DE102009046790A1 - Process for the production of hydrocarbons, in particular gasoline, from synthesis gas - Google Patents

Abstract

The invention relates to a process for producing gasoline hydrocarbons by converting synthesis gas to an oxygen-containing compound, such as methanol and / or dimethyl ether, in a first converter and the further conversion to hydrocarbons in a second converter. The process is characterized in particular by the fact that unreacted synthesis gas is returned to the first converter, light hydrocarbons and unreacted components of the synthesis gas are returned from the product stream of the second converter to the first or second converter. The return of these components allows the setting of partial pressures, in particular the methanol in the second converter, which improves the product quality. In order to further improve the product quality, the process is preferably run under isothermal conditions and conditions of incomplete conversion.

Description

The invention relates to a process for the production of hydrocarbons, in particular gasoline, from non-hydrocarbon compounds, in particular from synthesis gas containing 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 readily available solid and gaseous sources of carbon and hydrogen. The hydrocarbon raw material synthesized based on synthesis gas and the motor fuels are real alternatives to petroleum hydrocarbons and sometimes better in quality. Therefore, the effectiveness of the technology for converting synthesis gas into hydrocarbons has been a current problem for many years.

In the 1925 Fischer-Tropsch synthesis ( US 1,746,464 ) synthesis gas is directly catalytically converted to hydrocarbons.

It is known that synthesis gas gas can be produced in two stages: first, the synthesis of oxygen compounds (eg methanol or dimethyl ether or a mixture of both compounds), then the conversion of the oxygen compounds on a zeolite-containing catalyst into a mixture hydrocarbons. The "Mobil Oil" company has developed some methods of producing gasoline from syngas according to this scheme. Both process stages are described in scientific-technical and patent literature: the synthesis of methanol is described in detail in the book of Karavayeva MM and others "Technology of Synthetic Methanol", M .: Chimija, 1984 , explained; the synthesis of a mixture of methanol and dimethyl ether in US 3,894,102 ; the synthesis of hydrocarbons from methanol and dimethyl ether - in a review of CD Chang, Catal. Rev. Sci. Eng., V. 25, N1 (1983) and in US 4,404,414 from 1983.

US 6,191,175 discloses a process for the production of methanol or dimethyl ether. For this purpose, first, the synthesis of methanol from synthesis gas, which is preheated in a first reactor. The reaction product is optionally mixed with synthesis gas and reacted again in a second reactor, which also serves either the methanol synthesis or the synthesis of dimethyl ether. In order to achieve high product capacities, the process is preferably conducted adiabatically.

US 5,908,963 discloses a process for the preparation of dimethyl ether. The product may contain up to 20% by weight of methanol and up to 20% by weight of water. In a first process step, synthesis gas is converted into a gas mixture of dimethyl ether, methanol and water in one or more reactors. The catalysts used have both a methanol synthesis activity and the ability to dehydrate methanol. The gas mixture is separated by means of several distillation and washing steps to obtain pure dimethyl ether.

In the process of converting synthesis gas into gasoline accordingly US 3,894,102 (1975), in the first stage, the contact of the synthesis gas with a catalyst consisting of a mixture of a methanol synthesis catalyst and an acid catalyst of dehydration is realized at a temperature of 371 ° C under conditions for producing a product containing dimethyl ether , In the second stage, the contact of at least the dimethyl ether with a zeolite catalyst at a temperature of 288-454 ° C, a pressure up to 21 MPa and a mass rate of raw material feed of 0.5-1000 h ^{-1 is} realized, producing a product whose organic part is preferably gasoline. The first stage product can be passed directly to the second, or it is separated, for example, the water is separated (with or without methanol), and H ₂ and carbon monoxide (unreacted synthesis gas) are separated, which (possibly after removal of CO ₂ ) are returned to the first stage.

In the prior art, the process of converting methanol and dimethyl ether, which are usually synthesized in the first stage, realized under conditions of almost complete conversion, wherein the oxygen compounds accumulate in the water and there arises the problem of the utilization of the wastewater and / or the separation of the oxygen compounds from the hydrous streams, which significantly degrades the economic indicators of the process.

In this connection, the prior art proposes processes of converting oxygen compounds into hydrocarbons which solve the problem by maintaining a degree of conversion of the raw material at a level of more than 99%. The separated from the final product water is led away from the plant and fed to the biological or biochemical purification.

US 4,814,535 (1989) discloses a method of producing gasoline from oxygenated compounds having a number from 1 to 4 carbon atoms. Here, the conversion of the raw material is maintained at a level of 99.9% by the temperature at the inlet to the reactor is gradually increased and the raw material flow is reduced. If the degree of conversion falls below 99.9%, the supply of raw materials is interrupted.

US 4,523,046 (1985) discloses a method of producing gasoline from methanol. The catalyst is arranged in individual beds and upon contact of the raw material with the catalyst bed, a degree of conversion of the raw material of practically 100% is achieved. When reducing the degree of conversion of the raw material is passed to the next catalyst bed.

To improve the production process of gasoline from synthesis gas or from methanol or from methanol and dimethyl ether (DME), various aspects of the prior art are affected, including the temperature control in the zone of highly exothermic conversion of methanol or DME into hydrocarbons and the Benzinselektivität and quality, especially the content of aromatic hydrocarbons, in particular heavy hydrocarbons, in the gasoline produced.

The temperature control in the zone of conversion of the methanol or DME into hydrocarbons takes place with the aid of diluting components in the raw material stream, which themselves do not take part in the reaction. In the process according to US 4,035,430 (from 1977) are used for at least one compound of C ₁ - to C ₅ hydrocarbons and the cooled durol-containing product. The latter compound, together with the temperature, has an influence on the yield of aromatic hydrocarbons and the content of the fractions contained therein on BTX (benzene, toluene, xylene).

As a diluting component not participating in the main reaction, use is made according to US 4,788,369 (from 1988) also a fraction of the liquid product (C ₃ - / C ₄ - fraction), which is separated from the reaction product and recycled to the reactor. There is an additional effect - the increase in gasoline yield due to the oligomerization of the recycled olefins, as a side reaction.

In the method according to US 4,404,414 (1983) for the production of hydrocarbons are used inert diluting components: light gas, which was separated from the reaction product, and water vapor, hydrogen and C ₂ - and C ₃₊ hydrocarbons or their mixtures.

In US 5,602,289 is used as a diluting component, a gas which is mixed together from two returned to the reactor gas streams (C _2- hydrocarbons and C ₃₊ hydrocarbons). The partial pressure of the water, including the water which has formed in the reaction of the conversion of the methanol in the reactor, is less than 2.2 atm. The limitation of the partial pressure for water vapor is due to the known effect of the irreversible deactivation of the zeolite in the presence of water vapor. The composition of the diluent component in this preferred case is given by a ratio of C ₂ -C hydrocarbons / C ₃₊ hydrocarbons within the limits between 1/3 and 3/1 and a hydrogen content between 10 and 50% mol. The use of low heat capacity gases (hydrogen, C ₂ hydrocarbons) as diluting components increases the dilution factor, but allows the conversion of the methanol to hydrocarbons at a higher pressure (while maintaining the required upper limit for the water vapor partial pressure). perform.

task

The object of the invention is the development of an economical and simplified process of the production of gasoline hydrocarbons from synthesis gas and a simple plant scheme with simplified technological stages. The aim is also to achieve a high Benzselektektivität with high gasoline quality and the provision of a waste-free technology without environmentally harmful by-products.

Brief description of the invention.

• a.) Kontakt mit einem Katalysator in einem ersten Konverter zur Erzeugung des ersten Produktstromes, der mindestens eine chemische Verbindung des Typs R¹-O-R² enthält (wobei R¹-Alkylgruppen mit einer Kohlenstoffzahl von 1 bis 5 sind, R²-Wasserstoff, Alkyl- und Alkoxygruppen mit einer Kohlenstoffzahl von 1 bis 5 sind), die bevorzugt Methanol und/oder, bei Notwendigkeit, Dimethylether ist sowie auch nicht umgesetzte Komponenten von Synthesegas, welche von der flüssigen Phase abgetrennt werden können und zu mindest teilweise in den ersten Konverter eingespeist werden,
• b.) Kontakt des gesamten Produkts aus dem ersten Konverter oder nach Abtrennung von zu mindest einem Teil der nicht reagierten Komponenten des Synthesegases, mit einem Katalysator in einem zweiten Konverter bevorzugt bei einem Partialdruck des Wasserstoffs von größer als 0,07 MPa, der Oxide des Kohlenstoffs von größer als 0,008 MPa, der Verbindung des Typs R¹-O-R², bevorzugt des Methanols und/oder des Dimethylether, von weniger als 0,5 MPa, des Wassers von weniger als 0,3 MPa bevorzugt bei einem Umsatz der Verbindung des Typs R¹-O-R² von nicht weniger als 82%, bevorzugt bei einem Methanolumsatz von nicht weniger als 82% und nicht mehr als 99,5%, sowie, bei Notwendigkeit, bei einem Dimethylether-Umsatz von nicht weniger als 92% und nicht mehr als 99,8%, zur Erzeugung eines Produktstroms, der
• – Benzinkohlenwasserstoffe, mit bevorzugt bis zu 45 Mass.-% aromatischen Verbindungen, darin enthalten bis 1 Mass.-% Benzol und mit bevorzugt nicht weniger als 40 Ma.-% Isoparaffinen (verzweigte gesättigte aliphatische Kohlenwasserstoffe mit mindestens 5 C-Atomen),
• – C₁-C₄-Kohlenwasserstoffe, die sich bevorzugt in einer Menge von nicht mehr als 17 Mass.-% bilden (umgerechnet auf C im umgesetzten Methanol und/oder, bei Notwendigkeit, im umgesetzten Dimethylether),
• – nicht umgesetzte Verbindungen des Typs R¹-O-R²,
• – sowie auch nicht reagierte Komponenten des Synthesegases enthält,

wobei Synthesegas aus dem ersten und/oder zweiten Produktstrom abgetrennt wird und zu mindest teilweise als Kreislaufgas in den ersten Konverter rückgeführt wird,

• c.) Trennung des Produktes des zweiten Konverters der Synthese von instabilem Benzin, das mit bekannten Methoden stabilisiert wird, wobei
• – eine Benzinfraktion, aus welcher, bei Notwendigkeit, eine Schwerbenzin-Fraktion, die Durol (1,2,4,5-Tetramethylbenzol) enthält, abgetrennt wird,
• – eine Fraktion von C₃-C₄-Kohlenwasserstoffen,
• – sowie auch ein Gasstrom, welcher leichte Kohlenwasserstoffe (C₁ und C₂), nicht reagierte Komponenten des Synthesegases und andere Komponenten, die am Prozess teilnehmen, enthält, welcher zu mindest teilweise in den zweiten Konverter und/oder in den ersten Konverter zurückgeführt werden kann, und auch
• –eine wässrige Phase, die Methanol und/oder eine andere Verbindung des Typs R¹-O-R² enthält,

erhalten wird.According to the invention the object is achieved by a process for the production of hydrocarbons according to claim 1:
In the process of the invention, the production of hydrocarbons by the conversion of a CO and H ₂ -containing gas mixture (hereinafter also called syngas) by

• a.) contact with a catalyst in a first converter to produce the first product stream containing at least one chemical compound of the type R ¹ -OR ² (wherein R ^{1 are} alkyl groups having a carbon number of 1 to 5, R ² -hydrogen, Alkyl and alkoxy groups having a carbon number of 1 to 5), which is preferably methanol and / or, if necessary, dimethyl ether as well as unreacted components of synthesis gas which can be separated from the liquid phase and at least partially in the first converter be fed
• b.) contact of the entire product from the first converter or after separation of at least a portion of the unreacted components of the synthesis gas, with a catalyst in a second converter preferably at a partial pressure of hydrogen greater than 0.07 MPa, the oxides of Carbon of greater than 0.008 MPa, the compound of the type R ¹ -OR ² , preferably of methanol and / or dimethyl ether, of less than 0.5 MPa, the water of less than 0.3 MPa preferably at a conversion of the compound of Type R ¹ -OR ² of not less than 82%, preferably at a methanol conversion of not less than 82% and not more than 99.5%, and, if necessary, at a dimethyl ether conversion of not less than 92% and not more than 99.8%, to produce a product stream, the
• Petroleum hydrocarbons, preferably having up to 45% by mass of aromatic compounds, containing up to 1% by mass of benzene and preferably not less than 40% by mass of isoparaffins (branched saturated aliphatic hydrocarbons having at least 5 C atoms),
• C ₁ -C ₄ -hydrocarbons, which preferably form in an amount of not more than 17% by mass (converted to C in the methanol reacted and / or, if necessary, in the dimethyl ether reacted),
• Unreacted compounds of the type R ¹ -OR ² ,
• Contains as well as unreacted components of the synthesis gas,

wherein synthesis gas is separated from the first and / or second product stream and is at least partially recycled as recycle gas into the first converter,

• c.) Separation of the product of the second converter of the synthesis of unstable gasoline, which is stabilized by known methods, wherein
• A gasoline fraction from which, if necessary, a heavy fuel fraction containing durene (1,2,4,5-tetramethylbenzene) is separated,
• A fraction of C ₃ -C ₄ -hydrocarbons,
• - As well as a gas stream containing light hydrocarbons (C ₁ and C ₂ ), unreacted components of the synthesis gas and other components that participate in the process, which are at least partially recycled to the second converter and / or in the first converter can, and also
• An aqueous phase containing methanol and / or another compound of the R ¹ -OR ² type,

is obtained.

The aqueous phase containing the compound of the type R ¹ -OR ² is added either for purification or first for rectification. The rectification is followed by separation into a concentrated solution of the R ¹ -OR ² type compound in water (preferably not less than 75% of the R ¹ -OR ² type compound) and one with the R ¹ -OR ² type compound contaminated water (preferably content of compound of the type R ¹ -OR ² to 5%), which is added for purification. The purification of the compound R ¹ -OR ² in each case is carried out either by catalytic decomposition of the methanol and / or another compound of the type R ¹ -OR ² or by biological methods, as explained in more detail below.

The converters of the synthesis of compounds of the type R ¹ -OR ² and the synthesis of gasoline with removal of the heat of the exothermic reaction from the reaction zone, have heat transfer surfaces through which the heat of reaction is transferred to a boiling heat carrier. The heat carrier (or its vapor) condenses in a cooling zone, which preferably contains boiling water for generating water vapor. The condensate flows back to the heat of reaction zone (principle of the "heat pipe").

The reactions in the converters of the synthesis of compounds of the type R ¹ -OR ² and the synthesis of gasoline are preferably carried out under approximately isothermal conditions in which the temperature difference (AT) within the catalyst bed does not exceed 40 K, preferably at a ΔT of 10 -20 K, more preferably at a ΔT of less than 5 K.

The heat of reaction is preferably used to generate steam at a pressure of up to 4 MPa in the converter of the synthesis of compounds of the type R ¹ -OR ² and up to 22 MPa in the converter of the synthesis of gasoline.

The removal of heat through the heat transfer surface to generate the water vapor allows the dilution of the feed streams with circulation gas up to 150 real m ³ / m ³ catalyst in the methanol synthesis converter (hereinafter cycle gas) and 0-150 real m ³ / m ³ catalyst in Converters of gasoline synthesis (hereinafter circulating gas) limit.

The process of the invention for producing gasoline from synthesis gas involves the contact of the synthesis gas with the catalyst in the first converter (converter of the synthesis of oxygen-containing compounds) under the conditions of the synthesis of compounds of the type R ¹ -OR ² . The term "compound of the type R ¹ -OR ^2" denotes - with R ¹ -alkyl radicals having 1 to 5 C atoms, - with R ² -hydrogen, alkyl and alkoxy radicals having 1 to 5 C-atoms. Preferred compounds of the type R ¹ -OR ² are methanol (R ¹ = CH ₃ and R ² = H) and optionally dimethyl ether (R ¹ = R ² = CH ₃ ), in particular that in the converter of the synthesis of compounds of the type R ¹ -OR ² (hereinafter also referred to as converter of methanol synthesis) synthesized methanol or the mixture of methanol and dimethyl ether.

Synthesis of the compounds of the type R ¹ -OR ² :

Preference is given to using as starting material for the synthesis of the compounds of the type R ¹ -OR ² synthesis gas.

In the converter of the synthesis of compounds of the type R ¹ -OR ² find (if the compound of the type R ¹ -OR ^{2 is} methanol) in particular the following reactions: CO + H ₂ O ↔ CO ₂ + H ₂ Water gas reaction CO + 2H ₂ ↔ CH ₃ OH methanol formation and optionally when using an additional acidic catalyst component to the methanol synthesis catalyst for the synthesis of dimethyl ether: 2 CH ₃ OH ↔ CH ₃ -O-CH ₃ + H ₂ O DME formation

Whether methanol or a mixture of methanol and dimethyl ether (DME) or other compounds of the type R ¹ -OR ^{2 are} produced in the first step is controlled in particular by the catalysts used.

For the synthesis of methanol, preference is given to catalysts known from the prior art which are customarily used for the synthesis of methanol (for example zinc-chromium oxide catalysts, copper-based catalysts with additions of zinc oxide and / or aluminum oxide, combinations of copper and rare earth metals, copper oxide / zinc oxide). Catalysts and copper oxide / zinc oxide / chromium oxide catalysts and others) are used.

For the synthesis of a mixture of methanol and dimethyl ether, known from the prior art catalysts of the synthesis of methanol with a catalyst of dehydration, especially catalysts with pronounced acidic properties, eg. B. γ-Al ₂ O ₃ or zeolites in protonated form with high acidity, as a mixture or individually for use.

The corresponding catalysts and the conditions are well known and described, for. B. for the synthesis of methanol in the book of MM Karavaeva, etc. << Technologija sinteticheskogo metanola >>, M .: Khimiya, 1984 and for the DME synthesis in the patent US 3,894,102 ,

The product stream of the converter of the synthesis of compounds of the type R ¹ -OR ² is preferably cooled with subsequent separation of the liquid and gaseous phase in the separator. Alternatively, the (complete) product stream from the methanol synthesis converter is introduced directly into the second gasoline synthesis converter without separation.

If a separation, the unreacted components of the synthesis gas (CO, H ₂ , CO ₂ , nitrogen and others) are preferably partially recycled to the first converter of the synthesis of compounds of the type R ¹ -OR ² , ie they are the used gas mixture used which contains CO and H ₂ , and partly, the unreacted synthesis gas is fed to the gasoline synthesis synthesis suppression reactor for decomposing the compounds of the R ¹ -OR ² type. At the same time it is preferably discharged to another part of the process, to avoid the accumulation of inert components. The feeding of a part of unreacted components of the synthesis gas into the converter of the gasoline synthesis is realized with a volume flow at the inlet to the gasoline synthesis converter, which has a partial pressure of hydrogen of not less than 0.07 MPa and CO of not less than 0.08 MPa guaranteed.

For the synthesis of compounds of the type R ¹ -OR ² cooled converter with approximately isothermal conditions in the reaction chamber with a preferred heat transfer area of more than 50 m ² / m ³ catalyst is used, while the volume of the recycle gas, which is not in large part Reacted synthesis gas and short-chain hydrocarbon gases, based on 1 m ^{3 of} catalyst, preferably less than 150 m ³ .

Gasoline Synthesis:

In the gasoline synthesis converter, contact of at least a portion of the product stream from the converter results in the synthesis of the R ¹ -OR ² type compounds with the catalyst at a preferred level of conversion of the R ¹ -OR ² compound from 85% to 99.5 % instead of.

In the converter of the synthesis of gasoline, contact with the catalyst either of all the current from the converter for the synthesis of compounds of the type R ¹ -OR ² or the whole (or at least part) of the liquid component of the product stream with a part of the gas components of the Product flow of the converter for the synthesis of compounds of the type R ¹ -OR ² instead, which in the feed stream of the gasoline synthesis converter, converted to 1 m ³ (i. N.) Gas stream, a partial pressure of H ₂ of more than 0.07 MPa and ensures a partial pressure of CO of more than 0.008 MPa. These values for the partial pressures of H ₂ and CO ensure suppression of the decomposition reaction of the R ¹ -OR ² compounds in the gasoline synthesis converter.

There is a wide range of catalysts for the synthesis of hydrocarbons from methanol and dimethyl ether. Part of them is in the book of Nefjodow BK, Konovalchikov LD, Rostanin NN "Catalysts of Petroleum Processing and Petroleum Chemistry Based on High Silica Zeolites", M: ZNIITENEFTECHIM, 1987, 59 p. described. The catalyst for the synthesis of gasoline from compounds of the type R ¹ -OR ² preferably contains at least partly a protonated zeolite (eg HZSM-5), preferably from the group of the pentasils. Preferably, zeolites having a high SiO ₂ / Al ₂ O ₃ ratio of at least 12 are used, particularly preferably having a SiO ₂ / Al ₂ O ₃ ratio of at least 30. The use of silicon-rich zeolites reduces the formation of durene in the product , A water vapor stable catalyst can be obtained by modification with Group Ib elements. It is also possible to use combinations of silicon dioxide with oxides of metals (gallium oxide and / or indium oxide) ( US 4,507,404 from 1985, EP 0,070,690 from 1983, EP 0,124,999 from 1984). For example, if gallium oxide and / or indium oxide combined with thorium oxide and a silicon-rich zeolite, a high-quality, aromatic-rich gasoline can be obtained ( EP 0,070,690 from 1983).

The feedstock fed to the second converter is either the entire first product stream or the part containing the R ¹ -OR ² compound. The partial pressure of the compound of the type R ¹ - OR ² (preferably of the methanol and optionally of the dimethyl ether) in the starting material of the converter of the gasoline synthesis, converted to 1 m ³ (i. N.) Gas stream, particularly advantageously kept below 0.5 MPa (advantageous distinguishing feature).

The partial pressure of the steam in the starting material of the gasoline synthesis converter is particularly advantageously below 0.3 MPa (advantageous distinguishing feature).

The process in the gasoline synthesis converter is carried out particularly advantageously at a partial pressure of the hydrogen of at least 0.07 MPa and at a partial pressure of the carbon monoxide of at least 0.008 MPa (advantageous distinguishing feature).

The process according to the invention is characterized in that the contact of the starting material with the catalyst takes place in the second converter in the presence of hydrogen and carbon monoxide. This advantageously increases the selectivity of the reaction of the compound of the type R ¹ -OR ² (preferably methanol and optionally dimethyl ether) into hydrocarbons, since their decomposition to carbon oxides and hydrogen is suppressed.

For the gasoline synthesis, a coolable converter with almost isothermal conditions in the reaction zone with a heat transfer area of over 40 m ² / m ³ catalyst is preferably used, the volume of the circulating gas is, based on 1 m ³ catalyst less than 150 m ³ . The heat of reaction is preferably used to generate water vapor at a pressure of up to 22 MPa. This is also a distinguishing feature of the invention, which together with features of claim 1 allows to obtain a high gasoline quality at a selectivity of more than 83%, preferably more than 86%. By selectivity is meant here the yield of gasoline, based on the hydrocarbon portion of the reacted methanol.

Preferably, the conversion of the compound of the type R ¹ -OR ² (preferably of the methanol and optionally the dimethyl ether) in the converter of gasoline synthesis is 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 type R ¹ -OR ² is an essential distinguishing feature of the invention, which allows the selectivity of the process (yield of the gasoline fraction, based on the hydrocarbon content of the reacted compounds of the type R ¹ -OR ² ) in connection with the necessary quality of the gasoline produced and the duration of the Zwischenregenerationszyklusses (operating time of the process between the regenerations of the catalyst) to control. This is the reason why in the invention, gasoline containing less than 46% of aromatic compounds, with less than 1% by weight of benzene contained therein, and more than 40% of isoparaffins having high octane characteristics (93-96%) RON), which is also a distinguishing feature of the invention.

In addition to the gasoline hydrocarbons, the product of the gasoline synthesis of compounds of the type R ¹ -OR ² C ₃ -C ₄ hydrocarbons, water, unreacted methanol and other compounds of the type R ¹ -OR ² , as well as "dry" gas. This "dry" gas contains mainly gaseous substances (short-chain hydrocarbons (C ₁ -C ₂ ), CO, CO ₂ and H ₂ and other components of the synthesis gas).

Separation of the products of gasoline synthesis:

The product of the gasoline synthesis is cooled and separated into unstable gasoline, an aqueous phase and the uncondensed gas components. The separation is preferably carried out by a physical phase separation in a three-phase separator. The uncondensed gas constituents contain components of synthesis gas, light hydrocarbons (C ₁ and C ₂ ), traces of heavier hydrocarbons. This circulating gas is recycled, at least partially, to the converter of gasoline synthesis and / or to the converter for the synthesis of compounds of the type R ¹ -OR ² . With the volume of the circulating gas in the converter of the gasoline synthesis can advantageously be set, the partial pressure of the methanol and the water.

The liquid phase in the three-phase separator forms, due to the difference in density, a phase interface between hydrocarbons containing the gasoline hydrocarbons and water. The lower density liquid (gasoline hydrocarbons) collects above the phase interface, while the aqueous phase settles at the bottom.

The liquid hydrocarbons separated in the three-phase separator contain the gasoline hydrocarbons which are preferably passed to a rectification column, in which, if necessary, preferably components of the heavy gasoline (Durolfraktion) and head gases - mainly C ₃ -C ₄ hydrocarbons and radicals of C ₁ -C ₂ Hydrocarbons (short chain hydrocarbons) and synthesis gas components. With a permissible content of durene in the gasoline hydrocarbons, the heavy fuel gas is not separated.

The obtained stable gasoline fraction with a required saturated steam pressure below 500-700 mm QS (depending on the required type of gasoline) is either commercial gasoline or forms the basis for the production of commercial gasoline with an octane number of 92-98 (RON).

The water separated in the three-phase separator contains methanol. The methanol content of the water depends on the degree of methanol conversion in the gasoline synthesis, it is usually more than 3 mass .-% and less than 30 mass .-%.

Preferably, the aqueous phase with a defined methanol content or with other compounds of the type R ¹ -OR ^{2 is} first separated in a rectification column due to the different boiling temperatures in fractions, of which a fraction mainly methanol or another compound of the type R ¹ -OR ² with a low content of water (concentrated methanol) and the other fraction contains water with a small content of methanol (contaminated water). The concentrated methanol or optionally dimethyl ether or another compound of the type R ¹ -OR ² is preferably returned to the converter of the gasoline synthesis. The contaminated water still contains a residual content of methanol (usually at most 5% by mass) or another compound of the type R ¹ -OR ² .

To remove the residual methanol from the contaminated water of the process according to the invention, methanol and optionally another compound of the R ¹ -OR ² type are catalytically decomposed by contact with a catalyst (steam reforming or catalytic decomposition) into hydrogen and gaseous carbon oxides. The water is separated after cooling, by condensation, from the generated oxides of carbon (CO and CO ₂ ) and hydrogen. The carbon oxides and the hydrogen can advantageously be mixed with the synthesis gas and recycled to the process of synthesis of compounds of the type R ¹ -OR ² . After the separation of the gases, chemically purified water is advantageously obtained, with subsequent degassing of the water. The contact of the methanol-containing water with the catalyst is preferably carried out at a temperature below 380 ° C, more preferably below 350 ° C and preferably above 200 ° C.

The contact of the water containing a compound of the type R ¹ -OR ² (preferably methanol, optionally dimethyl ether) with the catalyst is preferably realized at a pressure which allows the generated components of the synthesis gas in the first converter directly or with the help of a cycle compressor in the first converter to initiate. This pressure corresponds to the sum of the reaction pressure for the synthesis of compounds of the type R ¹ -OR ² and the pressure loss between the exit of the product of the catalytic methanol decomposition and entry of the feedstock into the converter of the methanol synthesis. Alternatively, the residual content of the R ¹ -OR ² type chemical compound in the water may also be removed by a biological purification process. The biologically purified water can be introduced into the sewage network.

However, it has to be considered that the biological purification requires a methanol content in the water of less than 0.2-1 mass%, obtaining such a concentration by the rectification is associated with high energy expenditure or it is a large dilution of the contaminated water required with pure water, which also increases the cost of biological purification.

The use of the catalytic purification of the water of compounds of the type R ¹ -OR ² is another advantageous distinguishing feature, since it allows to control the process conditions in the gasoline synthesis converter with relatively little effort, the degree of conversion of the compounds of the type R ¹ -OR ² and thereby achieve a high selectivity and quality of the products.

Investment:

The invention also provides a system for carrying out the method according to the invention.

• a.) mindestens einen ersten Konverter, der einen Katalysator enthält, der geeignet ist, die Umsetzung von CO mit H₂ zu der chemischen Verbindung des Typs R¹-O-R² (bevorzugt Methanol) zu katalysieren,
• b.) mindestens einen zweiten Konverter; der einen Katalysator enthält, der geeignet ist, die Umsetzung der chemischen Verbindung des Typs R¹-O-R² in Kohlenwasserstoffe zu katalysieren,
• c.) mindestens einen Separator, der geeignet ist, Benzinkohlenwasserstoffe aus einem Produktstrom abzutrennen, der neben Benzinkohlenwasserstoffen auch chemische Verbindungen des Typs R¹-O-R², Wasser und Gas, welches kurzkettige Kohlenwasserstoffe, Komponenten des Synthesegases, Verbindungen des Typs R¹-O-R² und Spuren an Benzinkohlenwasserstoffen enthält,
• d.) mindestens einen dritten Konverter, der einen Katalysator enthält, der geeignet ist, die Umsetzung der im Wasser enthaltenen chemischen Verbindung des Typs R¹-O-R² (bevorzugt Methanol) in CO und H₂ zu katalysieren.

This attachment contains:

• a.) at least one first converter containing a catalyst suitable for catalyzing the reaction of CO with H ₂ to the chemical compound of the type R ¹ -OR ² (preferably methanol),
• b.) at least one second converter; containing a catalyst capable of catalyzing the reaction of the R ¹ -OR ² type chemical compound into hydrocarbons,
• c.) at least one separator which is suitable for separating off benzene hydrocarbons from a product stream which, besides benzine hydrocarbons, also contains chemical compounds of the type R ¹ -OR ² , water and gas, which short-chain hydrocarbons, components of the synthesis gas, compounds of the type R ¹ -OR ² and contains traces of gasoline hydrocarbons,
• d.) at least one third converter containing a catalyst which is suitable for catalyzing the conversion of the water-containing chemical compound of the type R ¹ -OR ² (preferably methanol) into CO and H ₂ .

The abovementioned components are preferably connected in series, ie the first converter is connected directly or indirectly to the second converter such that at least part of the product stream is introduced from the first converter into the second converter. The second converter is connected to the separator c.), So that the product stream from the second converter into the separator c.) Is passed. In this case, the separator c.) Is indirectly connected to the third converter so that the water which was separated in the separator c.) And contains the chemical compound of the type R ¹ -OR ² , if necessary, after a prior distillative separation of the main amount the connection of the type R ¹ -OR ^{2 is passed} to the third converter. The separator c.) Also has a connection with the second converter, which allows the short-chain hydrocarbons and the other components of the gas phase of the separator c.) To be returned to the input into the second converter.

The system preferably contains a connection line from the third converter to the first converter, which makes it possible to introduce CO and H ₂ formed in the third converter into the first converter.

To carry out the variant of the method with separation of the first product stream, the system contains an additional separator for separating the product stream from the first converter. In this case, the additional separator preferably has a connection line to the first converter, which makes it possible to introduce separated CO and H ₂ in the separator into the first converter. This (additional) separator preferably also has a first connection line to the second converter, which makes it possible to feed chemical compounds of the type R ¹ -OR ² , if necessary after separation of at least part of the water, into the second converter and a second one Connecting line to the second converter, which makes it possible, if necessary, to introduce at least a portion of the gas stream containing CO and H ₂ , in the second converter.

To carry out the variant with the direct introduction of the (complete) first product stream into the second converter, the first converter in the system is connected directly to the second converter by a stream, so that the complete product stream from the first converter without separation into the second converter is initiated. In this case, the separator c.) Preferably has a connection line to the first converter, which allows the dry gas (unreacted CO and H ₂ and short-chain hydrocarbons) to be returned to the first converter.

In any case, the second product stream is separated into hydrocarbons containing gasoline hydrocarbons, gas and water. The water containing the unreacted chemical compound of the type R ¹ -OR ² is preferably introduced into a separator (c.) Downstream of the separator (preferably a rectification column) which gives the possibility of obtaining a product with a high content of compound of the type R ¹ -OR ² (preferably methanol and optionally DME) in the water to separate, which can be added to the starting material of the second converter again. This device downstream of the separator c.) Therefore preferably has a connecting line for returning the separated concentrated solution of the chemical compound of the R ¹ -OR ^{2 type} in the water to the second converter. However, this additional device does not completely remove the R ¹ -OR ² compound from the water. The additional device therefore also has a connection line to the third converter, which makes it possible to supply the still contaminated water to the third converter, in which the compound of the type R ¹ -OR ^{2 is} decomposed.

For the decomposition of the compound of the type R ¹ -OR ² (preferably of the methanol and optionally of the DME) known catalysts can be used, an overview is in the article by Klabunowski EI et al "Catalysts of Conversion of Methanol into Synthesis Gas" (Catalysis in Industry, 2004, N. 6, pp. 3-9) given as well as the catalysts of steam reforming of CO, the catalysts of methanol synthesis and other catalysts.

In step d.), A converter of any type can be used, preferably a fixed-bed flow-through converter of a granulated catalyst. The converter used in step d.) Is hereafter called water purification converter. For the organization of a continuous process of production of synthetic gasoline from synthesis gas it is preferable not to use one, but two converters: one converter works in a reaction mode, the second converter works in a regeneration catalyst regeneration mode.

The term converter is used synonymously with reactor in the description of the invention. The converters used in step a.) And / or step b.) Are preferably flow-through reactors in which the catalyst is introduced as a fixed bed.

Preferably, the first and / or the second converter are cooled. The cooling is preferably carried out by indirect evaporation cooling. The reaction procedure in step a.) And / or step b.) Takes place as nearly as possible isothermally. The converters are preferably designed so that they allow a direct and complete removal of the heat of reaction generated in the catalyst bed and thus allow a reaction at an approximately constant temperature in the volume of the reaction space.

The heat of reaction dissipated by the cooling in the first and / or second reactor can be used to advantage for the production of water vapor.

The first converter (methanol synthesis and optionally DME synthesis) preferably has a ratio of the heat transfer area 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 of reaction dissipated in the first converter, water vapor having a pressure of not less than 0.6 MPa and not more than 4 MPa is preferably produced.

The second converter (gasoline synthesis) preferably has a ratio of the heat transfer area to the catalyst volume of not 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, water vapor having a pressure of not less than 3.0 MPa and not more than 22 MPa is preferably produced.

The heat of reaction removed by the generated steam can advantageously be used to produce a refrigerant which can be used for the product separation after step a) and / or after step b).

The synthesis gas used in the process can be obtained from a wide variety of starting materials. The starting materials may be of fossil or biological origin (eg coal, biomass, natural gas or biogas). The ratio of CO to H ₂ in the synthesis gas depends on the starting materials used for the preparation and on the production process. The syngas usually also contains inert components (such as N ₂ and water). The synthesis gas is preferably purified of catalyst poisons (sulfur compounds, nitrogen compounds) and foreign substances, dried and, if necessary, compressed.

For the methanol or DME synthesis, the ratio of H ₂ / CO in the synthesis gas is preferably not less than 2. In this case, a large yield of methanol (DME), based on C in CO, is obtained. With a smaller ratio, the yield of methanol (DME) decreases and the yield of CO _{2 increases} .

The individual method steps of the method according to the invention are explained in more detail below on the basis of preferred embodiments:
Gas from synthesis gas is produced in two stages: in step a.), The synthesis of compounds of the type R ¹ -OR ² - for example, methanol and / or dimethyl ether, in step b.), The conversion of compounds of the type R ¹ -OR takes place ² on a zeolite catalyst in a mixture of hydrocarbons. The compounds of the type R ¹ -OR ² which are produced in the first stage may be passed as a whole product stream from the first converter to the second stage or be separated from the product of the first converter in any variant and then added to the second stage ,

From the product of the first converter can be separated as starting material for the second stage methanol and optionally dimethyl ether, including in admixture with water. Unreacted synthesis gas is preferably separated from the product of the first converter or from the product of the second converter and recycled to the first converter for the synthesis of compounds of the type R ¹ -OR ² .

The synthesis gas can be used advantageously as a crude mixture, but is preferably dried and compressed if necessary and heated in admixture with the cycle gas to a temperature which is close to the reaction temperature, heated, for. B. in recuperator heat exchangers and / or heaters (steamer heaters, stoves and / or electric heater) and in the first converter (in the figures - block I ) for the synthesis of compounds of the type R ¹ -OR ² (methanol and optionally dimethyl ether) passed. In the preparation of compounds of the type R ¹ -OR ² , contact is made with the catalyst of the methanol synthesis or with the catalyst of the methanol synthesis and the catalyst of the dehydration of methanol to dimethyl ether (DME).

For the methanol synthesis in step a.) Copper-containing catalysts are preferably used at a temperature up to 260 ° C and a pressure up to 6 MPa. The reaction of CO and H ₂ to form methanol is exothermic with a heat effect of 90.73 kJ / mole of methanol. Therefore, an isothermal cooling converter is preferably used in step a.). This is capable of reducing the required volume of the recycle gas and performing the synthesis under optimum conditions, with concomitant reduction in the formation of by-products, increased methanol yield, catalyst life extension, and the generation of medium pressure steam for use as an energy source.

The product from the converter of the synthesis of the compounds of the type R ¹ -OR ² is preferably cooled in heat exchangers by preheating the raw material stream (synthesis gas). As a variant, the product stream may preferably be separated into a gas product and a condensate. For this, the product is preferably cooled in the air cooler and in the water cooler, and in the presence of dimethyl ether in the product, even using deep cold. The organic components and the water are condensed. The condensate (crude ethanol, water content up to 20% or mixture of dimethyl ether, methanol and water) is separated in the separator. The gas product from the separator is unreacted synthesis gas, a portion of which is returned to the first converter for mixing with the starting syngas for complete conversion.

As a variant, the separator can also be followed by a rectification column for separating the water from the mixture with the organic components, since the presence of water in the feedstock for the second converter for converting the compounds of the R ¹ -OR ^{2 type} into hydrocarbons irreversibly deactivates the accelerated in the second converter used zeolite catalyst. However, this is a very expensive operation and it is more economical to dilute the feed stream for the second converter with inert components to reduce the partial pressure of the water and the methanol.

The separated compounds of the type R ¹ -OR ² (methanol or methanol / DME mixture) or the product stream from the first converter (block I ) is put into the second converter (on the pictures - block III ) fed to the synthesis of gasoline, where it is preferred with the recycle stream of methanol (stream 11 on the + ) from the block V , with the recycle stream of light hydrocarbon gas (stream 7 on the ) from the block IV and the stream of unreacted synthesis gas (stream 5 on ) from the separator (block II ) is mixed. The mixed stream is preferably heated in the recuperator heat exchangers and in the heater and fed into the converter for gasoline synthesis.

The presence of hydrogen and carbon monoxide in the process of the invention in the zone of the reaction of methanol (and optionally dimethyl ether) reduces, at least in part, the undesired decomposition of methanol into hydrogen and carbon monoxide in step b.). This advantageously increases the selectivity of the formation of hydrocarbons. The partial pressure of the hydrogen is preferably higher than 0.07 MPa and the partial pressure of the carbon monoxide higher than 0.008 MPa. In order for the required effect to be achieved. either hydrogen and carbon monoxide with the previously separated from the first product stream of methanol (and optionally dimethyl ether), or the first product stream containing unreacted synthesis gas is passed directly into the second converter. The hydrogen and the carbon monoxide serve as diluting components in the second converter, i. H. they dilute the educt (methanol and possibly DME). The dilution of the methanol (of the methanol + of the DME) in the feed stream to the second converter must be such that the partial pressure of the methanol is less than 0.5 MPa and that of the water is less than 0.3 MPa.

The product from the converter of gasoline synthesis is preferably cooled in recuperator heat exchangers, wherein preferably the starting material of the converter (methanol and possibly DME), if possible in admixture with circulating gas, is heated. The cooled stream is preferably to the second separator (on the pictures block IV ) for the separation of the converter product of gasoline synthesis. Upon cooling in the recuperator and in the coolers, the gasoline hydrocarbons, some of the light hydrocarbons, the unreacted compounds of the R ¹ -OR ^{2 type} and water condense. In the separator are preferably 1. the water containing unreacted compounds of the type R ¹ -OR ² , 2. the gasoline hydrocarbons and 3. the gas phase, the hydrogen, carbon oxides and light hydrocarbons (mainly up to 4 carbon atoms, mainly methane and C ₂ -C ₄ hydrocarbons), which form in the conversion of methanol separated. Part of the gas phase is mixed with a portion of the CO and H ₂ -containing gases from the first separator (in Figures Block II ) and preferably as diluting components to the starting material (methanol and optionally DME) in the converter of the gasoline synthesis recycled.

The condensate of the gasoline hydrocarbons from the separator c.) Is preferably heated and led to the stabilizing column, in the light overhead gases (short-chain hydrocarbons, essentially propane, propylene, butane, butylene, as well as methane, ethane, ethylene and H ₂ ) from the stable gasoline (Electricity 8th on the pictures). Possibly. For example, the C ₃ -C ₄ -hydrocarbons can be separated off as liquid fraction C ₃ -C ₄ . From the benzene hydrocarbons, which are fed into the stabilizing column, heavy fuel (electricity 9 on the pictures) in the stabilizing column or in an additional column.

The aqueous phase (stream 10 on the pictures) from the separator c.) can be used as a variant in a rectification column (block V on the + ) and then to the converter of the water purification (block VI on the + ). In the rectification column, the concentration of the compound of the type R ¹ -OR ² (current 11 on the + ). This recycle stream is directed to the block of gasoline synthesis. The water obtained in the bottom of the column, which contains residual contents of R ¹ -OR ² , is passed to the converter for water purification. The aqueous phase from the separator c.) Can also be added directly to the water purification.

With reference to the following figures, two preferred variants of the method according to the invention are explained in more detail.

shows the block diagram for a preferred production process of gasoline from synthesis gas according to the inventive method with separation of the recycle stream of the synthesis gas from the product of the converter of the synthesis of compounds of the type R ¹ -OR ² and the catalytic decomposition of the methanol in the water following the distillative Separation of the main amount of methanol from the process water.

shows the block diagram for a preferred production process of gasoline from synthesis gas according to the inventive method with direct introduction of the product stream from the first converter into the second converter and separation of the recycle stream of the synthesis gas from the product of the gasoline synthesis converter and the catalytic decomposition of the methanol in the water Connection to the distillative separation of the main amount of methanol from the process water.

On becomes synthesis gas 1 , whose main components hydrogen and carbon monoxide in a ratio which depends on the method of their production, but which also contains inert components, purified by catalyst poisons and admixtures, compressed if necessary, and in the first converter (Block I ) of the synthesis of compounds of the Type R ¹ -OR ² fed where it is with the recycle gas 3 is mixed. The resulting mixture is preheated to the reaction temperature in recuperator heat exchangers and heaters (steam and / or electric heaters, ovens) and passed into the converter of the synthesis of compounds of the type R ¹ -OR ² . In the preparation of compounds of the type R ¹ -OR ² , contact is made with the catalyst of the methanol synthesis or with the catalyst of the methanol synthesis and the catalyst of the dehydration of methanol to dimethyl ether. In the synthesis of methanol, the use of copper-containing catalysts at a temperature of up to 260 ° C and a pressure of up to 8 MPa is preferred, but it can also zinc-chromium catalysts, at a temperature of up to 360 ° C and to work at a pressure of more than 8 MPa.

The product from the converter of the synthesis of compounds of type R ¹ -OR ² is cooled in heat exchangers by preheating the raw material stream, as well as in the air and water cooler, in the presence of dimethyl ether in the product is used for cooling and deep cold, the Condens compounds of type R ¹ -OR ² and water. The condensate (crude ethanol, water content up to 20% or mixture of dimethyl ether, methanol and water) is in the separator (block II ) deposited. The gas product from the separator is unreacted synthesis gas, part of it (stream 3 ) is passed to mix with the starting synthesis gas for more complete conversion of the raw material. The separated in the separator compounds of the type R ¹ -OR ² 4 (Methanol and possibly DME) are reacted with the recycle stream of methanol 11 from block V , the recycle stream 7 of the light hydrocarbon gas from the second separator (block IV ) and the stream 5 of unreacted synthesis gas from block II , preferably gas product from the separator, mixed. After mixing, the components are preferably heated in recuperator heat exchangers and / or in heaters and fed into the gasoline synthesis converter.

To obtain the best possible gasoline quality (low proportion of heavy gasoline and aromatics), the conversion of the compounds of the type R ¹ -OR ² (methanol and possibly DME) in the second converter (block III ) is preferably kept below 99.5%. The product of the gasoline synthesis converter contains the hydrocarbons (in particular gasoline hydrocarbons ⁾ produced in the reaction of the compounds of the R ¹ -OR ² type and unreacted compounds of the R ¹ -OR ^{2 type} , mainly methanol and components of the synthesis gas.

Both converters (block I and III ) are preferably cooled converters. The first converter has a heat transfer area of at least 50 m ² per 1 m ^{3 of} catalyst at a flow rate of the recycle gas of less than 150 real m ³ / m ³ 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 the circulating gas of gasoline synthesis of less than 150 real m ³ / m ³ catalyst. The steam generated in the cooling of the converter is, as described above, used to produce a refrigerant by means of an absorption refrigerator, in steam heaters for preheating the feed streams of the first converter and as bottom heating of the column for product separation.

The product of the converter of gasoline synthesis (block III ) is cooled in the recuperator heat exchangers, whereby the feed of the converter is heated, further it is cooled in coolers. In the process of cooling, condensation of the petroleum hydrocarbons and of the water takes place. The cooled stream 6 becomes separator c.) (block IV ) to separate the reactor product of the gasoline synthesis. In the separator c.) 1. The methanol-containing water 10 , 2. the petrol hydrocarbon phase 8th + 9 and 3. the gas phase 7 which contains hydrogen, carbon oxides and light hydrocarbons which form in the conversion of methanol.

The recycle stream of the light hydrocarbon gas 7 in the highlighted case with a portion of the CO and H ₂ -containing gases 5 from the first separator (block II ) to obtain a diluting component for the starting material of the synthesis of the compounds of the type R ¹ -OR ² .

The hydrocarbon condensate (inter alia C ₅₊ -hydrocarbons) 6 from the separator (block IV ) is added to the stabilizing column (block IV ), in which the light head gases 7 from stable gas 8th be separated. From the unstable petroleum hydrocarbons in a stabilizing or an additional column and heavy fuel 9 be separated.

The aqueous phase 10 from the separator is in the block V for concentrating the compounds of the type R ¹ -OR ² and from there into the block VI for the catalytic water purification of compounds of the type R ¹ -OR ^{2 passed} . The water contains here, depending on the degree of conversion, usually between 3.5 Mass .-% and 30 Mass .-% compounds of the type R ¹ -OR ² .

In the block V the concentration of the compounds of the type R ¹ -OR ² , the enrichment of the methanol in the head is realized in a rectification column and it is the recycle stream of methanol 11 get which to the block III the gasoline synthesis is promoted. The bottom product from the column (block V ) - the water 12 which contains between 1% and 5% methanol 5 contains, is placed in the converter of water purification (block VI ), where the catalytic decomposition of the methanol is carried out in the aqueous medium.

In the converter of water purification (block VI ) becomes the gas stream 13 obtained from the decomposition of the methanol - carbon oxides and hydrogen, which is the first converter (block I ) is supplied. It becomes chemically purified water fourteen which is used for the replenishment of the system of the recooling water, the steam generation system and for other purposes.

The on The manufacturing process shown is a simplified variant of and differs from this mainly in the following point: The product of the first Converter (block I ) is heated in heat exchangers and / or heaters and directly, without prior separation, to the converter (block III ) directed the gasoline synthesis.

As a diluting component of the oxygen-containing feedstock can here again recirculated recycle gas 3 (here from block IV ) are added.

Again, the synthesis gas 1 before or at the feed in the first converter next to the cycle gas 3 additionally hydrogen and carbon monoxide 13 , which in the converter of the catalytic water purification (block VI ) is added. The product from the first converter corresponds in its composition substantially to the product from the process ,

In order to achieve a maximum high gasoline quality (low proportion of heavy gasoline), the conversion of the compound of the type R ¹ -OR ² (methanol and optionally DME) is preferably kept below 99.5%.

The product from the gasoline synthesis converter is also preferably cooled first in the recuperator heat exchangers and in coolers. The partially cooled stream 6 will be in the block IV the separation of the products of the converter of the gasoline synthesis fed, where by the cooling in the coolers a condensation of the petrol hydrocarbons and the water takes place. In the separator becomes the water 10 , which contains unreacted compounds of the type R ¹ -OR ² , deposited and the gasoline hydrocarbon phase and the gas phase are separated. The gas product from the separator consists mainly of unreacted synthesis gas and light hydrocarbons, part of which (stream 3 ) is mixed with the starting synthesis gas for more complete conversion of the raw material into the first converter (block I ) returned.

The water formed in the converter of gasoline synthesis contains here, depending on the degree of conversion, usually between 3.5% and 40% methanol (and possibly DME). There is therefore a purification of the water in a rectification column (block V ) and then in a separate converter of water purification (block VI by catalytic decomposition of the methanol into hydrogen and carbon oxides (these gases are recycled as an admixture to the synthesis gas in the process - see description of ).

The hydrocarbon condensate from the separator (block IV ) is passed to the stabilizing column (block IV ), in which the gasoline 8th is separated. From the unstable petroleum hydrocarbons in a stabilizing column or an additional column and heavy fuel 9 be separated.

The water phase 10 from the separator is in the block V the enrichment of the compounds of the type R ¹ -OR ² and then in the converter of water purification (block VI ) fed. In the block V the concentration of the compounds of the type R ¹ -OR ² is realized in a rectification column, the enrichment of the methanol in the top part and there is a recycle stream of this methanol 11 get into the block III the gasoline synthesis is returned. The bottom product of the column - the water 12 which contains between 2 and 5% methanol 5 contains, is placed in the converter of water purification (block VI ) fed.

In the block VI For purification, the methanol-containing water stream is preferably conveyed through the recuperator heat exchangers and / or preheaters, where it is heated to the required reaction temperature, and then fed to the converter for water purification, where contact with the catalyst decomposes the methanol into hydrogen and carbon oxides is realized.

The product from the water purification converter is preferably cooled in recuperator heat exchangers and an air cooler. Subsequently, the gas phase is separated from the condensate in a separator. The thereby separated gases of decomposition of methanol 13 exit from the separator and are mixed with the raw synthesis gas in the first converter (block I ). The purified water is conveyed to the degasifier column. It becomes chemically purified water fourteen which is used for the replenishment of the system of the recooling water, the steam generation system and for other purposes.

By that on the and shown water, the converters are cooled indirectly. The water absorbs the heat from a heat carrier, which in turn dissipates the heat from the reaction zone. The water leaves block I and III as steam.

The invention will be explained in more detail below with a comparative example and exemplary embodiments.

Example 1 (comparative example)

This example was analogous to the process TIGAS the company Haldor Topsoe IJ. Topp-Jorgensen, reprinted from << Studies in Surface and Catalysis, v. 36, Methane Conversion >>, 1987 carried out.

On a block diagram of the process TIGAS is shown.

Synthesis gas is mixed with recycle gas containing unreacted components of the synthesis gas and light hydrocarbons, and enters the reactor of synthesis of methanol + DME with a bifunctional catalyst consisting of a catalyst component of methanol synthesis and a catalyst component of dehydration of methanol. The resulting mixture of methanol + DME + water and components of the unreacted synthesis gas is added to the gasoline synthesis stage where conversion of the methanol and DME to hydrocarbons occurs on a zeolite-containing catalyst. The product mixture is then separated into gasoline, an aqueous phase which is put to purification, a C ₃ -C ₄ fraction and gas, a part of which is conducted as a circulation gas to the stage of synthesis of oxygen compounds. All stages are performed at approximately 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, based on CH ₂ in the oxygen compounds, is 78%.

Overall, the yield of gasoline is 73.34%, based on CH ₂ in the synthesis gas without taking into account losses in the product separation, etc ..

In the following, examples of different variants of the process execution according to the invention are listed.

In this case, a real synthesis gas with the following composition, in Vol .-%, is used:
CO - 21.91; H ₂ - 61.16; CO ₂ - 6.38; CH ₄ - 1.83; H ₂ O - 8.72.

The volume flow of the synthesis gas is: 738.3 m ³ (i.N) / h.

For the synthesis of methanol from synthesis gas is a catalyst from Südchemie called MEGAMAX 700 ^® (components CuO, ZnO, Al ₂ O ₃ ) and for the synthesis of gasoline from methanol a zeolite-containing catalyst from Südchemie called SMA-2 used.

The operating conditions in the converter of the synthesis of compounds of the type R ¹ -OR ² are temperatures in the range of 210 to 260 ° C and pressures in the range of 50 to 55 MPa. The volume of the catalyst is 0.46 m ³ , the heat exchange surface in the reaction zone is 30 m ² . The pressure of the generated water vapor is 1.8 MPa.

In the converter of gasoline synthesis in Examples 2 to 4 is a pressure of 7 bar and in Example 5, a pressure of 45 bar before. The temperature of the process is in the range of 310 to 430 ° C in the reaction regime and in the range of 280 to 500 ° C in the regeneration regime.

The converters of methanol synthesis and gasoline synthesis are cooled. Converters with a heat transfer area of 60 m ² / m ^{3 of} catalyst are used.

The reactions in the converters of the synthesis of methanol and the synthesis of gasoline are carried out under approximately isothermal conditions in which the temperature difference within the catalyst bed is below 5 K.

In Examples 2 to 4, the separation of the products of the process of production of oxygen compounds takes place at a temperature of 40 ° C. The separation of the products of gasoline synthesis takes place in all examples at a temperature of + 5 ° C.

Examples 2 to 5 differ by a different choice of application of individual distinguishing features of the invention.

Example 2

The plant of production of synthetic gasoline corresponds mainly to the scheme on and includes: a block (block I ) Synthesis of methanol from synthesis gas, one block (block II ) Separation of methanol from the product stream of the block I , a block (block III ) of the synthesis of gasoline from crude methanol, a block (block IV ) fractionation with removal of the product gasoline, a block (block V ) the separation of methanol from the process water.

In contrast to the scheme in However, the block of water purification of methanol is not in operation. In addition, unlike in the plant are missing the streams 5 . 13 and fourteen ie in the block III will not the electricity 5 given. Table 2.1. Material balance of the plant Regime of production of synthetic gasoline from crude methanol, without supply of synthesis gas from the block of methanol synthesis in the block of gasoline synthesis, without the block of water purification Catalyst of the synthesis of gasoline: SMA-2 Conversion of methanol: 99% Selectivity of conversion of methanol to gasoline: 86% Sales of (CO + CO ₂ ) in methanol: 94.7% Annual operating hours 8,000.00 material flow kg / h t / year % Mass., Based on the raw material Input: synthesis gas 376.10 3,008.80 100.00 total: 376.10 3,008.80 100.00 Output: Blow-off gas of the block of methanol synthesis 29,00 232.00 7.71 Hydrocarbon-containing blow-off gases 23.00 184.00 6.12 Synthetic gasoline 97.00 776.00 25.79 82.76 * 78.39 ** water of reaction 180.50 1,444.00 47,99 Water from raw synthesis gas 46,60 372.80 12.39 total: 376.10 3,008.80 100.00 * based on CH _{2 of} the methanol, ** based on CH _{2 of} the synthesis gas. Table 2.2. Characterization of currents in the scheme on fig. 1 No. Physical properties of the material flows Composition of the streams [% by mass] T [° C] p [MPa] Mass flow [kg / h] H ₂ CO CO ₂ H ₂ O CHOH C ₁ -C ₄ C ₅₊ 1 60.0 5.70 329.5 11.68 58.17 26.61 0.76 - 2.78 - 2 123.8 5.20 2364 7.28 7.16 38.42 1.32 12.76 33.06 - 3 54 5.8 2,034.5 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 8th 40.4 0.70 80.1 - - - - 0.01 2.96 97.03 9 45.4 0.60 16.9 - - - - - - 100.00 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 - - - - - - - - - - fourteen - - - - - - - - - -

Example 3

The plant of production of synthetic gasoline corresponds mainly to the scheme on and includes: a block of synthesis of methanol from synthesis gas (block I ), a block (block II ) Separation of the methanol from the product stream of the block I , a block (block III ) of the synthesis of gasoline from crude methanol, a block (block IV ) fractionation with removal of the product gasoline, a block (block V ) the separation of methanol from the process water.

The block of water purification of methanol is not in operation. In addition, unlike the scheme in the streams 13 and fourteen , Table 3.1. Material balance of the plant Regime with production of synthetic gasoline from crude methanol, without the block of water purification Catalyst of gasoline synthesis: SMA-2 Conversion of methanol: 99% Selectivity of conversion of methanol to gasoline: 87% Sales of (CO + CO ₂ ) in methanol: 94.2% Annual operating hours 8,000.00 material flow kg / h t / year % Mass., Based on the raw material Input: synthesis gas 376.10 3,008.80 100.00 total: 376.10 3,008.80 100.00 Exit: blow-off gases of the block of methanol synthesis 28,00 224.00 7.44 Hydrocarbon-containing blow-off gases 24,20 193.60 6.43 Synthetic gasoline 97,40 779.20 25.90 83.53 * 78.71 ** water of reaction 179.90 1,439.20 47.84 Water from the raw synthesis gas 46,60 372.80 12.39 total: 376.10 3,008.80 100.00 * based on CH _{2 of} the methanol, ** based on CH _{2 of} the synthesis gas. Table 3.2. Characterization of currents in the scheme on fig. 1 No. Physical properties of the material flows Composition of the streams [% by mass] T [° C] p [MPa] Mass flow, [kg / h] H ₂ CO CO ₂ H ₂ O CH ₃ OH C ₁ -C ₄ C ₅₊ 1 60.0 5.70 329.5 11.68 58.17 26.61 0.76 - 2.78 - 2 123.7 5.20 2,406.5 6.89 7.00 37.55 1.29 12.53 34.74 - 3 54 5.8 2,077.0 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 8th 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 - - - - - - - - - fourteen - - - - - - - - - -

Example 4

The plant of production of synthetic gas corresponds to the scheme on and includes: a block (block I ) Synthesis of methanol from synthesis gas, one block (block II ) Separation of the methanol from the product stream of the block I , a block (block III ) of the synthesis of gasoline from crude methanol, a block (block IV ) fractionation with removal of the product gasoline, a block (block V ) the separation of methanol from the process water, a block (block VI ) of water purification of methanol. Table 4.1. Material balance of the plant Regime with production of synthetic gasoline from crude methanol Catalyst of gasoline synthesis SMA-2 Conversion of methanol conversion of 97% Selectivity of methanol in gasoline 87.5% Sales of (CO + CO ₂ ) in methanol 94.7% Annual operating hours 8,000.00 material flow kg / h t / year % Mass., Based on the raw material Input: synthesis gas 376.10 3,008.80 100.00 total: 376.10 3,008.80 100.00 Exit: blow-off gases of the block of methanol synthesis 28,00 224.00 7.44 Hydrocarbon-containing blow-off gases 24,10 192.80 6.41 Synthetic gasoline 98,40 787.20 26.16 83.92 * 79.52 ** Purified process water 179.00 1,432.00 47,60 Water of the raw synthesis gas 46,60 372.80 12.39 total: 376.10 3,008.80 100.00 * based on CH _{2 of} the methanol, ** based on CH _{2 of} the synthesis gas Table 4.2. Characterization of currents in the scheme on fig. 1 No. Physical properties of the material flows Composition of the streams [% by mass] T [° C] P [MPa] Mass flow [kg / h] H ₂ CO CO ₂ H ₂ O CH ₃ OH C ₁ -C ₄ C ₅₊ 1 60.0 5.70 329.5 11.68 58.17 26.61 0.76 - 2.78 - 2 123, 5 5.20 2,405.2 6.91 7.06 37.51 1.29 12.60 34.61 - 3 54 5.8 2,073.9 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 8th 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 - - - fourteen 70 5.42 179.0 - - traces 100.00 traces - -

Example 5

The plant of production of synthetic gas corresponds to the scheme on and includes: a block (block I ) Synthesis of methanol from synthesis gas, one block (block III ) the synthesis of gasoline without separation of methanol from the product stream of the block I , a block (block IV ) fractionation with removal of the product gasoline, a block (block V ) the separation of methanol from the process water, a block (block VI ) of water purification of methanol Table 5.1. Material balance of the plant Regime with production of synthetic gasoline from the stream of methanol synthesis Catalyst of gasoline synthesis: SMA-2 Methanol conversion: 99% Selectivity of conversion of methanol to gasoline: 85.5% Sales of (CO + CO ₂ ) in methanol: 94.2% Annual operating hours 8,000.00 material flows kg / h t / year % Mass., Based on the raw material Input: synthesis gas 376.10 3,008.80 100.00 total: 376.10 3,008.80 100.00 Output: hydrocarbon-containing blow-off gases 54,30 434.40 14.44 Synthetic gasoline 96.80 774.40 25.74 83.02 * 78.23 ** Purified process water 178.40 1 427.20 47.43 Water of the raw synthesis gas 46,60 372.80 12.39 total: 376.10 3,008.80 100.00 * based on CH _{2 of} the methanol, ** based on CH _{2 of} the synthesis gas. Table 5.2. Characterization of currents in the scheme on fig. 2 No. Physical properties of the material flows Composition of the streams, mass% T [° C] p [MPa] Mass flow [kg / h] H ₂ CO CO ₂ H ₂ O CH ₃ OH C ₁ -C ₄ C ₅₊ 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 1,931.7 6.94 8.59 44.88 0.04 - 37.68 1.87 6 176.3 3.9 2,264.0 6.02 7.45 39.21 7.92 0.12 33.45 5.83 8th 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 - - - fourteen 70.0 5.35 178.4 - - - 100.00 - - -

LIST OF REFERENCE NUMBERS

1

Output syngas

2

Product from the block of synthesis of compounds of the type R ¹ -OR ²

3

Recirculation gas (synthesis gas, which from the block II or IV in the block I recycled)

4

Raw methanol (or starting product of the compounds of the type R ¹ -OR ² )

5

Circulating gas (syngas coming from the block II in the block III is given)

6

Product from the block of gasoline synthesis

7

Circulating hydrocarbon gas (from block IV in block III recycled)

8th

petrol

9

naphtha

10

process water

11

Recycled compound of the type R ¹ -OR ² (preferably methanol)

12

Wastewater containing compounds of the type R ¹ -OR ² (preferably methanol)

13

Gases which form in the separation of the compounds of the type R ¹ -OR ² (preferably methanol)

14

Chemically purified water

15

gas

16

C ₃ -C ₄ fraction

I

Block of the synthesis of compounds of the type R ¹ -OR ² with the first converter

II

Block the separation with the first separator

III

Block of synthesis of gas with the second converter

IV

Block the separation with the second separator and the stabilizing column of the unstable gasoline

V

Block of the concentration of compounds of the type R ¹ -OR ² (preferably methanol) in a rectification column from the process water

VI

Block of catalytic water purification of compounds of the type R ¹ -OR ² (preferably methanol)

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US 1746464 [0003]
• US 3894102 [0004, 0007, 0030]
• US 4404414 [0004, 0015]
• US 6191175 [0005]
• US 5908963 [0006]
• US 4814535 [0010]
• US 4523046 [0011]
• US 4035430 [0013]
• US 4788369 [0014]
• US 5602289 [0016]
• US 4507404 [0036]
• EP 0070690 [0036, 0036]
• EP 0124999 [0036]

Cited non-patent literature

• Karavayeva MM et al. "Synthetic Methanol Technology", M .: Chimija, 1984 [0004]
• CD Chang, Catal. Rev. Sci. Eng., V. 25, N1 (1983) [0004]
• MM Karavaeva, etc. << Technologija sinteticheskogo metanola >>, M .: Chimija, 1984 [0030]
• Nefiodow BK, Konovalchikov LD, Rostanin NN "High-silica zeolites of petroleum processing and petroleum chemistry", M: ZNIITENEFTECHIM, 1987, 59 p. [0036]
• "Catalysts for the Conversion of Methanol into Synthesis Gas" (Catalysis in Industry, 2004, N. 6, pp. 3-9) [0061]
• << Studies in Surface and Catalysis, v. 36, Methane Conversion >>, 1987 [0107]

Claims (14)

A process for the production of 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 to produce a first product stream, the - at least one chemical compound of the type R ¹ -OR ² (wherein R ¹ are alkyl groups having a carbon number of 1 to 5 and R ^{2 is} hydrogen, alkyl and alkoxy groups having a carbon number of 1 to 5), wherein the chemical compound of the type R ¹ -OR ^{2 is} preferably methanol and / b) Contact of the entire product from the first converter or after separation of at least a portion of the unreacted components of the synthesis gas, with a catalyst in a second converter, for Production of a product stream comprising - petroleum hydrocarbons, including up to 45% by mass of aromatic compounds, containing up to 1% by mass of benzene and n not less than 40% by mass of isoparaffins, C ₁ -C ₄ -hydrocarbons, which preferably form in an amount of not more than 17% by mass (converted to C in the methanol reacted and / or, if necessary, im reacted dimethyl ether), - unreacted compound of the type R ¹ -OR ² , - as well as unreacted components of the synthesis gas containing synthesis gas is separated from the first and / or second product stream and at least partially recycled as recycle gas in the first converter , c.) separating the product of the second converter, wherein the obtained unstable gasoline is stabilized by known methods, i.) a gasoline fraction from which, if necessary, a fraction containing durol is separated, ii.) a fraction of C ₃ -C ₄ hydrocarbons iii.) a gas stream containing light hydrocarbons and unreacted components of the synthesis gas, and iv.) an aqueous phase, the unreacted used compound of the type R ¹ -OR ² , preferably methanol and / or dimethyl ether, are obtained, wherein the gas stream iii.) is at least partially recycled to the second converter and / or in the first converter as a circulating gas, and the aqueous phase iv.) directly for purification of the compound of the type R ¹ -OR ² or first for rectification, wherein the rectification into a concentrated solution of the compound of the type R ¹ -OR ² (preferably not less than 75 %) and a water contaminated with the compound of type R ¹ -OR ² (preferably content of compound of the type R ¹ -OR ² to 5%), which is added for purification. A method according to claim 1, characterized in that the feedstock of the second converter has a partial pressure of hydrogen of greater than 0.07 MPa, a partial pressure of the oxides of carbon of greater than 0.008 MPa, a partial pressure of the compound of the type R ¹ -OR ² ( preferably of the methanol and / or the dimethyl ether) of less than 0.5 MPa and a partial pressure of the water of less than 0.3 MPa. A method according to claim 1 or 2, characterized in that the conversion of the compound of the type R ¹ -OR ² (preferably methanol) in step b.) Not less than 82% and not more than 99.5%, and optionally a dimethyl ether - Sales of not less than 92% and not more than 99.8%. 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, which by the dissipation of the heat of reaction by the heat transfer surface at a ratio of the heat transfer surface to the volume of the catalyst of not less than 50 m ² / m ³ can be achieved. A method according to claim 4, characterized in that by the heat of reaction discharged from the first converter, steam is generated at a pressure of up to 4 MPa, wherein the volume of the recycle gas containing unreacted components of the synthesis gas, and which fed into the first converter will not exceed 150 real m ³ , based on 1 m ^{3 of} catalyst. Method according to one of claims 1 to 5, characterized in that the contact with the catalyst in the second converter takes place under approximately isothermal conditions, which by the dissipation of the heat of reaction through the heat transfer surface at a ratio of the heat transfer surface to the volume of the catalyst of not less than 40 m ² / m ³ can be achieved. A process according to claim 6, characterized in that steam is generated at a pressure of up to 22 MPa by reaction heat dissipated from the second converter, and the volume of the circulating gas stream iii), which does not react, is light hydrocarbons of the product stream of the second converter Components of the synthesis gas, a value up to 150 real m ³ , based on 1 m ^{3 of} catalyst has. Process according to any one of Claims 1 to 7, characterized in that the water contaminated with the R ¹ -OR ² compound, preferably methanol, is brought into contact with a methanol decomposition catalyst at a temperature of up to 360 ° C, as a result purified water and components of synthesis gas, in particular hydrogen, carbon monoxide and CO ₂ , form. A method according to claim 8, characterized in that the contact of the water contaminated with the compound of the type R ¹ -OR ² (preferably methanol) with the catalyst is carried out at a pressure which allows the generated components of the synthesis gas in the first converter directly or with the help of a recirculation compressor in the first converter to initiate. Method according to one of claims 2 to 9, characterized in that a portion of the separated from the first product stream of synthesis gas in the second converter for adjusting the partial pressures of the hydrogen and the oxides of carbon, in particular carbon monoxide, is fed. Plant for carrying out the process according to one of Claims 1 to 10, comprising: a) at least one first converter which comprises a catalyst which is suitable for the conversion of CO with H ₂ to the chemical compound of the type R ¹ -OR ² ( b.) at least one second converter containing a catalyst suitable for catalyzing the conversion of the chemical compound of the R ¹ -OR ^{2 type} into hydrocarbons, c.) at least one separator which is suitable Separating gasoline hydrocarbons from a product stream containing not only gasoline hydrocarbons but also chemical compounds of the type R ¹ -OR ² , water and gas containing short-chain hydrocarbons, components of the synthesis gas, compounds of the type R ¹ -OR ² and traces of gasoline hydrocarbons, d.) at least one third converter containing a catalyst suitable for the reaction of the chemical compound of the invention contained in the water Type R ¹ -OR ² (preferably methanol) in CO and H ₂ to catalyze. Installation according to claim 11, characterized in that it contains an additional separator for separating the product stream from the first converter, wherein the additional separator has a connection line to the first converter, which allows separated CO and H ₂ in the separator to be introduced into the first converter , wherein the (additional) separator preferably contains a first connecting line to the second converter, which makes it possible to feed chemical compounds of the type R ¹ -OR ² , optionally together with H ₂ O, into the second converter and a second connecting line to the second converter contains, which makes it possible, if necessary, to feed CO and H ₂ in the second converter. Plant according to claim 11, characterized in that the first converter is connected directly to the second converter, so that the complete product stream from the first converter is introduced into the second converter, wherein the separator c.) Preferably contains a connecting line to the first converter, which makes it possible to feed unreacted CO and H ₂ and short-chain hydrocarbons in the first converter. Installation according to one of claims 11 to 13, characterized in that it comprises at least one of the following additional components: i.) A connection line from the third converter to the first converter, which allows, formed in the third converter CO and H ₂ in the first converter initiate, and / or ii.) a device downstream of the separator c.), which enables the separation of the compound of the type R ¹ -OR ² , wherein the system comprises a connecting line for the return of the separated chemical compound of the type R ¹ -OR ² in contains the second converter and / or iii.) means for removing the heat of reaction in the first and / or second converter, which preferably allow the generation of water vapor, wherein the means for dissipating the heat of reaction in the first converter preferably a ratio of the heat exchange surface to the catalyst volume of at least 50 m ² / m ³ and in the second converter preferably have a ratio of the heat exchange surface to the catalyst volume of at least 40 m ² / m ³ .

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