JPH04122444A - Production of methanol from carbon dioxide - Google Patents
Production of methanol from carbon dioxideInfo
- Publication number
- JPH04122444A JPH04122444A JP2242941A JP24294190A JPH04122444A JP H04122444 A JPH04122444 A JP H04122444A JP 2242941 A JP2242941 A JP 2242941A JP 24294190 A JP24294190 A JP 24294190A JP H04122444 A JPH04122444 A JP H04122444A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- oxide
- copper
- selectivity
- catalyst
- 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 132
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 28
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 107
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- 239000011787 zinc oxide Substances 0.000 claims abstract description 53
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000005751 Copper oxide Substances 0.000 claims abstract description 42
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 42
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 10
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 3
- UFQXGXDIJMBKTC-UHFFFAOYSA-N oxostrontium Chemical compound [Sr]=O UFQXGXDIJMBKTC-UHFFFAOYSA-N 0.000 claims abstract description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract 3
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 15
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 2
- 229910003440 dysprosium oxide Inorganic materials 0.000 claims description 2
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 claims description 2
- ZXGIFJXRQHZCGJ-UHFFFAOYSA-N erbium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Er+3].[Er+3] ZXGIFJXRQHZCGJ-UHFFFAOYSA-N 0.000 claims description 2
- OWCYYNSBGXMRQN-UHFFFAOYSA-N holmium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ho+3].[Ho+3] OWCYYNSBGXMRQN-UHFFFAOYSA-N 0.000 claims description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims 1
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 claims 1
- 238000009903 catalytic hydrogenation reaction Methods 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
- 239000011949 solid catalyst Substances 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 156
- 229910052739 hydrogen Inorganic materials 0.000 description 54
- 239000001257 hydrogen Substances 0.000 description 53
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 50
- 229910052802 copper Inorganic materials 0.000 description 38
- 239000010949 copper Substances 0.000 description 38
- 238000001816 cooling Methods 0.000 description 23
- 239000006227 byproduct Substances 0.000 description 22
- 239000007789 gas Substances 0.000 description 21
- 239000000376 reactant Substances 0.000 description 13
- 239000012495 reaction gas Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 208000037386 Typhoid Diseases 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 201000008297 typhoid fever Diseases 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
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、二酸化炭素から効率的にメタノールを合成す
る新規な方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel method for efficiently synthesizing methanol from carbon dioxide.
［従来技術］
メタノールは重要な基礎化学品であり、世界で年間約２
Ｏ００万トンの需要がある。その合成は、天然ガスや石
油、石炭を水蒸気改質や部分酸化して得ることができる
一酸化炭素と水素の混合ガス（合成ガス）を原料として
、次式のように高温高圧下での触媒反応により合成され
、完成度の高い実用化プロセスとなっている。[Prior art] Methanol is an important basic chemical, and about 2
There is a demand of O million tons. Its synthesis uses a mixed gas (synthesis gas) of carbon monoxide and hydrogen, which can be obtained by steam reforming or partial oxidation of natural gas, oil, or coal, as a raw material, using a catalyst under high temperature and high pressure as shown in the following formula. It is synthesized through a reaction, making it a highly complete process for practical use.
ＧＯ＋２Ｈ２→ ＣＨ３０Ｉ］
一方、合成ガス以外からのメタノール合成法に関しては
、例えば二酸化炭素と水素からの合成が学術的見地から
基礎研究レベルで検討されている程度であった。−例と
して、銅−亜鉛混合酸化物しかし、昨今の世界的な産業
経済活動規模の拡大に伴い、地球レベルでの環境破壊が
重量な問題となり、その対応策が世界的に検討されはし
めている。なかでも、地球温暖化問題は人類のみならず
、地球そのものにも著しい悪影響を与えることが推定さ
れ、地球温暖化の主要因とされている二酸化炭素の大気
中への排出を防止すべく、その対応策の確立が強く要請
されている。GO+2H2→CH30I] On the other hand, regarding methanol synthesis methods from sources other than synthesis gas, for example, synthesis from carbon dioxide and hydrogen has only been studied at the basic research level from an academic standpoint. - For example, copper-zinc mixed oxide However, with the recent expansion of global industrial and economic activities, environmental destruction at the global level has become a serious issue, and countermeasures are being considered worldwide. . In particular, the problem of global warming is estimated to have a significant negative impact not only on humanity but also on the earth itself, and efforts are being made to prevent the emission of carbon dioxide into the atmosphere, which is considered the main cause of global warming. There is a strong need to establish countermeasures.
本発明者らは、排出される二酸化炭素を炭素資源と考え
、これを回収再資源化し、二酸化炭素から有用化学品を
合成できるプロセスを開発できれば、二酸化炭素の排出
抑制と資源利用の観点から最も有効な対策を確立するこ
とができると考え、二酸化炭素の有効利用技術について
、鋭意研究を行なった結果、二酸化炭素から効率的にメ
タツルを合成できる方法を発明するに至った。The inventors consider that emitted carbon dioxide is a carbon resource, and believe that if we can develop a process that can recover and recycle it and synthesize useful chemicals from carbon dioxide, it will be the best from the perspective of reducing carbon dioxide emissions and resource utilization. Thinking that an effective countermeasure could be established, he conducted intensive research into techniques for effectively utilizing carbon dioxide, and as a result, he came up with a method for efficiently synthesizing metal vines from carbon dioxide.
［発明が解決しようとする問題点コ
従って、本発明は二酸化炭素による地球温暖化るだめの
ものであり、地球温暖化の抑制と効率的なメタノール合
成の新しい方法を提供するものである。[Problems to be Solved by the Invention] Therefore, the present invention aims to prevent global warming caused by carbon dioxide, and provides a new method for suppressing global warming and efficiently synthesizing methanol.
［課題を解決するための手段］
すなわち本発明によれば、特定の金属酸化物を担体とし
て、これに銅と酸化亜鉛を担体に担持した新しい固体触
媒を使用することを特徴とし、酸化炭素の接触水素化法
による効率的なメタツルへの変換方法が提供される。[Means for Solving the Problems] That is, according to the present invention, a new solid catalyst in which copper and zinc oxide are supported on a specific metal oxide as a carrier is used. Provided is an efficient method for converting into metavine using a catalytic hydrogenation method.
以下に本発明の詳細な説明する。The present invention will be explained in detail below.
本発明に使用される触媒を構成する特定の金属酸化物は
、いかなる物理的な形態を持っていてもよい。すなわち
微粉末、粗粒子、ペレットなどその形態は任意である。The specific metal oxide that constitutes the catalyst used in the present invention may have any physical form. That is, the form thereof may be arbitrary, such as fine powder, coarse particles, pellets, etc.
また、表面積は０．１〜１０００ｍ／ｇ程度のものでよ
く、細孔が存在する場合でも、その大きさや分布が任意
のものを使用することができる。好ましくは、径］、、
５ｍｍ前後の粒子に成型したものがよい。Further, the surface area may be about 0.1 to 1000 m/g, and even if pores are present, any size and distribution of pores can be used. Preferably, the diameter],
It is best to use particles molded into particles of around 5 mm.
塩化物や更には酢酸塩などの有機塩が使用可能であり任
意である。好ましくは硝酸塩や酢酸塩を使用する。Organic salts such as chlorides and even acetates can be used and are optional. Preferably, nitrates and acetates are used.
本発明に使用される触媒を構成する銅及び酸化亜鉛の担
持量は任意であるが、好ましくは、銅担持量１〜３０ｗ
ｔ％を使用する。また銅／酸化亜鉛はモル比は１００／
１〜１ ／ １００でよく、好ましくは３／１〜１／３
の範囲で使用する。The supported amount of copper and zinc oxide constituting the catalyst used in the present invention is arbitrary, but preferably the supported amount of copper is 1 to 30 w.
Use t%. The molar ratio of copper/zinc oxide is 100/
It may be 1 to 1/100, preferably 3/1 to 1/3
Use within the range.
銅及び亜鉛化合物前駆体を金属酸化物に担持する方法は
、含浸法、沈殿法や物理的混合法など任意である。好ま
しくは硝酸塩前駆体溶液を含浸液とする含浸法が使用さ
れる。前駆体溶液を含浸する前に、金属酸化物は１５０
〜５００ ’Ｃの間で排気加熱処理を行なうことが好ま
しい。The method for supporting the copper and zinc compound precursors on the metal oxide may be any method such as an impregnation method, a precipitation method, or a physical mixing method. Preferably, an impregnation method using a nitrate precursor solution as the impregnation liquid is used. Before impregnating with the precursor solution, the metal oxide was heated to 150
It is preferable to carry out the exhaust heat treatment at a temperature between 500'C and 500'C.
銅及び亜鉛化合物が担持された金属酸化物は酸素気流中
または空気気流中で焼成することが好ましい。焼成温度
は２Ｏ０〜８００℃の間の温度で焼成を行なう。担持さ
れた銅及び酸化亜鉛前駆体しも必要ではない。The metal oxide supporting copper and zinc compounds is preferably calcined in an oxygen stream or an air stream. The firing temperature is between 200 and 800°C. Supported copper and zinc oxide precursors are also not required.
焼成された触媒は、水素気流中で還元処理を行なう。還
元温度は１００〜１０００ ’Ｃまでの間の温度で任意
である。好ましくは、２Ｏ０〜６００°Ｃの間の温度で
水素還元処理を行なう。The calcined catalyst is subjected to reduction treatment in a hydrogen stream. The reduction temperature is arbitrary between 100 and 1000'C. Preferably, the hydrogen reduction treatment is carried out at a temperature between 2O0 and 600°C.
本発明により製造された触媒は二酸化炭素と水素の混合
ガスからのメタノール合成に使用されるが、その反応の
形式は任意であり、気相固定床流通式、気相流動床、液
相懸濁床のいずれでもよい。The catalyst produced according to the present invention is used for methanol synthesis from a mixed gas of carbon dioxide and hydrogen, but the reaction format can be arbitrary: gas phase fixed bed flow type, gas phase fluidized bed, liquid phase suspension. Any floor is fine.
本発明に使用される触媒は、例えば反応管に充填した後
、反応に先立って水素還元処理を行なうことが好ましい
が、この処理はなくてもよい。The catalyst used in the present invention is preferably subjected to a hydrogen reduction treatment prior to the reaction, for example after being filled into a reaction tube, but this treatment may be omitted.
本発明を実施する条件、すなわち炭酸ガスと水素の混合
ガスからメタノールを合成する反応条件として、圧力は
常圧〜３００ ｋ ｇ／ｃＪ、好ましくは１０〜１００
ｋｇ／ｃＪで、反応温度は１００〜４００℃、好ましく
は１８０−３００°Ｃがよい。The conditions for implementing the present invention, that is, the reaction conditions for synthesizing methanol from a mixed gas of carbon dioxide gas and hydrogen, are such that the pressure is normal pressure to 300 kg/cJ, preferably 10 to 100 kg/cJ.
kg/cJ, and the reaction temperature is 100-400°C, preferably 180-300°C.
Ｃ○２／Ｈ２モル比は１７１０〜３／１であり、好まし
くは１／４〜１／１を使用する。また、反応ゝチフスの
流速は任意であるか、空間速度としてＧ ＨＳＶが５０
〜２Ｏ０００ｈ ’が好ましい。The C○2/H2 molar ratio is 1710 to 3/1, preferably 1/4 to 1/1. In addition, the flow rate of reactive typhoid fever is arbitrary, or the space velocity is GHSV 50.
~2000h' is preferred.
［実施例］ 次に本発明を実施例により、更に詳細に説明する。[Example] Next, the present invention will be explained in more detail with reference to Examples.
実施例１
固定床加圧流通式反応装置の反応管にＣｅ、のメタノー
ルへの変換用触媒としてアルミナ（Ａｌ２Ｏ３）に銅と
酸化亜鉛（銅担持量５ｗｔ％、銅／酸化並／酸化亜鉛：
１）を担持した触媒を１ｇ充填した。反応に先立って触
媒を３５０°Ｃで３０分水素還元処理した。水素気流中
で放冷した後、室温にて反応ガス（ＣＯ，／Ｈ２／Ａｒ
−３０／６０／１０、Ａｒは内部標準）に切り替え、反
応温度２２Ｏ°Ｃ１反応圧力３０ｋｇ／ｃＪ、流速１０
０ｍ］／ｍｎｉで反応を行った。反応開始１時間後のメ
タノール生成量は１３３０μｍｏｌ／Ｌ１１、選択率３
９％であった。副生成物としてはＣＯが２Ｏ６０ μｍ
ｏ１．／ｇ、ｈ（選択率６１％）、メタンが２μｍｏ１
．／ｇ、ｈ（選択率路Ｏ％）であった。反応結果を表に
示す。Example 1 Copper and zinc oxide (copper loading 5 wt%, copper/normal oxide/zinc oxide:
1 g of the catalyst supporting 1) was charged. Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350°C for 30 minutes. After cooling in a hydrogen stream, reactant gas (CO, /H2/Ar
-30/60/10, Ar is internal standard), reaction temperature 22O°C, reaction pressure 30kg/cJ, flow rate 10
0 m]/mni. The amount of methanol produced 1 hour after the start of the reaction was 1330 μmol/L11, and the selectivity was 3.
It was 9%. As a by-product, CO is 2O60 μm
o1. /g, h (selectivity 61%), methane is 2 μmol
．． /g, h (selectivity 0%). The reaction results are shown in the table.
実施例２
一
ゝ５固定床加圧流通式反応装置の反応管にＣｅ２のメタ
ノールへの変換用触媒としてシリカ（Ｓｉｎ２）に銅と
酸化亜鉛（銅担持量５ｗｔ％、銅／酸化並／酸化亜鉛：
１）を担持した触媒を１ｇ充填した。反応に先立って触
媒を３５０℃で３０分水素還元処理した。水素気流中で
放冷した後、室温にて反応ガス（ＣＯ２／１１２／ Ａ
ｒ３０／６０／１０、Ａｒは内部標準）に切り替え、反
応温度２２Ｏ℃、反応圧力３０ｋｇ／ａ＃、流速１００
ｍ１／ｍｎｉで反応を行った。反応開始１時間後のメタ
ノール生成量は１３６０μｍｏｌ／ｇ、ｈ、選択率３部
であった。副生成物としてはＣＯが７１０μｍｏｌ／ｇ
、ｈ（選択率３４％）、メタンが１μｍｏｌ／ｇ、ｈ（
選択率路Ｏ％）であった。反応結果を表に示す。Example 2 Copper and zinc oxide (copper supported amount: 5 wt%, copper/normal oxide/zinc oxide) were added to silica (Sin2) as a catalyst for converting Ce2 to methanol in the reaction tube of a 1.5 fixed bed pressurized flow reactor. :
1 g of the catalyst supporting 1) was charged. Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350°C for 30 minutes. After cooling in a hydrogen stream, reactant gas (CO2/112/A
r30/60/10, Ar is internal standard), reaction temperature 22O ℃, reaction pressure 30kg/a#, flow rate 100
The reaction was carried out at m1/mni. The amount of methanol produced 1 hour after the start of the reaction was 1360 μmol/g, h, and the selectivity was 3 parts. As a by-product, CO is 710 μmol/g.
, h (selectivity 34%), methane 1 μmol/g, h (
The selectivity was 0%). The reaction results are shown in the table.
実施例３
固定床加圧流通式反応装置の反応管にＣｅ２のメタノー
ルへの変換用触媒としてチタニア（ＴｊＯ□）に銅と酸
化亜鉛（銅担持量５ｔｉｔ％＋銅／酸化亜鉛モル比１：
１）を担持した触媒を１ｇ充填した。反応に先立って触
媒を３５０℃で３０分水素還元処理した。水素気流中で
放冷した後、室温にて反応ガス（ＣＯ２／１２／（（−
一
一−−Ａ〒＝３０／６０／１０． Ａｒは内部標準）に
切り替え、反応温度２２Ｏ°Ｃ１反応圧力３０ｋｇ／ａ
Ｋ、流速１００ｍ１／ｍｎｊで反応を行った。反応開始
１時間後のメタノール生成ｆｔハ１２８０μｍｏｌ／ｇ
、ｈ、選択率７８％テあった。副生成物としてはＣＯが
３６０ μｍｏｌ／ｇ、ｈ（選択率２２％）、メタンが
１μｍｏ１．／ｇ、ｈ（選択率路０％）であった。反応
結果を表に示す。Example 3 Copper and zinc oxide (copper loading amount 5 tit% + copper/zinc oxide molar ratio 1:
1 g of the catalyst supporting 1) was charged. Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350°C for 30 minutes. After cooling in a hydrogen stream, the reaction gas (CO2/12/((-
11--A〒=30/60/10. Ar is an internal standard), reaction temperature is 22O°C, reaction pressure is 30kg/a.
The reaction was carried out at a flow rate of 100 ml/mnj. Methanol production ft 1280 μmol/g 1 hour after the start of the reaction
, h, the selectivity was 78%. By-products include CO at 360 μmol/g (selectivity 22%) and methane at 1 μmol/g. /g, h (selectivity 0%). The reaction results are shown in the table.
実施例４
固定床加圧流通式反応装置の反応管にＣｅ２のメタノー
ルへの変換用触媒としてクロミア（Ｃｒ２Ｏ□）に銅と
酸化亜鉛（銅担持量５ｗｔ％ 、銅／酸化亜釦モル比１
：１）を担持した触媒を１ｇ充填した。反応に先立って
触媒を３５０℃で３０分水素還元処理した。水素気流中
で放冷した後、室温にて反応ガス（ＣＯ７／Ｈ２／Ａｒ
＝３０／６０／１０、Ａｒは内部標準）に切り替え、反
応温度２２Ｏ°Ｃ１反応圧力３０ｋｇ／ ｃｓＫ、流速
１００ｍ１／ｍｎ］で反応を行った。反応開始１時間後
のメタノール生成量は９６０μｍｏｌ−／ｇ、ＩＴ、選
択率７７％であった。副生成物としてはＣＯが２９０
μｍｏｌ／ｇ、ｈ（選択率２３％）、メタンが１μｍｏ
ｌ／ｇ、ｈ（選択率路０％）であった。反応結果を表に
示す。Example 4 Chromia (Cr2O□), copper and zinc oxide (copper loading amount 5 wt%, copper/zinc oxide molar ratio 1
:1 g of the catalyst supporting 1) was charged. Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350°C for 30 minutes. After cooling in a hydrogen stream, the reaction gas (CO7/H2/Ar
=30/60/10, Ar is an internal standard), reaction temperature was 220°C, reaction pressure was 30kg/csK, and flow rate was 100ml/mn]. The amount of methanol produced 1 hour after the start of the reaction was 960 μmol/g, IT, and the selectivity was 77%. As a by-product, CO is 290
μmol/g, h (selectivity 23%), methane is 1 μmol
l/g, h (selectivity 0%). The reaction results are shown in the table.
実施例５
固定床加圧流通式反応装置の反応管にＣＯ２のメタノー
ルへの変換用触媒としてジルコニア（ＺｒＯ２）に銅と
酸化亜鉛（銅担持量５ｗｔ％、銅／酸化亜釦モル比ｌ：
１）を担持した触媒を１ｇ充填した。反応に先立って触
媒を３５０°Ｃで３０分水素還元処理した。水素気流中
で放冷した後、室温にて反応ガス（Ｃｏ２／Ｈ、、／
Ａｒ３０／６０／１００． Ａｒは内部標準〕に切り替
え、反応温度２２Ｏ℃、反応圧力３０ｋｇ／ｄ、流速１
００ｍ１／ｍｎｊで反応を行った。反応開始１時間後の
メタノール生成量は９１０μｍｏｌ／ｇ、ｈ、選択率５
７％であった。副生成物としてはＣＯが７００μｍｏｌ
／ｇ、ｈ（選択率４３％）、メタンが１ μｍｏ１．／
ｇ、ｈ（選択１ｍ８ｏ％）であった。反応結果を表に示
す。Example 5 Copper and zinc oxide (copper supported amount 5 wt%, copper/zinc oxide molar ratio l:
1 g of the catalyst supporting 1) was charged. Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350°C for 30 minutes. After cooling in a hydrogen stream, reactant gas (Co2/H, , /
Ar30/60/100. Ar is an internal standard], the reaction temperature is 220°C, the reaction pressure is 30 kg/d, and the flow rate is 1.
The reaction was carried out at 00 m1/mnj. The amount of methanol produced 1 hour after the start of the reaction was 910 μmol/g, h, selectivity 5
It was 7%. 700 μmol of CO as a by-product
/g, h (selectivity 43%), methane was 1 μmo1. /
g, h (selection 1m8o%). The reaction results are shown in the table.
実施例６
固定床加圧流通式反応装置の反応管にＣｅ２のメタノー
ルへの変換用触媒としてセリア（ＣｅＯ□）に銅と酸化
亜鉛（銅担持量５ｗｔ％、銅／酸化並／酸化亜鉛：１）
を担持した触媒を１ｇ充填した。反応に先立って中で放
冷した後、室温にて反応ガス（Ｃｏ２／Ｈ，、／ Ａｒ
３０／６０／１．０、Ａｒは内部標準）に切り替え、反
応温度２２Ｏ℃、反応圧力３０ｋｇ／ ｄ、流速１００
ｍ１／ｍｎｉで反応を行った。反応開始１時間後のメタ
ノール生成量は８３０μｍｏ１．／ｇ、ｈ、選択率７９
″１であった。副生成物としてはＣＯが２２Ｏ ｐ ｍ
ｏｌ／ｇ、ｈ（選択＄２１％）、メタンが１μｍｏ１．
／ｇ、ｈ（選択率路０％）であった。反応結果を表に示
す。Example 6 Copper and zinc oxide (copper supported amount: 5 wt%, copper/normal oxide/zinc oxide: 1 )
1 g of the catalyst supporting the above was charged. Prior to the reaction, the reactant gas (Co2/H,,/Ar
30/60/1.0, Ar is internal standard), reaction temperature 22O℃, reaction pressure 30kg/d, flow rate 100
The reaction was carried out at m1/mni. The amount of methanol produced 1 hour after the start of the reaction was 830 μmol. /g, h, selectivity 79
``1.As a by-product, CO was 22O p m
ol/g, h (selection $21%), methane 1 μmol 1.
/g, h (selectivity 0%). The reaction results are shown in the table.
実施例７
固定床加圧流通式反応装置の反応管にＣｏ２のメタノー
ルへの変換用触媒としてイツトリア（Ｙ２Ｏ２）に銅と
酸化亜鉛（銅担持量５ｗｔ％、銅／酸化並／酸化亜鉛：
１）を担持した触媒を１ｇ充填した。反応に先立って触
媒を３５０℃で３０分水素還元処理した。水素気流中で
放冷した後、室温にて反応ガス（Ｃ０２／Ｈ２／Ａｒ＝
３０／６０／１０、Ａｒは内部標準）に切り替え、反応
温度２２Ｏ℃、反応圧力３０ｋｇ／ ｉ、流速Ｌｏｏｍ
］、／ｍｎｊで反応を行った。反応開始１時間後のメタ
ノール生成量は６５０μｍｏ１．／ｇ、ｈ、選択率８２
％であった。副一唖成物としてはＣＯが１４０ ｐ ｍ
ｏｌ、７ｇ、ｈ（選択率１８Ｉ）、メタンが１μｍｏｌ
／ｇ、ｈ（選択率路０１）であった。反応結果を表に示
す。Example 7 Copper and zinc oxide (copper loading 5 wt%, copper/normal oxide/zinc oxide:
1 g of the catalyst supporting 1) was charged. Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350°C for 30 minutes. After cooling in a hydrogen stream, the reaction gas (C02/H2/Ar=
30/60/10, Ar is internal standard), reaction temperature 22O℃, reaction pressure 30kg/i, flow rate Loom
], /mnj. The amount of methanol produced 1 hour after the start of the reaction was 650 μmol1. /g, h, selectivity 82
%Met. As a minor component, CO is 140 p m
ol, 7g, h (selectivity 18I), methane 1 μmol
/g, h (selectivity path 01). The reaction results are shown in the table.
実施例８
固定床加圧流通式反応装置の反応管にＣｏ２のメタノー
ルへの変換用触媒として酸化プラセオジム（Ｐｒ、Ｏ□
１）に銅と酸化亜鉛（銅担持量５ｔｉｔ％、銅／酸化亜
鉛モル比１：１）を担持した触媒を］ｇ充填した。Example 8 Praseodymium oxide (Pr, O□
1) was filled with ] g of a catalyst supporting copper and zinc oxide (copper supported amount: 5 tit %, copper/zinc oxide molar ratio 1:1).
反応に先立って触媒を３５０℃で３０分水素還元処理し
た。水素気流中で放冷した後、室温にて反応ガス（Ｃｏ
７／Ｈ，、／ Ａｒ・３０／６０／１．０、Ａｒは内部
標＄）に切り替え、反応温度２２Ｏ°Ｃ１反応圧力３０
ｋｇ／ ｃｉ、流速１００ｍ１／ｍｎｉで反応を行った
。反応開始１時間後のメタノール生成量は６５０ μｍ
ｏ］、／ｇ、ｈ、選択＄８２％であった。副生成物とし
てはＣＯが１４０μｍｏ］、／ｇ、ｈ（選択率１８％）
、メタンが２ μｍｏｌ／ｇ、ｈ （選択率路０％）で
あった。Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350°C for 30 minutes. After cooling in a hydrogen stream, the reaction gas (Co
7/H,,/Ar・30/60/1.0, Ar is internal standard $), reaction temperature 22O°C1 reaction pressure 30
The reaction was carried out at a flow rate of 100 ml/mni at a flow rate of 100 ml/mni. The amount of methanol produced 1 hour after the start of the reaction was 650 μm.
o], /g, h, selection $82%. As a by-product, CO is 140 μmo], /g, h (selectivity 18%)
, methane was 2 μmol/g, h (selectivity path 0%).
反応結果を表に示す。The reaction results are shown in the table.
実施例９
固定床加圧流通式反応装置の反応管にＣｏ２のメタノー
ルへの変換用触媒としてマグネシア（ＭｇＯ）し１
−に銅と酸化亜鉛（銅担持量５ｗｔ％、銅／酸化亜釦モ
ル比１：１）を担持した触媒を１ｇ充填した。反応に先
立って触媒を３５０°Ｃで３０分水素還元処理した。水
素気流中で放冷した後、室温にて反応ガス（Ｃｏ２／Ｈ
，、／Ａｒ−３０／６０／１０、Ａｒは内部標準）に切
り替え、反応温度２２Ｏ℃、反応圧力３０ｋｇ／ｄ、流
速１００ｍ１／ｍｎｊで反応を行った。反応開始１時間
後のメタノール生成量は５９０μｍｏｌ／ｇ、ｈ、選択
率９１％であった。副生成物としてはＣＯが６０μｍｏ
ｌ／ｇ、ｈ（選択率９％）、メタンが１μｍｏ］、／ｇ
、ｈ（選択率路ぼ）であった。反応結果を表に示す。Example 9 Magnesia (MgO) was used as a catalyst for converting Co2 into methanol in a reaction tube of a fixed bed pressurized flow reactor, and copper and zinc oxide (copper loading amount 5 wt%, copper/zinc oxide molar ratio 1 g of a catalyst supporting 1:1) was charged. Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350°C for 30 minutes. After cooling in a hydrogen stream, the reaction gas (Co2/H
,,/Ar-30/60/10, Ar is an internal standard), and the reaction was carried out at a reaction temperature of 220° C., a reaction pressure of 30 kg/d, and a flow rate of 100 ml/mnj. The amount of methanol produced 1 hour after the start of the reaction was 590 μmol/g, h, and the selectivity was 91%. As a by-product, CO is 60μmo
l/g, h (selectivity 9%), methane 1 μmo], /g
, h (selectivity road). The reaction results are shown in the table.
実施例１０
固定床加圧流通式反応装置の反応管にＣｏ２のメタノー
ルへの変換用触媒として酸化タンタル（Ｔａ２ＯＳ）に
銅と酸化亜鉛（銅担持量５ｗｔ％、銅／酸化並／酸化亜
鉛：１）を担持した触媒を１ｇ充填した。反応に先立っ
て触媒を３５０℃で３０分水素還元処理した。Example 10 Copper and zinc oxide (copper loading 5 wt%, copper/normal oxide/zinc oxide: 1 ) was charged in an amount of 1 g. Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350°C for 30 minutes.
水素気流中で放冷した後、室温にて反応ガス（Ｃｏ２／
Ｈ２／ Ａｒ−３０／６０／１０． Ａｒは内部標準）
に切り替え、反応温度２２Ｏ°Ｃ１反応圧力３０ｋｇ／
ｃｎ？、流速１００ｍ］、／ｍｎ→み反応を行った。反
応開始１時間後のメタノール生成量は５３０μｍｏ１／
ｇ、ｈ、選択率７９％であった。副生成物としてはＣＯ
が１３０ μｍｏｌ／ｇ、ｈ （選択率２１ｒ）、メタ
ンが１μｍｏｌ／ｇ、ｈ（選択率路０％）であった。反
応結果を表に示す。After cooling in a hydrogen stream, reactant gas (Co2/
H2/Ar-30/60/10. (Ar is internal standard)
, reaction temperature 22O°C, reaction pressure 30kg/
cn? , flow rate 100 m], /mn → reaction was carried out. The amount of methanol produced 1 hour after the start of the reaction was 530 μmol/
g, h, selectivity was 79%. CO as a by-product
was 130 μmol/g, h (selectivity 21r), and methane was 1 μmol/g, h (selectivity 0%). The reaction results are shown in the table.
実施例１１
固定床加圧流通式反応装置の反応管にＣｏ２のメタノー
ルへの変換用触媒として酸化イソテリビウム（Ｙｂ２Ｏ
３）に銅と酸化亜鉛（銅担持量５ｔｉｔ％、銅／酸化亜
釦モル比１：１）を担持した触媒を１ｇ充填した。Example 11 Isoterbium oxide (Yb2O) was added as a catalyst for converting Co2 to methanol in the reaction tube of a fixed bed pressurized flow reactor
3) was filled with 1 g of a catalyst supporting copper and zinc oxide (copper supported amount: 5 tit %, copper/zinc oxide molar ratio 1:1).
反応に先立って触媒を３５０℃で３０分水素還元処理し
た。水素気流中で放冷した後、室温にて反応ガス（Ｃｏ
２／Ｈ２／Ａｒ：３０／６０／１０、Ａｒは内部標＄）
に切り替え、反応温度２２Ｏ℃、反応圧力３０ｋｇ／ｃ
ｎ？、流速１００ｍ１／ｍｎｊで反応を行った。反応開
始１時間後のメタノール生成量は５００ ｐ ｍｏｌ／
ｇ、ｈ、選択率９０％であった。副生成物としてはＣＯ
が６０μｍｏｌ／ｇ、ｈ（選択率１０石）、メタンが１
μｍｏｌ／ｇ、ｈ（選択率路０％）であった。Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350°C for 30 minutes. After cooling in a hydrogen stream, the reaction gas (Co
2/H2/Ar: 30/60/10, Ar is internal standard $)
, the reaction temperature was 22O℃, and the reaction pressure was 30kg/c.
n? , the reaction was carried out at a flow rate of 100 m1/mnj. The amount of methanol produced 1 hour after the start of the reaction was 500 pmol/
g, h, selectivity was 90%. CO as a by-product
is 60 μmol/g, h (selectivity 10 stones), methane is 1
It was μmol/g, h (selectivity: 0%).
反応結果を表に示す。The reaction results are shown in the table.
実施例１２
ゝ５論定床加圧流通式反応装置の反応管にＣＯ２のメタ
ノールへの変換用触媒としてネオジア（Ｎｄ２Ｏ３）に
銅と酸化亜鉛（銅担持量５ｗｔ％、銅／酸化並／酸化亜
鉛：１）を担持した触媒を斥充填した。反応に先立って
触媒を３５０°Ｃで３０分水素還元処理した。水素気流
中て放冷した後、室温にて反応ガス（Ｃｏ、、／＋１２
／Ａｒ＝３０／６０／１０、Ａｒは内部標準）に切り替
え、反応温度２２Ｏ°Ｃ１反応圧力３０ｋｇ／ ａｌ、
流速１００ｍ１／ｍｎｉで反応を行った。反応開始１時
間後のメタノール生成量は４７０μｍＯ」／ε、ｈ、選
択率９４％であった。副生成物としてはＣＯが３０ ｐ
ｍｏｌ−／ｇ、ｈ（選択率６％）、メタンが１μｍｏ
１．／ｇ、ｈ（選択車路Ｏ％）であった。反応結果を表
に示す。Example 12 In a reaction tube of a fixed-bed pressurized flow reactor, neodia (Nd2O3) was used as a catalyst for converting CO2 into methanol, and copper and zinc oxide (copper loading amount 5 wt%, copper/normal oxide/zinc oxide) were used as a catalyst for converting CO2 into methanol. : A catalyst supporting 1) was charged. Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350°C for 30 minutes. After cooling in a hydrogen stream, the reaction gas (Co, , /+12
/Ar = 30/60/10, Ar is internal standard), reaction temperature 22O°C, reaction pressure 30kg/al,
The reaction was carried out at a flow rate of 100 ml/mni. The amount of methanol produced 1 hour after the start of the reaction was 470 μmO''/ε, h, and the selectivity was 94%. CO as a by-product is 30p
mol-/g, h (selectivity 6%), methane is 1 μmo
1. /g, h (selected road 0%). The reaction results are shown in the table.
実施例１３
固定床加圧流通式反応装置の反応管にＣＯ２のメタノー
ルへの変換用触媒として酸化ホルミウム（＋１０２Ｏ３
）に銅と酸化亜鉛（銅担持量５ｗｔ％、銅／酸化亜釦
モル比１：１）を担持した触媒を１ｇ充填した。反応に
先立って触媒を３５０℃で３０分水素還元処理した。Example 13 Holmium oxide (+102O3
) was filled with 1 g of a catalyst supporting copper and zinc oxide (copper supported amount: 5 wt %, copper/zinc oxide molar ratio 1:1). Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350°C for 30 minutes.
水素気流中て放冷した後、室温にて反応ガス（ＣＯ□／
Ｈ２／Ａｒ−３０／６０／１０、Ａｒは内部標準）に切
り替え、反応温度２２Ｏ℃、反応圧力３０ｋｇ／ｃＪ、
流速１００ｍ１／ｍｎｉで反応を行った。反応開始１時
間後のメタノール生成量は４５０μｍｏｌ／ｇ、ｌ’ｌ
、選択率９３％であった。副生成物としてはＣＯが３０
μｍｏ１．／ｇ、ｈ（選択率７％）、メタンが１μｍ
ｏｌ／ｇ、ｈ（選択車路０％）であった。反応結果を表
に示す。After cooling in a hydrogen stream, reactant gas (CO□/
H2/Ar-30/60/10, Ar is internal standard), reaction temperature 22O℃, reaction pressure 30kg/cJ,
The reaction was carried out at a flow rate of 100 ml/mni. The amount of methanol produced 1 hour after the start of the reaction was 450 μmol/g, l'l
, the selectivity was 93%. As a by-product, CO is 30
μmo1. /g, h (selectivity 7%), methane is 1 μm
ol/g, h (selected road 0%). The reaction results are shown in the table.
実施例１４
固定床加圧流通式反応装置の反応管にＣ０２のメタノー
ルへの変換用触媒として酸化エルビウム（Ｅｒ２Ｏ３）
に銅と酸化亜鉛（銅担持量５ｔｉｔ％、銅／酸化亜鉛モ
ル比１：１）を担持した触媒を１ｇ充填した。反応に先
立って触媒を３５０℃で３０分水素還元処理した。Example 14 Erbium oxide (Er2O3) was added as a catalyst for converting CO2 to methanol in the reaction tube of a fixed bed pressurized flow reactor.
was filled with 1 g of a catalyst supporting copper and zinc oxide (copper supported amount: 5 tit %, copper/zinc oxide molar ratio 1:1). Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350°C for 30 minutes.
水素気流中で放冷した後、室温にて反応ガス（ＣＯ２／
Ｈ２／ Ａｒ＝３０／６０／１０、Ａｒは内部標準）に
切り替え、反応温度２２Ｏ℃、反応圧力３０ｋｇ／ ａ
Ｋ、流速１００ｍ１．／ｍｎ１で反応を行った。反応開
始１時間後のメタノール生成量は４２Ｏμｍｏｌ／ｌＬ
ｈ、選択率９４％であった。副生成物としてはＣＯが３
０μｍｏｌ／ＬＭ選択率日）、メタンが１μｍｏｌ／ｇ
、ｈ（選択車路０％）であった。反応結”虻を表に示す
。After cooling in a hydrogen stream, reactant gas (CO2/
H2/Ar=30/60/10, Ar is internal standard), reaction temperature 22O℃, reaction pressure 30kg/a
K, flow rate 100 m1. /mn1. The amount of methanol produced 1 hour after the start of the reaction was 42 Oμmol/L
h, selectivity was 94%. As a by-product, CO is 3
0 μmol/LM selectivity day), methane is 1 μmol/g
, h (selected lane 0%). The reaction results are shown in the table.
実施例１５
固定床加圧流通式反応装置の反応管にＣＯ２のメタノー
ルへの変換用触媒として酸化サマリウム（Ｓｍ２Ｏ３）
に銅と酸化亜鉛（銅担持量５ｗｔ″１．銅／酸化亜鉛モ
ル比１：１）を担持した触媒を１ｇ充填した。反応に先
立って触媒を３５０℃で３０分水素還元処理した。Example 15 Samarium oxide (Sm2O3) was added as a catalyst for converting CO2 to methanol in the reaction tube of a fixed bed pressurized flow reactor.
was filled with 1 g of a catalyst supporting copper and zinc oxide (amount of copper supported: 5 wt''1. Copper/zinc oxide molar ratio: 1:1). Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350° C. for 30 minutes.
水素気流中で放冷した後、室温にて反応ガス（ＣＯ□／
Ｈ２／ Ａｒ＝３０／６０／１０、Ａｒは内部標準）に
切り替え、反応温度２２Ｏ℃、反応圧力３０ｋｇ／ｄ、
流速１００ｍ１／ｍｎｉで反応を行った。反応開始１時
間後のメタノール生成量は３８０μｍｏｌ／ｇ、ｈ、選
択率９４％であった。副生成物としてはＣＯが２Ｏ μ
ｍｏｌ／ｇ、ｈ（選択率６％）、メタンが１μｍｏｌ／
ｇ、ｈ（選択車路０％）であった。反応結果を表に示す
。After cooling in a hydrogen stream, reactant gas (CO□/
H2/Ar=30/60/10, Ar is internal standard), reaction temperature 22O℃, reaction pressure 30kg/d,
The reaction was carried out at a flow rate of 100 ml/mni. The amount of methanol produced 1 hour after the start of the reaction was 380 μmol/g, h, and the selectivity was 94%. As a by-product, CO is 2Oμ
mol/g, h (selectivity 6%), methane 1 μmol/
g, h (selected lane 0%). The reaction results are shown in the table.
実施例１６
固定床加圧流通式反応装置の反応管にＣＯ２のメタノー
ルへの変換用触媒として酸化カルシウム（Ｃａｂ）に銅
と酸化亜鉛（銅担持量５ｗｔ％、銅／酸化並／酸化亜鉛
：１）を担持した触媒を１ｇ充填した。反応にゝ舅立っ
て触媒を３５０℃で３０分水素還元処理した。Example 16 Calcium oxide (Cab), copper and zinc oxide (copper supported amount: 5 wt%, copper/normal oxide/zinc oxide: 1 ) was charged in an amount of 1 g. Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350°C for 30 minutes.
水素気流中で放冷した後、室温にて反応ガス（ＣＯ２／
Ｈ２／ Ａｒ＝３０／６０／１０、Ａｒは内部標ｌｌり
に切り替え、反応温度２２Ｏ°Ｃ１反応圧力３０ｋｇ／
ａ（、流速］００ｍ１／ｍｎｉで反応を行った。反応開
始１時間後のメタノール生成量は３４０μｍｏｌ／ｇ浦
、選択率８７％であった。副生成物としてはＣＯが５０
μｍｏｌ／ｇ、ｈ（選択率１３％）、メタンが１μｍ
ｏｌ／ｇ、ｈ（選択車路０％）であった。反応結果を表
に示す。After cooling in a hydrogen stream, reactant gas (CO2/
H2/Ar=30/60/10, Ar switched to internal standard, reaction temperature 220°C, reaction pressure 30kg/
The reaction was carried out at a flow rate of 00 ml/mni.The amount of methanol produced 1 hour after the start of the reaction was 340 μmol/g, and the selectivity was 87%.As a by-product, CO was 50 ml/mni.
μmol/g, h (selectivity 13%), methane is 1 μm
ol/g, h (selected road 0%). The reaction results are shown in the table.
実施例１７
固定床加圧流通式反応装置の反応管にＣＯ２のメタノー
ルへの変換用触媒として酸化ストロンチウム（ＳｒＯ）
に銅と酸化亜鉛（銅担持量５ｗｔ％、銅／酸化並／酸化
亜鉛：１）を担持した触媒を１ｇ充填した。反応に先立
って触媒を３５０℃で３０分水素還元処理した。水素気
流中で放冷した後、室温にて反応ガス（Ｃｏ□／Ｈ□／
Ａｒ：３０／６０／１０、Ａｒは内部標準）に切り替
え、反応温度２２Ｏ℃、反応圧力３０ｋｇ／ｃｒ＃、流
速１００ｍ１／ｍｎｉで反応を行った。反応開始１時間
後のメタノール生成量は３２Ｏμｍｏｌ／ｇ、ｈ、選択
率９０％であった。Example 17 Strontium oxide (SrO) was added as a catalyst for converting CO2 to methanol in the reaction tube of a fixed bed pressurized flow reactor.
was filled with 1 g of a catalyst supporting copper and zinc oxide (copper supported amount: 5 wt %, copper/normal oxide/zinc oxide: 1). Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350°C for 30 minutes. After cooling in a hydrogen stream, the reaction gas (Co□/H□/
Ar: 30/60/10 (Ar: internal standard), and the reaction was carried out at a reaction temperature of 220° C., a reaction pressure of 30 kg/cr#, and a flow rate of 100 ml/mni. The amount of methanol produced 1 hour after the start of the reaction was 320 μmol/g, h, with a selectivity of 90%.
−副生成物としてはＣＯが６９ μｍｏ１．／ｇ、ｈ（
選択率１０％）、メタンが１μｍｏ］、／ｇ、ｈ（選択
率路０％）であった。反応結果を表に示す。- As a by-product, CO is 69 μmol. /g,h(
The selectivity was 10%), and the methane was 1 μmo], /g, h (selectivity was 0%). The reaction results are shown in the table.
実施例１８
固定床加圧流通式反応装置の反応管にＣＯ，のメタノー
ルへの変換用触媒として酸化ジスプロシウム（Ｄｙ２Ｏ
：ｌ ）に銅と酸化亜鉛（銅和持量５ｔｉｔ％、銅／酸
化亜鉛モル比１：１）を担持した触媒を１ｇ充填した。Example 18 Dysprosium oxide (Dy2O
:1) was filled with 1 g of a catalyst supporting copper and zinc oxide (total copper content: 5 tit %, copper/zinc oxide molar ratio: 1:1).
反応に先立って触媒を３５０℃で３０分水素還元処理し
た。水素気流中で放冷した後、室温にて反応ガス（ＣＯ
２／Ｈ２／Ａｒ−３０／６０／１０、Ａｒは内部標７（
切に切り替え、反応温度２２Ｏ°Ｃ１反応圧力３０ｋｇ
／ｃｎ！、流速１００ｍ１／ｍｎｉで反応を行った。反
応開始１時間後のメタノール生成量は３１０μｍｏｌ／
ｇ、ｌ’ｌ、選択率９５％であった。副生成物としては
ＣＯが２Ｏμｍｏ１．／ｇ、ｈ（選択率５％）、メタン
が１μｍｏ１．／ｇ、ｈ（選択率路０％）であった。反
応結果を表に示す。Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350°C for 30 minutes. After cooling in a hydrogen stream, the reaction gas (CO
2/H2/Ar-30/60/10, Ar is internal standard 7 (
Switch to off, reaction temperature 22O°C, reaction pressure 30kg
/cn! The reaction was carried out at a flow rate of 100 ml/mni. The amount of methanol produced 1 hour after the start of the reaction was 310 μmol/
g, l'l, selectivity was 95%. As a by-product, CO is 20μmol1. /g, h (selectivity 5%), methane is 1 μmol1. /g, h (selectivity 0%). The reaction results are shown in the table.
実施例１９
固定床加圧流通式反応装置の反応管にＣＯ２のメタノー
ルへの変換用触媒として酸化ジスプロシ一万ム（ｏｙｚ
ｏ３）に銅と酸化亜鉛（銅担持景５シｔ％、銅／酸化亜
鉛モル比１：１）を担持した触媒を１ｇ充填した。Example 19 In a reaction tube of a fixed bed pressurized flow reactor, 10,000 ml of oxidized dysprosium (oyz
O3) was filled with 1 g of a catalyst supporting copper and zinc oxide (copper loading: 5 t%, copper/zinc oxide molar ratio 1:1).
反応に先立って触媒を３５０°Ｃで３０分水素還元処理
した。水素気流中で放冷した後、室温にて反応ガス（Ｃ
ｏ２／Ｈ，／ Ａｒ−３０／６０／１０、Ａｒは内部標
準）に切り替え、反応温度２２Ｏ°Ｃ１反応圧力３０ｋ
ｇ／ ｃｎｆ、流速１００ｍ１／ｍｎｊで反応を行った
。反応開始１時間後のメタノール生成量は１０５μｍｏ
ｌ／ｇ、ｈ、選択率９５％であった。副生成物としては
ＣＯが１０μｍｏ１．／ｇ、ｈ（選択率５％）、メタン
が］μｍｏｌ／ｇ、ｈ（選択率路Ｏ％）であった。反応
結果を表に示す。Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350°C for 30 minutes. After cooling in a hydrogen stream, the reaction gas (C
o2/H,/Ar-30/60/10, Ar is internal standard), reaction temperature 22O°C1 reaction pressure 30k
The reaction was carried out at a flow rate of 100 ml/mnj. The amount of methanol produced 1 hour after the start of the reaction was 105μmo
l/g, h, selectivity was 95%. As a by-product, CO is 10 μmol1. /g, h (selectivity 5%), methane was] μmol/g, h (selectivity 0%). The reaction results are shown in the table.
比較例１
固定床加圧流通式反応装置の反応管にＣＯ，のメタノー
ルへの変換用触媒として酸化亜鉛（ＺｎＯ）に銅（５ν
ｔ％）を担持した触媒を１ｇ充填した。反応に先立って
触媒を３５０℃で３０分水素還元処理した。Comparative Example 1 Zinc oxide (ZnO) and copper (5ν
t%) was charged. Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350°C for 30 minutes.
水素気流中で放冷した後、室温にて反応ガス（ＣＯ７／
Ｈ２／Ａｒ＝３０／６０／１０． Ａｒは内部標準）に
切り替え、反応温度２２Ｏ℃、反応圧力３０ｋｇ／ ａ
Ｋ、流速１００ｍ１／ｍｎｉで反応を行った。反応開始
１時間後のメタノール生成量は２８０μｍｏ］、／ｇ、
ｈ、選択率９２％であった。副生成物としてはＣＯが２
Ｏ μｍｏ１．／ｇ、ｈ （選択１８％）、メタンが１
μｍｏｌ／ｇ、ｈ（選択率路０％）であった。反応結果
を表に示す。After cooling in a hydrogen stream, reactant gas (CO7/
H2/Ar=30/60/10. Ar is an internal standard), reaction temperature is 22O℃, reaction pressure is 30kg/a.
The reaction was carried out at a flow rate of 100 ml/mni. The amount of methanol produced 1 hour after the start of the reaction was 280 μmo], /g,
h, selectivity was 92%. As a by-product, CO is 2
O μmo1. /g, h (selection 18%), methane is 1
It was μmol/g, h (selectivity: 0%). The reaction results are shown in the table.
比較例２
固定床加圧流通式反応装置の反応管にＣＯ２のメタノー
ルへの変換用触媒として酸化モリブデン（Ｍ２Ｏ３）に
銅と酸化亜鉛（銅担持量５ｗｔ％、銅／酸化並／酸化亜
鉛：１）を担持した触媒を１ｇ充填した。反応に先立っ
て触媒を３５０℃で３０分水素還元処理した。Comparative Example 2 Molybdenum oxide (M2O3) was used as a catalyst for converting CO2 into methanol in a reaction tube of a fixed bed pressurized flow reactor, and copper and zinc oxide (copper loading amount 5 wt%, copper/normal oxide/zinc oxide: 1 ) was charged in an amount of 1 g. Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350°C for 30 minutes.
水素気流中で放冷した後、室温にて反応ガス（ＣＯ２／
Ｈ２／Ａｒ−３０／６０／１０、Ａｒは内部標準）に切
り替え、反応温度２２Ｏ℃、反応圧力３０ｋｇ／ ｃｌ
、流速１００ｍ１／ｍｎｉで反応を行った。反応開始１
時間後のメタノール生成量は２９０μｍｏｌ−／ｇ、ｈ
、選択率４３％であった。副生成物としてはＣＯが３４
０ μｍｏ１．／ｇ、ｈ（選択率５２％）、メタンが３
５μｍｏｌ／ｇ、ｈ（選択率５％）であった。反応結果
を表に示す。After cooling in a hydrogen stream, reactant gas (CO2/
H2/Ar-30/60/10, Ar is internal standard), reaction temperature 22O℃, reaction pressure 30kg/cl
The reaction was carried out at a flow rate of 100 ml/mni. Reaction start 1
The amount of methanol produced after hours was 290 μmol-/g, h
, the selectivity was 43%. As a by-product, CO is 34
0 μmo1. /g, h (selectivity 52%), methane is 3
It was 5 μmol/g, h (selectivity 5%). The reaction results are shown in the table.
比較例３
固定床加圧流通式反応装置の反応管にＣＯ２のメタノー
ルへの変換用触媒として酸化タングステン（ＵＯ３）に
銅と酸化亜鉛（銅担持量５ｗｔ％、銅／酸化並／酸化亜
鉛：１）を担持した触媒を１ｇ充填した。反応に先立っ
て触媒を３５０℃で３０分水素還元処理した。Comparative Example 3 Copper and zinc oxide (copper loading 5 wt%, copper/normal oxide/zinc oxide: 1 ) was charged in an amount of 1 g. Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350°C for 30 minutes.
水素気流中で放冷した後、室温にて反応ガス（ＣＯ□／
Ｈ□／Ａｒ＝３０／６０／１．０、Ａｒは内部標準）に
切り替え、反応温度２２Ｏ℃、反応圧力３０ｋｇ／ｆｆ
ｌ、流速１００ｍ１／ｍｎｉで反応を行った。反応開始
１時間後のメタノール生成量は１０μｍｏ１．／ｇ浦、
選択率５％であった。副生成物としてはＣＯが２６０
μｍｏｌ／Ｈ，ｈ（選択率９２％）、メタンが８μｍｏ
ｌ／ｇ、ｈ（選択率３％）であった。反応結果を表に示
す。After cooling in a hydrogen stream, reactant gas (CO□/
H□/Ar=30/60/1.0, Ar is internal standard), reaction temperature 22O℃, reaction pressure 30kg/ff
The reaction was carried out at a flow rate of 100 ml/mni. The amount of methanol produced 1 hour after the start of the reaction was 10 μmol1. /gura,
The selectivity was 5%. As a by-product, CO is 260
μmol/H, h (selectivity 92%), methane is 8 μmol
l/g, h (selectivity 3%). The reaction results are shown in the table.
比較例４
固定床加圧流通式反応装置の反応管にＣＯ２のメタノー
ルへの変換用触媒としてニオビア（Ｎｂ２ＯＳ）に銅と
酸化亜鉛（銅担持量５ｗｔ％、銅／酸化並／酸化亜鉛：
１）を担持した触媒を１ｇ充填した。反応に先立って触
媒を３５０℃で３０分水素還元処理した。水素気流中で
放冷した後、室温にて反応ガス（Ｃｏ２／＋１２／Ａｒ
−３０／６０／１０、Ａｒは内部標準）に切り替え、反
応温−１２２Ｏ℃、反応圧力３０ｋｇ／ ａＫ、流速１
００ｍ１／ｍｎｊで反応を行った。反応開始１時間後の
メタノール生成量はほぼ０μｍｏｌ／ｇ、ｈ、選択率は
ぼ０％であった。副生成物としてはＣＯが５０ μｍｏ
ｌ／ｇ、ｈ （選択率９８ｚ）、メタンか１μｍｏｌ／
ｇ−ｈ（選択率２％）であった。反応結果を表に示す。Comparative Example 4 Copper and zinc oxide (copper loading 5 wt%, copper/normal oxide/zinc oxide:
1 g of the catalyst supporting 1) was charged. Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350°C for 30 minutes. After cooling in a hydrogen stream, the reaction gas (Co2/+12/Ar
-30/60/10, Ar is internal standard), reaction temperature -122O℃, reaction pressure 30kg/aK, flow rate 1
The reaction was carried out at 00 m1/mnj. One hour after the start of the reaction, the amount of methanol produced was approximately 0 μmol/g, h, and the selectivity was approximately 0%. CO as a by-product is 50 μmo
l/g, h (selectivity 98z), methane or 1 μmol/
gh (selectivity 2%). The reaction results are shown in the table.
比較例５
固定床加圧流通式反応装置の反応管にＣＯ２のメタノー
ルへの変換用触媒として酸化ビスマス（ｔ３ｊ、０．）
に銅と酸化亜鉛（銅担持量５ｔｉｔ％、銅／酸化亜釦モ
ル比ｌ：１）を担持した触媒を１．ｇ充填した。反応に
先立って触媒を３５０℃で３０分水素還元処理した。Comparative Example 5 Bismuth oxide (t3j, 0.) was added as a catalyst for converting CO2 to methanol in the reaction tube of a fixed bed pressurized flow reactor.
A catalyst supporting copper and zinc oxide (copper loading amount: 5 tit%, copper/zinc oxide molar ratio 1:1) was prepared in 1. g filled. Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350°C for 30 minutes.
水素気流中で放冷した後、室温にて反応ガス（ＣＯ７／
Ｈ２／Ａｒ＝３０／６０／１．０、Ａｒは内部標＄）に
切り替え、反応温度２２Ｏ℃、反応圧力３０ｋｇ／ａイ
、流速１００ｍ１／ｍｎｊで反応を行った。反応開始１
時間後のメタノール生成量はほぼＯμｍｏｌ／Ｌｈ、選
択率はぼ０％であった。After cooling in a hydrogen stream, reactant gas (CO7/
H2/Ar=30/60/1.0 (Ar is internal standard $), and the reaction was carried out at a reaction temperature of 220° C., a reaction pressure of 30 kg/a, and a flow rate of 100 ml/mnj. Reaction start 1
The amount of methanol produced after that time was approximately Oμmol/Lh, and the selectivity was approximately 0%.
他の生成物としてはメタンが１μｍｏ１．／ｇ、ｈ（選
択率１００％）であった。反応結果を表に示す。Other products include methane at 1 μmol. /g, h (selectivity 100%). The reaction results are shown in the table.
Claims (1)
持して調製された触媒で、担体とし て使用する金属酸化物として、アルミナ （Ａｌ＿２Ｏ＿３）、シリカ（ＳｉＯ＿２）、ジルコニ
ア（ＺｒＯ＿２）、マグネシア（ＭｇＯ）、セリア（Ｃ
ｅＯ＿２）、イットリア（Ｙ＿２Ｏ＿３）、ネオジア（
Ｎｄ＿２Ｏ＿３）、酸化ストロンチウム（ＳｒＯ）、酸
化カルシウム（Ｃ ａＯ）、クロミア（Ｃｒ＿２Ｏ＿３）、酸化タンタル（
Ｔａ＿２Ｏ＿５）、酸化プロセアジム（Ｐｒ＿６Ｏ＿１
＿１）、酸化イッテルビウム（Ｙｂ＿２Ｏ＿３）、酸化
ホルミウム（Ｈｏ＿２Ｏ＿３）、酸化エルビウム（Ｅｒ
＿２Ｏ＿３）、酸化サマリウム（Ｓｍ＿２Ｏ＿３）、酸
化ジスプロシウム（Ｄｙ＿２Ｏ＿３）、酸化ランタン（
Ｌａ＿２Ｏ＿３）のいずれか１種類を担体として用いる
ことを特徴 とする二酸化炭素を水素ガスにより接触水 素化し、メタノールに変換する方法。(1) A catalyst prepared by using a metal oxide as a carrier and supporting copper and zinc oxide on the carrier.The metal oxides used as the carrier include alumina (Al_2O_3), silica (SiO_2), zirconia (ZrO_2), Magnesia (MgO), ceria (C
eO_2), Yttria (Y_2O_3), Neodia (
Nd_2O_3), strontium oxide (SrO), calcium oxide (CaO), chromia (Cr_2O_3), tantalum oxide (
Ta_2O_5), protheazim oxide (Pr_6O_1
_1), ytterbium oxide (Yb_2O_3), holmium oxide (Ho_2O_3), erbium oxide (Er
_2O_3), samarium oxide (Sm_2O_3), dysprosium oxide (Dy_2O_3), lanthanum oxide (
A method for catalytically hydrogenating carbon dioxide with hydrogen gas and converting it into methanol, characterized by using any one of La_2O_3) as a carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2242941A JPH0635401B2 (en) | 1990-09-13 | 1990-09-13 | Method for producing methanol from carbon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2242941A JPH0635401B2 (en) | 1990-09-13 | 1990-09-13 | Method for producing methanol from carbon dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04122444A true JPH04122444A (en) | 1992-04-22 |
| JPH0635401B2 JPH0635401B2 (en) | 1994-05-11 |
Family
ID=17096501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2242941A Expired - Lifetime JPH0635401B2 (en) | 1990-09-13 | 1990-09-13 | Method for producing methanol from carbon dioxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0635401B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996016011A1 (en) * | 1994-11-22 | 1996-05-30 | Ube Industries, Ltd. | Process for producing methanol |
| US6649562B2 (en) | 1998-11-18 | 2003-11-18 | Honda Giken Kogyo Kabushiki Kaisha | Methanol-decomposing catalyst and methanol-decomposing apparatus comprising same |
| JP2010254666A (en) * | 2009-03-30 | 2010-11-11 | Tokyo Electric Power Co Inc:The | Method of methanol synthesis using microwave |
| CN105664954A (en) * | 2016-03-18 | 2016-06-15 | 昆明理工大学 | Method for promoting forming of aurichalcite phase in precursor of copper-based catalyst with calcium salt as additive |
| CN112517012A (en) * | 2020-12-01 | 2021-03-19 | 大连理工大学 | CO (carbon monoxide)2Preparation method and application of catalyst for preparing methanol by hydrogenation |
| JP2021146258A (en) * | 2020-03-18 | 2021-09-27 | 本田技研工業株式会社 | Carbon dioxide reduction catalyst |
| CN114950419A (en) * | 2022-04-20 | 2022-08-30 | 江南大学 | Metal catalyst for preparing methanol by carbon dioxide hydrogenation and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4917391A (en) * | 1972-04-20 | 1974-02-15 | ||
| JPS4942240A (en) * | 1972-03-06 | 1974-04-20 | ||
| JPS5932949A (en) * | 1982-08-13 | 1984-02-22 | Mitsubishi Gas Chem Co Inc | Catalyst for synthesis of methanol |
| JPS6084142A (en) * | 1983-10-17 | 1985-05-13 | Mitsubishi Gas Chem Co Inc | Fluidized catalyst for methanol synthesis |
| JPS60106534A (en) * | 1983-11-14 | 1985-06-12 | Mitsubishi Gas Chem Co Inc | Fluidized catalyst for methanol synthesis |
| JPS6253739A (en) * | 1985-08-31 | 1987-03-09 | Mitsubishi Gas Chem Co Inc | Preparation of methanol synthesizing catalyst |
-
1990
- 1990-09-13 JP JP2242941A patent/JPH0635401B2/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4942240A (en) * | 1972-03-06 | 1974-04-20 | ||
| JPS4917391A (en) * | 1972-04-20 | 1974-02-15 | ||
| JPS5932949A (en) * | 1982-08-13 | 1984-02-22 | Mitsubishi Gas Chem Co Inc | Catalyst for synthesis of methanol |
| JPS6084142A (en) * | 1983-10-17 | 1985-05-13 | Mitsubishi Gas Chem Co Inc | Fluidized catalyst for methanol synthesis |
| JPS60106534A (en) * | 1983-11-14 | 1985-06-12 | Mitsubishi Gas Chem Co Inc | Fluidized catalyst for methanol synthesis |
| JPS6253739A (en) * | 1985-08-31 | 1987-03-09 | Mitsubishi Gas Chem Co Inc | Preparation of methanol synthesizing catalyst |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996016011A1 (en) * | 1994-11-22 | 1996-05-30 | Ube Industries, Ltd. | Process for producing methanol |
| US6649562B2 (en) | 1998-11-18 | 2003-11-18 | Honda Giken Kogyo Kabushiki Kaisha | Methanol-decomposing catalyst and methanol-decomposing apparatus comprising same |
| JP2010254666A (en) * | 2009-03-30 | 2010-11-11 | Tokyo Electric Power Co Inc:The | Method of methanol synthesis using microwave |
| CN105664954A (en) * | 2016-03-18 | 2016-06-15 | 昆明理工大学 | Method for promoting forming of aurichalcite phase in precursor of copper-based catalyst with calcium salt as additive |
| JP2021146258A (en) * | 2020-03-18 | 2021-09-27 | 本田技研工業株式会社 | Carbon dioxide reduction catalyst |
| CN113492010A (en) * | 2020-03-18 | 2021-10-12 | 本田技研工业株式会社 | Carbon dioxide reduction catalyst |
| CN112517012A (en) * | 2020-12-01 | 2021-03-19 | 大连理工大学 | CO (carbon monoxide)2Preparation method and application of catalyst for preparing methanol by hydrogenation |
| CN112517012B (en) * | 2020-12-01 | 2022-01-04 | 大连理工大学 | CO (carbon monoxide)2Preparation method and application of catalyst for preparing methanol by hydrogenation |
| CN114950419A (en) * | 2022-04-20 | 2022-08-30 | 江南大学 | Metal catalyst for preparing methanol by carbon dioxide hydrogenation and application thereof |
| CN114950419B (en) * | 2022-04-20 | 2023-10-03 | 江南大学 | Metal catalyst for preparing methanol by carbon dioxide hydrogenation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0635401B2 (en) | 1994-05-11 |
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