JP2021031480A - Method for producing methanol, and methanol production catalyst - Google Patents
Method for producing methanol, and methanol production catalyst Download PDFInfo
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- JP2021031480A JP2021031480A JP2019156854A JP2019156854A JP2021031480A JP 2021031480 A JP2021031480 A JP 2021031480A JP 2019156854 A JP2019156854 A JP 2019156854A JP 2019156854 A JP2019156854 A JP 2019156854A JP 2021031480 A JP2021031480 A JP 2021031480A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 433
- 239000003054 catalyst Substances 0.000 title claims abstract description 127
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 69
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000007789 gas Substances 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 239000010949 copper Substances 0.000 claims abstract description 46
- 229910052802 copper Inorganic materials 0.000 claims abstract description 41
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 40
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000011701 zinc Substances 0.000 claims abstract description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 37
- 239000001257 hydrogen Substances 0.000 claims abstract description 37
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 34
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 29
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims description 46
- 229910052733 gallium Inorganic materials 0.000 claims description 25
- 239000003426 co-catalyst Substances 0.000 claims description 24
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 150000001879 copper Chemical class 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000011651 chromium Substances 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 238000000975 co-precipitation Methods 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 21
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- -1 ethylene, propylene Chemical group 0.000 description 12
- 235000019253 formic acid Nutrition 0.000 description 8
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 229910017518 Cu Zn Inorganic materials 0.000 description 4
- 229910017752 Cu-Zn Inorganic materials 0.000 description 4
- 229910017943 Cu—Zn Inorganic materials 0.000 description 4
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- ZFYIQPIHXRFFCZ-QMMMGPOBSA-N (2s)-2-(cyclohexylamino)butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NC1CCCCC1 ZFYIQPIHXRFFCZ-QMMMGPOBSA-N 0.000 description 1
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000027455 binding Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate trihydrate Substances [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- COTNUBDHGSIOTA-UHFFFAOYSA-N meoh methanol Chemical compound OC.OC COTNUBDHGSIOTA-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
本発明は，メタノールの製造方法、及びメタノール製造触媒に関するものである。 The present invention relates to a method for producing methanol and a catalyst for producing methanol.
メタノールは、汎用性樹脂（ポリエチレン、ポリプロピレン等）の原料である、オレフィン（エチレン、プロピレン等）の出発原料をはじめ、フェノール樹脂原料、合成繊維、塗料、医農薬、燃料添加剤、基礎化学品の原料（酢酸、ホルマリン等）など幅広い化学品の原料として利用される。
そのため、メタノールの製造は、化学工業において非常に重要であり、省エネルギー化、経済性などの観点から高効率化が絶えず求められている。
Methanol is used as a starting material for olefins (ethylene, propylene, etc.), which is a raw material for general-purpose resins (polyethylene, polypropylene, etc.), as well as phenol resin raw materials, synthetic fibers, paints, medical pesticides, fuel additives, and basic chemicals. It is used as a raw material for a wide range of chemical products such as raw materials (acetic acid, formalin, etc.).
Therefore, the production of methanol is very important in the chemical industry, and high efficiency is constantly required from the viewpoint of energy saving and economic efficiency.
例えば、特許文献１には、「溶媒としてのアルコールの存在下、一酸化炭素又は二酸化炭素の一方又は双方と水素を含む原料ガスからギ酸エステル及びギ酸エステルを経由してメタノールを合成するギ酸エステル及びメタノール合成用触媒であって、主成分としてＣｕとＺｎを同時に含有し助触媒として周期律表第４族、第６族、第７族、第１３族及びランタノイドから選ばれる一種類以上の成分を含有することを特徴とするギ酸エステル及びメタノール合成用触媒。」が開示されている。 For example, Patent Document 1 states, "In the presence of alcohol as a solvent, a formate ester that synthesizes methanol from a raw material gas containing one or both of carbon monoxide or carbon dioxide and hydrogen via a formate ester and a formate ester and A catalyst for methanol synthesis, which contains Cu and Zn as main components at the same time, and contains one or more components selected from Group 4, Group 6, Group 7, Group 13 and Lantanoid of the Periodic Table as an auxiliary catalyst. A formate ester and a catalyst for methanol synthesis, which are characterized by being contained. "
特許文献２には、「ＣｕとＭｇを同時に含有することを特徴とするギ酸エステル及びメタノール合成用触媒。」が開示されている。 Patent Document 2 discloses "a catalyst for synthesizing formate ester and methanol, which is characterized by containing Cu and Mg at the same time."
特許文献３には、「アルコール溶媒の存在下で、一酸化炭素、又は、一酸化炭素及び二酸化炭素と、水素とを含む原料ガスから、ギ酸エステルを経由してメタノールを合成する際に用いられるＣｕを含むメタノール合成用触媒の共沈法による製造方法であって、溶媒中で触媒成分のプレカーサーを反応させて前記触媒を共沈法で製造する際に、触媒成分のプレカーサーを溶解した溶液、沈殿剤を溶解した溶液、又はこれらの水溶液を滴下し沈殿が形成される場となる溶媒の少なくともいずれかに、ポリエチレングリコールを添加することを特徴とするメタノール合成用触媒の製造方法。」が開示されている。 Patent Document 3 states, "In the presence of an alcohol solvent, it is used when synthesizing methanol from a raw material gas containing carbon monoxide or carbon monoxide, carbon dioxide, and hydrogen via a formic acid ester. A method for producing a methanol synthesis catalyst containing Cu by a co-precipitation method, which is a solution in which a precursor of a catalyst component is dissolved when the precursor of the catalyst component is reacted in a solvent to produce the catalyst by the co-precipitation method. A method for producing a catalyst for methanol synthesis, which comprises adding polyethylene glycol to at least one of a solution in which a precipitant is dissolved or a solvent in which an aqueous solution thereof is dropped to form a precipitate. " Has been done.
特許文献４には、「アルコール溶媒の存在下に一酸化炭素と水素を含む原料ガスからギ酸エステルを経由してメタノールを合成する液相メタノール合成反応に用いられるメタノール合成用触媒の製造方法において、銅（Ｃｕ）系触媒成分及び第二触媒成分の前駆体物質の水溶液から共沈法で得られた沈殿物を乾燥する際に、当該沈殿物を超臨界流体と接触させることを特徴とするメタノール合成用触媒の製造方法。」が開示されている。 Patent Document 4 describes, "In a method for producing a catalyst for methanol synthesis used in a liquid-phase methanol synthesis reaction for synthesizing methanol from a raw material gas containing carbon monoxide and hydrogen in the presence of an alcohol solvent via a formic acid ester. Methanol characterized by bringing the precipitate into contact with a supercritical fluid when drying the precipitate obtained by the co-precipitation method from an aqueous solution of a precursor substance of a copper (Cu) -based catalyst component and a second catalyst component. A method for producing a synthetic catalyst. ”Is disclosed.
特許文献５には、「酸化銅、酸化亜鉛及び酸化ジルコニウムからなることを特徴とするメタノール合成用触媒。」が開示されている。
特許文献６には、「酸化銅および／または銅を含むメタノール合成用触媒において、ガリウムを配合したことを特徴とする触媒」が開示されている。
特許文献７には、「銅、亜鉛、アルミニウム及びガリウムの各酸化物と、アルカリ土類金属元素及び希土類元素の金属酸化物の一種以上とを含有するメタノール合成触媒。」が開示されている。
Patent Document 5 discloses "a catalyst for methanol synthesis characterized by being composed of copper oxide, zinc oxide and zirconium oxide."
Patent Document 6 discloses "a catalyst for blending gallium in a catalyst for synthesizing methanol containing copper oxide and / or copper".
Patent Document 7 discloses "a methanol synthesis catalyst containing each oxide of copper, zinc, aluminum and gallium, and one or more of metal oxides of alkaline earth metal elements and rare earth elements."
特許文献８には、「銅、亜鉛、アルミニウム、ケイ素およびチタン含み、（Ａ１）硫黄の含有率が０．００１〜０．２重量％であり、（Ａ２）アルカリ金属の含有率が０．２重量％以下である。（（但し、銅、亜鉛、アルミニウム、珪素、チタンの合計を１００重量％とする）を満たす酸化炭素を原料とするメタノール製造用触媒」が開示されている。 Patent Document 8 states that "containing copper, zinc, aluminum, silicon and titanium, (A1) sulfur content is 0.001 to 0.2% by weight, and (A2) alkali metal content is 0.2. A catalyst for producing methanol using carbon oxide as a raw material, which satisfies (however, the total of copper, zinc, aluminum, silicon, and titanium is 100% by weight) is disclosed.
その他、非特許文献１には「ＣｕＺｎＯｘとＧａ、Ａｌ、Ｚｒ、Ｃｒ等の助触媒とを含むメタノール製造用触媒」、非特許文献２には「Ｃｕ、Ｚｎ、Ｍ（Ｍ＝Ｇａ、Ｆｅ等）を含むメタノール製造用触媒」も開示されている。 In addition, Non-Patent Document 1 describes "catalyst for producing methanol containing CuZnOx and co-catalysts such as Ga, Al, Zr, Cr", and Non-Patent Document 2 includes "Cu, Zn, M (M = Ga, Fe, etc.)". ) Is also disclosed.
ここで、特許文献１〜８、非特許文献１〜２で開示されているように、メタノールの製造には、種々の触媒、及び手法が用いられている。 Here, as disclosed in Patent Documents 1 to 8 and Non-Patent Documents 1 to 2, various catalysts and methods are used for the production of methanol.
しかし、メタノールの製造において、原料ガスとして水素と一酸化炭素とを反応させてメタノールを生成するプロセスでは、比較的、低温及び低圧でも、反応が進行する。一方で、二酸化炭素（ＣＯ２）を有効活用するために、水素と二酸化炭素（ＣＯ２）の混合ガスを原料として、メタノールを製造することも要請されている。
しかし、水素と二酸化炭素とを原料ガスとした場合、二酸化炭素が化学的に不活性であること、また水が副生することから、水素と二酸化炭素との反応は非常に進行しにくい。また、水素と二酸化炭素の反応が進行する場合でも、高温（例えば２５０℃以上）とする必要があるが、加熱に必要なエネルギーのために排出される二酸化炭素量が多くなる課題がある。
However, in the production of methanol, in the process of reacting hydrogen with carbon monoxide as a raw material gas to produce methanol, the reaction proceeds even at relatively low temperature and low pressure. On the other hand, in order to effectively utilize the carbon dioxide (CO 2), a mixed gas of hydrogen and carbon dioxide (CO 2) as a raw material, it has also been requested to produce methanol.
However, when hydrogen and carbon dioxide are used as raw materials, the reaction between hydrogen and carbon dioxide is very difficult to proceed because carbon dioxide is chemically inactive and water is by-produced. Further, even when the reaction between hydrogen and carbon dioxide proceeds, it is necessary to raise the temperature to a high temperature (for example, 250 ° C. or higher), but there is a problem that the amount of carbon dioxide emitted due to the energy required for heating increases.
そのため、水素と二酸化炭素（ＣＯ２）とを原料ガスとした場合にも、低温で、かつ高効率にメタノールを製造する方法が要望されている。 Therefore, there is a demand for a method for producing methanol at a low temperature and with high efficiency even when hydrogen and carbon dioxide (CO 2) are used as raw material gases.
そこで、本発明の課題は、水素と二酸化炭素（ＣＯ２）とを原料ガスとした場合にも、低温で、かつ高効率にメタノールを製造できる、メタノールの製造方法、および、それに利用するメタノール製造触媒を提供することである。 Therefore, the subject of the present invention is a method for producing methanol, which can produce methanol at a low temperature and with high efficiency even when hydrogen and carbon dioxide (CO 2) are used as raw materials, and a method for producing methanol using the same. To provide a catalyst.
課題を解決するための手段は、次の態様を含む。 Means for solving the problem include the following aspects.
［１］ メタノールと、銅及び亜鉛を含む酸化物からなる触媒と、の存在下で、水素及び二酸化炭素を含み、かつ二酸化炭素／一酸化炭素のモル比が２倍以上である原料ガスを反応させて、メタノールを製造するメタノールの製造方法。
［２］ 気相中で、メタノールを製造する［１］に記載のメタノールの製造方法。
［３］ 前記触媒において、前記銅／前記亜鉛のモル比が、１／２〜２／１である［１］又は［２］に記載のメタノールの製造方法。
［４］ 前記触媒が、助触媒として、ガリウム、ジルコニウム、クロム、アルミニウムよりなる群から選択される少なくとも１種を含む［１］又は［２］に記載のメタノールの製造方法。
［５］ 前記触媒が、助触媒として、ガリウムを含む［１］又は［２］に記載のメタノールの製造方法。
［６］ 前記触媒において、前記銅／前記助触媒のモル比が、１／１〜１／０．１である［４］又は［５］に記載のメタノールの製造方法。
［７］ 前記触媒は、銅塩、亜鉛塩、助触媒金属塩および沈殿剤を溶解させた水溶液のｐＨをアルカリにすることで、共沈により、前記銅及び前記亜鉛を含む沈殿物を生成した後、前記沈殿物を乾燥及び焼成して製造される［１］〜［６］のいずれか１項に記載のメタノールの製造方法。
［８］ 前記原料ガスの反応場に、メタノールを前記触媒１ｇに対して、２．８〜７ｍＬ／ｍｉｎで導入する［１］〜［７］のいずれか１項に記載のメタノールの製造方法。
［９］ 銅及び亜鉛と、助触媒としてのガリウムと、を含む酸化物からなるメタノール製造触媒。
［１０］ 前記銅／前記亜鉛のモル比が、１／２〜２／１である［９］に記載のメタノール製造触媒。
［１１］ 前記銅／前記ガリウムのモル比が、１／１〜１／０．１である［９］又は［１０］に記載のメタノール製造触媒。
[1] In the presence of methanol and a catalyst composed of an oxide containing copper and zinc, a raw material gas containing hydrogen and carbon dioxide and having a carbon dioxide / carbon monoxide molar ratio of 2 times or more is reacted. A method for producing methanol.
[2] The method for producing methanol according to [1], wherein methanol is produced in the gas phase.
[3] The method for producing methanol according to [1] or [2], wherein the molar ratio of copper / zinc in the catalyst is 1/2 to 2/1.
[4] The method for producing methanol according to [1] or [2], wherein the catalyst contains at least one selected from the group consisting of gallium, zirconium, chromium, and aluminum as a co-catalyst.
[5] The method for producing methanol according to [1] or [2], wherein the catalyst contains gallium as a co-catalyst.
[6] The method for producing methanol according to [4] or [5], wherein in the catalyst, the molar ratio of copper / co-catalyst is 1/1 to 1 / 0.1.
[7] The catalyst produced a precipitate containing the copper and the zinc by co-precipitation by making the pH of the aqueous solution in which the copper salt, the zinc salt, the cocatalyst metal salt and the precipitant were dissolved alkaline. The method for producing methanol according to any one of [1] to [6], which is produced by drying and firing the precipitate afterwards.
[8] The method for producing methanol according to any one of [1] to [7], wherein methanol is introduced into the reaction field of the raw material gas at 2.8 to 7 mL / min with respect to 1 g of the catalyst.
[9] A methanol production catalyst composed of an oxide containing copper and zinc and gallium as a co-catalyst.
[10] The methanol production catalyst according to [9], wherein the molar ratio of copper / zinc is 1/2 to 2/1.
[11] The methanol production catalyst according to [9] or [10], wherein the molar ratio of copper / gallium is 1/1 to 1 / 0.1.
本発明によれば、水素と二酸化炭素（ＣＯ２）とを原料ガスとした場合にも、低温で、かつ高効率にメタノールを製造できる、メタノールの製造方法、および、それに利用するメタノール製造触媒を提供できる。 According to the present invention, a method for producing methanol capable of producing methanol at a low temperature and with high efficiency even when hydrogen and carbon dioxide (CO 2 ) are used as raw materials, and a methanol production catalyst used for the method for producing methanol. Can be provided.
以下、本発明について説明する。
なお、本明細書において、「〜」を用いて表される数値範囲は、「〜」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
段階的に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。
数値範囲において、ある数値範囲で記載された上限値又は下限値は、実施例に示されている値に置き換えてもよい。
組成物中の各成分の量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する上記複数の物質の合計量を意味する。
「工程」との語は、独立した工程だけでなく、他の工程と明確に区別できない場合であっても工程の所期の目的が達成されれば、本用語に含まれる。
「好ましい態様の組み合わせ」は、より好ましい態様である。
Hereinafter, the present invention will be described.
In the present specification, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
In the numerical range described stepwise, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise.
In the numerical range, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.
The amount of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified.
The term "process" is included in this term as long as the intended purpose of the process is achieved, not only in an independent process but also in cases where it cannot be clearly distinguished from other processes.
The "combination of preferred embodiments" is a more preferred embodiment.
（メタノール製造方法）
本発明のメタノール製造方法は、メタノールと、銅及び亜鉛を含む酸化物からなる触媒と、の存在下で、水素及び二酸化炭素を含み、かつ二酸化炭素／一酸化炭素の比が２倍以上である原料ガスを反応させて、メタノールを製造する方法である。
(Methanol production method)
The method for producing methanol of the present invention contains hydrogen and carbon dioxide in the presence of methanol and a catalyst composed of an oxide containing copper and zinc, and the ratio of carbon dioxide / carbon monoxide is more than double. This is a method for producing methanol by reacting a raw material gas.
本発明のメタノール製造方法では、水素分子を解離する機能の高い、銅及び亜鉛を含む酸化物からなる触媒上で、水素と二酸化炭素（ＣＯ２）から、ギ酸塩（銅塩又は亜鉛塩）を形成後、反応場内に溶媒として存在するメタノールとの間で、ギ酸塩（銅塩又は亜鉛塩）をギ酸化メチルに変換し、最終的に、ギ酸化メチルをメタノールへと変換する（下記スキーム参照）。
３Ｈ２＋ＣＯ２ ⇔ ５Ｈ＋ＨＣＯＯＣｕ（Ｚｎ）＋ＣＨ３ＯＨ → ４Ｈ＋ＨＣＯＯＣＨ３＋Ｈ２Ｏ → ２ＣＨ３ＯＨ＋Ｈ２Ｏ
In the method for producing methanol of the present invention, formate (copper salt or zinc salt) is formed from hydrogen and carbon dioxide (CO 2 ) on a catalyst composed of an oxide containing copper and zinc, which has a high function of dissociating hydrogen molecules. After formation, the formate (copper salt or zinc salt) is converted to methyl formate with methanol present as a solvent in the reaction field, and finally methyl formate is converted to methanol (see the scheme below). ).
3H 2 + CO 2 ⇔ 5H + HCOOCu (Zn) + CH 3 OH → 4H + HCOOCH 3 + H 2 O → 2CH 3 OH + H 2 O
ここで、水素と二酸化炭素（ＣＯ２）から、ギ酸塩を形成する触媒は、銅及び亜鉛を含む酸化物である。この触媒において、銅の酸化物はメタノール合成の主活性サイトとして機能する。亜鉛の酸化物は銅の酸化物と物質的相乗効果を示し、構造改質、水素貯蔵、又は結合活性の直接的な増進剤として機能することができる。つまり、亜鉛の酸化物は二酸化炭素（ＣＯ２）の水素化からメタノールの合成に対してより高い選択率を与える。また、助触媒、例えば、ガリウムなどは、原料ガスの水素分子を効率的に原子状へ解離、および、周辺へ拡散しやすくして、反応を大きく促進すると推定される。
また、水素と二酸化炭素（ＣＯ２）の反応の間、ギ酸は絶えず形成される。そのため、エステル化反応によってギ酸を転換するために、絶えずメタノールを供給する。
その結果、本来、水素と二酸化炭素（ＣＯ２）との反応は、一定以上の反応温度（２５０℃以上）で進行するが、メタノールの存在下では、比較的低温（２５０℃未満）でも進行することが可能となった。
Here, the catalyst for forming formate from hydrogen and carbon dioxide (CO 2 ) is an oxide containing copper and zinc. In this catalyst, the copper oxide functions as the main active site for methanol synthesis. Zinc oxide exhibits a material synergistic effect with copper oxide and can function as a direct enhancer of structural reforming, hydrogen storage, or binding activity. That is, zinc oxide gives higher selectivity for methanol synthesis from hydrogenation of carbon dioxide (CO 2). Further, it is presumed that the co-catalyst, for example, gallium, efficiently dissociates the hydrogen molecules of the raw material gas into atomic atoms and facilitates the diffusion to the surroundings, thereby greatly promoting the reaction.
Also, formic acid is constantly formed during the reaction of hydrogen and carbon dioxide (CO 2). Therefore, methanol is constantly supplied to convert formic acid by the esterification reaction.
As a result, the reaction between hydrogen and carbon dioxide (CO 2 ) originally proceeds at a reaction temperature (250 ° C or higher) above a certain level, but in the presence of methanol, it proceeds even at a relatively low temperature (less than 250 ° C). It became possible.
以上より、本発明のメタノールの製造方法では、水素と二酸化炭素（ＣＯ２）とを原料ガスとした場合にも、低温で、かつ高効率にメタノールを製造できる。 From the above, in the method for producing methanol of the present invention, methanol can be produced at low temperature and with high efficiency even when hydrogen and carbon dioxide (CO 2) are used as raw material gases.
特に、触媒として、銅及び亜鉛を含むと共に、助触媒としてガリウムを含む酸化物を適用すると、Ｔｉ，Ｚｒ，Ｃｒ，Ｍｎ，Ａｌ等の従来の助触媒に比べ、ガリウムにより、さらに、原料ガスの水素分子を効率的に原子状へ解離しやすくする。そのため、さらに、水素と二酸化炭素（ＣＯ２）との反応を大きく促進すると推測される。
また、触媒において、銅、亜鉛、助触媒（ガリウム等）は、一定の大きさのドメイン（領域）を有することが反応面で有利である。そのため、触媒は、担持法よりも沈殿法で製造された触媒が好ましい。
In particular, when an oxide containing copper and zinc as a catalyst and gallium as a co-catalyst is applied, gallium makes it possible to further increase the amount of raw material gas as compared with conventional co-catalysts such as Ti, Zr, Cr, Mn, and Al. Makes it easier to efficiently dissociate hydrogen molecules into atoms. Therefore, it is presumed that the reaction between hydrogen and carbon dioxide (CO 2) is further promoted.
Further, in the catalyst, it is advantageous in terms of reaction that copper, zinc, and a co-catalyst (gallium, etc.) have a domain (region) of a certain size. Therefore, the catalyst is preferably a catalyst produced by the precipitation method rather than the supporting method.
以下、本発明のメタノールの製造方法の詳細について説明する。 Hereinafter, the details of the method for producing methanol of the present invention will be described.
−原料ガス−
本発明のメタノールの製造方法において、原料ガスは、水素及び二酸化炭素を含み、かつ二酸化炭素／一酸化炭素のモル比が２倍以上であるガスとする。つまり、原料ガスは、一酸化炭素を含まない、含んでも少ないことが好ましい。本発明のメタノールの製造方法は、主として、水素と二酸化炭素との反応によりメタノールを合成するためである。
そのため、ここで、二酸化炭素／一酸化炭素のモル比は、２倍以上が好ましく、５倍以上がより好ましい。
なお、原料ガスが一酸化炭素を含まない場合、二酸化炭素／一酸化炭素のモル比が２倍以上である。
-Raw material gas-
In the method for producing methanol of the present invention, the raw material gas is a gas containing hydrogen and carbon dioxide and having a molar ratio of carbon dioxide / carbon monoxide of 2 times or more. That is, it is preferable that the raw material gas does not contain carbon monoxide or contains a small amount of carbon monoxide. The method for producing methanol of the present invention is mainly for synthesizing methanol by the reaction of hydrogen and carbon dioxide.
Therefore, here, the molar ratio of carbon dioxide / carbon monoxide is preferably 2 times or more, and more preferably 5 times or more.
When the raw material gas does not contain carbon monoxide, the molar ratio of carbon dioxide / carbon monoxide is twice or more.
原料ガスにおける、水素／二酸化炭素のモル比は、高効率なメタノール生成の観点から、１／１〜１０／１が好ましく、２／１〜５／１がより好ましい。 The molar ratio of hydrogen / carbon dioxide in the raw material gas is preferably 1/1 to 10/1, more preferably 2/1 to 5/1, from the viewpoint of highly efficient methanol production.
原料ガスは、高効率なメタノール生成の観点から、反応場（具体的には、反応容器）に、触媒１ｇに対して、気体状態換算で、１０〜２００ｍＬ／ｍｉｎ（好ましくは５０〜１００ｍＬ／ｍｉｎ）で導入することがよい。 From the viewpoint of highly efficient methanol production, the raw material gas is placed in a reaction field (specifically, a reaction vessel) at 10 to 200 mL / min (preferably 50 to 100 mL / min) in terms of gas state with respect to 1 g of the catalyst. ) Should be introduced.
−触媒−
本発明のメタノールの製造方法では、触媒として、銅及び亜鉛を含む酸化物からなる触媒を適用する。
-Catalyst-
In the method for producing methanol of the present invention, a catalyst composed of an oxide containing copper and zinc is applied as a catalyst.
触媒において、銅／亜鉛のモル比は、高効率なメタノール生成の観点から、１／２〜２／１が好ましく、４／６〜６／４がより好ましい。
銅／亜鉛のモル比が１／２未満又は２／１超えでは、触媒活性が十分でなく、高効率でメタノールが生成し難くなることがある。
In the catalyst, the molar ratio of copper / zinc is preferably 1/2 to 2/1, more preferably 4/6 to 6/4, from the viewpoint of highly efficient methanol production.
If the molar ratio of copper / zinc is less than 1/2 or more than 2/1, the catalytic activity may be insufficient and it may be difficult to produce methanol with high efficiency.
触媒は、高効率なメタノール生成の観点から、助触媒を含んでもよい。
助触媒としては、ガリウム、ジルコニウム、クロム、アルミニウムよりなる群から選択される少なくとも１種が挙げられる。
銅／助触媒のモル比は、高効率なメタノール生成の観点から、１／１〜１／０．１が好ましく、１／０．８〜１／０．４がより好ましい。
The catalyst may include a co-catalyst from the viewpoint of highly efficient methanol production.
Examples of the co-catalyst include at least one selected from the group consisting of gallium, zirconium, chromium and aluminum.
The molar ratio of copper / co-catalyst is preferably 1 / 1-1 / 0.1, more preferably 1 / 0.8-1 / 0.4, from the viewpoint of highly efficient methanol production.
これら触媒の中でも、特に、銅及び亜鉛と、助触媒としてガリウムと、を含む酸化物からなる触媒が好ましい。助触媒としてガリウムを含む触媒を適用すると、さらに、低温で高効率なメタノールを生成することができる。ガリウムは、Ｔｉ，Ｚｒ，Ｃｒ，Ｍｎ，Ａｌ等の従来の助触媒に比べ、原料ガスの水素分子を原子状へ解離する機能が高く、水素と二酸化炭素（ＣＯ２）との反応を大きく促進すると考えられる推測されるためである。 Among these catalysts, a catalyst composed of an oxide containing copper and zinc and gallium as a co-catalyst is particularly preferable. By applying a catalyst containing gallium as a co-catalyst, it is possible to further produce highly efficient methanol at a low temperature. Compared to conventional co-catalysts such as Ti, Zr, Cr, Mn, and Al, gallium has a higher function of dissociating hydrogen molecules in the raw material gas into atoms, and greatly promotes the reaction between hydrogen and carbon dioxide (CO 2). This is because it is presumed to be.
ここで、銅／ガリウムのモル比は、高効率なメタノール生成の観点から、１／１〜１／０．１が好ましく、１／０．５〜１／０．２がより好ましい。 Here, the molar ratio of copper / gallium is preferably 1 / 1-1 / 0.1, more preferably 1 / 0.5-1 / 0.2, from the viewpoint of highly efficient methanol production.
触媒は、触媒製造工程等で混入する不可避的不純物を含んでもよい。ただし、触媒活性向上の面からは不純物量が少ないほど好ましく、できるだけ不純物が混入しないようにすることが好ましい。 The catalyst may contain unavoidable impurities mixed in the catalyst manufacturing process or the like. However, from the viewpoint of improving the catalytic activity, it is preferable that the amount of impurities is small, and it is preferable that impurities are not mixed as much as possible.
触媒は、粉体であってもよいし、任意の形状の成形体であってもよい。
ただし、触媒の大きさは、平均粒径で１０μｍ〜１ｍｍが好ましい。本発明の触媒の大きさは、例えば、粉砕、篩い分け等により調整する。
触媒の大きさが平均粒径で１０μｍ未満である場合、触媒と生成物との固液分離操作の効率が大きく低下することがある。
本発明の触媒の大きさが平均粒径で１ｍｍを超える場合、触媒の表面積が小さくなり触媒活性が十分発揮できないことがある。
本発明の触媒の平均粒径は、レーザー式回折法により、粒度分布を得て、体積基準で、粒径の小さい方から累積した累積５０％径（体積平均粒径）である。
The catalyst may be a powder or a molded product having an arbitrary shape.
However, the size of the catalyst is preferably 10 μm to 1 mm in average particle size. The size of the catalyst of the present invention is adjusted by, for example, pulverization, sieving, or the like.
If the size of the catalyst is less than 10 μm in average particle size, the efficiency of the solid-liquid separation operation between the catalyst and the product may be significantly reduced.
When the size of the catalyst of the present invention exceeds 1 mm in average particle size, the surface area of the catalyst may become small and the catalytic activity may not be sufficiently exhibited.
The average particle size of the catalyst of the present invention is a cumulative 50% diameter (volume average particle size) accumulated from the smaller particle size on a volume basis after obtaining a particle size distribution by a laser diffraction method.
触媒の比表面積は、例えば、１〜４００ｍ２／ｇである。
ここで、一般的に、良好な触媒活性を発現させるためには、触媒の比表面積は大きいほど有利である。
一方で、触媒の比表面積が４００ｍ２／ｇより大きくなると、触媒強度の低下を招くことがある好ましくない。また、触媒の比表面積が１ｍ２／ｇより小さくなると、活性金属の反応への寄与効率が低下するため、十分な触媒活性が得られないことがある。
触媒の比表面積は、窒素ガスの吸脱着によるＢＥＴ法で求めた測定値である。
The specific surface area of the catalyst is, for example, 1 to 400 m 2 / g.
Here, in general, in order to exhibit good catalytic activity, the larger the specific surface area of the catalyst, the more advantageous it is.
On the other hand, if the specific surface area of the catalyst is larger than 400 m 2 / g, the catalyst strength may be lowered, which is not preferable. Further, when the specific surface area of the catalyst is smaller than 1 m 2 / g, the efficiency of contribution of the active metal to the reaction decreases, so that sufficient catalytic activity may not be obtained.
The specific surface area of the catalyst is a measured value obtained by the BET method by adsorption / desorption of nitrogen gas.
−触媒の方法−
触媒は、担持法または沈殿法を利用して製造できる。
一方で、沈殿法により得られた触媒は、担持法で得られた触媒に比べ、銅、亜鉛、助触媒（ガリウム等）が一定の大きさのドメイン（領域）を有するため、触媒能が高まり、水素と二酸化炭素（ＣＯ２）との反応を大きく促進できる。
そのため、触媒は、沈殿法により得られた触媒であることが好ましい。
-Catalyst method-
The catalyst can be produced using a carrier method or a precipitation method.
On the other hand, the catalyst obtained by the precipitation method has a higher catalytic ability than the catalyst obtained by the carrier method because copper, zinc, and co-catalysts (gallium, etc.) have domains (regions) of a certain size. , The reaction between hydrogen and carbon dioxide (CO 2 ) can be greatly promoted.
Therefore, the catalyst is preferably a catalyst obtained by the precipitation method.
沈殿法を利用した触媒は、例えば、銅塩、亜鉛塩および沈殿剤を溶解させた水溶液のｐＨをアルカリにすることで、共沈により、前記銅及び前記亜鉛を含む沈殿物を生成した後、沈殿物を乾燥及び焼成して製造する。
助触媒を含む触媒を製造する場合、銅塩、亜鉛塩と共に、助触媒の金属塩を溶解させた水溶液を適用する。
In the catalyst using the precipitation method, for example, the pH of an aqueous solution in which a copper salt, a zinc salt and a precipitant are dissolved is made alkaline, so that a precipitate containing the copper and the zinc is produced by coprecipitation, and then the precipitate is produced. The precipitate is produced by drying and firing.
When producing a catalyst containing a co-catalyst, an aqueous solution in which a metal salt of the co-catalyst is dissolved is applied together with a copper salt and a zinc salt.
銅塩、亜鉛塩および沈殿剤を溶解させた水溶液と沈殿剤水溶液とを混合して調製してもよいし、銅塩、亜鉛塩および沈殿剤を水に添加して調製してもよい。
銅塩、亜鉛塩、助触媒の金属塩としては、該当金属元素の、硝酸塩、酢酸塩、硫酸塩、塩化物等が挙げられる。各塩は、水に溶解すればよく、特に限定されることは無いが、溶解度の高い硝酸塩がよい。
It may be prepared by mixing an aqueous solution in which a copper salt, a zinc salt and a precipitant are dissolved and an aqueous solution of a precipitant, or by adding a copper salt, a zinc salt and a precipitant to water.
Examples of the copper salt, zinc salt, and metal salt of the co-catalyst include nitrates, acetates, sulfates, chlorides, and the like of the corresponding metal elements. Each salt may be dissolved in water and is not particularly limited, but a nitrate having a high solubility is preferable.
沈殿剤としては、アルカリ炭酸塩（炭酸ナトリウム等）、アンモニア水等が挙げられ、炭酸ナトリウムが好ましい。 Examples of the precipitant include alkaline carbonate (sodium carbonate and the like), aqueous ammonia and the like, and sodium carbonate is preferable.
銅塩、亜鉛塩および沈殿剤を溶解させた水溶液のｐＨは、例えば、７．５〜１０．５（好ましくは８〜１０）とする。水溶液のｐＨを上記範囲とし、アルカリ性にすると、共沈により、銅及び亜鉛を含む沈殿物（又は、銅、亜鉛および助触媒を含む沈殿物）が生成する。
このときの混合液の温度は、例えば、４０〜８０℃（好ましくは６０〜７０℃）とすることがよい。
The pH of the aqueous solution in which the copper salt, zinc salt and precipitant are dissolved is, for example, 7.5 to 10.5 (preferably 8 to 10). When the pH of the aqueous solution is set to the above range and made alkaline, coprecipitation produces a precipitate containing copper and zinc (or a precipitate containing copper, zinc and a co-catalyst).
The temperature of the mixed solution at this time is preferably, for example, 40 to 80 ° C. (preferably 60 to 70 ° C.).
得らえた共沈物（つまり、触媒の前駆体）を、熟成のため一定時間放置する。熟成時間は、例えば、５〜５００時間程度である。
次に、熟成後の共沈物を、ろ過した後、アルカリ炭酸塩等の沈殿剤成分を除去するため、イオン交換水等で洗浄する。
そして、洗浄後の共沈物を乾燥及び焼成する。焼成は、例えば、空気中２５０〜４００℃、０．５〜５時間で実施する。
The obtained coprecipitate (that is, the precursor of the catalyst) is left for a certain period of time for aging. The aging time is, for example, about 5 to 500 hours.
Next, the aging coprecipitate is filtered and then washed with ion-exchanged water or the like in order to remove the precipitant component such as alkaline carbonate.
Then, the co-precipitate after washing is dried and fired. The firing is carried out in air at 250 to 400 ° C. for 0.5 to 5 hours, for example.
以上の工程を経て、触媒が得られる。
なお、焼成により得られた触媒に、必要に応じて整粒後、還元（例えば、水素気流中等の活性化処理を施してもよい。また、空気中で触媒を取り扱う場合、触媒の表面に不動態化処理を施してもよい。
A catalyst is obtained through the above steps.
If necessary, the catalyst obtained by firing may be subjected to reduction (for example, activation treatment in a hydrogen stream or the like) after sizing, and when the catalyst is handled in air, the surface of the catalyst is non-existent. It may be subjected to a passivation treatment.
−反応−
本発明のメタノールの製造方法は、気相中で、メタノールを製造する方法であってもよいし、液相中で、メタノールを製造する方法であってもよい。
つまり、本発明のメタノールの製造方法は、メタノールガス及び触媒の存在下で、原料ガスを反応する方法であってもよいし、メタノール液及び触媒の存在下で、原料ガスを反応する方法であってもよい。
ただし、低温で高効率なメタノール合成を実現する観点から、本発明のメタノールの製造方法は、気相中で、メタノールを製造する方法が好ましい。
-Reaction-
The method for producing methanol of the present invention may be a method for producing methanol in the gas phase or a method for producing methanol in the liquid phase.
That is, the method for producing methanol of the present invention may be a method of reacting the raw material gas in the presence of methanol gas and a catalyst, or a method of reacting the raw material gas in the presence of a methanol solution and a catalyst. You may.
However, from the viewpoint of realizing highly efficient methanol synthesis at low temperature, the method for producing methanol of the present invention is preferably a method for producing methanol in the gas phase.
具体的には、本発明の炭化水素の製造方法では、例えば、反応場に触媒を配置した後（具体的には、反応容器に触媒を充填した後）、メタノールと共に、混合ガスを反応場（具体的は反応容器）流通する。それにより、メタノールの存在下で、混合ガスを触媒に接触させる。触媒は、混合ガスを触媒に接触させる前（つまり、メタノールの合成前）に、不活性ガス（窒素等）雰囲気下で加熱し、水素ガスを接触させて、還元処理を実施することがよい。
なお、反応容器の形式としては、固定床、噴流床、流動床、スラリー床のいずれも好適に用いることができる。
Specifically, in the method for producing a hydrocarbon of the present invention, for example, after arranging a catalyst in a reaction field (specifically, after filling a reaction vessel with a catalyst), a mixed gas is put into a reaction field (specifically, after filling a reaction vessel with a catalyst). Specifically, the reaction vessel) is distributed. Thereby, the mixed gas is brought into contact with the catalyst in the presence of methanol. The catalyst may be heated in an inert gas (nitrogen or the like) atmosphere before the mixed gas is brought into contact with the catalyst (that is, before the synthesis of methanol), and the hydrogen gas is brought into contact with the catalyst to carry out the reduction treatment.
As the type of reaction vessel, any of a fixed bed, a jet bed, a fluidized bed, and a slurry bed can be preferably used.
原料ガスは、高効率なメタノール生成の観点から、反応場（具体的には、反応容器）に、触媒１ｇに対して、１０〜２００ｍＬ／ｍｉｎ（好ましくは５０〜１００ｍＬ／ｍ）で導入することがよい。特に、原料ガスは、反応場中のメタノールガスの圧力が一定となるように導入することがよい。 From the viewpoint of highly efficient methanol production, the raw material gas should be introduced into the reaction field (specifically, the reaction vessel) at 10 to 200 mL / min (preferably 50 to 100 mL / m) with respect to 1 g of the catalyst. Is good. In particular, the raw material gas may be introduced so that the pressure of the methanol gas in the reaction field becomes constant.
メタノールは、低温で高効率なメタノール生成の観点から、原料ガスの反応場（具体的には、反応容器）に、触媒１ｇに対して、１．４〜１４ｍＬ／ｍｉｎ（好ましくは２．８〜７ｍＬ／ｍｉｎ）で導入することがよい。
そして、メタノールは、原料ガスと共に、反応場（具体的には、反応容器）に導入し続ける。二酸化炭素の水素化の間、ギ酸（ＨＣＯＯＨ）は絶えず形成される。そのため、エステル化反応によってギ酸（ＨＣＯＯＨ）を転換するために、絶えずメタノールを導入する。
From the viewpoint of highly efficient methanol production at low temperature, methanol is applied to the reaction field of the raw material gas (specifically, the reaction vessel) at 1.4 to 14 mL / min (preferably 2.8 to 2.8 to 1 g of the catalyst). It is recommended to introduce at 7 mL / min).
Then, methanol is continuously introduced into the reaction field (specifically, the reaction vessel) together with the raw material gas. During the hydrogenation of carbon dioxide, formic acid (HCOOH) is constantly formed. Therefore, methanol is constantly introduced to convert formic acid (HCOOH) by the esterification reaction.
ここで、反応場における、メタノール／水素及び二酸化炭素のモル比は、低温で高効率なメタノール生成の観点から、１／２００〜１／２０が好ましく、１／１００〜１／５０がより好ましい。 Here, the molar ratio of methanol / hydrogen and carbon dioxide in the reaction field is preferably 1/200 to 1/20, more preferably 1/100 to 1/50, from the viewpoint of highly efficient methanol production at low temperature.
以下、実施例により本発明をさらに詳細に説明するが、本発明はこれら実施例に限定されない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
（実施例１）
６．７ｇの硝酸銅（ＩＩ）三水和物、８．３ｇの硝酸亜鉛六水和物、１．４ｇの硝酸ガリウム（ＩＩＩ）九水和物、および炭酸ナトリウム溶液を、３００ｒｍｐおよび７００℃で、一定に撹拌した５００ｍＬの蒸留水中に同時に加えた。ｐＨは８．５に保ち、共沈により沈殿物を得た。
得られた沈殿物を１２時間熟成させ、漉過し、十分な蒸留水で洗浄し、そして１２００℃で一晩乾燥させ、触媒の前駆体を得た。次いで、触媒の前駆休を空気中で２０℃／ｍｉｎの速度で３５０℃まで加熱し３時間保持し、触媒を得た。
得られた触媒は、Ｃｕ、Ｚｎ、Ｇａを含み、モル比（Ｃｕ：Ｚｎ：Ｇａ）が１：１：０．１である酸化物（「Ｃｕ−Ｚｎ−Ｇａ（１：１：０．１）」とも表記）である。
(Example 1)
6.7 g copper (II) nitrate trihydrate, 8.3 g zinc nitrate hexahydrate, 1.4 g gallium nitrate (III) nine hydrate, and sodium carbonate solution at 300 mp and 700 ° C. , Simultaneously added to 500 mL of distilled water with constant stirring. The pH was kept at 8.5 and a precipitate was obtained by coprecipitation.
The resulting precipitate was aged for 12 hours, strained, washed with sufficient distilled water and dried overnight at 1200 ° C. to give a precursor of the catalyst. Next, the precursor rest of the catalyst was heated to 350 ° C. in air at a rate of 20 ° C./min and held for 3 hours to obtain a catalyst.
The obtained catalyst contains Cu, Zn, and Ga, and has an oxide (“Cu—Zn—Ga (1: 1: 0.1)” having a molar ratio (Cu: Zn: Ga) of 1: 1: 0.1. ) ”).
上記操作に準じて、Ｇａのモル比が０．２、０．３、０．６の異なる酸化物からなる触媒（各々、Ｃｕ−Ｚｎ−Ｇａ（１：１：０．１）、Ｃｕ−Ｚｎ−Ｇａ（１：１：０．１）、Ｃｕ−Ｚｎ−Ｇａ（１：１：０．１）と表記）も得た。 According to the above operation, catalysts composed of oxides having different Ga molar ratios of 0.2, 0.3, and 0.6 (Cu-Zn-Ga (1: 1: 0.1) and Cu-Zn, respectively). -Ga (1: 1: 0.1) and Cu-Zn-Ga (1: 1: 0.1)) were also obtained.
これら触媒を０．５ｇ用い、内径８ｍｍのＳＵＳ製反応管の中央に位置するよう石英ウールで固定し、触媒層中央位置に熱電対を挿入し、固定床反応管を所定の位置にセットした。
合成反応を始める前に、まず反応器に水素５％／Ｈｅの混合ガスを６０ｍＬ／ｍｉｎ流しながら、常圧で２９０℃、４ｈ還元処理を行った。
Using 0.5 g of these catalysts, they were fixed with quartz wool so as to be located at the center of a SUS reaction tube having an inner diameter of 8 mm, a thermocouple was inserted at the center position of the catalyst layer, and the fixed bed reaction tube was set at a predetermined position.
Before starting the synthesis reaction, first, a mixed gas of 5% hydrogen / He was flowed through the reactor at 60 mL / min, and a reduction treatment was carried out at 290 ° C. for 4 hours at normal pressure.
その後、室温に下げた後、反応容器に、水素：ＣＯ２＝３：１（モル比）、内部標準としてＡｒを４％含む原料ガスを５０ｍＬ／ｍｉｎになるよう導入すると共に、メタノールをガスとして１．４ｍｌ／ｍｉｎ又は２．８ｍｌ／ｍｉｎを導入しながら、反応温度７ＭＰａ、反応圧力２００℃で、反応時間２４ｈで、合成を行った。 Then, after lowering to room temperature, a raw material gas containing hydrogen: CO 2 = 3: 1 (molar ratio) and 4% Ar as an internal standard was introduced into the reaction vessel so as to be 50 mL / min, and methanol was used as the gas. Synthesis was carried out at a reaction temperature of 7 MPa, a reaction pressure of 200 ° C., and a reaction time of 24 hours while introducing 1.4 ml / min or 2.8 ml / min.
反応生成物は、水分を除去した後、二つのガスクロマトグラフィ（島津製作所製Ｇｃ−２０１４）に注入して、ＴＣＤ（Ｔｈｅｒｍａｌ Ｃｏｎｄｕｃｔｉｖｉｔｙ Ｄｅｔｅｃｔｏｒ）分析とＦＩＤ（Ｆｌａｍｅ Ｉｏｎｉｚａｔｉｏｎ Ｄｅｔｅｃｔｏｒ）分析を行った。そして、次の値を求めた。その結果を表１に示す。 After removing water, the reaction product was injected into two gas chromatography (Gc-2014 manufactured by Shimadzu Corporation) to perform TCD (Thermal Conductivity Detector) analysis and FID (Flame Ionization Detector) analysis. Then, the following value was obtained. The results are shown in Table 1.
−転化率（Conv.）−
・ＣＯ２転化率（％）＝（１−（ＣＯ２の減少量）／（供給されたＣＯ２の供給量））×１００
− Conversion rate (Conv.) −
-CO 2 conversion rate (%) = (1- ( decrease in CO 2 ) / (supply of CO 2 supplied)) x 100
−選択率（Hydrocarbon distribution）−
・ＣＯ選択率（％）＝（ＣＯの体積量）／（供給されたＣＯ２の供給量）×１００
・ＭｅＯＨ選択率（％）＝（ＭｅＯＨの体積量）／（供給されたＣＯ２の供給量）×１００
− Selectivity (Hydrocarbon distribution) −
-CO selectivity (%) = (volume of CO) / (supply of CO 2 supplied) x 100
MeOH selectivity (%) = (volume of MeOH) / (supplied amount of supplied CO 2) x 100
−空時収率（Space Time Yield (g/Kg-cat・h)）−
・ＭｅＯＨ空時収率(g/Kg-cat・h)＝メタノールの生成モル数（ｍｏｌ／ｋｇ−ｃａｔ・ｈ）×３２ｇ／ＣＨ３ＯＨ−ｍｏｌ
-Space Time Yield (g / Kg-cat · h)-
-MeOH air-time yield (g / Kg-cat · h) = number of moles produced of methanol (mol / kg-cat · h) x 32 g / CH 3 OH-mol
上記結果から、本条件（反応温度が２００℃という低温の条件）において、Ｃｕ−Ｚｎ−Ｇａ（１：１：０．１）触媒では、メタノールガス導入量が１．４ｍＬ／ｍｉｎのとき、３０７．６ｇ／Ｋｇ−ｃａｔ．ｈの空時収率で、また、メタノールガス導入量が２．８ｍＬ／ｍｉｎとき、２５８．９ｇ／Ｋｇ−ｃａｔ．ｈの空時収率で、メタノールは生成することがわかった。
また、Ｃｕ−Ｚｎ−Ｇａ（１：１：０．２）触媒では、メタノールガス導入量が１．４ｍＬ／ｍｉｎのとき、３２８．９ｇ／Ｋｇ−ｃａｔ．ｈの空時収率で、また、メタノールガス導入量が２．８ｍＬ／ｍｉｎとき、２４０．３ｇ／Ｋｇ−ｃａｔ．ｈの空時収率で、メタノールは生成することがわかった。
また、Ｃｕ−Ｚｎ−Ｇａ（１：１：０．３）触媒では、メタノールガス導入量が１．４ｍＬ／ｍｉｎのとき、３２６．７ｇ／Ｋｇ−ｃａｔ．ｈの空時収率で、また、メタノールガス導入量が２．８ｍＬ／ｍｉｎとき、２６８．７ｇ／Ｋｇ−ｃａｔ．ｈの空時収率で、メタノールは生成することがわかった。
また、Ｃｕ−Ｚｎ−Ｇａ（１：１：０．６）触媒では、メタノールガス導入量が１．４ｍＬ／ｍｉｎのとき、２９８．１ｇ／Ｋｇ−ｃａｔ．ｈの空時収率で、また、メタノールガス導入量が２．８ｍＬ／ｍｉｎとき、２９８．８ｇ／Ｋｇ−ｃａｔ．ｈの空時収率で、メタノールは生成することがわかった。
From the above results, under this condition (a low temperature condition of a reaction temperature of 200 ° C.), with a Cu-Zn-Ga (1: 1: 0.1) catalyst, 307 when the amount of methanol gas introduced is 1.4 mL / min. .6g / Kg-cat. In the air-time yield of h, and when the amount of methanol gas introduced was 2.8 mL / min, 258.9 g / Kg-cat. It was found that methanol was produced in the air-time yield of h.
Further, in the case of the Cu-Zn-Ga (1: 1: 0.2) catalyst, when the amount of methanol gas introduced was 1.4 mL / min, 328.9 g / Kg-cat. In the air-time yield of h, and when the amount of methanol gas introduced was 2.8 mL / min, 240.3 g / Kg-cat. It was found that methanol was produced in the air-time yield of h.
Further, in the case of the Cu-Zn-Ga (1: 1: 0.3) catalyst, when the amount of methanol gas introduced was 1.4 mL / min, 326.7 g / Kg-cat. In the air-time yield of h, and when the amount of methanol gas introduced was 2.8 mL / min, 268.7 g / Kg-cat. It was found that methanol was produced in the air-time yield of h.
In the case of the Cu-Zn-Ga (1: 1: 0.6) catalyst, when the amount of methanol gas introduced was 1.4 mL / min, 298.1 g / Kg-cat. In the air-time yield of h, and when the amount of methanol gas introduced was 2.8 mL / min, 298.8 g / Kg-cat. It was found that methanol was produced in the air-time yield of h.
（実施例２）
実施例１の触媒の製法に準じて、銅及び亜鉛を含む酸化物からなる触媒（Ｃｕ−Ｚｎと表記）、また、銅及び亜鉛に加え、助触媒として、Ｇａ、Ｚｒ、Ｃｒ、若しくはＡｌを含む酸化物からなる触媒（各々、Ｃｕ−Ｚｎ−Ｇａ、Ｃｕ−Ｚｎ−Ｚｒ、Ｃｕ−Ｚｎ−Ｃｒ、Ｃｕ−Ｚｎ−Ａｌと表記）を得た。なお、触媒中の各金属元素のモル比（Ｃｕ：Ｚｎ：Ｍ（Ｍ＝助触媒）は、１：１：０．２である。ただし、Ｃｕ−Ｚｎ触媒のモル比（Ｃｕ：Ｚｎ）は、１：１である。
そして、これら触媒を用いた以外は、実施例１と同様にして、メタノールを合成し、分析した。その結果を表２に示す。
(Example 2)
According to the method for producing a catalyst of Example 1, a catalyst composed of an oxide containing copper and zinc (denoted as Cu-Zn), and in addition to copper and zinc, Ga, Zr, Cr, or Al is used as an auxiliary catalyst. A catalyst composed of the containing oxide (denoted as Cu-Zn-Ga, Cu-Zn-Zr, Cu-Zn-Cr, and Cu-Zn-Al, respectively) was obtained. The molar ratio of each metal element in the catalyst (Cu: Zn: M (M = cocatalyst) is 1: 1: 0.2. However, the molar ratio of Cu—Zn catalyst (Cu: Zn) is It is 1: 1.
Then, methanol was synthesized and analyzed in the same manner as in Example 1 except that these catalysts were used. The results are shown in Table 2.
上記結果から、本条件（反応温度が２００℃という低温の条件）において、Ｃｕ−Ｚｎ−Ｇａ触媒では、３３３．５ｇ／Ｋｇ−ｃａｔ．ｈの空時収率で、メタノールは生成することがわかった。
また、Ｃｕ−Ｚｎ触媒では、２００．８ｇ／Ｋｇ−ｃａｔ．ｈの空時収率で、メタノールは生成することがわかった。
また、Ｃｕ−Ｚｎ−Ｚｒ触媒では、２９１．１ｇ／Ｋｇ−ｃａｔ．ｈの空時収率で、メタノールは生成することがわかった。
また、Ｃｕ−Ｚｎ−Ｃｒ触媒では、２９７．０ｇ／Ｋｇ−ｃａｔ．ｈの空時収率で、メタノールは生成することがわかった。
また、Ｃｕ−Ｚｎ−Ａｌ触媒では、３０５．２ｇ／Ｋｇ−ｃａｔ．ｈの空時収率で、メタノールは生成することがわかった。
From the above results, under this condition (a low temperature condition of a reaction temperature of 200 ° C.), 333.5 g / Kg-cat. It was found that methanol was produced in the air-time yield of h.
In the case of Cu-Zn catalyst, 200.8 g / Kg-cat. It was found that methanol was produced in the air-time yield of h.
In the case of Cu-Zn-Zr catalyst, 291.1 g / Kg-cat. It was found that methanol was produced in the air-time yield of h.
In the case of Cu-Zn-Cr catalyst, 297.0 g / Kg-cat. It was found that methanol was produced in the air-time yield of h.
In the case of Cu-Zn-Al catalyst, 305.2 g / Kg-cat. It was found that methanol was produced in the air-time yield of h.
（比較例１）
実施例２におけるＣｕ−Ｚｎ-Ｇａ触媒を３ｇ用い、原料ガスとしてＨ２／ＣＯ／ＣＯ２／Ａｒ（体積比＝６１／３１／５／３）の、ＣＯリッチの原料ガスを、２０ｍＬ／ｍｉｎで供給し、メタノール４０ｍＬの存在下、反応温度１７０℃、反応圧力５ｍＰａで反応させるほかは、実施例１と同様にして、メタノールを合成した。
そして、次の値を求めた。その結果を表３に示す。
(Comparative Example 1)
Using 3 g of the Cu-Zn-Ga catalyst in Example 2 , 20 mL / min of a CO-rich raw material gas of H 2 / CO / CO 2 / Ar (volume ratio = 61/31/5/3) as a raw material gas was used. Methanol was synthesized in the same manner as in Example 1 except that the reaction was carried out at a reaction temperature of 170 ° C. and a reaction pressure of 5 mPa in the presence of 40 mL of methanol.
Then, the following value was obtained. The results are shown in Table 3.
−転化率（Conv.）−
・ＣＯ転化率（％）＝（１−（ＣＯの減少量）／（供給されたＣＯの供給量））×１００
・ＣＯ２転化率（％）＝（１−（ＣＯ２の減少量）／（供給されたＣＯ２の供給量））×１００
・Ｔｏｔａｌ ｃａｒｂｏｎ Ｃ転化率（％）＝ＣＯ転化率×（原料ガス中ＣＯ濃度）／［（原料ガス中ＣＯ濃度）＋（原料ガス中ＣＯ２濃度）］＋ＣＯ2転化率×（原料ガス中ＣＯ２濃度）／［（原料ガス中ＣＯ濃度）＋（原料ガス中ＣＯ２濃度）］
− Conversion rate (Conv.) −
-CO conversion rate (%) = (1- (decrease in CO) / (supply of CO supplied)) x 100
-CO 2 conversion rate (%) = (1- ( decrease in CO 2 ) / (supply of CO 2 supplied)) x 100
-Total carbon C conversion rate (%) = CO conversion rate x (CO concentration in raw material gas) / [(CO concentration in raw material gas) + (CO 2 concentration in raw material gas)] + CO 2 conversion rate x (CO in raw material gas) 2 concentration) / [(CO concentration in raw material gas) + (CO 2 concentration in raw material gas)]
−選択率（Ｓｅｌｅｃｔｉｖｉｔｙ）−
メタノール（ＭｅＯＨ）とギ酸メチル（ＭＦ）との生成割合（％）
-Selectivity-
Production ratio (%) of methanol (methanol) and methyl formate (MF)
上記結果から、本条件では、メタノールは、原料ガス組成から考えて、そのほとんどがＣＯから生成し、一部ＣＯ２から生成されることがわかった。 From the above results, it was found that under these conditions, most of methanol is produced from CO and partly from CO 2 , considering the composition of the raw material gas.
（比較例２）
実施例１におけるＣｕ−Ｚｎ−Ｇａ（１：１：０．２）触媒を使用し、メタノールの代わりに、エタノール、１−プロパノール、２ープロパノール、２−ブタノールを導入するほかは、実施例１と同様にして、メタノールを合成し、分析した。その結果を表４に示す。
(Comparative Example 2)
The same as in Example 1 except that the Cu-Zn-Ga (1: 1: 0.2) catalyst in Example 1 was used and ethanol, 1-propanol, 2-propanol and 2-butanol were introduced instead of methanol. In the same manner, methanol was synthesized and analyzed. The results are shown in Table 4.
従って、本条件（反応温度が２００℃という低温の条件）において、エタノール導入では、２２５．３ｇ／Ｋｇ−ｃａｔ．ｈの空時収率で、メタノールは生成するにとどまることがわかった。
また、１−プロパノール導入では、２６２．８ｇ／Ｋｇ−ｃａｔ．ｈの空時収率で、メタノールは生成するにとどまることがわかった。
また、２−プロパノール導入では、２３１．９ｇ／Ｋｇ−ｃａｔ．ｈの空時収率で、メタノールは生成するにとどまることがわかった。
また、２−ブタノール導入では、１９９．５ｇ／Ｋｇ−ｃａｔ．ｈの空時収率で、メタノールは生成するにとどまることがわかった。
Therefore, under this condition (a low temperature condition of a reaction temperature of 200 ° C.), 225.3 g / Kg-cat. It was found that in the air-time yield of h, methanol was only produced.
In addition, with the introduction of 1-propanol, 262.8 g / Kg-cat. It was found that in the air-time yield of h, methanol was only produced.
In addition, with the introduction of 2-propanol, 231.9 g / Kg-cat. It was found that in the air-time yield of h, methanol was only produced.
In addition, with the introduction of 2-butanol, 199.5 g / Kg-cat. It was found that in the air-time yield of h, methanol was only produced.
以上の結果から、本実施例では、水素と二酸化炭素（ＣＯ２）とを原料ガスとした場合にも、低温で、かつ高効率にメタノールを製造できることがわかる。 From the above results, it can be seen that in this example, methanol can be produced at a low temperature and with high efficiency even when hydrogen and carbon dioxide (CO 2) are used as raw material gases.
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| JPH06312138A (en) * | 1992-12-11 | 1994-11-08 | Agency Of Ind Science & Technol | Catalyst for synthesizing methanol |
| JPH10309466A (en) * | 1997-03-11 | 1998-11-24 | Agency Of Ind Science & Technol | Copper-based catalyst and its production |
| WO2012067222A1 (en) * | 2010-11-19 | 2012-05-24 | 三井化学株式会社 | Methanol production process |
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| JPH06312138A (en) * | 1992-12-11 | 1994-11-08 | Agency Of Ind Science & Technol | Catalyst for synthesizing methanol |
| JPH10309466A (en) * | 1997-03-11 | 1998-11-24 | Agency Of Ind Science & Technol | Copper-based catalyst and its production |
| WO2012067222A1 (en) * | 2010-11-19 | 2012-05-24 | 三井化学株式会社 | Methanol production process |
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