JPH0635401B2 - Method for producing methanol from carbon dioxide - Google Patents
Method for producing methanol from carbon dioxideInfo
- Publication number
- JPH0635401B2 JPH0635401B2 JP2242941A JP24294190A JPH0635401B2 JP H0635401 B2 JPH0635401 B2 JP H0635401B2 JP 2242941 A JP2242941 A JP 2242941A JP 24294190 A JP24294190 A JP 24294190A JP H0635401 B2 JPH0635401 B2 JP H0635401B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- catalyst
- copper
- oxide
- selectivity
- 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.)
- Expired - Lifetime
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims description 189
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 42
- 239000001569 carbon dioxide Substances 0.000 title claims description 21
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 101
- 239000003054 catalyst Substances 0.000 claims description 84
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 75
- 239000001257 hydrogen Substances 0.000 claims description 57
- 229910052739 hydrogen Inorganic materials 0.000 claims description 57
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 54
- 239000005751 Copper oxide Substances 0.000 claims description 50
- 229910000431 copper oxide Inorganic materials 0.000 claims description 50
- 239000011787 zinc oxide Substances 0.000 claims description 50
- 229910052802 copper Inorganic materials 0.000 claims description 26
- 239000010949 copper Substances 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 150000004706 metal oxides Chemical class 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 3
- 229910003440 dysprosium oxide Inorganic materials 0.000 claims description 3
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 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 description 3
- 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 description 3
- 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 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 description 3
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 description 186
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 48
- 239000012495 reaction gas Substances 0.000 description 30
- 239000006227 byproduct Substances 0.000 description 22
- 238000011068 loading method Methods 0.000 description 20
- 238000000034 method Methods 0.000 description 15
- 238000001816 cooling Methods 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000002243 precursor Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 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 description 2
- UFQXGXDIJMBKTC-UHFFFAOYSA-N oxostrontium Chemical compound [Sr]=O UFQXGXDIJMBKTC-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910003454 ytterbium oxide Inorganic materials 0.000 description 2
- 229940075624 ytterbium oxide Drugs 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 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
- 230000010485 coping Effects 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
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material 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
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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。TECHNICAL FIELD 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
０００万トンの需要がある。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 10 million tons. The synthesis uses a mixed gas of carbon monoxide and hydrogen (synthesis gas), which can be obtained by steam reforming or partial oxidation of natural gas, petroleum, and coal, as a raw material, and a catalyst under high temperature and high pressure as shown in the following formula. It is synthesized by reaction and has become a highly practical process.
ＣＯ＋２Ｈ2→ＣＨ3ＯＨ 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。一例
として、銅−亜鉛混合酸化物触媒ではメタノール生成量
は非常に少ない（比較例１参照）。CO + 2H 2 → CH 3 OH On the other hand, regarding the method for synthesizing methanol from other than synthesis gas, for example, the synthesis from carbon dioxide and hydrogen has been studied at the basic research level from an academic point of view. As an example, the copper-zinc mixed oxide catalyst produces a very small amount of methanol (see Comparative Example 1).
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じめている。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。However, with the recent expansion of the scale of global industrial and economic activities, environmental destruction at the global level has become a serious problem, and countermeasures against it have been considered globally. In particular, the issue of global warming is estimated to have a significant adverse effect not only on humankind but also on the earth itself, and in order to prevent the emission of carbon dioxide into the atmosphere, which is the main cause of global warming, There is a strong demand for establishment of 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
メタノールを合成できる方法を発明するに至った。The present inventors consider carbon dioxide to be discharged as a carbon resource, and if they can develop a process that can recover and recycle this carbon dioxide to synthesize useful chemicals from carbon dioxide, from the viewpoint of carbon dioxide emission control and resource utilization, Considering that effective measures can be established, as a result of intensive research on technology for effectively using carbon dioxide, a method for efficiently synthesizing methanol from carbon dioxide was invented.
［発明が解決しようとする問題点］ 従って、本発明は二酸化炭素による地球温暖化を防ぐべ
く排出二酸化炭素を再資源化し、メタノールに効率的に
変換する新しいプロセスを確立するためのものであり、
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 is to establish a new process for recycling exhaust carbon dioxide to efficiently prevent carbon dioxide from global warming and efficiently converting it to methanol.
It provides a new method for suppressing global warming and efficient methanol synthesis.
［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、二酸化炭素の接触水素化
法による効率的なメタノー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 specific solid metal oxide is used as a carrier, and a new solid catalyst in which copper and zinc oxide are supported on the carrier is used. An efficient conversion method to methanol by a catalytic hydrogenation method is provided.
すなわち本発明は銅と酸化亜鉛を、アルミナ（Ａｌ
2Ｏ3）、シリカ（ＳｉＯ2）、ジルコニア（ＺｒＯ2）、
マグネシア（ＭｇＯ）、セリア（ＣｅＯ2）、イットリ
ア（Ｙ2Ｏ3）、ネオジア（Ｎｄ2Ｏ3）、酸化ストロンチ
ウム（ＳｒＯ）、酸化カルシウム（ＣａＯ）、クロミア
（Ｃｒ2Ｏ3）、酸化タンタル（Ｔａ2Ｏ5）、酸化プロセ
アジム（Ｐｒ6Ｏ11）、酸化イッテルビウム（Ｙｂ
2Ｏ3）、酸化ホルミウム（Ｈｏ2Ｏ3）、酸化エルビウム
（Ｅｒ2Ｏ3）、酸化サマリウム（Ｓｍ2Ｏ3）、酸化ジス
プロジウム（Ｄｙ2Ｏ3）のいずれか１種から選ばれた金
属酸化物に担持させてなる触媒であって、該触媒中銅と
酸化亜鉛が２９重量％以下、金属酸化物が７１重量％以
上である触媒を用い、該触媒に、実質的に一酸化炭素を
含まず、二酸化炭素と水素を含有するガスを接触させ、
メタノールを生成させることを特徴とする二酸化炭素か
らのメタノールの製造方法を提供するものである。That is, in the present invention, copper and zinc oxide are added to alumina (Al
2 O 3 ), silica (SiO 2 ), zirconia (ZrO 2 ),
Magnesia (MgO), ceria (CeO 2 ), yttria (Y 2 O 3 ), neodia (Nd 2 O 3 ), strontium oxide (SrO), calcium oxide (CaO), chromia (Cr 2 O 3 ), tantalum oxide ( Ta 2 O 5 ), protheazim oxide (Pr 6 O 11 ), ytterbium oxide (Yb)
2 O 3 ), holmium oxide (Ho 2 O 3 ), erbium oxide (Er 2 O 3 ), samarium oxide (Sm 2 O 3 ), and dysprosium oxide (Dy 2 O 3 ). A catalyst comprising metal oxide supported on copper oxide and zinc oxide of 29 wt% or less and metal oxide of 71 wt% or more, wherein the catalyst is substantially carbon monoxide. Not containing, contacting a gas containing carbon dioxide and hydrogen,
The present invention provides a method for producing methanol from carbon dioxide, which is characterized by producing methanol.
以下に本発明を詳細に説明する。The present invention will be described 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。また、表面積は０．１〜１０００ｍ2／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
１．５mm前後の粒子に成型したものがよい。The specific metal oxide constituting the catalyst used in the present invention may have any physical form. That is, the form thereof such as fine powder, coarse particles, and pellets is arbitrary. The surface area may be about 0.1 to 1000 m 2 / g, and even if pores are present, those having any size and distribution can be used. Preferably, it is molded into particles having a diameter of around 1.5 mm.
本発明に使用される触媒を構成する銅及び酸化亜鉛化合
物担持のための前駆体は硝酸塩、硫酸塩、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。As the precursor for supporting the copper and zinc oxide compounds constituting the catalyst used in the present invention, organic salts such as nitrates, sulfates, chlorides and acetates can be used and are optional. Preferably, nitrate or acetate is used.
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 molar ratio of copper / zinc oxide may be 100/1 to 1/100, preferably 3/1 to 1/3.
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１５
０〜５００℃の間で排気加熱処理を行なうことが好まし
い。The method of supporting the copper and zinc compound precursor on the metal oxide may be any of an impregnation method, a precipitation method and a physical mixing method. An impregnation method using a nitrate precursor solution as the impregnation liquid is preferably used. Prior to impregnation with the precursor solution, the metal oxide was
Exhaust gas heat treatment is preferably carried out between 0 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２００〜８００℃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が水素気流下で分解する触媒
は、焼成処理は必ずしも必要ではない。The metal oxide supporting the copper and zinc compound is preferably fired in an oxygen stream or an air stream. The firing temperature is between 200 and 800 ° C. The catalyst in which the supported copper and zinc oxide precursors are decomposed in a hydrogen stream does not necessarily need to be calcined.
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℃までの間の温度で任意であ
る。好ましくは、２００〜６００℃の間の温度で水素還
元処理を行なう。The calcined catalyst is reduced in a hydrogen stream. The reduction temperature may be any temperature between 100 and 1000 ° C. Preferably, the hydrogen reduction treatment is performed at a temperature between 200 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 in the synthesis of methanol from a mixed gas of carbon dioxide and hydrogen, but the reaction form is arbitrary, and it is a gas phase fixed bed flow system, gas phase fluidized bed, liquid phase suspension. It can be either floor.
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 hydrogen reduction treatment prior to the reaction, for example, after filling the reaction tube, but this treatment is not necessary.
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〜３００kg/cm2、好ましくは１０〜１００kg/cm
2で、反応温度は１００〜４００℃、好ましくは１８０
〜３００℃がよい。ＣＯ2／Ｈ2モル比は１／１０〜３／
１であり、好ましくは１／４〜１／１を使用する。ま
た、反応ガスの流速は任意であるが、空間速度としてＧ
ＨＳＶが５０〜２００００ｈ-1が好ましい。As a condition for carrying out the present invention, that is, a reaction condition for synthesizing methanol from a mixed gas of carbon dioxide gas and hydrogen, the pressure is normal pressure to 300 kg / cm 2 , preferably 10 to 100 kg / cm 2 .
2 , the reaction temperature is 100-400 ° C, preferably 180
~ 300 ° C is good. CO 2 / H 2 molar ratio is 1/10 to 3 /
1, preferably 1/4 to 1/1 are used. The flow velocity of the reaction gas is arbitrary, but the space velocity is G
The HSV is preferably 50 to 20000 h -1 .
本発明は前記のように、多量の金属酸化物担体に少量の
有効成分を担持させた触媒を用いるものであり、これに
より一酸化炭素を含まないで二酸化炭素のみを含むガス
を水素と接触反応させてメタノールを高収率で、選択性
よく合成することができる。したがって本発明方法は各
種工業の製造工程などから排出され、現在、地球温暖化
の主要因としてその対処が切望されている二酸化炭素を
回収再利用再資源化でき、極めて有益なものである。As described above, the present invention uses a catalyst in which a large amount of an active ingredient is supported on a large amount of a metal oxide carrier, whereby a gas containing only carbon dioxide without carbon monoxide is reacted with hydrogen. Thus, methanol can be synthesized with high yield and high selectivity. Therefore, the method of the present invention is extremely useful because it can collect, reuse, and recycle the carbon dioxide emitted from the manufacturing process of various industries and the coping with which it is currently desired as a main cause of global warming.
［実施例］ 次に本発明を実施例により、更に詳細に説明する。EXAMPLES Next, the present invention will be described 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ＣＯ2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3
0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/H2/Ar＝30/60/10、Arは内部標準）に
切り替え、反応温度220℃、反応圧力30kg/cm2、流速100
ml/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/g.h、選択率39%であった。副生成物
としてはCOが2060μmol/g.h（選択率61%）、メタンが２
μmol/g.h（選択率略0%）であった。反応結果を表に示
す。Example 1 Copper and zinc oxide (copper loading: 5 wt%, copper / zinc oxide molar ratio) were added to alumina (Al 2 O 3 ) as a catalyst for conversion of CO 2 into methanol in a reaction tube of a fixed bed pressure flow type reactor. 1 g of the catalyst carrying 1: 1) was loaded. Prior to the reaction, the catalyst was heated at 350 ° C for 3
Hydrogen reduction treatment was performed for 0 minutes. After cooling in a hydrogen stream, switch to reaction gas (CO 2 / H 2 / Ar = 30/60/10, Ar is internal standard) at room temperature, reaction temperature 220 ° C, reaction pressure 30kg / cm 2 , flow rate 100
The reaction was performed at ml / mni. One hour after the start of the reaction, the amount of methanol produced was 1330 μmol / gh, and the selectivity was 39%. As by-products, CO was 2060 μmol / gh (selectivity 61%) and methane was 2
It was μmol / gh (selectivity approximately 0%). The reaction results are shown in the table.
実施例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シリカ(SiO2)に銅と酸化亜鉛
（銅担持量5wt%、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/H2/Ar＝30/60/10、Arは内部標準）に切
り替え、反応温度220℃、反応圧力30kg/cm2、流速100ml
/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39%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１μm
ol/g.h（選択率略0%）であった。反応結果を表に示す。Example 2 Copper and zinc oxide (copper loading 5 wt%, copper / zinc oxide molar ratio 1: on silica (SiO 2 ) as a catalyst for conversion of CO 2 into methanol in a reaction tube of a fixed bed pressure flow type reactor. 1 g of the catalyst carrying 1) was loaded. Prior to the reaction, the catalyst was heated at 350 ° C for 30
A hydrogen reduction treatment was performed. After cooling in a hydrogen stream, switch to reaction gas (CO 2 / H 2 / Ar = 30/60/10, Ar is internal standard) at room temperature, reaction temperature 220 ° C, reaction pressure 30kg / cm 2 , flow rate 100 ml
The reaction was performed at / mni. The amount of methanol produced 1 hour after the start of the reaction was 1360 μmol / gh, and the selectivity was 39%. As by-products, CO is 710 μmol / gh (selectivity 34%), methane is 1 μm
It was ol / gh (selectivity approximately 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ＣＯ2のメタノー
ルへの変換用触媒としてチタニア(TiO2)に銅と酸化亜鉛
（銅担持量5wt%，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220℃、反応圧力30k
g/cm2、流速100ml/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1280μmol/g.h、選択率78%であ
った。副生成物としてはCOが360μmol/g.h（選択率22
%）、メタンが１μmol/g.h（選択率略0%）であった。反
応結果を表に示す。Example 3 Copper and zinc oxide were added to titania (TiO 2 ) as a catalyst for conversion of CO 2 into methanol in a reaction tube of a fixed-bed pressure-flow type reactor (copper loading: 5 wt%, copper / zinc oxide molar ratio 1: 1 g of the catalyst carrying 1) was loaded. Prior to the reaction, the catalyst was heated at 350 ° C for 30
A hydrogen reduction treatment was performed. After allowing to cool in a hydrogen stream, the reaction gas at room temperature is reacted gas (CO 2 / H 2 / Ar = 30/60/10, Ar at room temperature).
Is an internal standard), reaction temperature 220 ℃, reaction pressure 30k
The reaction was performed at g / cm 2 and a flow rate of 100 ml / mni. One hour after the start of the reaction, the amount of methanol produced was 1280 μmol / gh, and the selectivity was 78%. CO as a by-product is 360 μmol / gh (selectivity 22
%) And methane was 1 μmol / gh (selectivity approximately 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ＣＯ2のメタノー
ルへの変換用触媒としてクロミア(Cr2O2)に銅と酸化亜
鉛（銅担持量5wt%，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3
0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220℃、反応圧力3
0kg/cm2、流速100ml/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960μmol/g.h、選択率77%で
あった。副生成物としてはCOが290μmol/g.h（選択率23
%）、メタンが１μmol/g.h（選択率略0%）であった。反
応結果を表に示す。Example 4 Chromia (Cr 2 O 2 ) was used as a catalyst for conversion of CO 2 into methanol in a reaction tube of a fixed bed pressure flow type reactor, and copper and zinc oxide (copper supported amount 5 wt%, copper / zinc oxide molar ratio). 1 g of the catalyst carrying 1: 1) was loaded. Prior to the reaction, the catalyst was heated at 350 ° C for 3
Hydrogen reduction treatment was performed for 0 minutes. After allowing to cool in a hydrogen stream, the reaction gas at room temperature is the reaction gas at room temperature (CO 2 / H 2 / Ar = 30/60/10,
(Ar is internal standard), reaction temperature 220 ℃, reaction pressure 3
The reaction was performed at 0 kg / cm 2 and a flow rate of 100 ml / mni. The amount of methanol produced 1 hour after the start of the reaction was 960 μmol / gh, and the selectivity was 77%. CO as a by-product is 290 μmol / gh (selectivity 23
%) And methane was 1 μmol / gh (selectivity approximately 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3
0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220℃、反応圧力3
0kg/cm2、流速100ml/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910μmol/g.h、選択率57%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１μmol/g.h（選択率略0%）であった。反
応結果を表に示す。Example 5 Copper and zinc oxide were added to zirconia (ZrO 2 ) as a catalyst for conversion of CO 2 into methanol in a reaction tube of a fixed bed pressure flow type reactor (copper loading 5 wt%, copper / zinc oxide molar ratio 1: 1 g of the catalyst carrying 1) was loaded. Prior to the reaction, the catalyst was heated at 350 ° C for 3
Hydrogen reduction treatment was performed for 0 minutes. After allowing to cool in a hydrogen stream, the reaction gas at room temperature is the reaction gas at room temperature (CO 2 / H 2 / Ar = 30/60/10,
(Ar is internal standard), reaction temperature 220 ℃, reaction pressure 3
The reaction was performed at 0 kg / cm 2 and a flow rate of 100 ml / mni. One hour after the start of the reaction, the amount of methanol produced was 910 μmol / gh, and the selectivity was 57%. CO as a by-product is 700 μmol / gh (selectivity 43
%) And methane was 1 μmol / gh (selectivity approximately 0%). 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ＣＯ2のメタノー
ルへの変換用触媒としてセリア(CeO2)に銅と酸化亜鉛
（銅担持量5wt%，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220℃、反応圧力30k
g/cm2、流速100ml/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830μmol/g.h、選択率79%であ
った。副生成物としてはCOが220μmol/g.h（選択率21
%）、メタンが１μmol/g.h（選択率略0%）であった。反
応結果を表に示す。Example 6 Copper and zinc oxide were added to ceria (CeO 2 ) as a catalyst for conversion of CO 2 into methanol in a reaction tube of a fixed-bed pressure-flow type reactor (copper loading 5 wt%, copper / zinc oxide molar ratio 1: 1 g of the catalyst carrying 1) was loaded. Prior to the reaction, the catalyst was heated at 350 ° C for 30
A hydrogen reduction treatment was performed. After allowing to cool in a hydrogen stream, the reaction gas at room temperature is reacted gas (CO 2 / H 2 / Ar = 30/60/10, Ar at room temperature).
Is an internal standard), reaction temperature 220 ℃, reaction pressure 30k
The reaction was performed at g / cm 2 and a flow rate of 100 ml / mni. One hour after the start of the reaction, the amount of methanol produced was 830 μmol / gh and the selectivity was 79%. As a by-product, CO is 220 μmol / gh (selectivity 21
%) And methane was 1 μmol / gh (selectivity approximately 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ットリア(Y2O3)に銅と酸化亜
鉛（銅担持量5wt%，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3
0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220℃、反応圧力3
0kg/cm2、流速100ml/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650μmol/g.h、選択率82%で
あった。副生成物としてはCOが140μmol/g.h（選択率18
%）、メタンが１μmol/g.h（選択率略0%）であった。反
応結果を表に示す。Example 7 Copper and zinc oxide were added to yttria (Y 2 O 3 ) as a catalyst for converting CO 2 into methanol in a reaction tube of a fixed-bed pressure-flow type reactor (copper loading: 5 wt%, copper / zinc oxide molar ratio). 1 g of the catalyst carrying 1: 1) was loaded. Prior to the reaction, the catalyst was heated at 350 ° C for 3
Hydrogen reduction treatment was performed for 0 minutes. After allowing to cool in a hydrogen stream, the reaction gas at room temperature is the reaction gas at room temperature (CO 2 / H 2 / Ar = 30/60/10,
(Ar is internal standard), reaction temperature 220 ℃, reaction pressure 3
The reaction was performed at 0 kg / cm 2 and a flow rate of 100 ml / mni. One hour after the start of the reaction, the amount of methanol produced was 650 μmol / gh and the selectivity was 82%. CO as a by-product is 140 μmol / gh (selectivity 18
%) And methane was 1 μmol / gh (selectivity approximately 0%). 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(Pr6O11)に銅
と酸化亜鉛（銅担持量5wt%，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220
℃、反応圧力30kg/cm2、流速100ml/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650μmol/
g.h、選択率82%であった。副生成物としてはCOが140μm
ol/g.h（選択率18%）、メタンが２μmol/g.h（選択率略
0%）であった。反応結果を表に示す。Example 8 Praseodymium oxide (Pr 6 O 11 ) was used as a catalyst for converting CO 2 into methanol in a reaction tube of a fixed-bed pressure-flow type reactor, and copper and zinc oxide (copper loading 5 wt%, copper / zinc oxide mole) were used. Ratio 1:
1 g of the catalyst carrying 1) was loaded. Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350 ° C. for 30 minutes. After allowing to cool in a hydrogen stream, the reaction gas at room temperature is the reaction gas (CO 2 / H 2 / Ar =
30/60/10, Ar internal standard), reaction temperature 220
The reaction was carried out at a reaction temperature of 30 kg / cm 2 and a flow rate of 100 ml / mni. The amount of methanol produced 1 hour after the start of the reaction was 650 μmol /
gh, selectivity was 82%. CO as a by-product is 140 μm
ol / gh (selectivity 18%), methane 2 μmol / gh (selectivity omitted)
It was 0%). 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)に銅と酸化亜
鉛（銅担持量5wt%，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3
0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220℃、反応圧力3
0kg/cm2、流速100ml/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590μmol/g.h、選択率91%で
あった。副生成物としてはCOが60μmol/g.h（選択率9
%）、メタンが１μmol/g.h（選択率略0%）であった。反
応結果を表に示す。Example 9 Magnesia (MgO) was used as a catalyst for conversion of CO 2 into methanol in a reaction tube of a fixed-bed pressure-flow type reactor, copper and zinc oxide (copper loading: 5 wt%, copper / zinc oxide molar ratio: 1: 1). 1 g of the catalyst carrying) was loaded. Prior to the reaction, the catalyst was heated at 350 ° C for 3
Hydrogen reduction treatment was performed for 0 minutes. After allowing to cool in a hydrogen stream, the reaction gas at room temperature is the reaction gas at room temperature (CO 2 / H 2 / Ar = 30/60/10,
(Ar is internal standard), reaction temperature 220 ℃, reaction pressure 3
The reaction was performed at 0 kg / cm 2 and a flow rate of 100 ml / mni. One hour after the start of the reaction, the amount of methanol produced was 590 μmol / gh, and the selectivity was 91%. CO as a by-product is 60 μmol / gh (selectivity 9
%) And methane was 1 μmol / gh (selectivity approximately 0%). 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(Ta2O5)に銅と酸
化亜鉛（銅担持量5wt%，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220℃、反応
圧力30kg/cm2、流速100ml/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530μmol/g.h、選択率
79%であった。副生成物としてはCOが130μmol/g.h（選
択率21%）、メタンが１μmol/g.h（選択率略0%）であっ
た。反応結果を表に示す。Example 10 Copper and zinc oxide (copper loading 5 wt%, copper / zinc oxide mole) were added to tantalum oxide (Ta 2 O 5 ) as a catalyst for conversion of CO 2 into methanol in a reaction tube of a fixed bed pressure flow reactor. 1 g of catalyst carrying a ratio of 1: 1) was loaded. 350 catalyst prior to reaction
Hydrogen reduction treatment was performed at 30 ° C. for 30 minutes. After cooling in a hydrogen stream,
The reaction gases at a reaction gas at room temperature at room temperature (CO 2 / H 2 / Ar = 30/60 /
10, Ar was an internal standard), and the reaction was carried out at a reaction temperature of 220 ° C., a reaction pressure of 30 kg / cm 2 , and a flow rate of 100 ml / mni. The amount of methanol produced 1 hour after the start of the reaction was 530 μmol / gh, selectivity
It was 79%. As by-products, CO was 130 μmol / gh (selectivity 21%), and methane was 1 μmol / gh (selectivity approximately 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ッッテリビウム(Yg2O3)
に銅と酸化亜鉛（銅担持量5wt%，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22
0℃、反応圧力30kg/cm2、流速100ml/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500μmol/
g.h、選択率90%であった。副生成物としてはCOが60μmo
l/g.h（選択率10%）、メタンが１μmol/g.h（選択率略0
%）であった。反応結果を表に示す。Example 11 Ytterbium oxide (Yg 2 O 3 ) was used as a catalyst for converting CO 2 into methanol in a reaction tube of a fixed-bed pressure-flow reactor.
1 g of a catalyst supporting copper and zinc oxide (copper loading 5 wt%, copper / zinc oxide molar ratio 1: 1) was charged. Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350 ° C. for 30 minutes. After leaving it to cool in a hydrogen stream, the reaction gas is reacted at room temperature (CO 2 / H 2 /
Ar = 30/60/10, Ar is internal standard), reaction temperature 22
The reaction was carried out at 0 ° C., a reaction pressure of 30 kg / cm 2 , and a flow rate of 100 ml / mni. The amount of methanol produced 1 hour after the start of the reaction was 500 μmol /
gh, the selectivity was 90%. CO as a by-product is 60 μmo
l / gh (selectivity 10%), methane is 1 μmol / gh (selectivity approximately 0)
%)Met. The reaction results are shown in the table.
実施例12 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ネオジア(Nd2O3)に銅と酸化亜
鉛（銅担持量5wt%，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3
0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220℃、反応圧力3
0kg/cm2、流速100ml/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470μmol/g.h、選択率94%で
あった。副生成物としてはCOが30μmol/g.h（選択率6
%）、メタンが１μmol/g.h（選択率略0%）であった。反
応結果を表に示す。Example 12 Copper and zinc oxide (copper loading 5 wt%, copper / zinc oxide molar ratio) in neodia (Nd 2 O 3 ) as a catalyst for conversion of CO 2 into methanol in a reaction tube of a fixed-bed pressure-flow reactor. 1 g of the catalyst carrying 1: 1) was loaded. Prior to the reaction, the catalyst was heated at 350 ° C for 3
Hydrogen reduction treatment was performed for 0 minutes. After allowing to cool in a hydrogen stream, the reaction gas at room temperature is the reaction gas at room temperature (CO 2 / H 2 / Ar = 30/60/10,
(Ar is internal standard), reaction temperature 220 ℃, reaction pressure 3
The reaction was performed at 0 kg / cm 2 and a flow rate of 100 ml / mni. One hour after the start of the reaction, the amount of methanol produced was 470 μmol / gh and the selectivity was 94%. CO as a by-product is 30 μmol / gh (selectivity 6
%) And methane was 1 μmol / gh (selectivity approximately 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(Ho2O3)に銅と
酸化亜鉛（銅担持量5wt%，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35
0℃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/H2/Ar＝30/60/10、Arは内部
標準）に切り替え、反応温度220℃、反応圧力30kg/c
m2、流速100ml/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.h、選択率93%であっ
た。副生成物としてはCOが30μmol/g.h（選択率7%）、
メタンが１μmol/g.h（選択率略0%）であった。反応結
果を表に示す。Example 13 Copper and zinc oxide (copper loading 5 wt%, copper / zinc oxide mole) were added to holmium oxide (Ho 2 O 3 ) as a catalyst for conversion of CO 2 into methanol in a reaction tube of a fixed-bed pressure-flow type reactor. 1: 1)
1 g of a catalyst supporting was charged. 35 catalyst prior to reaction
Hydrogen reduction treatment was performed at 0 ° C. for 30 minutes. After cooling in a hydrogen stream, the reaction gas at room temperature (CO 2 / H 2 / Ar = 30/60/10, Ar is an internal standard) Switch to a reaction temperature of 220 ° C., a reaction pressure 30kg / c
The reaction was carried out at m 2 and a flow rate of 100 ml / mni. One hour after the start of the reaction, the amount of methanol produced was 450 μmol / gh and the selectivity was 93%. CO as a by-product is 30 μmol / gh (selectivity 7%),
Methane was 1 μmol / gh (selectivity approximately 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ＣＯ2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5wt%，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35
0℃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/H2/Ar＝30/60/10、Arは内部
標準）に切り替え、反応温度220℃、反応圧力30kg/c
m2、流速100ml/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420μmol/g.h、選択率94%であっ
た。副生成物としてはCOが30μmol/g.h（選択率6%）、
メタンが１μmol/g.h（選択率略0%）であった。反応結
果を表に示す。Example 14 Erbium oxide (Er 2 O 3 ) was used as a catalyst for conversion of CO 2 into methanol in a reaction tube of a fixed-bed pressure-flow type reactor, and copper and zinc oxide (copper loading 5 wt%, copper / zinc oxide mole) were used. 1: 1)
1 g of a catalyst supporting was charged. 35 catalyst prior to reaction
Hydrogen reduction treatment was performed at 0 ° C. for 30 minutes. After cooling in a hydrogen stream, the reaction gas at room temperature (CO 2 / H 2 / Ar = 30/60/10, Ar is an internal standard) Switch to a reaction temperature of 220 ° C., a reaction pressure 30kg / c
The reaction was carried out at m 2 and a flow rate of 100 ml / mni. One hour after the start of the reaction, the amount of methanol produced was 420 μmol / gh and the selectivity was 94%. CO as a by-product is 30 μmol / gh (selectivity 6%),
Methane was 1 μmol / gh (selectivity approximately 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%，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35
0℃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/H2/Ar＝30/60/10、Arは内部
標準）に切り替え、反応温度220℃、反応圧力30kg/c
m2、流速100ml/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20μmol/g.h（選択率6%）、
メタンが１μmol/g.h（選択率略0%）であった。反応結
果を表に示す。Example 15 Samarium oxide (Sm 2 O 3 ) was used as a catalyst for conversion of CO 2 into methanol in a reaction tube of a fixed-bed pressure-flow type reactor, and copper and zinc oxide (copper supported amount 5 wt%, copper / zinc oxide mole) were used. 1: 1)
1 g of a catalyst supporting was charged. 35 catalyst prior to reaction
Hydrogen reduction treatment was performed at 0 ° C. for 30 minutes. After cooling in a hydrogen stream, the reaction gas at room temperature (CO 2 / H 2 / Ar = 30/60/10, Ar is an internal standard) Switch to a reaction temperature of 220 ° C., a reaction pressure 30kg / c
The reaction was carried out at m 2 and a flow rate of 100 ml / mni. One hour after the start of the reaction, the amount of methanol produced was 380 μmol / gh and the selectivity was 94%. CO as a by-product is 20 μmol / gh (selectivity 6%),
Methane was 1 μmol / gh (selectivity approximately 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(CaO)に銅と酸
化亜鉛（銅担持量5wt%，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220℃、反応
圧力30kg/cm2、流速100ml/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.h、選択率
87%であった。副生成物としてはCOが50μmol/g.h（選択
率13%）、メタンが１μmol/g.h（選択率略0%）であっ
た。反応結果を表に示す。Example 16 Copper and zinc oxide were added to calcium oxide (CaO) as a catalyst for converting CO 2 into methanol in a reaction tube of a fixed-bed pressure-flow type reactor (copper loading: 5 wt%, copper / zinc oxide molar ratio 1: 1 g of the catalyst carrying 1) was loaded. 350 catalyst prior to reaction
Hydrogen reduction treatment was performed at 30 ° C. for 30 minutes. After cooling in a hydrogen stream,
The reaction gases at a reaction gas at room temperature at room temperature (CO 2 / H 2 / Ar = 30/60 /
10, Ar was an internal standard), and the reaction was carried out at a reaction temperature of 220 ° C., a reaction pressure of 30 kg / cm 2 , and a flow rate of 100 ml / mni. 1 hour after the start of the reaction, the amount of methanol produced is 340 μmol / gh, selectivity
It was 87%. As by-products, CO was 50 μmol / gh (selectivity 13%) and methane was 1 μmol / gh (selectivity approximately 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/H2/Ar＝30/60/10、Arは内
部標準）に切り替え、反応温度220℃、反応圧力30kg/cm
2、流速100ml/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320μmol/g.h、選択率90%であっ
た。副生成物としてはCOが69μmol/g.h（選択率10%）、
メタンが１μmol/g.h（選択率略0%）であった。反応結
果を表に示す。Example 17 Copper and zinc oxide were added to strontium oxide (SrO) as a catalyst for converting CO 2 into methanol in a reaction tube of a fixed-bed pressure-flow type reactor (copper loading: 5 wt%, copper / zinc oxide molar ratio 1:
1 g of the catalyst carrying 1) was loaded. Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350 ° C. for 30 minutes. After cooling in a hydrogen stream, switch to reaction gas (CO 2 / H 2 / Ar = 30/60/10, Ar is internal standard) at room temperature, reaction temperature 220 ℃, reaction pressure 30kg / cm
2. The reaction was carried out at a flow rate of 100 ml / mni. One hour after the start of the reaction, the amount of methanol produced was 320 μmol / gh, and the selectivity was 90%. CO as a by-product is 69 μmol / gh (selectivity 10%),
Methane was 1 μmol / gh (selectivity approximately 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ＣＯ2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(Dy2O3)に
銅と酸化亜鉛（銅担持量5wt%，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/H2/Ar＝30/60/10、Arは内
部標準）に切り替え、反応温度220℃、反応圧力30kg/cm
2、流速100ml/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.h、選択率95%であっ
た。副生成物としてはCOが20μmol/g.h（選択率5%）、
メタンが１μmol/g.h（選択率略0%）であった。反応結
果を表に示す。Example 18 Dysprosium oxide (Dy 2 O 3 ) was used as a catalyst for conversion of CO 2 into methanol in a reaction tube of a fixed-bed pressure-flow type reactor, and copper and zinc oxide (copper loading 5 wt%, copper / zinc oxide mole) were used. Ratio 1:
1 g of the catalyst carrying 1) was loaded. Prior to the reaction, the catalyst was subjected to hydrogen reduction treatment at 350 ° C. for 30 minutes. After cooling in a hydrogen stream, switch to reaction gas (CO 2 / H 2 / Ar = 30/60/10, Ar is internal standard) at room temperature, reaction temperature 220 ℃, reaction pressure 30kg / cm
2. The reaction was carried out at a flow rate of 100 ml / mni. One hour after the start of the reaction, the amount of methanol produced was 310 μmol / gh, and the selectivity was 95%. CO as a by-product is 20 μmol / gh (selectivity 5%),
Methane was 1 μmol / gh (selectivity approximately 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ＣＯ2のメタノー
ルへの変換用触媒として酸化亜鉛(ZnO)に銅(5wt%)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/H2/Ar＝30/60/10、Arは内部標準）
に切り替え、反応温度220℃、反応圧力30kg/cm2、流速1
00ml/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280μmol/g.h、選択率92%であった。副生成
物としてはCOが20μmol/g.h（選択率8%）、メタンが１
μmol/g.h（選択率略0%）であった。反応結果を表に示
す。Comparative Example 1 1 g of a catalyst in which copper (5 wt%) was supported on zinc oxide (ZnO) was charged as a catalyst for converting CO 2 into methanol into a reaction tube of a fixed bed pressure flow type reactor. Catalyst at 350 ° C prior to reaction
It was treated with hydrogen for 30 minutes. After cooling in a hydrogen stream, the reaction gas at room temperature (CO 2 / H 2 / Ar = 30/60/10, Ar internal standard)
Switch to, reaction temperature 220 ℃, reaction pressure 30kg / cm 2 , flow rate 1
The reaction was performed at 00 ml / mni. One hour after the start of the reaction, the amount of methanol produced was 280 μmol / gh, and the selectivity was 92%. As by-products, CO is 20μmol / gh (selectivity 8%), methane is 1
It was μmol / gh (selectivity approximately 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(MoO3)に銅と酸
化亜鉛（銅担持量5wt%，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/H2/Ar＝30/60/10、Arは内部標
準）に切り替え、反応温度220℃、反応圧力30kg/cm2、
流速100ml/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340μmol/g.h（選択率52%）、メ
タンが３５μmol/g.h（選択率略5%）であった。反応結
果を表に示す。Comparative Example 2 Copper and zinc oxide were added to molybdenum oxide (MoO 3 ) as a catalyst for conversion of CO 2 into methanol in a reaction tube of a fixed bed pressure flow type reactor (copper loading: 5 wt%, copper / zinc oxide molar ratio: 1). 1 g of the catalyst carrying 1) was loaded. 350 catalyst prior to reaction
Hydrogen reduction treatment was performed at 30 ° C. for 30 minutes. After cooling in a hydrogen stream,
At room temperature, switch to reaction gas (CO 2 / H 2 / Ar = 30/60/10, Ar is internal standard), reaction temperature 220 ℃, reaction pressure 30kg / cm 2 ,
The reaction was carried out at a flow rate of 100 ml / mni. One hour after the start of the reaction, the amount of methanol produced was 290 μmol / gh, and the selectivity was 43%.
As by-products, CO was 340 μmol / gh (selectivity: 52%) and methane was 35 μmol / gh (selectivity: approximately 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(WO3)に銅と
酸化亜鉛（銅担持量5wt%，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35
0℃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220℃、
反応圧力30kg/cm2、流速100ml/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10μmol/g.h、選
択率5%であった。副生成物としてはCOが260μmol/g.h
（選択率92%）、メタンが８μmol/g.h（選択率略3%）で
あった。反応結果を表に示す。Comparative Example 3 Copper and zinc oxide (copper loading 5 wt%, copper / zinc oxide molar ratio 1) on tungsten oxide (WO 3 ) as a catalyst for conversion of CO 2 into methanol in a reaction tube of a fixed bed pressure flow type reactor : 1)
1 g of a catalyst supporting was charged. 35 catalyst prior to reaction
Hydrogen reduction treatment was performed at 0 ° C. for 30 minutes. After allowing to cool in a hydrogen stream, the reaction gas at room temperature is reacted gas (CO 2 / H 2 / Ar = 30 at room temperature).
/ 60/10, Ar is internal standard), reaction temperature 220 ℃,
The reaction was performed at a reaction pressure of 30 kg / cm 2 and a flow rate of 100 ml / mni. The amount of methanol produced 1 hour after the start of the reaction was 10 μmol / gh, and the selectivity was 5%. CO as a by-product is 260 μmol / gh
(Selectivity 92%), methane was 8 μmol / gh (selectivity approximately 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(Ng2O5)に銅と酸化亜
鉛（銅担持量5wt%，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3
0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/H2/Ar＝30/60/10、Arは内部標準）に
切り替え、反応温度220℃、反応圧力30kg/cm2、流速100
ml/mniで反応を行った。反応開始１時間後のメタノール
生成量はほぼ０μmol/g.h、選択率ほぼ0%であった。副
生成物としてはCOが50μmol/g.h（選択率98%）、メタン
が１μmol/g.h（選択率2%）であった。反応結果を表に
示す。Comparative Example 4 Niobium (Ng 2 O 5 ) as a catalyst for converting CO 2 into methanol was used as a catalyst for conversion of CO 2 into methanol in a reaction tube of a fixed bed pressure flow type reactor (copper loading: 5 wt%, copper / zinc oxide molar ratio). 1 g of the catalyst carrying 1: 1) was loaded. Prior to the reaction, the catalyst was heated at 350 ° C for 3
Hydrogen reduction treatment was performed for 0 minutes. After cooling in a hydrogen stream, switch to reaction gas (CO 2 / H 2 / Ar = 30/60/10, Ar is internal standard) at room temperature, reaction temperature 220 ° C, reaction pressure 30kg / cm 2 , flow rate 100
The reaction was performed at ml / mni. One hour after the start of the reaction, the amount of methanol produced was almost 0 μmol / gh, and the selectivity was almost 0%. As by-products, CO was 50 μmol / gh (selectivity 98%) and methane was 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(Bi2O3)に銅と酸
化亜鉛（銅担持量5wt%，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/H2/Ar＝30/60/10、Arは内部標
準）に切り替え、反応温度220℃、反応圧力30kg/cm2、
流速100ml/mniで反応を行った。反応開始１時間後のメ
タノール生成量はほぼ０μmol/g.h、選択率ほぼ0%であ
った。他の生成物としてはメタンが１μmol/g.h（選択
率1%）であった。反応結果を表に示す。Comparative Example 5 Copper and zinc oxide were added to bismuth oxide (Bi 2 O 3 ) as a catalyst for converting CO 2 to methanol in a reaction tube of a fixed-bed pressure-flow type reactor (copper loading: 5 wt%, copper / zinc oxide mole). 1 g of catalyst carrying a ratio of 1: 1) was loaded. 350 catalyst prior to reaction
Hydrogen reduction treatment was performed at 30 ° C. for 30 minutes. After cooling in a hydrogen stream,
At room temperature, switch to reaction gas (CO 2 / H 2 / Ar = 30/60/10, Ar is internal standard), reaction temperature 220 ℃, reaction pressure 30kg / cm 2 ,
The reaction was carried out at a flow rate of 100 ml / mni. One hour after the start of the reaction, the amount of methanol produced was almost 0 μmol / gh, and the selectivity was almost 0%. The other product was methane at 1 μmol / gh (selectivity 1%). The reaction results are shown in the table.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭62−53739（ＪＰ，Ａ) 特開 昭60−106534（ＪＰ，Ａ) 特開 昭60−84142（ＪＰ，Ａ) 特開 昭59−32949（ＪＰ，Ａ) 特開 昭49−42240（ＪＰ，Ａ) 特開 昭49−17391（ＪＰ，Ａ) 特公 昭45−16682（ＪＰ，Ｂ１) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 62-53739 (JP, A) JP 60-106534 (JP, A) JP 60-84142 (JP, A) JP 59- 32949 (JP, A) JP-A-49-42240 (JP, A) JP-A-49-17391 (JP, A) JP-B-45-16682 (JP, B1)
Claims (1)
シリカ（ＳｉＯ2）、ジルコニア（ＺｒＯ2）、マグネシ
ア（ＭｇＯ）、セリア（ＣｅＯ2）、イットリア（Ｙ2Ｏ
3）、ネオジア（Ｎｄ2Ｏ3）、酸化ストロンチウム（Ｓ
ｒＯ）、酸化カルシウム（ＣａＯ）、クロミア（Ｃｒ2
Ｏ3）、酸化タンタル（Ｔａ2Ｏ5）、酸化プロセアジム
（Ｐｒ6Ｏ11）、酸化イッテルビウム（Ｙｂ2Ｏ3）、酸
化ホルミウム（Ｈｏ2Ｏ3）、酸化エルビウム（Ｅｒ
2Ｏ3）、酸化サマリウム（Ｓｍ2Ｏ3）、酸化ジスプロジ
ウム（Ｄｙ2Ｏ3）のいずれか１種から選ばれた金属酸化
物に担持させてなる触媒であって、該触媒中銅と酸化亜
鉛が２９重量％以下、金属酸化物が７１重量％以上であ
る触媒を用い、該触媒に、実質的に一酸化炭素を含ま
ず、二酸化炭素と水素を含有するガスを接触させ、メタ
ノールを生成させることを特徴とする二酸化炭素からの
メタノールの製造方法。1. Copper and zinc oxide are mixed with alumina (Al 2 O 3 ),
Silica (SiO 2 ), zirconia (ZrO 2 ), magnesia (MgO), ceria (CeO 2 ), yttria (Y 2 O)
3 ), neodia (Nd 2 O 3 ), strontium oxide (S
rO), calcium oxide (CaO), chromia (Cr 2 )
O 3 ), tantalum oxide (Ta 2 O 5 ), proceadim oxide (Pr 6 O 11 ), ytterbium oxide (Yb 2 O 3 ), holmium oxide (Ho 2 O 3 ), erbium oxide (Er)
2 O 3 ), samarium oxide (Sm 2 O 3 ), and dysprosium oxide (Dy 2 O 3 ), which are supported on a metal oxide selected from copper in the catalyst. Using a catalyst having a zinc oxide content of 29% by weight or less and a metal oxide content of 71% by weight or more, a gas containing substantially no carbon monoxide but containing carbon dioxide and hydrogen is brought into contact with the catalyst to remove methanol. A method for producing methanol from carbon dioxide, which comprises producing carbon dioxide.
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 JPH04122444A (en) | 1992-04-22 |
| JPH0635401B2 true 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) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996016011A1 (en) * | 1994-11-22 | 1996-05-30 | Ube Industries, Ltd. | Process for producing methanol |
| JP3624722B2 (en) | 1998-11-18 | 2005-03-02 | 本田技研工業株式会社 | Methanol reforming catalyst and methanol reforming catalyst apparatus using the same |
| JP2010254666A (en) * | 2009-03-30 | 2010-11-11 | Tokyo Electric Power Co Inc:The | Methanol synthesis method 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 |
| JP7092814B2 (en) * | 2020-03-18 | 2022-06-28 | 本田技研工業株式会社 | Carbon dioxide reduction catalyst |
| CN112517012B (en) * | 2020-12-01 | 2022-01-04 | 大连理工大学 | A kind of preparation method and application of CO2 hydrogenation to methanol catalyst |
| CN114950419B (en) * | 2022-04-20 | 2023-10-03 | 江南大学 | A metal catalyst for hydrogenating carbon dioxide to produce methanol and its application |
| CN119608171B (en) * | 2023-09-08 | 2026-04-03 | 中国科学院大连化学物理研究所 | A Cu@ZnOx core-shell structured nanocatalyst, its preparation method and application |
| CN119118791B (en) * | 2024-09-10 | 2025-04-22 | 江苏中鲈科技发展股份有限公司 | Method for preparing methanol based on carbon dioxide trapping and method for preparing ethylene glycol and environment-friendly polyester |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS545690B2 (en) * | 1972-03-06 | 1979-03-20 | ||
| CA1021354A (en) * | 1972-04-20 | 1977-11-22 | Alvin B. Stiles | Methanol synthesis catalyst |
| 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 | Method for manufacturing methanol synthesis catalyst |
-
1990
- 1990-09-13 JP JP2242941A patent/JPH0635401B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04122444A (en) | 1992-04-22 |
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