JP2007216178A - メタノール合成用触媒及び当該触媒の製造方法、並びにメタノールの製造方法 - Google Patents
メタノール合成用触媒及び当該触媒の製造方法、並びにメタノールの製造方法 Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 234
- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000002194 synthesizing effect Effects 0.000 title claims description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- -1 alkali metal formate Chemical class 0.000 claims abstract description 48
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 43
- 239000007789 gas Substances 0.000 claims abstract description 33
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 23
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- 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
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 27
- 238000003786 synthesis reaction Methods 0.000 claims description 27
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 12
- 150000001340 alkali metals Chemical class 0.000 claims description 12
- 239000011949 solid catalyst Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- 150000001298 alcohols Chemical class 0.000 claims description 9
- 238000000975 co-precipitation Methods 0.000 claims description 8
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical group [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 3
- 150000003138 primary alcohols Chemical class 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 23
- 239000002994 raw material Substances 0.000 abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 239000010949 copper Substances 0.000 description 42
- 239000011734 sodium Substances 0.000 description 23
- 235000019441 ethanol Nutrition 0.000 description 19
- 230000007423 decrease Effects 0.000 description 12
- 239000011777 magnesium Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000008859 change Effects 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 3
- 235000019254 sodium formate Nutrition 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004280 Sodium formate Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017947 MgOx Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- ATZQZZAXOPPAAQ-UHFFFAOYSA-M caesium formate Chemical compound [Cs+].[O-]C=O ATZQZZAXOPPAAQ-UHFFFAOYSA-M 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- ZIMBPNXOLRMVGV-UHFFFAOYSA-M rubidium(1+);formate Chemical compound [Rb+].[O-]C=O ZIMBPNXOLRMVGV-UHFFFAOYSA-M 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
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Abstract
【解決手段】一酸化炭素、二酸化炭素のいずれか、及び水素を含む原料ガスを反応させてメタノールを製造する方法であって、アルカリ金属ギ酸塩に加えて、Cu、Mg、Naを同時に含有する触媒、及びアルコール類の存在下に反応を行い、メタノールを得ることを特徴とするメタノールの製造方法。
【選択図】なし
Description
(1) 一酸化炭素、二酸化炭素の少なくともいずれか、及び水素を含む原料ガスと溶媒としてのアルコールの存在下で反応を行うギ酸エステルを経由するメタノール合成用触媒であって、アルカリ金属ギ酸塩に加えて、Cu、Mg、Naを含有することを特徴とするメタノール合成用触媒。
本発明者らは、鋭意検討した結果、触媒及び溶媒を反応器に仕込み原料ガスを供給する半回分式の連続反応においてアルカリ金属ギ酸塩に加えて、Cu、Mg、Naを含有する触媒を用いると、一酸化炭素、二酸化炭素の少なくともいずれか、及び水素とアルコール類からメタノールの製造において、高収率で製造可能であることを見出し、本発明に至った。
CO転化率(%)=[1−(反応後に回収されたCOモル数)/(仕込んだCOモル数)]×100
内容積100mlのオートクレーブを用い、溶媒としてメタノール27.8mlに、ギ酸カリウム10mmolと炭酸カルシウム2mmol、水素化分解触媒としてCu(NO3)2・3H2O、Mg(NO3)2・6H2Oを原料として、pH=10.0に保ちながら共沈法によりCu/MgOx(Xは化学的に許容し得る値)を調製し、これにCu/MgOXに対してNa2CO3を9.0mass%となるように含浸担持したCu/MgOX/Na2CO3(Xは化学的に許容し得る値)を3g添加し、合成ガス(CO 30.0vol%、H2 60.0vol%、Arバランス)を60ml/minで供給し、160℃-3.5MPaの条件で連続反応を行った。反応生成物はガスクロマトグラフで分析した。CO転化率の経時変化を図2に示す。比較例1に示すNa2CO3を担持しないCu/MgOXを使用した場合と比較して、CO転化率は安定した結果が得られた。
水素化分解触媒としてCu/MgOX/Na2CO3の代わりにNa2CO3を担持しないCu/MgOXを添加する他は、実施例1に記載の方法で反応を行った。CO転化率の経時変化を図2に示す。CO転化率は時間の経過と共に減少する傾向を示した。
水素化分解触媒としてCu/MgOX/Na2CO3の代わりにCu/MnOXを添加する他は、実施例1に記載の方法で反応を行った。CO転化率の経時変化を図3に示す。Cu/MgOX系触媒と比較するとCO転化率は低く、時間の経過と共に減少する傾向を示した。
2 半回分式反応器
3 生成物、未反応ガスの混合物
4 冷却器
5 未反応ガス
6 ギ酸エステルとメタノールの液体混合物
7 蒸留塔
8 ギ酸エステル
9 メタノール
Claims (14)
- 一酸化炭素、二酸化炭素の少なくともいずれか、及び水素を含む原料ガスと、溶媒としてのアルコールの存在下で反応を行うギ酸エステルを経由するメタノール合成用触媒であって、アルカリ金属ギ酸塩に加えて、Cu、Mg、Naを含有することを特徴とするメタノール合成用触媒。
- 前記アルカリ金属ギ酸塩がギ酸カリウムであることを特徴とする請求項1に記載のメタノール合成用触媒。
- 一酸化炭素、二酸化炭素の少なくともいずれか、及び水素を含む原料ガスと溶媒としてのアルコールの存在下で反応を行うギ酸エステルを経由するメタノール合成用触媒において、アルカリ金属ギ酸塩に変化し得るアルカリ金属系触媒に加えて、Cu、Mg、Naを含有することを特徴とするメタノール合成用触媒。
- 前記アルカリ金属ギ酸塩に変化し得るアルカリ金属系触媒が、アルカリ金属炭酸塩であることを特徴とする請求項3に記載のメタノール合成用触媒。
- 前記Naが炭酸塩又はギ酸塩としてCu/MgOの固体触媒に担持されることを特徴とする請求項1〜4のいずれか1項に記載のメタノール合成用触媒。
- 請求項5に記載のメタノール合成用触媒の製造方法であって、Cu/MgOの固体触媒を調製した後、該固体触媒にNaを担持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。
- 請求項5に記載のメタノール合成用触媒の製造方法であって、前記Cu/MgOを共沈法で調製した後、Cu/MgOにNaを含浸法で担持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。
- 請求項5に記載のメタノール合成用触媒の製造方法であって、前記Cu/MgOを共沈法においてpH=8〜11の範囲で一定に保ちながら調製することを特徴とするメタノール製造用触媒の製造方法。
- 一酸化炭素、二酸化炭素の少なくともいずれか、及び水素を含む原料ガスを反応させてメタノールを製造する方法であって、アルカリ金属ギ酸塩に加えて、Cu、Mg、Naを含有する固体触媒、及びアルコール類の存在下に反応を行い、ギ酸エステル及びメタノールを生成すると共に、生成したギ酸エステルを水素化してメタノールを製造することを特徴とするメタノールの製造方法。
- 一酸化炭素、二酸化炭素の少なくともいずれか、及び水素を含む原料ガスを、アルカリ金属ギ酸塩に加えて、Cu、Mg、Naを含有する固体触媒、及びアルコール類の存在下に反応を行うことで得られた生成物を反応系から分離した後、該生成物中のギ酸エステルを水素化分解触媒で水素化してメタノールを製造することを特徴とするメタノールの製造方法。
- 前記アルカリ金属ギ酸塩に替えて、反応中にアルカリ金属ギ酸塩に変化し得るアルカリ金属系触媒を用いることを特徴とする請求項9又は10に記載のメタノールの製造方法。
- 前記アルカリ金属ギ酸塩がギ酸カリウムであることを特徴とする請求項9〜11のいずれか1項に記載のメタノールの製造方法。
- 前記反応中にアルカリ金属ギ酸塩に変化し得るアルカリ金属系触媒がアルカリ炭酸塩であることを特徴とする請求項12記載のメタノールの製造方法。
- 前記アルコール類が第一級アルコールであることを特徴とする請求項9〜13のいずれか1項に記載のメタノールの製造方法。
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JP2006041575A JP5127145B2 (ja) | 2006-02-17 | 2006-02-17 | メタノール合成用触媒及び当該触媒の製造方法、並びにメタノールの製造方法 |
KR1020087020064A KR20080101918A (ko) | 2006-02-17 | 2007-02-16 | 메탄올 합성용 촉매 및 해당 촉매의 제조 방법 및 메탄올의제조 방법 |
US12/224,001 US20100228059A1 (en) | 2006-02-17 | 2007-02-16 | Catalyst for Methanol Synthesis and Production Method Thereof, and Method for Producing Methanol |
CNA2007800057169A CN101384362A (zh) | 2006-02-17 | 2007-02-16 | 甲醇合成用催化剂、该催化剂的制造方法以及甲醇的制造方法 |
RU2008134236/04A RU2008134236A (ru) | 2006-02-17 | 2007-02-16 | Катализатор для синтеза метанола, способ его получения и способ получения метанола |
CA002642387A CA2642387A1 (en) | 2006-02-17 | 2007-02-16 | Catalyst for methanol synthesis and production method thereof, adn method for producing methanol |
EP07714413A EP1987879A4 (en) | 2006-02-17 | 2007-02-16 | METHANOL SYNTHESIS CATALYST, PROCESS FOR PRODUCING SUCH CATALYST, AND PROCESS FOR PRODUCING METHANOL |
PCT/JP2007/052883 WO2007094468A1 (ja) | 2006-02-17 | 2007-02-16 | メタノール合成用触媒及び当該触媒の製造方法、並びにメタノールの製造方法 |
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WO2019193483A1 (en) * | 2018-04-06 | 2019-10-10 | Kamal Pharmachem Inc. | Catalytic conversion of carbon dioxide to methanol |
CN109731596B (zh) * | 2019-01-18 | 2020-07-10 | 厦门大学 | 一种糠醛加氢制糠醇的改性铜基催化剂制备方法 |
CN109759105B (zh) * | 2019-03-08 | 2020-12-08 | 宁夏大学 | 一种甲醇合成催化剂 |
US20230166242A1 (en) * | 2020-04-24 | 2023-06-01 | The Chugoku Electric Power Co., Inc. | Carbon dioxide reduction catalyst and carbon dioxide reduction method |
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- 2007-02-16 US US12/224,001 patent/US20100228059A1/en not_active Abandoned
- 2007-02-16 KR KR1020087020064A patent/KR20080101918A/ko not_active Application Discontinuation
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KR20080101918A (ko) | 2008-11-21 |
CA2642387A1 (en) | 2007-08-23 |
JP5127145B2 (ja) | 2013-01-23 |
EP1987879A4 (en) | 2009-07-29 |
WO2007094468A1 (ja) | 2007-08-23 |
RU2008134236A (ru) | 2010-02-27 |
US20100228059A1 (en) | 2010-09-09 |
EP1987879A1 (en) | 2008-11-05 |
CN101384362A (zh) | 2009-03-11 |
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