EA021044B1 - Method for generating hydrocarbons, in particular gasoline, from synthesis gas - Google Patents

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

The invention relates to a method for producing hydrocarbons, in particular gasoline, from hydrocarbon-free compounds, in particular from synthesis gas, which contains carbon monoxide and hydrogen.

State of the art

Synthesis gas, which is mainly a mixture of carbon monoxide and hydrogen, can be obtained from various readily available solid and gaseous sources of carbon and hydrogen. Hydrocarbons and motor fuels synthesized on the basis of synthesis gas are a real alternative to petroleum hydrocarbons and, in terms of quality, partially surpass them. Therefore, the problem of the effectiveness of the technology for converting synthesis gas to hydrocarbons has not lost its relevance for many years.

With the Fischer-Tropsch synthesis developed in 1925 (I8 patent 1746464), synthesis gas directly catalytically turns into hydrocarbons.

It is known that gasoline can be obtained from synthesis gas in two stages: first, the synthesis of oxygen compounds (for example, methanol or demethylether or a mixture of both compounds) occurs, and then the oxygen compounds on the zeolite-containing catalyst are converted into a mixture of hydrocarbons. The company Mobile Oil has developed several methods for producing gasoline from synthesis gas according to this scheme. Both stages of the process are described in the scientific, technical and patent literature: for example, the synthesis of methanol is discussed in detail in the book by M. M. Karavaeva. et al. Technology of synthetic methanol, M .: Chemistry, 1984; synthesis of a mixture of methanol and dimethylether in I8 patent 3894102; hydrocarbon synthesis from methanol and dimethylether in a review by S.I. Sayid, Ca1a1. Keu. - 8ek Eps., Ν. 25, No. 1 (1983) and in the patent I8 4404414 from 1983

Patent I8 6191175 discloses a method for producing methanol or dimethylether. For this, methanol is first synthesized from synthesis gas, which is introduced into the first reactor in a heated state. The reaction product, if necessary, is mixed with synthesis gas and converted again in a second reactor, which serves either for the synthesis of methanol or for the synthesis of dimethylether. To achieve high product productivity, the method is preferably carried out adiabatically.

Patent I8 5908963 discloses a method for producing dimethylether. The product may contain up to 20 wt.% Methanol and up to 20 wt.% Water. At the first stage of the process, in one or more reactors, the synthesis gas is converted into a gas mixture of dimethylether, methanol and water. The catalysts used exhibit both methanol synthesis activity and methanol dehydration ability. The gas mixture is separated by several stages of distillation and washing to obtain pure dimethylether.

In the method for converting synthesis gas to gasoline in accordance with I8 patent 3894102 (from 1975), at the first stage, the synthesis gas is contacted with a catalyst consisting of a mixture of a methanol synthesis catalyst and an acid dehydration catalyst at a temperature of 371 ° C under production conditions product containing dimethylether. At the second stage, at least dimethylether is contacted with a zeolite catalyst at a temperature of 288-454 ° С, a pressure of up to 21 MPa and a mass feed rate of 0.5-1000 h ^-1 , and a product is obtained, the organic part of which is mainly gasoline . The product of the first stage can be directly sent to the second stage, or it is separated, such separated water (and methanol or without it), in addition, separated H ₂ and carbon monoxide (unconverted synthesis gas), which (possibly after extraction via gateway CO ₂ ) return to the first stage.

According to the prior art, the conversion process of methanol and dimethylether, which, as a rule, are synthesized in the first stage, is carried out under conditions of their almost complete conversion, and oxygen compounds accumulate in water, and there is a problem of disposal of waste water and / or separation of oxygen compounds from aqueous streams, which significantly worsens the economic performance of the process.

In this regard, the prior art proposes processes for the conversion of oxygen compounds into hydrocarbons, which solve the problem by maintaining the degree of conversion of raw materials at a level above 99%. Water separated from the final product is removed from the unit and sent for biological or biochemical treatment.

Patent I8 4814535 (from 1989) shows a method for producing gasoline from oxygen-containing compounds with the number of carbon atoms from 1 to 4. Moreover, the conversion of the feed is maintained at the level of 99.9% so that the temperature at the inlet to the reactor is gradually increased and the flow decreases raw materials. When reducing the degree of conversion below 99.9%, the feed is interrupted.

Patent I8 4523046 (from 1985) shows a method for producing gasoline from methanol. In this case, the catalyst is placed in separate layers, and upon contact of the raw material with the catalyst layer, the degree of conversion of the raw material is achieved at the level of almost 100%. With a decrease in the degree of conversion, the feed goes to the next catalyst bed.

In order to improve the method for producing gasoline from synthesis gas or from methanol or from methanol and dimethylether (DME), various aspects are touched upon in accordance with the state of the art, including temperature control in the zone of highly exothermic conversion of methanol or DME to hydrocarbons and also selectivity and quality of gasoline, in particular the content of aromatic hydrocarbons in the gasoline produced, in particular heavy hydrocarbons.

Temperature control in the zone of conversion of methanol or DME to hydrocarbons occurs with the help of dilution components in the feed stream, which themselves do not participate in the reaction. In the method according to patent I8 4035430 (from 1977), at least one C ₁ -C ₅ hydrocarbon compound and a chilled durea-containing product are used for this. The latter compound, combined with temperature, affects the yield of aromatic hydrocarbons and the amount of BTX fractions contained therein (benzene, toluene, xylene).

As a diluent component not involved in the main reaction according to patent I8 4788369 (from 1988), a fraction of a liquid product (fraction C _3- / C _4- ) is also used, which is separated from the reaction product and returned to the reactor. Moreover, an additional effect is manifested as a side reaction - an increase in the yield of gasoline as a result of oligomerization of the returned olefins.

In the method according to patent I8 4404414 (from 1983), inert diluent components are used to produce hydrocarbons: a light gas separated from the reaction product, as well as water vapor, hydrogen and C _2- and C ₃ + hydrocarbons or mixtures thereof.

In invention I8 5602289, a gas is used as the dilution component, which is mixed from two gas streams returned to the reactor (C ₂ hydrocarbons and C ₃ + hydrocarbons). The partial pressure of water, including water, which was formed in the reactor during the methanol conversion reaction, 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 zeolite in the presence of water vapor. The composition of the dilution component in this preferred case is determined by the ratio of C _2- / C ₃ + hydrocarbons in the range from 1/3 to 3/1 and the hydrogen content from 10 to 50 mol%. The use of gases with low heat capacity (hydrogen, C2- hydrocarbons) as a diluting component increases the dilution factor, but allows the conversion of methanol to hydrocarbons at a higher pressure (subject to the required upper limit of the partial pressure of water vapor).

purpose

The purpose of the invention is to develop a cost-effective and simplified process for producing gasoline hydrocarbons from synthesis gas, as well as a simple installation scheme with simplified process steps. The goal is also to achieve high efficiency of gasoline while at the same time high quality gasoline and the creation of non-waste technology without by-products causing environmental damage.

SUMMARY OF THE INVENTION

According to the invention, the goal is achieved by a method for producing hydrocarbons in accordance with claim 1.

During the process according to the invention, hydrocarbons are produced by converting a gas mixture containing CO and H ₂ (hereinafter also referred to as synthesis gas) by

a) contacting the catalyst in a first converter to obtain a first product stream that contains at least one chemical compound of type K ¹ —O — K ² (wherein K ¹ are alkyl groups with the number of carbon atoms from 1 to 5, K ² - hydrogen, alkyl and alkoxyl groups with carbon atoms from 1 to 5), preferably being methanol and / or, if necessary, dimethylether, as well as non-converted components of the synthesis gas, which can be separated from the liquid phase and at least partially filed in the first converter,

b) contacting the entire product from the first converter, or after separating at least a portion of the unreacted components of the synthesis gas, with the catalyst in the second converter, preferably at a partial pressure of hydrogen of more than 0.07 MPa, carbon oxides of more than 0.008 MPa, type K compound '-O-K ² , preferably methanol and / or dimethylether, less than 0.5 MPa, water less than 0.3 MPa, preferably when converting at least 82% of a compound of type K'-O-K ² , preferably when converting at least 82 and not more than 99.5% methanol, as well as, if necessary, when converting not less than 92 and not more than 99.8% dimethylether, to obtain a product stream containing gasoline hydrocarbons, preferably up to 45 wt.% aromatic compounds, containing up to 1 wt.% benzene and preferably at least 40 wt.% isoparaffin hydrocarbons (branched saturated aliphatic hydrocarbons with a minimum of 5 C atoms), C'-C ₄ hydrocarbons, which are preferably formed in an amount of not more than 17 wt.% (in terms of C in converted methanol and / or, if necessary, in converted dimethylether ) not transformed with compounds of type K ¹ —O — K ² , as well as components of the synthesis gas that have not reacted,

- 2 021044 and the synthesis gas is released from the first and / or second product stream and, at least partially, is returned to the first converter as circulation gas,

c) separating the product of the second synthesis converter from unstable gasoline, which is stabilized by known methods, whereby a gasoline fraction is obtained, from which, if necessary, a heavy gasoline fraction containing durene (1,2,4,5-tetramethylbenzene) is separated, a C ₃ hydrocarbon fraction -C ₄ , as well as a gas stream that contains light hydrocarbons (C ₁ and C ₂ ) that have not reacted, components of the synthesis gas and other components involved in the process, which, at least partially, can be returned to the second converter and / or in ne vy converter, and also an aqueous phase containing methanol and / or other compound of the type of RS-O-K ^2.

The aqueous phase, which contains a compound of the type RZ-O-K ² , is sent either for purification or first for rectification. By distillation, a compound of type K? -O-K ² in water (preferably at least 75% of a compound of type KZ-O-B ² ) is separated into a concentrated solution of water and contaminated with a compound of type K ¹ -O-K ² (preferably the content of the compound type KZ-O-B ² up to 5%), which is sent for cleaning. The purification of a compound of type K ¹ —O — K ² carried out in each case either occurs, as will be described in detail below, by catalytic decomposition of methanol and / or another compound of type K ¹ —O — K ² , or by biological methods.

Converters for the synthesis of compounds of type K ¹ -O-K ² and gasoline synthesis with the removal of the heat of the exothermic reaction from the reaction zone have heat transfer surfaces through which the thermal effect of the reaction is transferred to the boiling coolant. The coolant (or its vapors) condenses in a cooling zone, which preferably contains boiling water to generate water vapor. Condensate flows back into the heat removal zone (heat pipe principle).

The reactions in the converters for the synthesis of compounds of the KZ-O-K ^{2 type} and gasoline synthesis are mainly carried out under almost isothermal conditions, under which the temperature difference (ΔΤ) within the catalyst filling does not exceed 40 K, preferably at Δ equal to 10-20 K, particularly preferably at ΔΤ less than 5 K.

In this case, the thermal effect of the reaction is preferably used to produce water vapor with a pressure of up to 4 MPa in the synthesis converter of compounds of the K'-O-K ^{2 type} and up to 22 MPa in the gasoline synthesis converter.

Heat removal by means of a heat transfer surface to generate water vapor allows one to limit the dilution of the feed substance circulating gas to 150 real m ³ / m ^{3 of} catalyst in a methanol synthesis converter (hereinafter referred to as circulation gas) and to 0-150 real m ³ / m ^{3 of} catalyst in a synthesis converter gasoline (hereinafter referred to as circulating gas).

According to the invention, a method for producing gasoline from synthesis gas involves contacting synthesis gas with a catalyst in a first converter (converter for the synthesis of oxygen-containing compounds) under conditions for the synthesis of compounds of type K ¹ —O — K ² . In the concept, a compound of type K ¹ -O-K ² K ¹ denotes alkyl residues with 1-5 C atoms, K ² is hydrogen, alkyl and alkoxyl residues with 1-5 C atoms. Preferred compounds of type K ¹ -O-K ² are methanol (K ¹ = CH 3 and K ² = H) and in some cases dimethylether (K ¹ = K ² = CH 3), especially synthesized in a synthesis converter for compounds of type K ¹ -O-K ² (hereinafter also referred to as methanol synthesis converter ) methanol or a mixture of methanol and dimethylether.

The synthesis of compounds of type K ¹ -O-K ²

Synthesis gas is preferably used as a starting material for the synthesis of compounds of type K ¹ —O — K ² .

In the converter for the synthesis of compounds of type K ¹ -O-K ² (if the compound of type K ¹ -O-K ² is methanol), the following reactions take place in particular:

СО + Н ₂ 0 <-> С0 ₂ + Н ₂ water gas production reaction

CO + 2H ₂ <-> CH ₃ OH formation of methanol and, accordingly, when using an additional acidic component of the catalyst to the methanol synthesis catalyst for the synthesis of dimethylether:

2CH ₃ OH <-> CH3-O-CH3 + H ₂ 0 formation of DME

Whether methanol, or a mixture of methanol and dimethylether (DME), or another compound of the type K ¹ —O — K ^{2 is} obtained in the first step, is controlled in particular by the catalysts used.

Catalysts (for example, zinc-chromium oxide catalysts, copper-based catalysts with addition of zinc oxide and / or alumina; combinations of copper and rare earth metals; catalysts of copper oxide / zinc oxide, as well as catalysts from copper oxide / zinc oxide / chromium oxide, etc.).

For the synthesis of a mixture of methanol and dimethylether, known from the prior art find application

- 3 021044 methanol synthesis catalysts with a dehydration catalyst, in particular catalysts with pronounced acidic properties, for example, γΑ1 ₂ 0 ₃ or zeolites in protonated form with high acidity, in a mixture or separately.

The corresponding catalysts and conditions are well known and described, for example, in relation to the synthesis of methanol in the book MM Karavaeva et al. Synthetic methanol technology, M .: Chemistry, 1984 and in relation to the synthesis of DME in the I8 patent 3894102.

The product stream of the P'-0-P ² type synthesis synthesis converter is preferably cooled, followed by separation of the liquid and gaseous phases in the separator. Alternatively (the entire) product stream from the methanol synthesis converter without separation is directly sent to the second gasoline synthesis converter.

If separation occurs, the unconverted components of the synthesis gas (CO, H ₂ , C0 ₂ , nitrogen, etc.) are preferably partially returned to the first converter for the synthesis of compounds of type K ^! -0-K ² , i.e. they are added to the loaded gas mixture, which contains CO and H2, and part of the unconverted synthesis gas is fed to a gasoline synthesis converter to suppress the decomposition reaction of compounds of type K ¹ 0-K ² . At the same time, another part is preferably removed from the process in order to avoid the enrichment of inert components. Part of the unreacted components of the synthesis gas is loaded into the gasoline synthesis converter by a volumetric flow at the inlet of the gasoline synthesis converter, providing a partial pressure of hydrogen of at least 0.07 MPa and CO of at least 0.08 MPa.

For the synthesis of compounds of type K ¹ -0-K ^2, cooled converters with almost isothermal conditions are used in a reaction chamber with a preferred heat transfer surface of more than 50 m ² / m ^{3 of} catalyst, while the volume of gas circulating, most of which consists of unreacted synthesis -gas and short-chain gaseous hydrocarbons, relative to 1 m ^{3 of} catalyst, is preferably less than 150 m ³ .

Gasoline synthesis

In a gasoline synthesis converter, at least a portion of the product stream from the synthesis converter of compounds of type K ¹ -0-K ² contacts with the catalyst at a preferred degree of conversion of the compound of type K ¹ -0-K ² at a level of 85-99.5%.

In the gasoline synthesis converter, the catalyst contacts either the entire stream from the K ¹ -0-K ² compounds synthesis converter, 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 stream of the K ¹ - compounds synthesis converter 0-K ² , which provides a gas synthesis converter in the feed stream of the gas, in terms of 1 m ³ (ί.Ν.) of gas flow, the partial pressure of Н _{2 is} more than 0.07 MPa and the partial pressure of CO is more than 0.008 MPa. These values of the partial pressure of H ₂ and CO provide suppression of the decomposition reaction of compounds of type K ¹ -0-K ² in the gasoline synthesis converter.

There is a wide range of catalysts for the synthesis of hydrocarbons from methanol and dimethylether. Some of them are described in the book Nefedov B.K., Konovalchikov L.D., Rostanin N.N. Oil refining and petrochemical catalysts based on high-silica zeolites, M: TsNIITEneftekhim, 1987, 59 pp. The catalyst for the synthesis of gasoline from compounds of type K ¹ -0-K ² preferably contains at least partially protonated zeolite (for example, ΗΖδΜ-5) mainly from the group of pentazyls. Zeolites with a high ratio of δί0 ₂ / Λ1 ₂ 0 ₃ at a minimum of 12 are predominantly used, particularly preferably with a ratio of δί0 ₂ / Λ1 ₂ 0 ₃ at a minimum of 30. Due to the use of high-silica zeolites, the formation of durene in the product is reduced. A water vapor resistant catalyst can be obtained by modification using elements of group 1b. Combinations of silicon dioxide with metal oxides (gallium oxide and / or indium oxide) can also be used (patents I8 4507404 from 1985, EP 0070690 from 1983, EP 0124999 from 1984). By combining, for example, gallium oxide and / or indium oxide with thorium oxide and a high silica zeolite, high-quality gasoline containing a large amount of aromatic compounds can be obtained (patent EP 0070690 from 1983).

The material supplied to the second converter is either the entire first product stream or the part containing a type K compound ^! -0-K ² The partial pressure of a compound of the type P'-0-P ² (preferably methanol and, in some cases, dimethylether) in the feed material of a gasoline synthesis converter in terms of 1 m ³ (ί.Ν.) of gas flow is particularly preferably maintained at below 0.5 MPa (primary distinguishing feature).

The partial pressure of water vapor in the feed material of the gasoline synthesis converter is particularly preferably at a level below 0.3 MPa (a primary distinguishing feature).

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

The method according to the invention is characterized in that the contact of the feed material with the catalyst in the second converter takes place in the presence of hydrogen and carbon monoxide. Due to this, the selectivity of the conversion of the K ¹ -0-K ² compound (preferably methanol and, in some cases, dimethyl ether) to hydrocarbons is predominantly increased, since their decomposition into carbon oxides and hydrogen is suppressed.

For the synthesis of gasoline, a cooled converter and almost isothermal conditions are preferably used in the reaction zone with a heat transfer surface of more than 40 m ² / m ^{3 of} catalyst, the volume of circulating gas is relatively 1 m ^{3 of} catalyst less than 150 m ³ . The thermal effect of the reaction is preferably used to produce water vapor with a pressure of up to 22 MPa. This is also a hallmark of the invention, which, together with the features of claim 1 of the claims, allows to obtain high quality gasoline with a selectivity of more than 83%, preferably more than 86%. Here, selectivity is understood to mean the yield of gasoline relative to a portion of the hydrocarbon that has reacted with methanol.

Preferably, the conversion of the K ¹ -O-K ² compound (preferably methanol and, in some cases, dimethylether) in a gasoline synthesis converter is more than 85 and less than 99.5% for methanol and more than 92 and less than 99.8% for dimethylether. Incomplete conversion of a compound of type K ¹ -O-K ² is an essential distinguishing feature of the invention, which makes it possible to control the selectivity of the process (yield of gasoline fraction relative to the hydrocarbon fraction of a converted compound of type K ¹ -O-K ² ) due to the required quality of the obtained gasoline and the duration of the intermediate cycle regeneration (duration of the process between catalyst regenerations). This is the reason that, in accordance with the invention, gasoline is obtained with a content of less than 46% of aromatic compounds, with a benzene content of less than 1 wt.% In them, with a content of more than 40% isoparaffins with high octane characteristics (93-96 GPI) , which is also a hallmark of the invention.

In addition to gasoline hydrocarbons, the product of the synthesis of gasoline from compounds of type K ¹ -O-K ² contains hydrocarbons C3-C4, water, unreacted methanol and other compounds of type K ¹ -O-K ² , as well as dry gas. This dry gas contains mainly gaseous substances (short-chain hydrocarbons (C1-C ₂ ), CO, CO ₂ and H ₂ and other components of the synthesis gas).

Separation of gasoline synthesis products

The product of gasoline synthesis is cooled and separated into unstable gasoline, the aqueous phase and non-condensed gas components. The separation is preferably carried out by physically separating the phases in a three-phase separator. Non-condensed gas constituents contain synthesis gas components, light hydrocarbons (C ₁ and C ₂ ), traces of heavy hydrocarbons. This circulating gas is at least partially returned to the gasoline synthesis converter and / or to the synthesis converter of compounds of type K ¹ —O — K ² . The volume of circulating gas to a gasoline synthesis converter can mainly control the partial pressure of methanol and water.

The liquid phase in the three-phase separator, due to the difference in density, forms the interface between the hydrocarbons containing gasoline hydrocarbons and water. A liquid of lower density (gasoline hydrocarbons) accumulates above the interface, while the aqueous phase settles in the lower part.

Liquid hydrocarbons separated in a three-phase separator contain gasoline hydrocarbons, which are preferably sent to a distillation column, in which, if necessary, it is preferable to separate the components of heavy gasoline (durene fraction) and the head gases, mainly C ₃ -C ₄ hydrocarbons and C ₁ -C hydrocarbon residues ₂ (short chain hydrocarbons) and synthesis gas components. With the acceptable content of durene in gasoline hydrocarbons, heavy gasoline does not separate.

The obtained stable gasoline fraction with the required saturated vapor pressure of less than 500-700 mm Hg (depending on the required type of gasoline) is either commercial gasoline or forms the basis for commercial gasoline with an octane rating of 92-98 (OCHI). The water separated in the three-phase separator contains methanol. The methanol content in water depends on the degree of conversion of methanol in the synthesis of gasoline, as a rule, it is more than 3 and less than 30 wt.%.

Preferably, the aqueous phase with a certain methanol content or with other compounds of type K ¹ -O-K ^2, due to different boiling points, is first divided into fractions in the distillation column, of which one fraction is mainly methanol or another type K ¹ -O compound -K ² With a low water content (concentrated methanol), and the other fraction contains water with a low methanol content (contaminated water). Concentrated methanol or, in some cases, dimethylether or another type K ¹ —O — K ² compound is preferably returned to a gasoline synthesis converter. Contaminated water also contains a residual amount of methanol (usually a maximum of 5 wt.%) Or another compound of type K ¹ -O-K ² .

To remove residual methanol from contaminated water in the method according to the invention, methanol and, in some cases, another K ¹ -O-K ² compound by contact with the catalyst (steam reforming or catalytic decomposition) is catalytically decomposed into hydrogen and gaseous carbon oxides. Water after cooling by condensation is separated from the obtained carbon oxides (CO and CO2) and hydrogen. Carbon oxides and hydrogen can be predominantly mixed with synthesis gas and returned to the synthesis of compounds of the type K ¹ -O-K ² . After gas separation during subsequent degassing of water, chemically purified water is predominantly obtained. The contact of methanol-containing water with the catalyst occurs preferably at a temperature below 380 ° C, particularly preferably below 350 ° C and preferably above 200 ° C.

The contact of water containing a compound of the type K'-O-K ² (preferably methanol, in some cases dimethylether) with the catalyst is preferably carried out at a pressure that allows the obtained components of the synthesis gas to be sent directly to the first converter or to the first converter using a circulation compressor. This pressure corresponds to the sum of the backpressure for the synthesis of K'-O-K ² compounds and the pressure loss between the output of the catalytic decomposition of methanol and the input of the feed substance into the methanol synthesis converter. Alternatively, the residual content of a chemical compound of the K'-O-K ^{2 type} in water can also be removed by a biological purification process. Biologically treated water can be sent to the sewer network.

However, it must be borne in mind that biological treatment requires that the methanol content in the water be less than 0.2-1 wt.%, And obtaining such a concentration through distillation is associated with high energy costs or requires a strong dilution of contaminated water with clean water, which also increases biological treatment cost.

Application of the catalytic purification of water from compounds of the type R'-O-K ² is another advantageous feature because it allows for relatively low cost process conditions are adjusted in the converter to synthesize gasoline, to reduce the degree of conversion of compounds of type K ¹ K ² -O-and thereby achieve high selectivity and product quality.

Installation

The subject of the invention is also an apparatus for implementing the method of the invention.

This installation contains:

a) at least a first converter that contains a catalyst suitable for catalysis of the conversion of CO with H ₂ into a chemical compound of the type K'-O-K ² (preferably methanol),

b) at least a second converter that contains a catalyst suitable for catalysis of the conversion of a chemical compound of the type K'-O-K ² into hydrocarbons,

c) at least a separator suitable for separating gasoline hydrocarbons from the product stream, which along with gasoline hydrocarbons also contains chemical compounds of the type K'-O-K ² , water and gas, which includes short-chain hydrocarbons, synthetic gas components, K'-O-K ² compounds and traces of gasoline hydrocarbons,

j) at least a third converter, which contains a catalyst suitable for catalysis of the conversion of a chemical compound of the type K'-O-K ² (preferably methanol) contained in water into CO and H2.

The above components are preferably connected in series, i.e. the first converter is connected directly or indirectly to the second converter in such a way that at least part of the product stream from the first converter is directed to the second converter. The second converter is connected to the separator c) in such a way that the product stream from the second converter is directed to the separator c). In this case, the separator c) is connected indirectly to the third converter in such a way that the water separated in the separator c) and containing a chemical compound of the type K'-O-K ² , if necessary, after preliminary separation by distillation of the main amount of the compound of the type K'-OK ² goes to the third converter. The separator c) also has a connection with the second converter, which allows you to return short-chain hydrocarbons and other components of the gas phase of the separator c) to the entrance to the second converter.

Preferably, the installation comprises a connecting pipe from the third converter to the first converter, which allows directing the CO and H2 formed in the third converter to the first converter.

To implement a variant of the method with separation of the first product stream, the installation includes an additional separator for separating the product stream from the first converter. In this case, the additional separator preferably has a connecting pipe to the first converter, which allows the CO and H ₂ separated in the separator to be directed to the first converter. This (optional) separator preferably also has a first connecting pipe with a second converter, allowing, if necessary, to supply chemical compounds of the K'-O-K ² type to the second converter after separating at least a part of the water, and a second connecting pipe with a second converter, allowing, if necessary, to send at least part of the gas stream containing CO and H2 to the second converter.

To implement the option of directly entering (all) the first product stream into the second converter, the first converter in the installation is directly connected to the second converter through the substance stream, so that the entire product stream from the first converter, without being subjected to separation, is sent to the second converter. In this case, the separator c) preferably has a connecting pipe to the first converter, which allows the return of dry gas (not converted CO and H ₂ , as well as short chain hydrocarbons) to the first converter.

In each case, the second product stream is divided into hydrocarbons containing gasoline hydrocarbons, gas and water. Water containing a non-converted chemical compound of the type K'-O-K ² is preferably sent to a device connected to the separator c) (preferably a distillation column), which makes it possible to separate a product with a high content of a compound of the type K'-O-K ² (preferably methanol and in some cases DME) in water, which can be added back to the starting material of the second converter. Moreover, the device connected to the separator c) preferably has a connecting pipe for returning the separated concentrated solution of a chemical compound of the type K'-O-K ² in water to the second converter. However, with this additional device, a K'-O-K ² compound is not completely removed from the water. Therefore, an additional device also has a connecting line to the third converter to send still contaminated water in a third vessel in which the compound of type K ^{'K 2} O-degradable.

Known catalysts can be used to decompose a compound of type K'-O-K ² (preferably methanol and, in some cases, DME), a review is given in an article by E. I. Klabunovsky. et al. Catalysts for the conversion of methanol to synthesis gas (Catalysis in Industry, 2004, No. 6, pp. 3-9), as well as steam reforming catalysts, methanol synthesis catalysts and other catalysts.

In step ά), any type of converter may be used; a flow converter with a fixed bed of granular catalyst is preferred. The converter used in step ά) is hereinafter referred to as the water purification converter.

To organize a continuous process for producing synthetic gasoline from synthesis gas, it is preferable to use not one but two converters: one converter operates in the reaction mode, the second converter operates in the catalyst regeneration mode.

The concept of a converter is used in the description of the invention as a synonym for a reactor. The converters used in step a) and / or step b) are preferably flow reactors in which the catalyst is placed as a fixed bed.

Preferably, the first and / or second converter is cooled. Cooling preferably takes place by indirect evaporation cooling.

The reaction in step a) and / or step b) occurs as nearly as isothermally as possible. Whenever possible, the converters are equipped in such a way that they allow direct and complete removal of the reaction heat obtained in the catalyst bed and, thus, enable the reaction to be carried out at an almost constant temperature in the volume of the reaction chamber.

The heat of reaction removed by cooling in the first and second reactors can be advantageously used to produce water vapor.

In the first converter (methanol synthesis and, in some cases, DME synthesis), the ratio of heat transfer surface to catalyst volume is preferably not less than 50 and not more than 400 m ² / m ³ . By means of the reaction heat withdrawn in the first converter, water vapor is preferably generated with a pressure of not less than 0.6 and not more than 4 MPa.

In the second converter (gasoline synthesis), the ratio of the heat transfer surface to the catalyst volume is preferably not less than 40 and not more than 200 m ² / m ³ . By means of the reaction heat withdrawn in the second converter, water vapor is preferably generated with a pressure of not less than 3.0 and not more than 22 MPa.

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

The synthesis gas used in the process can be obtained from various starting materials. The starting materials may be of fossil or biological origin (e.g. coal, biomass, natural gas or biogas). The ratio of CO and H2 in the synthesis gas depends on the starting materials used for its preparation and on the method for its preparation. As a rule, synthesis gas also contains inert components (for example, Ν ₂ and water). Synthetic gas is preferably cleaned of catalyst poisons (sulfur compounds, nitrogen compounds) and impurities, dried and, if necessary, compressed.

For the synthesis of methanol or DME, the ratio of H ₂ / CO in the synthesis gas is preferably not less than 2. In this case, a high yield of methanol (DME), relative to C in CO, is maintained. At a lower ratio, the yield of methanol (DME) decreases and the yield of CO ₂ increases.

The individual steps of the method of the invention will be discussed in detail below based on preferred embodiments of the invention.

Gasoline from synthesis gas is produced in two stages: at the stage a) the synthesis of compounds of type K ¹ O-K ² , for example methanol and / or dimethylether, takes place at stage b) the conversion of compounds of type K ^' -OK ² on the zeolite catalyst into a mixture from hydrocarbons. Compounds of the K'-O-K ^{2 type} , obtained in the first stage, can be, like the entire product stream, from the first converter directed to the second stage or separated from the product of the first converter in any embodiment and then transferred to the second stage.

- 7 021044

Methanol and, in some cases, dimethylether, including in a mixture with water, can be separated from the product of the first converter as feed material for the second stage. The unconverted synthesis gas is preferably separated from the product of the first converter or from the product of the second converter and returned to the first converter for the synthesis of compounds of type K ¹ —O — K ² .

The synthesis gas can be mainly used as a raw material mixture, however, it is preferably dried, if necessary, compressed and heated to a temperature close to the reaction temperature in a mixture with a circulation gas, for example, in heat exchangers-recuperators and / or heaters (steam heaters, furnaces and / or electric heaters) and sent to the first converter (block I in the drawings) for the synthesis of compounds of type K ¹ -O-K ² (methanol and, in some cases, dimethyl ether). In the preparation of compounds of type K ¹ —O — K ² , contact is made with a methanol synthesis catalyst or with a methanol synthesis catalyst and a methanol dehydration catalyst in dimethylether (DME).

For the synthesis of methanol in stage a), mainly copper-containing catalysts are used at temperatures up to 260 ° C and pressures up to 6 MPa. The reaction of CO and H ₂ with the formation of methanol occurs exothermically with a thermal effect of 90.73 kJ / mol of methanol. Therefore, in step a), an isothermal cooling converter is preferably used. It is able to reduce the required volume of circulation gas and produce synthesis under optimal conditions, with a corresponding decrease in the formation of by-products, increase in methanol yield, extend the life of the catalyst and generate medium-pressure water vapor for use as an energy carrier.

The product from the synthesis converter of compounds of type K ¹ —O — K ^{2 is} preferably cooled in heat exchangers, heating the feed stream (synthesis gas). Alternatively, the product stream may preferably be separated into a gas product and a condensate. For this, the product is predominantly cooled in an air cooler and a water cooler, and in the presence of dimethylether in the product, also with the use of deep cooling. Organic components and water condense. Condensate (crude methanol, water content up to 20% or a mixture of dimethylether, methanol and water) is separated in a separator. The gas product from the separator is not converted synthesis gas, part of it is returned to the first converter for mixing with the original synthesis gas for the purpose of complete conversion.

Alternatively, a distillation column can also be connected to the separator to separate water from the mixture with organic components, since the presence of water in the feed material for the second converter in order to convert the K ¹ -O-K ² V type hydrocarbons accelerates the irreversible deactivation of the second converter zeolite catalyst. However, this is a very expensive operation and it would be more economical to dilute the feed stream for the second converter with inert components to reduce the partial pressure of water and methanol.

Separated compounds of type K ¹ -O-K ² (methanol or a mixture of methanol / DME) or the product stream from the first converter (block I) is fed to a second gasoline synthesis converter (in the drawings - block III), where they are preferably mixed with a recycle methanol stream (stream 11 in FIG. 1 + 2) from block V, with a recycle stream of light gaseous hydrocarbon (stream 7 in FIG. 1) from block IV and with a stream of unreacted synthesis gas (stream 5 in FIG. 1) from separator (block II). The mixed stream is preferably heated in heat exchangers-recuperators and in a heater and fed to a gasoline synthesis converter.

The presence of hydrogen and carbon monoxide in the process according to the invention in the methanol conversion zone (and in some cases dimethylether) reduces at least partially the undesirable decomposition of methanol into hydrogen and carbon monoxide in step b). As a result of this, the selectivity of hydrocarbon formation is predominantly increased. The partial pressure of hydrogen is preferably above 0.07 MPa, and the partial pressure of carbon monoxide is above 0.008 MPa. To achieve the desired effect, either hydrogen and carbon monoxide are mixed with methanol (and in some cases dimethylether) previously separated from the first product stream, or the first product stream, containing synthesis gas not yet converted, is sent directly to the second converter. Hydrogen and carbon monoxide serve as diluent components in the second converter, i.e. they dilute educt (methanol and, in some cases, DME). The dilution of methanol (methanol + DME) in the stream loaded into the second converter of the substance should be such that the partial pressure of methanol is less than 0.5 MPa and water less than 0.3 MPa.

The product from the gasoline synthesis converter is preferably cooled in recuperator heat exchangers, wherein the feed of the converter (methanol and, in some cases, DME) is preferably heated, if possible, in a mixture with the circulation gas. The cooled stream is preferably transferred to a second separator (block IV in the drawings) to separate the converter product of gasoline synthesis. During cooling, gasoline hydrocarbons, part of light hydrocarbons, K'-O-K ² compounds and water, which do not enter the reaction, condense in the recuperator and in the coolers. The separator preferably separates: 1) water containing unreformed K-type compounds ^! -O-K ² , 2) gasoline hydrocarbons and 3) a gas phase containing hydrogen, carbon oxides and light hydrocarbons (mainly up to 4 carbon atoms, mainly methane and C ₂ -C ₄ hydrocarbons) formed during the conversion of methanol. Part of the gas phase is mixed with part containing CO and H ₂

- 8 021044 gases from the first separator (block II); and preferably, as diluents to the feed material (methanol and, in some cases, DME), it is returned to the gasoline synthesis converter.

The condensate of gasoline hydrocarbons from the separator c) is preferably heated and conducted to a stabilization column in which light overhead gases (short-chain hydrocarbons, mainly propane, propylene, butane, butylene, as well as methane, ethane, ethylene and H ₂ ) are separated from stable gasoline ( stream 8 in the drawings). If necessary, C ₃ -C ₄ hydrocarbons can be separated as a liquid C ₃ -C ₄ fraction. Heavy gasoline can also be isolated from gasoline hydrocarbons that are fed to the stabilization column, in the stabilization column or in an additional column (stream 9 in the drawings).

The aqueous phase (stream 10 in the drawings) from the separator c) can, as an option, be directed to a distillation column (block V in Fig. 1 + 2), and then to the water treatment converter (block VI in Fig. 1 + 2). In the distillation column, a concentration of a KZ-O-K ² type compound occurs (stream 11 in FIG. 1 + 2). This recycle stream is directed to a gasoline synthesis unit. The water stored in the cube of the column containing the residual concentration K'-O-K ² is sent to the water treatment converter. The aqueous phase from the separator c) can also be directly fed to the water treatment.

Using the following drawings, two preferred embodiments of the method of the invention are described in detail.

FIG. 1 shows a flowchart of a preferred process for producing gasoline from synthesis gas according to the invention according to the method with separation of a recycle stream of synthesis gas from a product of a synthesis converter of compounds of type K'-O-K ² and catalytic decomposition of methanol in water, followed by distillation of the bulk of methanol from process water.

FIG. 2 shows a flowchart of a preferred process for producing gasoline from synthesis gas according to the invention according to the method, by directly introducing the product stream from the first converter into the second converter and separating the recycle stream of the synthesis gas from the product of the gasoline synthesis converter and catalytic decomposition of methanol in water followed by distillation bulk methanol from process water.

In FIG. 1 synthesis gas 1, the main components of which are hydrogen and carbon monoxide in a ratio depending on the method of their preparation, but which also contains inert components, is purified from catalyst poisons and impurities, if necessary, is compressed and fed to the first converter (block I) synthesis of compounds of type K ¹ -O-K ² , where it is mixed with circulation gas 3. The resulting mixture is heated in heat exchangers, recuperators and heaters (steam and / or electric heaters, furnaces) to the reaction temperature and sent to the convoy Rter synthesis of compounds of type K ¹ -O-K ² . Upon receipt of compounds of type K ¹ —O — K ² , contact is made with a methanol synthesis catalyst or a methanol synthesis catalyst and a catalyst for methanol dehydration to dimethylether. In the synthesis of methanol, it is preferable to use copper-containing catalysts at temperatures up to 260 ° C and pressures up to 8 MPa, but zinc-chromium catalysts operating at temperatures up to 360 ° C and pressures above 8 MPa can also be used.

The product from the synthesis converter for compounds of type K ¹ -O-K ^{2 is} cooled in heat exchangers, heating the feed stream, as well as in air and water coolers, and if dimethylether is present in the product, deep cold is also used for cooling, and compounds of type K ¹ -O -K ² and the water condenses. Condensate (crude methanol with a water content of up to 20% or a mixture of dimethylether, methanol and water) is separated in a separator (block II). The gas product from the separator is an unformed synthesis gas, part of which (stream 3) is sent to mixing with the original synthesis gas in order to completely transform the feedstock. Compounds of type K ¹ -O-K ² 4 separated in the separator (methanol and, in some cases, DME) are mixed with the recycle stream of methanol 11 from block V, the recycle stream 7 of light gaseous hydrocarbon from the second separator (block IV) and the stream 5 which has not entered the reaction of synthesis gas from block II, preferably a gas product from a separator. After mixing, the components are preferably heated in heat exchangers, recuperators and / or in heaters and fed to a gasoline synthesis converter.

To obtain the highest quality gasoline (with a small proportion of heavy gasoline and aromatic compounds), the conversion of K ¹ -O-K ² compounds (methanol and, in some cases, DME) in the second converter (block III) is preferably maintained below 99.5%. The product comprises a gasoline synthesis converter obtained by the reaction of compounds of type K ¹ -O-C ² hydrocarbons (particularly gasoline hydrocarbons) or conversion of compounds of type K ¹ K ² -O-mainly methanol and synthesis gas components.

Both converters (block I and III) are preferably cooled converters. The first converter has a heat transfer surface of at least 50 m ² per 1 m ^{3 of} catalyst with a volumetric flow of gas circulating less than 150 real m ³ per 1 m ^{3 of} catalyst. In the second converter, the heat transfer surface is at least 40 m ² per 1 m ^{3 of} catalyst with a volumetric flow of circulating gas of gasoline synthesis of less than 150 real m ³ per 1 m ^{3 of} catalyst. The steam obtained by cooling the converters, as described above, is used to generate refrigerant using absorption refrigeration

- 9 021044 machines, in steam heaters for heating the feed streams of the first converter and as a column cube heater for product separation.

The product from the gasoline synthesis converter (block III) is cooled in heat exchanger-recuperators, and the material loaded into the converter is heated and then cooled in coolers. In the process of cooling, condensation of gasoline hydrocarbons and water occurs. The cooled stream 6 is transferred to the separator c) (block IV) to separate the product of the gasoline synthesis reactor. Separator c) separates 1) water containing methanol 10, 2) a gasoline hydrocarbon phase 8 + 9, and 3) a gas phase 7 containing hydrogen, carbon oxides, and light hydrocarbons, which are formed during methanol conversion.

The recycle stream of light gaseous hydrocarbon 7 in this case is mixed with part of the CO and H ₂ -containing gases 5 from the first separator (block II) to obtain a dilution component for the feed material for the synthesis of compounds of the K? -O-K ^{2 type} .

Hydrocarbon condensate (including C ₅ + hydrocarbons) 6 from the separator (block IV) is directed to a stabilization column (block IV), in which light head gases 7 are separated from stable gasoline 8. From unstable gasoline hydrocarbons in a stabilization or additional column heavy gasoline 9 may also be separated.

The aqueous phase 10 from the separator is sent to block V for the concentration of compounds of type KZ-O-B ² and from there to block VI for the catalytic purification of water from compounds of type K ¹ -O-K ² . Water here, depending on the degree of conversion, contains, as a rule, from 3.5 to 30 wt.% Compounds of the type K ¹ -O-K ² .

In block V, the concentration of compounds of type K ¹ -O-K ² in the distillation column in the head part is enriched in methanol and a recycle stream of methanol 11 is obtained, which moves to block III of gasoline synthesis. The bottoms product from the column (block V) - water 12, containing from 1 to 5% methanol 5, is sent to the water treatment converter (block VI), where the catalytic decomposition of methanol in an aqueous medium is carried out.

In the water treatment converter (block VI), from the decomposition of methanol, a gas stream 13 is obtained — carbon oxides and hydrogen, which is supplied to the first converter (block I). It turns out chemically purified water 14, which is used to feed the circulating water system, the steam generation system and for other purposes.

Depicted in FIG. 2, the manufacturing process is a simplified version of FIG. 1 method and differs from it, first of all, the following.

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

As the dilution component of the oxygen-containing feed material, return gas 3 can also be added here (here from block IV).

Here, synthesis gas 1, before or during supply to the first converter, is additionally mixed with hydrogen and carbon monoxide 13, which is formed in the catalytic water treatment converter (block VI), along with the circulation gas 3. The product from the first converter in its composition mainly corresponds to the product according to the method of FIG. one.

To achieve the highest quality gasoline (a small proportion of heavy gasoline), the conversion of the K? -O-K ² type compound (methanol and, in some cases, DME) is preferably maintained below 99.5%.

The product from a gasoline synthesis converter is here also preferably first cooled in heat exchangers, recuperators and coolers. The partially cooled stream 6 is fed to the unit IV for separation of the products of the gasoline synthesis converter, where, as a result of cooling, gasoline hydrocarbons and water are condensed in the coolers. In the separator, water 10 is collected containing non-converted compounds of the type K'-O-K ² . and the gasoline hydrocarbon phase and the gas phase are separated. The gas product from the separator consists mainly of unconverted synthesis gas and light hydrocarbons, some of them (stream 3) are returned to the first converter (block I) for mixing with the original synthesis gas in order to more fully convert the feedstock.

The water formed in the gasoline synthesis converter here, depending on the degree of conversion, usually contains from 3.5 to 40% methanol (and in some cases DME). Therefore, water is purified in a distillation column (block V) and then in a separate water treatment converter (block VI) by catalytic decomposition of methanol into hydrogen and carbon oxides (these gases being returned to the process as an admixture to synthesis gas, see description of Fig. 1 )

The hydrocarbon condensate from the separator (block IV) is conducted to a stabilization column (block IV), in which gasoline 8 is separated. Heavy gasoline 9 can also be separated from unstable gasoline hydrocarbons in a stabilization column or additional column.

The aqueous phase 10 from the separator is fed to the block V enrichment of compounds of the type KZ-O-K ² 2 and then to the water treatment converter (block VI). In block V, the concentration of compounds of type K ¹ -O-K ² in the distillation column in the head part is enriched in methanol and a recycle stream of this methanol 11 is obtained, which is returned to gasoline synthesis block III. The bottoms product of the column - water 12, containing from 2 to 5% methanol 5, is fed to the water treatment converter (block VI).

- 10 021044

In the purification unit VI, the methanol-containing water stream is preferably advanced through heat exchangers-recuperators and / or heaters, where it is heated to the desired reaction temperature, and then fed to the water treatment converter, where it contacts the catalyst for the decomposition of methanol into hydrogen and carbon oxides.

The product from the water treatment converter is preferably cooled in heat exchangers, recuperators and an air cooler. Then the gas phase in the separator is separated from the condensate. The methanol decomposition gases separated at the same time 13 exit the separator and are sent to the first converter (block I) for mixing with the crude synthesis gas. The purified water moves to a degassing column. It turns out chemically purified water 14, which is used to feed the circulating water system, the steam generation system and for other purposes.

By means of FIG. Water converters 1 and 2 are indirectly cooled. Water receives heat from the coolant, which in turn removes heat from the reaction zone. Water leaves block I and III in the form of steam.

Below the invention will be described in detail by means of a comparative example and embodiments.

Example 1 (comparative example).

This example was performed similarly to the TIGAZ process of the company Na1bog Tornoe N. Torr1gdeei8ei, reprinted from Zyuyek ίη ZigGase apb SaYuyf. ν, 36, MeUap Sopuegmop. in 1987

In FIG. 3 shows a block diagram of the TIGAZ process.

The synthesis gas is mixed with the circulation gas, which contains the unconverted components of the synthesis gas and light hydrocarbons, and enters the methanol synthesis reactor + DME with a bifunctional catalyst, which consists of a methanol synthesis catalyst component and a methanol dehydration catalyst component. The resulting mixture from methanol + DME + water and from the components of the unreacted synthesis gas is fed to the gasoline synthesis stage, where methanol and DME are converted to hydrocarbons on the zeolite-containing catalyst. Then the product mixture is separated into gasoline, the aqueous phase, which is sent for purification, the C ₃ -C ₄ fraction and gas, one part of which is carried out as a circulating gas to the stage of synthesis of oxygen compounds. All stages are carried out at approximately the same pressure in the range of 50-100 bar.

Used synthesis gas with a content of H ₂ : CO = 3.

According to the source, the yield of oxygen compounds relative to CH ₂ in the synthesis gas is 94%. The gasoline yield relative to CH ₂ in oxygen compounds is 78%.

In general, the gasoline yield is 73.34% relative to CH ₂ in the synthesis gas without taking into account losses during product separation, etc.

The following are examples of various embodiments of the process of the invention.

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

The volumetric flow of synthesis gas is 738.3 m (ΐ.Ν.) / Π.

For the synthesis of methanol from synthesis gas, a Südhemie catalyst called MEOAMAX 700® (components CuO, ΖηΟ, A1 ₂ O ₃ ) is used, and for the synthesis of gasoline from methanol, a Züdhemi zeolite-containing catalyst under the name ZMA-2 is used.

Production conditions in the synthesis converter for compounds of the K'-O-K ^{2 type} are temperatures in the range from 210 to 260 ° C and pressures in the range from 50 to 55 MPa. The volume of the catalyst is 0.46 m ³ , the heat transfer surface in the reaction zone is 30 m ^{2 the} pressure of the generated water vapor is 1.8 MPa.

In the gasoline synthesis converter in examples 2-4, the pressure is at 7 bar, and in example 5 at 45 bar. The process temperature is in the range from 310 to 430 ° C in the reaction mode and in the range from 280 to 500 ° C in the regeneration mode.

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

The reactions in methanol synthesis and gasoline synthesis converters are carried out under almost isothermal conditions, in which the temperature difference inside the catalyst bed is less than 5 K.

In examples 2-4, the separation of the products of the process of obtaining oxygen compounds occurs at a temperature of 40 ° C. The separation of gasoline synthesis products in all examples occurs at a temperature of + 5 ° C.

Examples 2-5 are distinguished by the choice for application of the individual distinguishing features of the invention.

Example 2

A plant for producing synthetic gasoline basically corresponds to the circuit in FIG. 1 and contains a block (block I) for the synthesis of methanol from synthesis gas, a block (block II) for the separation of methanol from the product stream of block I, a block (block III) for the synthesis of gasoline from crude methanol, a block (block IV) for fractionation with separation of the produced gasoline, block (block V) methanol separation from process water.

- 11 021044

However, unlike the circuit in FIG. 1 block of water purification from methanol does not work. In addition, in the installation, in contrast to FIG. 1 there are no streams 5, 13 and 14, i.e. block 5 does not feed stream 5.

Table 2.1

Installation Material Balance

Receive mode Catalyst Transformations Selectivity Turning synthetic gasoline from synthesis e methanol transformations (CO + CO _g ) in crude methanol gasoline: methanol in methanol without supplying synthesis gas from 99% petrol methanol synthesis unit 5MA-2 94.7% gasoline synthesis unit, without 86%

water treatment unit

Number of operating hours per year 8000.00

Substance flow kg / hour t / year % by weight, relative raw materials Input; synthesis gas 376.10 3008.80 100.00 Total 376.10 3008.80 100.00 Exit: Methanol synthesis unit exhaust gas 29.00 232.00 7.71

Hydrocarbon-containing exhaust gas 23.00 184.00 6.12 Synthetic gasoline 97.00 776.00 25.79 82.76 * 78.39 ** Reaction water 180.50 1444.00 47,99 Raw Syngas Water 46.60 372.80 12.39 Total: 376.10 3008.80 100.00

* relative to CH ₂ methanol, ** relative to CH ₂ synthesis gas.

Table 2.2

The flow characteristic in the circuit of FIG. one

Example 3

A plant for producing synthetic gasoline basically corresponds to the circuit in FIG. 1 and co 12 021044 holds a block for synthesizing methanol from synthesis gas (block I), a block (block II) for separating methanol from the product stream of block I, a block (block III) for synthesizing gasoline from crude methanol, a block (block IV) for fractionation with separation of the produced gasoline, block (block V) of methanol separation from process water.

The methanol water purification unit does not work. Moreover, in the installation, unlike the circuit in FIG. 1 there are no streams 13 and 14.

Table 3.1

Installation Material Balance

The mode of production of synthetic gasoline from crude methanol, without water purification unit

Number of operating hours per year

Gasoline synthesis catalyst;

8MA-2

Methanol conversion

99%

The selectivity of the conversion of methanol to gasoline is 87%

Conversion of (CO + CO ₂ ) to Methanol 94.2%

8,000.00

Substance flow kg / hour t / year % by mass "relatively raw materials Input: synthesis gas 376.10 3008.80 100.00 Total 376.10 3008.80 100.00 Exit: Methanol synthesis unit exhaust gas 28.00 224.00 7.44 Hydrocarbon-containing exhaust gas 24.20 193.60 6.43 Synthetic gasoline 97.40 779.20 25.90 83.53 * 78.71 ** Reaction water 179.90 1439.20 47.84 Raw Syngas Water 46.60 372.80 12.39 Total: 376.10 3008.80 100.00

* relative to CH ₂ methanol, ** relative to CH ₂ synthesis gas.

Table 3.2

The flow characteristic in the circuit of FIG. one

No. Physical properties of substance flows The composition of the streams (% by weight) t [•FROM] R [MPa] Mass flow [kg / hour.] n ₂ With from ₂ H ₂ O sun ₃ he C | -C ₄ C ₅ one 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 5.50 780.1 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 nine 45.4 0.60 18.2 - - - - - - 100.00 10 5,0 0.40 180.9 - - 0.01 98.52 1.47 - - eleven 60.0 1,0 1,0 - - 0.46 14.38 85.16 - - 12 61.9 5.65 179.9 - - - 99.00 1.00 - - thirteen - - - - - - - - - - 14 - - - - - - - - - -

Example 4

A plant for producing synthetic gasoline basically corresponds to the circuit in FIG. 1 and co 13 021044 holds a block (block I) for the synthesis of methanol from synthesis gas, a block (block II) for the separation of methanol from the product stream of block I, a block (block III) for the synthesis of gasoline from crude methanol, a block (block IV) for fractionation with separation of produced gasoline, block (block V) of methanol separation from process water, block (block VI) of methanol purification of water.

Table 4.1

Installation Material Balance

Receive mode Catalyst Turning Selectivity Turning synthetic gasoline from synthesis methanol transformations (CO + CO ₂ ) in crude methanol gasoline: methanol in methanol 97% petrol 8MA-2 94.7% 87.5% Number of hours operation per year 8,000.00

Substance flow kg / hour t / year % by weight, relative raw materials Input: synthesis gas 376.10 3008.80 100.00 Total 376.10 3008.80 100.00 Exit: Methanol synthesis unit exhaust gas 28.00 224.00 7.44 Hydrocarbon-containing exhaust gas 24.10 192.80 6.41 Synthetic gasoline 98.40 787.20 26.16 83.92 * 79.52 ** Reaction water 179.00 1432.00 47.60 Raw Syngas Water 46.60 372.80 12.39 Total: 376.10 3008.80 100.00

* relative to CH ₂ methanol, ** relative to CH ₂ synthesis gas.

Table 4.2

The flow characteristic in the circuit of FIG. one

No. Physical properties substance flows The composition of the streams (% by weight) t [•FROM] R [MPa] Mass flow [kg / hour.] n ₃ With from ₂ H ₂ O CH ₃ OH s, s ₄ from ₅ . one 60.0 5.70 329.5 11.68 58.17 26.61 0.76 - 2.78 - 2 123.5 5.20 2405.2 6.91 7.06 37.51 1.29 12.60 34.61 - 3 54 5.8 2073.9 7.93 8.10 42.56 0,03 1.68 39.70 - 4 40.7 5.20 301.1 - - 1.12 10.06 88.80 0.01 - 5 40 5.1 2,5 7.93 8.10 42.56 0,03 1.68 39.70 - 6 86.9 5.50 793.5 2.19 1.41 21.41 22.80 1,04 34.79 16.36 7 58 1.00 482.4 3.53 2.27 34.33 0.16 - 52.96 6.75 8 40,4 0.70 79.6 - - - - 0.04 2.94 97.02 nine 45.4 0.60 18.8 - - - - - - 100.00 10 5,0 0.40 188.3 - - 0.01 95.65 4.34 - - AND 60.0 1,0 7.5 - - 0.2 14.80 85.00 - - 12 61.9 5.65 180.8 - - - 99.00 1.00 - - thirteen 70 5.42 1.8 12.51 86.21 - 1.28 - - - 14 70 5.42 179.0 - - traces 100.00 traces - -

- 14 021044

Example 5

A plant for producing synthetic gasoline corresponds to the circuit of FIG. 2 and contains a block (block I) for the synthesis of methanol from synthesis gas, a block (block III) for the synthesis of gasoline without isolating methanol from the product stream of block I, a block (block IV) for fractionation with the separation of the produced gasoline, block (block V) for separating methanol from process water, block (block VI) for the purification of water from methanol.

Table 5.1

Installation Material Balance

Receive mode Catalyst Turning Selectivity Turning synthetic gasoline from synthesis methanol transformations (CO + COg) in methanol synthesis stream gasoline: methanol in methanol 99% petrol 8MA-2 94.2% 85.5% Number of hours operation per year 8,000.00

Substance flow kg / hour t / year % by weight regarding raw materials Input: synthesis gas 376.10 3008.80 100.00 Total 376.10 3008.80 100.00 Exit: Hydrocarbon-containing exhaust gas 54.30 434.4 14.44 Synthetic gasoline 96.80 774.40 25.74 83.02 * 78.23 ** Purified Process Water 178.40 1427.20 47.43 Raw Syngas Water 46.60 372.80 12.39 Total: 376.10 3008.80 100.00

* relative to CH ₂ methanol, ** relative to CH ₂ synthesis gas.

Table 5.2

The flow characteristic in the circuit of FIG. 2

No. Physical properties substance flows The composition of the streams (% by weight) t HS] R [MPa] Mass flow [kg / hour.] n ₂ With CO ₂ H ₂ O SNzone C1-C4 Cn one 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 nine 45.4 0.60 16.9 - - - - - - 100.00 10 5,0 0.40 181.2 - - 0.02 98.51 1.47 - - eleven 62,2 4,5 one - - 0.46 14.38 85.16 - - 12 62.6 5.65 180.2 - - - 99.00 1.00 - - thirteen 70.0 5.35 1.8 12.5 86.2 - 1.3 - - - 14 70.0 5.35 178.4 - - - 100.00 - - -

- 15 021044

Reference List

The following notation is used in the drawings and in the text:

Source synthesis gas

The product from the block synthesis of compounds of the type K'-O-K ²

Circulation gas (synthesis gas that returns from block II or IV to block I)

Crude methanol (or starting material of compounds of type K ^{1 II III IV V VI} -O-K ² )

Circulating gas (synthesis gas that is supplied from block II to block III)

Product from gasoline synthesis unit

Circulating gaseous hydrocarbon (returns from block IV to block III)

Petrol

Heavy gasoline

Process water

Returned K'-O-K ² compound (preferably methanol)

Wastewater containing compounds of the type K'-O-K ² (preferably methanol)

Gases generated by the separation of compounds of the type K'-O-K ² (preferably methanol)

Chemically Purified Water

Gas

Fraction C3-C4

I 2

I Block for the synthesis of compounds of type K-O-K with the first converter

II Separation unit with a first separator

III Gasoline synthesis unit with a second converter

IV Separation unit with a second separator and stabilization column of unstable gasoline

V Block concentration of compounds of the type K'-O-K ² (preferably methanol) in a distillation column from process water

VI Block catalytic water purification from compounds of type K-O-K (preferably methanol)

Claims (20)

CLAIM 1. The method of producing hydrocarbons by converting containing CO and H ₂ gas mixture (synthesis gas), comprising: a) contacting the gas mixture with the catalyst in the first converter to obtain a first product stream that contains at least one chemical compound of type K ¹ -O-K ² (wherein K ¹ are alkyl groups with the number of carbon atoms from 1 to 5, and K ² - these are hydrogen, alkyl and alkoxyl groups with the number of carbon atoms from 1 to 5), as well as not converted components of the synthesis gas, 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 that contains at least partially protonated zeolite in a second cooled converter under close isothermal conditions under which the difference temperatures within the catalyst filling does not exceed 40 K at - 16 021044 partial pressure: compounds of type K ¹ -O-K ² less than 0.5 MPa, water less than 0.3 MPa, to obtain a product stream that contains gasoline hydrocarbons, including up to 45 wt.% aromatic compounds, with a content of up to 1 wt.% benzene and not less than 40 wt.% isoparaffins, C ₁ -C ₄ hydrocarbons that are formed in an amount of not more than 17 wt.% calculated as C in converted methanol and / or, if necessary, in converted dimethylether, not converted compound of type K ^1- O-K ² , as well as the components of the synthesis gas that have not reacted, the process temperature being in the range a zone from 310 to 430 ° C. in a reaction mode, the synthesis gas being separated from the first and / or second product stream and at least partially returned to the first converter as circulation gas, c) the separation of the product of the second converter, and the resulting unstable gasoline is stabilized by known methods, and the result is: ί) gasoline fraction, from which, if necessary, a fraction containing durene is separated, ίί) С ₃ -С ₄ hydrocarbon fraction, ίίί) gas stream containing light hydrocarbons and unreacted synthesis gas components, and ίν) water a phase containing an unreformed K'-O-K ² compound. moreover, the gas stream ίίί) is at least partially directed as circulating gas back to the second converter and / or to the first converter, while the aqueous phase ίν) is fed directly to the purification of the type K ¹ -O-K ² compound or first to rectification moreover, by distillation, separation of a compound of type K ¹ —O — K ² and a water contaminated with a compound of type K ¹ —O — K ² occurs, which is supplied for purification. 2. The method according to claim 1, characterized in that the chemical compound of type K ¹ —O — K ² is methanol and / or dimethylether. 3. The method according to claim 1, characterized in that the concentrated solution of the compound of type K ¹ —O — K ² is at least 75%. 4. The method according to claim 1, characterized in that the contaminated water contains a compound of type K ¹ -O-K ² less than 5%. 5. The method according to claim 1, characterized in that the material loaded into the second converter has a partial pressure of hydrogen of more than 0.07 MPa and a partial pressure of carbon oxides of more than 0.008 MPa. 6. The method according to one of claims 2 to 5, characterized in that the conversion of the compound of type K ¹ —O — K ² in step b) is at least 82 and not more than 99.8%. 7. The method according to one of claims 2 to 6, characterized in that the conversion of dimethylether in step b) is not less than 92 and not more than 99.8%. 8. The method according to one of claims 2 to 7, characterized in that the conversion of methanol in step b) is at least 82 and not more than 99.5%. 9. The method according to one of claims 1 to 8, characterized in that contact with the catalyst in the first converter occurs under close to isothermal conditions, which are achieved by removing the heat of reaction through the heat transfer surface with a heat transfer surface to catalyst volume ratio of at least 50 m ² / m ³ . 10. The method according to claim 9, characterized in that due to the heat of reaction removed from the first converter, steam is generated with a pressure of up to 4 MPa, the volume of the circulation gas, which contains unreacted components of the synthesis gas and which is supplied to the first converter, does not exceed 150 real m ³ relative to 1 m ^{3 of} catalyst. 11. The method according to one of claims 1 to 10, characterized in that contact with the catalyst in the second converter occurs under close to isothermal conditions, which are achieved by removing the heat of reaction through the heat transfer surface with a heat transfer surface to catalyst volume ratio of at least 40 m ² / m ³ . 12. The method according to claim 11, characterized in that due to the heat of reaction removed from the second converter, steam is generated with a pressure of up to 22 MPa and a volume of circulating gas stream ίίί) containing light hydrocarbons from the product stream of the second converter, as well as components that have not reacted synthesis gas, has a value of up to 150 real m ³ relative to 1 m ^{3 of} catalyst. 13. The method according to one of claims 1 to 12, characterized in that the water contaminated with a compound of type K ¹ —O — K ² is contacted with a catalyst to decompose methanol at a temperature of up to 360 ° C., resulting in the formation of purified water and components synthesis gas, in particular hydrogen, carbon monoxide and CO2. 14. The method according to item 13, wherein the contact of the water contaminated with a compound of type K ¹ -O-K ² with the catalyst is made at a pressure that allows the obtained components to be directed - 17 021044 synthesis gas directly to the first converter or to the first converter using a circulation compressor. 15. The method according to one of claims 6 to 13, characterized in that a part of the synthesis gas separated from the first product stream is supplied to a second converter for adjusting the partial pressures of hydrogen and carbon oxides, in particular carbon monoxide. 16. Installation for implementing the method according to one of claims 1 to 15, containing: a) a first converter that contains a catalyst suitable for catalysis of the conversion of CO with H ₂ into a chemical compound of type K ¹ —O — K ² , b) a second converter, which contains a catalyst suitable for catalysis of the conversion of a chemical compound of type K ¹ -O-K ² into hydrocarbons, c) a separator suitable for separating gasoline hydrocarbons from the product stream, which along with gasoline hydrocarbons also contains chemical compounds of type K ¹ -O-K ² , water and gas containing short-chain hydrocarbons, components of synthesis gas, compounds of type K ¹ -O -K ² and traces of gasoline hydrocarbons, g) a third converter, which contains a catalyst suitable for catalysis of the conversion of a chemical compound of the type K ¹ —O — K ² contained in water into CO and H ₂ . 17. The installation according to clause 16, characterized in that it contains an additional separator for separating the product stream from the first converter, and the additional separator has a connecting pipe to the first converter, allowing you to send separated in the separator CO and H2 in the first converter. 18. Installation according to clause 16, characterized in that this separator comprises a first connecting pipe with a second converter, allowing to supply chemical compounds of type K ¹ -O-K ² together with H ₂ O to the second converter, and a second connecting pipe with a second converter , allowing under certain conditions to supply CO and H2 to the second converter. 19. Installation according to clause 16, characterized in that the first converter is directly connected to the second converter so that the entire product stream from the first converter is directed to the second converter, the separator comprising a connecting pipe to the first converter, allowing the unformed CO to be fed into the first converter and H2, as well as short chain hydrocarbons. 20. Installation according to one of paragraphs.16-19, characterized in that it has at least one of the following additional components: ί) a connecting pipe from the third converter to the first converter, which allows directing the CO and H ₂ formed in the third converter to the first converter, and / or ίΐ) a device connected to the separator, which allows you to separate the connection type K ¹ -O-K ² , and the installation contains a connecting pipe for returning the separated chemical compound of type K ¹ -O-K ² to the second converter, and / or ίίί) a device for removing the heat of reaction in the first and / or second converter, which allow the generation of water vapor, To remove the heat of reaction in the first converter, the ratio of the heat transfer surface and the volume of the catalyst is at least 50 m ² / m ³ , and in the second converter the ratio of the heat transfer surface and the volume of the catalyst is at least 40 m ² / m ³ .