JPH02212437A - Method for reacting methane - Google Patents
Method for reacting methaneInfo
- Publication number
- JPH02212437A JPH02212437A JP3265289A JP3265289A JPH02212437A JP H02212437 A JPH02212437 A JP H02212437A JP 3265289 A JP3265289 A JP 3265289A JP 3265289 A JP3265289 A JP 3265289A JP H02212437 A JPH02212437 A JP H02212437A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- methane
- steam reforming
- gas
- containing gas
- 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 127
- 238000000034 method Methods 0.000 title claims description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 86
- 238000000629 steam reforming Methods 0.000 claims abstract description 35
- 238000005691 oxidative coupling reaction Methods 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 abstract description 47
- 239000003054 catalyst Substances 0.000 abstract description 38
- 239000002994 raw material Substances 0.000 abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 abstract description 9
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 239000006227 byproduct Substances 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 8
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- -1 nickel and cobalt Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 229910003443 lutetium oxide Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Hydrogen, Water And Hydrids (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〕
本発明はメタンの反応方法に関し、より詳しく言うと、
メタンや天然ガス等のメタン含有ガスからメタノール合
成をはじめとする有用化合物の合成原料等として好適に
利用することができるスチームリフォーミングガス（Ｃ
ＯとＨｔを主成分とする混合ガス）及びエチレン、エタ
ン等の炭素数２以上の有用炭化水素を同時にかつ有効に
製造することができる新規なメタンの反応方法に関する
。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for reacting methane, and more specifically,
Steam reforming gas (C
The present invention relates to a novel methane reaction method that can simultaneously and effectively produce a mixed gas containing O and Ht as main components) and useful hydrocarbons having 2 or more carbon atoms such as ethylene and ethane.
発熱反応と吸熱反応を同一反応装置内で組み合わせて行
い、正と負の反応熱を互いに補償する形で反応熱を有効
に利用しようとする反応方法は、特開昭６３−１２９０
０２号公報等により知られているが、この反応方法を実
用的に有効なものとするにはどのような反応を組み合わ
せて行うかが重要となっている。A reaction method in which an exothermic reaction and an endothermic reaction are combined in the same reactor and the positive and negative reaction heats are compensated for each other to effectively utilize the reaction heat is disclosed in Japanese Patent Application Laid-Open No. 63-1290.
This reaction method is known from Japanese Patent Application No. 02, etc., but in order to make this reaction method practically effective, it is important to decide what kind of reactions to combine.
しかしながら、そのような反応方法として、メタンの酸
化カップリング反応とスチームリフォーミングの組み合
わせに限定した例は知られていない。However, there is no known example of such a reaction method limited to a combination of methane oxidative coupling reaction and steam reforming.
ところで、このメタンの酸化カップリング反応は、酸素
の存在下、メタンや天然ガスなどのメタンを含有するガ
スからエチレン、エタン等の炭素数２以上の炭化水素を
製造する方法であり、例えば、触媒としてＬ ｉ ／
Ｍ ｇ Ｏを用いる方法〔触媒学会誌 ２７．６． Ｐ
１９９ （１９８５） ］ 、Ｍｎ、 Ｓｎ、 Ｐｂ、
Ｓｂ。By the way, this oxidative coupling reaction of methane is a method for producing hydrocarbons having two or more carbon atoms, such as ethylene and ethane, from methane or a methane-containing gas such as natural gas in the presence of oxygen. As L i /
Method using M g O [Journal of Catalysis Society 27.6. P
199 (1985) ], Mn, Sn, Pb,
Sb.
Ｂ１５Ｔｌ、Ｃｄなどを用いる方法（Ｊ、 Ｃａｔａｌ
ｙｓｉｓ＋ ７３゜９４９−１９８２） 、５ｔａｔｕ
ｓ 、Ｌｕｔｅｓなどを用いる方法（ＣｈｅＩｌ、
Ｌｅｔｔｅｒｓ、 （４）、 ４９９． １９８５
） 、Ｐｂ／ＡｌｚＯ１を用いる方法（西ドイツ公開特
許公報第３２３０７９号）、アルカリ金属と第一遷移系
列元素を含有する触媒を用いる方法（特開昭６２−２３
８２２０号公報）、カルシウム、バリウム及びストロン
チウムから選ばれる１種以上の金属元素を含有する触媒
を用いる方法（特開昭６２−２６７２４３号公報）など
が知られている。しかし、この反応は発熱反応であり完
全燃焼によるＣＯ□の副生が比較的多いこともあって発
熱量が大きく、反応熱を回収するための特別の反応装置
や冷却機構を必要とし、しかもＣＯ２の副生による炭素
源の損失が大きく製造コストが大きくなるなどの問題点
がある。Method using B15Tl, Cd, etc. (J, Catal
ysis+ 73°949-1982), 5tatu
s, Lutes, etc. (CheIl,
Letters, (4), 499. 1985
), a method using Pb/AlzO1 (West German Patent Publication No. 323079), a method using a catalyst containing an alkali metal and a first transition series element (JP-A-62-23
8220) and a method using a catalyst containing one or more metal elements selected from calcium, barium, and strontium (Japanese Patent Application Laid-Open No. 62-267243). However, this reaction is exothermic and generates a relatively large amount of CO□ as a by-product due to complete combustion, so it generates a large amount of heat and requires a special reaction device and cooling mechanism to recover the reaction heat. There are problems such as a large loss of carbon source due to the by-product of carbon dioxide, which increases manufacturing costs.
一方、メタンのスチームリフォーミングは、メタンと水
蒸気との反応により、種々の化学合成の原料として有用
な水素と一酸化炭素との混合ガスの製造を意図したもの
であり、例えば、ニッケルーアルミナをベースとする触
媒をはじめとするニッケルやコバルトなどの遷移金属等
を成分とする種々の触媒を用いる方法が知られている。On the other hand, methane steam reforming is intended to produce a mixed gas of hydrogen and carbon monoxide, which is useful as a raw material for various chemical syntheses, through the reaction of methane and water vapor. Methods using various catalysts containing transition metals such as nickel and cobalt, including catalysts based on nickel and cobalt, are known.
しかしながらこの方法においては、主反応である次の〔
１〕式
％式％（１）
が吸熱反応であり多量の熱の供給を必要とし、しかも得
られる生成ガス中のＨ２とＣＯのモル比（ＣＯ／ｌは上
記の（１）式から通常１／３付近の値となるので、メタ
ノールや混合アルコールの製造原料として用いる場合に
はその反応式が（ＧＯ＋２）１ｚ→ ＣＨ３０Ｈ；
ｍｃＯ＋２ｍ１ｌ□→ ＣＯＨｚｓ。＋ＯＨ＋ （ｍ−
１）ＨｚＯ）となることからそのモル比（ＣＯ／ｌ１ｚ
）を世論比１／２付近となるように組成を調整する必要
が生じるなどの問題点がある。また、前記熱の供給方法
として、反応系に酸素を供給しメタンのかなりの部分を
完全燃焼せしめてその反応熱により前記供給熱量を補う
などの方法が採用されることがあるが、その場合酸化生
成物は完全燃焼によるＣＯ２であるので炭素源の損失が
多くなるなどの問題が発生するのである。However, in this method, the main reaction is the following [
1] Formula % Formula % (1) is an endothermic reaction that requires the supply of a large amount of heat, and the molar ratio of H2 and CO in the resulting product gas (CO/l is usually 1 from the above formula (1). The value is around /3, so when used as a raw material for producing methanol or mixed alcohol, the reaction formula is (GO+2)1z→CH30H;
mcO+2ml□→ COHzs. +OH+ (m-
1) HzO), so its molar ratio (CO/l1z
), it is necessary to adjust the composition so that it is about 1/2 of the public opinion ratio. In addition, as a method of supplying the heat, a method is sometimes adopted in which oxygen is supplied to the reaction system to completely burn a considerable portion of methane, and the heat of reaction is used to supplement the amount of heat supplied. Since the product is CO2 from complete combustion, problems such as increased loss of carbon sources occur.
すなわち、前記酸化カップリング反応とスチームリフォ
ーミングをそれぞれ別々に、個別の反応装置内で行う場
合には、前記それぞれの問題点が生じるという問題点が
あった。That is, when the oxidative coupling reaction and the steam reforming are performed separately in separate reaction apparatuses, the above-mentioned problems arise.
本発明は、前記の事情に鑑みてなされたものである。 The present invention has been made in view of the above circumstances.
本発明の目的は、前記問題点を解決し、前記酸化カップ
リングにおける発熱量を前記スチームリフォーミングに
おける吸熱量を補う形で反応熱を有効に利用しつつ、エ
チレン、エタン等の炭素数２以上の有用炭化水素と各種
の化合物の合成原料として有用なスチームリフオーミン
グ生成ガス（ＣＯとＨ！の混合ガス若しくはそれを主成
分とする混合ガス）を効率よく製造することができ、し
かも該メタンの酸化カップリングにおいて副生ずるＣＯ
！と該スチームリフオーミングにより生成するＨ２の一
部とを次の〔２〕式
％式％（２）
で表される反応を利用して有用なＣＯに変換し炭素源の
損失を抑制するとともに、スチームリフォーミング生成
ガス中のモル比（ＣＯ／Ｌ）をメタノールや混合アルコ
ール等の原料として好適な量論比である１／２付近に近
づけるべく調整することもできるなど実用上著しく有利
な新規なメタンの反応方法を提供することにある。An object of the present invention is to solve the above-mentioned problems and effectively utilize the reaction heat in a manner that supplements the heat generated in the oxidative coupling with the heat absorbed in the steam reforming, while It is possible to efficiently produce a steam reforming product gas (mixed gas of CO and H! or a mixed gas containing CO and H! as the main components) which is useful as a raw material for synthesis of useful hydrocarbons and various compounds. CO as a by-product in the oxidative coupling of
! and a part of H2 generated by the steam reforming are converted into useful CO using the reaction expressed by the following [2] formula % formula % (2) to suppress the loss of carbon source and , it is possible to adjust the molar ratio (CO/L) in the steam reforming gas to be close to 1/2, which is the stoichiometric ratio suitable as a raw material for methanol, mixed alcohol, etc., which is a novel technology that is extremely advantageous in practical terms. The purpose of the present invention is to provide a method for reacting methane.
本発明者らは、鋭意研究を重ねた結果、メタンの酸化カ
ップリングとスチームリフオーミングを同一の反応装置
内で該酸化カップリングにおける反応熱を該スチームリ
フォーミング系に供給する形で行うという特定の反応を
組み合わせた反応方法を用いることによりそれぞれの反
応における前記問題点が有効に解決され、前記目的が容
易に達成することができることを見出し、その知見に基
づいて本発明を完成するに至った。As a result of extensive research, the present inventors have discovered that methane oxidative coupling and steam reforming are carried out in the same reactor by supplying the reaction heat in the oxidative coupling to the steam reforming system. We have discovered that by using a reaction method that combines specific reactions, the above-mentioned problems in each reaction can be effectively solved and the above-mentioned object can be easily achieved, and based on this knowledge, we have completed the present invention. Ta.
すなわち、本発明はメタンの酸化カップリングとスチー
ムリフォーミングを同一反応装置内で行わせることを特
徴とするメタンの反応方法を提供するものである。That is, the present invention provides a methane reaction method characterized by performing methane oxidative coupling and steam reforming in the same reaction apparatus.
本発明においては、前記メタンの酸化カップリングは適
当な触媒の存在下に少なくともメタン含有ガスと酸素含
有ガスを供給反応原料として用いて行い、一方前記メタ
ンのスチームリフォーミングを適当な触媒の存在下に少
なくともメタン含有ガスと水蒸気含有ガスを供給反応原
料として用いて行い、しかも該酸化カップリングと該ス
チームリフォーミングを発熱反応である前者の反応熱を
吸熱反応である後者の反応に利用する形で同一の反応装
置内で行い、エチレン、エタン等の炭素数２以上の炭化
水素とＣＯとＨ７の混合ガス若しくはそれを主成分とす
る混合ガスを生産する。In the present invention, the oxidative coupling of the methane is carried out in the presence of a suitable catalyst using at least a methane-containing gas and an oxygen-containing gas as feed reaction materials, while the steam reforming of the methane is carried out in the presence of a suitable catalyst. is carried out using at least a methane-containing gas and a water vapor-containing gas as feed reaction raw materials, and the oxidative coupling and the steam reforming are carried out in such a way that the reaction heat of the former, which is an exothermic reaction, is used for the latter, which is an endothermic reaction. It is carried out in the same reactor to produce a mixed gas of a hydrocarbon having 2 or more carbon atoms such as ethylene or ethane, CO, and H7, or a mixed gas containing the same as the main component.
本発明において、前記酸化カップリングとスチームリフ
ォーミングは、上記の形式で行うものであれば、それぞ
れ個別の反応器内で行ってもよく、同一の反応器内の別
々の反応領域で行ってもよく、あるいは前記メタン含有
ガスと前記酸素含有ガスと前記水蒸気含有ガスとを同時
に又は段階的に混合して同一の反応器内で行ってもよく
、いずれでもよい、これらの各種の反応方式の中でも、
生成物の分離が容易であり、前記それぞれの反応に用い
る触媒の性能を十分に発揮させることができるという点
などから、例えば、同心若しくはそれに類似の二重管式
反応器等の多量管式反応器又は多管式反応器などを用い
て、前記それぞれの反応を個別の反応領域で行う方式が
好ましく、中でも特に反応熱の移動を効率よ（達成させ
ることができるという点などから、例えば二重管型等の
多重管型の反応器を用い前記それぞれの反応を別々の反
応領域で行う方式が好適に採用することができる。In the present invention, the oxidative coupling and steam reforming may be carried out in separate reactors, or may be carried out in separate reaction zones within the same reactor, as long as they are carried out in the above-mentioned manner. Among these various reaction methods, the methane-containing gas, the oxygen-containing gas, and the water vapor-containing gas may be mixed simultaneously or in stages in the same reactor. ,
For example, a multi-tubular reaction such as a concentric or similar double-tube reactor is used because it is easy to separate the products and the performance of the catalyst used in each of the above reactions can be fully demonstrated. It is preferable to carry out each of the above reactions in separate reaction zones using a reactor or multi-tubular reactor. A system in which each of the reactions described above is performed in separate reaction regions using a multitubular reactor such as a tubular reactor can be suitably employed.
具体的にはシェルアンドチューブリアクターのような内
部熱交換型反応器が用いられる。Specifically, an internal heat exchange type reactor such as a shell and tube reactor is used.
前記メタン含有ガスとしては、純メタン、天然ガス、石
油系メタン含有ガス、石炭系メタン含有ガス、消化ガス
系メタン含有ガス、その他のメタン化反応により得られ
るメタン含有ガスや回収メタン含有ガスなどのメタンを
主成分として含有する混合ガスなどを使用することがで
きる。これらの中でも、特に天然ガスなどが好適に使用
される。Examples of the methane-containing gas include pure methane, natural gas, petroleum-based methane-containing gas, coal-based methane-containing gas, digestion gas-based methane-containing gas, methane-containing gas obtained by other methanation reactions, and recovered methane-containing gas. A mixed gas containing methane as a main component can be used. Among these, natural gas and the like are particularly preferably used.
前記酸素含有ガスとしては、純酸素、空気等の酸素を含
有するガスを使用することができる。As the oxygen-containing gas, a gas containing oxygen such as pure oxygen or air can be used.
前記水蒸気含有ガスとしては、水蒸気又は水蒸気を含有
する混合ガスを使用することができる。As the water vapor-containing gas, water vapor or a mixed gas containing water vapor can be used.
なお、本発明において、前記反応は必要に応じて、例え
ば、窒素、ヘリウム、アルゴン等の不活性ガスで希釈し
て行ってもよく、また本発明の目的に支障のない範囲内
で上記以外の他の成分を含有させて行ってもよい。具体
的には例えば、前記酸化カップリングは、反応原料中に
例えばハロゲン化メタン、ハロゲン化水素、ハロゲン等
のハロゲン含有化合物などを添加して行うこともでき、
また前記スチームリフォーミングは、反応原料中にＣＯ
ｌを適宜添加若しくは含有させて行うこともできる。こ
のようにＣＯｚを含有させて反応を行うことにより、ス
チームリフォーミンク生成ガス中のＣＯ／Ｈオを適宜調
節することも可能である。なお、ＣＯｔを添加して反応
を行う場合には、このＣＯｔとして前記酸化カップリン
グの副生物であるＣＯ□を有効に利用することができる
。In the present invention, the reaction may be carried out by diluting with an inert gas such as nitrogen, helium, or argon, if necessary, and other substances other than the above may be used within the range that does not interfere with the purpose of the present invention. Other components may also be included. Specifically, for example, the oxidative coupling can be carried out by adding, for example, a halogen-containing compound such as halogenated methane, hydrogen halide, or halogen to the reaction raw material,
In addition, in the steam reforming, CO is added to the reaction raw material.
It can also be carried out by appropriately adding or containing 1. By carrying out the reaction by including COz in this manner, it is also possible to appropriately adjust the CO/H2 ratio in the steam reforming gas. Note that when the reaction is carried out by adding COt, CO□, which is a by-product of the oxidative coupling, can be effectively used as the COt.
本発明において、前記酸化カップリングを行うに際して
供給するメタンと酸素の割合としては、モル比（島／Ｃ
Ｈａ ）で、通常０．０１〜１０程度の範囲内とするの
が適当である。。In the present invention, the molar ratio (island/C
Ha), which is usually within the range of about 0.01 to 10. .
本発明において、前記スチームリフォーミングを行うに
際して供給するメタンと水蒸気の割合としては、モル比
（ＨｔＯ／ ＣＨ４）で、達常１〜１０程度、好ましく
は２〜７程度の範囲内とするのが適当である。In the present invention, the ratio of methane and steam to be supplied when performing the steam reforming is preferably within the range of about 1 to 10, preferably about 2 to 7, in terms of molar ratio (HtO/CH4). Appropriate.
本発明において、前記酸化カップリングに使用する触媒
としては該酸化カップリングに有効なものであれば特に
制限がなく、公知の触媒等の各種のものを適宜選定して
使用することができる。このうち公知の触媒として、例
えば、前記文献〔触媒学会誌、訂、 ６． Ｐ１９９
（１９８５））に記載の触媒、すなわち、Ｌｉ／ＭｇＯ
など、前記文献（Ｊ、Ｃａｔａｌｙｓｉｓ、 ７３．
９−１９．１９８２）に記載の触媒、すなわち、Ｍｎ５
Ｓｎ、 Ｐｂ、 Ｓｂ、 Ｂｉ、 ＴＩ、 Ｃｄなとの
１種以上を一合有する触媒など、前記文献（Ｃｈｅｓ、
Ｌｅｔｔｅｒｓ、 （４）、 ４９９．１９８５）に
記載のすなわち、５１１２０３． Ｌｕ２Ｏ３など、特
開昭６１−１６５３４０号公報に記載の触媒すなわち、
スカンジウム、イツトリウム、ランタン、ネオジム、サ
マリウム、ユーロピウム、ガドリニウム、ジスプロシウ
ム、ホルミウム、エルビウム、ツリウム、イッテルビウ
ム、ルテチウムをはじめとする希土類元素のうちの少な
くとも一種を含有する触媒、中でも特に前記希土類元素
の酸化物のうちの少なくとも一種を含有する単独酸化物
系又は複合酸化物系又はシリカ、アルミナ、マグネシア
、チタニア、ジルコニア等の酸化物担体などの担体に担
持された担持酸化物系触媒、あるいはこれらにさらに酸
化カルシウム、酸化マグネシウム、酸化ナトリウム、酸
化カリウム等のアルカリ金属及び／又はアルカリ土類金
属の酸化物を添加した各種の触媒など、西ドイツ公開特
許公報第３２３０７９号に記載の触媒すなわち、Ｐｂ／
Ａｌ□０．など、特開昭６２−２３８２２０号公報に記
載の触媒すなわち、リチウム、ナトリウム、カリウム、
ルビジウム、セシウム等のアルカリ金属の１種又は２種
以上とチタン、マンガン、コバルト、ニッケル等の第一
遷移系列元素の１種又は２種以上を含有する触媒、中で
もこれらアルカリ金属のハロゲン化物、炭酸塩、硝酸塩
、水酸化物など特に塩化゛リチウム、硝酸リチウム、炭
酸リチウムなどの１種又は２種以上と前記第一遷移系列
元素の酸化物の１種又は２種以上からなる触媒など、特
開昭６２−２６７２４３号公報に記載の触媒すなわち、
カルシウム、バリウム及びストロンチウムから選ばれる
１種以上の金属元素を含有する触媒、中でもこれらの金
属元素の酸化物、炭酸塩などの少なくとも１種以上から
なる触媒あるいはこれらにリチウム、ナトリウム、カリ
ウム、ルビジウム等のアルカリ金属を添加した各種の触
媒などを挙げることができる。In the present invention, the catalyst used for the oxidative coupling is not particularly limited as long as it is effective for the oxidative coupling, and various known catalysts can be appropriately selected and used. Among these, known catalysts include, for example, the above-mentioned document [Journal of Catalysis Society, revised edition, 6. P199
(1985)), i.e., Li/MgO
et al. (J, Catalysis, 73.
9-19.1982), that is, Mn5
Catalysts containing one or more of Sn, Pb, Sb, Bi, TI, Cd, etc., as described in the above literature (Ches,
Letters, (4), 499.1985), i.e., 511203. Catalysts described in JP-A-61-165340, such as Lu2O3, ie,
A catalyst containing at least one of rare earth elements such as scandium, yttrium, lanthanum, neodymium, samarium, europium, gadolinium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium, especially an oxide of the rare earth element. A supported oxide catalyst supported on a support such as a single oxide catalyst or a composite oxide catalyst containing at least one of these, or an oxide support such as silica, alumina, magnesia, titania, or zirconia, or further calcium oxide. , various catalysts added with alkali metal and/or alkaline earth metal oxides such as magnesium oxide, sodium oxide, potassium oxide, etc.
Al□0. Catalysts described in JP-A-62-238220, such as lithium, sodium, potassium,
Catalysts containing one or more alkali metals such as rubidium and cesium and one or more first transition series elements such as titanium, manganese, cobalt, and nickel, especially halides of these alkali metals, and carbonic acid. Catalysts consisting of one or more salts, nitrates, hydroxides, etc., especially lithium chloride, lithium nitrate, lithium carbonate, etc., and one or more oxides of the first transition series elements, etc. The catalyst described in Publication No. 62-267243, that is,
Catalysts containing one or more metal elements selected from calcium, barium, and strontium, especially catalysts containing at least one of oxides and carbonates of these metal elements, or lithium, sodium, potassium, rubidium, etc. Examples include various catalysts to which alkali metals are added.
なお、これらの触媒は必要に応じて２種以上を組み合わ
せて用いることもできる。In addition, these catalysts can also be used in combination of two or more types as required.
本発明において、前記スチームリフォーミングに使用す
る触媒としては該スチームリフォーミングに有効に用い
ることができるものであれば特に制限はなく、公知の触
媒など各種のものを使用することができる。具体的には
例えば、ガードラー社製のＧ−５６ＨＩ触媒、ＩＣ１社
製のＩＣｌ３７−３触媒、トブソ社製のＲＫＳ−１触媒
などのニッケルーアルミナをベースとする市販の触媒な
どを好適に使用することができる。In the present invention, the catalyst used for the steam reforming is not particularly limited as long as it can be effectively used for the steam reforming, and various catalysts such as known catalysts can be used. Specifically, commercially available catalysts based on nickel-alumina such as G-56HI catalyst manufactured by Girdler, ICl37-3 catalyst manufactured by IC1, and RKS-1 catalyst manufactured by Tobso are preferably used. be able to.
前記酸化カップリング及びスチームリフォーミングの反
応条件としては、用いる触媒の種類や反応ガスの組成な
どの他の条件により異なるので、−様に規定することが
できないが、反応温度を、通常５００〜１０００℃の範
囲内とし、空間速度（ＧＨ３Ｖ）を、通常３０〜４００
． ＯＯ０ｈｒ−’の範囲内とするのが適当である。The reaction conditions for the oxidative coupling and steam reforming cannot be specified as they vary depending on other conditions such as the type of catalyst used and the composition of the reaction gas, but the reaction temperature is usually 500 to 1000. ℃, and the space velocity (GH3V) is usually 30 to 400.
．． It is appropriate to set it within the range of OO0hr-'.
反応温度が５００°Ｃ未満では反応速度が不十分となる
ことがあり、１０００″Ｃを超えると触媒の劣化が大き
くなることがある０反応圧力は、減圧下、常圧、加圧下
のいずれでも可能であるが、通常０．１〜１００ｋｇ／
ｃｉｉＧ程度の範囲内とするのが好適である。If the reaction temperature is less than 500°C, the reaction rate may be insufficient, and if it exceeds 1000°C, catalyst deterioration may increase.0Reaction pressure may be under reduced pressure, normal pressure, or elevated pressure. Possible, but usually 0.1-100kg/
It is preferable to set it within a range of approximately ciiG.
本発明において、重要な点のひとつは前記酸化カップリ
ングと前記スチームリフォーミングを前記したように該
酸化カップリングの反応熱を該スチームリフォーミング
への供給熱量として利用する形で反応装置内で行う点で
ある。なお、前記酸化カップリングにおいては、エチレ
ン、エタン等の炭素数２以上の炭化水素の生成のほかに
メタンの完全酸化によるＣＯ，の副体がヰじることが知
られている。これらの点を考慮して、酸化カップリング
とスチームリフォーミングの熱バランスを下記の０〜０
式
％式％
で表される基本反応に注目して考察すると次の通りであ
る。In the present invention, one of the important points is that the oxidative coupling and the steam reforming are performed in a reactor in such a way that the reaction heat of the oxidative coupling is used as the amount of heat supplied to the steam reforming, as described above. It is a point. It is known that in the above-mentioned oxidative coupling, in addition to producing hydrocarbons having two or more carbon atoms such as ethylene and ethane, a by-product of CO is produced by complete oxidation of methane. Considering these points, the heat balance between oxidation coupling and steam reforming is set to 0 to 0 below.
The basic reaction represented by the formula % is considered as follows.
すなわち、第１図は、上記の０〜０式で表される３つの
反応の絶対温度１０００°Ｋにおける熱バランスを示す
もので、メタンの酸化反応（上記の■と■）におけるメ
タンの転化率２をパラメーターとして、スチームリフォ
ーミング（上記の■）におけるメタンの転化率Ｘと該メ
タンの酸化反応（■と■）でのエチレンへの選択率ｙ（
■と■の反応のうち■の割合を百分率で表したもの）の
関係を示すグラフである。第１図から、例えば、そのメ
タンの酸化反応でのメタンの転化率ｚ＝４０％で前記エ
チレンへの選択率ｙ＝５０％の場合、この反応の発熱量
を利用してメタンのスチームリフォーミング（■）を行
うとするとＸ−８３％に相当する熱量を賄えることにな
る。ところが、絶対温度１０００’Ｋ、圧力１ａｔｍに
おけるメタンのスチームリフオーミング（■）の平衡転
化率は、８１．４％であるので、上記のように反応熱を
十分に利用した場合にはその反応熱のみで平衡転化率ま
で行くことになることになる。In other words, Figure 1 shows the heat balance at an absolute temperature of 1000°K for the three reactions represented by equations 0 to 0 above, and shows the conversion rate of methane in the methane oxidation reaction (■ and ■ above). 2 as parameters, the conversion rate of methane X in steam reforming (■ above) and the selectivity to ethylene in the oxidation reaction of methane (■ and ■) y (
It is a graph showing the relationship between ■ and the proportion of ■ in the reactions of ■ expressed as a percentage. From Figure 1, for example, if the conversion rate of methane in the oxidation reaction of methane is z = 40% and the selectivity to ethylene is y = 50%, the heat value of this reaction is used to steam reform the methane. If (■) is performed, the amount of heat equivalent to X-83% can be provided. However, the equilibrium conversion rate of steam reforming (■) of methane at an absolute temperature of 1000'K and a pressure of 1 atm is 81.4%, so if the reaction heat is fully utilized as described above, the reaction This means that the equilibrium conversion rate will be reached by heat alone.
ところで、メタンのスチームリフオーミングでは、上記
の０式からＣＯ／Ｌ（モル比）が１／３若しくは１／３
付近の組成を有する生成物が得られる。従って、この組
成のスチームリフオーミング生成ガスからメタノールや
混合アルコールを合成しようとする場合、これらの合成
反応はその反応式が（ＣＯ＋２Ｈｆｆｉ４Ｃ■ｓＯＨ；
ｓｃｏ ＋ ２■Ｈ３→Ｃ，Ｈｚ−−＋ＯＨ＋ （
ＩＩ＋−１）ＨｚＯ）であることから原料モル比（ＣＯ
／Ｈｚ）を量論比１／２若しくは１／２付近に例えば次
の〔２〕式
％式％（２）
で表される反応を利用して変える必要が生じる。By the way, in steam reforming of methane, CO/L (molar ratio) is 1/3 or 1/3 from the above formula 0.
Products with similar compositions are obtained. Therefore, when attempting to synthesize methanol or mixed alcohol from the steam reforming product gas with this composition, the reaction formula for these synthesis reactions is (CO+2Hffi4C■sOH;
sco + 2■H3→C,Hz--+OH+ (
II+-1)HzO), the raw material molar ratio (CO
/Hz) to 1/2 or around 1/2 of the stoichiometric ratio, for example, by using the reaction expressed by the following formula [2].
その際、従来の方法ではこのＣＯ！を別途に手当する必
要があるが、本発明では、前記メタンの酸化カップリン
グの際に副生ずるＣＯｔを有効に利用することができる
。At that time, in the conventional method, this CO! However, in the present invention, COt produced as a by-product during the oxidative coupling of methane can be effectively utilized.
以上のように、本発明によると天然ガス等のメタン若し
くはメタン含有ガスから反応熱を有効に利用しつつ、ま
た反応副生物のＣＯｔを有効に利用しつつ、エチレン、
エタン等の炭素数２以上の有用な炭化水素とメタノール
、混合アルコールなどの各種の化合物の合成原料等とし
て有用なＣＯとＨ２の混合ガス若しくはこれを含有する
混合ガスを有利に製造することができる。As described above, according to the present invention, ethylene, ethylene,
It is possible to advantageously produce a mixed gas of CO and H2, or a mixed gas containing the same, which is useful as a raw material for synthesis of various compounds such as useful hydrocarbons having two or more carbon atoms such as ethane, methanol, and mixed alcohols. .
実施例１
塩化リチウム水溶液中に所定量の酸化マンガン粉末を添
加し、蒸発乾固し、１２０°Ｃで乾燥し、次いで空気中
で７００°Ｃにて３時間焼成して２０モル％の塩化リチ
ウムを含有する触媒を調整した。Example 1 A predetermined amount of manganese oxide powder was added to a lithium chloride aqueous solution, evaporated to dryness, dried at 120°C, and then calcined in air at 700°C for 3 hours to obtain 20 mol% lithium chloride. A catalyst containing the following was prepared.
この触媒１ｇを石英ガラス製二重反応管の内側に充填し
、その外側にスチームリフォーミング用触媒Ｇ−５６Ｈ
１（ガートラー製）Ｉｇを充填した。1 g of this catalyst was packed inside a double reaction tube made of quartz glass, and the outside was filled with steam reforming catalyst G-56H.
1 (manufactured by Gertler) Ig was filled.
次に、この反応管を電気炉で７５０″Ｃに加熱しながら
、メタン、酸素及びヘリウムの混合ガスを二重反応管の
内側に供給した。メタン分圧０．０５ ａ【ｍ、酸素分
圧０．０２５ａｔｍ、全圧１ａｔｍとなるように混合し
、この混合ガスを１００Ｎａｔｅ／ｍａｉｎの割合で供
給した。二重反応管の外側には、メタン分圧０．１ａｔ
ｍ、スチーム分圧０．６ａＬｒｎ。Next, while heating this reaction tube to 750"C in an electric furnace, a mixed gas of methane, oxygen, and helium was supplied to the inside of the double reaction tube. Methane partial pressure was 0.05 a [m, oxygen partial pressure was 0.025atm and total pressure of 1atm, and this mixed gas was supplied at a rate of 100Nate/main.Methane partial pressure of 0.1atm was supplied to the outside of the double reaction tube.
m, steam partial pressure 0.6aLrn.
全圧１ａｔｍとなるように混合したガスを１００Ｎｄ／
ｓｉｎの割合で供給して反応させた。２時間後に二重管
内外のガスをそれぞれガスクロマトグラフィーで分析し
た。結果を次に示す。100Nd/gas mixed so that the total pressure is 1atm
The reaction was carried out by supplying at a sin ratio. After 2 hours, the gas inside and outside the double tube was analyzed by gas chromatography. The results are shown below.
内側（メタンの酸化カップリング）
転化率：（ＣＨ４） ４４．８％
選択率＝ （エチレン）５５％
（エタン）５．８％
（ＣＯｚ） ３８．５％
（Ｃｏ） ０．７％
外側（メタンのスチームリフォーミング）転化率１ｃＨ
４） ９９％
選択率：（ｏ２） ７７％
（ＣＯ） １３％
（Ｃ（ｈ） １０％
〔発明の効果〕
本発明によるとメタンの酸化カシプリングとスチームリ
フォーミングを同一反応装置内で行うので、天然ガス等
のメタン若しくはメタン含有ガスから反応熱を有効に利
用しつつ、また該酸化カップリングの反応副生物のＣＯ
２を有効に利用しつつ、エチレン、エタン等の炭素数２
以上の有用な炭化水素とメタノール、混合アルコールな
どの各種の化合物の合成原料等として有用なＣＯとＨ２
の混合ガス若しくはこれを含有する混合ガスを有利に製
造することができる新規なメタンの反応方法を提供する
ことができる。Inside (oxidative coupling of methane) Conversion rate: (CH4) 44.8% Selectivity = (ethylene) 55% (ethane) 5.8% (COz) 38.5% (Co) 0.7% Outside (methane) steam reforming) conversion rate 1 cH
4) 99% Selectivity: (o2) 77% (CO) 13% (C(h) 10% [Effects of the Invention] According to the present invention, methane oxidation capping and steam reforming are performed in the same reactor, so While effectively utilizing the reaction heat from methane or methane-containing gas such as natural gas, CO
While making effective use of carbon atoms such as ethylene and ethane,
The above useful hydrocarbons and CO and H2, which are useful as raw materials for the synthesis of various compounds such as methanol and mixed alcohols.
It is possible to provide a novel methane reaction method that can advantageously produce a mixed gas containing the same or a mixed gas containing the same.
第１図は、本発明の反応方法に係る反応の熱バランスを
示すグラフである。
図中の各直線ごとに示す数値（パラメーター２）は、メ
タンの酸化反応におけるメタンの転化率（％）を表し、
横軸（Ｘ）は、スチームリフォーミングにおけるメタン
の転化率（％）を表し、縦軸（ｙ）は、メタンの酸化反
応でのエチレンへの選択率を表す。FIG. 1 is a graph showing the heat balance of the reaction according to the reaction method of the present invention. The numerical value (parameter 2) shown for each straight line in the figure represents the conversion rate (%) of methane in the methane oxidation reaction,
The horizontal axis (X) represents the conversion rate (%) of methane in steam reforming, and the vertical axis (y) represents the selectivity to ethylene in the oxidation reaction of methane.
Claims (1)
グを同一反応装置内で行わせることを特徴とするメタン
の反応方法。1. A methane reaction method characterized by performing methane oxidative coupling and steam reforming in the same reaction apparatus.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3265289A JPH02212437A (en) | 1989-02-14 | 1989-02-14 | Method for reacting methane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3265289A JPH02212437A (en) | 1989-02-14 | 1989-02-14 | Method for reacting methane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02212437A true JPH02212437A (en) | 1990-08-23 |
Family
ID=12364796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3265289A Pending JPH02212437A (en) | 1989-02-14 | 1989-02-14 | Method for reacting methane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02212437A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010069488A1 (en) * | 2008-12-20 | 2010-06-24 | Bayer Technology Services Gmbh | Method for oxidative coupling of methane and producing syngas |
| CN102093157A (en) * | 2009-12-09 | 2011-06-15 | 中国科学院兰州化学物理研究所 | Joint process for preparing ethylene and synthesis gas by direct conversion of methane |
| JP2012515785A (en) * | 2009-01-26 | 2012-07-12 | ルムス テクノロジー インコーポレイテッド | Adiabatic reactor for olefin production |
| WO2016209507A1 (en) * | 2015-06-23 | 2016-12-29 | Sabic Global Technologies, B.V. | A method for producing hydrocarbons by oxidative coupling of methane without catalyst |
-
1989
- 1989-02-14 JP JP3265289A patent/JPH02212437A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010069488A1 (en) * | 2008-12-20 | 2010-06-24 | Bayer Technology Services Gmbh | Method for oxidative coupling of methane and producing syngas |
| JP2012515785A (en) * | 2009-01-26 | 2012-07-12 | ルムス テクノロジー インコーポレイテッド | Adiabatic reactor for olefin production |
| CN102093157A (en) * | 2009-12-09 | 2011-06-15 | 中国科学院兰州化学物理研究所 | Joint process for preparing ethylene and synthesis gas by direct conversion of methane |
| WO2016209507A1 (en) * | 2015-06-23 | 2016-12-29 | Sabic Global Technologies, B.V. | A method for producing hydrocarbons by oxidative coupling of methane without catalyst |
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