AU2010320947A1 - 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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- AU2010320947A1 AU2010320947A1 AU2010320947A AU2010320947A AU2010320947A1 AU 2010320947 A1 AU2010320947 A1 AU 2010320947A1 AU 2010320947 A AU2010320947 A AU 2010320947A AU 2010320947 A AU2010320947 A AU 2010320947A AU 2010320947 A1 AU2010320947 A1 AU 2010320947A1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
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- 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
j ransialon OT VVU/ZUl 1/Ub1 1 Ub HUI /LP2U1U/U67606 METHOD FOR GENERATING HYDROCARBONS, IN PARTICULAR GASOLINE, FROM SYNTHESIS GAS The invention relates to a method for the generation of hydrocarbons, particularly gasoline, from non-hydrocarbon-containing compounds, in particular from synthesis gas, which contain carbon monoxide and hydrogen. State of the art Synthesis gas, which is primarily a mixture of carbon monoxide and hydrogen, can be generated from various easily accessible solid and gaseous sources of carbon and hydrogen. The hydrocarbon feedstock synthesized on the basis of synthesis gas and the motor fuels are real alternatives to the gasoline hydrocarbons and partially better in their quality. Therefore, the effectiveness of the technology for converting synthesis gas into hydrocarbon is a topical problem for many years. In the Fischer-Tropsch-synthesis (US 1,746,464) developed 1925 synthesis gas is directly catalytically converted to hydrocarbons. It is known that gasoline from synthesis gas can be generated in two stages: first, the synthesis of oxygen compounds (such as methanol or also dimethyl ether, or a mixture of both compounds) is carried out, then the conversion of oxygen compounds on a zeolite containing catalyst in a mixture of hydrocarbons. Some methods in the generation of gasoline from synthesis gas were developed by the company "Mobil Oil" according to this scheme. Both stages of the process are described in scientific, technical and patent literature: the synthesis of methanol is explained in detail for example in the book by Karawajewa M. M. et al "Technology of synthetic methanol", M.: Chimija, 1984; the synthesis of a mixture of methanol and dimethyl ether in US 3,894,102; the synthesis of hydrocarbons from methanol and dimethyl ether - a review of C. D. Chang, Catal. Rev. - Sei. Eng., Vol 25, No. 1 (1983) and US 4 404 414 from 1983. US 6,191,175 discloses a process for the generation of methanol and dimethyl ether. Here, first the synthesis of methanol from synthesis gas takes place, which is preheated and guided into a first reactor. The reaction product is possibly mixed with synthesis gas and once again transferred into a second reactor, which serves for either methanol synthesis or synthesis of dimethyl ether. In order to achieve high product capacities, the method is carried out preferably adiabatically.
i ransiation OT VVU/2U1 1/Ul 196 C I I /LP2U10/067606 US 5,908,963A discloses a method for the generation of dimethyl ether. The product can contain up to 20 wt.-% methanol and up to 20 wt.- % water. In a first process step, synthesis gas in a gas mixture of dimethyl ether, methanol and water is converted in one or more reactors. The used catalysts have a methanol synthesis activity as well as the ability for dehydration of methanol. The gas mixture is separated by means of multiple distillation- and washing steps to get pure dimethyl ether. In the process of converting synthesis gas into gasoline according to US 3,894,102 (from 1975), the contact of synthesis with a catalytic converter, which consists of a mixture of a methanol synthesis catalyst and an acidic catalyst of dehydration, at a temperature of 371 *C under conditions for generation of a product that contains dimethyl ether, is realised. In the second stage, the contact of at least the dimethyl ether with a zeolite catalyst at a temperature of 288-454 0C, pressure up to 21 MPa and a mass flow of feedstock supply of 0.5-1000 h 1 is realized, whereby a product is generated, the organic portion of which is preferably gasoline. The product of the first stage can be directly conducted to the second, or it is separated, for example, the water is separated (with or without methanol), also H 2 and carbon monoxide (not converted synthesis gas) is separated, which are recycled to the first stage (possibly after outward transfer of C02). According to the state of the art, the process of conversion of methanol and dimethyl ether, which are synthesized typically in the first stage, is realized under conditions of almost complete conversion, whereby the oxygen compounds accumulate in water and there is the problem of utilization of waste water and I or the separation of the oxygen compounds from aqueous flows, what significantly worsened the economic indicators of the process, In this context, processes of conversion of oxygen compounds into hydrocarbons are proposed in the state of the art,, which solve the problem by maintaining a degree of conversion of feedstock at a level of more than 99%. The water separated from the final product is led away from the system and supplied to the biological or biochemical purification. US 4,814,535 (from 1989) discloses a method of generation of gasoline from oxygen containing compounds with a number of 1 to 4 carbon atoms. Conversion of feedstock is maintained thereby at a level of 99.9% by increasing the temperature gradually at the inlet to the reactor and the feedstock flow is decreased. While decreasing the degree of conversion below 99.9%, the supply of feedstock is interrupted.
I I driatiun101 UT VV U I U i I 'I-'U I /|--ZU'IU/Ubtbub US 4,523,046 (from 1985) discloses a method of creating gasoline from methanol is disclosed in. Here, the catalyst is placed in single beds and by contact of the feedstock with the catalyst bed a degree of conversion of the feedstock of virtually 100% is achieved. In case of decrease of degree of conversion, the feedstock is directed to the next catalyst bed. In order to improve the generation process of gasoline from synthesis gas or methanol or from methanol and dimethyl ether (DME) various aspects are considered according to the state of the art, including the temperature control in the zone of high exothermal conversion of methanol and DME into hydrocarbons and gasoline selectivity and -quality, specifically the content of aromatic hydrocarbons, especially the heavy hydrocarbons, in the generated gasoline. The temperature control in the zone of conversion of methanol and DME in hydrocarbons is done using diluting constituents , which itself do not take part in the reaction, in the feedstock. In the method according to US 4 035 430 (from 1977), at least a compound from C1 to C 5 -hydrocarbons and the cooled durene-containing product are used. The latter compound along with temperature has an influence on the yield of aromatic hydrocarbons and the content of the contained fractions of BTX (benzene, toluene, xylene). As diluting constituents, not participating in the main reaction, a fraction of liquid product (C3 / C4- fraction) is used according to US 4,788,369 (from 1988), which is separated from the reaction product and recycled to the reactor. Thereby, there is an additional effect - the increase of the gasoline yield by the oligomerization of recycled olefins, as a secondary reaction. In the method according to US 4 404 414 (from 1983) for the generation of hydrocarbons, inert diluted constituents are used: light gas, which was separated from the reaction product as well as steam, hydrogen and C2. - and C3+ - hydrocarbons or their mixtures. In US 5 602 289, as diluted constituent a gas is used, which consists of two mixed gas flows (C2- - hydrocarbons and C3+ - hydrocarbons) recycled to the reactor. The partial pressure of the water, including the water, which was formed in the reaction of methanol conversion in the reactor, is under 2.2 atm. The limit of the partial pressure of steam is determined by the known effect of irreversible deactivation of zeolite in the presence of water vapour. The composition of the diluting constituents is specified in this preferred case by a ratio of C2- hydrocarbons / C3, hydrocarbons in the limits between 1/3 to 3/1 and hydrogen content between 10 and 50% Mol. The use of gases with a low heat capacity (hydrogen, C2- - I ransiation OT VU/2eU1 IU il 19805 PG/EP2010/067606 hydrocarbons) as diluting constituents increases the dilution factor, but allows the conversion of methanol into hydrocarbons at a higher pressure (in compliance with the required upper limit for the water vapour partial pressure). Objective The objective of the invention is the development of an economic and simplified process of generation of hydrocarbons from synthesis gas as well as a simple device scheme with simplified technological stages. It also aims at achieving a high selectivity of gasoline with simultaneously a high gasoline quality and the provision of a waste-free technology without polluting secondary products. Brief description of the invention According to the invention, the objective is achieved by a method for the generation of hydrocarbons, according to claim 1: In the process according to the invention, the generation of hydrocarbons takes place conversion of CO- and H 2 -containing gas mixture (called subsequently also synthesis gas) by a.) Contact with a catalyst in a first converter for the generation of the first product flow, which contains at least a chemical compound of the type R 1
-O-R
2 (where R'- are alkyl groups with a carbon number from 1 to 5, R 2 - hydrogen, alkyl- and alkoxy groups with a carbon number from 1 to 5), which is preferably methanol and/or, if required, dimethyl ether, as well as unconverted constituents of synthesis gas, which can be separated from the liquid phase and are at least partially fed into the first converter, b.) Contact of the entire product from the first converter or after separation by minimum one part of the non-reacted constituents of synthesis gas, with a catalytic converter in a second converter preferably at a partial pressure of hydrogen by greater than 0.07 MPa, the oxides of carbon by greater than 0,008 MPa, the compound of the type R 1
-O-R
2 , preferably methanol and/or of dimethyl ether, of less than 0.5 MPa, I [Udiidliul or VVU/4Ul Il /Uwol ' do MU I /Ut- 2U1 U 1UUi/UU of water of less than 0.3 MPa, preferably at a conversion rate of the compound of the type RI-0-R 2 of not less than 82 %, preferably at a methanol conversion rate of not less than 82 % and not more than 99.5 %, as well as, if necessary, at a dimethyl ether-conversion rate of not less than 92 % and not more than 99.8, for generation of a product flow, that contains: - gasoline hydrocarbons, with preferably up to 45 wt.-% aromatic compounds, which contain up to 1 wt.-% gasoline and preferably no less than 40 wt.-% Iso-paraffins (branched saturated aliphatic hydrocarbons with at least 5 C atoms), -C1-C4- hydrocarbons, which are preferably formed in an amount of not more than 17 wt.-% (converted to C in the converted methanol and/or, if necessary, in the converted dimethyl ether), - unconverted compounds of the type R 1
-O-R
2 , - as well as non-reacting constituents of synthesis gas, whereby synthesis gas is separated from the first and / or second product flow and is fed back at least partly as circuit gas into the first converter, c.) separation of the product of the second converter for synthesis of instable gasoline, which is stabilized with known methods, whereby - a gasoline fraction, from which, if necessary, a heavy gasoline fraction, which contains durene (1,2,4,5 tetramethyl benzene), is separated, - a fraction of C3-C4 hydrocarbons, - and also a gas flow which contains light hydrocarbons (C1 and C2), non-reacting constituents of synthesis gas and other constituents that participate in the process, which at least partially can be recycled to the second converter and/or the first converter, and also -an aqueous phase, which contains methanol and/or a different compound of the type R 1 -0-R 2 iransiation OT VVU/U11 /U01' HUU I /LPU1U/U0(0U are obtained. The aqueous phase, which contains the compound of the type R 1
-O-R
2 , is given either to cleaning or to rectification. A separation takes place due to rectification in a concentrated solution of the compound of the type R 1
-O-R
2 in water (preferably not less than 75% compound of the type R 1
-O-R
2 ) and in a water contaminated with the compound of the type
R
1
-O-R
2 (preferred amount of compound of the type R 1
-O-R
2 ), which is given for cleaning. In any case, the cleaning of the compound of the type R 1
-O-R
2 takes place either, as explained below, through a catalytic decomposition of methanol and/or any other compound of the type
R'-O-R
2 or by biological methods. The converters of the synthesis of compounds of the type R 1
-O-R
2 and of the synthesis of gasoline with discharge of heat of exothermal reaction from the reaction zone have heat transfer surfaces, through which reaction heat is transferred to a boiling heat carrier. The heat carrier (or its vapours) condenses in a cooling zone, which contains preferably boiling water for generating steam. The condensate flows back into the zone of the reaction heat (principle of "heat pipe"). The reactions in the converters of the synthesis of compounds of the type R 1
-O-R
2 and the synthesis of gasoline are carried out preferably under nearly isothermal conditions, in which the temperature difference (AT) within the catalyst filling does not exceed 40 K, preferably at a AT of 10-20 K, especially preferred at a AT of under 5 K. Thereby, the reaction heat is used preferably for generation of steam with a pressure of up to 4 MPa in the converter for synthesis of compounds of the type R 1
-O-R
2 and up to 22 MPa in the converter for synthesis of gasoline. The dissipation of heat through the heat transfer surface for the generation of vapour facilitates to limit the dilution of input material flows with circulation gas up to 150 real M 3 / M 3 catalyst in the converter of methanol synthesis (hereinafter circuit gas) and 0-150 real M 3 / M 3 catalyst in the converter of gasoline synthesis (hereinafter circulating gas). The method according to the invention for the generation of gasoline from synthesis gas includes the contact of synthesis with the catalyst in the first converter (converter for synthesis of oxygen-containing compounds) under the conditions of the synthesis of compounds of the type R'-O-R 2 . The term "compound of the type R 1 -O-R2" denotes -with R 1 - alkyl radical with 1 to 5 C atoms, - R2 - hydrogen, alkyl and alkoxy radical with 1 to 5 C i rd 1isiation oT vvu/'Iu 'I /Ui'i 'i t-u i /t|-'2U IU/UO/(OUO atoms. Preferred compounds of the type R'-O-R 2 are methanol (CH 3 = R 1 and H = R 2 ) and if necessary dimethyl ether (R 1 = R2 = CH 3 ), in particular the methanol synthesized in the converter for synthesis of compounds of the type R 1 -0-R 2 (called subsequently also converter for methanol synthesis) or the mixture of methanol and dimethyl ether. Synthesis of compounds of the tve R 1 -0-R 2 : Preferably, synthesis gas is used as starting material for the synthesis of compounds of the type R 1
-O-R
2 . In the converter for synthesis of compounds of the type R'-O-R 2 (if the compound of the type R 1 -0-R 2 is methanol), particularly following reactions take place: CO + H 2 0 <--+ 0 02 + H 2 water gas reaction CO + 2 H 2 +-+ CH 3 0H methanol formation and if necessary in case of use of an additional acidic catalyst component for methanol synthesis catalyst for the synthesis of dimethyl ether: 2 CH 3 0H +---> CH 3
-O-CH
3 + H 2 0 DME-formation The catalyst used controls whether in the first stage methanol or a mixture of methanol and dimethyl ether (DME) or other compounds of the type R 1
-O-R
2 are generated. For methanol synthesis, preferably catalysts used usually for the methanol synthesis according to the state of the art (for example zinc chromium oxide catalysts, copper-based catalysts with additives of zinc oxide and / or aluminium oxide; Combinations of copper and rare-earth metals; Copper oxide / zinc oxide catalysts as well as copper oxide / zinc oxide / chromium oxide catalysts and others). For the synthesis of a mixture of methanol and dimethyl ether, according to the state of the art, known catalysts for the synthesis of methanol with a catalyst of dehydration, particularly catalytic converters with strong acidic properties, for example, yAl 2
O
3 or zeolite in protonated form with high acidity, as mixture or individually for application. The corresponding catalysts and conditions are well known and described, for example, for methanol synthesis in the book by M.M. Karawaewa and others "Technologija sintetitscheskogo metanolan, M.: Chimija, 1984 and for the synthesis of DME in the patent US 3,894,102.
i ransiation ot wUI2U1 1/0U1198 PCI/EP2010/067606 The product flow of the converter for synthesis of compounds of the type R'-O-R 2 is preferably cooled with subsequent separation of the liquid and gaseous phase in the separator. Alternatively, the (complete) product flow from the converter for methanol synthesis without separation is fed directly into the second converter of synthesis of gasoline. If a separation takes place, the unconverted constituents of synthesis (CO, H 2 , CO 2 , nitrogen and others) are fed preferably partly into the first converter of synthesis of compounds of the type R'-O-R 2 , i.e. they are mixed with the applied used gas mixture containing CO and H 2 , mixed and partly the unconverted synthesis gas is fed into the converter for synthesis of gasoline for suppressing the reaction of decomposition of compounds of the type R 1
-O-R
2 . At the same time, it is preferably transferred out to another part from the process, in order to avoid the accumulation of inert constituents. The supply of a part of non-reacted constituents of synthesis gas into the converter of gasoline synthesis is realized with a volume flow at the inlet to the converter of gasoline synthesis, which ensures a partial pressure of hydrogen of not less than 0.07 MPa and of CO of not less than 0.08 MPa. For the synthesis of compounds of the type R 1
-O-R
2 , cooled converters with nearly isothermal conditions in the reaction chamber are used with a preferred heat transfer surface of more than 50 m 2 / m 3 catalyst. Thereby, the volume of the circuit gas, which to a large extent consists of non-reacted synthesis gas and short-chain hydrocarbon gas is preferably less than 150 M 3 , relative to 1 m 3 catalyst. Gasoline synthesis: In the converter of gasoline synthesis, the contact of at least a part of product flow from the converter for synthesis of compounds of the type R'-O-R 2 takes place with the catalyst in a preferred degree of conversion of the compound of the type R 1
-O-R
2 from 85% to 99.5%. In the converter for synthesis of gasoline, contact with the catalyst takes place either of the entire flow from the converter to the synthesis of compounds of the type R'-O-R 2 or of total (at least a part) liquid constituent of the product flow with a part of the constituents of the gas of the product flow of the converter for the synthesis of compounds of the type R 1
-O-R
2 , which ensures in the feedstock flow of the converter of gasoline synthesis, converted to 1 M 3 (i. N.) gas flow, a partial pressure of H 2 of more than 0.07 MPa and a partial pressure of CO more than 0.008 MPA. These values for the partial pressures of H 2 and CO ensure the I Idi lsidlu[n UI VVU/4U I I /UO-I I t I'U I /-1U'l U/U /bUt suppression of the reaction of decomposition of compounds of the type R 1
-O-R
2 in the converter of gasoline synthesis. There is a wide range of catalysts for the synthesis of hydrocarbons from methanol and dimethyl ether. A part of them is described in the book Nefjodow BK., Konowaltschikow L., Rostanin N. N. "Catalysts of petroleum processing and petrochemicals based on zeolite with high silicon content", M: ZNIITENEFTECHIM, 1987. The catalyst for the synthesis of gasoline from compounds of the type R 1
-O-R
2 contains preferably at least partially a protonated zeolite (such as HZSM-5), preferably from the group of the pentasils. Preferably, zeolites with a high SiO 2
O
3 / A1 2 0 3 -ratio of at least 12 are used, especially preferred with a Si0203 / A1 2 0 3 -ratio of at least 30. The use of silicon-rich zeolite reduces the formation of Durene in the product. A steam-stable catalyst can be obtained by modifying with elements of the group lb. Combinations of silicon dioxide with oxides of metals (gallium oxide and / or Indium oxide) can also be used (US 4,507,404 of 1985, EP 0,070,690 of 1983, EP 0,124,999 of 1984). If, for example, gallium oxide and / or Indium oxide is combined with thorium oxide and a silicon-rich zeolite, a high-quality, aromatic-rich gasoline can be obtained (EP 0,070,690 of 1983). The input substance fed to the second converter is either the entire first product flow or the part, which contains the compound of the type R 1 -0-R 2 . The partial pressure of the compound of the type R 1 -0-R 2 (preferably of methanol and if any of dimethyl ether) in the input substance of the converter of gasoline synthesis, converted to 1 m 3 (i. N.) gas flow, is particularly advantageously maintained under 0.5 MPa (favourable distinctive feature). The partial pressure of the vapour in the input substance of converter of gasoline synthesis lies particularly advantageously under 0.3 MPa (favourable distinctive feature). The process in the converter of gasoline synthesis is carried out especially advantageously at a partial pressure of hydrogen of at least 0.07 MPa and at a partial pressure of carbon monoxide of at least 0.008 MPa (favourable distinctive feature). The inventive process is characterized by the fact that the contact of the input substance with the catalyst in the second converter takes place in the presence of hydrogen and carbon monoxide. Thus, the selectivity of the conversion of the compound of the type R 1 -0
R
2 (preferably methanol and dimethyl ether) is advantageously increased in hydrocarbons, as their decomposition to oxides of carbon and hydrogen is suppressed.
I I .la LIoI I ui VV'J,4U I I/UU I I ZO r'.. I /[: 4U IIU/UO DUD A cool able converter under near isothermal conditions in the reaction zone with a heat transfer surface of about 40 M2/ m 3 catalyst is preferably used for gasoline synthesis. The volume of circulating gas amounts to less than 150 m 3 with reference to 1 m 3 catalyst . The reaction heat is used preferably for producing water vapour with a pressure up to 22 MPa. This is also a distinctive feature of the invention, which along with features of the claim 1 allows a high quality of gasoline with a selectivity of more than 83 %, preferably more than 86 %. The term selectivity is here understood as the yield of gasoline relative to the hydrocarbon portion of reacted methanol. Preferably the conversion of the compound of the type R'-O-R 2 (preferably of methanol and if any of dimethyl ether) in the converter of gasoline synthesis amounts to more than 85% and less than 99.5% for methanol and more than 92% and less than 99.8% for dimethyl ether. The incomplete conversion of the compound of the type R 1
-O-R
2 is a key distinctive feature of the invention, which allows to control the selectivity of the process (yield of the gasoline group relative to the hydrocarbon content of the converted compound of the type
R
1
-O-R
2 ) in connection with the necessary quality of generated gasoline and the duration of intermediate generation cycle (operating life of the process between the regeneration of the catalyst). This is the reason for the fact that in the invention gasoline with a content of aromatic compounds of less than 46%, with a gasoline volume contained therein of less than 1 Mass-% of iso-paraffins of more than 40% with high octane number patterns (93-96 ROZ), which is also a distinctive feature of the invention. Besides the hydrocarbons, the product of gasoline synthesis from compounds of the type
R
1
-O-R
2 C3- C4 - hydrocarbons, water, contains no-reacting methanol and other compounds of the type R 1
-O-R
2 , as well as "dry" gas. This "dry" gas contains mainly gaseous substances (short-chain hydrocarbons (C1-C2), CO, C02 and H 2 and other constituents of synthesis gas). Separation of the products of the gasoline synthesis: The product of the gasoline synthesis is cooled and separated in unstable gasoline, an aqueous phase and in the non-condensed constituents of the gas. The separation takes place preferably by a physical phase separation in a three-phase separator. The non condensed gas constituents contain constituents of synthesis gas, light hydrocarbons (C, and C2), traces of heavier hydrocarbons. This circulating gas is recycled at least partially into the converter of gasoline synthesis and/or into the converter for synthesis of compounds of the type R'-O-R 2 . With the volume of circulating gas into the converter of gasoline synthesis, the partial pressure of methanol and water can be set advantageously.
I ransiation OT VVU/ZU1 I/Ub1 196 8IC [/EP2010/067606 The liquid phase in the three-phase separator forms a phase boundary between water and hydrocarbons, which contains the hydrocarbons, due to the density difference. The liquid with the lower density (hydrocarbons) collects above the phase boundary, while the aqueous phase settles at the bottom. The liquid hydrocarbons separated in the three phase separator contain the hydrocarbons that preferably are directed to a distillation column, in which, if necessary, preferred constituents of heavy gasoline (Durene fraction) and overhead gases - mainly C3-C4 hydrocarbons and remains of C-C 2 -hydrocarbons (short-chain hydrocarbons) and synthesis gas constituents are separated. In case of a permissible content of Durene in the hydrocarbons the heavy gasoline is not separated. The obtained stable gasoline fraction with a necessary saturated steam pressure of under 500 - 700 mm QS (as a function of the required gasoline type) is either a commercial petrol or forms the basis for the generation of commercial petrol with an octane number of 92-98 (ROZ). The water separated in the three-phase separator contains methanol. The methanol content of water depends on the methanol conversion rate in the gasoline synthesis, generally it is more than 3 wt.-% and less than 30 wt.-%. Preferably, the aqueous phase with a defined methanol content or with others compounds of the type R 1 -0-R 2 is first separated into fractions in a distillation column due to the different boiling temperatures, of which a fraction is mainly methanol or a different compound of the type R 1 -0-R 2 with a low water content (concentrated methanol) and the other fraction contains water with a small content of methanol (contaminated water). The concentrated methanol and if applicable dimethyl ether or a another compound of the type R 1
-O-R
2 is preferably recycled into the converter of gasoline synthesis. Contaminated water contains a residual content of methanol (usually max. 5 wt.-%) or another compound of the type R 1 -0
R
2 For removal of residual methanol from the contaminated water of the inventive method, methanol and possibly another compound of the type R 1 -0-R 2 is decomposed catalytically by the contact with a catalyst (steam reformation or catalytic decomposition) into hydrogen and gaseous oxides of carbon. The water is separated after cooling, by condensation, of the generated oxides of carbon (CO and C02) and of hydrogen. The carbon oxides and hydrogen can be advantageously mixed with the synthesis gas and recycled into the process of synthesis of compounds of the type R 1
-O-R
2 . After separation of gases, in subsequent i ransiation ot wo/201 1/061198 PCTIEP2010/067606 degasification of water, chemically purified water is obtained. The contact of the methanol containing water with the catalytic converter is preferred at a temperature below 380 *C, particularly preferred under 350 0C and preferably above 200 *C. The contact of the water, which contains a compound of the type R'-O-R 2 (preferably methanol, possibly dimethyl ether), with the catalyst is realised preferably at a pressure, which allows it to conduct the generated constituents of synthesis in the first converter directly or with the help of a cycle compressor into the first converter. This pressure corresponds to the sum of the pressure of the reaction for the synthesis of compounds of the Type R 1
-O-R
2 and the pressure loss between exit of the product of the catalytic decomposition of methanol and entry of the input substance into the converter for methanol synthesis. Alternatively, the remaining content of the chemical compound of the type R 1 -0-R 2 in the water are removed by a biological cleaning method. The biologically purified water can be supplied into the waste water network. Thereby, one needs to consider however that the biological cleaning requires a methanol content in water under 0.2 - 1 wt.-% and obtaining such concentrations by fractionation is associated with high energy costs, or requires a large dilution of contaminated water with pure water, which increases the cost of biological cleaning. The use of catalytic purification of water from compounds of the type R 1
-O-R
2 is another advantageous distinctinctive feature, because it allows control of process conditions in the converter of gasoline synthesis with relatively low effort, to reduce degree of conversion of compounds of the type R 1
-O-R
2 and to achieve thereby a high selectivity and quality of the products. Device (plant): An object of the invention is also a device (plant) to execute the method according to the invention. This device (plant)comprises: a.) at least one first converter containing a catalyst that is suitable to catalyze the conversion of CO with H 2 to the chemical compound of the type R 1
-O-R
2 (preferably methanol), I ranslation ot WO/2011/061198 PCT/EP2010/067606 b.) at least one second converter containing a catalyst that is suitable to catalyze the chemical compound of the type R 1
-O-R
2 into hydrocarbons, c.) at least one separator, which is suitable to separate hydrocarbons from a product flow, which in addition to hydrocarbons also contains chemical compounds of the type
R
1
-O-R
2 water and gas, comprising short-chain hydrocarbons, constituents of synthesis gas, compounds of the type R 1
-O-R
2 and traces of hydrocarbons, d.) at least one third converter containing a catalyst that is suitable to catalyze the conversion of the chemical compound of the type R'-O-R 2 (preferably methanol) contained in the water into CO and H 2 . The above components are connected preferably in series, i.e. the first converter is connected with the second converter directly or indirectly, so that at least a part of the product flow is fed from the first converter to the second converter. The second converter is connected with the separator c.), so that the product flow from the second converter is fed into the separator c.). Thereby, the separator c.) is indirectly connected with the third converter in a way that the water, which was separated in the separator c.) and contains the chemical compound of the type R 1
-O-R
2 , is fed, if necessary, after a previous distillate separation of main quantity of the compound of the type R'-O-R 2 to the third converter. The separator c.) has a connection with the second converter, which allows the short-chain hydrocarbons and the other constituents of the gas phase of the separator c.) to be recycled to the inlet of the second converter. Preferably, the device contains a connection from the third converter to the first converter, which enables to feed CO and H, formed in the third converter, into the first converter. To carry out the variant of the method with the separation of the first product flow, the device contains an additional separator for separation of the product flow from the first converter. In this case, the additional separator has preferably a connection to the first converter, which enables to feed CO and H separated in the separator into the first converter, This (additional) separator has preferably also a first connection to the second converter, which enables the feeding of chemical compounds of the type R 1
-O-R
2 , if necessary, after separation of at least one part of water into the second converter and a second connection to the second converter, which enables, if necessary, the feeding of at least a portion of the gas flow, which contains CO and H 2 , to the second converter.
i ranslation of WO/20111061198 PCT/EP2010/067606 To carry out the variant with the direct introduction of (complete) first product flow to the second converter, the first converter is connected in the device directly with the second converter with a material flow, so that the complete product flow from the first converter in the second converter is fed without separation. In this case, the separator is c.) has preferably a connection to the first converter, which allows recycling of dry gas (not converted CO and H 2 , and short-chain hydrocarbons) into the first converter. In either case, a separation of the second product flow, containing hydrocarbons, gasoline hydrocarbons, gas and water, takes place. The water, which contains the non-reacted chemical compound of the type R 1
-O-R
2 , is preferably in an apparatus downstream the separator c.) (preferably a distillation column), which provides the possibility of separating a product with a high content of the compound of the type R 1
-O-R
2 (preferably methanol and DME, if required) in water, which can be added to the source material of the second converter again. Thus, this apparatus located downstream the separator c.) has preferably a connection for recycling the separated concentrated solution of the chemical compound of the type R 1
-O-R
2 in water into the second converter. Through this additional apparatus the compound of the type R 1
-O-R
2 is not completely removed from the water. The additional apparatus therefore has also a connection to the third converter that allows feeding of the still contaminated water into the third converter, in which the compound of the type R 1
-O-R
2 is separated. For the decomposition of the compound of the type R 1
-O-R
2 (preferably methanol and possibly DME) known catalysts can be used, an overview is given in the article by Klabunowski E. 1, and others "Catalysts of conversion of methanol into synthesis gas" (Katalyse in der Industrie, 2004, No.6, pp. 3-9), and also catalysts of the steam reforming or CO, methanol synthesis catalysts and other catalysts. In step d.) a converter of any type can be used, however a through flow converter with fixed bed of granulated catalyst is preferred. The converter used in step d.) is hereinafter called converter of water purification. For organizing a continuous process of generation of synthetic gasoline from synthesis gas, not one but two converters are preferably used: a converter works in the regime of the reaction, the second converter works in the regime of regeneration of the catalyst. The term converter is in the description of the invention used synonymously with reactor. The converters used in step a.) and/or step b.) are preferably through flow reactors where the catalyst is mounted as fixed bed.
I [Idbatun UT VVIU/ZU I - 1 ] -'U I / t-:-2U1U/U UUbbU Preferably, the first and/or the second converters are cooled. The cooling takes place in a preferred manner by indirect evaporative cooling. The reaction regime in step a.) and/or step b.) is performed preferably nearly isotherm. The converters are preferably designed such that they allow a direct and complete dissipation of reaction heat generated in the catalyst bed, and thus allow a reaction regime at a nearly constant temperature in the volume of the reaction chamber. The reaction heat dissipated by cooling in the first and/or second reactor can be advantageously used to generate steam (water vapour). The first converter (methanol synthesis and possibly DME-synthesis) has preferably a ratio of heat transfer surface to the catalyst volume of not less than 50 m 2 /m 3 and not more than 400 m 2 /m 3 . With the heat dissipated in the first converter steam is generated preferably with a pressure of not less than 0.6 MPa and not more than 4 MPa. The second converter (gasoline synthesis) has preferably a ratio of heat transfer surface to the catalyst volume of no less than 40 m 2 /m 3 and not more than 200 m 2 /m 3 . With the reaction heat dissipated in the second converter preferably water vapour is generated with a pressure of not less than 3.0 MPa and not more than 22 MPa. The reaction heat dissipated by the steam generated can advantageously be used for the production of a coolant, which can be used for product separation after step a.) and/or step b.). The synthesis gas used in the process can be produced from various feedstock. The feedstock can be of fossil or biological origin (such as coal, biomass, natural gas or biogas). The ratio of CO to H 2 in the synthesis gas depends on raw materials used for generation and the process of production. The synthesis gas usually contains also inert constituents (like N 2 and water). The synthesis gas is preferably cleaned of catalyst poisons (sulphur compounds, nitrogen compounds) and foreign matter, dried and, if necessary, compressed. For methanol or DME-synthesis, the ratio of H 2 /CO in the synthesis gas is preferably not less than 2. In this case, a high yield of methanol (DME), relative to C in CO, is obtained. At smaller ratio, the yield of methanol (DME) is decreased and the yield of C02 is increased. The individual process steps of the method according to the invention are further explained with reference to preferred embodiments: i ransiauion oT VVU/ZU'l'lUv llUOS IU I /t-P2UlU/UO 00u0 Gasoline is produced from synthesis gas in two stages: in step a.) synthesis of compounds of the type R'-O-R 2 - for example, methanol and/or dimethyl ether takes place, in step b.) the conversion of the compounds of the type R 1
-O-R
2 in a mixture of hydrocarbons takes place on a zeolite catalyst. The compounds of the type R'-O-R 2 , generated in the first stage, can be directed as entire product flow from the first converter to the second stage or be separated from the product of the first converter by any variant and then passed to the second stage. From the product of the first converter methanol and possibly dimethyl ether may be separated as a feedstock for the second stage, including in the mixture with water. Not converted synthesis gas is preferably separated from the product of the first converter or from the product of the second converter and recycled in the first converter for the synthesis of the compounds of the type R'-O-R 2 . The synthesis gas can be advantageously used as raw mixture, but is preferably dried and compressed, if necessary and heated-up in the mixture with the circuit gas up to a temperature that is close to the reaction temperature, such as in recuperator heat exchangers and/or boilers (steam boilers, furnaces and/or electric heater) and introduced in the first converter (in figures - Unit 1) for the synthesis of compounds of the type R'-O-R 2 (methanol and possibly dimethyl ether). For producing the compounds of the type R'-O-R 2 there is the contact with the catalyst of the methanol synthesis or with the methanol synthesis catalyst and catalyst of dehydration of methanol to dimethyl ether (DME). For methanol synthesis in step a.), preferably copper-containing catalysts are used at a temperature up to 260 0C and at a pressure up to 6 MPa. The reaction of CO and H 2 under the formation of methanol runs exothermically with a heating effect of 90,73 kJ/Mol methanol. This is why, in step a.) an isothermal cooling converter is preferably used. This converter is able to reduce the required volume of circuit gas and to carry out the synthesis under optimal conditions, with corresponding reduction in the formation of by-products, an increased yield of methanol, an extension of the runtime of the catalyst and the generation of intermediate pressure - steam for use as energy carrier. The product from the converter of synthesis of compounds of the type R 1
-O-R
2 is preferably cooled in heat exchanger, in which the feedstock flow (synthesis gas) is preheated. As a variant the product flow is preferably be separated in a gas product and a condensate. For this purpose the product is preferably cooled in the air cooler and water cooler, and in case of the presence of dimethyl ether in the product, by additional application of low temperature.
i ransialon of Wu/2mub1U11 1 PC 1 IEP2010/067606 The organic constituents and water are condensed. The condensate (crude methanol, water content up to 20% or a mixture of dimethyl ether, methanol and water) is segregated in the separator. The gas product from the separator is not converted synthesis gas, part of it is recycled for pre-mixing with raw synthesis gas for complete conversion in the first converter. As a variant, a distillation column for separating water from the mixture containing organic constituents can be connected downstream the separator, since the presence of water in the feedstock for the second converter for converting the compounds of the type R 1
-O-R
2 in hydrocarbons accelerates irreversible deactivation of zeolite catalysts used in the second converter. However, this is a very expensive operation and it is more economical to dilute the material flow for the second converter with inert constituents to reduce partial pressure of water and methanol. The separated compounds of the type R 1
-O-R
2 (methanol or methanol / DME mixture) or the product flow from the first converter (Unit 1) is fed into the second converter (in the diagram Unit l1l) for synthesis of gasoline, where it is preferably mixed with the recycling flow of methanol (flow 11 in figures 1 + 2) from Unit V, with the recycling flow of light hydrocarbon gases (flow 7 in Fig. 1) from Unit IV and the flow of not reacted synthesis gas (flow E 5 in Fig. 1) from the separator (Unit II). The mixed flow is preferably fed in the recuperator - heat exchangers and heated in the boiler and fed in the converter for gasoline synthesis. The presence of hydrogen and carbon monoxide in the inventive method during conversion of methanol (and if necessary, dimethyl ether) reduces, albeit partly, the unwanted decomposition of methanol into hydrogen and carbon monoxide in step b.). This advantage increases the selectivity of forming hydrocarbons. The partial pressure of hydrogen is preferably higher than 0,07 MPa and the partial pressure of carbon monoxide higher than 0.008 MPa. To achieve the required effect, either hydrogen and carbon monoxide are mixed with methanol separated previously from the first product flow (and if necessary, dimethyl ether), or the first product flow containing not yet converted synthesis gas is introduced directly into the second converter. The hydrogen and the carbon monoxide in the second converter serve as diluting components, i.e. they dilute the educt (methanol and DME, if necessary). Dilution of methanol (methanol + DME) in the material flow in the second converter shall be such that the partial pressure of methanol is less than 0.5 MPa and that of water less than 0.3 MPa. The product from the converter of gasoline synthesis is cooled preferably in recuperator heat exchangers, in which the feedstock of the converter (methanol and possibly DME) is i ransiation ot wO/2011/061198 PCT/EP2010/067606 preferably heated, if possible in the mixture with circuit gas. The cooled flow is preferably fed into the second separator (in figures, Unit IV) for separating the converter product of gasoline synthesis. When cooled down in the recuperator and in the condensers, the gasoline hydrocarbons, a part of the light hydrocarbons, the not reacted compounds of the type R 1
-O-R
2 and water condense. In the separator preferably are separated: 1. Water containing non-reacted compounds of the type R 1
-O-R
2 , 2. the gasoline hydrocarbons and 3. the gas phase, the hydrogen, oxides of carbon, and light hydrocarbons (mainly up to 4 carbon atoms, predominantly methane and C2-C4 - hydrocarbons), which are formed during the conversion of methanol. A part of the gas phase is mixed with a part of the CO- and H 2 containing gases from the first separator (in figures Unit II), and recycled preferably as diluting constituents to the feedstock (methanol and DME, if necessary) in the converter of gasoline synthesis. The Condensate of gasoline hydrocarbons from the separator c.) is preferably heated and led to the stabilization column, in which the light overhead gases (short-chain hydrocarbons, essentially propane, propylene, butane, butylene as well as methane, ethane, ethylene and
H
2 ) are separated from stable gasoline (flow 8 in figures). If necessary, the C3-C4 hydrocarbons can be separated as liquid fraction C3-C4. From gasoline hydrocarbons that are fed into the stabilization column, even heavy gasoline (flow 9 in figures) can be separated in the stabilization column or in an additional column. The aqueous phase (flow 10 in figures) from the separator c.) can be directed as a variant into a distillation column (Unit V in figures 1 + 2) and then to the converter of water purification (Unit VI in figures 1 + 2). In the distillation column the of the compound of the type R'-O-R 2 (flow 11 in figures 1 + 2) concentrated. This recycling flow is redirected into the Unit for gasoline synthesis. The water preserved in the swamp of the column containing the residual levels of R 1
-O-R
2 is directed to the converter of water purification. The aqueous phase from the separator c.) may be added directly for water purification. Two preferred variants of the method according to the invention are described on the basis of the following figures. Fig. 1 shows the block diagram for a preferred method of generating gasoline from synthesis gas according to the invention with separation of recycling flow of synthesis gas from the product of the converter of synthesis of compounds of the type R 1
-O-R
2 and the catalytic decomposition of methanol in water following the distillation separation of the main amount of methanol from process water.
I ranslation ot WO/20111061198 PCT/EP2101067606 Fig. 2 shows the block diagram for a preferred method of generating gasoline from synthesis gas according to the invention with direct introduction of the product flow from the first converter into the second converter and separation of recycling flow of synthesis from the product of the converter of gasoline synthesis and catalytic decomposition of methanol in water following the distillation separation of the main amount of methanol from process water. In Fig. 1 synthesis gas 1, whose main constituents hydrogen and carbon monoxide is in a ratio depending on the method of their generation, that contains also inert components, is purified of catalyst poisons and additives, if necessary compressed, and fed into the first converter (Unit 1) of synthesis of compounds of the type R 1
-O-R
2 , where it is mixed with the circuit gas 3. The resulting mixture is pre-heated to reaction temperature in recuperator heat exchangers and boilers (boilers and/or electric heaters, furnaces) and supplied to the converter for synthesis of compounds of the type R 1
-O-R
2 . In the generation of compounds of the type R'-O-R 2 , there is the contact with the catalyst of methanol synthesis or with the methanol synthesis catalyst and the catalyst of dehydration of methanol to dimethyl ether. During synthesis of methanol, the use of copper-containing catalysts is preferred at a temperature of up to 2600C and a pressure of up to 8 MPa, but even zinc-chrome catalysts can be used, which work at a temperature of up to 3600C and at a pressure of more than 8 MPa. The product from the converter of synthesis of compounds of the type R'-O-R 2 is cooled in heat exchangers, in which the flow of feedstock is preheated as well as in air and water coolers, also low temperature is used in the presence of dimethyl ether in the product, where the compounds of the type R 1
-O-R
2 and water condense. The condensate (crude methanol, water content up to 20% and/or mixture of dimethyl ether, methanol and water) is deposited in the separator (Unit II). The gaseous product from the separator is not-reacted synthesis gas, a part of which (flow 3) is introduced for mixing with the raw synthesis gas for a complete conversion of feedstock. The compounds of the type R 1
-O-R
2 4 (methanol and DME, if necessary), separated in the separator, are mixed with the recycling flow of methanol 11 from Unit V, the recycling flow 7 of light carburetted hydrogen gas from the second separator (Unit IV) and flow 5 of not reacted synthesis from Unit II, preferably gas product from the separator. The constituents are heated after mixing preferably in recuperator - heat exchangers, and/or in boilers and fed into the converter of gasoline synthesis.
i ranslation of VVU/2Ul l /Ub1 1 90 IC I /EP2010/067606 In order to obtain a good gasoline quality (low share of heavy gasoline and aromatics), the conversion of compounds of the type R 1
-O-R
2 (methanol and DME, if necessary) in the second converter (Unit Ill) is kept preferably below 99.5%. The product of the converter of gasoline synthesis contains the hydrocarbons (particularly hydrocarbons) generated during conversion of the compounds of the type R 1 -0-R 2 and non-reacted compounds of the type
R
'
-0-R 2 , mainly methanol and constituents of synthesis gas. Both converters (Unit I and 111) are preferably cooled converters. The first converter has a heat transfer surface of at least 50 m 2 per 1 m 3 of catalyst at a flow rate of circulating gas of below 150 real m 3 /m 3 of catalyst. In the second converter the heat transfer surface is at least 40 m 2 per 1 m 3 of catalyst at a flow rate of circulating gas of gasoline synthesis of below 150 real m 3 / m 3 catalyst. The steam generated while cooling the converter, as described above, is used to generate a coolant through an absorption-type refrigerating machine, in steam heaters to preheat the feedstock flows of the first converter and as sump heating of column for product separation. The product of the converter of gasoline synthesis (Unit li1) is cooled in the recuperator heat exchangers, in which the feedstock of the converter is heated, is further cooled in coolers. During the process of cooling, condensation of gasoline hydrocarbons and water takes place. The cooled flow 6 is transferred to separator c.) (Unit IV) for separation of the reactor product of gasoline synthesis, In separator c.), the following are separated: 1. methanol-containing water 10, 2. gasoline hydrocarbon phase 8 + 9 and 3. gas phase 7, which contains hydrogen, carbon oxides and light hydrocarbons formed during the conversion of methanol. The recycling flow of light hydrocarbon gas 7 is mixed in the aforesaid event with a part of the CO - and H 2 - containing gases 5 from the first separator (Unit 11), in order to obtain a diluting component for the feedstock of synthesis of compounds of the type R 1
-O-R
2 . The hydrocarbon condensate (including C5+ - hydrocarbons) 6 from the separator (Unit IV) is guided to the stability column (Unit IV), where the light overhead gas 7 is separated from stable gasoline 8. From the unstable gasoline hydrocarbons, even heavy gasoline 9 can be separated in a stabilisation column or in an additional column. The aqueous phase 10 from the separator is led in Unit V for concentration of compounds of the type R 1
-O-R
2 , and from there into the Unit VI for catalytic water purification of i wriiaion OT VVU/ZUI'l/U ' 1 ' 1I'[U I /t2U1 U/Ub(0Ut compounds of the type R'-O-R 2 . Depending on the level of conversion, water here usually contains between 3.5 wt.-% and 30 wt.-% of the compounds of the type R'-O-R 2 In Unit V of the concentration of compounds of the type R'-O-R 2 , the enrichment of methanol is achieved in an overhead distillation column and it will retain the recycling flow of methanol 11, which is conveyed to Unit IlIl of gasoline synthesis. The residues from the column (Unit V) - water 12, which contains methanol 5 between 1% and 5%, is guided into the converter of water purification (Unit VI), where the catalytic decomposition of methanol is carried out in the aqueous medium. In the converter of water purification (Unit VI), the gas flow 13 from the decomposition of methanol contains oxides of carbon and hydrogen, which is led to the first converter (Unit 1). Chemically purified water 14 is obtained, which is used to refill the system of recycling cooling water, the steam generation system, and for other purposes. The manufacturing process as shown in Fig. 2 is a simplified version of the method shown in Fig. 1 and differs from it primarily in the following aspect: The product of the first converter (Unit I) is heated in heat exchangers and/or boilers and without previous separation, directly guided to the converter (Unit 111) of gasoline synthesis. As a diluting component of oxygen-containing feedstock, once again the circuit gas 3 (here from Unit IV) can be used. Also here, additional hydrogen and carbon monoxide 13 is admixed with the synthesis gas 1 before or while feeding into the first converter in addition to the circuit gas 3, which is formed in the converter of catalytic water purification (Unit VI). The product of the first converter corresponds to the product of the method in Fig. 1, essentially in its composition. In order to achieve maximum gasoline quality (low content of heavy gasoline), the conversion of the compound of the type R'-O-R 2 (methanol and DME, if necessary) is preferably kept below 99.5%. The product of the converter of gasoline synthesis is cooled here first in the recuperator heat exchangers and in coolers. In Unit IV, the partially-cooled flow 6 is fed to the separation of the products of the converter of gasoline synthesis, where, thanks to cooling in the coolers, a condensation of hydrocarbons and water takes place. In the separator, the water Translation of WO/2011/061198 PCT/EP2010/067606 10, which contains the non-reacted compounds of the type R 1
-O-R
2 , is deposited and the gasoline hydrocarbon phase and the gas phase are separated. The gas product from the separator consists mainly of not reacted synthesis gas and light hydrocarbons, a part of which (flow 3) is recycled for mixing with the starting synthesis gas for complete conversion of feedstock in the first converter (Unit 1). Depending on the degree of conversion, water formed in the converter of gasoline synthesis contains methanol (and occasionally DME) generally between 3.5% and 40%. Thus, a purification of water takes place in a distillation column (Unit V) and then in a separate converter of water purification (Unit VI) by catalytic decomposition of methanol into hydrogen and carbon oxide (where these gases are recycled as admixture to the synthesis gas in the process, see description in Fig. 1. The hydrocarbon condensate from the separator (Unit IV) is led to the stabilization column (Unit IV), in which gasoline 8 is separated. From the unstable gasoline hydrocarbons, even heavy gasoline 9 can be separated in a column of stabilization or an additional column. The water phase 10 from the separator is fed to Unit V for enrichment of the compounds of the type R 1
-O-R
2 , and then in the converter of water purification (Unit VI). In Unit V of concentration of compounds of the type R 1
-O-R
2 , enrichment of methanol is realised in the overhead portion in a distillation column and it will receive a recycling flow of this methanol 11, which is recycled to Unit Ill of gasoline synthesis. The residues of the column - water 12, containing methanol 5 between 2 and 5% is fed into the converter of water purification (Unit VI). In the Unit VI of cleaning, the methanol-containing water flow is preferably conveyed through the recuperator - heat exchangers and/or pre-heaters, where it is heated to the required reaction temperature, and then fed to the converter of water purification, where the contact with the catalyst of decomposition of methanol into hydrogen and carbon oxides is realised. The product from the converter of water purification is preferably cooled in recuperator - heat exchangers and in an air cooler. Subsequently, the gas phase is separated from the condensate in a separator. The hereby separated gases of decomposition of methanol 13 exit from the separator and are guided for mixing with raw synthesis gas in the first converter (Unit 1). The purified water is sent to the degasser column. Chemically purified water 14 is obtained, which is used to refill the system of circulating cooling water, the steam generation system, and for other purposes.
I ransiation or vvU/v 1 I/Utl 1 Jts P lU 1 EP2010/067606 Through the water as shown in figures 1 and 2, the converters are indirectly cooled. The water absorbs the heat from a heat carrier, which in turn derives the heat from the reaction zone. The water leaves the Unit I and IlII as steam. In the following the invention is explained with the help of a comparative example and embodiments. Example 1 (comparative example) This example was carried out similar to the method TIGAS of the company Haldor Topsoe IJ Topp-Jorgensen, reprinted from "Studies in surface and catalysis, V, 36, methane conversion", 1987. A block diagram of the TIGAS method is shown on Fig. 3. Synthesis gas is mixed with circuit gas, which includes non-reacted constituents of synthesis and light hydrocarbons, and occurs in the reactor of synthesis of methanol + DME with a bi functional catalyst consisting of a catalyst component of methanol synthesis and a catalyst component of dehydration of methanol. The mixture derived from methanol + DME + water and from components of not reacted synthesis gas is given to the stage of gasoline synthesis, where in a zeolite-containing catalyst, the transformation of methanol and DME into hydrocarbons takes place. The product mixture is then separated in gasoline, an aqueous phase, which is added for cleaning, a C3-C4 group and gas, from which a part is supplied as circulation gas for the synthesis stage of oxygen compounds. All stages are performed almost at the same pressure in the range of 50-100 bar. Synthesis gas containing H 2 : CO = 3 is used. According to the source, the yield of oxygen compounds, based on CH 2 in the synthesis gas, is 94%. The yield of gasoline, relative to CH 2 in the oxygen compounds, is 78%. Overall, the yield of gasoline is 73,34 %, relative to CH 2 in the synthesis gas without taking into account of losses during product separation, etc. Further, examples of different variants of the process scheme according to the invention are enumerated.
1 rablat]un OT VVU/4U. I 'IUfa I I-U I /t-H2U1U/Ub (IiUt A real synthesis gas is used with the following composition in vol.- CO - 21.91; H 2 - 61.16; C02 - 6.38; CH 4 - 1.83; H 2 0 - 8.72. The flow rate of synthesis is: 738,3 m (i. N.)/ h. For the generation of methanol from synthesis gas, a catalyst of M/s. Sudchemie is used with the nomenclature MEGAMAX 700* (components CuO, ZnO, A1 2 0 3 ) and for the generation of gasoline from methanol a zeolite-containing catalyst of M/s. Sudchemie with the nomenclature SMA-2 is used. The working conditions in the converter for synthesis of compounds of the type R 1
-O-R
2 are temperatures in the range from 210 to 260 *C and pressures in the range of 50 to 55 MPa. The volume of the catalyst is 0.46 m, the heat exchange surface in the reaction zone is 30 m. The pressure of the vapour generated is 1.8 MPa. In the converter of gasoline synthesis, a pressure of 7 bar is available for the examples 2-4 and a pressure of 45 bar for the example 5. The process temperature lies in the range from 310 to 4300C in the reaction regime and in the range from 280 to 5000C in the regeneration regime. The converters of methanol synthesis and gasoline synthesis are cooled. Converters with a heat transfer surface of 60 M 2 / M 3 are used. The reactions in the converters of synthesis of methanol and gasoline synthesis are carried out in nearly isothermal conditions, where the temperature difference lies within the catalyst grain below 5 K. In the examples 2 to 4, the separation of the products of the process of generating oxygen compounds takes place at a temperature of 400C. The separation of products of gasoline synthesis takes in all of the samples at a temperature from + 5*C. The examples of 2 to 5 are characterized by a different selection of the application of individual distinctive features of the invention. Example 2 The device (plant) for generation of synthetic gasoline corresponds mainly to the schema in Fig. 1 and includes: a unit (Unit 1) for synthesis of methanol from synthesis gas, a unit (Unit I ranslation OT wU/2011/061198 PCT/EP2010/067606 II) for separation of methanol from the product flow of Unit I, a unit (Unit Ill) for synthesis of gasoline from crude methanol, a unit (Unit IV) for fractionation with separation of product gasoline, a unit (Unit V) for separation of methanol from process water. In contrast to the schemata in Fig. 1, the unit for water purification of methanol is not in operation. As against Fig. 1, flows 5, 13 and 14 are missing in the device, i.e. in Unit III, flow 5 is not provided.
i ransiation OT WU/ZU1 1/U0i 11 PCI/EP2010/067606 Table 2.1.Material balance in the system Regime of production of synthetic Catalyst for Conversion Selectivity of conversion gasoline from crude methanol, the synthesis of conversion of of (CO + C0 2 ) without the addition of synthesis gas of gasoline: methanol: methanol to into from the unit for methanol synthesis SMA-2 99 % gasoline: methanol: into the Unit for gasoline synthesis' 86 % 94.7 % without the unit for water purification Annual operating hours 8000.00 Substance flow kg/h t/a wt.-% with reference to feedstock Input synthesis gas 376.10 3 008.80 100.00 total: 376.10 3008.80 100.00 Output: blow down gas for the unit for methanol synthesis 29.00 232.00 7.71 hydrocarbon-containing blow down gas 23.00 184.00 6.12 synthetic gasoline 97.00 776.00 25.79 82.76* 78.39** reaction water 180.50 1444.00 47.99 water from crude synthesis gas 46.60 372.80 12.39 total: 376.10 3008.80 100.00 * relative to CH 2 of methanol, ** relative to CH 2 of synthesis gas.
I ranslation ot wO/2011/061198 PCT/EP2010/067606 Table 2.2. Characteristics of the flows in the schemata in Fiq. 1 N2 Physical characteristics of Composition of flows [in wt.-%] substance flow T p mass flow H 2 CO CO 2
H
2 0 CHOH C 1
C
4 Cs.
[
0 C] [MPa] [kg/h] 1 60.0 5.70 329.5 11.68 58.17 26.61 0.76 - 2.78 2 123. 5.20 2364 7.28 7.16 38.42 1.32 12.76 33.06 8 3 54 5.8 2034.5 8.37 8.23 43.69 0.03 1.69 37.99 4 40.7 5.20 300.4 - - 1.14 10.15 88.7 0.01 5 - - - - 6 89.7 5.50 895.1 1.23 0.23 26.31 20.06 0.3 37.66 14.21 7 58 1.00 593.7 1.84 0.35 39.10 0.13 - 53.24 5.34 8 40.4 0.70 80.1 - - - - 0.01 2.96 97.03 9 45.4 0.60 16.9 - - - - - - 100.0 0 10 5.0 0.40 181.5 - - 0.01 98.52 1.47 - 11 60.0 1.0 1.0 - - 0.47 13.98 85.55 - 12 61.9 5.65 180.5 - - - 99.00 1.00 - 13 - - - - - -- - 14 - Example 3 The device for the generation of synthetic gasoline corresponds mainly to the schemata in Fig. 1 and includes: a Unit for the synthesis of methanol from synthesis gas (Unit 1), a Unit (Unit II) for separation of methanol from the product flow of Unit I, a Unit (Unit Ill) for synthesis of gasoline from crude methanol, a Unit (Unit IV) for fractionation with separation of product gasoline, a Unit (Unit V) the separation of methanol from the process water. The unit for water purification of methanol is not in operation. As against the schemata in Fig. 1, the flows 13 and 14 are missing in the device.
I I dIlidLIUn1 U1 VVVIZU I I/UO'l'10 -U I/LI-'ZU' U/Ut/ IbUt Table 3.1. Material balance of the system Regime of production of synthetic Catalyst for Conversion Selectivity of conversion gasoline from crude methanol, the synthesis of conversion of of (CO + C0 2 ) without the unit for water of gasoline: methanol: methanol to into purification SMA-2 99 % gasoline: methanol: 87% 94.2% Annual operating hours 8000.00 Substance flow kg/h t/a wt.-% with reference to feedstock Input synthesis gas 376.10 3 008.80 100.00 total: 376.10 3008.80 100.00 Output: blow down gas for the unit for methanol synthesis 28.00 224.00 7.44 hydrocarbon-containing blowdown gas 24.20 193.60 6.43 synthetic gasoline 97.40 779.20 25.90 83.53* 78.71** reaction water 179.90 1 439.20 47.84 water from crude synthesis gas 46.60 372.80 12.39 total: 376,10 3 008,80 100,00 * relative to CH 2 of methanol, ** relative to CH 2 of synthesis gas.
i translation oT VVU1/zU i/U ' '1 O Mi-U I /t-zu iU/U (jub Table 3.2. Characteristics of flows in the schemata in Fig. 1 Nq Physical characteristics of Composition of flows [in wt.-%] substance flow T [ 0 C] p mass flow H 2 CO CO 2
H
2 0 CH 3 0H C 1
C
4
C
5 1 [MPa] [kg/h] 1 60.0 5.70 329.5 11.68 58.17 26.61 0.76 - 2.78 2 123.7 5.20 2406.5 6.89 7.00 37.55 1.29 12.53 34.74 3 54 5.8 2077.0 7.89 8.02 42.57 0.03 1.67 39.82 4 40.7 5.20 299.4 - - 1.12 10.12 88.74 0.02 5 40 5.1 2.5 7.89 8.02 42.57 0.03 1.67 39.82 6 88.7 5.50 789.1 2.19 1.35 21.70 22.69 0.34 35.42 16.31 7 61.5 1.00 486.2 3.49 2.15 34.32 0.16 - 53.19 6.69 8 40.4 0.70 79.2 - - - - 0.01 2.97 97.02 9 45.4 0.60 18.2 - - - - - - 100.00 10 5.0 0.40 180.9 - - 0.01 98.52 1.47 - 11 60.0 1.0 1.0 - - 0.46 14.38 85.16 12 61.9 5.65 179.9 - - - 99.00 1.00 13 - - - - 14 - - Example 4 The device of generation of synthetic gasoline conforms to the schemata in Fig. 1 and includes: a Unit (Unit 1) for synthesis of methanol from synthesis gas, a Unit (Unit II) for separation of methanol from the product flow of Unit I, a Unit (Unit Ill) for synthesis of gasoline from crude methanol, a Unit (Unit IV) for fractionation with separation of product gasoline, a Unit (Unit V) for separation of methanol from the process water, a Unit (Unit VI) for water purification of methanol.
I ranslation of WO/2011/061198 PCT/EP2010/067606 Table 4.1. Material balance of the system Regime of production of synthetic Catalyst for Conversion Selectivity of conversion gasoline from crude methanol the synthesis of conversion of of (CO + C0 2 ) of gasoline: methanol: methanol to into SMA-2 97 % gasoline: methanol: 87.5 % 94.7 % Annual operating hours 8000.00 Substance flow kg/h t/a wt.-% with reference to feedstock Input synthesis gas 376.10 3 008.80 100.00 total: 376.10 3008.80 100.00 Output: blow down gas for the unit for methanol synthesis 28.00 224.00 7.44 hydrocarbon-containing blowdown gas 24.10 192.80 6.41 synthetic gasoline 98.40 787.20 26.16 83.92* 79.52** reaction water 179.00 1 432.00 47.60 water from crude synthesis gas 46.60 372.80 12.39 total: 376,10 3 008,80 100,00 * relative to CH 2 of methanol, ** relative to CH 2 of synthesis gas.
i ransiaion OT VVU/ZUI l/Ul 196 P. I /LP201U/067606 Table 4.2. Characteristics of flows in the schemata in Fig. 1 Ng Physical characteristics of Composition of flows [in wt.-%] substance flow T P mass flow H 2 CO CO 2
H
2 0 CH 3 0H CrC 4
C
5 , [OC] [MPa] [kg/h] 1 60.0 5.70 329.5 11.68 58.17 26.61 0.76 - 2.78 2 123. 5.20 2405.2 6.91 7.06 37.51 1.29 12.60 34.61 5 3 54 5.8 2073.9 7.93 8.10 42.56 0.03 1.68 39.70 4 40.7 5.20 301.1 - - 1.12 10.06 88.80 0.01 5 40 5.1 2.5 7.93 8.10 42.56 0.03 1.68 39.70 6 86.9 5.50 793.5 2.19 1.41 21.41 22.80 1.04 34.79 16.36 7 58 1.00 482.4 3.53 2.27 34.33 0.16 - 52.96 6.75 8 40.4 0.70 79.6 - - - - 0.04 2.94 97.02 9 45.4 0.60 18.8 - - - - - - 100.00 10 5.0 0.40 188.3 - - 0.01 95.65 4.34 - 11 60.0 1.0 7.5 - - 0.2 14.80 85.00 - 12 61.9 5.65 180.8 - - - 99.00 1.00 13 70 5.42 1.8 12.51 86.21 - 1.28 - - 14 70 5.42 179.0 - - traces 100.00 traces - Example 5 The device of generation of synthetic gasoline conforms to the schemata in Fig. 2 and includes: a Unit (Unit I) for synthesis of methanol from synthesis gas, a Unit (Unit 111) for synthesis of gasoline without separation of methanol from the product flow of Unit I, a Unit (Unit IV) for fractionation with separation of product gasoline, a Unit (Unit V) for separation of methanol from the process water, a Unit (Unit VI) for water purification of methanol I ranslation of WO/2011/061198 PCT/EP2010/067606 Table 5.1. Material balance of the system Regime of production of synthetic Catalyst for Conversion Selectivity of conversion gasoline from the flow of methanol the synthesis of conversion of of (CO + C0 2 ) synthesis of gasoline: methanol: methanol to into SMA-2 99 % gasoline: methanol: 85.5 % 94.2 % Annual operating hours 8000.00 Substance flow kg/h t/a wt.-% with reference to feedstock Input synthesis gas 376.10 3 008.80 100.00 total: 376.10 3008.80 100.00 Output: hydrocarbon-containing blowdown gas 54.30 434.40 14.44 synthetic gasoline 96.80 774.40 25.74 83.02* 78.23** reaction water 178.40 1 427.20 47.43 water from crude synthesis gas 46.60 372.80 12.39 total: 376,10 3 008,80 100,00 * relative to CH 2 of methanol, ** relative to CH 2 of synthesis gas.
i ransiation oT VVU/2U1 1/U61198 PCT/EP2010/067606 Table 5.2. Characteristics of flows in the schemata in Fig. 2 Ng Physical characteristics of Composition of flows, in wt.-% substance flow T p masflow H 2 CO CO 2
H
2 0 CH 3 0H C 1
C
4 C5.
[
0 C] [MPa] [kg/h] 1 60.0 5.70 329.5 11.68 58.17 26.61 0.76 - 2.78 2 117.5 4.35 2263 6.01 7.46 39.23 1.37 11.77 32.56 1.6 3 29.9 4.9 1931.7 6.94 8.59 44.88 0.04 - 37.68 1.87 6 176.3 3.9 2264.0 6.02 7.45 39.21 7.92 0.12 33.45 5.83 8 40.4 0.70 79.9 - - - - 0.01 3.07 96.92 9 45.4 0.60 16.9 - - - - - - 100.00 10 5.0 0.40 181.2 - - 0.02 98.51 1.47 - 11 62.2 4.5 1 - - 0.46 14.38 85.16 - 12 62.6 5.65 180.2 - - - 99.00 1.00 - 13 70.0 5.35 1.8 12.5 86.2 - 1.3 - - 14 70.0 5.35 178.4 - - - 100.0 - - 0 i ranilaion OT VVU/ZUI I /U' I I HU I /LIU1' U/U6i76U6 Reference list: In the figures and in the text, the following terms are used: 1 - Output synthesis gas 2 - Product from the Unit for the synthesis of compounds of the type R 1
-O-R
2 3 - Circuit gas (synthesis gas, which is recycled from Unit 11 or IV to Unit 1) 4 - Raw methanol (and/or feedstock of compounds of the type R 1
-O-R
2 ). 5 - Circulating gas (synthesis gas, which is supplied from Unit 11 to Unit 111) 6 - Product from the Unit for gasoline synthesis 7 - Circulating hydrocarbon gas (recycled from Unit IV into Unit Ill) 8 - Gasoline 9 - Heavy gasoline 10 - Process water 11 - Recycled compound of the type R 1 - O-R 2 (preferably methanol) 12 - Waste water containing the compounds of the type R 1
-O-R
2 (preferably methanol) 13 - Gases, which are formed during separation of compounds of the type R 1
-O-R
2 (preferably methanol) 14 - Chemically purified water 15 - Gas 16 - C3-C4 group I - Unit for synthesis of compounds of the type R 1
-O-R
2 with the first converter II - Unit for separation with the first separator Ill - Unit for synthesis of gasoline with the second converter IV - Unit for separation with the second separator and the column of stabilization of unstable gasoline V - Unit for concentrating the compounds of the type R 1
-O-R
2 (preferably methanol) in a distillation column from process water VI - Unit for catalytic water purification of compounds of the type R 1
-O-R
2 (preferably methanol)
Claims (14)
1. A method for generating hydrocarbons by the conversion of a CO and H 2 -containing gas mixture (synthesis gas) by a.) contact with a catalyst in a first converter for generating a first product flow, which contains - at least one chemical compound of the type R'-O-R 2 (wherein R 1 - are alkyl groups having a carbon number of 1 to 5, and R2 - are hydrogen, alkyl and alkoxy groups having a carbon number of 1 to 5), wherein the chemical compound of the type R 1 -O-R 2 preferably is methanol and / or dimethyl ether, as well as - non-reacted components of synthesis gas, b.) contact of the entire product from the first converter or after separation of at least a portion of the non-reacted components of the synthesis gas with a catalyst in a second converter, to generate a product flow, which contains - gasoline hydrocarbons, including up to 45 wt.-% of aromatic compounds, wherein up to 1 wt.-% benzene and not less than 40 wt.-% iso-paraffins are contained, - C 1 -C 4 - hydrocarbons, which are preferably formed in an amount of not more than 17 wt.-% (converted to C in the reacted methanol and/or, if necessary, in the reacted dimethyl ether), - non-reacted compound of the type R'-O-R 2 - as well as non-reacted components of the synthesis gas, wherein synthesis gas is separated from the first and/or second product flow and is at least partially fed back as circuit gas to the first converter, c.) separation of the product of the second converter, wherein the obtained instable gasoline is stabilized by known methods, wherein i.) a gasoline fraction, from which if necessary a fraction containing durene, is separated, ii.) a fraction of C 3 -C 4 hydrocarbons, iii.) a gas flow containing light hydrocarbons and non-reacted components of the synthesis gas, as well as iv.) an aqueous phase containing non-reacted compound of the type R 1 -O-R 2 preferably methanol and/or dimethyl ether, I IdiIdulul IU VVU/4U I I/UK-1-l VO tl I /tJ-.1ZU'lUIUO /Ub are obtained, wherein the gas flow iii.) is at least partially fed back to the second converter and/or to the first converter as circulating gas, and the aqueous phase iv.) is directly fed to the purification of the compound of the type R ' -O-R 2 or is initially fed to rectification, wherein by the rectification a separation in a concentrated solution of the compound of the type R'-O-R 2 (preferably not less than 75%) and water contaminated with the compound of the type R'-O-R 2 (preferred content of compound of the type R'-O-R 2 up to 5%) occurs, wherein the water contaminated with the compound of the type R'-O-R 2 is routed to the purification.
2. A method according to claim 1, characterized in that the feedstock of the second converter exhibits a partial pressure of hydrogen greater than 0.07 MPa, a partial pressure of carbon oxides greater than 0.008 MPa, a partial pressure of the compound of the type R'-O-R 2 (preferably of methanol and/or of dimethyl ether) of less than 0.5 MPa and a partial pressure of water of less than 0.3 MPa.
3. A method according to claim 1 or 2, characterized in that the conversion of the compound of the type R'-O-R 2 (preferably methanol) in step b.) is not less than 82 % and not more than 99.5 %, and optionally a conversion of dimethyl ether is not less than 92 % and not more than 99.8 %.
4. A method according to one of claims 1 to 3, characterized in that the contact with the catalyst in the first converter takes place under approximately isothermal conditions that are achieved by the removal of reaction heat by the heat transfer surface at a ratio of the heat transfer surface area to the volume of the catalyst of not less than 50 m 2 / M 3 .
5. A method according to claim 4, characterized in that from the reaction heat removed from the first converter steam of a pressure of up to 4 MPa is generated, wherein the volume of the circulating gas, which contains non-reacted components of the synthesis gas, and which is fed into the first converter, does not exceed 150 real M 3 , relative to 1 m 3 catalyst.
6. A method according to any one of claims 1 to 5, characterized in that the contact with the catalyst in the second converter takes place under approximately isothermal conditions that are achieved by the removal of reaction heat by the heat transfer surface at a ratio of the heat transfer surface area to the volume of the catalyst of not less than 40 m 2 /m 3 . I I lal0dIIU1 I U1 vvt.'/ \ U I I 1O r - /''L - ZU I /UO OVO
7. A method according to claim 6, characterized in that from the reaction heat removed from the second converter steam of a pressure of up to 22 MPa is generated, and that the volume of the circulating gas flow iii), which contains light hydrocarbons of the product flow of the second converter, as well as non-reacted components of the synthesis gas, amounts up to 150 real M 3 , relative to 1 M 3 catalyst.
8. A method according to any one of claims 1 to 7, characterized in that water contaminated with the compound of the type R'-O-R 2 , preferably methanol, is contacted with a catalyst for methanol decomposition at a temperature of up to 360 0C, wherein as a result purified water and components of synthesis gas, in particular hydrogen, carbon monoxide and C02 are formed.
9. A method according to claim 8, characterized in that the contact of water contaminated with the compound of the type R'-0-R 2 (preferably methanol) with the catalyst is carried out at a pressure that allows direct feeding of the generated components of the synthesis gas into the first converter or feeding in the first converter by means of a cycle compressor.
10. A method according to any one of claims 2 to 9, characterized in that a portion of the synthesis gas separated from the first product flow is fed into the second converter for adjusting the partial pressures of hydrogen and carbon oxides, particularly carbon monoxide.
11. Device for carrying out the method according to any one of claims 1 to 10 comprising: a.) at least one first converter that contains a catalyst suitable to catalyze the conversion of CO with H 2 to the chemical compound of the type R 1 -O-R 2 (preferably methanol), b.) at least one second converter that contains a catalyst suitable to catalyze the conversion of the chemical compound of the type R'-O-R 2 into hydrocarbons, c.) at least one separator that is capable of separating gasoline hydrocarbons from a product flow, which in addition to gasoline hydrocarbons and chemical compounds of the type R'-O-R 2 , contains water and gas that contains short-chain hydrocarbons, synthesis gas components, compounds of the type R 1 -O-R 2 and traces of gasoline hydrocarbons, i ransiation OTVVU/ZU' I/UIl 1 V U I /LP2U1U/0U7606 d.) at least one third converter that contains a catalyst suitable to catalyze the conversion of the chemical compound of the type R'-O-R 2 (preferably methanol) contained in water into CO and H 2 .
12. Device according to claim 11, characterized in that it comprises an additional separator for separating the product flow from the first converter, wherein the additional separator comprises a connecting pipe to the first converter, which enables feeding of CO and H 2 , separated in the separator, into the first converter, wherein the (additional) separator preferably comprises a first connecting pipe to the second converter that allows feeding of chemical compounds of the type R'-O-R 2 , optionally together with H 2 0, into the second converter and comprises a second connection pipe to the second converter that allows an optional feeding of CO and H 2 into the second converter.
13. Device according to claim 11, characterized in that the first converter is directly connected to the second converter, so that the entire product flow is fed from the first converter into the second converter, wherein the separator c.) preferably comprises a connecting pipe to the first converter that allows feeding of non-reacted CO and H 2 and short-chain hydrocarbons into the first converter.
14. Device according to any one of claims 11 to 13, characterized in that it comprises at least one of the following additional components: i.) a connecting pipe from the third converter for the first converter that allows introduction of CO and H 2 , formed in the third converter, into the first converter and/or ii.) an apparatus arranged downstream to the separator c.) that enables separation of the compound of the type R'-O-R 2 , in which the device comprises a connecting pipe for recirculating the separated chemical compound of the type R 1 -O-R 2 into the second converter and/or iii.) apparatuses to remove the reaction heat in the first and/or second converter that preferably enable the generation of water vapour, wherein the apparatuses to remove the reaction heat preferably exhibit a ratio of the heat exchange surface to the catalyst volume of at least 50 m 2 /m 3 in the first converter and preferably exhibit a ratio of the heat exchange surface to the catalyst volume of at least 40 m 2 /m 3 in the second converter.
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DE102009046790.4 | 2009-11-17 | ||
DE102009046790A DE102009046790B9 (en) | 2009-11-17 | 2009-11-17 | Process for the production of hydrocarbons, in particular gasoline, from synthesis gas |
PCT/EP2010/067606 WO2011061198A1 (en) | 2009-11-17 | 2010-11-16 | Method for generating hydrocarbons, in particular gasoline, from synthesis gas |
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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 |
US20180029003A1 (en) * | 2015-02-25 | 2018-02-01 | SGC Energia Co., LLC | Systems, methods, and apparatuses for fischer-tropsch reactor cascade |
RU2614956C1 (en) * | 2016-03-31 | 2017-03-31 | Публичное акционерное общество "Газпром" | Plant for producing synthetic liquid fuel |
RU186042U1 (en) * | 2017-12-29 | 2018-12-27 | Общество с ограниченной ответственностью "Ухтинский государственный технический университет-Инвест" | COMBINED REACTOR FOR THE PRODUCTION OF OXYGENATES AND LIQUID HYDROCARBONS FROM SYNTHESIS GAS |
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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US1746464A (en) | 1925-07-21 | 1930-02-11 | Fischer Franz | Process for the production of paraffin-hydrocarbons with more than one carbon atom |
US3894102A (en) | 1973-08-09 | 1975-07-08 | Mobil Oil Corp | Conversion of synthesis gas to gasoline |
US4035430A (en) | 1976-07-26 | 1977-07-12 | Mobil Oil Corporation | Conversion of methanol to gasoline product |
CA1173064A (en) | 1981-07-17 | 1984-08-21 | Malcolm P. Heyward | Catalyst composition for conversion of synthesis gas to hydrocarbons |
US4523046A (en) | 1982-02-25 | 1985-06-11 | Mobil Oil Corporation | Method for gasoline yield enhancement in the fixed bed methanol-to-gasoline process |
DK147705C (en) * | 1982-09-07 | 1985-05-13 | Haldor Topsoe As | METHOD FOR MANUFACTURING CARBON HYDRADES FROM SYNTHESE GAS |
US4404414A (en) | 1982-09-28 | 1983-09-13 | Mobil Oil Corporation | Conversion of methanol to gasoline |
EP0120510B1 (en) | 1983-03-10 | 1986-09-10 | Shell Internationale Researchmaatschappij B.V. | Preparation of hydrocarbon mixtures |
GB8309585D0 (en) | 1983-04-08 | 1983-05-11 | British Petroleum Co Plc | Catalyst composition |
US4788369A (en) | 1985-12-31 | 1988-11-29 | Mobil Oil Corporation | Conversion of methanol to gasoline |
US4814535A (en) | 1987-12-15 | 1989-03-21 | Mobil Oil Corporation | Conversion of oxygenates to gasoline at variable inlet temperature |
US5602289A (en) | 1994-11-09 | 1997-02-11 | Starchem, Inc. | Conversion of methanol to gasoline |
DK171707B1 (en) | 1995-02-03 | 1997-04-01 | Topsoe Haldor As | Process for producing fuel grade dimethyl ether |
DK173614B1 (en) | 1999-02-02 | 2001-04-30 | Topsoe Haldor As | Process for preparing methanol / dimethyl ether mixture from synthesis gas |
EP2121873A2 (en) * | 2006-12-13 | 2009-11-25 | Haldor Topsoe A/S | Process for the synthesis of hydrocarbon constituents of gasoline |
ZA200904142B (en) * | 2006-12-13 | 2010-08-25 | Haldor Topsoe As | Process for the synthesis of hydrocarbon constituents of gasoline |
US8529865B2 (en) * | 2008-02-29 | 2013-09-10 | Phillips 66 Company | Conversion of produced oxygenates to hydrogen or synthesis gas in a carbon-to-liquids process |
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CA2780483C (en) | 2013-03-05 |
EA201200731A1 (en) | 2012-10-30 |
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DE102009046790A1 (en) | 2011-05-19 |
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CN102686540B (en) | 2014-10-08 |
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