WO2011061198A1

WO2011061198A1 - Method for generating hydrocarbons, in particular gasoline, from synthesis gas

Info

Publication number: WO2011061198A1
Application number: PCT/EP2010/067606
Authority: WO
Inventors: Joachim Engelmann; Genrikh Falkevich; Rashit Temirbulatovich Sarsenov
Original assignee: Chemieanlagenbau Chemnitz Gmbh; Sapr - Neftekhim Llc.; Too Techno Trading Ltd.
Priority date: 2009-11-17
Filing date: 2010-11-16
Publication date: 2011-05-26
Also published as: CA2780483C; CN102686540B; DE102009046790A1; AU2010320947B2; EA021044B1; AU2010320947A1; CN102686540A; DE102009046790B9; EA201200731A1; CA2780483A1; DE102009046790B4

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

Process for the production of hydrocarbons, in particular gasoline,

from synthesis gas

The invention relates to a process for the production of hydrocarbons, in particular gasoline, from non-hydrocarbon compounds, in particular from synthesis gas, which contains 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 Fischer-Tropsch synthesis developed in 1925 (US 1,746,464), synthesis gas is catalytically converted directly into 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. Several methods of producing gasoline from synthesis gas have been developed according to this scheme by the company "Mobil Oil." Both process stages are described in scientific-technical and patent literature: the synthesis of methanol is described in detail in the book by Karavayeva MM et al., "Technology of Synthetic Gas Methanol's, 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 - reviewed by C. D. Chang, Catal. Rev. - Be. Eng., V. 25, N 1 (1983) and in US 4,404,414 from 1983.

US Pat. No. 6,191,175 discloses a process for the preparation 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 according to US 3,894,102 (from 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 carried out 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 Mas sengesch windiness of raw material feed of 0.5 - 1000 h ^"1 realized, wherein a The product of the first stage may be passed directly to the second or it may be separated, for example the water is separated (with or without methanol) and H ₂ and carbon monoxide (unreacted synthesis gas ), which (possibly after discharge of C0 ₂ ) are recycled 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 acidic compounds from the hydrous streams, which substantially degrades the economic indicators of the process.

In this connection, the prior art proposes processes of conversion of oxygen compounds to hydrocarbons which overcomes the problem by maintaining a degree of conversion of the raw material at a level of more than 99%. to solve. 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 help of diluting components in the raw material Ström, which themselves do not take part in the reaction. In the process according to US Pat. No. 4,035,430 (from 1977), at least one compound of Crbis Cs-hydrocarbons and the cooled product containing durol are used for this purpose. 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).

According to US 4,788,369 (from 1988), a fraction of the liquid product (C ₃ - / C ₄ _ fraction) which is separated off from the reaction product and recycled into the reactor is used as the diluting component which does not participate in the main reaction. There is an additional effect - the increase in gasoline yield due to the oligomerization of the recycled olefins, as a side reaction.

In the process according to US 4,404,414 (from 1983) for the production of hydrocarbons, use is made of inert diluting components: light gas, which is obtained from the reaction product as well as water vapor, hydrogen and C ₂ and C _{3 +} hydrocarbons or their mixtures.

No. 5,602,289 uses a gas which is mixed together from two gas streams (C ₂ -hydrocarbons and C ₃₊ -hydrocarbons) returned to the reactor as diluting component. 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 diluting component is given in this preferred case by a ratio of the C _{2 -C} hydrocarbons / C ₃₊ hydrocarbons in 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.

According to the invention the object is achieved by a process for the production of hydrocarbons according to claim 1:

In the process according to the Invention, the production of hydrocarbons is effected by the conversion of a CO- and H2-containing gas mixture (also referred to below as synthesis gas)

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 -O-R 2 (wherein R 1 are alkyl groups having a carbon number of 1 to 5, R is hydrogen, alkyl and alkoxy groups having a carbon number of 1 to 5), 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 are at least partially fed into the first converter,

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 greater than 0.008 MPa,

the compound of the type R 1 -O-R 2, preferably of the methanol

and / or the dimethyl ether, of less than 0.5 MPa,

of water of less than 0,3 MPa

preferably at a conversion of the compound of the 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,

for producing a product stream, the - petroleum hydrocarbons,

preferably up to 45 mass. -% of aromatic compounds, containing up to 1 mass. -% benzene and preferably not less than 40 Ma. -%

Isoparaffins (branched saturated aliphatic hydrocarbons having at least 5 carbon atoms),

- CrC ₄ - hydrocarbons,

which is preferably in an amount of not more than 17 mass. -% form (converted to C in the methanol reacted and / or, if necessary, in the reacted dimethyl ether),

unreacted compounds of the type R 1 -O-R 2,

- As well as unreacted components of the synthesis gas

contains

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 Durol (1,2,4,5-tetramethylbenzene) is separated,

a fraction of C3-C4 hydrocarbons,

- as well as a gas stream,

which contains light hydrocarbons (C ₁ and C ₂ ), unreacted components of the synthesis gas and other components that participate in the process, which can be at least partially recycled to the second converter and / or to the first converter,

and also

an aqueous phase containing methanol and / or another compound of the type R ¹ -OR ² ,

is obtained. 1 2

The aqueous phase containing the compound R-O-R is added either for purification or first for rectification. The rectification is followed by a

1 2

Separation into a concentrated solution of the compound R -O-R in water

1 2

(preferably not less than 75% of the compound R -O-R) and in one with the

1 2

Compound of the type R -O-R polluted water (preferably content of compound of

1 2

Type R-O-R to 5), which is added for purification. Which in any case

1 2

Purification of the compound of the type R-O-R is carried out either by catalytic decomposition of the methanol and / or another, as explained in more detail below

1 2

Compound of the type R-O-R or by biological methods.

1 2

The converters of the synthesis of compounds of the type R-O-R 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 vapors) 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").

1 2

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

The heat of reaction is preferred for generating water vapor with a

1 2

Pressure of up to 4 MPa in the converter of synthesis of compounds of type R -O-R and up to 22 MPa used in the converter of the synthesis of gasoline.

The removal of heat through the heat transfer surface to generate the steam allows the dilution of 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 the gasoline synthesis converter (hereinafter referred to as circulating gas).

The process according to the invention for the production of 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 -0-R2. The term "compound of the type R 1 -O-R 2" denotes - with R 1 - alkyl radicals having 1 to 5 C atoms, - with R 2 - hydrogen, alkyl and alkoxy radicals with

1 to 5 carbon atoms. Preferred compounds of the type R 1 -O-R2 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

Synthesis of compounds of the type R 1 -O-R 2 (hereinafter also referred to as converters of methanol synthesis) synthesized methanol or the mixture of methanol and dimethyl ether.

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

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

In the converter of the synthesis of compounds of the type R 1 -O-R 2 find (if the

Compound of the type R 1 -O-R 2 methanol is) in particular the following reactions:

CO + H ₂ 0 <-> C0 ₂ + H ₂ Water gas reaction

CO + 2H ₂ i-> 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 i-> CH ₃ -O-CH ₃ + H ₂ 0 DME formation

Whether methanol or a mixture of methanol and dimethyl ether (DME) or other compounds of the type R 1 -O-R 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. ^ Al ₂ 0 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, e.g. for methanol synthesis in the book by M.M. Karawaewa et al. "Technologija sinteticheskogo metanola", M .: Chimija, 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 -O-R 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 occurs, the unreacted components of the synthesis gas (CO, H ₂ , CO ₂ , nitrogen and others) are preferably partially incorporated in the first converter of the synthesis of

Recycled compounds of the type R 1 -OR 2, ie, they are mixed with the used gas mixture used, which contains CO and H ₂ , and partly unreacted synthesis gas in the converter of the synthesis of gasoline to suppress the reaction of decomposition of the compounds Type R 1 -OR 2 fed. 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 converter of gasoline synthesis, the contact of at least part of the

Product stream from the converter of the synthesis of compounds of the type R 1 -O-R 2 with the

Catalyst at a preferred degree of conversion of the compound of the type R 1 -O-R 2 from 85% to 99.5% instead.

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 take place, which in the feed stream of the gasoline synthesis converter converted to 1 m ³ (i.N.) gas flow, a partial pressure of H ₂ of more than 0.07 MPa and a CO partial pressure of more guaranteed as 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 described in the book by Nefjodow BK, Konovalchikov LD, Rostanin NN "Catalysts of petroleum processing and petroleum chemistry based on high-silica zeolites", M: ZNIITENEFTECHIM, 1987, 59 pp. The catalyst of gasoline synthesis out

Compounds of the type R 1 -OR 2 preferably contain at least partly a protonated zeolite (eg HZSM-5), preferably from the group of the pentasils. Preferably, zeolites with a high Si0 ₂ / A1 ₂ 0 ₃ - used ratio of at least 12, more preferably with a Si0 ₂ / A1 ₂ 0 ₃ - ratio of at least 30. The use of high silicon zeolites, the formation of durene is reduced 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 Pat. No. 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 into the second converter is either the entire first

Product stream or the part containing the compound of the type R 1 -OR 2. Of the Partial pressure of the compound of the type R 1 -O-R 2 (preferably of the methanol and optionally 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 less than 0.5 MPa held (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 the selectivity of the implementation of

Compound of the type R 1 -O-R 2 (preferably methanol and optionally dimethyl ether) in hydrocarbons increases, 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 -O-R 2 (preferably of the methanol and optionally of the dimethyl ether) in the gasoline synthesis converter is more than 85% and less than 99.5% for methanol and more than 92% and less 99.8% for dimethyl ether. The incomplete conversion of the compound of the type R 1 -O-R 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 produced gasoline and the duration of the Zwischenregenerationszyklusses (operating time of the Process between the regenerations of the catalyst). This is the reason why in the invention gasoline containing less than 46% of aromatic compounds, with a benzene amount of less than 1% by mass contained therein, of isoparaffins of more than 40% having high octane characteristics (93-96 RON), which is also a distinguishing feature of the invention.

Besides gasoline hydrocarbons, the product contains gasoline synthesis

1 2

Compounds of the type R -OR C ₃ -C ₄ -hydrocarbons, water, unreacted

1 2

Methanol and other compounds of the type ROR, as well as "dry" gas. This "dry" gas contains mainly gaseous substances (short-chain hydrocarbons (Q-C ₂ ), CO, CO ₂ and H ₂ and other components of the synthesis gas).

Separation of the products of the Benzinsvnthese:

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 (Ci and C ₂ ), traces of heavier hydrocarbons. This circulating gas is, at least partially in the converter of gasoline synthesis and / or in the

1 2

Converter of the synthesis of compounds of the type R -O-R returned. 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 are separated. With a permissible content of durene in the gasoline hydrocarbons, the heavy fuel gas is not separated. The obtained stable gasoline fraction with a necessary saturated steam pressure below 500 - 700 mm QS (depending on the required gasoline grade) 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, as a rule it is more than 3% by mass and less than 30% by mass.

Preference is given to the aqueous phase having a defined methanol content or with others

Compounds of the type R 1 -OR 2 are initially separated in a rectification column due to the different boiling temperatures in fractions, of which one fraction is 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 Invention according

Method is catalytically decomposed methanol and optionally another compound of the type R 1 -OR 2 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 C0 ₂ ) and hydrogen. The carbon oxides and the hydrogen can be advantageously mixed with the synthesis gas and in the process of synthesis of compounds of the type

R 1 -O-R 2 are recycled. 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 the compounds of the Type R 1 -0-R 2 and the pressure loss between exit of the product of the catalytic methanol decomposition and entry of the feedstock in the converter of the methanol synthesis.

Alternatively, the residual content of the R 1 -O-R 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 involves 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 ^x -O-R 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, thereby achieving a high selectivity and quality of the products.

Investment:

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

This attachment contains:

a. ) at least one first converter containing a catalyst capable of 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 suitable for catalyzing the conversion of the chemical compound of the type R 1 -O-R 2 into hydrocarbons,

c. ) at least one separator which is suitable, petroleum hydrocarbons from a

Separate product stream, in addition to gasoline hydrocarbons and chemical

Compounds of the type R 1 -OR 2, water and gas, which are short-chain hydrocarbons, components of the synthesis gas, compounds of the type R ¹ -

Contains O-R and traces of gasoline hydrocarbons,

d. ) at least one third converter containing a catalyst suitable for reacting the water-containing chemical compound of the type R ^x -0-

R (preferably methanol) in CO and H ₂ to catalyze.

The above-mentioned components are preferably connected in series, i. H. the first converter is connected directly or indirectly to the second converter so that at least part of the product flow from the first converter is introduced 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 of 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 which contains the unreacted chemical compound of the type R 1 -O-R 2 is preferably introduced into a separator (c.) Downstream of the apparatus (preferably a rectification column), which contains the

Possibility to separate a product with a high content of compound of the type R 1 -O-R 2 (preferably methanol and optionally DME) in the water, which can be added to the starting material of the second converter again. This separator 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 -O-R 2 type in the water to the second converter. By this additional device is the

However, R 1 -OR 2 compound is not completely removed 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,

1 2

in which the compound of the type R -O-R is decomposed.

1 2

Known catalysts can be used for the decomposition of the compound of the type R-O-R (preferably of the methanol and, if appropriate, of the DME). An overview is provided in the article by Klabunowski E.I. a. "Catalysts of the conversion of methanol into synthesis gas" (Catalysis in the industry, 2004, N. 6, p 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

2 3

m Im 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 source 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 C0 _{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 syngas is generated in two stages: in step a.) The synthesis of

Compounds of the type R 1 -O-R 2 - for example methanol and / or dimethyl ether, im

Step b.), The conversion of compounds of the type R 1 -OR 2 on a zeolite catalyst into a mixture of hydrocarbons takes place. The compounds of the type R ¹ - OR 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 selected from the product of the first converter or separated from the product of the second converter and in the first converter for the synthesis of

Compounds of the type R 1 -O-R 2 attributed.

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. In recuperator heat exchangers and / or heaters (steamer heaters, stoves and / or electric heaters) and in the first converter (in the figures - block I) for the synthesis of the compounds of the type

R 1 -O-R 2 (methanol and optionally dimethyl ether) passed. In the preparation of the compounds of the type R 1 -O-R 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.). It is capable of reducing the required volume of cycle gas and performing the synthesis under optimum conditions, with concomitant reduction in the formation of byproducts, increased yield of methanol, catalyst life extension, and generation of medium pressure water vapor for use as an energy source.

The product from the converter of the synthesis of the compounds of the type R 1 -O-R 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 may also be followed by a rectification column for separating off the water from the mixture with the organic components, since the Presence of water in the feed to the second converter to convert the

Compounds of the type R 1 -O-R 2 in hydrocarbons accelerates the irreversible deactivation of the zeolite catalyst used in the second converter. 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 fed into the second converter (in the figures - block III) of the synthesis of gasoline, where it prefers with the recycle stream of methanol (stream 11 in Figures 1 + 2) from the block V, with the recycle stream of the light hydrocarbon gas (stream 7 in Fig. 1) from the block IV and the stream of unreacted synthesis gas (Stream 5 on Fig. 1) 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 are mixed with the methanol previously separated from the first product stream (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 the 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 added to the second separator (in Figures Block IV) to separate the Converted converter product of gasoline synthesis. When cooled in the recuperator and in the coolers, the petrol hydrocarbons condense, part of the light ones

Hydrocarbons, the unreacted compounds of the type R 1 -O-R 2 and water. In the separator are preferably 1. the water, which unreacted compounds of the type

R 1 -OR 2 contains, 2. the gasoline hydrocarbons and 3. the gaseous phase, which contain hydrogen, carbon oxides and light hydrocarbons (mainly up to 4 carbon atoms, predominantly methane and C ₂ -C ₄ hydrocarbons) resulting from the conversion of methanol form, separated. A portion of the gas phase is mixed with a portion of the CO and H ₂ -containing gases from the first separator (in the block II) and preferably as diluting components to the feedstock (methanol and possibly DME) in the converter of the gasoline synthesis.

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 (Stream 8 on the pictures) are separated. Possibly. For example, the C ₃ -C ₄ -hydrocarbons can be separated off as liquid fraction C ₃ -C ₄ . From the petroleum hydrocarbons which are fed into the stabilizing column, heavy fuel (stream 9 in the figures) in the stabilizing column or in an additional column can be separated.

The aqueous phase (stream 10 in the figures) from the separator c.) Can be used as a variant in a rectification column (block V in Fig. 1 + 2) and then to the converter of water purification (block VI in Fig. 1 + 2) be directed. In the

Rectification column, the concentration of the compound of the type R 1 -O-R 2 (stream 11 in Figs. 1 + 2) takes place. 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 -O-R 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.

Fig. 1 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 removal by distillation of the main amount of methanol from the process water.

Figure 2 shows the block diagram for a preferred synthetic gasoline synthesis process of the present invention with direct introduction of the product stream from the first converter to 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 after the separation by distillation of the main amount of methanol from the process water.

In Fig. 1, synthesis gas 1 whose major components hydrogen and carbon monoxide in a ratio depending on the method of production but which also contains inert components is purified of catalyst poisons and impurities, compressed as necessary, and injected into the first converter (block I ) of the synthesis of compounds of the type

R 1 -O-R 2 is fed, where it is mixed with the cycle gas 3. The resulting mixture is preheated to the reaction temperature in recuperator heat exchangers and heaters (steam and / or electric heaters, ovens) and in the converter of the synthesis of

Conducted compounds of the type R 1 -O-R2. In the preparation of the compounds of the type R 1 - O-R, the contact 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, which 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 the type R 1 -O-R 2 is cooled in heat exchangers by the raw material stream is preheated, as well as in the air and water cooler, in the presence of dimethyl ether in the product is also deep

Used cold, the compounds of the type R 1 -O-R 2 and water condense. The condensate (crude ethanol, water content up to 20% or mixture of dimethyl ether, methanol and water) is separated in the separator (block II). The gas product from the separator is unreacted synthesis gas, part of which (stream 3) is passed to mix with the starting syngas for more complete conversion of the feedstock. The im

Separator separated compounds of the type R 1 -OR 2 4 (methanol and optionally DME) are reacted with the recycle stream of methanol 11 from block V, the recycle stream 7 of the light Hydrocarbon gases from the second separator (block IV) and the stream 5 of the 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.

In order to obtain the best possible gasoline quality (low proportion of heavy gasoline and aromatics), the conversion of the compounds of the type R 1 -O-R 2 (methanol and optionally DME) in the second converter (block III) is preferably kept below 99.5%. The product of the gasoline synthesis converter contains the hydrocarbons (especially gasoline hydrocarbons) produced in the reaction of the compounds of type R 1 -O-R 2 and unreacted

Compounds of the type R 1 -O-R 2, mainly methanol and components of the synthesis gas.

Both converters (blocks 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 from the converter of gasoline synthesis (block III) is cooled in the recuperator heat exchangers, whereby the feed material of the converter is heated, furthermore 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 is transferred to the separator c.) (Block IV) for separation of the reactor product of gasoline synthesis. In the separator c.) 1. the methanol-containing water 10, 2. the petrol hydrocarbon phase 8 + 9 and 3. the gas phase 7, which contains hydrogen, carbon oxides and light hydrocarbons, which form in the conversion of methanol, separated.

The recycle stream of the light hydrocarbon gas 7 is mixed in the highlighted case with a portion of the CO and H ₂ -containing gases 5 from the first separator (Block II) to form a diluting component for the feedstock of the synthesis of

To obtain compounds of the type R 1 -OR 2. The hydrocarbon condensate (inter alia C ₅₊ hydrocarbons) 6 from the separator (block IV) is passed to the stabilization column (block IV), in which the light overhead gases 7 are separated from the stable gasoline 8. From the unstable petroleum hydrocarbons heavy spirit 9 can be separated in a stabilizing or an additional column.

The aqueous phase 10 from the separator is added to the block V to concentrate the

Compounds of the type R 1 -O-R 2 and from there into the block VI for the catalytic

Water purification of compounds of the type R 1 -O-R 2 passed. Depending on the degree of conversion, the water usually contains between 3.5% by mass and 30% by mass.

Compounds of the type R 1 -O-R 2.

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

In the converter of water purification (block VI), the gas Ström 13 is obtained from the decomposition of the methanol - carbon oxides and hydrogen, which is the first converter (block I) is supplied. It is obtained chemically purified water 14, which is used for the replenishment of the system of the recooling water, the system of steam generation and for other purposes.

The manufacturing process shown in Fig. 2 is a simplified variant of the method shown in Fig. 1 and differs from this in particular in the following point:

The product of the first converter (block I) is heated in heat exchangers and / or heaters and passed directly, without prior separation, to the converter (block III) of the gasoline synthesis.

As a diluting component of the oxygen-containing starting material, recycled cycle gas 3 (here from block IV) can also be added here again.

Again, the synthesis gas 1 before or at the feed in the first converter in addition to the cycle gas 3 in addition hydrogen and carbon monoxide 13, which in the Converter of catalytic water purification (block VI) is formed, mixed. The product from the first converter essentially corresponds in its composition to the product from the process on FIG. 1.

In order to achieve a maximum high gasoline quality (low proportion of heavy gasoline), the conversion of the compound of the type R 1 -O-R 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 is fed into the block IV of the separation of the products of the gasoline synthesis converter, where condensation of the gasoline hydrocarbons and the water takes place due to the cooling in the coolers. In the separator, the water 10, which contains unreacted compounds of the type R 1 -O-R 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 recycled to the first converter (block I) for mixing with the starting syngas for more complete conversion of the feedstock.

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 Fig. 1).

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

The water phase 10 from the separator is in the block V of the enrichment of the

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

In block VI of 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 for decomposition of the methanol in 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 the methanol 13 emerge from the separator and are passed for mixing with the crude synthesis gas in the first converter (block I). The purified water is conveyed to the degasifier column. It is obtained chemically purified water 14, which is used for the replenishment of the system of the recooling water, the system of steam generation and for other purposes.

By the water shown in Figs. 1 and 2, 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 blocks 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.

Fig. 3 shows a block diagram of the TIGAS process.

Synthesis gas is mixed with cycle 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 C3-C4 fraction and gas, part of which as a circulation gas is led 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.

A real synthesis gas with the following composition, in vol., Is used: CO - 21.91; H ₂ - 61.16; C0 ₂ - 6.38; CH ₄ - 1.83; H ₂ 0 - 8.72.

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

For the synthesis of methanol from synthesis gas is a catalyst from Südchemie called MEGAMAX 700 ^® (components CuO, ZnO, A1 ₂ 0 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 -O-R 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, the heat exchange surface in the reaction zone is 30 m. 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 instead.

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

The synthesis gas production facility is mainly similar to the scheme shown in Figure 1 and includes: one block (Block I) of synthesis of methanol from synthesis gas, one block (Block II) of methanol separation from the product stream of Block I, one block (Block III) the synthesis of gasoline from crude methanol, one block (Block IV) of the fractionation with removal of the product gasoline, one block (Block V) of the separation of methanol from the process water.

In contrast to the scheme in Fig. 1, however, the block of water purification of methanol is not in operation. In contrast to Fig. 1, the currents 5, 13 and 14, d. H. in the block III, the current 5 is not given.

Table 2.1. Material balance of the plant

Regime of the production of catalyst conversion of the selectivity of the conversion of synthetic gasoline from the synthesis methanol: Conversion (CO + C0 ₂ ) in raw methanol, without supply of the gasoline: by methanol methanol:

99%

Synthesis gas from the block of gasoline:

SMA-2 94.7%

Methanol synthesis in the block of

86%

Gasoline synthesis, without the block of

water purification

Annual operating hours 8000,00

* 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

Example 3

The synthesis gas production plant is mainly similar to the one shown in Fig. 1 and includes: one block of the synthesis of methanol from synthesis gas (block I), one block (block II) of the separation of methanol from the product stream of block I, one block (Block III) the synthesis of gasoline from crude methanol, one block (Block IV) of the fractionation with removal of the product gasoline, one block (Block V) of the separation of methanol from the process water.

The block of water purification of methanol is not in operation. In contrast to the scheme in Fig. 1, the currents 13 and 14 are also missing in the system. Table 3.1. Material balance of the plant

Regime with production of catalyst the conversion of the selectivity conversion of synthetic gasoline from gasoline synthesis: Methanols: the (CO + C0 ₂ ) in

Raw methanol, without the block SMA-2 99% conversion methanol: the water purification of methanol 94.2% in gasoline:

87%

Annual operating hours 8000,00

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

Physical properties Composition of the flows [Mass.-]

the material flows

T [ ^U C] P mass flow H ₂ CO co ₂ H ₂ 0 CH ₃ 0 C1 -C4 c ₅₊

[MPa] m, [kg / h] 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 synthetic gas production facility corresponds to the scheme of Figure 1 and includes: a block (Block I) of the synthesis of methanol from synthesis gas, a block (Block II) of the separation of methanol from the product stream of Block I, a block ( Block III) of the synthesis of gasoline from crude methanol, one block (block IV) of the fractionation with removal of the product gasoline, one block (block V) of the separation of methanol from the process water, one block (block VI) of the water purification of methanol.

Table 4.1. Material balance of the plant

Regime with generation catalyst of the conversion of the selectivity of the conversion of synthetic gasoline synthesis of methanol conversion of (CO + C0 ₂ ) in gasoline from raw methanol ". , , """Methanol in gasoline methanol

9 l / o

87.5% 94.7%

Annual operating hours 8000,00

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

Example 5

The synthetic gas production facility is as shown in Figure 2 and includes: one block (block I) of synthesis of methanol from synthesis gas, one block (block III) of the synthesis of gasoline without methanol separation from the product stream of block I. , one block (block IV) of the fractionation with removal of the product gasoline, one block (block V) of the separation of methanol from the process water, one block (block VI) of the water purification of methanol Table 5.1. Material balance of the plant

Regime with production of catalyst the conversion of selectivity the conversion of synthetic gasoline from gasoline synthesis: Methanol: Conversion of (CO + C0 ₂ ) in the stream of methanol in gasoline: Methanol:

SMA-2 99%

methanol synthesis

85.5% 94.2%

Annual operating hours 8000,00

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

Physical properties Composition of flows, mass%

the material flows

TP mass H ₂ CO co ₂ H ₂ O CH ₃ OH C1 -C4 c ₅₊ stream [

[° 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 - - - - - - 100.000 5.0 0.40 181.2 - - 0.02 98.51 1.47 - - 1 62.2 4.5 1 - - 0 , 46 14,38 85,16 - -2 62,6 5,65 180,2 - - - 99,00 1,00 - -3 70,0 5,35 1,8 12,5 86,2 - 1, 3 - - -4 70.0 5.35 178.4 - 100.0 - - - 0

LIST OF REFERENCE NUMBERS

The illustrations and text use the following terms:

1 - Starting synthesis gas

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

3 - recycle gas (synthesis gas which is returned from block II or IV to block I)

4 - crude methanol (or starting product of the compounds of the type R 1 -O-R 2)

5 - circulating gas (synthesis gas given from block II to block III)

6 - Product from the block of gasoline synthesis

7 - Circulating hydrocarbon gas (returned from block IV to block III)

8 - gasoline

9 - heavy fuel

10 - process water

11 - recycled compound of the type R 1 -O-R 2 (preferably methanol)

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

13 - Gases which are preferred in the separation of compounds of the type R 1 -O-R 2 (preferred

Methanol)

14 - Chemically purified water

15 - gas

16 - C3-C4 fraction

I - block of the synthesis of compounds of the type R 1 -O-R 2 with the first converter

II - block of 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 concentration of compounds of the type R 1 -O-R 2 (preferred

Methanol) in a rectification column from the process water

VI - Block of catalytic water purification of compounds of the type R 1 -O-R 2

(preferably methanol)

Claims

claims

1. 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 -O-R2 (wherein R 1 are alkyl groups having a carbon number of 1 to 5 and

R - 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 is preferably methanol and / or dimethyl ether, as well as

unreacted components of synthesis gas,

contains

b. Contact 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 to produce a product stream, the

- petroleum hydrocarbons, including up to 45 mass. -% aromatic compounds, containing up to 1 mass. % Benzene and not less than 40 mass% isoparaffins,

- Q-Gr 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 compound of the type R 1 -O-R 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, wherein the obtained unstable gasoline is stabilized by known methods, wherein

i. ) a gasoline fraction from which, if necessary, a fraction containing durol is separated,

ii. ) a fraction of C3-C4 hydrocarbons

iii. ) a gas stream which was light hydrocarbons and did not react

Contains components of the synthesis gas, and also

iv. ) an aqueous phase containing unreacted compound of the type R 1 -O-R 2, preferably methanol and / or dimethyl ether,

to be obtained

wherein the gas stream iii.) is at least partially recycled to the second converter and / or to the first converter as circulating gas,

and the aqueous phase iv.) is added directly for purification of the compound of the type R ^x -O-R or first for rectification, wherein by rectification a

Separation into a concentrated solution of the compound of the type R 1 -O-R 2

(preferably not less than 75%) and a water contaminated with the compound of type R 1 -O-R 2 (preferably content of compound of the type R 1 -O-R 2 to 5%), which is added for purification.

2. The method according to claim 1, characterized in that the feedstock of the second converter has a partial pressure of the hydrogen greater than 0.07 MPa, a partial pressure of the oxides of carbon 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.

3. The method according to claim 1 or 2, characterized in that the turnover of

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 conversion of not less than 92% and not more than 99.8 % is.

4. The method according to any 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 be achieved as 50 m ² / m ³ .

5. The method according to claim 4, characterized in that is generated by the heat dissipated from the first converter reaction steam at a pressure of up to 4 MPa, wherein the volume of the circulation gas containing unreacted components of the synthesis gas, and which in the first converter is fed, not 150 real m ³ , based on 1 m ³ catalyst exceeds.

6. The method according to any one of claims 1 to 5, characterized in that the contact with the catalyst takes place in the second converter under approximately isothermal conditions, which by the removal 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 be achieved as 40 m ² / m ³ .

7. The method according to claim 6, characterized in that by the heat dissipated from the second converter, steam is generated at a pressure of up to 22 MPa, and the volume of the circulating gas stream iii), which light hydrocarbons of the product stream of the second converter, as well contains unreacted components of the synthesis gas, a value up to 150 real m ³ , based on 1 m ^{3 of} catalyst has.

8. The method according to any one of claims 1 to 7, characterized in that with the

Compound of the type R 1 -OR 2 _, preferably methanol, contaminated water is brought into contact with a catalyst for methanol decomposition at a temperature of up to 360 ° C, as a result of which purified water and components of synthesis gas, in particular hydrogen, carbon monoxide and C0 ₂ , form.

9. The method according to claim 8, characterized in that the contact of the with

Compound of the type R 1 -OR 2 (preferably methanol) contaminated water is carried out with the catalyst at a pressure that allows the generated Introduce components of the synthesis gas in the first converter directly or by means of a circulation compressor in the first converter.

10. The method according to any one of claims 2 to 9, characterized in that a portion of the separated from the first product stream 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.

11. Plant for carrying out the method according to one of claims 1 to 10 comprising:

e. ) at least one first converter containing a catalyst capable of catalyzing the reaction of CO with H ₂ to the chemical compound of the type R 1 -OR 2 (preferably methanol),

f. ) at least one second converter containing a catalyst suitable for catalyzing the conversion of the chemical compound of the type R 1 -O-R 2 into hydrocarbons,

G. ) at least one separator which is suitable, petroleum hydrocarbons from a

Separate product stream, in addition to gasoline hydrocarbons and chemical

Contains O-R and traces of gasoline hydrocarbons,

H. ) at least one third converter containing a catalyst suitable for reacting the water-containing chemical compound of the type R ^x -0-

R (preferably methanol) in CO and H ₂ to catalyze.

12. Plant 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 in the separator CO and H ₂ in the first Converter, wherein the (additional) separator preferably contains a first connection line to the second converter, which allows chemical compounds of the type

R 1 -OR 2, possibly together with H ₂ 0, to feed into the second converter and includes a second connection line to the second converter, which makes it possible to feed CO and H ₂ in the second converter.

13. 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 a connecting line to the first converter contains, which allows unreacted CO and H ₂ and short-chain hydrocarbons feed into the first converter.

14. Plant 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 makes it possible to introduce CO formed in the third converter and H ₂ in the first converter, and / or ii. ) a device downstream of the separator c.), which the separation

1 2

the compound of the type R -O-R allows, the plant a connecting line for the return of the separated chemical

1 2

Contains compound of the type R-O-R in the second converter and / or iii. ) Devices 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

2 3

at least 50 m in and in the second converter, a ratio of the preferred

2 3

Have heat exchange surface to the catalyst volume of at least 40 m Im.