GB2092172A - A process for the preparation of oxygen-containing organic compounds and paraffinic hydrocarbons - Google Patents
A process for the preparation of oxygen-containing organic compounds and paraffinic hydrocarbons Download PDFInfo
- Publication number
- GB2092172A GB2092172A GB8137057A GB8137057A GB2092172A GB 2092172 A GB2092172 A GB 2092172A GB 8137057 A GB8137057 A GB 8137057A GB 8137057 A GB8137057 A GB 8137057A GB 2092172 A GB2092172 A GB 2092172A
- Authority
- GB
- United Kingdom
- Prior art keywords
- catalyst
- mixture
- oxygen
- organic compounds
- conversion
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 79
- 150000002894 organic compounds Chemical class 0.000 title claims description 49
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims description 47
- 229910052760 oxygen Inorganic materials 0.000 title claims description 47
- 239000001301 oxygen Substances 0.000 title claims description 47
- 229930195733 hydrocarbon Natural products 0.000 title claims description 34
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 34
- 238000002360 preparation method Methods 0.000 title claims description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 101
- 239000000203 mixture Substances 0.000 claims description 97
- 238000006243 chemical reaction Methods 0.000 claims description 69
- 239000007795 chemical reaction product Substances 0.000 claims description 36
- 229910001868 water Inorganic materials 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 31
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 22
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 22
- 230000003197 catalytic effect Effects 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 230000000694 effects Effects 0.000 claims description 18
- 150000001336 alkenes Chemical class 0.000 claims description 15
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 13
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 230000001588 bifunctional effect Effects 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052914 metal silicate Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 4
- 238000002474 experimental method Methods 0.000 description 40
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 38
- 229910002092 carbon dioxide Inorganic materials 0.000 description 20
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 14
- 239000001569 carbon dioxide Substances 0.000 description 14
- 150000004760 silicates Chemical class 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical group O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 10
- 239000010949 copper Substances 0.000 description 8
- 235000014692 zinc oxide Nutrition 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000004064 recycling Methods 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 7
- 229910052681 coesite Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- -1 tetrapropylammonium compound Chemical class 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 229910000423 chromium oxide Inorganic materials 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 239000006069 physical mixture Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 210000002196 fr. b Anatomy 0.000 description 2
- 210000003918 fraction a Anatomy 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 150000002892 organic cations Chemical group 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KJFVTCXFSVKLHU-UHFFFAOYSA-N [Cr].[Rh] Chemical compound [Cr].[Rh] KJFVTCXFSVKLHU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/0445—Preparation; Activation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0455—Reaction conditions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0485—Set-up of reactors or accessories; Multi-step processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1512—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by reaction conditions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/47—Catalytic treatment characterised by the catalyst used containing platinum group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/46—Ruthenium, rhodium, osmium or iridium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/75—Cobalt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/80—Additives
- C10G2300/802—Diluents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/80—Additives
- C10G2300/805—Water
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
Syngas with a H2/CO mol. ratio of at least 0.5 is partly converted in a first stage into oxygenates and the unconverted syngas having as such or after adjustment a H2/CO molar ratio of at least 1.5 is converted in a second stage into paraffins over a (Ni-, Co-, or Ru-Fischer-Tropsch catalyst.
Description
SPECIFICATION
A process for the preparation of oxygen-containing organic compounds and paraffinic hydrocarbons
The invention relates to a process for the preparation of oxygen-containing organic compounds and paraffinic hydrocarbons from a mixture of carbon monoxide and hydrogen.
Oxygen-containing organic compounds such as methanol, ethanol and dimethyl ether are valuable end products, and intermediate products, for instance for the preparation of aromatic hydrocarbons and lower olefins. The said oxygen-containing organic compounds can be prepared by catalytic conversion of mixtures of carbon monoxide and hydrogen with an H2/CO molar ratio bf at least 0.5. A drawback of these reactions is that they are thermodynamically strongly limited, so that a considerable part of the
H2/CO mixture is not converted. According as higher space velocities are used in the processes, lower conversions are obtained. It is true that a higher conversion can be reached by recycling the unconverted HCO mixture, but recycling on a technical scale is an expensive process, which should be avoided if at all possible.Moreover, recycling the unconverted H2/CO mixture entails another serious drawback. As a rule, the reaction product contains in addition to oxygen-containing organic compounds formed and unconverted hydrogen and carbon monoxide a considerable amount of carbon dioxide.
This carbon dioxide has formed by the reaction of water with carbon monoxide according to the known
CO-shift reaction. The water required for the CO-shift reaction may originate from an external source or may have been formed in the preparation of the oxygen-containing organic compounds. Addition of water to the H2/CO mixture in order to make the CO-shift reaction proceed is carried out if the available HCO mixture has too low an H2/CO molar ratio. According to the CO-shift reaction the CO content falls and the H2 content rises, resulting in an increase of the H2/CO molar ratio.The CO-shift reaction can be carried out as an external shift (also designated pre-shift), inwhich the H2/CO mixture to be converted, together with added water, is first conducted over a separate CO-shift catalyst, before being contacted with the catalyst which has activity for the conversion of an H2/CO mixture into oxygen-containing organic compounds. As the latter catalysts generally have CO-shift activity as well, an external shift can be omitted in a number of cases and the desired increase of the H2/CO molar ratio of the feed can be achieved simply by conducting this feed together with added water over the catalyst which has activity for the conversion of an HCO mixture into oxygen-containing organic compounds.It is also the COshift activity of the latter catalyst which is responsible for the formation of carbon dioxide, if water is formed in the preparation of the oxygen-containing organic compounds. This situation presents itself if ether is formed in the preparation of oxygen-containing organic compounds. To avoid the building up of carbon dioxide in the process, the carbon dioxide should be removed from the recycle stream. Removal of carbon dioxide from recycle streams on a technical scale is, just as the recycling itself, an expensive process.
The applicant has carried out an investigation to find out to what extent it is possible in the preparation of oxygen-containing organic compounds to realize by catalytic conversion of an H2/CO mixture a high conversion of the H2/CO mixture into valuable organic compounds, without the necessity of recycling the unconverted H2/CO mixture and removing the carbon dioxide. This possibility was indeed found to exist.To this end carbon monoxide and hydrogen present in the reaction product obtained in the catalytic conversion of the H2/CO mixture into oxygen-containing organic compounds, if desired together with other components of this reaction product, should be contacted with a monofunctional catalyst containing one or more metal components with catalytic activity for the conversion of an HCO mixture into paraffinic hydrocarbons, which metal components have been chosen from the group formed by cobalt, nickel and ruthenium.If the H2/CO mixture that is available as the feed for the preparation of the paraffinic hydrocarbons has an H2/CO molar ratio lower than 1.5, water should be added to this feed in an amount sufficient to bring the reaction with CO the H2/CO molar ratio at a value of at least 1.5, and use should be made of a bifunctional catalyst combination which, in addition to containing the metal components with catalytic activity for the conversion of an H2/CO mixture into paraffinic hydrocarbons, also contains one or more metal components with CO-shift activity. if the conversion of the H2/CO mixture is carried out in this way, it is possible, using a high space velocity, to reach a very high conversion of the H2/CO mixture intq oxygen-containing organic compounds and paraffinic hydrocarbons.The paraffinic hydrocarbons obtained in the process are valuable as end product and as starting material for carrying out catalytic hydrocarbon conversion processes such as aromatization, isomerization, cracking and hydro-cracking.
The present patent application therefore relates to a process for the preparation of oxygencontaining organic compounds and paraffinic hydrocarbons, in which process a mixture of carbon monoxide and hydrogen with an H2/CO molar ratio of at least 0.5 is contacted in a first step with a catalyst containing one or more metal components with catalytic activity for the conversion of an H2/CO mixture into oxygen-containing organic compounds and in which process carbon monoxide and hydrogen present in the reaction product from the first step, if desired together with other components of this reaction product, are contacted in a second step with a monofunctional catalyst as defined above, on the understanding that if the feed for the second step has an H2/CO molar ratio lower than 1.5, water is added to this feed in an amount sufficient to bring, by reaction with CO, the H2/CO molar
ratio at a value of at least 1.5, and that in the second step use is made of a bifunctional catalyst
combination as defined above.
The process according to the invention is highly flexible as regards the ratio of the amounts of
oxygen-containing organic compounds to paraffinic hydrocarbons which can be prepared. If it is
intended to effect the highest possible yield of oxygen-containing organic compounds, the
circumstances under which the first step of the process is carried out can be chosen such that this wish
is satisfied, and the unconverted H2/CO mixture can be converted in the second step into paraffinic
hydrocarbons. If it is intended to effect a high yield of paraffinic hydrocarbons, the circumstances under
which the first step of the process is carried out can be chosen such that the reaction product of the first
step contains a sufficient amount of unconverted HdCO mixture to guarantee in the second step the
desired high yield of paraffinic hydrocarbons.
In the process according to the invention use is made of an H2/CO mixture with an H2/CO molar
ratio of at least 0.5 as the feed for the first step. Such H2/CO mixtures can very suitably be prepared by
steam gasification of a carbon-containing material such as coal. The steam gasification is preferably
carried out at a temperature of 900-1 5000C and a pressure of 10--100 bar. Preferred H2/CO
mixtures are those withan HCO molar ratio of 0.75-2.5. If the H2CO mixture there is available as the
feed for the first step has an H2/CO molar ratio lower than 0.5, water should be added to the H2/CO
mixture in an amount sufficient to bring, by reaction with CO, the H2/CO molar ratio at a value of at least
0.5, and the mixture should be contacted with a catalyst having CO-shift activity.Adding water to the H2/CO mixture and contacting the mixture with a catalyst having CO-shift activity is also possible in
those cases where the HJCO mixture already has an H2/CO molar ratio of at least 0.5, but where it is
desirable to use an HCO mixture with a higher H2/CO molar ratio. The increase of the H2/CO molar ratio
can be carried out as a so-called external CO-shift, in which the water-containing H2/CO mixture is
contacted, in a separate step previous to the first step of the process according to the invention, with a
separate catalyst with CO-shift activity.As the catalysts used in the first step of the process according
to the invention as.a rule have, in addition to their activity for the conversion of an H2/CO mixture into
oxygen-containing organic compounds, CO-shift activity, the increase of the H2/CO molar ratio may also
be carried out as an internal CO-shift, in which process the water-containing H2/CO mixture is contacted
directly with the catalyst in the first step of the process according to the invention. If in the process use
is made of an external CO-shift, it is preferred not to apply carbon dioxide removal to the reaction
product.In the first step of the process according to the invention an HdCO mixture which may contain
water and/or carbon dioxide, is contacted with a catalyst containing one or more metal components with catalytic activity for the conversion of an HCO mixture into oxygen-containing organic
compounds. It is preferred to use in the first step a catalyst capable of converting an H2/CO mixture into
substantially methanol or dimethyl ether. Examples of suitable catalysts capable of converting an H2/CO
mixture into substantially methanol are catalysts containing: (a) zinc oxide and chromium oxide,
(b) copper, zinc oxide and chromium oxide,
(c) copper, zinc oxide and aluminium oxide, and
(d) copper, zinc oxide, and oxides of rare earths.
Examples of suitable catalysts having the capability of converting an H2/CO mixture into
substantially dimethyl ether are catalysts containing one of the methanol synthesis functions under (a)-(d) and, in addition, an acid function, such as a physical mixture of gamma alumina and a
composition containing copper, zinc oxide and chromium oxide. The first step of the process according
to the invention is preferably carried out at a temperature of 1 75-3500C and a pressure of 30-300 bar and in particular at a temperature of 225-3250C and a pressure of 50-1 50 bar.
In the process according to the invention carbon monoxide and hydrogen present in the reaction
product from the first step, if desired together with other components of this reaction product, are used
as the feed for the second step. If necessary, the complete reaction product from the first step may be
used as the feed for the second step. In the second step of the process according to the invention as
much as possible of the CO present in the feed for the second step is to be converted into paraffinic
hydrocarbons over a monofunctional catalyst containing one or more metal components with catalytic
activity for the conversion of an H2/CO mixture into paraffinic hydrocarbons, which metal components
have been chosen from the group formed by cobalt, nickel and ruthenium.To this end the H2/CO molar
ratio in the feed for the second step should be at least 1.5 and preferably 1.75-2.25. If use is made of
an HCO mixture with a higher H2/CO molar ratio as the feed for the first step, the first step of the
process according to the invention can yield a reaction product in which an Hz/CO mixture is present
which has an HCO molar ratio of at least 1.5 and which is as such suitable for conversion over the said
catalyst in the second step. An attractive way of ensuring that in the process according to the invention
the reaction product from the first step has an H2/CO molar ratio of at least 1.5, is adding water to the feed for the first step. Thanks to the CO-shift activity of the catalyst in the first step this water reacts with CO from the feed to form an H2/CO2 mixture. Adding water to the feed for the first step may be
employed in the process according to the invention both in cases in which, without water addition, a reaction product would have been obtained from the first step with an H2/CO molar ratio lower than 1.5, and in cases in which, also without water addition, a reaction product would have been obtained already from the first step with an HCO molar ratio of at least 1.5, but where it is desirable that the feed contacted with the catalyst in the second step should have a higher H2/CO molar ratio.
If in the process according to the invention, whether or not after water addition to the feed for the first step, a reaction product is obtained from the first step with an H2/CO molar ratio lower than 1.5, water should be added to the feed for the second step in an amount sufficient to bring, by reaction with
CO, the H2/CO molar ratio at a value of at least 1.5, and in the second step use should be made of a bifunctional catalyst combination which, in addition to the metal components with catalytic activity for the conversion of an HCO mixture into paraffinic hydrocarbons, also contains one or more metal components with CO-shift activity.The bifunctional catalyst combinations that may be used in the second step of the process according to the invention are preferably composed of two separate catalysts, which for convenience will be designated catalyst A and catalyst B. Catalyst A is the one containing the metal components with catalytic activity for the conversion of an H2/CO mixture into paraffinic hydrocarbons and which metal components have been chosen from the group formed by cobalt, nickel and ruthenium. Catalyst B is the one containing the metal components with CO-shift activity. Both if a monofunctional catalyst is used and if a bifunctional catalyst combination is used in the second step of the process according to the invention, it is preferred to use as catalyst A a cobalt catalyst such as cobalt catalyst prepared by impregnation.Very suitable for the present purpose are catalysts that contain 1 0-40 pbw cobalt and 0.25-5 pbw zirconium, titanium or chromium per 100 pbw silica and which have been prepared by impregnating a silica carrier with one or more aqueous solutions of salts of cobalt and zirconium, titanium or chromium, followed by drying the composition, calcining at 350-7000C and reducing at 200--3 50"C. Suitable B-catalysts are the usual CO-shift catalysts. In the bifuntional catalyst combinations the catalysts A and B may be present as physical mixture. When the second step of the process is carried out using a fixed catalyst bed, this bed is preferably built up of two or more alternating layers of particles of, successively, catalyst B and catalyst
A.Water addition to the feed for the second step together with the use of a bifunctional catalyst combination in the second step can be used in the process according to the invention both in cases in which the reaction product from the first step has an HCO molar ratio lower than 1.5, and in cases in which the reaction product from the first step already has an H2/CO molar ratio of at least 1.5, but where it is desired that the feed contacted in the second step with catalyst A should have a higher H2/CO molar ratio. The second step of the process according to the invention is preferably carried out at a temperature of 125-3000C and a pressure of 1-150 bar and in particular at a temperature of 1 75-2750C and a pressure of 5-100 bar.
The oxygen-containing organic compounds prepared in the two-step process can very suitably be used as starting material for the catalytic conversion into lower olefins and/or aromatic hydrocarbons.
This conversion is preferably carried out by contacting the oxygen-containing organic compounds at a temperature of 300--6000C, a pressure of 1-50 bar and a space velocity of 0.2-1 I < g 5 l < g kg kg1 h1 with a crystalline metal silicate as the catalyst. It is preferred to use in this conversion pressures of 1-10 bar.
Very suitable catalysts for the con
Very suitable catalysts for the conversion of the oxygen-containing organic compounds are crystalline metal silicates characterized in that after one hour's calcining in air at 5000C they have the following properties:
(a) thermally stable up to a temperature of at least 6000C
(b) an X-ray powder diffraction pattern showing as the strongest lines the four lines given in
Table A.
TABLE A
D(A) Relative intensity
11.1 +0.2 VS
10.0 +0.2 VS
3.84 + 0.07 S
3.72 + 0.06 S
wherein the letters used have the following meanings: VS = very strong; S = strong, and
(c) in the formula which represents the composition of the silicate expressed in moles of the
oxides, and in which in addition to oxides of hydrogen, alkali metal and silicon, one or more oxides of a
trivalent metal A chosen from the group formed by aluminium, iron, gallium, rhodium chromium and
scandium are present, the SiO2/A2O3 molar ratio (further designated M in this patent application ) is
more than 10. These crystalline metal silicates will in this patent application further be designated: "silicates of type 1".The expression "thermally stable up to a temperature of at least toy", as used in this patent application, means that when the silicate is heated up to a temperature of t C, the X-ray powder diffraction pattern of the silicate does not substantially change. The silicates of type 1 can be prepared starting from an aqueous mixture containing the following compounds: one or more compounds of an alkali metal (M), one or more compounds containing a quaternary organic cation (R), one or more silicon compounds and one or more compounds in which a trivalent metal A chosen from the group formed by aluminium, iron, gallium, rhodium, chromium and scandium is present.The preparation of the silicates of type 1 is effected by maintaining the mixture at elevated temperature until the silicate has formed, separating it from the mother liquor and calcining it. In the aqueous mixture from which the silicates of type 1 are prepared the various compounds should be present in the following ratios, expressed in moles of the oxides: MzO: SiOz = 0.01-0.35, R20 :SiO2 = 0.01--0.4, SiO2:A2O3 > and
H2O : SiO2 =5-65.
Variation of the quaternary organic cation incorporated into the aqueous mixture yields silicates of type 1 which differs at significant points as regards their complete X-ray powder diffraction pattern.
The complete X-ray powder diffraction pattern of an iron silicate and of an aluminium silicate both prepared using a tetrapropylammonium compound is given in Table B.
TABLE B
Relative Relative
d(A) intensity d(A) intensity
11.1 100 3.84(D) 57 10.0(D) 70 3.70 (D) 31
8.93 1 3.63 16
7.99 1 3.47 < 1
7.42 2 3.43 5
6.68 7 3.34 2
6.35 11 3.30 5
5.97 17 3.25 1
5.70 7 3.05 8
5.56 10 2.98 11
5.35 2 2.96 3
4.98 (D) 6 2.86 2
4.60 4 2.73 2
4.35 5 2.60 2
4.25 7 2.48 3
4.07 2 2.40 2
4.00 4
(D) = doublet
The complete X-ray powder diffraction pattern of an iron silicate and of an aluminium silicate prepared using a tetrabutylammonium compound or a tetrabutylphosphonium compound is given in
Table C.
TABLE C
Relative Relative
d(A) intensity d(A) intensity
11.1 100 3.84 65
10.0 70 3.70 20
7.42 2 3.63 < 2
6.68 5 3.47 2
6.35 2 3.34 1
5.97 1 6 3.30 4
5.70 < 1 3.05 5
5.56 8 2.98 9
4.98 6 2.86 1
4.60 3 2.60 2
4.35 5 2.48 3
4.25 < 1 2.40 2
4.00 < 1
When silicates of type 1 are used as catalysts for the conversion of the oxygen-containing organic
compounds, preferance is given to silicates containing only one of the above mentioned trivalent metals
and in particular to silicates containing as trivalent metal aluminium, iron or gallium.
Other very suitable catalysts for the conversion of the oxygen-containing organic compounds are
the following crystalline aluminosilicates: faujasite, zeolite Y, zeolite X, mordenite, erionite, offretite,
zeolite w, ferririte, chabasite and zeolite ZSM-34. These crystalline alluminosilicates will in this patent
application further designated: "silicates of type 2".
Other very suitable catalysts for the conversion of the oxygen-containing organic compounds are
silicates of type 1 or type 2 upon which one or more catalytically active metals have been deposited by
impregnation or ion exchange. These crystalline silicates will in this patent application further be
designated: "silicates of type 3". Preference is given to silicates of type 3 upon which magnesium or
manganese has been deposited.
If it is intended to convert the oxygen-containing oganic compounds into substantially aromatic
hydrocarbons, the conversion is preferably carried out at a temperature of 300-4000C and a space
velocity of 0.5-5 kg kg~' h-' and the preferred catalyst is a silicate of type 1, whose m is less than 200.
- If it is intended to convert the oxygen-containing organic compounds into substantially lower olefins, the conversion is preferably carried out either at a temperature of 400--600"C, a space velocity of 1-10 kg kg~ h- and using as the catalyst a silicate of type 1, whose m is more than 200, or at a temperature of 300--5000C, a pressure of 1-5 bar, a space velocity of 0.2-2 kg kg~' h-' and
using as the catalyst a silicate of type 2 or type 3.
For the catalytic conversion of oxygen-containing organic compounds into lower olefins and/or
aromatic hydrocarbons it is preferred to start from a feed of dimethyl ether or a mixture of oxygen
containing organic compounds consisting substantially of dimethyl either. In addition to C4 olefins and
C5+ hydrocarbons, C4 paraffins are formed in the catalytic conversion of oxygen-containing organic
compounds. In the conversion it is desirable to suppress the formation of C4 paraffins as much as
possible. An investigation by the Applicant has shown that in the catalytic conversion of the oxygencontaining organic compounds the selectivity to CJ paraffins is lower if the oxygen-containing organic
compounds are not used as such as the feed, but diluted.Suitable diluents are, inter alia, water, carbon
monoxide, carbon dioxide, hydrogen and C4 paraffins.
The combination of the two-step process according to the invention with a process for the
catalytic conversion of oxygen-containing organic compounds into lower olefins and/or aromatic
hydrocarbons is very attractive, because the reaction product from the first step of the process
according to the invention contains at least a number of the above-mentioned diluents, viz.:
unconverted hydrogen and carbon monoxide and further water and/or dioxide and/or C4- paraffins.
The combination of the two-step process according to the invention with a process for the
catalytic conversion of oxygen-containing organic compounds into lower olefins and/or aromatic
hydrocarbons may be carried in three ways.
According to the first embodiment the reaction product from the first step consisting of oxygen
containing organic compounds, hydrogen, carbon monoxide and a by-product containing carbon dioxide
and/or water and/or C4 paraffins is separated into at least two fractions of which one contains all the
oxygen-containing organic compounds and at least 50%v of the by-product, and one contains all of the
hydrogen and carbon monoxide. The latter fraction may contain the rest of the by-product. The fraction
containing the oxygen-containing organic compounds is catalytically converted into lower olefins and/or
aromatic hydrocarbons and the fraction containing hydrogen and carbon monoxide is catalytically
converted in the previously mentioned second step of the process according to the invention.In this
embodiment the reaction product from the first step is separated preferably into two fractions, of which
one contains all the oxygen-containing organic compounds and all of the by-product, and the other
contains all of the hydrogen and carbon monoxide,
According to the second embodiment, at least all of the hydrogen, carbon monoxide and oxygen
containing organic compounds of the reaction product from the first step are together used as the feed
for the second step of the process according to the invention. By preference, the complete reaction
product from the first step is used as the feed for the second step.The reaction product of the second
step, which consists substantially of oxygen-containing organic compounds formed in the first step and
of paraffinic hydrocarbons formed in the second step, and which contains in addition, inter alia,
unconverted hydrogen and carbon monoxide, water and possible carbon dioxide, may be used as such
as the feed for the additional process step in which catalytic conversion of the oxygen-containing organic compounds into lower olefins and/or aromatic hydrocarbons takes place. In view of the - possibility that part of the C5+ paraffinic hydrocarbons formed in the second step is converted in the
additional process step into aromatic hydrocarbons, which may be undesirable, it is preferred to
separate the C5+ hydrocarbons from the reaction product of the second step before using this reaction
product as the feed for the additional process step.
According to the third embodiment, at least all of the hydrogen, carbon monoxide and oxygen containing organic compounds of the reaction product from the first step are together contacted in the
additional process step with the catalyst converting the oxygen-containing organic compounds into lower olefins and/or aromatic hydrocarbons. By preference, the complete reaction product from the first -step is used as the feed for the additional process step. Of the reaction product from the additional
process step, which contains hydrogen, carbon monoxide, C4- olefins, a C5+ fraction rich in aromatics, C4- paraffins, water and possibly carbon dioxide originating from the first step, at least hydrogen and
carbon monoxide should be used as the feed for the second step of the process according to the
invention.If desired, the complete reaction product from the additional process step may be used as the
feed for the second step of the process according to the invention. It is preferred to separate the C4
olefins from the reaction product of the additional process step before using this reaction product as the
feed for the second step of the process according to the invention.
The Applicant has found that if in the second step of the process use is made of the previously
mentioned cobalt-impregnation catalyst promoted with zirconium, titanium or chromium, a mixture of
heavy paraffinic hydrocarbons is obtained, which is pre-eminently suitable for high-yield conversion
into middle distillate by hydrocracking. The hydrocracking operation is characterized by a very low gas
production and hydrogen consumption.
The invention will now be explained with reference to the following example.
EXAMPLE
In the investigation use was made of the following catalysts.
Catalyst 1
A Cu/ZnO/Cr203 catalyst with a Cu/Zn/Cr atomic ratio of 5:3:2.
Catalyst 2 p-Al203 calcined at 8000 C.
Catalyst 3
A Cu/ZnO/Al203 catalyst with a Cu/Zn atomic ratio of 0.55.
Catalyst 4
A Co/Zr/SiO2 catalyst that contained 25 pbw cobalt and 0.9 pbw zirconium per 100 pbw silica and which had been prepared by impregnating a silica carrier with an aqueous solution containing a cobalt and a zirconium salt, followed by drying the composition, calcining it at 5000C and reducing it at 2500C.
Catalyst 5
A crystalline aluminium silicate which, after one hour's calcining in air at 5000 C, had the following properties:
(a) thermally stable up to a temperature of at least 8000 C, (b) an X-ray powder diffraction pattern substantially as shown in Table B, and
(c) in the formula representing the composition of the silicate, expressed in moles of the oxides, the SiO2/AI203 molar ratio was higher than 1 0.
CATALYST MIXTURE I
A physical mixture of catalyst 1 and catalyst 2 in a weight ratio of 1:1.
CATALYST MIXTURE II
A layer of catalyst 3 and a layer of catalyst 4 in a volume ratio of 1:2.
The catalysts 1 and 4 and the catalyst mixtures I and II were tested for the preparation of methanol or dimethyl ether in one step and for the preparation of paraffinic hydrocarbons and methanol or dimethyl ether in two steps. The test was carried out in one or two 50-ml reactors containing a fixed catalyst bed. Seven experiments were carried out. The experiments 1 , 2 and 4 were carried out in one step; the other experiments were carried out in two steps. In all the experiments a pressure of 60 bar was used in the first step. In all the experiments carried out in two steps the complete reaction product from the first step was used as the feed for the second step.The feed for the first step of experiment 7 has been obtained from an HdCO starting mixture with an H2/CO molar ratio of 0.5.
To this HCO mixture so much water was added that after performing an external CO-shift over
catalyst 3 an HJCO molar ratio of 1.0 was reached. The CO2 formed in the CO-shift ( 1 4.3%v based on the gas mixture) was not separated off. The C02-containing H2/CO mixture with an H2/CO molar ratio of
1.0 was used as the feed for the first step of experiment 7.
The results of the experiments 1-7 are listed in Table D.
In experiment 8 a three-step process was simulated for the conversion of an H2/CO mixture into aromatic hydrocarbons, lower olefins and paraffinic hydrocarbons, using the composition of the product from the first step of experiment 7 listed in Table D.
EXPERIMENT 8
The product from the first step of experiment 7 can be separated into two fractions, viz. a fraction
A consisting of hydrogen and carbon monoxide with an H2/CO molar ratio of 0.88 and a fraction B consisting of dimethyl ether, carbon dioxide and water in a volume ratio of 24,1:70.5:5.4. In experiment 8 the two fractions were converted separately.
Fraction A was conducted over catalyst mixture il at a temperature of 2400 C, a pressure of 36 bar, a space velocity of 1000 N1.1-1 h~1 and with addition of 0.171 water per 1 catalyst per hour. The conversion of the HCO mixture was 87%v. When the conversion of the H2/CO mixture in the first step of experiment 7 is taken into account, this means a total conversion of the H2/C0 mixture of 93%v.
Fraction B was conducted over catalyst 5 at a temperature of 5000 C, and a pressure of 1 bar and a space velocity of 1 g dimethyl ether/g catalyst/h. The conversion of dimethyl ether was 100%. The hydrocarbon mixture formed had the following composition:
30%w of a CJ fraction rich in aromatics,
60%w of a CJ olefin fraction,
1 0%w of a C4 paraffin fraction.
Of the experiments 1-8 described above, only two-step experiments 3 and 5-7 and the three-step experiment 8 are experiments according to the invention. The one-step experiments 1, 2 and 4 are outside the scope of the invention. They have been included in the patent application for comparison.
The following remarks can be made with regard to the results listed in Table D.
TABLE D
Experiment No. 1 2 3 4 5 6 7
Catalyst in the first step, No. 1 1 1 1 I I Amount of catalyst in the first step, ml 10 10 2.5 10 5 6 5
Temperature in the first step, C 250 250 250 300 300 300 300
Space velocity of the H2/CO mixture 4000 1000 1000 1000 1000 1000 1000
based on the total catalyst volume (1st+2nd step), 1,1-1.h-1
H2/CO molar ratio in the feed for the 2.0 2.0 2.0 1.0 1.0 1.5 1.0
first step
Amount of CO2 in the feed for the 4 4 4 - - - 14.3
first step, %v
Conversion of the H2/CO mixture in the 41 56 41 66 48 40 46
first step, %v
Composition of the product from the
first step, %v
CO 27.0 23.4 27.0 30.4 38.2 27.3 33.4
H2 50.0 42.2 50.0 30.4 38.2 54.5 29.3
CH3OH 17.6 28.1 17.6 - - -
CH30CH3 - - - 19.6 11.8 9.1 9.0
CO2 4.0 4.7 4.0 19.6 11.8 9.1 26.3 1.4 1.6 1.4 - - - 2.0
H2/CO molar ratio of the product 1.85 1.80 1.85 1.0 1.0 2.0 0.88
from the first step
Catalyst in the second step, No. - - 4 - # 4 11
Amount of catalyst in the second step, ml - - 7.5 - 5 4 5
Amount of water added to the feed for the - - - - 140 - 170
second step, ml (1 cat. in the
second step)-1.h-1
Temperature in the second step, C - - 230 - 240 240 240
Pressure in the second step, bar - - 40 - 45 40 55
Conversion of the H2/CO - - 90 - 86 85 84
mixture of the second step, %v
TABLE D-continued Experiment No. 1 2 3 4 5 6 7
Composition of the paraffinic hydrocarbon
fraction of the product from the
second step, %w C4 - 13 11.5 - 13 12.5 12 C5-C12 - - 30 - 33 33 32 C13-C19 - - 23 - 23 22.5 23 C20 -. - 35.5 - 31 32 33
Total conversion of the HCO mixture(1st+2ndstep),%v 41 56 94 66 93 91 91
The experiments 1 and 2 show the one-step preparation of methanol. In experiment 1 a low conversion of the H2/CO mixture is reached (41 %v). In comparison with experiment 1 the space velocity in experiment 2 has been reduoed by a factor of 4.The result of experiment 2 shows that this causes an increase in the conversion of the H2/CO mixture (from 41 to 56%v), but the conversion achieved is still much too low for using the process on a technical scale without recycling the unconverted H2/CO mixture.
Experiment 3 demonstrates the preparation of methanol and paraffinic hydrocarbons using the two-step process according to the invention. With use of the same space velocity as in experiment 2 (now based on the total catalyst volume in the first step and the second step) a conversion of the H2/CO
mixture of 94%v is reached now.
Experiment 4 shows the one-step preparation of dimethyl ether. In comparison with experiment 2 (one-step preparation of methanol) the conversion of the H2/CO mixture is higher now (66 instead of 56%v), but the conversion achieved is still far too low for using the process on a technical scale without recycling the unconverted HdCO mixture.
Experiments 5-7 show the preparation of dimethyl ether and paraffinic hydrocarbons using the two-step process according to the invention. In comparison with experiment 4, in experiment 5 a conversion of the HCO mixture is reached of 93%v, using the same total amount of catalyst.
Experiments 5 and 6 demonstrate the two-step process according to the invention, starting from H2/CO mixtures with different HCO molar ratios. In view of the low HCO molar ratio of the product from the first step of experiment 5 (1.0), water is added to the feed for the second step in this experiment.
Experiment 7 is a variant of experiment 5, in which the HCO mixture with H2/CO molar ratio 1.0, which is used as the feed for the first step, has been obtained by applying an external CO-shift to an H2/CO mixture with an H2/CO molar ratio of 0.5 and in which the CO2 formed is not removed. Just as in experiment 5, in experiment 7 water is added to the feed for the second step in view of the low H2/CO molar ratio of the product from the first step (0.88).
Claims (10)
1. A process for the preparation of oxygen-containing organic compounds and paraffinic hydrocarbons, characterized in that a mixture of carbon monoxide and hydrogen with an H2/CO molar ratio of at least 0.5 is contacted in a first step with a catalyst containing one or more metal components with catalytic activity for the conversion of an H2/CO mixture into oxygen-containing organic compounds and in that carbon monoxide and hydrogen present in the reaction product from the first step, if desired together with other components of this reaction product, are contacted in a second step with a monofunctional catalyst containing one or more metal components with catalytic activity for the conversion of an HCO mixture into paraffinic hydrocarbons, which metal components have been chosen from the group formed by cobalt, nickel and ruthenium, on the understanding that if the feed for the second step has an HCO molar ratio lower than 1.5, water is added to this feed in an amount sufficient to bring, by reaction with CO, the H2/CO molar ratio at a value of at least 1.5 and that in the second step use is made of a bifunctional catalyst combination which, in addition to the metal components with catalytic activity for the conversion of an H2/CO mixture into paraffinic hydrocarbons, also contains one or more metal components with CO-shift activity.
2. A process according to claim 1, characterized in that in the first step of the process use is made of a catalyst capable of converting an H2/CO mixture into substantially methanol or dimethyl ether.
3. A process according to claim 1 or 2 characterized in that the first step of the process is carried out at a temperature of 225-3250C and a pressure of 50-1 50 bar.
4. A process according to any of claims 1-3, characterized in that the catalyst with activity for the conversion of an HJCO mixture into paraffinic hydrocarbons used in the second step of the process is a catalyst containing 10 40 pbw cobalt and 0.25-5 pbw zirconium, titanium or chromium per 100 pbw silica and has been prepared by impregnating a silica carrier with one or more aqueous solutions of salts of cobalt and zirconium, titanium or chromium followed by drying the composition, calcining at 350-7000C and reducing at 200-3500C.
5. A process according to any one of claims 1 1--4, characterized in that water is added to the feed for the second step and in that the second step is carried out using a fixed catalyst bed built up of two or more alternating layers of particles of successively the CO-shift catalyst and the catalyst having activity for the conversion of an HJCO mixture into paraffinic hydrocarbons.
6. A process according td any one of claims 1-5, characterized in that the second step is carried out at a temperature of 1 75-2750C and a pressure of 5-100 bar.
7. A process according to any one of claims 1-6, characterized in that the oxygen-containing organic compounds formed in the first step of the process are catalytically converted in an additional process step in the presence of a diluent into lower olefins and/or aromatic hydrocarbons.
8. A process according to claim 7, characterized in that the additional process step is carried out at a temperature of 300-6000C, a pressure of 1-50 bar, a space velocity of 0.2-15 kg kg-1 - h-' and using a crystalline metal silicate as the catalyst.
9. A process according to claim 7 or 8, characterized in that for the preparation of substantially aromatic hydrocarbons from the oxygen-containing organic compounds the catalyst in the additional process step is a silicate of type 1, as defined hereinbefore, of which silicate m is less than 200.
10. A process according to claim 7 or 8, characterized in that for the preparation of substantially low olefins from the oxygen-containing organic compounds the catalyst in the additional process step is a silicate of type 1, as defined hereinbefore, of which silicate m is higher than 200, and in that the additional process step is carried out at a temperature of 400-6000C and a space velocity of 1-10 kg.kg-1.h-1.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8006751A NL8006751A (en) | 1980-12-12 | 1980-12-12 | PROCESS FOR PREPARING OXYGEN-BASED ORGANIC COMPOUNDS AND PARAFFINIC HYDROCARBONS. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2092172A true GB2092172A (en) | 1982-08-11 |
| GB2092172B GB2092172B (en) | 1984-01-18 |
Family
ID=19836321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8137057A Expired GB2092172B (en) | 1980-12-12 | 1981-12-09 | Compounds and paraffinic hydrocarbons a process for the preparation of oxygencontaining organic |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPS57131728A (en) |
| AU (1) | AU542036B2 (en) |
| BE (1) | BE891195A (en) |
| BR (1) | BR8107995A (en) |
| CA (1) | CA1260019A (en) |
| DE (1) | DE3148745A1 (en) |
| FR (1) | FR2496094A1 (en) |
| GB (1) | GB2092172B (en) |
| IN (1) | IN155483B (en) |
| IT (1) | IT1140322B (en) |
| NL (1) | NL8006751A (en) |
| NZ (1) | NZ199221A (en) |
| ZA (1) | ZA818539B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2149813A (en) * | 1983-11-15 | 1985-06-19 | Shell Int Research | Process for the preparation of hydrocarbons |
| GB2154602A (en) * | 1984-02-28 | 1985-09-11 | Shell Int Research | Process for the preparations of hydrocarbons |
| GB2164054A (en) * | 1983-04-28 | 1986-03-12 | Exxon Research Engineering Co | Liquid hydrocarbon synthesis using supported ruthenium catalysts |
| US4637993A (en) * | 1984-10-04 | 1987-01-20 | Shell Oil Company | Process for preparation of catalyst |
| WO2002026676A3 (en) * | 2000-09-27 | 2002-06-20 | Exxonmobil Chem Patents Inc | A methanol, olefin, and hydrocarbon synthesis process |
| WO2002026677A3 (en) * | 2000-09-28 | 2002-08-15 | Exxonmobil Chem Patents Inc | A methanol, olefin, and hydrocarbon synthesis process |
| US6479557B1 (en) | 1999-02-15 | 2002-11-12 | Shell Oil Company | Process for the preparation of hydrocarbons from carbon monoxide and hydrogen |
| WO2005075386A3 (en) * | 2004-02-05 | 2005-10-27 | Sasol Tech Pty Ltd | Co-production of hydrocarbons and dimethyl ether |
| WO2006033025A1 (en) * | 2004-02-05 | 2006-03-30 | Sasol Technology (Proprietary) Limited | Hydrocarbon synthesis |
| RU2337874C2 (en) * | 2003-03-06 | 2008-11-10 | ДжФЕ ХОЛДИНГЗ, ИНК. | Method for obtaining synthetic gas (gas synthesis), method for obtaining dimethyl ether through gas synthesis (versions), and furnace for gas synthesis (versions) |
| WO2010143980A1 (en) * | 2009-06-08 | 2010-12-16 | Ignite Energy Resources Nz Limited | A process for integration of a methanol plant and an oil hydroprocessing plant |
| WO2011019436A1 (en) | 2009-08-12 | 2011-02-17 | Catalytic Distillation Technologies | Process for the production of dimethyl ether |
| US8536385B2 (en) | 2003-03-06 | 2013-09-17 | Inpex Corporation | Process for preparing dimethyl ether and process for preparing a mixture of dimethyl ether and methanol |
| US20220119254A1 (en) * | 2018-12-27 | 2022-04-21 | Gascontec Gmbh | Method for synthesising a hydrogen-containing compound |
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|---|---|---|---|---|
| US3725018A (en) * | 1971-04-19 | 1973-04-03 | Fmc Corp | Form coke coated with glanz carbon and methods of production |
| DE3365337D1 (en) * | 1982-11-22 | 1986-09-18 | Shell Int Research | Process for the preparation of a fischer-tropsch catalyst, a catalyst so prepared and use of this catalyst in the preparation of hydrocarbons |
| CA1240708A (en) * | 1983-11-15 | 1988-08-16 | Johannes K. Minderhoud | Process for the preparation of hydrocarbons |
| FR2573998B1 (en) * | 1984-12-05 | 1987-01-09 | Charbonnages Ste Chimique | CARBON MONOXIDE HYDROCONDENSATION CATALYST, PROCESS FOR THE PREPARATION THEREOF, AND APPLICATION THEREOF TO MANUFACTURE HYDROCARBONS AND OXYGENIC ALIPHATIC COMPOUNDS |
| KR930004376B1 (en) * | 1990-09-28 | 1993-05-26 | 주식회사 신도리코 | Automatic document transfer apparatus |
| JP5086658B2 (en) * | 2006-02-10 | 2012-11-28 | 日本ガス合成株式会社 | Method for producing liquefied petroleum gas |
| WO2018004992A1 (en) | 2016-07-01 | 2018-01-04 | Res Usa, Llc | Conversion of methane to dimethyl ether |
| WO2018004994A1 (en) | 2016-07-01 | 2018-01-04 | Res Usa, Llc | Fluidized bed membrane reactor |
| WO2018004993A1 (en) | 2016-07-01 | 2018-01-04 | Res Usa, Llc | Reduction of greenhouse gas emission |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH245986A (en) * | 1943-12-13 | 1946-12-15 | Montedison Spa | Process for the successive synthesis of alcohols and hydrocarbons from technical CO / H2 mixtures. |
| FR2295118A1 (en) * | 1974-12-17 | 1976-07-16 | Brusset Henry | Hydrocarbons prodn. from carbonate minerals - by thermal decomposition and conversion of carbon dioxide formed |
| NL8003215A (en) * | 1980-06-03 | 1982-01-04 | Shell Int Research | PROCESS FOR PREPARING HYDROCARBONS. |
-
1980
- 1980-12-12 NL NL8006751A patent/NL8006751A/en unknown
-
1981
- 1981-10-05 CA CA000387310A patent/CA1260019A/en not_active Expired
- 1981-10-14 IN IN1125/CAL/81A patent/IN155483B/en unknown
- 1981-11-20 BE BE1/10361A patent/BE891195A/en not_active IP Right Cessation
- 1981-12-09 DE DE19813148745 patent/DE3148745A1/en active Granted
- 1981-12-09 IT IT25494/81A patent/IT1140322B/en active
- 1981-12-09 NZ NZ199221A patent/NZ199221A/en unknown
- 1981-12-09 GB GB8137057A patent/GB2092172B/en not_active Expired
- 1981-12-09 ZA ZA818539A patent/ZA818539B/en unknown
- 1981-12-09 AU AU78409/81A patent/AU542036B2/en not_active Ceased
- 1981-12-09 JP JP56197058A patent/JPS57131728A/en active Granted
- 1981-12-09 BR BR8107995A patent/BR8107995A/en unknown
- 1981-12-09 FR FR8123034A patent/FR2496094A1/en active Granted
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2164054A (en) * | 1983-04-28 | 1986-03-12 | Exxon Research Engineering Co | Liquid hydrocarbon synthesis using supported ruthenium catalysts |
| GB2164054B (en) * | 1983-04-28 | 1989-06-07 | Exxon Research Engineering Co | Liquid hydrocarbon synthesis using supported ruthenium catalysts |
| GB2149813A (en) * | 1983-11-15 | 1985-06-19 | Shell Int Research | Process for the preparation of hydrocarbons |
| GB2154602A (en) * | 1984-02-28 | 1985-09-11 | Shell Int Research | Process for the preparations of hydrocarbons |
| US4637993A (en) * | 1984-10-04 | 1987-01-20 | Shell Oil Company | Process for preparation of catalyst |
| US6479557B1 (en) | 1999-02-15 | 2002-11-12 | Shell Oil Company | Process for the preparation of hydrocarbons from carbon monoxide and hydrogen |
| US6486219B1 (en) | 2000-09-27 | 2002-11-26 | Exxonmobil Chemical Patents, Inc. | Methanol, olefin, and hydrocarbon synthesis process |
| WO2002026676A3 (en) * | 2000-09-27 | 2002-06-20 | Exxonmobil Chem Patents Inc | A methanol, olefin, and hydrocarbon synthesis process |
| US6444712B1 (en) | 2000-09-28 | 2002-09-03 | Exxonmobil Chemical Patents, Inc. | Methanol, olefin, and hydrocarbon synthesis process |
| WO2002026677A3 (en) * | 2000-09-28 | 2002-08-15 | Exxonmobil Chem Patents Inc | A methanol, olefin, and hydrocarbon synthesis process |
| CN101028997B (en) * | 2000-09-28 | 2010-12-15 | 埃克森美孚化学专利公司 | A methanol, olefin, and hydrocarbon synthesis process |
| US8536385B2 (en) | 2003-03-06 | 2013-09-17 | Inpex Corporation | Process for preparing dimethyl ether and process for preparing a mixture of dimethyl ether and methanol |
| RU2337874C2 (en) * | 2003-03-06 | 2008-11-10 | ДжФЕ ХОЛДИНГЗ, ИНК. | Method for obtaining synthetic gas (gas synthesis), method for obtaining dimethyl ether through gas synthesis (versions), and furnace for gas synthesis (versions) |
| WO2005075386A3 (en) * | 2004-02-05 | 2005-10-27 | Sasol Tech Pty Ltd | Co-production of hydrocarbons and dimethyl ether |
| CN1938401B (en) * | 2004-02-05 | 2011-06-22 | 沙索技术有限公司 | Co-production of hydrocarbons and dimethyl ether |
| CN1938400B (en) * | 2004-02-05 | 2012-01-04 | 沙索技术有限公司 | Hydrocarbon synthesis |
| WO2006033025A1 (en) * | 2004-02-05 | 2006-03-30 | Sasol Technology (Proprietary) Limited | Hydrocarbon synthesis |
| WO2010143980A1 (en) * | 2009-06-08 | 2010-12-16 | Ignite Energy Resources Nz Limited | A process for integration of a methanol plant and an oil hydroprocessing plant |
| WO2011019436A1 (en) | 2009-08-12 | 2011-02-17 | Catalytic Distillation Technologies | Process for the production of dimethyl ether |
| US8378150B2 (en) | 2009-08-12 | 2013-02-19 | Catalytic Distillation Technologies | Process for the production of dimethyl ether |
| US20220119254A1 (en) * | 2018-12-27 | 2022-04-21 | Gascontec Gmbh | Method for synthesising a hydrogen-containing compound |
Also Published As
| Publication number | Publication date |
|---|---|
| IT1140322B (en) | 1986-09-24 |
| AU542036B2 (en) | 1985-01-31 |
| BE891195A (en) | 1982-05-21 |
| CA1260019A (en) | 1989-09-26 |
| GB2092172B (en) | 1984-01-18 |
| IN155483B (en) | 1985-02-09 |
| DE3148745A1 (en) | 1982-08-12 |
| FR2496094A1 (en) | 1982-06-18 |
| FR2496094B1 (en) | 1985-04-26 |
| BR8107995A (en) | 1982-09-14 |
| JPS57131728A (en) | 1982-08-14 |
| JPH0262535B2 (en) | 1990-12-26 |
| AU7840981A (en) | 1982-09-23 |
| NL8006751A (en) | 1982-07-01 |
| NZ199221A (en) | 1985-01-31 |
| ZA818539B (en) | 1982-11-24 |
| IT8125494A0 (en) | 1981-12-09 |
| DE3148745C2 (en) | 1989-12-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19971209 |