CN102686540A - Method for generating hydrocarbons, in particular gasoline, from synthesis gas - Google Patents
Method for generating hydrocarbons, in particular gasoline, from synthesis gas Download PDFInfo
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- CN102686540A CN102686540A CN2010800521102A CN201080052110A CN102686540A CN 102686540 A CN102686540 A CN 102686540A CN 2010800521102 A CN2010800521102 A CN 2010800521102A CN 201080052110 A CN201080052110 A CN 201080052110A CN 102686540 A CN102686540 A CN 102686540A
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- gasoline
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- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 93
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 78
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 58
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 55
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 599
- 239000007789 gas Substances 0.000 claims abstract description 165
- 150000001875 compounds Chemical class 0.000 claims abstract description 139
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 116
- 239000004215 Carbon black (E152) Substances 0.000 claims description 97
- 229910052739 hydrogen Inorganic materials 0.000 claims description 50
- 239000003054 catalyst Substances 0.000 claims description 38
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 34
- 239000001257 hydrogen Substances 0.000 claims description 33
- 239000002994 raw material Substances 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 15
- 150000002431 hydrogen Chemical class 0.000 claims description 13
- 238000012546 transfer Methods 0.000 claims description 13
- 230000009466 transformation Effects 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 239000008246 gaseous mixture Substances 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 230000006641 stabilisation Effects 0.000 claims description 3
- 238000011105 stabilization Methods 0.000 claims description 3
- 238000006140 methanolysis reaction Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 19
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 82
- 239000000203 mixture Substances 0.000 description 46
- 239000000463 material Substances 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 18
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 14
- 238000004821 distillation Methods 0.000 description 14
- 229910021536 Zeolite Inorganic materials 0.000 description 13
- 238000001816 cooling Methods 0.000 description 13
- 239000012071 phase Substances 0.000 description 13
- 238000011084 recovery Methods 0.000 description 13
- 230000002194 synthesizing effect Effects 0.000 description 13
- 239000010457 zeolite Substances 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 11
- 238000000746 purification Methods 0.000 description 11
- 238000010586 diagram Methods 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 238000010790 dilution Methods 0.000 description 8
- 239000012895 dilution Substances 0.000 description 8
- 238000005194 fractionation Methods 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 101100257127 Caenorhabditis elegans sma-2 gene Proteins 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- PZZOEXPDTYIBPI-UHFFFAOYSA-N 2-[[2-(4-hydroxyphenyl)ethylamino]methyl]-3,4-dihydro-2H-naphthalen-1-one Chemical compound C1=CC(O)=CC=C1CCNCC1C(=O)C2=CC=CC=C2CC1 PZZOEXPDTYIBPI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910001195 gallium oxide Inorganic materials 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- -1 sulphur compound Chemical class 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
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
- C10G3/42—Catalytic treatment
-
- 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
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
-
- 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
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1022—Fischer-Tropsch products
-
- 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
- C10G2400/02—Gasoline
Abstract
The invention relates to a method for generating gasoline hydrocarbons by means of converting synthesis gas into a compound comprising oxygen, such as methanol and/or dimethyl ether, in a first converter and further converting said gas into hydrocarbons in a second converter. The method is in particular characterized in that synthesis gas that is not converted in the first converter is fed back, and light hydrocarbons and unreacted components of the synthesis gas are fed back from the product flow of the second converter into the first or second converter. The return flow of said components allows partial pressures to be adjusted, in particular that of methanol in the second converter, wherein product quality is improved. In order to further improve product quality, the process is preferably run under isothermal conditions and conditions of incomplete conversion.
Description
Technical field
The present invention relates in the compound of hydrocarbonaceous never, especially from the synthetic gas that comprises carbon monoxide and hydrogen, produce the particularly method of gasoline of hydrocarbon.
Background technology
Can from the solid-state and gaseous state source of the various easy acquisitions of carbon and hydrogen, produce the synthetic gas of the mixture that mainly is carbon monoxide and hydrogen.Based on synthetic gas institute synthetic hydrocarbon feed and motor spirit be gasoline hydrocarbon actual substitute and its be qualitatively part better.Therefore, the efficient that synthetic gas is changed into the technology of hydrocarbon is a problem of subject for many years.
In the Fischer-Tropsch synthetic (US 1,746,464) of nineteen twenty-five exploitation, synthetic gas is a hydrocarbon by direct catalytic conversion.
Knownly can produce gasoline from synthetic gas according to following two steps: at first carrying out the synthetic of oxygenatedchemicals (like the mixture of methyl alcohol or dme or these two kinds of compounds), is the mixture of hydrocarbon containing on the catalyzer of zeolite oxygenate then.According to this scheme, produce the certain methods of gasoline from synthetic gas and develop by " mobil oil " company.Two steps of this method are described in science, technology and the patent documentation: methyl alcohol synthetic for example is set forth in people's such as Karawajewa M.M. works " Technology of synthetic methanol (technology of synthesizing methanol) " in detail; M.:Chimija is in 1984; Synthesizing at US 3,894 of the mixture of methyl alcohol and dme is in 102; From methyl alcohol and the synthetic hydrocarbon of dme, referring to summary Catal.Rev. (catalysis journal)-Sei.Eng. of C.D.Chang, the 25th volume, the US 4404414 of the 1st phase (1983) and nineteen eighty-three.
US 6,191, and 175 disclose the method for producing methyl alcohol and dme.In this patent, at first carry out the synthetic of methyl alcohol from synthetic gas, this synthetic gas is by in preheating and introducing first reactor drum.Reaction product possibly be mixed with synthetic gas and this reaction product is transferred in second reactor drum once more, and this second reactor drum is used for the synthetic of the synthetic or dme of methyl alcohol.In order to realize high throughput, this method is preferred carries out adiabaticly.
US 5,908, and 963A discloses the method for producing dme.This product can contain methyl alcohol that is up to 20 weight % and the water that is up to 20 weight %.In first method steps, in one or more reactor drums, synthetic gas changed into the gaseous mixture of dme, first alcohol and water.Employed catalyzer not only has the methyl alcohol composite reactive but also have the methanol dehydration ability.This gaseous mixture is separated with washing step through a plurality of distillations, to obtain pure dme.
According to US 3; 894; 102 (1975) and synthetic gas is changed in the method for gasoline; Realized under production contains the condition of product of dme, synthetic gas being contacted with the catalyzed conversion agent under 371 ℃ the temperature, said catalyzed conversion agent is made up of methanol synthesis catalyst and the acid mixture of catalysts of dehydration.In second step, the temperature at 288-454 ℃, the pressure that is up to 21Mpa and 0.5-1000h have been realized
-1The raw material supply mass rate contact with zeolite catalyst down to major general's dme, thereby produce product, its organic moiety is gasoline preferably.The product of first step can be introduced directly in second step, or with its separation, for example, water (being with or without methyl alcohol) is separated, also with H
2Separate with carbon monoxide (unconverted synthetic gas), they are recovered to the fs (maybe be at CO
2After outwards discharging).
According to prior art; Usually the methyl alcohol that in the fs, is synthesized and the method for transformation of dme are realized under situation about almost completely transforming; Oxygenatedchemicals is accumulated in water thus; The problem of using waste water and/or from aqueous stream, separating oxygenatedchemicals has then been arranged, and this has significantly worsened the economic target of this method.
In this case, proposed oxygenate is become the method for hydrocarbon in the prior art, it has solved because conversion of raw material is maintained the caused problem of level above 99%.Isolating water is pulled away and is provided to biological or biochemical purifying from system from final product.
US 4,814, and 535 (1989) disclose the method for from the oxygenatedchemicals with 1 to 4 carbonatoms, producing gasoline.Through increasing temperature gradually, thus conversion of raw material is maintained 99.9% level, and reduced feedstream at the reactor inlet place.When transformation efficiency being reduced to when being lower than 99.9%, then supply of raw material is interrupted.
US 4,523, and 046 (1985) discloses from the method for disclosed methanol production gasoline therein.In this patent, catalyzer is placed in single and through the contacting of raw material and catalyst bed, conversion of raw material has almost reached 100%.Under the situation that transformation efficiency reduces, raw material is introduced into next catalyst bed.
In order to improve from synthetic gas or methyl alcohol or from the method for methyl alcohol with dme (DME) production gasoline; According to prior art; All respects have been considered; Be included in methyl alcohol and DME and change into temperature control and gasoline selective and quality, the content of the aromatic content in the gasoline of being produced, especially heavy hydrocarbon specifically in the high exothermic zone of hydrocarbon.
Temperature control in that methyl alcohol and DME change in the section of hydrocarbon assigns to carry out through in raw material, using to be diluted to, and said diluted composition itself is not participated in reaction.In method, use at least a from C according to US 4035430 (1977)
1To C
5The compound of hydrocarbon and refrigerative contain the product of durol.Back one compound has influenced the content of the cut of the productive rate of aromatic hydrocarbon and contained BTX (benzene,toluene,xylene) with temperature.
As the diluted composition of not participating in main reaction, according to US 4,788,369 (1988) have used the cut (C of liquid prod
3-/C
4-cut), it is separated from reaction product and is recycled in the reactor drum.Thus, there is other effect: because as the increase of the oligomeric gasoline yield that causes of the alkene of the recovery of side reaction.
Producing in the method for hydrocarbon according to US 4404414 (1983), using the inertia diluted composition: lighter-than-air gas, its quilt is from reaction product and steam, hydrogen and C
2-Hydrocarbon and C
3+Separate in hydrocarbon or its mixture.
In US 5602289, use a kind of gas as diluted composition, this gas is by two kinds of blended air-flow (C that are recycled in the reactor drum
2-Hydrocarbon and C
3+Hydrocarbon) forms.The water partial pressure that is included in the water that forms in the methanol conversion reaction in the reactor drum is 2.2 normal atmosphere.In the presence of water vapour, the limit of vapor partial pressure is measured through the effect of the irreversible inactivation of known zeolite.Under this preferred situation, the composition of diluted composition is used C
2-Hydrocarbon/C
3+The proportional range of hydrocarbon between 1/3 to 3/1 and hydrogen richness between 10 to 50 moles of %, represent.Gas (hydrogen, the C that will have heat capacity
2-Hydrocarbon) improves dilution factor as diluted composition, but made the conversion of methyl alcohol to hydrocarbon under higher pressure, to carry out (upper limit of abideing by necessary steam partial pressure).
Summary of the invention
Purpose
The objective of the invention is to develop a kind of economy and simply produce the method for hydrocarbon and have the simple device scheme of simplifying technological step from synthetic gas.It also is intended to realize have simultaneously the gasoline of the highly selective of high quality of gasoline, and the no waste that does not have contaminating by-products technology is provided.
Brief description of the present invention
According to the present invention, its purpose realizes through the method according to the production hydrocarbon of claim 1:
In the method according to the invention, contain CO and H
2Gaseous mixture (also the being known as synthetic gas subsequently) production that take place to transform the hydrocarbon that is carried out realize through following steps:
A.) contact with catalyzer in first convertor and produce first product stream,
It contains at least a R
1-O-R
2Type (R wherein
1-be alkyl group with 1 to 5 carbon number, R
2-for hydrogen, have the alkyl and the alkoxy base of 1 to 5 carbon number) compound, it is methyl alcohol and/or be dme if necessary preferably, and
The unconverted composition of synthetic gas, it can separate from liquid phase and deliver at least in part in first convertor,
B.) in second convertor, make from whole products of first convertor or after the unreacted component of the synthetic gas that separates a minimum part and contact with the catalyzed conversion agent; Produce product stream, said contact is preferably greater than the hydrogen dividing potential drop of 0.07Mpa, greater than the oxycarbide dividing potential drop of 0.008Mpa, less than the R of 0.5Mpa
1-O-R
2The compound particular methanol of type and/or the dividing potential drop of dme, less than carrying out under the water partial pressure of 0.3Mpa, and preferably at R
1-O-R
2The conversion of compounds rate of type is not less than 82%, preferably is not less than 82% and be not higher than 99.5% at methanol conversion, and, if necessary, being not less than 92% and be not higher than 99.8 times and carry out in the dimethyl ether conversion rate, said product stream contains:
-gasoline hydrocarbon, it has the aromatic substance that preferably is up to 45 weight %, and it comprises benzene that is up to 1 weight % and the isoparaffin that preferably is no less than 40 weight % (the branching saturated aliphatic hydrocarbon with at least 5 C atoms),
-C
1-C
4Hydrocarbon, it preferably forms with the amount (if change into the C in the methyl alcohol that transforms and/or be necessary the C in the dme that transforms) that is not higher than 17 weight %,
-unconverted R
1-O-R
2The compound of type,
-and synthetic gas in unreacted component,
Wherein synthetic gas is separated also from first and/or second product stream and be transmitted back in first convertor as recycle gas at least in part;
C.) product that separates in second convertor synthesizes unsettled gasoline, and this gasoline uses known method to come stabilization, wherein obtains:
-gasoline fraction, if necessary, from wherein separating the heavy gasoline cut contain durol (1,2,4,5 tetramethyl-benzene),
-C
3-C
4The cut of hydrocarbon,
-and air-flow, it contains light hydrocarbon (C
1And C
2), the unreacted component of synthetic gas and other participate in the composition of this method, this air-flow can be recycled in second convertor and/or first convertor at least in part,
And
-water, it contains methyl alcohol and/or R
1-O-R
2The compound that is different from methyl alcohol of type.
With the said R that contains
1-O-R
2The water of the compound of type cleans or rectifying.Through at R
1-O-R
2The compound of type (preferably is no less than 75% R at the enriching soln of water
1-O-R
2The compound of type) in and by R
1-O-R
2The water compound polluted, that be used to clean of type (preferred R
1-O-R
2The amount of type compound) carries out rectifying in and separate.Under any circumstance, be described below R
1-O-R
2The cleaning of the compound of type is through methyl alcohol and/or any other R
1-O-R
2The catalytically decomposed of the compound of type or carry out through biological method.
Heat through from reaction section, discharging thermopositive reaction synthesizes R
1-O-R
2The compound of type with come the convertor of synthetic gasoline to have heat transfer surface, be transferred to the ebullient perolene through this heat transfer surface reaction heat.This perolene (or its steam) is condensate in the cooling section, and it preferably contains the boiling water that is useful on production steam.This condensation product flows back in the section that reacts heating and (is " heat pipe " in principle).
At synthetic R
1-O-R
2Reaction in the compound of type and the convertor of synthetic gasoline is preferably almost being carried out under the isothermal condition, and wherein the temperature head in catalyst filling (Δ T) is no more than 40K, and preferred Δ T is 10-20K, and preferred especially Δ T is below 5K.
Thereby reaction heat is used to preferred in convertor, the generation to have the steam that is up to 4MPa pressure and synthesizes R
1-O-R
2The compound of type and in convertor, produce and be up to 22Mpa and come synthetic gasoline.
Being used for vaporific thermal losses through heat transfer surface allows at the methyl alcohol synthesis converter with being up to 150 actual m
3/ m
3The recycle gas of catalyzer (being known as recycle gas hereinafter) limit the dilution of input material stream and in gasoline synthetic convertor with the actual m of 0-150
3/ m
3The recycle gas of catalyzer (being known as recycle gas hereinafter) limits the dilution of input material stream.
The method that is used for producing from synthetic gas gasoline according to the present invention comprises: make synthetic gas and catalyzer first convertor (convertor of synthesizing oxygen-containing compounds) can synthesize R
1-O-R
2Contact under the condition of the compound of type.Term " R
1-O-R
2The compound of type " expression: R
1-be alkyl group with 1 to 5 C atom, R
2-be hydrogen, have the alkyl and an alkoxy base of 1 to 5 C atom.Preferred R
1-O-R
2The compound of type is methyl alcohol (CH
3=R
1And H=R
2) and be dme (R in case of necessity
1=R
2=CH
3), especially be used for synthetic R
1-O-R
2Institute's synthetic methyl alcohol in the conversion of compounds device of type (hereinafter also is known as the synthetic convertor of using of methyl alcohol), or the mixture of methyl alcohol and dme.
R
1
-O-R
2
Synthesizing of type compound:
Preferably, synthetic gas is as synthetic R
1-O-R
2The starting material of type compound.
At synthetic R
1-O-R
2(if R in the conversion of compounds device of type
1-O-R
2The compound of type is a methyl alcohol), reaction below especially taking place:
CO+H
2O ← → CO
2+ H
2Water-gas reaction
CO+2H
2← → CH
3OH methyl alcohol forms
And in methanol synthesis catalyst, use other an acidic catalyst component to come under the situation of dimethyl ether synthesis in case of necessity:
2CH
3OH ← → CH
3-O-CH
3+ H
2O forms DME
Using catalyzer to be controlled at first step is to produce methyl alcohol or methyl alcohol and the mixture of dme (DME) or other R
1-O-R
2The compound of type.
Synthetic for methyl alcohol, the preferred catalyzer that uses normally according to the methanol synthesis catalyst of prior art (for example the zinc chrome oxide catalyst, have the copper-based catalysts of zinc oxide and/or aluminum oxide additive; The binding substances of copper and rare earth metal; Cupric oxide/Zinc oxide catalytic and cupric oxide/zinc oxide/chromium oxide catalyst etc.).
Synthetic for the mixture of methyl alcohol and dme according to prior art, used the known catalyzer with dehydration catalyst that is used for synthesizing methanol, especially has highly acid catalyzed conversion agent, for example, has the γ-Al of the protonated form of peracidity
2O
3Or zeolite, it is used or uses separately as mixture.
Corresponding catalyzer and condition are known and for example: synthesize for methyl alcohol; Be described in people's such as M.M.Karawaewa works " Technologija sintetitscheskogo metanola (technology of synthesizing methanol) "; M.:Chimija is in 1984; And synthetic for DME, be described among the patent US 3,894,102.
Be used for synthetic R
1-O-R
2Product stream in the conversion of compounds device of type preferably cools off with isolating subsequently liquid and gas in the separator.Alternatively, flow at second convertor that does not have directly to be admitted under the isolating situation synthetic gasoline from (completely) product that is used for methyl alcohol synthetic convertor.
If separate, then unconverted gas composition (CO, H
2, CO
2, nitrogen etc.) preferably partly be sent to synthetic R
1-O-R
2In first convertor of type compound, promptly they be mixed with employed, contain CO and H
2Gaseous mixture, the unconverted synthetic gas of blended and part is sent to the convertor that is used for synthetic gasoline and suppresses R
1-O-R
2The decomposition reaction of the compound of type.Simultaneously, it preferably is transferred in another part of this technology, to avoid the accumulation of inert fraction.Use realizes the part of the unreacted component of synthetic gas is fed in the gasoline synthesis converter in the volumetric flow rate to the ingress of gasoline synthesis converter, and it guarantees that hydrogen dividing potential drop is not less than 0.07MPa and the CO dividing potential drop is not less than 0.08MPa.
For R
1-O-R
2Synthesizing of the compound of type, use the almost refrigerative convertor of isothermal condition that has in reaction chamber, wherein be preferably greater than 50m
2Heat transfer surface/m
3Catalyzer.Thereby the volume of recycle gas is with respect to 1m
3Catalyzer preferably is lower than 150m
3, wherein said recycle gas is basically by unreacted synthetic gas and short hydrocarbon gas composition.
Gasoline is synthetic:
In the gasoline synthesis converter, from synthetic R
1-O-R
2At least a portion of the product stream of the convertor of type compound, the R according to 85% to 99.5%
1-O-R
2The preferred transformation efficiency of type compound contacts with catalyzer.
In gasoline synthetic convertor, occur in from the convertor to R with contacting of catalyzer
1-O-R
2The whole flow process of the synthetic of type compound, or at total (at least a portion) liquid component of product stream and be used for R
1-O-R
2The part of the gaseous constituent of the product stream of the synthetic convertor of type compound, it guarantees in gasoline synthesis converter feedstream: be converted into 1m
3(i.N.) air-flow, surpass the H of 0.07MPa
2Dividing potential drop and surpass the CO dividing potential drop of 0.008MPA.These H
2In the gasoline synthesis converter, guaranteed inhibition R with the value of CO dividing potential drop
1-O-R
2The decomposition reaction of type compound.
Synthesize the catalyzer that there is wide region in hydrocarbon from methyl alcohol and dme.Part in them is described in Nefjodow B.K.; Konowaltschikow L.; The works of Rostanin N.N. " Catalysts of petroleum processing and petrochemicals based on zeolite with high silicon content (the catalyzer with high silicon content of petrolize and petroleum chemicals) " based on zeolite; M:ZNIITENEFTECHIM, 1987.From R
1-O-R
2The compound of type comes the catalyzer of synthetic gasoline preferably to comprise protonated zeolite (for example HZSM-5) at least in part, preferably has the pentasil group.Preferably, use has at least 12 high SiO
2O
3/ Al
2O
3Ratio, especially preferably has a SiO of at least 30
2O
3/ Al
2O
3The zeolite of ratio.The use of persilicic zeolite has reduced the formation of the durol in product.The catalyzer of steam stable can carry out modification and obtain through the element with Ib. family.Also can use the combining of silicon-dioxide and MOX (gallium oxide and/or Indium sesquioxide) (US4 in 1985,507,404, the EP in 0,070,690,1984 years of EP 0,124,999 of nineteen eighty-three).For example, if when gallium oxide and/or Indium sesquioxide are combined with Thorotrast and Silicon-rich zeolite, then can obtain high-quality, be rich in the gasoline (EP 0,070,690 of nineteen eighty-three) of aromatic substance.
The input material that is fed to second convertor is whole first product stream or part, and it comprises R
1-O-R
2The compound of type.R
1-O-R
2The dividing potential drop of the compound of type (be preferably methyl alcohol and be dme if any) in the input material of gasoline synthesis converter is converted into 1m
3(i.N.) during air-flow, be maintained at below the 0.5MPa (favourable distinguishing characteristics) particularly advantageous.
The dividing potential drop particularly advantageous ground of the steam in the input material of gasoline synthetic convertor (favourable distinguishing characteristics) below 0.3MPa.
Method particularly advantageous ground in the gasoline synthesis converter (favourable distinguishing characteristics) under the hydrogen dividing potential drop of 0.07Mpa at least and the carbon monoxide pressure of tension at 0.008Mpa at least carries out.
Method of the present invention is characterised in that the following fact: in second convertor, the input material carries out with contacting in the presence of hydrogen and carbon monoxide of catalyzer.Therefore, R
1-O-R
2Type compound (particular methanol and dme) is advantageously improved to the selectivity that hydrocarbon transforms, because suppressed its decomposition to the oxide compound of carbon and hydrogen.
Preferably will under intimate isothermal condition, have about 40m
2Heat transfer surface/m
3It is synthetic that coolable convertor in the conversion zone of catalyzer is used for gasoline.With respect to 1m
3Catalyzer, the volume of recycle gas is lower than 150m altogether
3Reaction heat is preferred for producing the water vapour that pressure is up to 22MPa.This also is a distinguishing characteristics of the present invention, and its characteristic with claim 1 allows selectivity to be higher than 83%, preferably is higher than 86% the high-quality gasoline that has.Here, term " selectivity " is understood that the productive rate of gasoline with respect to the hydrocarbon part of the methyl alcohol of reaction.
R preferably
1-O-R
2The compound of type (particular methanol and dme) if any in the gasoline synthesis converter for conversion of methanol be higher than altogether 85% be lower than 99.5% and for dme be higher than 92% be lower than 99.8%.R
1-O-R
2The incomplete conversion of type compound is key difference characteristic of the present invention, and this characteristic allows the selectivity (R that the gasoline group is transformed with respect to quilt of this method of control
1-O-R
2The productive rate of the hydrocarbon content of type compound) together with the essential quality of controlling the gasoline of being produced and the time length (working life of the process between the regeneration of catalyzer) of middle production cycle.This is the reason of the following fact; The said fact is: the content of the aromatic substance that gasoline had in the present invention is lower than 46%; Contained therein benzene content is lower than 1 quality %; And isoparaffin is higher than 40% and have high-octane numerical characteristic (93-96ROZ), and this also is a distinguishing characteristics of the present invention.
Except that hydrocarbon, from R
1-O-R
2The compound of type, C
3-C
4The gasoline synthetic product of hydrocarbon, water contains unreacted methanol and other R
1-O-R
2The compound of type and " drying " gas.Should mainly contain gaseous state material (short hydrocarbon (C by " drying " gas
1-C
2), CO, CO
2And H
2And other composition of synthetic gas).
The separation of gasoline synthetic product:
With gasoline synthetic product cooling and in unsettled gasoline, water with in the NC composition of gas, separate.This separation preferably is separated through physics in triphase separator and carries out.NC gaseous constituent comprises following composition: synthetic gas, light hydrocarbon (C
1And C
2), the hydrocarbon of the more heavy of trace.This recycle gas is recycled in the gasoline synthesis converter at least in part and/or arrives synthetic R
1-O-R
2In the convertor of type compound.Along with a large amount of recycle gas enters in the gasoline synthesis converter, can be advantageously provided the dividing potential drop of first alcohol and water.
Liquid phase in triphase separator is because the density difference forms the phase border of hydrocarbonaceous between water and hydrocarbon.Have low-density liquid (hydrocarbon) and on said phase border, assemble, and water sinks to the bottom.
Institute's liquid separated hydrocarbon comprises the hydrocarbon that preferably is imported in the distillation tower in triphase separator, wherein if desired, separates preferred heavy gasoline composition (durol cut) and overhead gas, and said overhead gas is mainly C
3-C
4Hydrocarbon and residual C
1-C
2Hydrocarbon (short hydrocarbon) and gas composition.Under the admissible situation of the content of durol in hydrocarbon, do not separate heavy gasoline.
The stable gasoline fraction that is obtained with the essential saturated vapor pressure below 500 – 700mm QS (as the necessary function of gasoline class) is the basis of production of the commercial gasoline of octane value with 92-98 (ROZ) of commercial gasoline or formation.
Isolating water comprises methyl alcohol in triphase separator.Methanol content in the water depends on the conversion of methanol in gasoline is synthetic, and generally it is for being higher than 3 weight % and being lower than 30 weight %.
Preferably, because different boiling temperatures has defined methanol content or has other R
1-O-R
2The water of type compound at first is separated into each cut in distillation tower, wherein a kind of cut mainly is methyl alcohol or the R different with methyl alcohol
1-O-R
2The compound of type, it has the water (contaminated water) that the low water yield (spissated methyl alcohol) and another cut contain the methyl alcohol with low levels.Spissated methyl alcohol and if possible dme or another R
1-O-R
2The compound of type preferably is recycled in the gasoline synthesis converter.Contaminated water comprises methyl alcohol (being 5 weight % usually to the maximum) or another R of residual content
1-O-R
2The compound of type.
For from the water of the pollution of the inventive method, removing remaining methyl alcohol, through contacting (steam reformation or catalytically decomposed) with catalyzer with methyl alcohol and another possible R
1-O-R
2The compound of type carries out catalytically decomposed and changes into hydrogen and gasiform oxycarbide.With water sepn, this cooling is through oxide compound (CO and the CO of carbon generation after cooling
2) and the condensation of hydrogen carry out.Oxycarbide and hydrogen can advantageously be mixed with synthetic gas and be recycled to R
1-O-R
2In the compound method of type compound.After divided gas flow, in the degassing of water subsequently, obtained the water of chemical purification.Contacting preferably of the water that comprises methyl alcohol and catalytic converter in the temperature that is lower than 380 ℃, particularly preferably in being lower than 350 ℃ and preferably be higher than under 200 ℃ the temperature and carry out.
Contain R
1-O-R
2The water of type compound (particular methanol, dme) if possible contacts with catalyzer; Realizing with under the overdraft that preferably said pressure makes it possible to directly or the synthetic ingredient of in first convertor, producing is got in first convertor.This pressure is corresponding to being used for R
1-O-R
2The summation of the pressure of the synthetic of type compound reaction and the pressure-losses between the inlet of the outlet of the product of the catalytically decomposed of methyl alcohol and input material entering methyl alcohol synthesis converter.
Alternatively, R
1-O-R
2The residue content of type compound in water is removed by biological cleaning method.The water of said biologically pure can be discharged into the waste water network.
Yet therefore need to consider; Biological cleaning requires the methanol content in water to be lower than 0.2-1 weight %; And obtain such concentration through fractionation and link together with the high-energy cost, perhaps requiring to dilute significantly with the water of purified water to pollution, this has increased the cost of biological cleaning.
From R
1-O-R
2The application of the catalytic purification of the water of type compound is another favourable distinguishing characteristics, because it makes it possible to control for the processing condition in the gasoline synthesis converter with low relatively effort, reduces R
1-O-R
2The conversion of compounds rate of type, thus and reach the highly selective and the high quality of product.
Equipment (device):
The object of the invention also is the equipment of carrying out according to the inventive method (device).
This equipment (device) comprising:
A.) at least one first convertor, it contains and is suitable for CO and H
2Be catalytically converted into R
1-O-R
2The catalyzer of the compound of type (particular methanol);
B.) at least one second convertor, it contains and is suitable for R
1-O-R
2The compound for catalysis of type changes into the catalyzer of hydrocarbon;
C.) at least one separator, it can be suitable for from product stream, separating gasoline hydrocarbon, and said product stream also contains R except hydrocarbon
1-O-R
2The compound of type, water and gas, said gas contains short hydrocarbon, synthesis gas components, R
1-O-R
2The compound of type and the hydrocarbon of trace;
D.) at least one the 3rd convertor, it contains the R that is suitable for contained in water
1-O-R
2The compound of type (particular methanol) is catalytically converted into CO and H
2Catalyzer.
Said modules preferably is connected in series, and promptly first convertor is connected with second convertor directly or indirectly, so that at least a portion of product stream is delivered to second convertor from first convertor.Second convertor and separator c.) be connected, therefore the product stream from second convertor is sent to separator c.) in.Thereby, separator c.) be connected with the 3rd convertor indirectly so that at separator c.) in the separated R that contains
1-O-R
2The water of type compound, and if desired, with contained R
1-O-R
2The main quantity of type compound is sent in the 3rd convertor after the fractionation by distillation in advance.Separator c.) have and being connected of second convertor, it makes short hydrocarbon and separator c.) other gas phase composition can be recycled to the ingress of second convertor.
Preferably, said equipment comprises the connection from the 3rd convertor to first convertor, and it makes the CO and the H that in the 3rd convertor, form can be sent in first convertor.
In order to carry out the distortion of the first product flow point from method, said equipment comprises and is used for from first convertor product stream being carried out isolating other separator.In this case, said other separator preferably has the connection of first convertor, and it makes in separator isolating CO of institute and H can be sent in first convertor.Should preferably also have first connection to second convertor by (other) separator, if desired, it makes after at least a portion of water is separated, R
1-O-R
2The compound of type can be sent in second convertor, and preferably also has second connection to second convertor, and if desired, it makes and comprises CO and H
2At least a portion of air-flow can be sent in second convertor.
Be introduced directly into the deformation program in second convertor in order to carry out first product stream (all); Then first convertor directly, is connected with second convertor with the mode with material stream, so that whole product flows is not sent to second convertor from first convertor under having isolating situation on equipment.In this case, separator is c.), its preferably have with first convertor in be connected, this connection makes dry gas (non-switched CO and H
2And short hydrocarbon) can be recycled in first convertor.
Under both of these case, all second product stream that comprises hydrocarbon, gasoline hydrocarbon, gas and water is separated.Comprise unreacted R
1-O-R
2The water of type compound is preferably at separator c.) in the device in downstream (preferred distillation tower), it provides in water, to separate has high-load R
1-O-R
2The possibility of the product of type compound (particular methanol and DME) if necessary, this isolating R
1-O-R
2The compound of type can be added in the source material in second convertor once more.Therefore, this is arranged in separator c.) device in downstream preferably has the R at water
1-O-R
2The isolating enriching soln of the compound of type is recovered to the connection in second convertor.Through this other device, R
1-O-R
2The compound of type is removed from water by halves.Therefore, this other device also has to the connection of the 3rd convertor, and it makes that still contaminated water can be sent in the 3rd convertor, wherein with R
1-O-R
2The compound of type separates.
For R
1-O-R
2The decomposition of type compound (be preferably methyl alcohol and be DME if possible); Can use known catalyzer; A summary is described in the following article, and its author is people such as Klabunowski E.I., and title is " Catalysts of conversion of methanol into synthesis gas (methanol conversion is the catalyzer of synthetic gas) " (Katalyse in der Industrie; 2004; The 6th phase, the 3-9 page or leaf), also can use CO steam reforming catalyst, methanol synthesis catalyst and other catalyzer.
In steps d .) in, can use the convertor of any kind, yet, the throughflow type convertor (through flow converter) of the fixed bed of granular catalyzer preferably had.Be used for steps d .) convertor be called as the desalt convertor hereinafter.
In order to arrange the continuous production method of synthetic gasoline from synthetic gas, do not use one but preferably use two convertors: first convertor is worked under response behaviour, and second convertor worked under the catalyst regeneration state.
The term convertor uses with the free burial ground for the destitute with reactor drum in specification sheets of the present invention.Be used for step a.) and/or step b.) the convertor throughflow type reactor drum installed as fixed bed of catalyzer wherein preferably.
Preferably, first and/or second convertor is cooled off.This cooling is carried out with optimal way through the indirect evaporation cooling.At step a.) and/or step b.) in response behaviour preferably carry out almost carrying out under the isothermal.The said convertor of preferred design, thus make its reaction heat that allows in catalyst bed, to be produced directly with fully to dissipate, and so make response behaviour in the volume of reaction chamber can remain on almost under the constant temperature.
Can be advantageously used in generation steam (water vapour) through in first and/or second reactor drum, cooling off the reaction heat that is dissipated.
First convertor (methyl alcohol is synthetic and DME the is synthetic if possible) heat transfer surface area that preferably has and the ratio of catalyst volume are not less than 50m
2/ m
3, and be not higher than 400m
2/ m
3The pressure that the steam that heat produced that use is dissipated in first convertor preferably has is not less than 0.6Mpa, and is not higher than 4MPa.
Second convertor (gasoline the is synthetic) heat transfer surface area that preferably has and the ratio of catalyst volume are not less than 40m
2/ m
3, and be not higher than 200m
2/ m
3The pressure that the water vapor that reaction heat produced that use is dissipated in second convertor preferably has is not less than 3.0Mpa, and is not higher than 22MPa.
The reaction heat that steam dissipated by producing can advantageously be used to produce refrigerant, and it can be used at step a.) and/or step b.) separation of later product.
The synthetic gas that is used for technology can be from various raw material production.Said raw material can be fossil or biogenetic derivation (for example coal, biomass, Sweet natural gas or biogas).CO and H in synthetic gas
2Ratio depend on the starting material and the working method of production usefulness.Synthetic gas also comprises inert fraction usually (like N
2And water).Synthetic gas does not preferably contain catalyzer poison (sulphur compound, nitrogen compound) and foreign matter, is dried and be compressed if desired.
Synthetic for methyl alcohol or DME, H in synthetic gas
2The ratio of/CO preferably is not less than 2.In this case, the relative C in CO has obtained the methyl alcohol (DME) of high yield.When littler ratio, the productive rate of methyl alcohol (DME) reduces and CO
2Gain in yield.
Each process step according to the method for the invention is further with reference to preferred embodiment explaining:
From synthetic gas, produce gasoline according to following two steps: at step a.) in, carry out R
1-O-R
2-type compound is methyl alcohol and/or dme synthetic for example, at step b.) in, R
1-O-R
2Type compound carries out on zeolite catalyst to the conversion of hydrocarbon mixture.Be created in the R in the first step
1-O-R
2Type compound can be introduced in second step from first convertor with the mode of whole product stream, or from the product of first convertor, separated by any deformation program, sends into then in second step.
From the product of first convertor, can methyl alcohol included in aqueous mixture be separated with possible dme, with raw material as second step.Unconverted synthetic gas preferably separates from the product of first convertor, or from the product of second convertor, separates and be recovered to and be used for R
1-O-R
2In synthetic first convertor of type compound.
Synthetic gas can advantageously use unprocessed mixture; But preferably carry out drying and compression; Then in this mixture, heat if desired with recycle gas; The highest temperature of this heating is the temperature near temperature of reaction, and this heating and is incorporated in first convertor (at accompanying drawing-unit I) and is used for R for example in recuperation heat exchanger and/or boiler (steam boiler, smelting furnace and/or electric furnace)
1-O-R
2Type compound (methyl alcohol and dme) if possible synthetic.In order to produce R
1-O-R
2The compound of type exists and the contacting of methyl alcohol synthetic catalyzer, or existence and methanol synthesis catalyst contact the contacting of catalyzer that becomes dme (DME) with methanol dehydration.
For at step a.) in methyl alcohol synthetic, preferably copper bearing catalyzer is used be up under 260 ℃ the temperature and be up under the pressure of 6Mpa.CO and H
2Reaction under methyl alcohol forms is with heat release ground operation under the exothermic effects of the methyl alcohol of 90.73kJ/Mol.Here it is why at step a.) in the preferred isothermal refrigerative convertor that uses.This convertor can reduce the volume of essential recycle gas; And under optimal conditions, synthesize; Wherein these conditions are: the corresponding reduction of the formation of by product, increased the productive rate of methyl alcohol, prolonged the working time of catalyzer and the MP steam that produced as energy carrier.
From R
1-O-R
2The product of the synthetic convertor of type compound preferably cools off in heat exchanger, and wherein feedstream (synthetic gas) is by preheating.As the scheme of a modification, product stream preferably is separated into gaseous product and phlegma.For this reason, product preferably cools off in air-cooler and watercooler, and in product, exists under the situation of dme, additionally cools off through cryogenic applying again.Organic composition and water are carried out condensation.Phlegma (water-content is up to 20% thick methyl alcohol, or the mixture of dme, first alcohol and water) is separated in separator.Gaseous product from separator is non-switched synthetic gas, and this non-switched synthetic gas of a part is recovered and is used for carrying out pre-mixing with material synthesis gas, in order that the conversion fully in first convertor.
As deformation program, be used for dividing dried up distillation tower from comprising organic mixture of ingredients, can be connected the downstream of separator, because be used for R
1-O-R
2Type compound changes into the existence of the water in the raw material of second convertor of hydrocarbon, has quickened to be used for the irreversible inactivation of the zeolite catalyst of second convertor.Yet this is very expensive operation, and the feedstream that dilutes second convertor with inert fraction is more cost effective with the dividing potential drop that reduces water and methyl alcohol.
With the isolating R of institute
1-O-R
2Type compound (methyl alcohol or methyl alcohol/DME mixture) or deliver to from the product of first convertor (unit I) stream that to be used for gasoline in second convertor (in the accompanying drawings-unit III) synthetic; Wherein, it preferably be mixed with recovery stream (streams 11 in Fig. 1+2) from the methyl alcohol of unit V, from the recovery stream (at the stream 7 of Fig. 1) of the light hydrocarbon gas of unit IV and from the stream (the stream E5 in Fig. 1) of the unreacted synthetic gas of separator (unit II).Mixed flow preferably is sent in the recuperation heat exchanger, and in boiler, heats, and delivers to then in the gasoline synthesis converter.
Existence between the transition phase of in the method for the invention methyl alcohol of hydrogen and carbon monoxide (and dme) if necessary is though reduced just partly at step b.) in methyl alcohol to the unwanted decomposition of hydrogen and carbon monoxide.This advantage has increased the selectivity of formed hydrocarbon.The hydrogen dividing potential drop preferably is higher than 0.07Mpa, and the dividing potential drop of carbon monoxide is higher than 0.008MPa.In order to reach essential effect, hydrogen and carbon monoxide are mixed with in advance isolating methyl alcohol from first product stream (with dme if necessary), perhaps contain also first product of unconverted synthetic gas and flow and directly be incorporated in second convertor.Hydrogen in second convertor and carbon monoxide are taken on the component of dilution, i.e. their dilution eductss (educt) (methyl alcohol and be DME if necessary).(dividing potential drop that the dilution of methyl alcohol+DME) in the feedstream of second convertor, carry out will make the dividing potential drop of methyl alcohol be lower than 0.5Mpa and water is lower than 0.3MPa to methyl alcohol.
Product from the gasoline synthesis converter preferably cools off in recuperation heat exchanger, and wherein the raw material of convertor (methyl alcohol and possible DME) preferably is heated, and if possible in having the mixture of recycle gas, is heated.Cooling flow preferably is sent to (unit IV in the accompanying drawings) in second separator, to separate the product of gasoline synthesis converter.When cooling off, to light hydrocarbon, the unreacted R of gasoline hydrocarbon, a part in recuperation heat exchanger with in condensing surface
1-O-R
2The compound of type and water carry out condensation.In separator preferably with following separating substances: 1. comprise unreacted R
1-O-R
2The water of type compound, 2. gasoline hydrocarbon and 3. gas phases: (great majority are up to 4 carbon atoms, are mainly methane and C for hydrogen, oxycarbide and light hydrocarbon
2-C
4Hydrocarbon), they form in the methanol conversion process.What the gas phase of a part was mixed with a part contains CO and H
2Gas, it is from first separator (unit II in the accompanying drawings), and preferably is recovered in the raw material in the gasoline synthesis converter (methyl alcohol and DME) if necessary as diluted composition.
From separator c.) the gasoline hydrocarbon phlegma preferably be heated and be introduced in the stabilizer tower, (short hydrocarbon is propane, propylene, butane, butylene and methane, ethane, ethene and H to wherein light overhead gas basically
2) from stable gasoline (stream 8 in the accompanying drawings), separate.If desired, C
3-C
4Hydrocarbon can be as liquid distillate C
3-C
4Separate.From the gasoline hydrocarbon that is sent to stabilizer tower, even heavy gasoline (stream 9 in the accompanying drawings) also can separate at stabilizer tower or in other tower.
As deformation program, from separator c.) water (stream 10 in the accompanying drawings) can be introduced in the distillation tower (the unit V in accompanying drawing 1+2), be introduced in then in the desalt convertor (the unit VI in accompanying drawing 1+2).R in distillation tower
1-O-R
2The compound of type (stream 11 in accompanying drawing 1+2) is concentrated.The direction that changes this recovery stream is in gasoline synthetic unit.The R that will contain remaining contents level
1-O-R
2, the water preserved in the polywater place of tower introduces in the desalt convertor.Can directly add from separator c.) water, to be used for desalt.
Description of drawings
Two preferred distortion are according to the method for the invention described according to following accompanying drawing.
Fig. 1 has shown the block diagram of from synthetic gas according to the present invention, producing the preferable methods of gasoline, wherein the recovery of synthetic gas is flowed from synthetic R
1-O-R
2Separate in the product of the convertor of type compound and at the methyl alcohol of main quantity from process water after the fractionation by distillation, methyl alcohol catalytically decomposed that will be in water.
Fig. 2 has shown the block diagram of from synthetic gas according to the present invention, producing the preferable methods of gasoline; Wherein will be introduced directly in second convertor from the product stream of first convertor; And the recovery of synthetic gas stream separated from the product of gasoline synthesis converter; And the methyl alcohol in main quantity after the fractionation by distillation, carries out catalytically decomposed with the methyl alcohol in water from process water.
Embodiment
In Fig. 1, with ratio depend on the staple of its production method be hydrogen and carbon monoxide, also comprise the synthetic gas 1 of inerts e, slough catalyzer poison and additive and purifying if necessary, is compressed and is sent to R
1-O-R
2In synthetic first convertor (unit I) of type compound, it is mixed with recycle gas 3 at this place.The mixture of gained is preheating to temperature of reaction in recuperation heat exchanger and boiler (boiler and/or electric furnace, smelting furnace), and is provided to synthetic R
1-O-R
2In the convertor of type compound.At R
1-O-R
2In the production of type compound, exist with methyl alcohol synthetic catalyzer contact or with methanol synthesis catalyst and methyl alcohol contacting to the catalyzer of the dehydration of dme.In the methyl alcohol building-up process, preferably with copper bearing catalyst applications be up to 260 ℃ temperature be up to the pressure of 8Mpa, still, even the zinc chrome catalyzer also can use, it operates down with the pressure that is higher than 8Mpa in the temperature that is up to 360 ℃.
From R
1-O-R
2The product of the synthesis converter of type compound cools off in heat exchanger, and feedstream carries out preheating in air-cooler He in the watercooler therein, in product, exist under the situation of dme also will use low temperature, this moment R
1-O-R
2The compound of type and water condensation.Phlegma (water-content is up to 20% thick methyl alcohol, and/or the mixture of dme, first alcohol and water) is stored in the separator (unit II).Gaseous product from separator is unreacted synthetic gas, a part (stream 3) is wherein introduced to mix with material synthesis gas, in order that raw material is changed fully.Isolating R in separator
1-O-R
2The compound 4 of type (methyl alcohol and DME) if necessary; Be mixed with: from the recovery stream of the methyl alcohol 11 of unit V, from the recovery stream 7 of the light hydrocarbon gas of second separator (unit IV) and from the stream 5 of the unreacted synthetic gas of unit II, preferably from the gaseous product of separator.Preferably, heat after each composition is mixed in recuperation heat exchanger and/or in boiler and deliver to then in the gasoline synthesis converter.
For the quality of gasoline (heavy gasoline and the aromatic substance of low share) that obtains, R
1-O-R
2The transformation efficiency of the compound of type (methyl alcohol and DME) if necessary in second convertor (unit III) preferably remains below 99.5%.The product of gasoline synthesis converter contains: at R
1-O-R
2The hydrocarbon that is produced in the conversion process of type compound (particularly gasoline hydrocarbon) and unreacted mainly be the R of methyl alcohol
1-O-R
2Type compound and gas composition.
Two convertors (unit I and III) preferably all are the refrigerative convertors.Be lower than 150 actual m
3/ m
3The flow velocity of recycle gas of catalyzer under, first convertor has 50m at least
2The every 1m of heat transfer surface area
3Catalyzer.Be lower than 150 actual m
3/ m
3Under the flow velocity of the recycle gas during the gasoline of catalyzer is synthetic, the heat transfer surface area in second convertor is 40m at least
2Every 1m
3Catalyzer.As stated, the steam that cooling is produced during convertor is used in steam heater, produce refrigerant through the absorption-type refrigerator, with the feedstream of preheating first convertor with as the kerve heating (sump heating) of product knockout tower.
The product of synthetic (unit III) convertor of gasoline cools off in recuperation heat exchanger, and the raw material of convertor is heated therein, in water cooler, is further cooled.In the refrigerative process, the condensation of gasoline hydrocarbon and water has taken place.Cooling flow 6 is transferred to separator c.) be used for the separation of gasoline synthesis reactor product in (unit IV).At separator c.) in, separate following material: 1. contain the water 10 of methyl alcohol, 2. gasoline hydrocarbon phase 8+9 and 3. gas phases 7, it contains formed hydrogen, oxycarbide and light hydrocarbon in the methyl alcohol switching process.
Under above-mentioned situation, the recovery of light hydrocarbon gas 7 stream be mixed with a part from first separator (unit II), contain CO and H
2Gas 5, in order that obtain being used for R
1-O-R
2The dilution component of the synthesis material of type compound.
To (comprise C from the hydrocarbon phlegma 6 of separator (unit IV)
5+Hydrocarbon) is directed in the stabilizer tower (unit IV), from stable gasoline 8, separates at this light overhead gas 7 in place.From unsettled gasoline hydrocarbon, even heavy gasoline 9 also can separate in stabilizer tower or in other tower.
To be incorporated among the unit V from the water 10 of separator and be used for R
1-O-R
2Concentrating of type compound, and be introduced in from here among the unit VI and be used for R
1-O-R
2The catalysis desalt of type compound.According to the level that transforms, the water here contains the R between 3.5 weight % and 30 weight % usually
1-O-R
2The compound of type.
At R
1-O-R
2Among the upgrading unit V of the compound of type, the enrichment of methyl alcohol is implemented in the top of distillation tower, and it will keep Methanol Recovery stream 11, and this Methanol Recovery stream 11 is sent among the gasoline synthesis unit III.Residuum from tower (unit V): water 12 is directed in the desalt convertor (unit VI), carries out in water-bearing media in the catalytically decomposed of this place's methyl alcohol, and the methyl alcohol 5 that wherein said water 12 contains is between 1% and 5%.
In desalt convertor (unit VI), contain oxycarbide and hydrogen from the air-flow 13 of methanolysis, it is directed in first convertor (unit I).Obtained the water 14 of chemical purification, it is used to refill recycling cooling water system, steam generating system and is used for other purpose.
Like the method for manufacture that Fig. 2 showed is that of the method that shows of Fig. 1 simplifies version, and mainly different with Fig. 1 in the following areas:
The product of first convertor (unit I) is heated in heat exchanger and/or boiler and under not separating in advance, directly be directed in the gasoline synthesis converter (unit III).
As the component of the dilution that contains the oxygen raw material, can reuse recycle gas 3 (being) here from unit IV.
And here, except that recycle gas 3, other hydrogen and carbon monoxide 13 are before delivering to first convertor or also be mixed with synthetic gas 1 at that time, and said other hydrogen and carbon monoxide 13 form in catalysis desalt convertor (unit VI).With regard to its composition, the product of first convertor corresponds essentially to the product of the method in Fig. 1.
In order to realize best quality of gasoline (heavy gasoline of low levels), R
1-O-R
2The transformation efficiency of type compound (methyl alcohol and DME) if necessary preferably is maintained at and is lower than 99.5%.
At first the product of gasoline synthesis converter is cooled off in recuperation heat exchanger and in water cooler, cools off then here.Part refrigerative stream 6 is fed among the unit IV, is used for the separation of the product of gasoline synthesis converter, herein, because the condensation of hydrocarbon and water has taken place in the cooling in water cooler.Contain unreacted R
1-O-R
2The water 10 of type compound is stored in the separator, and separates mutually the gasoline hydrocarbon phase is gentle.Gaseous product from separator mainly is made up of unreacted synthetic gas and light hydrocarbon, and the synthetic gas that general's wherein a part of (stream 3) retrieves to be used for beginning mixes at first convertor (unit I), in order that raw material is transformed fully.
Depend on transformation efficiency, the methyl alcohol that the water that in the gasoline synthesis converter, forms comprised (and being DME once in a while) is generally between 3.5% and 40%.Therefore; Desalt occurs in the distillation tower (unit V); In independent desalt convertor (unit VI), carry out (these gases are recycled to as mixture in the synthetic gas in technology herein) to the catalytically decomposed of hydrogen and oxycarbide then, referring to the description in Fig. 1 through methyl alcohol.
Hydrocarbon phlegma from separator (unit IV) is directed in the stabilizer tower (unit IV), wherein gasoline 8 is separated.Even heavy gasoline 9 also can separate from unsettled gasoline hydrocarbon in stabilizer tower or in other tower, from unsettled gasoline hydrocarbon, separate.
To be fed among the unit V with enrichment R from the water 10 of separator
1-O-R
2The compound of type is fed in the desalt convertor (unit VI) then.At R
1-O-R
2Among the upgrading unit V of the compound of type, the top, top that is enriched in distillation tower of methyl alcohol realizes, and it will accept the recovery stream 11 of this methyl alcohol, and this recoverys is flowed and is recycled among the gasoline synthesis unit III.Residuum-the water 12 of the contained tower of methyl alcohol 5 between 2 and 5% is sent in the desalt convertor (unit VI).
In cleaning unit VI; The current that comprise methyl alcohol are preferably delivered in recuperation heat exchanger and/or the preheater; It is heated to essential temperature of reaction herein, is sent to the desalt convertor then, has realized herein and methyl alcohol contacting to the decomposition catalyst of hydrogen and oxycarbide.
Product from the desalt convertor preferably cools off in recuperation heat exchanger and in air-cooler.Subsequently, gas phase is separated from phlegma in separator.Gas separated is left separator and is guided it in first convertor (unit I), to mix with material synthesis gas thus in methyl alcohol 13 decomposes.The water of this purifying is sent in the degassing tower.Obtained the water 14 of chemical purification, it is used to refill round-robin cooling water system, steam generating system and is used for other purpose.
Through water as illustrated in fig. 1 and 2, cool off convertor indirectly.Water absorbs the heat in the heating carrier, and it obtains heat again from conversion zone.Water leaves unit I and III as steam.
Following, by means of Comparative Examples and embodiment explanation the present invention.
Embodiment 1 (Comparative Examples)
This embodiment implements with the TIGAS method that is similar to Haldor Topsoe IJ Topp-Jorgensen company; This method is recorded in " Studies in surface and catalysis (surface and catalyst research); V; 36, the methane conversion (methanol conversion) " of second edition in 1987.
Fig. 3 has shown the block diagram of TIGAS method.
Synthetic gas is mixed with the circulation gas that comprises unreacted component of synthetic gas and light hydrocarbon, and in the reactor drum of synthesizing methanol+DME, use the dual-function catalyst of forming by methanol synthesis catalyst component and methanol dehydration catalyst component to react.Be provided for the gasoline synthesis step from methyl alcohol+DME+ water with from the mixture of unreacted synthesis gas components, the conversion reaction that methyl alcohol and DME become hydrocarbon takes place in it under the situation of the catalyzer that contains zeolite.Then product mixtures be separated into gasoline, the water for cleaning phase of being added, C3-C4 group and gas, wherein a part supplies to the synthesis step of oxygenatedchemicals as circulation gas.Carry out under the pressure much at one in 50-100 crust scope in steps.
Use contains H
2: the synthetic gas of CO=3.
According to the source, based on the CH in the synthetic gas
2, the productive rate of oxygenatedchemicals is 94%.With respect to the CH in the oxygenatedchemicals
2, the productive rate of gasoline is 78%.
Generally, do not consider the loss of product separation etc., with respect to the CH in the synthetic gas
2, the productive rate of gasoline is 73.34%.
In addition, enumerated the embodiment that changes according to the difference of process program of the present invention.
Use has the actual synthetic gas of forming with lower volume: CO-21.91; H
2– 61.16; CO
2– 6.38; CH4-1.83; H
2O – 8.72.
The flow velocity of synthetic gas is 738.3m (i.N.)/h.
Use called after MEGAMAX
(component CuO, ZnO, Al
2O
3) M/s.S ü dchemie catalyzer be used for generating methyl alcohol from synthetic gas, and use the M/s.S ü dchemie zeolite containing catalyst of called after SMA-2 to be used for generating gasoline from methyl alcohol.
Synthetic R in convertor
1-O-R
2The working conditions of type compound is: 210 to 260 ℃ of TRs, pressure range 50 is to 55MPa.Catalyst volume is 0.46m, and the heat exchange surface in conversion zone is 30m.The vapor pressure that generates is 1.8MPa.
In the convertor of synthetic gasoline, the pressure of embodiment 2-4 can be 7 crust, and the pressure of embodiment 5 is 45 crust.Process temperature is in 310 to 430 ℃ scope in response behaviour, and process temperature is 280 to 500 ℃ scope in reproduced state.
Convertor cooling with synthesizing methanol and synthetic gasoline.Use has 60m
2/ m
3The convertor of heat exchange surface.
Being reflected at almost in synthesizing methanol transmodulator and synthetic gasoline convertor carried out under the homothermic condition, and wherein the temperature contrast of granules of catalyst is less than 5K.
In embodiment 2 to 4, the product of the technology that produces oxygenatedchemicals is separated under 40 ℃ the temperature and carries out.In all samples, gasoline synthetic product is separated under 5 ° of temperature more than the C carries out.
Be used for generating the main diagram of equipment (device) of synthetic gasoline corresponding to Fig. 1; And comprise unit (unit I) from the synthetic gas synthesizing methanol; The unit (unit II) of separation of methanol from the product stream of unit I; From the unit (unit III) of thick methanol synthesized gasoline, separate the fractionation unit (unit IV) of gasoline products, from the unit (unit V) of process water separation of methanol.
Compare with the diagram among Fig. 1, be used to contain the not operation of purification unit of the water of methyl alcohol.With respect to Fig. 1, stream 5,13 and 14 does not occur in equipment,, in unit III, stream 5 is not provided that is.
Material balance in the table 2.1. system
From the production status of thick methanol synthesized gasoline, the commentaries on classics methanol conversion with the methyl alcohol of synthetic gasoline is not vapour (CO+CO
2)
Add to from the synthetic gas of methyl alcohol synthesis unit and to close catalyzer: change rate: the selectivity of oil: be converted into methyl alcohol
Become the unit of gasoline, do not have the transformation efficiency of water purification unit SMA-2 99% 86%:
94.7%
Year service hours several 8000.00
* with respect to the CH of methyl alcohol
2, * * is with respect to the CH of synthetic gas
2
The characteristic of illustrated stream among table 2.2. Fig. 1
The equipment that is used for producing synthetic gasoline is mainly corresponding to the diagram of Fig. 1; And comprise: from the unit (unit I) of synthetic gas synthesizing methanol; The unit (unit II) of separation of methanol from the product stream of unit I; From the unit (unit III) of thick methanol synthesized gasoline, separate the fractionation unit (unit IV) of gasoline products, from the unit (unit V) of process water separation of methanol.
Be used to contain the not operation of unit of purifying of the water of methyl alcohol.With respect to the diagram of Fig. 1, stream 13 and 14 does not occur in equipment.
The material balance of table 3.1. system
From the conversion methanol conversion of the methyl alcohol of the synthetic gasoline of thick methanol production synthetic gasoline is vapour (CO+CO
2)
State does not have the water purification unit catalyzer: rate: the selectivity of oil: be converted into methyl alcohol
The transformation efficiency of SMA-2 99% 87%:
94.2%
Year hours of operation 8000.00
* with respect to the CH of methyl alcohol
2, * * is with respect to the CH of synthetic gas
2
The characteristic of illustrated stream among table 3.2. Fig. 1
Embodiment 4
Producing the equipment and the diagram among Fig. 1 of synthetic gasoline coincide; And comprise: from the unit (unit I) of synthetic gas synthesizing methanol; The unit (unit II) of separation of methanol from the unit (unit III) of thick methanol synthesized gasoline, separates the fractionation unit (unit IV) of gasoline products from the product stream of unit I; The unit of separation of methanol from process water (unit V) contains the purification unit (unit VI) of the water of methyl alcohol.
The material balance of table 4.1. system
From the conversion methanol conversion of the methyl alcohol of the state synthetic gasoline of thick methanol production synthetic gasoline is vapour (CO+CO
2)
Catalyzer: rate: the selectivity of oil: be converted into methyl alcohol
The transformation efficiency of SMA-2 97% 87.5%:
94.7%
Year hours of operation 8000.00
* with respect to the CH of methyl alcohol
2, * * is with respect to the CH of synthetic gas
2
The characteristic of illustrated stream among table 4.2. Fig. 1
Producing the equipment and the diagram among Fig. 2 of synthetic gasoline coincide; And comprise: from the unit (unit I) of synthetic gas synthesizing methanol; From the product of unit I stream in the unit that does not have synthetic gasoline under the situation of separation of methanol (unit III); Separate the fractionation unit (unit IV) of gasoline products, be used for unit (unit V), contain the purification unit (unit VI) of the water of methyl alcohol from the process water separation of methanol.
The material balance of table 5.1. system
The conversion methanol conversion of from methyl alcohol synthetic stream, producing the methyl alcohol of synthetic gasoline is vapour (CO+CO
2)
The state catalyzer of synthetic gasoline: rate: oil be selectively converted to methyl alcohol
The transformation efficiency of SMA-2 99% 85.5%:
94.2%
Year hours of operation 8000.00
* with respect to the CH of methyl alcohol
2, * * is with respect to the CH of synthetic gas
2
The characteristic of illustrated stream among table 5.2. Fig. 2
Reference listing:
In accompanying drawing and literary composition, use following term:
1-exports synthetic gas
2-is from synthetic R
1-O-R
2The unitary product of type compound
3-recycle gas (synthetic gas, it is recovered to the unit I from unit II or IV)
4-material benzenemethanol (and/or R
1-O-R
2The raw material of type compound)
5-recycle gas (synthetic gas, II supplies to unit III from the unit for it)
6-is from the product of gasoline synthesis unit
7-recycle hydrocarbons gas (IV is recycled to unit III from the unit)
8-gasoline
The 9-heavy gasoline
The 10-process water
The R that 11 – are recovered
1-O-R
2The compound of type (particular methanol)
12-contains R
1-O-R
2The waste water of type compound (particular methanol)
13-gas, it is at R
1-O-R
2Form in the sepn process of type compound (particular methanol)
14-chemical purification water
15-gas
The 16-C3-C4 group
I – has the R of first convertor
1-O-R
2The synthesis unit of type compound,
II-has the separating unit of first separator
III-has the gasoline synthesis unit of second convertor
IV-has the separating unit of second separator and unsettled stabilization of gasoline tower
V-R
1-O-R
2Type compound (particular methanol) comes spissated unit from process water in distillation tower
VI-contains R
1-O-R
2The unit of the catalytic purification of the water of type compound (particular methanol)
Claims (14)
1. through containing CO and H
2Being converted of gaseous mixture (synthetic gas) produce the method for hydrocarbon, this method is carried out through following steps:
A.) contact with catalyzer in first convertor and produce first product stream, it contains:
-at least a R
1-O-R
2Type (R wherein
1-be alkyl group with 1 to 5 carbon number, and R
2-for hydrogen, have the alkyl and the alkoxy base of 1 to 5 carbon number) compound, R wherein
1-O-R
2This compound of type is methyl alcohol and/or dme preferably, and
The unreacted components of-synthetic gas;
B.) in second convertor, make from whole products of first convertor or after the unreacted components of separating at least a portion synthetic gas and contact with catalyzer, produce product and flow, it contains:
-gasoline hydrocarbon, it comprises the aromatic substance that is up to 45 weight %, wherein comprises benzene that is up to 1 weight % and the isoparaffin that is not less than 40 weight %,
-C
1-C
4Hydrocarbon, its preferably with the amount that is no more than 17 weight % (change into the methyl alcohol of reaction and/or, if be necessary, the C in the dme of reaction) form,
-unreacted R
1-O-R
2The compound of type
-and synthetic gas in unreacted component,
Wherein synthetic gas separates from first and/or second product stream and is transmitted back in first convertor as recycle gas at least in part;
C.) product in separation second convertor, the unsettled gasoline that is wherein obtained comes stabilization through known method, wherein obtains:
I.) gasoline fraction, if necessary, from wherein separating the cut contain durol,
Ii) C
3-C
4The cut of hydrocarbon,
Iii.) contain the air-flow of the unreacted components of light hydrocarbon and synthetic gas, and
Iv.) contain R
1-O-R
2The water of unreacted compound, particular methanol and/or the dme of type,
Wherein said air-flow iii.) be sent back in second convertor and/or first convertor as round-robin gas at least in part,
And said water iv.) directly be sent to purifying R
1-O-R
2The compound of type or at first be sent to rectifying, wherein through rectifying at R
1-O-R
2The enriching soln of the compound of type (preferably being not less than 75%) and by R
1-O-R
2The water that type compound pollutes (preferred R
1-O-R
2The content of the compound of type is up to 5%) in separate, wherein by R
1-O-R
2The water that type compound pollutes is sent to purifying.
2. method according to claim 1 is characterized in that, the hydrogen partial pressure that the raw material of said second convertor demonstrates is greater than 0.07Mpa, and the dividing potential drop of oxycarbide is greater than 0.008MPa, R
1-O-R
2The dividing potential drop of type compound (particular methanol and/or dme) less than the dividing potential drop of 0.5MPa and water less than 0.3Mpa.
3. method according to claim 1 and 2 is characterized in that, at step b.) in R
1-O-R
2The transformation efficiency of type compound (particular methanol) is not less than 82% and be not higher than 99.5%, and randomly the transformation efficiency of dme is not less than 92% and be not higher than 99.8%.
4. according to a described method in the claim 1 to 3; It is characterized in that; In first convertor, occur under the approximate isothermal condition with contacting of catalyzer; Should approximate isothermal condition realize through removing reaction heat that this is removed reaction heat and carries out through heat transfer surface, the ratio of heat transfer surface area and catalyst volume is not less than 50m
2/ m
3
5. method according to claim 4; It is characterized in that; Produce the pressure be up to 4MPa in the reaction heat of from the first convertor steam, removing, wherein contain the unreacted component of synthetic gas and be admitted to the volume of the recycle gas in first convertor, with respect to 1m
3Catalyzer is no more than 150 actual m
3
6. according to each the described method in the claim 1 to 5; It is characterized in that; In second convertor, occur under the approximate isothermal condition with contacting of catalyzer; Should approximate isothermal condition realize through removing reaction heat that this is removed reaction heat and carries out through heat transfer surface, the ratio of heat transfer surface area and catalyst volume is not less than 40m
2/ m
3
7. method according to claim 6; It is characterized in that; The reaction heat of from the second convertor steam, removing produces the pressure that is up to 22Mpa; And the recycle volume iii) of unreacted component that contains light hydrocarbon and the synthetic gas of the product stream in second convertor is with respect to 1m
3Catalyzer is up to 150 actual m
3
8. according to each the described method in the claim 1 to 7, it is characterized in that, make by R
1-O-R
2The water that the compound particular methanol of type is polluted and methanolysis contact being up under 360 ℃ the temperature with catalyzer, and wherein the result is component, especially hydrogen, carbon monoxide and the CO that has formed the water and the synthetic gas of purifying
2
9. method according to claim 8 is characterized in that, by R
1-O-R
2The water that the compound of type (particular methanol) pollutes carries out with contacting under certain pressure of catalyzer, and this pressure allows directly the component that is produced in the synthetic gas to be sent in first convertor or by means of recycle compressor to send in first convertor.
10. according to each the described method in the claim 2 to 9, it is characterized in that, will be from first product stream the part of isolating synthetic gas be sent in second convertor to be used to regulate the dividing potential drop of hydrogen and oxycarbide, especially carbon monoxide.
11. carry out the equipment according to each the described method in the claim 1 to 10, it comprises:
A.) at least one first convertor, it contains and is suitable for CO and H
2Be catalytically converted into R
1-O-R
2The catalyzer of the compound of type (particular methanol);
B.) at least one second convertor, it contains and is suitable for R
1-O-R
2The compound for catalysis of type changes into the catalyzer of hydrocarbon;
C.) at least one separator, it can separate gasoline hydrocarbon from product stream, and said product stream is except gasoline hydrocarbon and R
1-O-R
2Also contain water and gas outside the compound of type, said gas contains short hydrocarbon, synthesis gas components, R
1-O-R
2The compound of type and the gasoline hydrocarbon of trace;
D.) at least one the 3rd convertor, it contains the R that is suitable for contained in water
1-O-R
2The compound of type (particular methanol) is catalytically converted into CO and H
2Catalyzer.
12. equipment according to claim 11; Be characterised in that it comprises other being used for from the separator of first convertor separated product stream; Wherein said other separator comprises the pipe connecting that is connected on first convertor, and this makes in this separator isolating CO of institute and H
2Can be admitted in first convertor, wherein should (other) separator preferably include first pipe connecting that is connected on second convertor, it makes R
1-O-R
2The compound of type randomly with H
2O is admitted in second convertor together, and comprises second pipe connecting that is connected on second convertor, and it makes CO and H
2Optional being admitted in second convertor.
13. equipment according to claim 11; It is characterized in that; First convertor is directly connected on second convertor; From first convertor, be admitted in second convertor so that whole products flows, wherein separator c.) preferably include the pipe connecting that is connected on first convertor, so that unreacted CO and H
2And short hydrocarbon can be fed in first convertor.
14., be characterised in that it comprises at least a in the following other assembly according to each the described equipment in the claim 11 to 13:
I.) pipe connecting from the 3rd convertor to first convertor, it makes formed CO and H in the 3rd convertor
2Can be introduced in first convertor, and/or
Ii.) be arranged in separator c.) device in downstream, it makes R
1-O-R
2The compound of type can be separated, and wherein this equipment comprises and is used for the isolating R with institute
1-O-R
2The compound of type is recycled to the pipe connecting in second convertor, and/or
Iii.) in first and/or second convertor, remove the device of reaction heat, it preferably allows the generation of water vapour,
The heat exchange surface area that the wherein said device of removing reaction heat preferably demonstrates and the ratio of catalyst volume are at least 50m in first convertor
2/ m
3The heat exchange surface area that preferably demonstrates and the ratio of catalyst volume are at least 40m in second convertor
2/ m
3
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102009046790.4 | 2009-11-17 | ||
| DE102009046790A DE102009046790B9 (en) | 2009-11-17 | 2009-11-17 | Process for the production of hydrocarbons, in particular gasoline, from synthesis gas |
| PCT/EP2010/067606 WO2011061198A1 (en) | 2009-11-17 | 2010-11-16 | Method for generating hydrocarbons, in particular gasoline, from synthesis gas |
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| Publication Number | Publication Date |
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| CN102686540A true CN102686540A (en) | 2012-09-19 |
| CN102686540B CN102686540B (en) | 2014-10-08 |
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| CN201080052110.2A Active CN102686540B (en) | 2009-11-17 | 2010-11-16 | Method for generating hydrocarbons, in particular gasoline, from synthesis gas |
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| CN (1) | CN102686540B (en) |
| AU (1) | AU2010320947B2 (en) |
| CA (1) | CA2780483C (en) |
| DE (1) | DE102009046790B9 (en) |
| EA (1) | EA021044B1 (en) |
| WO (1) | WO2011061198A1 (en) |
Cited By (5)
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|---|---|---|---|---|
| RU2544241C1 (en) * | 2014-01-22 | 2015-03-20 | Общество С Ограниченной Ответственностью "Новые Газовые Технологии-Синтез" | Method of producing aromatic hydrocarbons from natural gas and apparatus therefor |
| CN105218326A (en) * | 2014-06-28 | 2016-01-06 | 孙立 | A kind of method of dimethyl ether synthesis |
| CN111770978A (en) * | 2018-02-16 | 2020-10-13 | 开姆尼茨化工工程有限公司 | Method and device for producing synthetic gasoline |
| CN114437772A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Method for preparing gasoline by coupling synthesis gas with naphtha |
| CN115010567A (en) * | 2022-06-08 | 2022-09-06 | 明士新材料有限公司 | Novel process for preparing methanol and co-producing high-purity durene from synthesis gas |
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| JP6116801B2 (en) | 2012-01-17 | 2017-04-19 | 三菱重工業株式会社 | System or method for producing gasoline |
| CN103540334A (en) * | 2012-07-11 | 2014-01-29 | 北京中超海奇科技有限公司 | Fischer-Tropsch synthesis reaction method based on in-situ temperature regulation |
| US20180029003A1 (en) * | 2015-02-25 | 2018-02-01 | SGC Energia Co., LLC | Systems, methods, and apparatuses for fischer-tropsch reactor cascade |
| RU2614956C1 (en) * | 2016-03-31 | 2017-03-31 | Публичное акционерное общество "Газпром" | Plant for producing synthetic liquid fuel |
| RU186042U1 (en) * | 2017-12-29 | 2018-12-27 | Общество с ограниченной ответственностью "Ухтинский государственный технический университет-Инвест" | COMBINED REACTOR FOR THE PRODUCTION OF OXYGENATES AND LIQUID HYDROCARBONS FROM SYNTHESIS GAS |
| DE102019200245A1 (en) | 2019-01-10 | 2020-07-16 | Forschungszentrum Jülich GmbH | Method and device for producing liquid fuel |
| EP3670443A1 (en) | 2018-12-20 | 2020-06-24 | Forschungszentrum Jülich GmbH | Method and device for producing liquid fluid |
| FR3135264A1 (en) | 2022-05-06 | 2023-11-10 | Totalenergies Onetech | Process for manufacturing jet fuel, jet fuel and associated installation |
| FR3135263A1 (en) | 2022-05-06 | 2023-11-10 | Totalenergies Onetech | Process for manufacturing jet fuel comprising a step of converting a stream of alcohol in a fluidized bed, associated jet fuel and installation |
| FR3135265A1 (en) | 2022-05-06 | 2023-11-10 | Totalenergies Onetech | Process for obtaining hydrocarbons, and associated installation |
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- 2010-11-16 CN CN201080052110.2A patent/CN102686540B/en active Active
- 2010-11-16 AU AU2010320947A patent/AU2010320947B2/en active Active
- 2010-11-16 CA CA2780483A patent/CA2780483C/en active Active
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| WO2015112056A1 (en) * | 2014-01-22 | 2015-07-30 | Общество С Ограниченной Ответственностью "Новые Газовые Технологии-Синтез" | Method for producing aromatic hydrocarbons from natural gas and installation for implementing same |
| CN105218326A (en) * | 2014-06-28 | 2016-01-06 | 孙立 | A kind of method of dimethyl ether synthesis |
| CN111770978A (en) * | 2018-02-16 | 2020-10-13 | 开姆尼茨化工工程有限公司 | Method and device for producing synthetic gasoline |
| CN111770978B (en) * | 2018-02-16 | 2023-02-21 | 开姆尼茨化工工程有限公司 | Method and device for producing synthetic gasoline |
| CN114437772A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Method for preparing gasoline by coupling synthesis gas with naphtha |
| CN114437772B (en) * | 2020-10-19 | 2023-07-28 | 中国石油化工股份有限公司 | Method for preparing gasoline by coupling synthetic gas with naphtha |
| CN115010567A (en) * | 2022-06-08 | 2022-09-06 | 明士新材料有限公司 | Novel process for preparing methanol and co-producing high-purity durene from synthesis gas |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102686540B (en) | 2014-10-08 |
| EA201200731A1 (en) | 2012-10-30 |
| CA2780483C (en) | 2013-03-05 |
| DE102009046790B9 (en) | 2013-05-08 |
| CA2780483A1 (en) | 2011-05-26 |
| WO2011061198A1 (en) | 2011-05-26 |
| AU2010320947B2 (en) | 2014-01-23 |
| AU2010320947A1 (en) | 2012-06-07 |
| EA021044B1 (en) | 2015-03-31 |
| DE102009046790B4 (en) | 2012-05-16 |
| DE102009046790A1 (en) | 2011-05-19 |
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