CN102686540B - 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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- CN102686540B CN102686540B CN201080052110.2A CN201080052110A CN102686540B CN 102686540 B CN102686540 B CN 102686540B CN 201080052110 A CN201080052110 A CN 201080052110A CN 102686540 B CN102686540 B CN 102686540B
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- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 92
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 74
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 65
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 59
- 239000007789 gas Substances 0.000 claims abstract description 164
- 150000001875 compounds Chemical class 0.000 claims abstract description 139
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 119
- 229910001868 water Inorganic materials 0.000 claims description 118
- 239000004215 Carbon black (E152) Substances 0.000 claims description 96
- 229910052739 hydrogen Inorganic materials 0.000 claims description 51
- 239000003054 catalyst Substances 0.000 claims description 39
- 238000000926 separation method Methods 0.000 claims description 39
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 35
- 239000001257 hydrogen Substances 0.000 claims description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 20
- 230000009466 transformation Effects 0.000 claims description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 15
- 238000012546 transfer Methods 0.000 claims description 15
- 150000002431 hydrogen Chemical class 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000003421 catalytic decomposition reaction Methods 0.000 claims description 8
- 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
- 238000006555 catalytic reaction Methods 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
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000006140 methanolysis reaction Methods 0.000 claims description 3
- 230000006641 stabilisation Effects 0.000 claims description 3
- 238000011105 stabilization Methods 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 576
- 230000008569 process Effects 0.000 abstract description 18
- 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 49
- 238000001816 cooling Methods 0.000 description 30
- 238000004519 manufacturing process Methods 0.000 description 20
- 239000000463 material Substances 0.000 description 19
- 238000004821 distillation Methods 0.000 description 14
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 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
- 229910021536 Zeolite Inorganic materials 0.000 description 12
- 239000010457 zeolite Substances 0.000 description 12
- 238000000746 purification Methods 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 9
- 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
- 238000005516 engineering process Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 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
- 101100257127 Caenorhabditis elegans sma-2 gene Proteins 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-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
- 238000004140 cleaning Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 239000008246 gaseous mixture Substances 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
- 238000002156 mixing Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 230000001131 transforming effect Effects 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012545 processing Methods 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 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
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229960004643 cupric oxide Drugs 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
- 229910001195 gallium oxide Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000002779 inactivation Effects 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
- 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
- 239000000243 solution Substances 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
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000013459 approach Methods 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
- 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
- 239000007859 condensation product Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 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
- 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
- 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
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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 is mainly carbon monoxide and hydrogen.Hydrocarbon feed based on synthetic gas synthesized and motor spirit are the actual substitutes of gasoline hydrocarbon and are that part is better qualitatively at it.Therefore the efficiency 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 hydrocarbon by direct catalytic conversion.
Knownly can from synthetic gas, produce gasoline according to following two steps: first carry out the synthetic of oxygenatedchemicals (as the mixture of methyl alcohol or dme or these two kinds of compounds), then containing on the catalyzer of zeolite, oxygenatedchemicals being converted into the mixture of hydrocarbon.According to this scheme, from synthetic gas, produce the certain methods of gasoline and developed by " mobil oil " company.Two steps of the method are described in science, technology and patent documentation: the synthesis example of methyl alcohol is as elaborated works people such as Karawajewa M.M. " technology of Technology of synthetic methanol(synthesizing methanol) ", M.:Chimija, in 1984; Synthesizing at US 3,894 of the mixture of methyl alcohol and dme, in 102; From methyl alcohol and the synthetic hydrocarbon of dme, referring to the summary Catal.Rev.(catalysis journal of C.D.Chang)-Sei.Eng., the 25th volume, the US 4404414 of the 1st phase (1983) and nineteen eighty-three.
US 6,191, and 175 disclose the method for methanol and dme.In this patent, first from synthetic gas, carry out the synthetic of methyl alcohol, this synthetic gas is preheated and introduces in the first reactor.Reaction product may be mixed with synthetic gas this reaction product is transferred in the second reactor again, this second reactor synthetic or dme for methyl alcohol synthetic.In order to realize high throughput, the method is preferred carries out adiabaticly.
US 5,908, and 963A discloses the method for producing dme.This product can contain the methyl alcohol that is up to 20 % by weight and the water that is up to 20 % by weight.In the first method steps, synthetic gas is changed into the gaseous mixture of dme, first alcohol and water in one or more reactors.The catalyzer using not only has methyl alcohol composite reactive but also have methanol dehydration ability.This gaseous mixture is separated with washing step by a plurality of distillations, to obtain pure dme.
According to US 3,894,102(1975) synthetic gas is changed in the method for gasoline, realized at the temperature of 371 ℃ and under the condition of producing the product that contains dme, synthetic gas has been contacted with catalytic conversion agent, described catalytic conversion agent is by the compositions of mixtures of methanol synthesis catalyst and dehydration an acidic catalyst.In second step, the temperature at 288-454 ℃, the pressure that is up to 21Mpa and 0.5-1000h have been realized
-1raw material supply mass rate down to major general's dme, contact with zeolite catalyst, thereby produce product, its organic moiety is gasoline preferably.The product of first step can be introduced directly in second step, or is isolated, for example, and by water (being with or without methyl alcohol) separation, also by H
2separated with carbon monoxide (unconverted synthetic gas), they are recovered to the first stage (may be at CO
2after outwards discharging).
According to prior art, conventionally the methyl alcohol being synthesized in the first stage and the method for transformation of dme are realized in the situation that almost transforming completely, oxygenatedchemicals is accumulated in water thus, had use waste water and/or from aqueous stream the problem of separated oxygenatedchemicals, this has significantly worsened the economic target of the method.
In this case, proposed in the prior art oxygenatedchemicals to change into the method for hydrocarbon, it has solved the caused problem of level that surpasses 99% due to the transformation efficiency of raw material is maintained.From final product, separated water is pulled away and is provided to biological or biochemical purifying from system.
US 4,814,535(1989) disclose the method for producing gasoline from have the oxygenatedchemicals of 1 to 4 carbonatoms.By increasing gradually temperature at reactor inlet place, thus the transformation efficiency of raw material is maintained to 99.9% level, and reduced feedstream.When transformation efficiency being reduced to lower than 99.9% time, the supply of raw material is interrupted.
US 4,523,046(1985) disclose from the method for disclosed methanol production gasoline therein.In this patent, catalyzer is placed in single and by the contacting of raw material and catalyst bed, the transformation efficiency of raw material has almost reached 100%.In 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 the method for producing gasoline from methyl alcohol and dme (DME), according to prior art, all respects have been considered, be included in temperature control and gasoline selective and quality in the high exothermic zone that methyl alcohol and DME change into hydrocarbon, specifically the content of the aromatic content in produced gasoline, especially heavy hydrocarbon.
At methyl alcohol and DME, change into temperature in the section of hydrocarbon and control by using to be diluted in raw material and assign to carry out, described diluted composition itself does not participate in reaction.According to US 4035430(1977) method in, use at least one from C
1to C
5the compound of hydrocarbon and the cooling product containing durol.A rear compound has affected the productive rate of aromatic hydrocarbon and contained BTX(benzene,toluene,xylene together with temperature) the content of cut.
As the diluted composition that does not participate in main reaction, according to US 4,788,369(1988) used the cut (C of liquid product
3-/C
4-cut), it is by separated from reaction product and be recycled in reactor.Thus, there is other effect: due to the increase of the oligomeric gasoline yield causing of the alkene of the recovery as side reaction.
According to US 4404414(1983) produce in the method for hydrocarbon, used inertia diluted composition: lighter-than-air gas, it is by from reaction product and steam, hydrogen and C
2-hydrocarbon and C
3+separated in hydrocarbon or its mixture.
In US 5602289, as diluted composition, use a kind of gas, this gas is by the air-flow (C that is recycled to two kinds of mixing in reactor
2-hydrocarbon and C
3+hydrocarbon) form.The water partial pressure that is included in the water forming in the reaction of methanol conversion in reactor is 2.2 normal atmosphere.Under water vapour exists, the limit of vapor partial pressure is measured by the effect of the irreversible inactivation of known zeolite.In this preferred situation, the composition C of diluted composition
2-hydrocarbon/C
3+the proportional range of hydrocarbon between 1/3 to 3/1 and hydrogen richness between 10 to 50 % by mole, represent.Gas (hydrogen, the C of low heat capacity will be there is
2-hydrocarbon) as diluted composition, improve dilution factor, but made methyl alcohol to the conversion of hydrocarbon will under higher pressure, carry out (in accordance with the upper limit of necessary steam partial pressure).
Summary of the invention
object
The object of the invention is to develop a kind of economy and simply from synthetic gas, produce the method for hydrocarbon and there is the simple device scheme of simplifying technological step.It is also intended to realize the gasoline of the highly selective simultaneously with high quality of gasoline, and provides and there is no the no waste of contaminating by-products technology.
Brief description of the present invention
According to the present invention, its object is by realizing according to the method for the production hydrocarbon of claim 1:
In the method according to the invention, containing CO and H
2gaseous mixture (being also the known as subsequently synthetic gas) production that occur to transform the hydrocarbon carrying out by following steps, realize:
A.) contact to produce the first product stream with the catalyzer in the first convertor,
It contains at least one R
1-O-R
2type (R wherein
1-be the alkyl group with 1 to 5 carbon number, R
2-for hydrogen, there is 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 separatedly from liquid phase also be delivered in the first convertor at least in part,
B.) in the second convertor, make from whole products of the first convertor or contact with catalytic conversion agent after the unreacted component of separated minimum a part of synthetic gas, produce product stream, described contact preferably being greater than the hydrogen dividing potential drop of 0.07Mpa, be greater than 0.008Mpa oxycarbide dividing potential drop, be less than the R of 0.5Mpa
1-O-R
2the compound particular methanol of type and/or the dividing potential drop of dme, be less than under the water partial pressure of 0.3Mpa and carry out, and preferably at R
1-O-R
2the transformation efficiency of the compound of type is not less than 82%, preferably at methanol conversion, is not less than 82% and not higher than 99.5%, and, if necessary, in dimethyl ether conversion rate, being not less than 92% and higher than 99.8 times, do not carry out, described product stream contains:
-gasoline hydrocarbon, it has the aromatic substance that is preferably up to 45 % by weight, and it comprises the isoparaffin (the branching saturated aliphatic hydrocarbon with at least 5 C atoms) that is up to the benzene of 1 % by weight and is preferably no less than 40 % by weight,
-C
1-C
4hydrocarbon, it is preferably not form higher than the amount of 17 % by weight (change into C in the methyl alcohol transforming and/or if necessary the C in the dme transforming),
-unconverted R
1-O-R
2the compound of type,
-and synthetic gas in unreacted component,
Wherein using synthetic gas is separated from the first and/or second product stream, also as recycle gas, be transmitted back in the first convertor at least in part;
C.) product in separated the second convertor synthesizes unsettled gasoline, and this gasoline carrys out stabilization by known method, wherein obtains:
-gasoline fraction, if necessary, from the heavy gasoline cut that wherein separation contains 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 the method, this air-flow can be recycled in the second convertor and/or the 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.
Described in inciting somebody to action, contain R
1-O-R
2the water of the compound of type cleans or rectifying.By at R
1-O-R
2the compound of type (is preferably no less than 75% R at the concentrated solution of water
1-O-R
2the compound of type) in and by R
1-O-R
2type compound polluted, for the water that cleans (preferred R
1-O-R
2the amount of type compound) in, carry out rectifying and carry out separation.Under any circumstance, as described below, R
1-O-R
2the cleaning of the compound of type is by methyl alcohol and/or any other R
1-O-R
2the catalytic decomposition of the compound of type or undertaken by biological method.
By discharge the heat of thermopositive reaction from reaction section, synthesize R
1-O-R
2the compound of type and come the convertor of synthetic gasoline to have heat transfer surface, is transferred to the thermophore of boiling by this heat transfer surface reaction heat.This thermophore (or its steam) is condensate in cooling section, and it preferably contains the boiling water for the production of steam.This condensation product flows back to (being " heat pipe " in principle) in the section that reacts heating.
At synthetic R
1-O-R
2reaction in the compound of type and the convertor of synthetic gasoline is preferably carried out under the condition of isothermal almost, and wherein the temperature head in catalyst filling (Δ T) is no more than 40K, and preferably Δ T is 10-20K, and particularly preferably Δ T is below 5K.
Thereby reaction heat is used to preferably produce in convertor to be had the steam that is up to 4MPa pressure and synthesizes R
1-O-R
2the compound of type and produce in convertor and be up to 22Mpa and carry out synthetic gasoline.
The thermal losses of passing through heat transfer surface for generation of steam allows in methyl alcohol synthesis converter with being up to 150 actual m
3/ m
3the recycle gas of catalyzer (being known as hereinafter recycle gas) limits the dilution of input material stream and in the synthetic convertor of gasoline, uses the actual m of 0-150
3/ m
3the recycle gas of catalyzer (being known as hereinafter recycle gas) limits the dilution of input material stream.
According to of the present invention, for produce the method for gasoline from synthetic gas, comprise: make synthetic gas and the catalyzer the first convertor (convertor of synthesizing oxygen-containing compounds) can synthesize R
1-O-R
2under the condition of the compound of type, contact.Term " R
1-O-R
2the compound of type " represent: R
1-be the alkyl group with 1 to 5 C atom, R
2-be hydrogen, there is alkyl and the 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 if desired
1=R
2=CH
3), especially for the synthesis of R
1-O-R
2the methyl alcohol of synthesized in the convertor of the compound of type (being below also known as methyl alcohol synthetic with convertor), 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 convertor of the compound of type
1-O-R
2the compound of type is methyl alcohol), especially there is following reaction:
CO+H
2o ← → CO
2+ H
2water-gas reaction
CO+2H
2← → CH
3oH the formation of methanol
And if desired in the situation that carry out dimethyl ether synthesis by other an acidic catalyst component in methanol synthesis catalyst:
2CH
3oH ← → CH
3-O-CH
3+ H
2o forms DME
With catalyzer, being 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 catalyzer preferably using normally according to the methanol synthesis catalyst of prior art (for example zinc chrome oxide catalyst, there is 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, is used the known catalyzer with dehydration catalyst for the synthesis of methyl alcohol, especially has highly acid catalytic conversion agent, for example, has the γ-Al of the protonated form of peracidity
2o
3or zeolite, it is as mixture application or application separately.
Corresponding catalyzer and condition are known and for example: synthetic for methyl alcohol, be described in the people's such as M.M.Karawaewa works " technology of Technologija sintetitscheskogo metanola(synthesizing methanol) ", M.:Chimija, in 1984; And synthetic for DME, be described in patent US 3,894,102.
For the synthesis of R
1-O-R
2product stream in the convertor of the compound of type is preferably with in separator, the liquid and gas of separation are next cooling subsequently.Alternatively, from (completely) product stream for the synthetic convertor of methyl alcohol, the second convertor that is not directly admitted to synthetic gasoline in separative situation.
If carry out separation, unconverted gas composition (CO, H
2, CO
2, nitrogen etc.) be preferably partly sent to synthetic R
1-O-R
2in the first convertor of type compound, their mix use to some extent, contain CO and H
2gaseous mixture, being sent in the convertor for the synthesis of gasoline and suppressing R with the unconverted synthetic gas of part of mixing
1-O-R
2the decomposition reaction of the compound of type.Meanwhile, it is preferably transferred in another part of this technique, to avoid the accumulation of inert fraction.Use volumetric flow rate in the ingress to gasoline synthesis converter to realize a part for the unreacted component of synthetic gas is fed in gasoline synthesis converter, it guarantees that hydrogen dividing potential drop is not less than 0.07MPa and CO dividing potential drop is not less than 0.08MPa.
For R
1-O-R
2synthesizing of the compound of type, use the almost cooling convertor of isothermal condition that has in reaction chamber, be wherein preferably greater than 50m
2heat transfer surface/m
3catalyzer.Thereby the volume of recycle gas is with respect to 1m
3catalyzer, preferably lower than 150m
3, wherein said recycle gas is substantially by unreacted synthetic gas and short hydrocarbon gas composition.
gasoline is synthetic:
In 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 the synthetic convertor of gasoline, occur in from convertor to R with contacting of catalyzer
1-O-R
2the synthetic whole flow process of type compound, or at total (at least a portion) liquid component of product stream and for R
1-O-R
2a part for 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 gasoline synthesis converter, guaranteed inhibition R with the value of CO dividing potential drop
1-O-R
2the decomposition reaction of type compound.
From methyl alcohol and dme, synthesize the catalyzer that hydrocarbon exists wide region.A part in them is described in Nefjodow B.K., Konowaltschikow L., the works of Rostanin N.N. " catalyzer based on zeolite with high silicon content of Catalysts of petroleum processing and petrochemicals based on zeolitewith high silicon content(petrolize and petroleum chemicals) ", M:ZNIITENEFTECHIM, 1987.From R
1-O-R
2the compound of type comes the catalyzer of synthetic gasoline preferably to comprise at least in part protonated zeolite (for example HZSM-5), preferably has pentasil group.Preferably, use the high SiO with at least 12
2o
3/ Al
2o
3ratio, particularly preferably there is at least 30 SiO
2o
3/ Al
2o
3the zeolite of ratio.The use of the zeolite of Silicon-rich has reduced the formation of the durol in product.The catalyzer of steam stable can carry out modification and obtain by the element of YongIb. family.Also can use the combination (US4 of 1985,507,404, the EP EP of 0,070,690,1984 years 0,124,999 of nineteen eighty-three) of silicon-dioxide and metal oxide (gallium oxide and/or Indium sesquioxide).For example, if when gallium oxide and/or Indium sesquioxide are combined with Thorotrast and Silicon-rich zeolite, 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 the second convertor is whole the 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 if any for dme) in the input material of gasoline synthesis converter is converted into 1m
3(i.N.), during air-flow, be particularly advantageously maintained at 0.5MPa following (favourable distinguishing characteristics).
The dividing potential drop of the steam in the input material of the synthetic convertor of gasoline is below 0.3MPa (favourable distinguishing characteristics) particularly advantageously.
Method in gasoline synthesis converter particularly advantageously under the hydrogen dividing potential drop of 0.07Mpa at least and the carbon monoxide pressure of tension at 0.008Mpa at least (favourable distinguishing characteristics) carry out.
Method of the present invention is characterised in that the following fact: in the second convertor, input material carries out with contacting under the existence of hydrogen and carbon monoxide of catalyzer.Therefore, R
1-O-R
2the selectivity that type compound (particular methanol and dme) transforms to hydrocarbon is advantageously improved, because suppressed its decomposition to the oxide compound of carbon and hydrogen.
Preferably will under intimate isothermal condition, there is about 40m
2heat transfer surface/m
3coolable convertor in the conversion zone of catalyzer is synthetic for gasoline.With respect to 1m
3catalyzer, the volume of recycle gas amounts to lower than 150m
3.Reaction heat is preferred for producing the water vapour that pressure is up to 22MPa.This is also distinguishing characteristics of the present invention, its with together with the feature of claim 1, allow selectivity higher than 83%, preferably higher than 86% the high-quality gasoline that has.Herein, term " selectivity " is understood to that gasoline is with respect to the productive rate of the hydrocarbon part of the methyl alcohol of reaction.
R preferably
1-O-R
2the compound of type (particular methanol and if any dme) in gasoline synthesis converter for the transformation efficiency of methyl alcohol amount to higher than 85% and lower than 99.5% and for dme higher than 92% with lower than 99.8%.R
1-O-R
2the incomplete conversion of type compound is key difference feature of the present invention, and (gasoline group is with respect to the R being converted for the selectivity of this feature permission control the method
1-O-R
2the productive rate of the hydrocarbon content of type compound) together with essential quality and the time length (working life of the process between the regeneration of catalyzer) of middle production cycle of controlling the gasoline of producing.This is the reason of the following fact, the described fact is: the content of the aromatic substance that gasoline has is in the present invention lower than 46%, contained benzene content is lower than 1 quality % therein, and isoparaffin is higher than 40% and have high-octane numerical characteristic (93-96ROZ), this is also distinguishing characteristics of the present invention.
Except hydrocarbon, from R
1-O-R
2the compound of type, C
3-C
4the gasoline synthetic product of hydrocarbon, water contains unreacted methyl alcohol and other R
1-O-R
2the compound of type and " being dried " gas.Should mainly contain gaseous substance (short hydrocarbon (C by " being dried " gas
1-C
2), CO, CO
2and H
2and other composition of synthetic gas).
the separation of the product that gasoline is synthetic:
By the synthetic product of gasoline cooling and in unsettled gasoline, water is with separated in the NC composition of gas.This separation is preferably separated to carry out by physics in triphase separator.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 gasoline synthesis converter and/or to synthetic R at least in part
1-O-R
2in the convertor of type compound.Along with a large amount of recycle gas enters in gasoline synthesis converter, can be advantageously provided the dividing potential drop of first alcohol and water.
Liquid phase in triphase separator is because density is distinguished the phase border that forms hydrocarbonaceous between water and hydrocarbon.There is low-density liquid (hydrocarbon) and assemble on described phase border, and water sinks to bottom.
In triphase separator, separated liquid hydrocarbon comprises the hydrocarbon being preferably imported in distillation tower, if wherein needed, and separated preferred heavy gasoline composition (durol cut) and overhead gas, described overhead gas is mainly C
3-C
4hydrocarbon and residual C
1-C
2hydrocarbon (short hydrocarbon) and gas composition.In the admissible situation of content at durol in hydrocarbon, not separated heavy gasoline.
Have at 500 – 700mm QS(as the necessary function of gasoline class) below the stable gasoline fraction obtaining of essential saturated vapor pressure be that business gasoline or formation have 92-98(ROZ) the basis of production of business gasoline of octane value.
Water separated in triphase separator comprises methyl alcohol.Methanol content in water depends on the transformation efficiency of the methyl alcohol in gasoline is synthetic, and generally it is higher than 3 % by weight with lower than 30 % by weight.
Preferably, due to different boiling temperatures, there is defined methanol content or there is other R
1-O-R
2first the water of type compound is separated into each cut in distillation tower, and wherein a kind of cut is mainly methyl alcohol or the R different from methyl alcohol
1-O-R
2the compound of type, it has the water (contaminated water) that the low water yield (concentrated methyl alcohol) and another cut contain the methyl alcohol with low levels.Concentrated methyl alcohol and if possible dme or another R
1-O-R
2the compound of type is preferably recycled in gasoline synthesis converter.The methyl alcohol that contaminated water comprises residual content (being conventionally 5 % by weight to the maximum) or another R
1-O-R
2the compound of type.
Water for the pollution from the inventive method, remove remaining methyl alcohol, by contacting (steam reformation or catalytic decomposition) with catalyzer by methyl alcohol and another possible R
1-O-R
2the compound of type carries out the oxycarbide that catalytic decomposition changes into hydrogen and gaseous state.Cooling later that water is separated, this cooling oxide compound producing by carbon (CO and CO
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 synthetic method of type compound.After divided gas flow, in water subsequently degassed, obtained the water of chemical purification.Contacting preferably in the temperature lower than 380 ℃, particularly preferably in lower than 350 ℃ with preferably carry out at the temperature higher than 200 ℃ of the water that comprises methyl alcohol and catalytic converter.
Contain R
1-O-R
2the water of type compound (particular methanol, if possible dme) contacts with catalyzer, preferably with under overdraft, realizing, described pressure makes it possible to directly or under the help of recycle compressor, makes the synthetic ingredient of producing in the first convertor enter in the first convertor.This pressure is corresponding to for R
1-O-R
2the summation of the pressure of the synthetic reaction of type compound and the pressure-losses between the outlet of the product of the catalytic decomposition of methyl alcohol and entrance that input material enters 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 described biologically pure can be discharged into waste water network.
Yet therefore need to consider, the methanol content of biological clean requirement in water is lower than 0.2-1 % by weight, and by fractionation, obtain such concentration and link together with high-energy cost, or require with pure water, the water of pollution significantly to be diluted, this has increased biological clean cost.
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 gasoline synthesis converter with relatively low effort, reduces R
1-O-R
2the transformation efficiency of the compound of type, thus and reach highly selective and the high quality of product.
equipment (device):
Object of the present invention is also to carry out according to the equipment of 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 separated gasoline hydrocarbon from product stream, and described product stream also contains R except hydrocarbon
1-O-R
2the compound of type, water and gas, described 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 being suitable for contained in water
1-O-R
2the compound of type (particular methanol) is catalytically converted into CO and H
2catalyzer.
Said modules is preferably connected in series, and the first convertor is connected with the second convertor directly or indirectly, so that at least a portion of product stream is delivered to the second convertor from the first convertor.The second convertor and separator c.) be connected, therefore the product stream from the second convertor is sent to separator c.) in.Thereby, separator c.) be indirectly connected with the 3rd convertor so that at separator c.) in the separated R that contains
1-O-R
2the water of type compound, and if need, by contained R
1-O-R
2the main quantity of type compound is sent in the 3rd convertor after fractionation by distillation in advance.Separator c.) have and being connected of the second convertor, it makes short hydrocarbon and separator c.) other gas phase composition can be recycled to the ingress of the second convertor.
Preferably, described equipment comprises the connection from the 3rd convertor to the first convertor, and it can be sent in the first convertor the CO and the H that in the 3rd convertor, form.
In order to carry out the distortion of the first product stream separation method, described equipment comprises for product stream being carried out to separated other separator from the first convertor.In this case, described other separator preferably has the connection of the first convertor, and it can be sent in the first convertor CO separated in separator and H.Should (other) separator preferably also have to first of the second convertor and connect, if needed, after it makes at least a portion at water separated, R
1-O-R
2the compound of type can be sent in the second convertor, and preferably also has the second connection to the second convertor, if needed, it makes to comprise CO and H
2at least a portion of air-flow can be sent in the second convertor.
In order to carry out the first product stream (all), be introduced directly into the deformation program in the second convertor, the first convertor on equipment directly, to there is the mode of material stream, be connected with the second convertor, so that whole product stream is not sent to the second convertor from the first convertor under having separative situation.In this case, separator is c.), it preferably has and being connected in the first convertor, and this connection makes dry gas (non-switched CO and H
2and short hydrocarbon) can be recycled in the first convertor.
In both cases, all to the second product stream that comprises hydrocarbon, gasoline hydrocarbon, gas and water, carry out separated.Comprise unreacted R
1-O-R
2the water of type compound, preferably at separator c.) in the device in downstream (preferably distillation tower), it provides the separated R with high-content in water
1-O-R
2the possibility of the product of type compound (particular methanol and if necessary DME), the R that this is separated
1-O-R
2the compound of type can be added in the source material in the second convertor again.Therefore, this is arranged in separator c.) device in downstream preferably has the R at water
1-O-R
2the separated concentrated solution of the compound of type is recovered to the connection in the second convertor.By this other device, R
1-O-R
2the compound of type is removed by halves from water.Therefore, this other device also has to the connection of the 3rd convertor, and it can be sent in the 3rd convertor, wherein by R still contaminated water
1-O-R
2the compound of type carries out separation.
For R
1-O-R
2the decomposition of type compound (be preferably methyl alcohol and if possible for DME), can use known catalyzer, a summary is described in following article, its author is the people such as Klabunowski E.I., title is " catalyzer that Catalysts of conversion of methanol intosynthesis gas(methanol conversion is synthetic gas) " (Katalyse in der Industrie, 2004, the 6th phase, 3-9 page), also can use CO steam reforming catalyst, methanol synthesis catalyst and other catalyzer.
In steps d .) in, can use the convertor of any type, yet, the throughflow type convertor (through flow converter) of the fixed bed of granular catalyzer preferably there is.For steps d .) convertor hereinafter referred to as desalt convertor.
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 catalyst regeneration state.
Term convertor synonymously uses with reactor in specification sheets of the present invention.For step a.) and/or step b.) the convertor throughflow type reactor that preferably wherein catalyzer is installed as fixed bed.
Preferably, the first and/or second convertor is carried out cooling.This is cooling carries out with optimal way by indirect evaporation is cooling.At step a.) and/or step b.) in response behaviour preferably carry out almost under isothermal, carrying out.Convertor described in preferred design, thus make it allow the reaction heat produce in catalyst bed directly and fully to dissipate, and so response behaviour in the volume of reaction chamber can be remained on almost under constant temperature.
By carry out cooling dissipated reaction heat in the first and/or second reactor, can be advantageously used in generation steam (water vapour).
The first convertor (methyl alcohol is synthetic and DME is synthetic if possible) heat transfer surface area preferably having and the ratio of catalyst volume are not less than 50m
2/ m
3, and not higher than 400m
2/ m
3.The pressure that the steam that the heat that use is dissipated in the first convertor produces preferably has is not less than 0.6Mpa, and not higher than 4MPa.
The second convertor (gasoline is synthetic) heat transfer surface area preferably having and the ratio of catalyst volume are not less than 40m
2/ m
3, and not higher than 200m
2/ m
3.The pressure that the water vapor that the reaction heat that use is dissipated in the second convertor produces preferably has is not less than 3.0Mpa, and not higher than 22MPa.
The reaction heat being dissipated by the steam producing can advantageously be used to produce refrigerant, and it can be used at step a.) and/or step b.) separation of later product.
Synthetic gas for technique can be from various raw material production.Described 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 starting material and the production method of production use.Synthetic gas also comprises inert fraction conventionally (as N
2and water).Synthetic gas is not preferably containing catalyzer poison (sulphur compound, nitrogen compound) and foreign matter, if be dried and need compressed.
For synthesizing of methyl alcohol or DME, H in synthetic gas
2the ratio of/CO is preferably not less than 2.In this case, the relative C in CO, has obtained the methyl alcohol (DME) of high yield.When less ratio, the productive rate of methyl alcohol (DME) reduces and CO
2gain in yield.
Each processing step of the method according to this invention is with further 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 first step
1-O-R
2type compound, can be introduced in second step from the first convertor in the mode of whole product stream, or carrys out separation from the product of the first convertor by any deformation program, then sends in second step.
From the product of the first convertor, methyl alcohol included in moisture mixture and possible dme can be carried out separated, the raw material of usining as second step.Unconverted synthetic gas is preferably separated from the product of the first convertor, or separated and be recovered to for R from the product of the second convertor
1-O-R
2in the first synthetic convertor of type compound.
Synthetic gas can advantageously be used unprocessed mixture, but be preferably dried and compress, if need, heat with recycle gas in this mixture, the highest temperature of this heating is the temperature that approaches temperature of reaction, this heating for example in recuperation heat exchanger and/or boiler (steam boiler, smelting furnace and/or electric furnace), and is incorporated in the first convertor (at accompanying drawing-unit I) to come for R
1-O-R
2synthesizing of type compound (methyl alcohol and if possible dme).In order to produce R
1-O-R
2, there is contacting of the catalyzer synthetic with methyl alcohol in the compound of type, 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 the catalyzer of cupric is used and is being up at the temperature of 260 ℃ and is being up under the pressure of 6Mpa.CO and H
2reaction under the formation of methanol is to move to heat release under the exothermic effects of the methyl alcohol of 90.73kJ/Mol.Here it is why at step a.) in preferably use the cooling convertor of isothermal.This convertor can reduce the volume of essential recycle gas, and synthesize under optimal conditions, wherein these conditions are: the corresponding reduction of formation of by product, increased the productive rate of methyl alcohol, extended the working time of catalyzer and the middle pressure steam that produces as energy carrier.
From R
1-O-R
2the product of the synthetic convertor of type compound preferably carries out cooling in heat exchanger, and wherein feedstream (synthetic gas) is preheated.As the scheme of a modification, product stream is preferably separated into gaseous product and phlegma.For this reason, product preferably carries out cooling in air-cooler and watercooler, and there is dme in product in the situation that, more additionally by low temperature apply carry out cooling.Organic composition and water are carried out to 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 for carrying out pre-mixing with material synthesis gas, in order that the conversion completely in the first convertor.
As deformation program, for the distillation tower of the mixture Separation of Water from comprising organic composition, can be connected the downstream of separator, because for by R
1-O-R
2type compound changes into the existence of the water in the raw material of the second convertor of hydrocarbon, has accelerated the irreversible inactivation for the zeolite catalyst of the second convertor.Yet this is very expensive operation, and the feedstream that dilutes the second convertor with inert fraction is more cost effective to reduce the dividing potential drop of water and methyl alcohol.
By separated R
1-O-R
2type compound (methyl alcohol or methyl alcohol/DME mixture) or from the product stream of the first convertor (unit I) deliver in the second convertor (in the accompanying drawings-unit III), come for gasoline synthetic, wherein, it be preferably 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 is preferably sent in recuperation heat exchanger, and heats in boiler, then delivers in gasoline synthesis converter.
Existence between the transition phase of methyl alcohol in the method for the invention of hydrogen and carbon monoxide (and if necessary dme), although 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.Hydrogen dividing potential drop is preferably 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 methyl alcohol separated from the first product stream (with dme if necessary), or are directly incorporated in the second convertor containing the first product stream of unconverted synthetic gas also.Hydrogen in the second convertor and carbon monoxide are taken on the component of dilution, i.e. their dilution educts (educt) (methyl alcohol and be DME if necessary).The dilution that methyl alcohol (methyl alcohol+DME) carries out in the feedstream of the second convertor by the dividing potential drop that makes methyl alcohol lower than the dividing potential drop of 0.5Mpa and water lower than 0.3MPa.
From the product of gasoline synthesis converter, preferably in recuperation heat exchanger, carry out coolingly, wherein the raw material of convertor (methyl alcohol and possible DME) is preferably heated, and if possible in having the mixture of recycle gas, is heated.Cooling flow is preferably sent to (unit IV in the accompanying drawings) in the second separator, with the product of separated gasoline synthesis converter.When carrying out in recuperation heat exchanger with in condenser when cooling, light hydrocarbon, unreacted R to gasoline hydrocarbon, a part
1-O-R
2the compound of type and water carry out condensation.In separator preferably by 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 methanol conversion process.The gas phase of a part be mixed with a part containing CO and H
2gas, it is from the first separator (unit II in the accompanying drawings), and preferably as diluted composition, is recovered in the raw material (methyl alcohol and if necessary DME) in gasoline synthesis converter.
From separator c.) gasoline hydrocarbon phlegma be preferably heated and be introduced in stabilizer tower, wherein (short hydrocarbon is propane, propylene, butane, butylene and methane, ethane, ethene and H to light overhead gas substantially
2) next separated from stable gasoline (stream 8 in the accompanying drawings).If need C
3-C
4hydrocarbon can be as liquid distillate C
3-C
4come separated.From being sent to the gasoline hydrocarbon of stabilizer tower, even heavy gasoline (stream 9 in the accompanying drawings) also can carry out at stabilizer tower or in other tower separation.
As deformation program, from separator c.) water (stream 10 in the accompanying drawings) can be introduced in distillation tower (the unit V in accompanying drawing 1+2), be then introduced in 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.Change the direction of this recovery stream in the synthetic unit of gasoline.The R of remaining contents level will be contained
1-O-R
2, the water preserved in the polywater place of tower introduces in desalt convertor.Can directly add from separator c.) water, for desalt.
Accompanying drawing explanation
Two preferred distortion of the method according to this invention, are described according to the following drawings.
Fig. 1 has shown the block diagram of producing the preferred method of gasoline from synthetic gas according to the present invention, wherein the recovery of synthetic gas is flowed from synthetic R
1-O-R
2separated and after fractionation by distillation, the methanol oxidation in water is decomposed from process water at the methyl alcohol of main quantity in the product of the convertor of type compound.
Fig. 2 has shown the block diagram of producing the preferred method of gasoline from synthetic gas according to the present invention, wherein the product stream from the first convertor is introduced directly in the second convertor, and the recovery stream of synthetic gas is separated from the product of gasoline synthesis converter, and the methyl alcohol in main quantity after fractionation by distillation, carries out catalytic decomposition by the methyl alcohol in water from process water.
Embodiment
In Fig. 1, ratio is depended on to the main component of its production method is synthetic gas 1 hydrogen and carbon monoxide, that also comprise inert component, slough catalyzer poison and additive and purifying, if necessary, compressed and be sent to R
1-O-R
2in synthetic first convertor (unit I) of type compound, at this place, it is mixed with recycle gas 3.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 the catalyzer synthetic with methyl alcohol contact or with methanol synthesis catalyst and methyl alcohol contacting to the catalyzer of the dehydration of dme.In Production of methanol, preferably the catalyzer of cupric is applied in to the temperature that is up to 260 ℃ and the pressure that is up to 8Mpa, still, even zinc chrome catalyzer also can be used, it operates being up under the temperature of 360 ℃ and the pressure higher than 8Mpa.
From R
1-O-R
2the product of the synthesis converter of type compound carries out cooling in heat exchanger, and feedstream carries out preheating in air-cooler He in watercooler therein, the in the situation that of there is dme, also will use low temperature, now R in product
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 separator (unit II).Gaseous product from separator is unreacted synthetic gas, a part wherein (stream 3) is introduced to mix with material synthesis gas, in order that raw material is changed completely.Separated R in separator
1-O-R
2the compound 4(methyl alcohol of type and if necessary DME), 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 the 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 then deliver in gasoline synthesis converter.
For the quality of gasoline (heavy gasoline of low share and aromatic substance) obtaining, R
1-O-R
2the transformation efficiency of the compound of type (methyl alcohol and if necessary DME) in the second convertor (unit III) preferably remains on lower than 99.5%.The product of gasoline synthesis converter contains: at R
1-O-R
2the hydrocarbon producing in the conversion process of type compound (particularly gasoline hydrocarbon) and unreacted be mainly the R of methyl alcohol
1-O-R
2type compound and gas composition.
Two convertors (unit I and III) are preferably all cooling convertors.Lower than 150 actual m
3/ m
3the flow velocity of recycle gas of catalyzer under, the first convertor has at least 50m
2the every 1m of heat transfer surface area
3catalyzer.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 the second convertor is 40m at least
2every 1m
3catalyzer.As mentioned above, the steam producing during cooling convertor, is used in steam heater, produce refrigerant by absorption-type refrigerator, usings the feedstream of preheating the first convertor and as the kerve heating (sump heating) of product separation tower.
The product of synthetic (unit III) convertor of gasoline is cooling in recuperation heat exchanger, and the raw material of convertor is heated therein, in water cooler, is further cooled.In cooling process, there is the condensation of gasoline hydrocarbon and water.Cooling flow 6 is transferred to separator c.) carry out the separation for gasoline synthesis reactor product in (unit IV).At separator c.) in, separated following material: 1. containing 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 methyl alcohol switching process.
In these cases, the recovery stream of light hydrocarbon gas 7 be mixed with a part from the first separator (unit II), containing CO and H
2gas 5, in order that obtain for R
1-O-R
2the dilution component of the synthesis material of type compound.
The hydrocarbon phlegma 6(of self-separation device (unit IV) comprises C in the future
5+hydrocarbon) be directed in stabilizer tower (unit IV), at this, locate light overhead gas 7 separated from stable gasoline 8.From unsettled gasoline hydrocarbon, even heavy gasoline 9 also can carry out separation in stabilizer tower or in other tower.
The water 10 of self-separation device is incorporated in unit V to come for R in the future
1-O-R
2concentrating of type compound, and be introduced in from here in unit VI to come for R
1-O-R
2the catalysis desalt of type compound.According to the level transforming, water herein contains the R between 3.5 % by weight and 30 % by weight conventionally
1-O-R
2the compound of type.
At R
1-O-R
2in the upgrading unit V of the compound of type, the enrichment of methyl alcohol realizes in the top of distillation tower, and it will keep Methanol Recovery stream 11, and this Methanol Recovery stream 11 is sent in gasoline synthesis unit III.Residuum from tower (unit V): water 12 is directed in desalt convertor (unit VI), carries out in water-bearing media in the catalytic decomposition 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), from the air-flow 13 of methanolysis, contain oxycarbide and hydrogen, it is directed in the first convertor (unit I).Obtained the water 14 of chemical purification, it is used to refill recycling cooling water system, steam generating system and for other object.
Manufacture method is that of the method that shows of Fig. 1 simplifies version as shown in Figure 2, and mainly different from Fig. 1 in the following areas:
The product of the first convertor (unit I), in heat exchanger and/or boiler and not heating under separation in advance, is directly directed in gasoline synthesis converter (unit III).
As the component of the dilution containing oxygen raw material, can reuse recycle gas 3(is from unit IV herein).
And herein, except recycle gas 3, other hydrogen and carbon monoxide 13 are before delivering to the first convertor or be also mixed with at that time synthetic gas 1, and described other hydrogen and carbon monoxide 13 form in catalysis desalt convertor (unit VI).With regard to its composition, the product of the 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 if necessary DME) is preferably maintained at lower than 99.5%.
First that the product of gasoline synthesis converter is cooling and then cooling in water cooler in recuperation heat exchanger herein.The stream 6 that part is cooling is fed in unit IV, carrys out the separation for the product of gasoline synthesis converter, and herein, cooling due in water cooler, the condensation of hydrocarbon and water has occurred.Containing unreacted R
1-O-R
2the water 10 of type compound is stored in separator, and carries out mutually separation by gasoline hydrocarbon phase is gentle.Gaseous product from separator is mainly comprised of unreacted synthetic gas and light hydrocarbon, and a part (stream 3) is wherein retrieved for mixing at the first convertor (unit I) with the synthetic gas starting, in order that raw material is transformed completely.
Depend on transformation efficiency, the methyl alcohol that the water forming in gasoline synthesis converter comprises (and being DME once in a while) is generally between 3.5% and 40%.Therefore, desalt occurs in distillation tower (unit V), then in independent desalt convertor (unit VI), by methyl alcohol, to the catalytic decomposition of hydrogen and oxycarbide, carry out (these gases are recycled in the synthetic gas in technique as mixture herein), referring to the description in Fig. 1.
Hydrocarbon phlegma from separator (unit IV) is directed in stabilizer tower (unit IV), wherein gasoline 8 is carried out to separation.Even heavy gasoline 9 also can carry out separation or in other tower, from unsettled gasoline hydrocarbon, carry out separation in stabilizer tower from unsettled gasoline hydrocarbon.
The water 10 of self-separation device is fed in unit V with enrichment R in the future
1-O-R
2the compound of type, is then fed in desalt convertor (unit VI).At R
1-O-R
2in the upgrading unit V of the compound of type, on the top that is enriched in distillation tower of methyl alcohol, part realizes, and it will accept the recovery stream 11 of this methyl alcohol, and this recovery stream is recycled in gasoline synthesis unit III.Residuum-the water 12 of the tower of contained methyl alcohol 5 between 2 and 5%, is sent in desalt convertor (unit VI).
In cleaning unit VI, the current that comprise methyl alcohol are preferably delivered in recuperation heat exchanger and/or preheater, it is heated to essential temperature of reaction herein, is then sent to desalt convertor, has realized herein and methyl alcohol contacting to the decomposition catalyst of hydrogen and oxycarbide.
Product from desalt convertor preferably comes cooling in recuperation heat exchanger and in air-cooler.Subsequently, gas phase is carried out in separator from phlegma to separation.In methyl alcohol 13 decomposes, the gas of separation leaves separator and guides it in the first convertor (unit I), to mix with material synthesis gas thus.The water of this purifying is sent in degassing tower.Obtained the water 14 of chemical purification, it is for refilling the cooling water system, steam generating system of circulation and for other object.
By water as illustrated in fig. 1 and 2, cooling convertor indirectly.Water absorbs the heat in heating carrier, and it obtains again heat from conversion zone.Water leaves unit I and III as steam.
Below, by means of comparative example and embodiment explanation the present invention.
Embodiment 1(comparative example)
This embodiment implements to be similar to the TIGAS method of Haldor Topsoe IJ Topp-Jorgensen company, the method be recorded in 1987 second edition " Studies in surface and catalysis(surface and catalyst research); V; 36, methane conversion(methanol conversion) ".
Fig. 3 has shown the block diagram of TIGAS method.
Synthetic gas is mixed with the circulation gas that comprises the unreacted component of synthetic gas and light hydrocarbon, and in the reactor of synthesizing methanol+DME, use the dual-function catalyst being formed by methanol synthesis catalyst component and methanol dehydration catalyst component to react.From methyl alcohol+DME+ water with from the mixture of unreacted synthesis gas components, being provided for gasoline synthesis step, in the situation that containing the catalyzer of zeolite, there is the conversion reaction that methyl alcohol and DME become hydrocarbon in it.Then product mixtures is separated into gasoline, adds water for cleaning phase, C3-C4 group and gas, wherein a part is supplied to the synthesis step of oxygenatedchemicals as circulation gas.Under the almost identical pressure within the scope of 50-100 bar, carry out in steps.
Use containing H
2: the synthetic gas of CO=3.
According to source, the CH based in synthetic gas
2, the productive rate of oxygenatedchemicals is 94%.With respect to the CH in 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 synthetic gas
2, the productive rate of gasoline is 73.34%.
In addition, enumerated the embodiment changing according to the difference of process program of the present invention.
Use has the actual synthetic gas 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 come for from synthetic gas methanol, and come for generating gasoline from methyl alcohol with the M/s.S ü dchemie zeolite containing catalyst of called after SMA-2.
Synthetic R in convertor
1-O-R
2the working conditions of type compound is: 210 to 260 ℃ of temperature ranges, pressure range 50 is to 55MPa.Catalyst volume is 0.46m, and the heat exchange surface in conversion zone is 30m.The vapor pressure generating is 1.8MPa.
In the convertor of synthetic gasoline, the pressure of embodiment 2-4 can be 7 bar, and the pressure of embodiment 5 is 45 bar.In response behaviour, process temperature is in the scope of 310 to 430 ℃, and in reproduced state, process temperature is the scope of 280 to 500 ℃.
The convertor of synthesizing methanol and synthetic gasoline is cooling.Use has 60m
2/ m
3the convertor of heat exchange surface.
Reaction in synthesizing methanol transmodulator and synthetic gasoline convertor is carried out under the condition of constant temperature almost, and wherein the temperature contrast of granules of catalyst is less than 5K.
In embodiment 2 to 4, the product separation that produces the technique of oxygenatedchemicals is carried out at the temperature of 40 ℃.In all samples, the product separation that gasoline is synthetic carries out at 5 ° of temperature more than C.
Embodiment 2 to 5 is characterised in that the different choice of application each distinguishing characteristics of the present invention.
Embodiment 2
For generating the main diagram corresponding to Fig. 1 of equipment (device) of synthetic gasoline, and comprise the unit (unit I) from synthetic gas synthesizing methanol, the unit of separation of methanol from the product stream of unit I (unit II), unit (unit III) from thick methanol synthesized gasoline, the fractionation unit (unit IV) of separated gasoline products, from the unit (unit V) of process water separation of methanol.
Compare with the diagram in Fig. 1, for the not operation of purification unit of the water containing methyl alcohol.With respect to Fig. 1, stream 5,13 and 14 does not occur in equipment,, in unit III, does not provide stream 5 that is.
material balance in table 2.1. system
From the production status of thick methanol synthesized gasoline, by the methanol conversion that turns of the methyl alcohol of synthetic gasoline, be not vapour (CO+CO
2)
From the synthetic gas of methyl alcohol synthesis unit, add to and close catalyzer: rate: the selectivity of oil: be converted into methyl alcohol
Become the unit of gasoline, there is no the transformation efficiency of water purification unit SMA-2 99% 86%:
94.7%
Year service hours number 8000.00
* with respect to the CH of methyl alcohol
2, * * is with respect to the CH of synthetic gas
2
the feature of illustrated stream in table 2.2. Fig. 1
Embodiment 3
For the production of the equipment of synthetic gasoline mainly corresponding to the diagram in Fig. 1, and comprise: from the unit (unit I) of synthetic gas synthesizing methanol, the unit of separation of methanol from the product stream of unit I (unit II), unit (unit III) from thick methanol synthesized gasoline, the fractionation unit (unit IV) of separated gasoline products, from the unit (unit V) of process water separation of methanol.
Not operation of unit for the purifying containing 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, be vapour (CO+CO
2)
State, does not have 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 feature of illustrated stream in table 3.2. Fig. 1
Embodiment 4
Producing equipment and the diagram in Fig. 1 of synthetic gasoline coincide, and comprise: from the unit (unit I) of synthetic gas synthesizing methanol, the unit of separation of methanol from the product stream of unit I (unit II), unit (unit III) from thick methanol synthesized gasoline, the fractionation unit (unit IV) of separated gasoline products, the unit of separation of methanol from process water (unit V), containing 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, be 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 feature of illustrated stream in table 4.2. Fig. 1
embodiment 5
Producing equipment and the diagram in Fig. 2 of synthetic gasoline coincide, and comprise: from the unit (unit I) of synthetic gas synthesizing methanol, from the product stream of unit I in the situation that there is no separation of methanol the unit of synthetic gasoline (unit III), the fractionation unit (unit IV) of separated gasoline products, for the unit (unit V) from process water separation of methanol, contain the purification unit (unit VI) of the water of methyl alcohol.
the material balance of table 5.1. system
The conversion methanol conversion of producing the methyl alcohol of synthetic gasoline from the synthetic stream of methyl alcohol 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 feature of illustrated stream in 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 product of the unit of type compound
3-recycle gas (synthetic gas, it is recovered to 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, it is supplied to unit III from unit II)
6-is from the product of gasoline synthesis unit
7-recycle hydrocarbons gas (being recycled to unit III from unit IV)
8-gasoline
9-heavy gasoline
10-process water
The R that 11 – are recovered
1-O-R
2the compound of type (particular methanol)
12-is containing R
1-O-R
2the waste water of type compound (particular methanol)
13-gas, it is at R
1-O-R
2in the sepn process of type compound (particular methanol), form
14-chemical purification water
15-gas
16-C3-C4 group
I – has the R of the first convertor
1-O-R
2the synthesis unit of type compound,
II-has the separating unit of the first separator
III-has the gasoline synthesis unit of the second convertor
IV-has the separating unit of the second separator and unsettled stabilization of gasoline tower
V-R
1-O-R
2type compound (particular methanol) comes concentrated unit in distillation tower from process water
VI-contains R
1-O-R
2the unit of the catalytic purification of the water of type compound (particular methanol)
Claims (14)
1. by being converted of synthetic gas, produce the method for hydrocarbon, the method is undertaken by following steps:
A.) contact to produce the first product stream with the catalyzer in the first convertor, it contains:
-at least one R
1-O-R
2the compound of type, wherein R
1-be the alkyl group with 1 to 5 carbon number, and R
2-for hydrogen, there is alkyl and the alkoxy base of 1 to 5 carbon number, and
The unreacted components of-synthetic gas;
Wherein in the first convertor, carry out with contacting under the condition of isothermal of catalyzer, wherein the temperature head in catalyst filling is no more than 40K, the condition of this isothermal realizes by removing reaction heat, this is removed reaction heat and is undertaken by heat transfer surface, and the ratio of heat transfer surface area and catalyst volume is not less than 50m
2/ m
3catalyzer, the heat of removing from the first convertor is used to produce has the steam that is up to 4MPa pressure,
B.) in the second convertor, make from whole products of the first convertor or contact with catalyzer after the unreacted components of separated at least a portion synthetic gas, produce product stream, the hydrogen partial pressure that the raw material of wherein said the second convertor demonstrates is greater than 0.07Mpa, the dividing potential drop of oxycarbide is greater than 0.008MPa, R
1-O-R
2the dividing potential drop that the dividing potential drop of type compound is less than 0.5MPa and water is less than 0.3Mpa, and described product stream contains:
-gasoline hydrocarbon, it comprises the aromatic substance that is up to 45 % by weight, wherein comprises the benzene that is up to 1 % by weight and the isoparaffin that is not less than 40 % by weight,
-C
1-C
4hydrocarbon,
-unreacted R
1-O-R
2the compound of type
-and synthetic gas in unreacted component,
Wherein in the second convertor, carry out with contacting under the condition of isothermal of catalyzer, wherein the temperature head in catalyst filling is no more than 40K, the condition of this isothermal realizes by removing reaction heat, this is removed reaction heat and is undertaken by heat transfer surface, and the ratio of heat transfer surface area and catalyst volume is not less than 40m
2/ m
3catalyzer, the heat of removing from the second convertor is used to produce has the steam that is up to 22MPa pressure,
Wherein synthetic gas is separated from the first and/or second product stream is also transmitted back in the first convertor as recycle gas at least in part;
C.) product in separated the second convertor, the unsettled gasoline that wherein obtained carrys out stabilization by known method, wherein obtains:
I.) gasoline fraction,,
Ii.) C
3-C
4the cut of hydrocarbon,
The air-flow of the unreacted components that iii.) contains light hydrocarbon and synthetic gas, and
Iv.) contain R
1-O-R
2the water of the unreacted compound of type,
Wherein said air-flow iii.) as the gas circulating, be sent back in the second convertor and/or the first convertor at least in part,
And described water iv.) be directly sent to purifying R
1-O-R
2the compound of type or be first sent to rectifying, wherein by rectifying at R
1-O-R
2the concentrated solution of the compound of type and by R
1-O-R
2in the water that type compound pollutes, carry out separation, wherein by R
1-O-R
2the water that type compound pollutes is sent to purifying, and wherein said purifying passes through R
1-O-R
2the catalytic decomposition of the compound of type is carried out, and wherein the oxycarbide of formation and hydrogen is mixed with synthetic gas and is recycled to R
1-O-R
2in the synthetic method of type compound.
2. method according to claim 1, is characterized in that, from step c) i.) the separated cut containing durol gasoline fraction.
3. method according to claim 1, is characterized in that, at step b.) in R
1-O-R
2the transformation efficiency of type compound is not less than 82% and not higher than 99.5%.
4. according to the method described in claim 1,2 or 3, it is characterized in that, make by R
1-O-R
2the compound polluted water of type and methanolysis contact being up at the temperature of 360 ℃ with catalyzer, and wherein result is the component that has formed water and the synthetic gas of purifying.
5. according to the method described in claim 1,2 or 3, it is characterized in that, make by R
1-O-R
2the compound polluted water of type and methanolysis contact being up at the temperature of 360 ℃ with catalyzer, and wherein result is water and hydrogen, carbon monoxide and the CO that has formed purifying
2.
6. method according to claim 4, is characterized in that, by R
1-O-R
2the compound polluted water of type carries out with contacting under certain pressure of catalyzer, and this pressure allows directly the component producing in synthetic gas to be sent in the first convertor or by means of recycle compressor and sent in the first convertor.
7. according to the method described in any one in claims 1 to 3, it is characterized in that, a part for synthetic gas separated from the first product stream is sent in the second convertor for regulating the dividing potential drop of hydrogen and oxycarbide.
8. according to the method described in any one in claims 1 to 3, it is characterized in that, a part for synthetic gas separated from the first product stream is sent in the second convertor for regulating the dividing potential drop of hydrogen and carbon monoxide.
9. carry out according to the equipment of the method described in any one in claim 1 to 8, 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;
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, its can be from product stream separated gasoline hydrocarbon, described product stream is except gasoline hydrocarbon and R
1-O-R
2outside the compound of type, also contain water and gas, described 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 being suitable for contained in water
1-O-R
2the compound for catalysis of type changes into CO and H
2catalyzer,
E.) pipe connecting from the 3rd convertor to the first convertor, it makes formed CO and H in the 3rd convertor
2can be introduced in the first convertor
F.) 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 for by separated R
1-O-R
2the compound of type is recycled to the pipe connecting in the second convertor,
G.) in the first and second convertors, remove the device of reaction heat, wherein saidly for removing the device of reaction heat, show below ratio: the ratio at the first convertor heat transfer surface area and catalyst volume is not less than 50m
2/ m
3, in the second convertor, the ratio of heat transfer surface area and catalyst volume is not less than 40m
2/ m
3.
10. equipment according to claim 9, be characterised in that it comprises the other separator for flowing from the first convertor separated product, wherein said other separator comprises the pipe connecting being connected on the first convertor, and this makes CO separated in this separator and H
2can be admitted in the first convertor.
11. equipment according to claim 10, is characterized in that, described other separator comprises the first pipe connecting being connected on the second convertor, and it makes R
1-O-R
2the compound of type optionally with H
2o is admitted in the second convertor together, and comprises the second pipe connecting being connected on the second convertor, and it makes CO and H
2optionally be admitted in the second convertor.
12. equipment according to claim 9, is characterized in that, the first convertor is directly connected on the second convertor, so that whole product streams is admitted in the second convertor from the first convertor.
13. equipment according to claim 12, is characterized in that, wherein separator c.) comprise the pipe connecting being connected on the first convertor, so that unreacted CO and H
2and short hydrocarbon can be fed in the first convertor.
14. according to the equipment described in any one in claim 9 to 13, is characterised in that the generation of the device permission water vapour of removing reaction heat in the first and/or second convertor.
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 |
Publications (2)
| Publication Number | Publication Date |
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| CN102686540A CN102686540A (en) | 2012-09-19 |
| CN102686540B true 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) |
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| WO (1) | WO2011061198A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016138165A1 (en) * | 2015-02-25 | 2016-09-01 | Sgc Energia S.A. (Formerly-Gi-Gasification International S.A.) | Systems, methods, and apparatuses for fischer-tropsch reactor cascade |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| DE102018103552B4 (en) * | 2018-02-16 | 2024-01-25 | Cac Engineering Gmbh | Process and system for producing a synthetic gasoline |
| 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 |
| 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 |
| FR3135265A1 (en) | 2022-05-06 | 2023-11-10 | Totalenergies Onetech | Process for obtaining hydrocarbons, 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 |
| FR3135264A1 (en) | 2022-05-06 | 2023-11-10 | Totalenergies Onetech | Process for manufacturing jet fuel, jet fuel and associated installation |
| CN115010567B (en) * | 2022-06-08 | 2024-05-14 | 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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- 2009-11-17 DE DE102009046790A patent/DE102009046790B9/en active Active
-
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- 2010-11-16 EA EA201200731A patent/EA021044B1/en not_active IP Right Cessation
- 2010-11-16 WO PCT/EP2010/067606 patent/WO2011061198A1/en active Application Filing
- 2010-11-16 CA CA2780483A patent/CA2780483C/en active Active
- 2010-11-16 AU AU2010320947A patent/AU2010320947B2/en active Active
- 2010-11-16 CN CN201080052110.2A patent/CN102686540B/en active Active
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| US4788369A (en) * | 1985-12-31 | 1988-11-29 | Mobil Oil Corporation | Conversion of methanol to gasoline |
| US5602289A (en) * | 1994-11-09 | 1997-02-11 | Starchem, Inc. | Conversion of methanol to gasoline |
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| WO2016138165A1 (en) * | 2015-02-25 | 2016-09-01 | Sgc Energia S.A. (Formerly-Gi-Gasification International S.A.) | Systems, methods, and apparatuses for fischer-tropsch reactor cascade |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102009046790B4 (en) | 2012-05-16 |
| CA2780483A1 (en) | 2011-05-26 |
| CA2780483C (en) | 2013-03-05 |
| AU2010320947A1 (en) | 2012-06-07 |
| EA201200731A1 (en) | 2012-10-30 |
| AU2010320947B2 (en) | 2014-01-23 |
| CN102686540A (en) | 2012-09-19 |
| DE102009046790A1 (en) | 2011-05-19 |
| EA021044B1 (en) | 2015-03-31 |
| DE102009046790B9 (en) | 2013-05-08 |
| WO2011061198A1 (en) | 2011-05-26 |
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