JP5258617B2 - 銅系触媒の製造方法 - Google Patents
銅系触媒の製造方法 Download PDFInfo
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- JP5258617B2 JP5258617B2 JP2009040055A JP2009040055A JP5258617B2 JP 5258617 B2 JP5258617 B2 JP 5258617B2 JP 2009040055 A JP2009040055 A JP 2009040055A JP 2009040055 A JP2009040055 A JP 2009040055A JP 5258617 B2 JP5258617 B2 JP 5258617B2
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- 239000003054 catalyst Substances 0.000 title claims description 81
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title description 10
- 239000010949 copper Substances 0.000 title description 10
- 229910052802 copper Inorganic materials 0.000 title description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 79
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 14
- 238000010304 firing Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000012018 catalyst precursor Substances 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 9
- 239000005751 Copper oxide Substances 0.000 claims description 7
- 229910000431 copper oxide Inorganic materials 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 7
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 6
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 150000002736 metal compounds Chemical class 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 26
- 238000000034 method Methods 0.000 description 19
- 239000007789 gas Substances 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- 239000002244 precipitate Substances 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 10
- 238000000465 moulding Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- -1 alkali metal salts Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XYQRXRFVKUPBQN-UHFFFAOYSA-L Sodium carbonate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]C([O-])=O XYQRXRFVKUPBQN-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229940001593 sodium carbonate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940018038 sodium carbonate decahydrate Drugs 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
- ZVNABXPZAOWOEF-UHFFFAOYSA-J zirconium(4+) tetranitrite dihydrate Chemical compound O.O.[Zr+4].[O-]N=O.[O-]N=O.[O-]N=O.[O-]N=O ZVNABXPZAOWOEF-UHFFFAOYSA-J 0.000 description 1
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Classifications
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- 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
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明の製造方法によって製造される銅系触媒は、酸化銅、酸化亜鉛、酸化アルミニウムを必須成分とし、さらに酸化ジルコニウム、酸化ガリウム、および酸化ケイ素を任意成分とする金属酸化物で構成された触媒である。また、本発明の趣旨を損なわない範囲であれば、他の酸化物を含んでいてもよい。
本発明における触媒製造法は、成形時の工程簡略化を目指したものであるが、その触媒の組成を目的とする反応に合わせて最適化することは、先に述べたように、その性能を最大限に引き出すために重要である。
上記の触媒は、水素と炭素酸化物からメタノールを合成する反応またはその逆反応のための触媒として有用である。
本発明の銅系触媒にあっては、必須成分である酸化銅、酸化亜鉛および酸化アルミニウム(および任意成分である酸化ジルコニウム、酸化ガリウム、酸化パラジウム、酸化ケイ素)が骨格であって、前記の乾燥工程を経た後480〜690℃という温度領域で焼成処理を行うことにより、触媒は高活性となり、しかもその活性が長期にわたって維持された耐久性のすぐれたものとなる。
(触媒粉体の製造)
(ケーキ1)激しく撹拌した125Lの蒸留水中に、A液とB液を同時にいずれも200ml/minの速度で滴下した(この方法を共沈法と称する)。これを一昼夜放置した後、得られた沈澱物を2.4m3の蒸留水で洗浄した後、加圧濾過器により、ケーキを回収した。
(ケーキ2)ケーキ1と同様にして得られた沈殿物を10m3の蒸留水で洗浄した後、加圧濾過器により、ケーキを回収した。
得られた回収ケーキ1を280℃で2時間乾燥後(含水率13%)、50〜100メッシュに粒径をそろえ、滑剤を添加し、そのまま3mmタブレットに成形した。成形後、600℃で焼成し、製品としての触媒を得た。
得られた回収ケーキ1を、500℃で2時間乾燥後(含水率1%)、50〜100メッシュに粒径をそろえ、滑剤を添加した。さらに、水を触媒に対して12wt%添加後、1日養生した。この粉体を、3mmタブレットに成形した。成形後、600℃で焼成し、製品としての触媒を得た。
Claims (4)
- 酸化銅、酸化亜鉛、酸化アルミニウムを必須成分とし、酸化ジルコニウム、酸化ガリウム、酸化ケイ素を任意成分とする金属酸化物で構成された触媒を製造する方法であって、上記金属成分を含む酸性金属塩水溶液と塩基性水溶液とを接触させて得られる金属化合物前駆体を乾燥する工程において、乾燥後の触媒前駆体中の水分が、8〜17重量%の範囲になるように温度、圧力を制御した後、焼成することを特徴とする水素と炭素酸化物からメタノールを合成する触媒の製造方法。
- 金属化合物前駆体の乾燥が100〜400℃の範囲で実施されることを特徴とする請求項1に記載の触媒の製造方法。
- 前記触媒が打錠により成形されることを特徴とする、請求項1に触媒の製造方法。
- 焼成が300〜700℃の範囲で実施されることを特徴とする請求項1に記載の触媒の製造方法。
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
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JP2009040055A JP5258617B2 (ja) | 2009-02-23 | 2009-02-23 | 銅系触媒の製造方法 |
PCT/JP2010/052211 WO2010095599A1 (ja) | 2009-02-23 | 2010-02-15 | 銅系触媒の製造方法、銅系触媒およびその前処理方法 |
CN2010800072743A CN102316983B (zh) | 2009-02-23 | 2010-02-15 | 铜基催化剂的制造方法、铜基催化剂及其预处理方法 |
US13/202,266 US8623782B2 (en) | 2009-02-23 | 2010-02-15 | Process for preparing copper-based catalyst, copper-based catalyst, and pretreatment method of the same |
EP10743725.3A EP2399671B1 (en) | 2009-02-23 | 2010-02-15 | Copper-based catalyst manufacturing method and pretreatment method for same |
CA2753056A CA2753056C (en) | 2009-02-23 | 2010-02-15 | Process for preparing copper-based catalyst, copper-based catalyst, and pretreatment method of the same |
KR1020117021793A KR20110119804A (ko) | 2009-02-23 | 2010-02-15 | 구리계 촉매의 제조 방법, 구리계 촉매 및 그의 전처리 방법 |
SG2011060423A SG173804A1 (en) | 2009-02-23 | 2010-02-15 | Copper-based catalyst manufacturing method, copper-based catalyst, and pretreatment method for same |
TW099105151A TW201034756A (en) | 2009-02-23 | 2010-02-23 | Process for preparing copper-based catalyst, copper-based catalyst, and pretreatment method of the same |
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JP2009040055A JP5258617B2 (ja) | 2009-02-23 | 2009-02-23 | 銅系触媒の製造方法 |
Publications (2)
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JP2010194419A JP2010194419A (ja) | 2010-09-09 |
JP5258617B2 true JP5258617B2 (ja) | 2013-08-07 |
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JP5863964B2 (ja) | 2012-06-04 | 2016-02-17 | 三井化学株式会社 | メタノール製造用触媒とその製造方法、およびメタノールの製造方法 |
CA3086707A1 (en) * | 2017-12-20 | 2019-06-27 | Basf Se | Catalyst system and process for preparing dimethyl ether |
CN113842920B (zh) * | 2021-09-24 | 2023-10-31 | 中国科学院上海高等研究院 | 一种二氧化碳加氢制甲醇催化剂及其成型方法和用途 |
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JP4577464B2 (ja) * | 2000-06-27 | 2010-11-10 | 三菱瓦斯化学株式会社 | 銅−亜鉛系触媒前駆体組成物および該触媒の製造法 |
JP4016100B2 (ja) * | 2002-06-11 | 2007-12-05 | 独立行政法人産業技術総合研究所 | 水性ガスシフト反応用触媒 |
JP2005329362A (ja) * | 2004-05-21 | 2005-12-02 | Mitsubishi Chemicals Corp | 不飽和カルボン酸の製造用触媒の製造方法 |
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