JP2001179104A - Catalyst for producing dimethyl ether - Google Patents
Catalyst for producing dimethyl etherInfo
- Publication number
- JP2001179104A JP2001179104A JP36901599A JP36901599A JP2001179104A JP 2001179104 A JP2001179104 A JP 2001179104A JP 36901599 A JP36901599 A JP 36901599A JP 36901599 A JP36901599 A JP 36901599A JP 2001179104 A JP2001179104 A JP 2001179104A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- dimethyl ether
- ion
- hours
- aqueous solution
- 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.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 131
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 72
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 111
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 30
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 30
- 239000011651 chromium Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011575 calcium Substances 0.000 claims abstract description 8
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 239000011733 molybdenum Substances 0.000 claims abstract description 7
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 7
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 7
- 239000010937 tungsten Substances 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 150000002739 metals Chemical class 0.000 claims abstract description 6
- 239000003426 co-catalyst Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 62
- 239000007789 gas Substances 0.000 description 47
- 238000006243 chemical reaction Methods 0.000 description 42
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 40
- 239000007864 aqueous solution Substances 0.000 description 35
- 239000000203 mixture Substances 0.000 description 34
- 229910002091 carbon monoxide Inorganic materials 0.000 description 29
- 229910052739 hydrogen Inorganic materials 0.000 description 29
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 28
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 28
- 239000001257 hydrogen Substances 0.000 description 28
- 229910000029 sodium carbonate Inorganic materials 0.000 description 20
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 15
- 238000006297 dehydration reaction Methods 0.000 description 14
- 239000011787 zinc oxide Substances 0.000 description 14
- 230000018044 dehydration Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 11
- -1 oxides Chemical class 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 230000002431 foraging effect Effects 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000011949 solid catalyst Substances 0.000 description 7
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 5
- 229910000423 chromium oxide Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000005751 Copper oxide Substances 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 101000851376 Homo sapiens Tumor necrosis factor receptor superfamily member 8 Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 102000003729 Neprilysin Human genes 0.000 description 1
- 108090000028 Neprilysin Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 101000725126 Spinacia oleracea 50S ribosomal protein L35, chloroplastic Proteins 0.000 description 1
- 102100036857 Tumor necrosis factor receptor superfamily member 8 Human genes 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- WVYYHSKIGBEZCQ-UHFFFAOYSA-N [O-2].[O-2].[Cr+3].[Fe+2] Chemical compound [O-2].[O-2].[Cr+3].[Fe+2] WVYYHSKIGBEZCQ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 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
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- PGTIPSRGRGGDQO-UHFFFAOYSA-N copper;oxozinc Chemical compound [Zn].[Cu]=O PGTIPSRGRGGDQO-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- JLQFVGYYVXALAG-CFEVTAHFSA-N yasmin 28 Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1.C([C@]12[C@H]3C[C@H]3[C@H]3[C@H]4[C@@H]([C@]5(CCC(=O)C=C5[C@@H]5C[C@@H]54)C)CC[C@@]31C)CC(=O)O2 JLQFVGYYVXALAG-CFEVTAHFSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- LJFCDOMDEACIMM-UHFFFAOYSA-N zinc chromium(3+) oxygen(2-) Chemical compound [O-2].[Cr+3].[Zn+2] LJFCDOMDEACIMM-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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ジメチルエーテル
製造用触媒に関するものである。この触媒は溶媒に懸濁
したスラリーにして使用され、そのなかに一酸化炭素と
水素の混合ガスを流通させてジメチルエーテルを製造す
る。[0001] The present invention relates to a catalyst for producing dimethyl ether. This catalyst is used in the form of a slurry suspended in a solvent, and a mixed gas of carbon monoxide and hydrogen is passed through the slurry to produce dimethyl ether.
【０００２】[0002]
【従来の技術】従来、溶媒に懸濁した触媒の存在下で、
一酸化炭素および水素の混合ガスからジメチルエーテル
を製造する方法は、いくつか知られている。2. Description of the Related Art Conventionally, in the presence of a catalyst suspended in a solvent,
Several methods for producing dimethyl ether from a mixed gas of carbon monoxide and hydrogen are known.
【０００３】例えば、特開平２−９８３３号公報、特開
平３−１８１４３５号公報、特開平３−５２８３５号公
報、特開平４−２６４０４６号公報、特表平５−８１０
０６９号公報(ＷＯ９３／１００６９)には、不活性液体
に懸濁したメタノール合成触媒とメタノール脱水触媒の
混合物に合成ガスを触媒させて、ジメチルエーテルまた
はジメチルエーテルとメタノールの混合物を製造する方
法が開示されている。For example, JP-A-2-9833, JP-A-3-181435, JP-A-3-52835, JP-A-4-264046, and JP-A-5-810
No. 069 (WO93 / 10069) discloses a method for producing dimethyl ether or a mixture of dimethyl ether and methanol by catalyzing a synthesis gas in a mixture of a methanol synthesis catalyst and a methanol dehydration catalyst suspended in an inert liquid. I have.
【０００４】特開平２−９８３３号公報に開示されてい
る方法は、水素、一酸化炭素および二酸化炭素から成る
合成ガスを固体触媒と接触させ、また固体触媒の存在に
おいて反応させる前記合成ガスからのジメチルエーテル
の直接合成法において、前記合成ガスを固体触媒系の存
在において接触させることから成り、そこにおいて前記
固体触媒は３相（液相）反応器系において液状媒体の懸
濁された単一触媒または複数の触媒の混合物であり、そ
こにおいて前記３相反応器系は少くとも１基の３相反応
器から成る合成ガスからのジメチルエーテルの直接合成
法である。[0004] The method disclosed in Japanese Patent Application Laid-Open No. 2-9833 discloses a method of contacting a synthesis gas composed of hydrogen, carbon monoxide and carbon dioxide with a solid catalyst and reacting the synthesis gas in the presence of the solid catalyst. In the direct synthesis of dimethyl ether, the method comprises contacting the synthesis gas in the presence of a solid catalyst system, wherein the solid catalyst is a single catalyst suspended in a liquid medium or a three-phase (liquid phase) reactor system. A mixture of a plurality of catalysts, wherein the three-phase reactor system is a process for the direct synthesis of dimethyl ether from synthesis gas consisting of at least one three-phase reactor.
【０００５】特開平３−１８１４３５号公報に開示され
ている方法は、一酸化炭素と水素の混合ガス、あるいは
これにさらに二酸化炭素および／または水蒸気が含まれ
る混合ガスからジメチルエーテルを製造する方法におい
て、触媒を溶媒に懸濁してスラリー状態で使用すること
を特徴とするジメチルエーテルの製造方法である。The method disclosed in Japanese Patent Application Laid-Open No. 3-181435 discloses a method for producing dimethyl ether from a mixed gas of carbon monoxide and hydrogen or a mixed gas further containing carbon dioxide and / or steam. A method for producing dimethyl ether, wherein a catalyst is suspended in a solvent and used in a slurry state.
【０００６】特開平３−５２８３５号公報に開示されて
いる方法は、合成ガスを固体メタノール合成触媒の存在
において反応させてメタノールを生産し、又生産された
メタノールを固体脱水触媒の存在において反応させてジ
メチルエーテルを生産する。水素、一酸化炭素及び二酸
化炭素から成る合成ガスからジメチルエーテルを合成す
る方法において、前記合成ガスを、メタノール合成成分
と脱水(エーテル形成)成分から成る固体触媒系の存在に
おいて接触させて反応させ、その際前記固体触媒系３相
（液相）反応器系にある液状媒体中の単一触媒又は複数
の触媒混合物であり、前記反応器系を操作して、最小有
効メタノール速度を少くとも１時間当り触媒１ｋｇ当り
１．０ｇモルのメタノールに維持することを特徴とする
ジメチルエーテル合成法である。[0006] The method disclosed in Japanese Patent Application Laid-Open No. 3-52835 is to react methanol in the presence of a solid methanol synthesis catalyst to produce methanol, and to react the produced methanol in the presence of a solid dehydration catalyst. To produce dimethyl ether. In a method of synthesizing dimethyl ether from a synthesis gas consisting of hydrogen, carbon monoxide and carbon dioxide, the synthesis gas is brought into contact with and reacted in the presence of a solid catalyst system comprising a methanol synthesis component and a dehydration (ether formation) component. A solid catalyst or a mixture of catalysts in a liquid medium in a three-phase (liquid-phase) reactor system in said solid catalyst system, operating said reactor system to reduce the minimum effective methanol rate to at least one hour A dimethyl ether synthesis method characterized by maintaining methanol at 1.0 g mole per 1 kg of a catalyst.
【０００７】特表平５−８１００６９号公報に開示され
ている方法は、一酸化炭素と水素および水蒸気のいずれ
か一方または両方が含まれる混合ガス、あるいはこれに
さらに二酸化炭素が含まれる混合ガスからジメチルエー
テルを製造する方法において、少なくとも酸化亜鉛と、
酸化銅又は酸化クロムと酸化アルミニウムを含む混合触
媒を粉砕した後、加圧密着させ、その後再度粉砕した触
媒を溶媒に懸濁してスラリー状態で使用することを特徴
とするジメチルエーテルの製造方法である。[0007] The method disclosed in Japanese Patent Application Laid-Open No. Hei 5-810069 discloses a method for producing a mixed gas containing carbon monoxide and one or both of hydrogen and water vapor, or a mixed gas further containing carbon dioxide. In a method for producing dimethyl ether, at least zinc oxide,
This is a method for producing dimethyl ether, characterized in that a mixed catalyst containing copper oxide or chromium oxide and aluminum oxide is pulverized, adhered under pressure, and then the pulverized catalyst is suspended in a solvent and used in a slurry state.
【０００８】[0008]
【発明が解決しようとする課題】本発明の目的は、従来
の触媒より高いジメチルエーテル収率および空時収率が
得られるジメチルエーテル製造用触媒を提供することに
ある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a catalyst for producing dimethyl ether which can provide a higher yield of dimethyl ether and a higher space-time yield than conventional catalysts.
【０００９】[0009]
【課題を解決するための手段】一酸化炭素と水素からジ
メチルエーテルを合成する反応は次のように進行する。 ＣＯ＋２Ｈ2 → ＣＨ3ＯＨ (１) メタノール合成反応 ２ＣＨ3ＯＨ → ＣＨ3ＯＣＨ3＋Ｈ2Ｏ (２) 脱水反応 ＣＯ＋Ｈ2Ｏ → Ｈ2＋ＣＯ2 (３) シフト反応The reaction to synthesize dimethyl ether from carbon monoxide and hydrogen proceeds as follows. CO + 2H 2 → CH 3 OH (1) Methanol synthesis reaction 2CH 3 OH → CH 3 OCH 3 + H 2 O (2) Dehydration reaction CO + H 2 O → H 2 + CO 2 (3) Shift reaction
【００１０】すなわち本反応は、まず一酸化炭素と水素
からメタノール合成触媒上でメタノールが生成し、次い
でメタノールがメタノール脱水触媒上に移行して脱水縮
合によりジメチルエーテルと水が生成する。さらに、水
が水性ガスシフト触媒および／またはメタノール合成触
媒に移動し、一酸化炭素と反応して二酸化炭素と水素を
生成する。That is, in this reaction, first, methanol is produced from carbon monoxide and hydrogen on a methanol synthesis catalyst, and then methanol is transferred onto a methanol dehydration catalyst, and dimethyl ether and water are produced by dehydration condensation. Further, water moves to the water gas shift catalyst and / or the methanol synthesis catalyst and reacts with carbon monoxide to produce carbon dioxide and hydrogen.
【００１１】これらの反応を進行させるのに一般にメタ
ノール合成触媒とメタノール脱水触媒と水性ガスシフト
触媒が用いられるが、本発明者らはこれらのうち、メタ
ノール合成触媒として新たな触媒を開発し、これにメタ
ノール脱水触媒と水性ガスシフト触媒を組み合わせるこ
とによって前記目的を達成したものである。この発明の
メタノール合成触媒が水性ガスシフト機能も有している
場合には水性ガスシフト触媒を兼ねさせることができ
る。In general, a methanol synthesis catalyst, a methanol dehydration catalyst, and a water gas shift catalyst are used to advance these reactions. The present inventors have developed a new catalyst among them as a methanol synthesis catalyst. The object has been achieved by combining a methanol dehydration catalyst and a water gas shift catalyst. When the methanol synthesis catalyst of the present invention also has a water gas shift function, it can also serve as a water gas shift catalyst.
【００１２】この触媒は、特定の助触媒を添加して水性
ガスシフト機能を付与しあるいは高揚させ、耐水性を向
上させ、あるいは耐硫黄性および耐塩素性を向上させた
ものである。This catalyst has a water gas shift function imparted or enhanced by adding a specific co-catalyst to improve the water resistance or the sulfur resistance and the chlorine resistance.
【００１３】すなわち、本発明の触媒は、メタノール脱
水触媒および水性ガスシフト触媒（本発明の触媒がこの
機能を併有している場合にはその添加を省略できる。）
と組み合わせて用いられ、一酸化炭素と水素からジメチ
ルエーテルを合成する触媒であって、メタノール合成触
媒に、助触媒として、クロム、レニウム、ジルコニウ
ム、マンガン、マグネシウム、硅素、モリブデン、タン
グステンおよびカルシウムから選択された１種または２
種以上の金属または化合物を組み合わせてなるジメチル
エーテル製造用触媒よりなる。That is, the catalyst of the present invention is a methanol dehydration catalyst and a water gas shift catalyst (if the catalyst of the present invention also has this function, its addition can be omitted).
A catalyst for synthesizing dimethyl ether from carbon monoxide and hydrogen, which is selected from chromium, rhenium, zirconium, manganese, magnesium, silicon, molybdenum, tungsten and calcium as a co-catalyst for a methanol synthesis catalyst. One or two
It comprises a catalyst for producing dimethyl ether obtained by combining at least one kind of metal or compound.
【００１４】[0014]
【発明の実施の形態】メタノール合成触媒としては、酸
化銅−酸化亜鉛−アルミナ、酸化亜鉛−酸化クロム−ア
ルミナなどがある。酸化銅と酸化亜鉛、アルミナの比率
は重量比で酸化銅１に対し酸化亜鉛０.０５〜２０程
度、好ましくは０.１〜５程度、アルミナ０.０１〜２程
度、好ましくは０.０２〜１程度であり、酸化亜鉛と酸
化クロム、アルミナの場合の比率は重量比で酸化亜鉛１
に対し酸化クロム０．１〜１０程度、好ましくは０．５
〜５程度、アルミナ０.０１〜２程度、好ましくは０.０
２〜１程度である。DESCRIPTION OF THE PREFERRED EMBODIMENTS Examples of methanol synthesis catalysts include copper oxide-zinc oxide-alumina and zinc oxide-chromium oxide-alumina. The weight ratio of copper oxide to zinc oxide and alumina is about 0.05 to 20, preferably about 0.1 to 5, zinc oxide about 0.01 to 2, and preferably about 0.01 to 2 for copper oxide 1 per weight of copper oxide. The ratio of zinc oxide to chromium oxide and alumina is about 1 by weight.
Chromium oxide is about 0.1 to 10, preferably 0.5
~ 5, alumina about 0.01 ~ 2, preferably 0.0
It is about 2 to 1.
【００１５】助触媒として添加される、クロム、レニウ
ム、ジルコニウム、マンガン、マグネシウム、硅素、モ
リブデン、タングステンおよびカルシウムは金属または
化合物であり、化合物の例としては、酸化物、炭酸塩、
水酸化物、硝酸塩などがある。これらの助触媒のうち、
クロム、レニウムおよびジルコニウムはメタノール合成
触媒に水性ガスシフト機能を付与しあるいは高揚させて
ジメチルエーテル合成全体の反応を促進させ、高い空時
収率でジメチルエーテルが得られるようにするものであ
り、これらの１種または２種以上を使用することができ
る。また、マンガン、マグネシウムおよび硅素は触媒の
耐水性を向上させて長期間にわたって高い空時収率でジ
メチルエーテルが得られるようにするものであり、これ
らの１種または２種以上を使用することができる。モリ
ブデン、タングステンおよびカルシウムは触媒の耐硫黄
性および耐塩素性を向上させて長期間にわたって高い空
時収率でジメチルエーテルが得られるようにするもので
あり、これらの１種または２種以上を使用することがで
きる。上記の３つのグループの助触媒の２つ以上のグル
ープのものを組み合わせることも好ましい。これらの助
触媒の含有量は、クロム、レニウム、ジルコニウム、マ
ンガン、マグネシウムおよび硅素の場合には触媒全重量
の０．０１〜５０重量％、好ましくは０．０５〜３０重
量％が適当である。モリブデン、タングステンおよびカ
ルシウムの場合には０．０１〜３０重量％、好ましくは
０．０５〜２０重量％が適当である。Chromium, rhenium, zirconium, manganese, magnesium, silicon, molybdenum, tungsten and calcium, which are added as cocatalysts, are metals or compounds, such as oxides, carbonates,
There are hydroxides and nitrates. Of these promoters,
Chromium, rhenium, and zirconium impart a water gas shift function to the methanol synthesis catalyst or raise it to promote the reaction of the entire dimethyl ether synthesis so that dimethyl ether can be obtained with a high space-time yield. Alternatively, two or more kinds can be used. Manganese, magnesium and silicon improve the water resistance of the catalyst so that dimethyl ether can be obtained with a high space-time yield over a long period of time, and one or more of these can be used. . Molybdenum, tungsten and calcium improve the sulfur resistance and chlorine resistance of the catalyst so that dimethyl ether can be obtained with a high space-time yield over a long period, and one or more of these are used. be able to. It is also preferred to combine two or more of the above three groups of promoters. In the case of chromium, rhenium, zirconium, manganese, magnesium and silicon, the content of these cocatalysts is suitably 0.01 to 50% by weight, preferably 0.05 to 30% by weight of the total weight of the catalyst. In the case of molybdenum, tungsten and calcium, 0.01 to 30% by weight, preferably 0.05 to 20% by weight is appropriate.
【００１６】本発明の触媒に組み合わせるメタノール脱
水触媒および水性ガスシフト触媒は公知のものでよく、
メタノール脱水触媒としては、γ−アルミナ、シリカ・
アルミナ、ゼオライトなどがある。ゼオライトの金属酸
化物成分としてはナトリウム、カリウム等のアルカリ金
属の酸化物、カルシウム、マグネシウム等のアルカリ土
類金属の酸化物等である。水性ガスシフト触媒は前述の
ようにメタノール合成触媒が兼ねることできるが、その
ほか酸化鉄−酸化クロムなどがある。酸化鉄と酸化クロ
ムの比率は重量比で酸化鉄１に対し酸化クロム０．１〜
２０程度、好ましくは０．５〜１０程度である。The methanol dehydration catalyst and water gas shift catalyst to be combined with the catalyst of the present invention may be known ones,
As a methanol dehydration catalyst, γ-alumina, silica
Examples include alumina and zeolite. Examples of the metal oxide component of zeolite include oxides of alkali metals such as sodium and potassium, and oxides of alkaline earth metals such as calcium and magnesium. As described above, the water gas shift catalyst can also serve as the methanol synthesis catalyst, and other examples include iron oxide-chromium oxide. The ratio of iron oxide to chromium oxide is 0.1 to chromium oxide per iron oxide by weight.
It is about 20 and preferably about 0.5 to 10.
【００１７】これらの各触媒は公知の方法によって製造
すればよく、例えば各金属成分の水溶性塩を用いてこれ
らを含む水溶液を調製する。塩の種類は水溶性であれば
無機酸塩、有機酸塩のいずれであってもよい。ただし、
水中に投入すると加水分解して水酸化物を生じやすいも
のは適当でない。例えば硝酸塩、炭酸塩、有機酸塩、ハ
ロゲン化物、等を使用できる。各成分の濃度としては
０．１〜３モル／ｌ程度でよい。次いで、この水溶液に
塩基を加えて中和し水酸化物を沈澱させ、固液分離して
洗浄後乾燥し、さらに焼成することによって製造でき
る。焼成は２５０〜５００℃程度、好ましくは３００〜
４５０℃程度で２〜１０時間程度行なえばよい。また、
メタノール合成触媒は市販品を使用することもできる。Each of these catalysts may be produced by a known method. For example, an aqueous solution containing these is prepared using a water-soluble salt of each metal component. The salt may be any of an inorganic acid salt and an organic acid salt as long as it is water-soluble. However,
Those which are easily hydrolyzed to form hydroxides when put into water are not suitable. For example, nitrates, carbonates, organic acid salts, halides and the like can be used. The concentration of each component may be about 0.1 to 3 mol / l. Then, the aqueous solution is neutralized by adding a base to precipitate a hydroxide, separated into solid and liquid, washed, dried, and then calcined. Calcination is about 250-500 ° C., preferably 300-500 ° C.
It may be performed at about 450 ° C. for about 2 to 10 hours. Also,
A commercial product can be used as the methanol synthesis catalyst.
【００１８】前述のメタノール合成触媒、メタノール脱
水触媒および水性ガスシフト触媒の混合割合は、特に限
定されることなく各成分の種類あるいは反応条件等に応
じて適宜選定すればよいが、通常は重量比でメタノール
合成触媒１に対しメタノール脱水水性ガスシフト触媒
０．０５〜２０程度、好ましくは０．１〜１０程度の範
囲が適当である。The mixing ratio of the above-mentioned methanol synthesis catalyst, methanol dehydration catalyst and water gas shift catalyst is not particularly limited, and may be appropriately selected according to the type of each component or the reaction conditions. The methanol dehydration water gas shift catalyst is preferably in the range of about 0.05 to 20, more preferably about 0.1 to 10 with respect to the methanol synthesis catalyst 1.
【００１９】焼成後は粉砕して使用に供する。After firing, it is pulverized and used.
【００２０】粉砕は平均粒子径で２００μｍ以下、好ま
しくは１〜１００μｍ程度、特に１〜５０μｍ程度にな
るようにするのがよい。The pulverization is carried out so that the average particle diameter is 200 μm or less, preferably about 1 to 100 μm, particularly about 1 to 50 μm.
【００２１】上記触媒は溶媒に懸濁してスラリー化した
状態で使用される。溶媒中に存在させる触媒量は、溶媒
の種類、反応条件などによって適宜決定されるが、通常
は溶媒に対して１〜５０重量％である。The above catalyst is used in the form of a slurry suspended in a solvent. The amount of the catalyst to be present in the solvent is appropriately determined depending on the type of the solvent, reaction conditions, and the like, but is usually 1 to 50% by weight based on the solvent.
【００２２】本発明でジメチルエーテル合成の際に使用
される溶媒は、反応条件下において液体状態を呈するも
のであれば、そのいずれもが使用可能である。例えば、
脂肪族、芳香族および脂環族の炭化水素、アルコール、
エーテル、エステル、ケトンおよびハロゲン化物、これ
らの化合物の混合物等を使用できる。As the solvent used in the synthesis of dimethyl ether in the present invention, any solvent can be used as long as it exhibits a liquid state under the reaction conditions. For example,
Aliphatic, aromatic and alicyclic hydrocarbons, alcohols,
Ethers, esters, ketones and halides, mixtures of these compounds and the like can be used.
【００２３】また、硫黄分を除去した軽油、減圧軽油、
水素化処理したコールタールの高沸点留分等も使用でき
る。Gas oil from which sulfur has been removed, vacuum gas oil,
High-boiling fractions of the hydrogenated coal tar can also be used.
【００２４】このようにして形成された触媒−溶媒スラ
リー中に一酸化炭素と水素の混合ガスを流通させること
により、ジメチルエーテルが高収率で得られる。水素と
一酸化炭素の混合割合(Ｈ2／ＣＯ比)は広範囲のものが
適用可能である。例えばＨ2／ＣＯモル比で２０〜０．
１、好ましくは１０〜０．２の混合比のものを使用でき
る。By passing a mixed gas of carbon monoxide and hydrogen through the catalyst-solvent slurry thus formed, dimethyl ether can be obtained in high yield. A wide range of mixing ratio (H 2 / CO ratio) of hydrogen and carbon monoxide is applicable. For example 20-0 with H 2 / CO molar ratio.
A mixing ratio of 1, preferably 10 to 0.2 can be used.
【００２５】これは本反応系では、気固触媒反応のよう
に混合ガスが直接触媒に接触することなく、一度、一酸
化炭素と水素が溶媒に溶解した後、触媒と接触するため
に、一酸化炭素と水素の溶媒への溶解性を考慮して溶媒
を選択することにより、ガス組成によらず一定の一酸化
炭素と水素の組成を溶媒中で達成させ、さらに触媒表面
に供給することが可能である。This is because, in the present reaction system, the mixed gas does not come into direct contact with the catalyst as in the gas-solid catalytic reaction, but once carbon monoxide and hydrogen are dissolved in the solvent and then comes into contact with the catalyst. By selecting the solvent in consideration of the solubility of carbon oxide and hydrogen in the solvent, it is possible to achieve a constant composition of carbon monoxide and hydrogen in the solvent regardless of the gas composition, and further supply it to the catalyst surface It is possible.
【００２６】一方、水素と一酸化炭素の割合（Ｈ2／Ｃ
Ｏ比）が著しく小さな（例えば０.１以下）混合ガスあ
るいは水素を含まない一酸化炭素の場合には、別途スチ
ームを供給して反応器中で一酸化炭素の一部をスチーム
により水素と二酸化炭素に変換することが必要である。On the other hand, the ratio of hydrogen to carbon monoxide (H 2 / C
In the case of a mixed gas having extremely small O ratio (for example, 0.1 or less) or carbon monoxide containing no hydrogen, steam is separately supplied to partially remove carbon monoxide in the reactor using steam and hydrogen monoxide. It needs to be converted to carbon.
【００２７】また、原料ガスと触媒の間に溶媒が存在し
ているため、ガス組成と触媒表面での組成が必ずしも一
致しないことから、一酸化炭素と水素の混合ガス、ある
いは一酸化炭素ガス中に比較的高濃度（２０〜５０％）
の二酸化炭素が存在してもよい。Further, since a solvent is present between the raw material gas and the catalyst, the gas composition and the composition on the surface of the catalyst do not always match, so that a mixed gas of carbon monoxide and hydrogen or a carbon monoxide gas is used. Relatively high concentration (20-50%)
Of carbon dioxide may be present.
【００２８】また、本反応系では、原料ガス中に硫化水
素等の硫黄化合物、シアン化水素等のシアン化合物、塩
化水素等の塩素化合物など触媒毒となる成分が存在して
いても、触媒に対する影響が気固接触法に比べ著しく軽
減されている。なお、触媒が被毒され、その活性が低下
した場合には、反応器よりスラリーを抜き出し、新たに
高活性触媒を含有するスラリーを反応器へ圧入すること
により、反応器全体の生産性を一定に保持することがで
きる。Further, in the present reaction system, even if a raw material gas contains a sulfur-containing compound such as hydrogen sulfide, a cyanide compound such as hydrogen cyanide, or a chlorine compound such as hydrogen chloride, which is a catalyst poison, the effect on the catalyst is not affected. It is significantly reduced compared to the gas-solid contact method. When the catalyst is poisoned and its activity decreases, the slurry is extracted from the reactor, and a slurry containing a highly active catalyst is newly injected into the reactor to keep the productivity of the entire reactor constant. Can be held.
【００２９】なお、反応熱は、反応器内へ冷却コイルを
設置し、それに熱水を通過させることにより中圧蒸気と
して回収される。これにより反応温度を自由に制御でき
る。The reaction heat is recovered as medium-pressure steam by installing a cooling coil in the reactor and passing hot water through it. Thereby, the reaction temperature can be freely controlled.
【００３０】反応温度は１５０〜４００℃が好ましく、
特に２００〜３５０℃の範囲が好ましい。反応温度が１
５０℃より低くても、また４００℃より高くても一酸化
炭素の転化率が低くなる。The reaction temperature is preferably from 150 to 400 ° C.,
Particularly, the range of 200 to 350 ° C is preferable. Reaction temperature is 1
If it is lower than 50 ° C. or higher than 400 ° C., the conversion of carbon monoxide is low.
【００３１】反応圧力は１０〜３００ｋｇ／ｃｍ2が好
ましく、 特に１５〜１５０ｋｇ／ｃｍ2である。反応圧
力が１０ｋｇ／ｃｍ2より低いと一酸化炭素の転化率が
低く、また３００ｋｇ／ｃｍ2より高いと反応器が特殊
なものとなり、 また昇圧のために多大なエネルギーが
必要であって経済的でない。The reaction pressure is preferably 10~300kg / cm 2, in particular 15~150kg / cm 2. When the reaction pressure is lower than 10 kg / cm 2, the conversion rate of carbon monoxide is low. When the reaction pressure is higher than 300 kg / cm 2 , the reactor becomes special, and a large amount of energy is required for pressurization, and it is economical. Not.
【００３２】空間速度(触媒１ｇあたりの標準状態にお
ける混合ガスの供給速度)は、１００〜５００００ｍｌ
／ｇ・ｈが好ましく、特に５００〜３００００ｍｌ／ｇ
・ｈである。空間速度が５００００ｍｌ／ｇ・ｈより大
きいと一酸化炭素の転化率が低くなり、また１００ｍｌ
／ｇ・ｈより小さいと反応器が極端に大きくなって経済
的でない。The space velocity (supply rate of the mixed gas in a standard state per 1 g of the catalyst) is 100 to 50,000 ml.
/ G · h is preferred, especially 500 to 30000 ml / g
H. If the space velocity is greater than 50,000 ml / g · h, the conversion rate of carbon monoxide decreases,
If the ratio is smaller than / g · h, the reactor becomes extremely large and is not economical.
【００３３】本発明のジメチルエーテル製造用触媒およ
びその製造方法は、メタノール合成触媒、メタノール脱
水触媒および水性ガスシフト触媒を、バインダーを使用
して一体化するため、これらの各触媒成分が反応中に分
離することがない。In the catalyst for producing dimethyl ether and the method for producing the same according to the present invention, since a methanol synthesis catalyst, a methanol dehydration catalyst and a water gas shift catalyst are integrated using a binder, these catalyst components are separated during the reaction. Nothing.
【００３４】[0034]
【実施例】［実施例１〜３，比較例１］ Ｉ．触媒の調製 １）触媒Ａの調製 硝酸銅(Ｃｕ(ＮＯ3)2・３Ｈ2Ｏ)１７９ｇ、硝酸亜鉛(Ｚ
ｎ(ＮＯ3)2・６Ｈ2Ｏ)１１３ｇ、硝酸クロム(Ｃｒ(Ｎ
Ｏ)3・３Ｈ2Ｏ）１５.８ｇおよび硝酸アルミニウム（Ａ
ｌ(ＮＯ3)3・９Ｈ2Ｏ）４４.２ｇをイオン交換水約１ｌ
に溶解した水溶液と、炭酸ナトリウム（Ｎａ2ＣＯ3）約
２００ｇをイオン交換水約１ｌに溶解した水溶液とを、
約６０℃に保温したイオン交換水約３ｌの入ったステン
レス製容器中に、ｐＨが７.０±０.５に保持されるよう
に調節しながら、約２時間かけて滴下した。滴下終了
後、そのまま約１時間保持して熟成を行った。なお、こ
の間にｐＨが７.０±０.５から外れるようであれば、約
１ｍｏｌ／ｌの硝酸水溶液または約１ｍｏｌ／ｌの炭酸
ナトリウム水溶液を滴下して、ｐＨを７.０±０.５にあ
わせた。次に、生成した沈澱を濾過した後、洗浄液に硝
酸イオンが検出されなくなるまでイオン交換水を用いて
洗浄した。得られたケーキを１２０℃で２４時間乾燥し
た後、さらに空気中３５０℃で３時間焼成した。さらに
このものを１２０μｍ以下に分級して目的の触媒Ａを得
た。得られた触媒Ａの組成は、ＣｕＯ：ＺｎＯ：Ｃｒ2
Ｏ3：Ａｌ2Ｏ3＝５９：３１：３：７（重量比）であっ
た。EXAMPLES [Examples 1 to 3, Comparative Example 1] Preparation of Catalyst 1) Preparation of Catalyst A 179 g of copper nitrate (Cu (NO 3 ) 2 .3H 2 O) and zinc nitrate (Z
n (NO 3 ) 2 .6H 2 O) 113 g, chromium nitrate (Cr (N
O) 3 · 3H 2 O) 15.8g and aluminum nitrate (A
l (NO 3) 3 · 9H 2 O) Ion-exchanged water of about 1l to 44.2g
And an aqueous solution obtained by dissolving about 200 g of sodium carbonate (Na 2 CO 3 ) in about 1 liter of ion-exchanged water.
The solution was added dropwise to a stainless steel container containing about 3 liters of ion-exchanged water kept at about 60 ° C. over about 2 hours while adjusting the pH to be maintained at 7.0 ± 0.5. After the completion of the dropping, the mixture was kept for about 1 hour for aging. If the pH deviates from 7.0 ± 0.5 during this time, an aqueous solution of about 1 mol / l nitric acid or an aqueous solution of about 1 mol / l sodium carbonate is added dropwise to adjust the pH to 7.0 ± 0.5. According to. Next, the resulting precipitate was filtered and washed with ion-exchanged water until no nitrate ion was detected in the washing solution. After the obtained cake was dried at 120 ° C. for 24 hours, it was further baked at 350 ° C. in air for 3 hours. This was further classified to 120 μm or less to obtain the desired catalyst A. The composition of the obtained catalyst A was CuO: ZnO: Cr 2
O 3 : Al 2 O 3 = 59: 31: 3: 7 (weight ratio).
【００３５】２）触媒Ｂの調製 触媒Ａの調製方法において、硝酸クロムの代わりに硝酸
ジルコニルＺｒＯ（ＮＯ)2・２Ｈ2Ｏ）６.５ｇを使用す
ること以外、触媒Ａと同一の方法で触媒を調製した。得
られた触媒Ｂの組成は、ＣｕＯ：ＺｎＯ：ＺｒＯ2：Ａ
ｌ2Ｏ3＝５９：３１：３：７（重量比）であった。2) Preparation of catalyst B The catalyst A was prepared in the same manner as the catalyst A, except that 6.5 g of zirconyl nitrate (ZrO (NO) 2 .2H 2 O) was used instead of chromium nitrate. Was prepared. The composition of the obtained catalyst B is CuO: ZnO: ZrO 2 : A
l 2 O 3 = 59: 31: 3: 7 (weight ratio).
【００３６】３）触媒Ｃの調製 硝酸銅(Ｃｕ(ＮＯ3)2・３Ｈ2Ｏ)１８２ｇ、硝酸亜鉛(Ｚ
ｎ(ＮＯ3)2・６Ｈ2Ｏ)１１３ｇおよび硝酸アルミニウム
（Ａｌ(ＮＯ3)3・９Ｈ2Ｏ）４４.２ｇをイオン交換水約
１ｌに溶解した水溶液と、炭酸ナトリウム（Ｎａ2Ｃ
Ｏ3）約２００ｇおよび過レニウム酸アンモニウム(ＮＨ
4ＲｅＯ4）１.１ｇをイオン交換水約１ｌに溶解した水
溶液とを、約６０℃に保温したイオン交換水約３ｌの入
ったステンレス製容器中に、ｐＨが７.０±０.５に保持
されるように調節しながら、約２時間かけて滴下した。
滴下終了後、そのまま約１時間保持して熟成を行った。
なお、この間にｐＨが７.０±０.５から外れるようであ
れば、約１ｍｏｌ／ｌの硝酸水溶液または約１ｍｏｌ／
ｌの炭酸ナトリウム水溶液を滴下して、ｐＨを７．０±
０．５にあわせた。次に、生成した沈澱を濾過した後、
洗浄液に硝酸イオンが検出されなくなるまでイオン交換
水を用いて洗浄した。得られたケーキを１２０℃で２４
時間乾燥した後、さらに空気中３５０℃で３時間焼成し
た。さらにこのものを１２０μｍ以下に分級して目的の
触媒Ｃを得た。得られた触媒Ｃの組成は、ＣｕＯ：Ｚｎ
Ｏ：Ｒｅ2Ｏ7：Ａｌ2Ｏ3＝６０：３２：１：７（重量
比）であった。3) Preparation of Catalyst C 182 g of copper nitrate (Cu (NO 3 ) 2 .3H 2 O) and zinc nitrate (Z
n (NO 3 ) 2 .6H 2 O) and 44.2 g of aluminum nitrate (Al (NO 3 ) 3 .9H 2 O) dissolved in about 1 liter of ion-exchanged water, and sodium carbonate (Na 2 C).
O 3 ) and ammonium perrhenate (NH
4 ReO 4 ) An aqueous solution prepared by dissolving 1.1 g of ion-exchanged water in about 1 liter was placed in a stainless steel container containing about 3 liters of ion-exchanged water kept at about 60 ° C. to adjust the pH to 7.0 ± 0.5. The solution was added dropwise over about 2 hours while adjusting so as to be maintained.
After the completion of the dropping, the mixture was kept for about 1 hour for aging.
If the pH deviates from 7.0 ± 0.5 during this time, about 1 mol / l nitric acid aqueous solution or about 1 mol / l
l of sodium carbonate aqueous solution was added dropwise to adjust the pH to 7.0 ±.
Adjusted to 0.5. Next, after filtering the formed precipitate,
Washing was performed using ion-exchanged water until no nitrate ion was detected in the washing solution. The obtained cake is heated at 120 ° C. for 24 hours.
After drying for an hour, it was further fired in air at 350 ° C. for 3 hours. This was further classified to 120 μm or less to obtain a desired catalyst C. The composition of the obtained catalyst C was CuO: Zn.
O: Re 2 O 7 : Al 2 O 3 = 60: 32: 1: 7 (weight ratio).
【００３７】４）触媒Ｄの調製 イオン交換水約２００ｍｌに硝酸銅(Ｃｕ(ＮＯ)3・３Ｈ
2Ｏ）１９.０ｇを溶解し、これにアルミナ（日揮化学
製，Ｎ６１２）９５ｇを投入した後、蒸発乾固した。次
にこのものを空気中、１２０℃で２４時間乾燥した後、
空気中４５０℃で３時間焼成した。ついで水素気流中、
４００℃で３時間処理した。さらにこのものを１２０μ
ｍ以下に分級して目的の触媒Ｄを得た。このものの組成
は、Ｃｕ：Ａｌ2Ｏ3＝５：９５（重量比）であった。[0037] 4) copper nitrate preparation of ion-exchanged water of about 200ml of catalyst D (Cu (NO) 3 · 3H
It was dissolved 2 O) 19.0 g, which alumina (Nikki Chemical Co., N612) was poured 95 g, and evaporated to dryness. Next, after drying this in air at 120 ° C. for 24 hours,
It was calcined in air at 450 ° C. for 3 hours. Then, in a stream of hydrogen,
Treated at 400 ° C. for 3 hours. Furthermore, this is 120μ
m to obtain the target catalyst D. The composition was Cu: Al 2 O 3 = 5: 95 (weight ratio).
【００３８】５）触媒Ｅの調製 硝酸銅(Ｃｕ(ＮＯ3)2・３Ｈ2Ｏ)１８５ｇ、硝酸亜鉛(Ｚ
ｎ(ＮＯ3)2・６Ｈ2Ｏ)１１７ｇおよび硝酸アルミニウム
(Ａｌ(ＮＯ3)3・９Ｈ2Ｏ）５２ｇをイオン交換水約１ｌ
に溶解した水溶液と、炭酸ナトリウム（Ｎａ2ＣＯ3）約
２００ｇをイオン交換水約１ｌに溶解した水溶液とを、
約６０℃に保温したイオン交換水約３ｌの入ったステン
レス製容器中に、ｐＨが７．０±０．５に保持されるよ
うに調節しながら、約２時間かけて滴下した。滴下終了
後、そのまま約１時間保持して熟成を行った。なお、こ
の間にｐＨが７．０±０．５から外れるようであれば、
約１ｍｏｌ／ｌの硝酸水溶液または約１ｍｏｌ／ｌの炭
酸ナトリウム水溶液を滴下して、ｐＨを７．０±０．５
にあわせた。次に、生成した沈澱を濾過した後、洗浄液
に硝酸イオンが検出されなくなるまでイオン交換水を用
いて洗浄した。得られたケーキを１２０℃で２４時間乾
燥した後、さらに空気中３５０℃で３時間焼成した。さ
らにこのものを１２０μｍ以下に分級して目的の触媒Ｅ
を得た。得られた触媒Ｅの組成は、ＣｕＯ：ＺｎＯ：Ａ
ｌ2Ｏ3＝６１：３２：７（重量比）であった。5) Preparation of Catalyst E 185 g of copper nitrate (Cu (NO 3 ) 2 .3H 2 O) and zinc nitrate (Z
117 g of n (NO 3 ) 2 .6H 2 O) and aluminum nitrate
(Al (NO 3) 3 · 9H 2 O) Ion-exchanged water of about 1l to 52g
And an aqueous solution obtained by dissolving about 200 g of sodium carbonate (Na 2 CO 3 ) in about 1 liter of ion-exchanged water.
The solution was added dropwise to a stainless steel container containing about 3 liters of ion-exchanged water kept at about 60 ° C. over about 2 hours while adjusting the pH to be maintained at 7.0 ± 0.5. After the completion of the dropping, the mixture was kept for about 1 hour for aging. During this time, if the pH deviates from 7.0 ± 0.5,
About 1 mol / l nitric acid aqueous solution or about 1 mol / l sodium carbonate aqueous solution is added dropwise to adjust the pH to 7.0 ± 0.5.
According to. Next, the resulting precipitate was filtered and washed with ion-exchanged water until no nitrate ion was detected in the washing solution. After the obtained cake was dried at 120 ° C. for 24 hours, it was further baked at 350 ° C. in air for 3 hours. This was further classified to 120 μm or less to obtain the desired catalyst E
I got The composition of the obtained catalyst E was CuO: ZnO: A
l 2 O 3 = 61: 32: 7 (weight ratio).
【００３９】II．触媒の活性化方法および反応方法 内径２ｃｍ、高さ２ｍの気泡塔式反応器に、ｎ−ヘキサ
デカン２４ｇ(３１.１ｍｌ）を加え、これにさらに上記
の触媒を所定量加えて懸濁状態にした。次いで、この気
泡塔に水素、一酸化炭素および窒素からなる混合ガス
（Ｈ2：ＣＯ：Ｎ2＝１：１：９、モル比）を約３００ｍ
ｌ／ｍｉｎの流速で流通させつつ、室温より２２０℃ま
で数時間かけて徐々に昇温し、同時に混合ガス中の窒素
の濃度を最終的に０まで徐々に減少させて、さらに２２
０℃で約３時間保持して触媒の活性化を行った。II. Catalyst activation method and reaction method 24 g (31.1 ml) of n-hexadecane was added to a bubble column reactor having an inner diameter of 2 cm and a height of 2 m, and a predetermined amount of the above-mentioned catalyst was further added thereto to bring into a suspended state. . Next, a mixed gas (H 2 : CO: N 2 = 1: 1: 9, molar ratio) consisting of hydrogen, carbon monoxide and nitrogen was added to the bubble column for about 300 m.
While flowing at a flow rate of 1 / min, the temperature was gradually raised from room temperature to 220 ° C. over several hours, and at the same time, the concentration of nitrogen in the mixed gas was gradually reduced to finally zero.
The catalyst was activated by holding at 0 ° C. for about 3 hours.
【００４０】反応は、所定の反応温度、反応圧力で、Ｈ
2／ＣＯ／ＣＯ2比がモル比で４７．５／４７．５／５．
０の水素、一酸化炭素、二酸化炭素の混合ガスを常温、
常圧換算で３３６ｍｌ／ｍｉｎの流速で流通させて行っ
た。The reaction is carried out at a predetermined reaction temperature and reaction pressure at a predetermined reaction temperature.
The 2 / CO / CO 2 ratio is 47.5 / 47.5 / 5.5 in molar ratio.
0 mixed gas of hydrogen, carbon monoxide and carbon dioxide at room temperature,
The flow was carried out at a flow rate of 336 ml / min in terms of normal pressure.
【００４１】以上の操作により得られた反応生成物およ
び未反応物はガスクロマトグラフにより分析した。The reaction products and unreacted products obtained by the above operations were analyzed by gas chromatography.
【００４２】III．反応条件および実験結果 反応条件および実験結果を表１、２に示す。III. Reaction conditions and experimental results Reaction conditions and experimental results are shown in Tables 1 and 2.
【００４３】[0043]
【表１】 [Table 1]
【００４４】[0044]
【表２】 [Table 2]
【００４５】［実施例４〜６，比較例２］ Ｉ．触媒の調製 １）触媒Ｆの調製 硝酸銅(Ｃｕ(ＮＯ3)2・３Ｈ2Ｏ)１７９ｇ、硝酸亜鉛(Ｚ
ｎ(ＮＯ3)2・６Ｈ2Ｏ)１１３ｇ、硝酸マンガン（Ｍｎ
(ＮＯ3)2・６Ｈ2Ｏ）９.９ｇおよび硝酸アルミニウム
(Ａｌ(ＮＯ3)3・９Ｈ2Ｏ)４４.２ｇをイオン交換水約１
ｌに溶解した水溶液と、炭酸ナトリウム（Ｎａ2ＣＯ3）
約２００ｇをイオン交換水約１ｌに溶解した水溶液と
を、約６０℃に保温したイオン交換水約３ｌの入ったス
テンレス製容器中に、ｐＨが７.０±０.５に保持される
ように調節しながら、約２時間かけて滴下した。滴下終
了後、そのまま約１時間保持して熟成を行った。なお、
この間にｐＨが７.０±０.５から外れるようであれば、
約１ｍｏｌ／ｌの硝酸水溶液または約１ｍｏｌ／ｌの炭
酸ナトリウム水溶液を滴下して、ｐＨを７.０±０.５に
あわせた。次に、生成した沈澱を濾過した後、洗浄液に
硝酸イオンが検出されなくなるまでイオン交換水を用い
て洗浄した。得られたケーキを１２０℃で２４時間乾燥
した後、さらに空気中３５０℃で３時間焼成した。さら
にこのものを１２０μｍ以下に分級して目的の触媒Ｆを
得た。得られた触媒Ｆの組成は、ＣｕＯ：ＺｎＯ：Ｍｎ
Ｏ2：Ａｌ2Ｏ3＝５９：３１：３：７（重量比）であっ
た。[Examples 4 to 6, Comparative Example 2] Preparation of Catalyst 1) Preparation of Catalyst F 179 g of copper nitrate (Cu (NO 3 ) 2 .3H 2 O) and zinc nitrate (Z
n (NO 3 ) 2 .6H 2 O) 113 g, manganese nitrate (Mn)
(NO 3) 2 · 6H 2 O) 9.9g and aluminum nitrate
44.2 g of (Al (NO 3 ) 3 .9H 2 O) was added to about 1 deionized water.
and sodium carbonate (Na 2 CO 3 )
An aqueous solution in which about 200 g is dissolved in about 1 liter of ion-exchanged water is placed in a stainless steel container containing about 3 liters of ion-exchanged water kept at about 60 ° C. so that the pH is maintained at 7.0 ± 0.5. It dripped over about 2 hours, adjusting. After the completion of the dropping, the mixture was kept for about 1 hour for aging. In addition,
If during this time the pH deviates from 7.0 ± 0.5,
About 1 mol / l nitric acid aqueous solution or about 1 mol / l sodium carbonate aqueous solution was added dropwise to adjust the pH to 7.0 ± 0.5. Next, the resulting precipitate was filtered and washed with ion-exchanged water until no nitrate ion was detected in the washing solution. After the obtained cake was dried at 120 ° C. for 24 hours, it was further baked at 350 ° C. in air for 3 hours. This was further classified to 120 μm or less to obtain a desired catalyst F. The composition of the obtained catalyst F was CuO: ZnO: Mn.
O 2 : Al 2 O 3 = 59: 31: 3: 7 (weight ratio).
【００４６】２）触媒Ｇの調製 硝酸銅(Ｃｕ(ＮＯ3)2・３Ｈ2Ｏ)１７３ｇ、硝酸亜鉛(Ｚ
ｎ(ＮＯ3)2・６Ｈ2Ｏ)１１３ｇおよび硝酸アルミニウム
(Ａｌ(ＮＯ3)3・９Ｈ2Ｏ)４４.２ｇをイオン交換水約１
ｌに溶解した水溶液と、炭酸ナトリウム（Ｎａ2ＣＯ3）
約２００ｇおよびケイ酸ナトリウム(Ｎａ2ＳｉＯ3；３
６.５％ＳｉＯ2含有品）１３.７ｇをイオン交換水約１
ｌに溶解した水溶液とを、約６０℃に保温したイオン交
換水約３ｌの入ったステンレス製容器中に、ｐＨが７．
０±０．５に保持されるように調節しながら、約２時間
かけて滴下した。滴下終了後、そのまま約１時間保持し
て熟成を行った。なお、この間にｐＨが７．０±０．５
から外れるようであれば、約１ｍｏｌ／ｌの硝酸水溶液
または約１ｍｏｌ／ｌの炭酸ナトリウム水溶液を滴下し
て、ｐＨを７．０±０．５にあわせた。次に、生成した
沈澱を濾過した後、洗浄液に硝酸イオンが検出されなく
なるまでイオン交換水を用いて洗浄した。得られたケー
キを１２０℃で２４時間乾燥した後、さらに空気中３５
０℃で３時間焼成した。さらにこのものを１２０μｍ以
下に分級して目的の触媒Ｇを得た。得られた触媒Ｇの組
成は、ＣｕＯ：ＺｎＯ：ＳｉＯ2：Ａｌ2Ｏ3＝５７：３
１：５：７（重量比）であった。2) Preparation of Catalyst G 173 g of copper nitrate (Cu (NO 3 ) 2 .3H 2 O) and zinc nitrate (Z
113 g of n (NO 3 ) 2 .6H 2 O) and aluminum nitrate
44.2 g of (Al (NO 3 ) 3 .9H 2 O) was added to about 1 deionized water.
and sodium carbonate (Na 2 CO 3 )
About 200 g and sodium silicate (Na 2 SiO 3 ; 3)
13.7 g of 6.5% SiO 2 content) in about 1 deionized water
of the aqueous solution dissolved in 1 l in a stainless steel container containing about 3 l of ion-exchanged water kept at a temperature of about 60 ° C.
The solution was added dropwise over about 2 hours while adjusting to be maintained at 0 ± 0.5. After the completion of the dropping, the mixture was kept for about 1 hour for aging. During this period, the pH was 7.0 ± 0.5.
If so, the pH was adjusted to 7.0 ± 0.5 by dropping about 1 mol / l nitric acid aqueous solution or about 1 mol / l sodium carbonate aqueous solution. Next, the resulting precipitate was filtered and washed with ion-exchanged water until no nitrate ion was detected in the washing solution. After drying the obtained cake at 120 ° C. for 24 hours, the cake was further dried in air.
Baking at 0 ° C. for 3 hours. This was further classified to 120 μm or less to obtain a desired catalyst G. The composition of the obtained catalyst G was CuO: ZnO: SiO 2 : Al 2 O 3 = 57: 3.
1: 5: 7 (weight ratio).
【００４７】３）触媒Ｈの調製 硝酸銅(Ｃｕ(ＮＯ3)2・３Ｈ2Ｏ)１８５ｇ、硝酸亜鉛(Ｚ
ｎ(ＮＯ3)2・６Ｈ2Ｏ)１１７ｇおよび硝酸アルミニウム
（Ａｌ(ＮＯ3)3・９Ｈ2Ｏ）５２.０ｇをイオン交換水約
１ｌに溶解した水溶液と、炭酸ナトリウム（Ｎａ2Ｃ
Ｏ3）約２００ｇをイオン交換水約１ｌに溶解した水溶
液とを、約６０℃に保温したイオン交換水約３ｌの入っ
たステンレス製容器中に、ｐＨが７.０±０.５に保持さ
れるように調節しながら、約２時間かけて滴下した。滴
下終了後、そのまま約１時間保持して熟成を行った。な
お、この間にｐＨが７.０±０.５から外れるようであれ
ば、約１ｍｏｌ／ｌの硝酸水溶液または約１ｍｏｌ／ｌ
の炭酸ナトリウム水溶液を滴下して、ｐＨを７.０±０.
５にあわせた。次に、生成した沈澱を濾過した後、洗浄
液に硝酸イオンが検出されなくなるまでイオン交換水を
用いて洗浄した。得られたケーキを１２０℃で２４時間
乾燥した後、さらに空気中３５０℃で３時間焼成した。
次にイオン交換水約２００ｍｌに水酸化マグネシウム
（Ｍｇ（ＯＨ）2）２．９ｇを溶解し、これに上記の焼
成物９８ｇを投入した後、蒸発乾固した。ついでこのも
のを空気中、１２０℃で２４時間乾燥した後、空気中４
５０℃で３時間焼成した。そして水素気流中、４００℃
で３時間処理した。さらにこのものを１２０μｍ以下に
分級して目的の触媒Ｈを得た。このものの組成は、Ｃｕ
Ｏ：ＺｎＯ：ＭｇＯ：Ａｌ2Ｏ3＝６０：３１：２：７
（重量比）であった。3) Preparation of Catalyst H 185 g of copper nitrate (Cu (NO 3 ) 2 .3H 2 O) and zinc nitrate (Z
An aqueous solution in which 117 g of n (NO 3 ) 2 .6H 2 O) and 52.0 g of aluminum nitrate (Al (NO 3 ) 3 .9H 2 O) were dissolved in about 1 liter of ion-exchanged water, and sodium carbonate (Na 2 C)
An aqueous solution in which about 200 g of O 3 was dissolved in about 1 liter of ion-exchanged water was placed in a stainless steel container containing about 3 liters of ion-exchanged water kept at about 60 ° C., and the pH was maintained at 7.0 ± 0.5. It dripped over about 2 hours, adjusting so that it might be. After the completion of the dropping, the mixture was kept for about 1 hour for aging. If the pH deviates from 7.0 ± 0.5 during this time, about 1 mol / l nitric acid aqueous solution or about 1 mol / l
Sodium carbonate aqueous solution was added dropwise to adjust the pH to 7.0 ± 0.1.
Adjusted to 5. Next, the resulting precipitate was filtered and washed with ion-exchanged water until no nitrate ion was detected in the washing solution. After the obtained cake was dried at 120 ° C. for 24 hours, it was further baked at 350 ° C. in air for 3 hours.
Next, 2.9 g of magnesium hydroxide (Mg (OH) 2 ) was dissolved in about 200 ml of ion-exchanged water, 98 g of the above calcined product was added thereto, and the mixture was evaporated to dryness. Then, the product was dried in air at 120 ° C. for 24 hours.
Baking was performed at 50 ° C. for 3 hours. And 400 ° C in a stream of hydrogen
For 3 hours. This was further classified to 120 μm or less to obtain a desired catalyst H. Its composition is Cu
O: ZnO: MgO: Al 2 O 3 = 60: 31: 2: 7
(Weight ratio).
【００４８】４）触媒Ｉの調製 硝酸銅(Ｃｕ(ＮＯ3)2・３Ｈ2Ｏ)１８５ｇ、硝酸亜鉛(Ｚ
ｎ(ＮＯ3)2・６Ｈ2Ｏ)１１７ｇおよび硝酸アルミニウム
(Ａｌ(ＮＯ3)3・９Ｈ2Ｏ）５２ｇをイオン交換水約１ｌ
に溶解した水溶液と、炭酸ナトリウム（Ｎａ2ＣＯ3）約
２００ｇをイオン交換水約１ｌに溶解した水溶液とを、
約６０℃に保温したイオン交換水約３ｌの入ったステン
レス製容器中に、ｐＨが７．０±０．５に保持されるよ
うに調節しながら、約２時間かけて滴下した。滴下終了
後、そのまま約１時間保持して熟成を行った。なお、こ
の間にｐＨが７．０±０．５から外れるようであれば、
約１ｍｏｌ／ｌの硝酸水溶液または約１ｍｏｌ／ｌの炭
酸ナトリウム水溶液を滴下して、ｐＨを７．０±０．５
にあわせた。次に、生成した沈澱を濾過した後、洗浄液
に硝酸イオンが検出されなくなるまでイオン交換水を用
いて洗浄した。得られたケーキを１２０℃で２４時間乾
燥した後、さらに空気中３５０℃で３時間焼成した。さ
らにこのものを１２０μｍ以下に分級して目的の触媒Ｉ
を得た。得られた触媒Ｉの組成は、ＣｕＯ：ＺｎＯ：Ａ
ｌ2Ｏ3＝６１：３２：７（重量比）であった。4) Preparation of Catalyst I 185 g of copper nitrate (Cu (NO 3 ) 2 .3H 2 O) and zinc nitrate (Z
117 g of n (NO 3 ) 2 .6H 2 O) and aluminum nitrate
(Al (NO 3) 3 · 9H 2 O) Ion-exchanged water of about 1l to 52g
And an aqueous solution obtained by dissolving about 200 g of sodium carbonate (Na 2 CO 3 ) in about 1 liter of ion-exchanged water.
The solution was added dropwise to a stainless steel container containing about 3 liters of ion-exchanged water kept at about 60 ° C. over about 2 hours while adjusting the pH to be maintained at 7.0 ± 0.5. After the completion of the dropping, the mixture was kept for about 1 hour for aging. During this time, if the pH deviates from 7.0 ± 0.5,
About 1 mol / l nitric acid aqueous solution or about 1 mol / l sodium carbonate aqueous solution is added dropwise to adjust the pH to 7.0 ± 0.5.
According to. Next, the resulting precipitate was filtered and washed with ion-exchanged water until no nitrate ion was detected in the washing solution. After the obtained cake was dried at 120 ° C. for 24 hours, it was further baked at 350 ° C. in air for 3 hours. This was further classified to 120 μm or less to obtain the desired catalyst I
I got The composition of the obtained catalyst I is CuO: ZnO: A
l 2 O 3 = 61: 32: 7 (weight ratio).
【００４９】II．触媒の活性化方法および反応方法 内径２ｃｍ、高さ２ｍの気泡塔式反応器に、ｎ−ヘキサ
デカン２４ｇ(３１.１ｍｌ）を加え、これにさらに上記
の触媒を所定量加えて懸濁状態にした。次いで、この気
泡塔に水素、一酸化炭素および窒素からなる混合ガス
（Ｈ2：ＣＯ：Ｎ2＝１：１：９、モル比）を約３００ｍ
ｌ／ｍｉｎの流速で流通させつつ、室温より２２０℃ま
で数時間かけて徐々に昇温し、同時に混合ガス中の窒素
の濃度を最終的に０まで徐々に減少させて、さらに２２
０℃で約３時間保持して触媒の活性化を行った。II. Catalyst activation method and reaction method 24 g (31.1 ml) of n-hexadecane was added to a bubble column reactor having an inner diameter of 2 cm and a height of 2 m, and a predetermined amount of the above-mentioned catalyst was further added thereto to bring into a suspended state. . Next, a mixed gas (H 2 : CO: N 2 = 1: 1: 9, molar ratio) consisting of hydrogen, carbon monoxide and nitrogen was added to the bubble column for about 300 m.
While flowing at a flow rate of 1 / min, the temperature was gradually raised from room temperature to 220 ° C. over several hours, and at the same time, the concentration of nitrogen in the mixed gas was gradually reduced to finally zero.
The catalyst was activated by holding at 0 ° C. for about 3 hours.
【００５０】反応は、所定の反応温度、反応圧力で、Ｈ
2／ＣＯ／ＣＯ2比がモル比で４７．５／４７．５／５．
０の水素、一酸化炭素、二酸化炭素の混合ガスを常温、
常圧換算で３３６ｍｌ／ｍｉｎの流速で流通させて行っ
た。The reaction is carried out at a predetermined reaction temperature and at a predetermined reaction pressure.
The 2 / CO / CO 2 ratio is 47.5 / 47.5 / 5.5 in molar ratio.
0 mixed gas of hydrogen, carbon monoxide and carbon dioxide at room temperature,
The flow was carried out at a flow rate of 336 ml / min in terms of normal pressure.
【００５１】反応を１００時間継続して行った後に、反
応生成物および未反応物をガスクロマトグラフにより分
析した。After the reaction was continued for 100 hours, reaction products and unreacted products were analyzed by gas chromatography.
【００５２】III．反応条件および実験結果 反応条件および実験結果を表３、４に示す。III. Reaction conditions and experimental results Reaction conditions and experimental results are shown in Tables 3 and 4.
【００５３】[0053]
【表３】 [Table 3]
【００５４】[0054]
【表４】 [Table 4]
【００５５】［実施例７〜９，比較例３］ Ｉ．触媒の調製 １）触媒Ｊの調製 硝酸銅(Ｃｕ(ＮＯ3)2・３Ｈ2Ｏ)１７９ｇ、硝酸亜鉛(Ｚ
ｎ(ＮＯ3)2・６Ｈ2Ｏ)１１３ｇおよび硝酸アルミニウム
（Ａｌ(ＮＯ3)3・９Ｈ2Ｏ）４４.２ｇをイオン交換水約
１ｌに溶解した水溶液と、炭酸ナトリウム(Ｎａ2ＣＯ3)
約２００ｇおよびモリブデン酸アンモニウム((ＮＨ4)6
Ｍｏ7Ｏ24・４Ｈ2Ｏ）３.７ｇをイオン交換水約１ｌに
溶解した水溶液とを、約６０℃に保温したイオン交換水
約３ｌの入ったステンレス製容器中に、ｐＨが７.０±
０.５に保持されるように調節しながら、約２時間かけ
て滴下した。滴下終了後、そのまま約１時間保持して熟
成を行った。なお、この間にｐＨが７．０±０．５から
外れるようであれば、約１ｍｏｌ／ｌの硝酸水溶液また
は約１ｍｏｌ／ｌの炭酸ナトリウム水溶液を滴下して、
ｐＨを７.０±０.５にあわせた。次に、生成した沈澱を
濾過した後、洗浄液に硝酸イオンが検出されなくなるま
でイオン交換水を用いて洗浄した。得られたケーキを１
２０℃で２４時間乾燥した後、さらに空気中３５０℃で
３時間焼成した。さらにこのものを１２０μｍ以下に分
級して目的の触媒Ｊを得た。得られた触媒Ｊの組成は、
ＣｕＯ：ＺｎＯ：ＭｏＯ3：Ａｌ2Ｏ3＝５９：３１：
３：７（重量比）であった。[Examples 7 to 9, Comparative Example 3] Preparation of Catalyst 1) Preparation of copper nitrate catalyst J (Cu (NO 3) 2 · 3H 2 O) 179g, zinc nitrate (Z
An aqueous solution obtained by dissolving 113 g of n (NO 3 ) 2 .6H 2 O) and 44.2 g of aluminum nitrate (Al (NO 3 ) 3 .9H 2 O) in about 1 liter of ion-exchanged water, and sodium carbonate (Na 2 CO 3 )
About 200 g and ammonium molybdate ((NH 4 ) 6
And an aqueous solution of Mo 7 O 24 · 4H 2 O ) 3.7g were dissolved in deionized water of about 1l, Entered in a stainless steel container with ion-exchanged water to about 3l was kept at about 60 ° C., pH 7.0 ±
The mixture was added dropwise over a period of about 2 hours while maintaining the pH at 0.5. After the completion of the dropping, the mixture was kept for about 1 hour for aging. If the pH deviates from 7.0 ± 0.5 during this time, an aqueous solution of about 1 mol / l nitric acid or an aqueous solution of about 1 mol / l sodium carbonate is added dropwise.
The pH was adjusted to 7.0 ± 0.5. Next, the resulting precipitate was filtered and washed with ion-exchanged water until no nitrate ion was detected in the washing solution. 1 cake obtained
After drying at 20 ° C. for 24 hours, it was further fired in air at 350 ° C. for 3 hours. This was further classified to 120 μm or less to obtain a desired catalyst J. The composition of the obtained catalyst J is as follows:
CuO: ZnO: MoO 3 : Al 2 O 3 = 59: 31:
3: 7 (weight ratio).
【００５６】２）触媒Ｋの調製 触媒Ｊの調製方法において、モリブデン酸アンモニウム
の代わりにタングステン酸アンモニウム(５(ＮＨ4)2・
Ｏ・１２ＷＯ3・５Ｈ2Ｏ）３.４ｇを使用すること以
外、触媒Ｊと同一の方法で触媒を調製した。得られた触
媒Ｋの組成は、ＣｕＯ：ＺｎＯ：ＷＯ3：Ａｌ2Ｏ3＝５
９：３１：３：７（重量比）であった。2) Preparation of Catalyst K In the preparation method of Catalyst J, ammonium tungstate (5 (NH 4 ) 2.
Except using O · 12WO 3 · 5H 2 O ) 3.4g, to prepare a catalyst in the catalyst J in the same manner. The composition of the obtained catalyst K was CuO: ZnO: WO 3 : Al 2 O 3 = 5.
9: 31: 3: 7 (weight ratio).
【００５７】３）触媒Ｌの調製 硝酸銅(Ｃｕ(ＮＯ3)2・３Ｈ2Ｏ)１８５ｇ、硝酸亜鉛(Ｚ
ｎ(ＮＯ3)2・６Ｈ2Ｏ)１１７ｇおよび硝酸アルミニウム
（Ａｌ(ＮＯ3)3・９Ｈ2Ｏ）５２.０ｇをイオン交換水約
１ｌに溶解した水溶液と、炭酸ナトリウム（Ｎａ2Ｃ
Ｏ3）約２００ｇをイオン交換水約１ｌに溶解した水溶
液とを、約６０℃に保温したイオン交換水約３ｌの入っ
たステンレス製容器中に、ｐＨが７.０±０.５に保持さ
れるように調節しながら、約２時間かけて滴下した。滴
下終了後、そのまま約１時間保持して熟成を行った。な
お、この間にｐＨが７.０±０.５から外れるようであれ
ば、約１ｍｏｌ／ｌの硝酸水溶液または約１ｍｏｌ／ｌ
の炭酸ナトリウム水溶液を滴下して、ｐＨを７.０±０.
５にあわせた。次に、生成した沈澱を濾過した後、洗浄
液に硝酸イオンが検出されなくなるまでイオン交換水を
用いて洗浄した。得られたケーキを１２０℃で２４時間
乾燥した後、さらに空気中３５０℃で３時間焼成した。
次にイオン交換水約２００ｍｌに水酸化カルシウム（Ｃ
ａ(ＯＨ)2）１.３ｇを溶解し、これに上記の焼成物９９
ｇを投入した後、蒸発乾固した。ついでこのものを空気
中、１２０℃で２４時間乾燥した後、空気中４５０℃で
３時間焼成した。そして水素気流中、４００℃で３時間
処理した。さらにこのものを１２０μｍ以下に分級して
目的の触媒Ｌを得た。このものの組成は、ＣｕＯ：Ｚｎ
Ｏ：ＣａＯ：Ａｌ2Ｏ3＝６０：３２：１：７（重量比）
であった。3) Preparation of Catalyst L 185 g of copper nitrate (Cu (NO 3 ) 2 .3H 2 O) and zinc nitrate (Z
An aqueous solution in which 117 g of n (NO 3 ) 2 .6H 2 O) and 52.0 g of aluminum nitrate (Al (NO 3 ) 3 .9H 2 O) were dissolved in about 1 liter of ion-exchanged water, and sodium carbonate (Na 2 C)
An aqueous solution in which about 200 g of O 3 was dissolved in about 1 liter of ion-exchanged water was placed in a stainless steel container containing about 3 liters of ion-exchanged water kept at about 60 ° C., and the pH was maintained at 7.0 ± 0.5. It dripped over about 2 hours, adjusting so that it might be. After the completion of the dropping, the mixture was kept for about 1 hour for aging. If the pH deviates from 7.0 ± 0.5 during this time, about 1 mol / l nitric acid aqueous solution or about 1 mol / l
Sodium carbonate aqueous solution was added dropwise to adjust the pH to 7.0 ± 0.1.
Adjusted to 5. Next, the resulting precipitate was filtered and washed with ion-exchanged water until no nitrate ion was detected in the washing solution. After the obtained cake was dried at 120 ° C. for 24 hours, it was further baked at 350 ° C. in air for 3 hours.
Next, about 200 ml of calcium hydroxide (C
a (OH) 2 ) was dissolved in 1.3 g, and the calcined product 99 was added thereto.
g, and evaporated to dryness. Next, this was dried in air at 120 ° C. for 24 hours, and then calcined in air at 450 ° C. for 3 hours. And it processed at 400 degreeC in hydrogen stream for 3 hours. This was further classified to 120 μm or less to obtain a desired catalyst L. Its composition is CuO: Zn
O: CaO: Al 2 O 3 = 60: 32: 1: 7 (weight ratio)
Met.
【００５８】４）触媒Ｍの調製 硝酸銅(Ｃｕ(ＮＯ3)2・３Ｈ2Ｏ)１８５ｇ、硝酸亜鉛(Ｚ
ｎ(ＮＯ3)2・６Ｈ2Ｏ)１１７ｇおよび硝酸アルミニウム
(Ａｌ(ＮＯ3)3・９Ｈ2Ｏ）５２ｇをイオン交換水約１ｌ
に溶解した水溶液と、炭酸ナトリウム（Ｎａ2ＣＯ3）約
２００ｇをイオン交換水約１ｌに溶解した水溶液とを、
約６０℃に保温したイオン交換水約３ｌの入ったステン
レス製容器中に、ｐＨが７.０±０.５に保持されるよう
に調節しながら、約２時間かけて滴下した。滴下終了
後、そのまま約１時間保持して熟成を行った。なお、こ
の間にｐＨが７．０±０．５から外れるようであれば、
約１ｍｏｌ／ｌの硝酸水溶液または約１ｍｏｌ／ｌの炭
酸ナトリウム水溶液を滴下して、ｐＨを７．０±０．５
にあわせた。次に、生成した沈澱を濾過した後、洗浄液
に硝酸イオンが検出されなくなるまでイオン交換水を用
いて洗浄した。得られたケーキを１２０℃で２４時間乾
燥した後、さらに空気中３５０℃で３時間焼成した。さ
らにこのものを１２０μｍ以下に分級して目的の触媒Ｍ
を得た。得られた触媒Ｍの組成は、ＣｕＯ：ＺｎＯ：Ａ
ｌ2Ｏ3＝６１：３２：７（重量比）であった。4) Preparation of Catalyst M 185 g of copper nitrate (Cu (NO 3 ) 2 .3H 2 O) and zinc nitrate (Z
117 g of n (NO 3 ) 2 .6H 2 O) and aluminum nitrate
(Al (NO 3) 3 · 9H 2 O) Ion-exchanged water of about 1l to 52g
And an aqueous solution obtained by dissolving about 200 g of sodium carbonate (Na 2 CO 3 ) in about 1 liter of ion-exchanged water.
The solution was added dropwise to a stainless steel container containing about 3 liters of ion-exchanged water kept at about 60 ° C. over about 2 hours while adjusting the pH to be maintained at 7.0 ± 0.5. After the completion of the dropping, the mixture was kept for about 1 hour for aging. During this time, if the pH deviates from 7.0 ± 0.5,
About 1 mol / l nitric acid aqueous solution or about 1 mol / l sodium carbonate aqueous solution is added dropwise to adjust the pH to 7.0 ± 0.5.
According to. Next, the resulting precipitate was filtered and washed with ion-exchanged water until no nitrate ion was detected in the washing solution. After the obtained cake was dried at 120 ° C. for 24 hours, it was further baked at 350 ° C. in air for 3 hours. Further, this is classified into 120 μm or less to obtain the desired catalyst M
I got The composition of the obtained catalyst M is CuO: ZnO: A
l 2 O 3 = 61: 32: 7 (weight ratio).
【００５９】II．触媒の活性化方法および反応方法 内径２ｃｍ、高さ２ｍの気泡塔式反応器に、ｎ−ヘキサ
デカン２４ｇ(３１.１ｍｌ）を加え、これにさらに上記
の触媒を所定量加えて懸濁状態にした。次いで、この気
泡塔に水素、一酸化炭素および窒素からなる混合ガス
（Ｈ2：ＣＯ：Ｎ2＝１：１：９、モル比）を約３００ｍ
ｌ／ｍｉｎの流速で流通させつつ、室温より２２０℃ま
で数時間かけて徐々に昇温し、同時に混合ガス中の窒素
の濃度を最終的に０まで徐々に減少させて、さらに２２
０℃で約３時間保持して触媒の活性化を行った。II. Catalyst activation method and reaction method 24 g (31.1 ml) of n-hexadecane was added to a bubble column reactor having an inner diameter of 2 cm and a height of 2 m, and a predetermined amount of the above-mentioned catalyst was further added thereto to bring into a suspended state. . Next, a mixed gas (H 2 : CO: N 2 = 1: 1: 9, molar ratio) consisting of hydrogen, carbon monoxide and nitrogen was added to the bubble column for about 300 m.
While flowing at a flow rate of 1 / min, the temperature was gradually raised from room temperature to 220 ° C. over several hours, and at the same time, the concentration of nitrogen in the mixed gas was gradually reduced to finally zero.
The catalyst was activated by holding at 0 ° C. for about 3 hours.
【００６０】反応は、所定の反応温度、反応圧力で、４
７.５％Ｈ2−４７．５％ＣＯ−５％ＣＯ2−１０ｐｐｍ
Ｈ2Ｓ−１０ｐｐｍＨＣｌの混合ガスを常温、常圧換算
で３３６ｍｌ／ｍｉｎの流速で流通させて行った。The reaction is carried out at a predetermined reaction temperature and a predetermined reaction pressure.
7.5% H 2 -47.5% CO-5% CO 2 -10 ppm
The mixed gas of H 2 S-10 ppm HCl was allowed to flow at normal temperature and a flow rate of 336 ml / min in terms of normal pressure.
【００６１】反応を１００時間継続して行った後に、反
応生成物および未反応物をガスクロマトグラフにより分
析した。After the reaction was continued for 100 hours, reaction products and unreacted products were analyzed by gas chromatography.
【００６２】III．反応条件および実験結果 反応条件および実験結果を表５、６に示す。III. Reaction conditions and experimental results Reaction conditions and experimental results are shown in Tables 5 and 6.
【００６３】[0063]
【表５】 [Table 5]
【００６４】[0064]
【表６】 [Table 6]
【００６５】[0065]
【発明の効果】本発明の触媒を用いることにより、一酸
化炭素と水素からジメチルエーテルを高い収率および空
時収率で得ることができる。By using the catalyst of the present invention, dimethyl ether can be obtained from carbon monoxide and hydrogen with high yield and space-time yield.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０１Ｊ 23/88 Ｃ０７Ｃ 41/01 Ｃ０７Ｃ 41/01 41/09 41/09 43/04 Ｄ 43/04 Ｃ０７Ｂ 61/00 ３００ // Ｃ０７Ｂ 61/00 ３００ Ｂ０１Ｊ 23/84 ３１１Ｚ (72)発明者 鹿田 勉 東京都千代田区丸の内一丁目１番２号 日 本鋼管株式会社内 (72)発明者 大野 陽太郎 東京都千代田区丸の内一丁目１番２号 日 本鋼管株式会社内 Ｆターム(参考） 4G069 AA02 AA08 AA09 BA01A BA01B BA01C BB12C BC09A BC09B BC09C BC10A BC10B BC10C BC31A BC31B BC31C BC51A BC51B BC51C BC58A BC58B BC58C BC59A BC59B BC59C BC60A BC60B BC60C BC62A BC62B BC62C BC64A BC64B BC64C BD05A BD05B BD05C CB33 DA08 EA01Y FA01 FB08 FB09 4H006 AC43 BA05 BA06 BA07 BA09 BA10 BA14 BA16 BA29 BA30 BA32 BA33 BA34 BE20 BE40 GN24 GP30 4H039 CA61 CB20 CD10 CD30 CL35──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) B01J 23/88 C07C 41/01 C07C 41/01 41/09 41/09 43/04 D 43/04 C07B 61 / 00 300 // C07B 61/00 300 B01J 23/84 311Z (72) Inventor Tsutomu Shikata 1-1-2 Marunouchi, Chiyoda-ku, Tokyo Nihon Kokan Co., Ltd. (72) Yotaro Ono Chiyoda-ku, Tokyo 1-2-2 Marunouchi Nihon Kokan Co., Ltd. F-term (reference) 4G069 AA02 AA08 AA09 BA01A BA01B BA01C BB12C BC09A BC09B BC09C BC10A BC10B BC10C BC31A BC31B BC31C BC51A BC51B BC51C BC58A BC58BBC60BBC BCBC BCBC BC64A BC64B BC64C BD05A BD05B BD05C CB33 DA08 EA01Y FA01 FB08 FB09 4H006 AC43 BA05 BA06 BA07 BA09 BA10 BA14 BA16 BA29 BA30 BA32 BA33 BA3 4 BE20 BE40 GN24 GP30 4H039 CA61 CB20 CD10 CD30 CL35
Claims (4)
クロム、レニウム、ジルコニウム、マンガン、マグネシ
ウム、硅素、モリブデン、タングステンおよびカルシウ
ムから選択された１種または２種以上の金属または化合
物を組み合わせてなるジメチルエーテル製造用触媒1. A methanol synthesis catalyst, wherein
Catalyst for producing dimethyl ether comprising one or more metals or compounds selected from chromium, rhenium, zirconium, manganese, magnesium, silicon, molybdenum, tungsten and calcium
ニウムから選択された１種または２種以上の金属または
化合物である請求項１記載のジメチルエーテル製造用触
媒2. The catalyst for producing dimethyl ether according to claim 1, wherein the co-catalyst is one or more metals or compounds selected from chromium, rhenium and zirconium.
硅素から選択された１種または２種以上の金属または化
合物である請求項１記載のジメチルエーテル製造用触媒3. A catalyst for producing dimethyl ether according to claim 1, wherein the promoter is one or more metals or compounds selected from manganese, magnesium and silicon.
びカルシウムから選択された１種または２種以上の金属
または化合物である請求項１記載のジメチルエーテル製
造用触媒4. A catalyst for producing dimethyl ether according to claim 1, wherein the promoter is one or more metals or compounds selected from molybdenum, tungsten and calcium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36901599A JP2001179104A (en) | 1999-12-27 | 1999-12-27 | Catalyst for producing dimethyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36901599A JP2001179104A (en) | 1999-12-27 | 1999-12-27 | Catalyst for producing dimethyl ether |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001179104A true JP2001179104A (en) | 2001-07-03 |
Family
ID=18493343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP36901599A Withdrawn JP2001179104A (en) | 1999-12-27 | 1999-12-27 | Catalyst for producing dimethyl ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001179104A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006298782A (en) * | 2005-04-15 | 2006-11-02 | National Univ Corp Shizuoka Univ | Method for producing dimethyl ether using synthesis gas by dimethyl ether synthesis catalyst |
| JP2008132467A (en) * | 2006-11-28 | 2008-06-12 | Korea Gas Corp | Method of producing catalyst used for synthesizing dimethyl ether from synthesis gas containing carbon dioxide |
| CN101934232A (en) * | 2010-09-13 | 2011-01-05 | 浙江大学 | Method for preparing catalyst for directly synthesizing dimethyl ether by biomass gasifiable synthesis gas |
-
1999
- 1999-12-27 JP JP36901599A patent/JP2001179104A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006298782A (en) * | 2005-04-15 | 2006-11-02 | National Univ Corp Shizuoka Univ | Method for producing dimethyl ether using synthesis gas by dimethyl ether synthesis catalyst |
| JP2008132467A (en) * | 2006-11-28 | 2008-06-12 | Korea Gas Corp | Method of producing catalyst used for synthesizing dimethyl ether from synthesis gas containing carbon dioxide |
| CN101934232A (en) * | 2010-09-13 | 2011-01-05 | 浙江大学 | Method for preparing catalyst for directly synthesizing dimethyl ether by biomass gasifiable synthesis gas |
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