oxidative dehydrogen trimerization reaction of methane.
［従来技術］
メタンと分子状酸素を触媒の存在下において高温で反応
させ、、エタンとエチレンを主成分とする炭素数２以上
の炭化水素類〈以下、Ｃ２＋化合物という）を合成する
方法においては数多くの触媒系を使用した提案がなされ
ている０例えば、■ 触媒として例えば、Ｓｍ２Ｏ３、
Ｄ ’／ ２０５ｒＨＯ２０Ｓ 、Ｇｄ２０ｓ 、Ｅｒ
２０ｓ等の希土類酸化物を単独で用い、温度７００〜８
００℃で反応させる方法（ＣｈｅＩＩｌ、 Ｌｅｔｔ、
、 ４９９ 、１９８５） 。[Prior art] In a method of reacting methane and molecular oxygen at high temperature in the presence of a catalyst to synthesize hydrocarbons with a carbon number of 2 or more (hereinafter referred to as C2+ compounds) whose main components are ethane and ethylene, A number of proposals have been made using catalyst systems. For example, ■ As a catalyst, for example, Sm2O3,
D'/205rHO20S, Gd20s, Er
Rare earth oxide such as 20s is used alone at a temperature of 700 to 8
Method of reacting at 00°C (CheIII, Lett,
, 499, 1985).
■ 触媒として、ＢａＯ−ＣａＯをはじめとするアルカ
リ土類金属酸化物を組み合わせたものを用い、温度８０
０℃以上で反応させる方法（Ｃｈｅｗ。■ As a catalyst, a combination of alkaline earth metal oxides including BaO-CaO is used, and the temperature is 80℃.
A method of reacting at 0°C or higher (Chew).
Ｌｅｔ、ｔ、 、 ８１． １９８７） 。Let, t, , 81. 1987).
■ 触媒として、ペロブスカイト型酸化物、例えば、Ｌ
ａＡ！；Ｉ＋０３ 、ＬａＢＯ３、ＢａＣｅＯ３を用い
、温度７５０〜８５０℃で反応させる方法（Ｊ、 Ｃ，
Ｓ、 Ｃｈｅｗ、 Ｃｍｍｕｍ 、 、 ５２．１９８
６；ＣｈｅＩＩｌ、 Ｌｅｔｔ、 、 １８’３
５． １９８７） 。■ As a catalyst, perovskite-type oxides such as L
aA! ; A method of reacting at a temperature of 750 to 850°C using I+03, LaBO3, and BaCeO3 (J, C,
S, Chew, Cmmum, , 52.198
6; CheIIl, Lett, , 18'3
5. 1987).
などがある。and so on.
［発明が解決しようとする問題点］
しかし、前述の触媒系においては、種々の問題点を有し
ている。すなわち、
■の方法について使用される触媒は、メタンの転化活性
〈以下、活性という）および０２″化合物選択率（以下
、選択率という）が高価なＳｍ２０）を除いてはあまり
高くないという問題がある。[Problems to be Solved by the Invention] However, the above catalyst system has various problems. That is, the catalyst used in method (2) has the problem that its methane conversion activity (hereinafter referred to as activity) and selectivity for 02'' compounds (hereinafter referred to as selectivity) are not very high except for the expensive Sm20). be.
また、■または■の方法において使用される触媒は、反
応温度が７５０°Ｃあるいは８００℃以上の高温でない
と、十分な活性１選択性が得られないという欠点がある
。Further, the catalyst used in the method (1) or (2) has the disadvantage that sufficient selectivity to one activity cannot be obtained unless the reaction temperature is as high as 750°C or 800°C or higher.
このように、従来の方法において使用される触媒系には
、低温での活性および選択性そして価格の面で全ての条
件を満足するものは開発されていない。As described above, no catalyst system has been developed that satisfies all the requirements in terms of low-temperature activity, selectivity, and price among the catalyst systems used in conventional methods.
本発明は、このような従来技術の問題点を解決するため
になされたもので、低温においても高い活性および選択
性を有し、かつ安価な触媒の存在下において、メタンと
分子状酸素を反応させるメタンの酸化的転化方法を提供
することを目的とする。The present invention was made to solve the problems of the prior art, and involves reacting methane with molecular oxygen in the presence of an inexpensive catalyst that has high activity and selectivity even at low temperatures. The object of the present invention is to provide a method for oxidative conversion of methane.
［問題点を解決するための手段］
本発明は、メタンと分子状酸素を触媒の存在下において
高温で反応させ、エタンとエチレンを主成分とする炭素
数２以上の炭化水素類を合成する方法において、反応条
件下で、触媒がアルカリ土類金属酸化物と希土類酸化物
による複合酸化物であることを特徴とするメタンの酸化
的転化方法である。[Means for Solving the Problems] The present invention is a method of reacting methane and molecular oxygen at high temperature in the presence of a catalyst to synthesize hydrocarbons having 2 or more carbon atoms, the main components of which are ethane and ethylene. is a method for oxidative conversion of methane, characterized in that the catalyst is a composite oxide of an alkaline earth metal oxide and a rare earth oxide under reaction conditions.
さらに詳述すれば、メタンの酸化的脱水素二重化による
Ｃ２＋化合物への転化反応であり、触媒としてアルカリ
土類金属酸化物と希土類酸化物の複合酸化物を存在させ
、メタンと分子状酸素を含むガスとを反応゛させる方法
である。More specifically, it is a conversion reaction of methane to a C2+ compound by double oxidative dehydrogenation, in which a composite oxide of an alkaline earth metal oxide and a rare earth oxide is present as a catalyst, and it contains methane and molecular oxygen. This is a method of reacting with gas.
本発明において使用する触媒は、アルカリ土類金属酸化
物と希土類酸化物の複合酸化物であることが必要である
。前記複合酸化物はアルカリ土類金属化合物と希土類化
合物の混合物を焼成する方法によって得られるが、前記
混合物を、メタンと分子状酸素を反応させる反応条件下
に存在させることによっても得ることができる。The catalyst used in the present invention needs to be a composite oxide of an alkaline earth metal oxide and a rare earth oxide. The composite oxide can be obtained by firing a mixture of an alkaline earth metal compound and a rare earth compound, but it can also be obtained by placing the mixture under reaction conditions in which methane and molecular oxygen are reacted.
前記複合酸化物を焼成法によって製造する方法としては
、機械的混合法あるいは共沈法等によって得られたアル
カリ土類金属化合物と希土類化合物の混合物を焼結する
方法、アルカリ土類金属化合物と希土類化合物を含む溶
液を滴下熱分解する方法等がある。Methods for producing the composite oxide by a sintering method include a method of sintering a mixture of an alkaline earth metal compound and a rare earth compound obtained by a mechanical mixing method or a coprecipitation method, a method of sintering a mixture of an alkaline earth metal compound and a rare earth compound, There are methods such as dropwise pyrolysis of a solution containing a compound.
触媒の組成として、アルカリ土類金属酸化物はＭｇＯ，
Ｃａｂ、Ｓｒ○、ＢａＯの中がら選択される１種または
２種以上であり、好ましくはＣａｂ、ＢａＯの中から選
択される１種または２種、さらに好ましくはＣａＯであ
る。また、希土類酸化物はＹ２Ｏ３、Ｌａ２Ｏ３、Ｎｄ
２０３の中から選択される１種または２種以上であり、
好ましくはＹ２０ｓ 、Ｎｄ２０３の中から選択される
１種または２種、さらに好ましくはＹ ２０３である。As for the composition of the catalyst, the alkaline earth metal oxides are MgO,
One or more types selected from Cab, Sr○, and BaO, preferably one or two types selected from Cab and BaO, and more preferably CaO. In addition, rare earth oxides include Y2O3, La2O3, Nd
One or more types selected from 203,
Preferably, one or two selected from Y20s and Nd203, more preferably Y203.
さらに、触媒中の希土類酸化物の含有率は１〜８０ｍｏ
１％、好ましくは２０〜５ｏＩＩｌｏ看％である場合に
良好の結果が得られる。Furthermore, the content of rare earth oxide in the catalyst is 1 to 80 mo
Good results are obtained when the amount is 1%, preferably 20 to 5%.
反応温度は６００℃を超え８５０”Ｃ以下の範囲で好結
果が得られ、好ましくは６５０〜８００℃の範囲である
のがよい０反応温度が６００℃以下であると、メタンの
転化率が低く、また８５０℃を超えると、完全酸化性が
増大してＣ２＋化合物の選択率が低下する。Good results are obtained when the reaction temperature is in the range of more than 600°C and less than 850"C, preferably in the range of 650 to 800"C. If the reaction temperature is less than 600°C, the conversion rate of methane is low. Moreover, when the temperature exceeds 850°C, the complete oxidation property increases and the selectivity of C2+ compounds decreases.
なお、上述の触媒組成の説明において、触媒組成を酸化
物で表示したが、これは複合酸化物をつくる段階におけ
る化合物の形態を称したものである。アルカリ土類金属
酸化物は、通常、原子番号が増すにつれてＣＯ２を吸収
し易くなり、条件によっては炭酸塩になる。メタンと分
子状酸素の反応条件下においても、触媒は反応の過程で
生成するＣｏ２を吸収して一部が炭酸塩になることもあ
るが、著しい）支障を生ずるものではない。In the above description of the catalyst composition, the catalyst composition was expressed as an oxide, but this refers to the form of the compound at the stage of producing the composite oxide. Generally, alkaline earth metal oxides absorb CO2 more easily as their atomic number increases, and depending on the conditions, they become carbonates. Even under the reaction conditions of methane and molecular oxygen, the catalyst may absorb Co2 produced during the reaction process and some of it may become carbonate, but this does not cause any significant trouble.
また、本発明における触媒と反応ガスとの接触方法は、
流動床、固定床のいずれをも採用することができる。Further, the method of contacting the catalyst and the reaction gas in the present invention is as follows:
Either a fluidized bed or a fixed bed can be employed.
［作用］
本発明における触媒は構造が高温において安定なアルカ
リ土類金属酸化物と希土類酸化物の複合酸化物であり、
この複合化により、低温での活性および選択性が向上す
ると共に、触媒活性が長期にわたって持続する。[Function] The catalyst in the present invention is a composite oxide of an alkaline earth metal oxide and a rare earth oxide whose structure is stable at high temperatures,
This complexation improves activity and selectivity at low temperatures and maintains catalytic activity over a long period of time.
メタンの酸化脱水素三量化反応における触媒反応機構に
ついては諸説があり、未だ確定的な説明がなされたもの
はないが、その中で、塩基性酸化物であるアルカリ土類
金属酸化物および希土類酸化物の触媒作用は、これらの
酸化物に吸着された酸素がスーパーオキサイドイオン（
０□−）を形成し、これがメタンの水素引き抜き能を増
加させ。There are various theories regarding the catalytic reaction mechanism in the oxidative dehydrogen trimerization reaction of methane, and no definitive explanation has been given yet. The catalytic action of substances is due to the fact that oxygen adsorbed on these oxides forms superoxide ions (
0□-), which increases the hydrogen abstraction ability of methane.
メチルラジカルを生成し易くするという説がある。アル
カリ土類金属酸化物と希土類酸化物とを複合酸化物にし
た本発明の触媒が低温領域から高活性、高選択性を発現
するするのは、前記酸化物の複合化によって、スーパー
オキサイドイオンがより低温で生成し易くなると共に、
活性点が相乗的に増加したものと考えられる。There is a theory that it makes it easier to generate methyl radicals. The catalyst of the present invention, which is a composite oxide of an alkaline earth metal oxide and a rare earth oxide, exhibits high activity and high selectivity from low temperature ranges because superoxide ions are generated by the composite of the oxides. It becomes easier to generate at lower temperatures, and
It is thought that the number of active sites increased synergistically.
本発明の方法による反応に供する反応ガスは、メタンと
酸素を含むガスとの混合ガスであり、酸素に対するメタ
ンの比率が高いほどメタンの完全酸化が抑制され、Ｃ２
＋化合物の選択率はよくなる。酸素を含むガスは、空気
として、あるいは酸素と不活性ガスとの混合ガスとして
供給される。The reaction gas used in the reaction according to the method of the present invention is a mixed gas of methane and a gas containing oxygen, and the higher the ratio of methane to oxygen, the more complete oxidation of methane is suppressed, and the more
+Selectivity of compounds improves. The oxygen-containing gas is supplied as air or as a mixed gas of oxygen and an inert gas.
［発明の実施例コ 以下、本発明の実施例について説明する。[Embodiments of the invention] Examples of the present invention will be described below.
（実施例１） （触媒の調製） アルカリ土類金属であるＭｇ、Ｃａ、Ｓｒ。(Example 1) (Preparation of catalyst) Mg, Ca, and Sr, which are alkaline earth metals.
Ｂａの炭酸塩をそれぞれ硝酸で溶解した溶液と、希土類
であるＹ、Ｌａ、Ｎｄの硝酸塩をそれぞれ水に溶解した
溶液とを調整した。この２グループの溶液を各種の元素
の組み合わせにより混合して多数のアルカリ土類金属化
合物と希土類化合物の混合溶液とし１、これに各々アル
カリ土類金属と希土類元素の含有量の２倍当量以上のシ
ュウ酸を加え、シュウ酸塩の共沈物を得た。これらの沈
殿物をろ別後、１２０℃で乾燥し、空気中８００℃。A solution in which Ba carbonate was dissolved in nitric acid, and a solution in which nitrates of rare earth elements Y, La, and Nd were dissolved in water were prepared. These two groups of solutions are mixed with various combinations of elements to form a mixed solution of a large number of alkaline earth metal compounds and rare earth compounds1. Oxalic acid was added to obtain a coprecipitate of oxalate. After filtering these precipitates, they were dried at 120°C and then heated in air at 800°C.
６時間焼成してアルカリ土類金属酸化物と希土類酸化物
の各種複合酸化物の触媒を得た。この際の希土類酸化物
の含有率はいずれも１０ｍ０ρ％とした。After firing for 6 hours, catalysts of various composite oxides of alkaline earth metal oxides and rare earth oxides were obtained. The content of rare earth oxides at this time was 10m0ρ% in all cases.
（反応）
上述のようにして調製した触媒０．５ｇを充填した固定
床常圧流通式反応装置に、メタン、酸素、ヘリウムを１
５ニア、５ニア７．５のモル比で混合したガスを流量４
０ｍρ／分で送入した。(Reaction) Methane, oxygen, and helium were added to a fixed bed normal pressure flow reactor filled with 0.5 g of the catalyst prepared as described above.
Gas mixed at a molar ratio of 5 nia and 5 nia 7.5 at a flow rate of 4
It was fed at a rate of 0 mρ/min.
反応温度は６５０℃と７５０℃の２条件で実施した。こ
れと同一条件での実験を前記各種複合酸化物の触媒につ
いても実施した９反応後のガスは氷温で水分をトラップ
した後、ガスクロマトグラフィーで分析し、メタンの転
化率と、エタン、エチレン、プロパン、プロピレンの合
計（Ｃ２＋化合物）の選択率を算出した。なお、エタン
、エチレン、プロパン、プロピレン以外の炭化水素は分
析限界以下であり、炭化水素以外の反応生成物は主とし
て一酸化炭素と二酸化炭素であった。この結果を第１表
に示す。The reaction was carried out under two conditions: 650°C and 750°C. Experiments under the same conditions were also conducted for the various composite oxide catalysts mentioned above.9 The gas after the reaction was analyzed by gas chromatography after trapping moisture at ice temperature, and the conversion rate of methane, ethane, ethylene, etc. , propane, and propylene (C2+ compound) was calculated. Note that hydrocarbons other than ethane, ethylene, propane, and propylene were below the analysis limit, and reaction products other than hydrocarbons were mainly carbon monoxide and carbon dioxide. The results are shown in Table 1.
（実施例２）
実施例１と同様にして調製したＹ２０Ｙ２Ｏ３１Ｏ％−
Ｃａ０９０ｍｏ！；！％の触媒について、実施例１と同
じ反応装置、触媒量、反応ガス条件により、反応温度を
５５０〜８５０℃に変化させてメタンの酸化的転化反応
を行った。この結果を第１図に示す０図中の表示におい
て、Ｃ２＋収率はメタンの転化率に０２＋選択率を乗じ
た値である。(Example 2) Y20Y2O31O%- prepared in the same manner as Example 1
Ca090mo! ;! % catalyst, an oxidative conversion reaction of methane was carried out using the same reactor, catalyst amount, and reaction gas conditions as in Example 1, with the reaction temperature varied from 550 to 850°C. The results are shown in Figure 1, where the C2+ yield is the value obtained by multiplying the methane conversion rate by the 02+ selectivity.
（実施例３）
実施例１と同様にして調製しなＹ２Ｏ３−ＣａＯの触媒
について、Ｙ２Ｏ３の含有率を種々変えた実験を行った
。実験条件は、反応温度を７００℃に固定したこと以外
は実施例１と同一の条件でメタンの酸化的転化反応を行
った。この結果を第２図に示す。(Example 3) Experiments were conducted using a Y2O3-CaO catalyst prepared in the same manner as in Example 1, with various Y2O3 contents. The oxidative conversion reaction of methane was carried out under the same experimental conditions as in Example 1, except that the reaction temperature was fixed at 700°C. The results are shown in FIG.
（比較例１）
実施例１の触媒の調製と同様の方法により、Ｙ２Ｏ，お
よびＣａＯそれぞれ単独の触媒を調製し、この触媒を実
施例１と同一の条件でメタンの酸化的転化反応を行った
。この結果は第１表の下欄に示す。(Comparative Example 1) In the same manner as in the preparation of the catalyst in Example 1, a single catalyst of Y2O and CaO was prepared, and this catalyst was subjected to an oxidative conversion reaction of methane under the same conditions as in Example 1. . The results are shown in the lower column of Table 1.
（比較例２）
実施例１の触媒の調製と同様の方法により、Ｙ２０３お
よびＣａＯそれぞれ単独の触媒を調製し、この触媒を実
施例２と同一の条件でメタンの酸化的転化反応を行った
。この結果は実施例２の結果と共に第１図に示す。(Comparative Example 2) A single catalyst of Y203 and CaO was prepared in the same manner as in the preparation of the catalyst of Example 1, and the oxidative conversion reaction of methane was performed on this catalyst under the same conditions as in Example 2. The results are shown in FIG. 1 together with the results of Example 2.
上述の実験結果について説明する。The above experimental results will be explained.
第１表において、メタン転化率、Ｃ２＋選択率について
実施例１の結果と比較例１の結果を比較すると、実施例
１は比較例１に対し大差のある高値を得ている。このよ
うに比較例１のごとくＣａＯやＹ２Ｏ，をそれぞれ単独
で触媒とするよりも、アルカリ土類金属酸化物と希土類
酸化物を複合酸化物とした場合の方が触媒性能を高めう
ろことが明らかに認められる。In Table 1, when the results of Example 1 and Comparative Example 1 are compared with respect to methane conversion rate and C2+ selectivity, Example 1 obtains higher values that are significantly different from Comparative Example 1. In this way, it is clear that using a composite oxide of an alkaline earth metal oxide and a rare earth oxide will improve the catalytic performance, rather than using CaO or Y2O as a catalyst alone as in Comparative Example 1. recognized.
第１図は反応温度とＣ２″収率について実施例２と比較
例２の結果を比較した図であるが、反応温度が６００℃
を超えると、実施例２と比較例２の差が歴然となり、実
施例２のＣ２“収率は極めて高い値となっている。Figure 1 is a diagram comparing the results of Example 2 and Comparative Example 2 regarding reaction temperature and C2'' yield.
When it exceeds , the difference between Example 2 and Comparative Example 2 becomes obvious, and the C2'' yield of Example 2 becomes an extremely high value.
第２図は本発明の実施例単独の図であり、触媒のＹ２Ｏ
３の含有率と０２＋収率の関係を示しな図である。この
図においてＡはＹ２Ｏ３含有率がｌ ｍｏρ％の点であ
り、Ｙ２Ｏ３が僅かでも含まれていれば、Ｃ２＋収率は
著しく向上することがわかる。この図で明らかなように
、触媒のＹ２Ｏ３の含有率の好ましい範囲は１〜８０ｍ
ｏρ％である。FIG. 2 is a diagram of a single example of the present invention, in which the Y2O of the catalyst
FIG. 3 is a diagram showing the relationship between the content of 3 and the yield of 02+. In this figure, A is a point where the Y2O3 content is 1 moρ%, and it can be seen that if even a small amount of Y2O3 is contained, the C2+ yield is significantly improved. As is clear from this figure, the preferable range of the Y2O3 content of the catalyst is 1 to 80 m
oρ%.
Ｙ２Ｏ３が８Ｑｍｏｆ％を超えると０２＋収率の低下の
度合いが大きくなるので好ましくない。さらに好ましい
範囲は２０〜５０ｍｏｆ％である。If Y2O3 exceeds 8Qmof%, the degree of decrease in 02+ yield will increase, which is not preferable. A more preferable range is 20 to 50 mof%.
触媒の組成；
実施例１の実験番号１〜６は希土類酸化物の含有率が１
０ｍｏ、Ｒ％、実験番号７はＹ２Ｏ３−ＣａＯ−３ｒＯ
の組成が１０−４５−４５ｍｏ、＆％、実験番号８はＹ
２０Ｂ −Ｌａ２０ｇ −ＣａＯの組成が５−５−５−
９Ｏρ％である。Composition of catalyst: Experiment numbers 1 to 6 of Example 1 had a rare earth oxide content of 1
0mo, R%, experiment number 7 is Y2O3-CaO-3rO
The composition of is 10-45-45mo, &%, experiment number 8 is Y
20B -La20g -CaO composition is 5-5-5-
It is 9Oρ%.
［発明の効果］
本発明によるメタンの転化方法は、アルカリ土類金属酸
化物と希土類酸化物の複合酸化物を触媒としてメタンと
分子状酸素を反応させる方法であり、この反応に使用す
る触媒は、従来技術におけるアルカリ土類金属酸化物ま
たは希土類酸化物単独の触媒に比べ、メタンの転化活性
およびＣ２＋化合物選択性が高く、したがって、ｃ２＋
化合物の収率が極めて高い触媒である。また、この触媒
は反応温度が６００℃近傍の低温においても、メタンの
転化活性および０２４″化合物選択性が発現する。この
ため、メタンから炭素数２以上の炭化水素類を収率よく
、しかも低温で合成することができ、炭化水素類を安価
に製造することができる。[Effect of the invention] The method for converting methane according to the present invention is a method in which methane and molecular oxygen are reacted using a composite oxide of an alkaline earth metal oxide and a rare earth oxide as a catalyst, and the catalyst used for this reaction is , has higher methane conversion activity and C2+ compound selectivity than the prior art alkaline earth metal oxide or rare earth oxide alone catalysts, and therefore c2+
This is a catalyst with extremely high compound yield. In addition, this catalyst exhibits methane conversion activity and selectivity to 024'' compounds even at low reaction temperatures of around 600°C.For this reason, it is possible to convert hydrocarbons having 2 or more carbon atoms from methane in high yields and at low temperatures. Hydrocarbons can be synthesized at low cost.
以上のように、メタンから炭化水素類を安価に製造でき
る方法である本発明は、メタンを燃料としての用途から
合成化学原料への転換をなさしめる得る発明であり、極
めて優れた発明である。As described above, the present invention, which is a method for producing hydrocarbons from methane at low cost, is an extremely excellent invention that allows methane to be converted from being used as a fuel to being used as a raw material for synthetic chemicals.
第１図は反応温度と０２４−収率について実施例２と比
較例２の結果を比較した図、第２図は本発明の実施例に
おける触媒中のＹ２Ｏ３の含有率と０２＋収率の関係を
示した図である。Figure 1 is a diagram comparing the results of Example 2 and Comparative Example 2 regarding the reaction temperature and 024-yield, and Figure 2 is a diagram showing the relationship between the content of Y2O3 in the catalyst and the 02+ yield in the example of the present invention. FIG.
Claims (6)
で反応させ、エタンとエチレンを主成分とする炭素数２
以上の炭化水素類を合成する方法において、反応条件下
で、触媒がアルカリ土類金属酸化物と希土類酸化物によ
る複合酸化物であることを特徴とするメタンの酸化的転
化方法。(1) Methane and molecular oxygen are reacted at high temperature in the presence of a catalyst, and the main components are ethane and ethylene, which have a carbon number of 2.
A method for oxidative conversion of methane, which is characterized in that the catalyst is a composite oxide of an alkaline earth metal oxide and a rare earth oxide under the reaction conditions in the above method for synthesizing hydrocarbons.
ｇＯ、ＣａＯ、ＳｒＯ、ＢａＯの中から選択される１種
または２種以上である特許請求範囲第１項記載のメタン
の酸化的転化方法。(2) The alkaline earth metal oxide that is the composition of the catalyst is M
The method for oxidative conversion of methane according to claim 1, wherein the methane is one or more selected from gO, CaO, SrO, and BaO.
、Ｌａ＿２Ｏ＿３、Ｎｄ＿２Ｏ＿３の中から選択される
１種または２種以上である特許請求範囲第１項記載のメ
タンの酸化的転化方法。(3) The rare earth oxide that is the composition of the catalyst is Y_2O_3
, La_2O_3, and Nd_2O_3. The method for oxidative conversion of methane according to claim 1.
８０ｍｏｌ％である特許請求範囲第１項又は第２項又は
第３項記載のメタンの酸化的転化方法。(4) The content of rare earth oxides in the catalyst composition is 1 to 1.
A method for oxidative conversion of methane according to claim 1 or 2 or 3, wherein the amount is 80 mol%.
〜５０ｍｏｌ％である特許請求範囲第１項〜第４項から
選ばれる１つの項に記載のメタンの酸化的転化方法。(5) The content of rare earth oxides in the catalyst composition is 20
The method for oxidative conversion of methane according to one of claims 1 to 4, wherein the amount is 50 mol %.
応温度で行う特許請求範囲第１項〜第５項から選ばれる
１つの項に記載のメタンの酸化的転化方法。(6) A method for oxidative conversion of methane according to one of claims 1 to 5, wherein the oxidative conversion reaction of methane is carried out at a reaction temperature of 600 to 850°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62328208A JPH01168626A (en) | 1987-12-24 | 1987-12-24 | Oxidative conversion of methane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62328208A JPH01168626A (en) | 1987-12-24 | 1987-12-24 | Oxidative conversion of methane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01168626A true JPH01168626A (en) | 1989-07-04 |
Family
ID=18207657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62328208A Pending JPH01168626A (en) | 1987-12-24 | 1987-12-24 | Oxidative conversion of methane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01168626A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010113993A1 (en) | 2009-04-01 | 2010-10-07 | 三井化学株式会社 | Process for producing olefin |
-
1987
- 1987-12-24 JP JP62328208A patent/JPH01168626A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010113993A1 (en) | 2009-04-01 | 2010-10-07 | 三井化学株式会社 | Process for producing olefin |
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