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

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

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Publication number
WO2011061198A1
WO2011061198A1 PCT/EP2010/067606 EP2010067606W WO2011061198A1 WO 2011061198 A1 WO2011061198 A1 WO 2011061198A1 EP 2010067606 W EP2010067606 W EP 2010067606W WO 2011061198 A1 WO2011061198 A1 WO 2011061198A1
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Patent type
Prior art keywords
synthesis
converter
methanol
gas
water
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PCT/EP2010/067606
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German (de)
French (fr)
Inventor
Joachim Engelmann
Genrikh Falkevich
Sarsenov Rashit Temirbulatovich
Original Assignee
Chemieanlagenbau Chemnitz Gmbh
Sapr - Neftekhim Llc.
Too Techno Trading Ltd.
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00Production of liquid hydrocarbon mixtures from oxygen-containing or organic materials, e.g. fatty oils, fatty acids
    • C10G3/42Catalytic treatment
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516Multisteps
    • C07C29/1518Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01Preparation of ethers
    • C07C41/09Preparation of ethers by dehydration of compounds containing hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/04Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/06Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1022Fischer-Tropsch products
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02Gasoline
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Bio-feedstock

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

A process for the production of hydrocarbons, especially gasoline,

from synthesis gas

The invention relates to a process for the production of hydrocarbons, especially gasoline, from non-hydrocarbon-containing compounds, in particular from synthesis gas containing carbon monoxide and hydrogen.

State of the art.

Synthesis gas which is primarily a mixture of carbon monoxide and hydrogen can be produced from various readily available solid and gaseous sources of carbon and hydrogen. The synthesized on the basis of synthesis gas hydrocarbon raw material and motor fuels are real alternatives to petroleum hydrocarbons and in their quality partially better. Therefore, the effectiveness of the technology for the conversion of synthesis gas into hydrocarbons for many years is a current problem.

In 1925 developed Fischer-Tropsch synthesis (US 1,746,464), synthesis gas catalytically reacted directly to hydrocarbons.

It is known that gasoline can be produced from synthesis gas in two stages: first, the synthesis of oxygenates (such as methanol or dimethyl ether or a mixture of both compounds.), Then from the conversion of oxygenates to a zeolite-containing catalyst in a mixture hydrocarbons. . By the company "Mobil Oil" some method of producing gasoline were developed from synthesis gas according to this scheme, both stages of the procedure are described in scientific-technical and patent literature: the synthesis of methanol, for example, in detail in the book by Karawajewa MM including "Technology of synthetic methanol ", M .: Chimija, 1984, explained; the synthesis of a mixture of methanol and dimethyl ether in US 3,894,102; the synthesis of hydrocarbons from methanol and dimethyl ether - an overview of CD Chang, Catal. Rev. - Sci. Eng., V. 25, N 1 (1983) and in US 4,404,414 from the 1983rd

US 6,191,175 discloses a process for the production of methanol or dimethyl ether. For this purpose is first the synthesis of methanol from synthesis gas, which is fed pre-heated into a first reactor. The reaction product is optionally mixed with synthesis gas and further reacted in a second reactor, which either also is used for methanol synthesis or the synthesis of dimethyl ether. In order to achieve high product capacity, the process is preferably conducted adiabatically.

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

In the process of conversion of synthesis gas into gasoline according to US 3,894,102 (from 1975) is in the first stage of the contact of the synthesis gas with a catalyst consisting of a mixture of a methanol synthesis catalyst and an acid catalyst to dehydration at a temperature of 371 ° C under conditions to produce a product containing dimethyl ether, realized. In the second stage of the contact of at least of the dimethyl ether with a zeolite catalyst at a temperature of 288 - 454 ° C, a pressure up to 21 MPa and a Mas scorching esch of Rohstoffzuspeisung windiness 0.5 to 1000 h "1 realized with a product is generated whose organic part is preferably petrol. the product of the first stage may be passed directly to the second, or it is separated, for example, the water is separated (with or without methanol), also be H 2 and carbon monoxide (unreacted synthesis gas ) separated, which (possibly be recycled after discharge of C0 2) to the first stage.

According to the prior art, the process of converting methanol and dimethyl ether, which are usually synthesized in the first stage is realized under conditions of their almost complete conversion, with the oxygen compounds accumulate in the water and there is the problem of recycling the waste water and / or the separation of the sour material compounds from the water-containing streams, which substantially impairs the economic parameters of the process.

In this context, processes are proposed the conversion of oxygenates into hydrocarbons in the art, which solve the problem by maintaining a degree of conversion of the raw material at a level of more than 99%. The separated from the final product water is carried away from the plant and sent to biological or biochemical purification.

US 4,814,535 (of 1989) discloses a method of producing gasoline from oxygen-containing compounds having a number of 1 to 4 carbon atoms. In this case, the conversion of the raw material is maintained at a level of 99.9% by the temperature at the inlet is increased in the reactor stages and the raw material stream is reduced. With decrease in the degree of conversion at 99.9%, the raw material supply is interrupted.

US 4,523,046 (of 1985) discloses a method of producing gasoline from methanol. The catalyst is placed in individual beds and upon contact of the feedstock with the catalyst bed, a degree of conversion of the raw material of substantially 100% is achieved. With reduction in the degree of conversion of the raw material is fed to the next catalyst bed.

In order to improve the manufacturing process of gasoline from synthesis gas or methanol or of methanol and dimethyl ether (DME), various aspects are touched by the prior art, including the temperature control in the zone of the highly exothermic conversion of the methanol or DME to hydrocarbons, and the gasoline selectivity and quality, particularly the content of aromatic hydrocarbons, particularly heavy hydrocarbons in the produced gas.

The temperature control in the zone of the conversion of the methanol or DME to hydrocarbons is carried out by means of thinning components in the raw material Ström that do not participate in the reaction itself. In the method according to US 4,035,430 (from 1977) to use for at least one compound selected from Crbis Cs-hydrocarbons and the cooled durolhaltige product. The latter compound, together with the temperature influence on the yield of aromatic hydrocarbons and the content of the fractions contained therein to BTX (benzene, toluene, xylene).

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

In the process according to US 4,404,414 (from 1983) for the preparation of hydrocarbons to use inert diluent components: light gas, which was separated from the reaction product, as well as water vapor, hydrogen and C 2 - and C 3 + - hydrocarbons or their mixtures.

In US 5,602,289, a gas consisting of two recycled to the reactor gas flows (C 2 - hydrocarbons and C 3 + - hydrocarbons) is used as a diluting component, are mixed together. The partial pressure of the water, including the water which has formed in the reaction of conversion of the methanol in the reactor there is, less than 2.2 atm. The limit of the partial pressure of water vapor is due to the known effect of irreversible deactivation of the zeolite in the presence of water vapor. The composition of the diluent component is in this preferred case of a ratio of the C 2 - hydrocarbons specified in the boundaries between 1/3 to 3/1 and a hydrogen content of between 10 and 50% moles - hydrocarbons / C 3+. The use of gases having a low thermal capacity (hydrogen, C 2 - hydrocarbons) as diluent components increases the factor of dilution, but allows the conversion of methanol to hydrocarbons at a higher pressure (with respect to the required upper limit of the water vapor partial pressure) perform.

task

The object of the invention is to develop an economical and simplified the process of production of petroleum hydrocarbons from synthesis gas, as well as a simple system diagram with simplified technological stages. The aim is also to achieve high gasoline selectivity combined with high fuel quality and the provision of a waste-free technology without environmentally harmful by-products.

Short description of the invention.

According to the invention the object is achieved by a method for producing hydrocarbons according to claim 1:

In the fiction, modern process, the production of hydrocarbons by the conversion of a H2 and CO-containing gas mixture takes place (also hereinafter referred to as synthesis gas) by

a. ) Contact with a catalyst in a first converter for generating the first

Product stream,

R 1 contains at least one chemical compound of the type -O-R2 (wherein R 1 - are alkyl groups having a carbon number of 1 to 5, R - hydrogen, alkyl and alkoxy groups having a carbon number of 1 to 5), which preferably methanol and / or is in need dimethyl ether

as well as unreacted components of synthesis gas, which can be separated from the liquid phase and are fed to at least partly in 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

the hydrogen of greater than 0.07 MPa,

the oxides of carbon of greater than 0,008 MPa,

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

and / or 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, as well as, at need, with a dimethyl ether conversion of not less than 92% and not more than 99.8,

to produce a product stream comprising - petroleum hydrocarbons,

with preferably up to 45 degree. -% of aromatic compounds contained therein to 1 degree. -% 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 degree. -% form (converted to ether C in unreacted methanol and / or, when necessary, in the converted Dimethy)

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

- and also did not react components of the synthesis gas

contains

wherein synthesis gas from the first and / or second product stream is separated and is partially recycled to minimum as circulation gas in 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, when necessary,

a heavy gasoline fraction which contains durene (1,2,4,5 -Tetramethylbenzol), is separated off,

- a fraction of C3-C4 hydrocarbons

- as well as a gas stream,

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

and also

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

is obtained. 1 2

The aqueous phase containing the compound of the type R -0-R is given either for cleaning or to the first rectification. By rectification takes place

1 2

Separating into a concentrated solution of the compound of the type R is -OR in water

1 2

(Preferably not less than 75% compound of the type R -OR) and in a with

1 2

Compound of the type R is -OR polluted water (preferred content of the compound of

1 2

Type R is -OR to 5), which is applied for cleaning. In any case

1 2

made purification of the compound of the type R is -OR carried out either as described in more detail below, by a catalytic decomposition of methanol and / or other

1 2

Compound of the type R -OR, or by biological methods.

1 2

The converter of the synthesis of compounds of type R and -OR synthesizing gasoline with removal of the heat of the exothermic reaction from the reaction zone, have heat transfer surfaces, by which the reaction heat is transferred to a boiling heat transfer. The heat carrier (or its vapors) is condensed in a cooling zone, which preferably contains boiling water to generate steam. The condensate flows into the zone of the heat of reaction back (principle of "heat pipe").

1 2

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

The heat of reaction is preferred for generation of steam with a

1 2

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

The transfer of heat through the heat transfer area for generating the water vapor permitted, the dilution of the feed streams with circulating gas up to 150 real m 3 / m 3 catalyst in the converter of the methanol synthesis (hereinafter referred to cycle gas) and 0 - 150 real m 3 / m 3 catalyst in the converter of gasoline synthesis (hereinafter circulating gas) limit.

The inventive method for production of gasoline from synthesis gas involves contacting the synthesis gas with the catalyst in the first converter (converter of the synthesis of oxygenates) under the conditions of the synthesis of compounds of type R 1 -0-R2. The term "compound of the type R 1 -0-R 2" - where R 1 - alkyl radicals having 1 to 5 carbon atoms, - R 2 - hydrogen, alkyl and alkoxy groups having

1 to 5 C-atoms. Preferred compounds of the type R 1 -O-R2 include methanol (R 1 = CH 3 and R 2 = H) and optionally dimethyl ether (R 1 = R 2 = CH 3), in particular in the converter of

Synthesis of compounds of the type R 1 -OR 2 (hereinafter also called the methanol synthesis converter) synthesized methanol or mixture of methanol and dimethyl ether.

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

Is preferably used as starting material for the synthesis of compounds of the type R 1 -OR 2 synthesis gas.

found in the converter of the synthesis of compounds of the type R 1 -OR 2 (when the

Compound of the type R 1 -OR 2 is methanol), in particular the following reactions take place:

CO + H 2 0 <-> C0 2 + H 2 water gas shift reaction

CO + 2 H 2 i> CH 3 OH methanol formation and optionally with the use of an additional acid catalyst component for methanol synthesis catalyst for the synthesis of dimethyl ether:

2 CH 3 OH i> CH 3 -0-CH 3 + H 2 0 DME formation

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

For methanol synthesis preferably come from the prior art known, conventionally used for methanol synthesis catalysts (such as zinc chromium oxide catalysts, copper-based catalysts with the addition of zinc oxide and / or aluminum oxide;. Combinations of copper and rare earth elements; copper oxide / zinc oxide catalysts and copper / zinc oxide / chromium oxide catalysts and others) are used.

For the synthesis of a mixture of methanol and dimethyl ether come from the prior-art catalysts in the synthesis of methanol with a catalyst of dehydration, in particular, catalysts with pronounced acidic properties, z. B. ^ Al 2 0 3 or zeolites in protonated form having a high acidity, as a mixture or individually used.

The corresponding catalysts and conditions are well known and are described, for example, for methanol synthesis in the book by MM Karawaewa among others "Technologija sintetitscheskogo metanola», M .: Chimija, 1984 and for the DME synthesis in patent US 3,894,102.

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

Separation takes place, the unreacted components of the synthesis gas (CO, H 2, C0 2, nitrogen and others) are preferably partly in the first converter of the synthesis of

Compounds of the type R 1 -OR 2 is returned, ie they are the gas mixture used used, which contains CO and H 2, is mixed and, in part, the unreacted synthesis gas in the converter of the synthesis of gasoline to suppress the reaction of the decomposition of the compounds of the type R 1 -OR 2 fed. At the same time, it is preferable to another part of the process to prevent the accumulation of inert components discharged. The feed a portion of unreacted components of the synthesis gas in the converter of the gasoline synthesis is realized with a volume flow at the inlet to the converter of the gasoline synthesis which includes a hydrogen partial pressure of not less than 0.07 MPa, and the CO of not less than 0.08 MPa ensured.

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 are used catalyst, while the volume of the recycle gas which does not to a large extent from unreacted synthesis gas and short chain hydrocarbon gases exists, based on 1 m 3 of catalyst, preferably less than 150 m 3. Gasoline Synthesis:

In the converter of the gasoline synthesis of the contact of at least part of the place

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

Catalyst held in a preferred degree of conversion of the compound of the type R 1 -OR 2 from 85% to 99.5%.

In the converter of the synthesis of gasoline, the contact with the catalyst, either the entire current from the converter for the synthesis of compounds of the type R 1 -OR 2 or all of (or at least a part of) the liquid component of the product stream with a portion of the gas components takes place of product stream of the converter for the synthesis of

Compounds of the type R 1 -OR 2 instead of what in the feed current of the converter of the gasoline synthesis, converted to 1 m 3 (i. N.) gas flow, a partial pressure of H 2 greater than 0.07 MPa and a partial pressure of CO of more than 0.008 MPa ensured. These values for the partial pressures of H 2 and CO ensure the suppression of the reaction of the decomposition of the compounds of the type R 1 -OR 2 in the converter of the gasoline synthesis.

There are a wide range of catalysts for the synthesis of hydrocarbons from methanol and dimethyl ether. A part of them is in the book by Nefjodow BK, Konowaltschikow LD, Rostanin NN "catalysts Petroleum and Petrochemicals, on the basis of zeolites with high silicon content," M: ZNIITENEFTECHIM, 1987, 59 p described The catalyst of the synthesis of gasoline. out

Compounds of the type R 1 -OR 2 preferably contains at least in part, a protonated zeolite (z. B. HZSM-5), preferably from the group of 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 elements of group Ib. Also, combinations of silicon dioxide with oxides of metals (gallium and / or indium oxide) may be used (US 4,507,404 from 1985 EP 0,070,690 from 1983 EP 0,124,999 from 1984). For example, gallium and / or indium oxide with thorium oxide and a silicon-rich zeolites combined a high-quality, aromatics-rich gasoline can be obtained (EP 0,070,690 from 1983).

The fed into the second converter input material is either the entire first

The product stream or the part which contains the compound of the type R 1 -OR. 2 The partial pressure of the compound of the type R 1 -0-R 2 (preferably of the methanol and the dimethyl ether if necessary) is in the feed of the converter of the gasoline synthesis, converted to 1 m 3 (i. N.) gas stream, particularly advantageously less than 0.5 held MPa (advantageous distinguishing feature).

The partial pressure of water vapor in the feed of the converter of the gasoline synthesis is particularly advantageous under 0.3 MPa (advantageous distinguishing feature).

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

The inventive method is characterized in that the contact of the feedstock with the catalyst in the second converter is carried out in the presence of hydrogen and carbon monoxide. This advantageously the selectivity of the reaction of

Compound of the type R 1 -OR 2 (preferably methanol and dimethyl ether if necessary) increases in hydrocarbons, as their decomposition is suppressed to carbon oxides and hydrogen.

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

Preferably, the reaction of the compound of the type R 1 R 2 -O- is (preferably of the methanol and the dimethyl ether if necessary) in the converter of the gasoline synthesis more than 85% and less than 99.5% for methanol and more than 92% and less than 99.8% of dimethyl ether. The non-complete conversion of the compound of the type R 1 -OR 2 is an essential distinguishing feature of the invention, which permits the selectivity of the process (yield of the gasoline fraction, based on the hydrocarbon content of the unreacted

Compounds of the type R 1 -OR 2) to control (operating time of the process between regenerations of the catalyst) in connection with the necessary quality of the produced gasoline and the duration of Zwischenregenerationszyklusses. This is the reason that in the present invention fuel having a content of aromatic compounds of less than 46%, with a contained amount of benzene from less than 1 Mass.-%, of isoparaffins of over 40% (with high octane number characteristics 93-96 RON) is obtained, which is also a distinctive feature of the invention.

In addition to the petroleum hydrocarbons the product of the synthesis gas contains from

1 2

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

1 2

Methanol and other compounds of the type R -OR, as well as a "dry" gas. This "dry" gas mainly containing 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 Benzinsvnthese:

The product of the gasoline synthesis is cooled and separated into unstable gasoline, an aqueous phase and in the non-condensed gas components. The separation is preferably performed by a physical separation phase in a three phase separator. The uncondensed gas components include components of synthesis gas, light hydrocarbons (C, and C 2), traces of heavier hydrocarbons. This circulating gas is to at least partly to the converters of gasoline synthesis and / or

1 2

Converter of the synthesis of compounds of type R is -OR returned. With the volume of the circulating gas in the converter of the gasoline synthesis of the partial pressure of the methanol and water can be adjusted advantageously.

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

The separated in the three phase liquid hydrocarbons include petroleum hydrocarbons, which are preferably sent to a rectification column in which, when necessary, preferably the components of the heavy gasoline (Durolfraktion) and overhead gases - mainly C 3 -C 4 - hydrocarbons and residues of C 1 -C 2 - hydrocarbons (short-chain hydrocarbons) and synthesis gas components are separated off. With a permissible content of durene in gasoline hydrocarbons, the heavy gasoline is not separated. The resulting stable gasoline fraction with a necessary saturated vapor pressure of less than 500 to 700 mm Hg (in function of the required type of gasoline) is either commercial gasoline or forms the basis for the production of commercial gasolines having an octane number of 92-98 (RON).

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

the aqueous phase is preferably at a defined methanol content or with other

Compounds of the type R 1 -OR 2 is first separated in a rectifying column because of 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 with a small methanol content (contaminated water) contains the other fraction of water. The concentrated methanol or optionally dimethyl ether or other compound of the type R 1 -OR 2 is preferably returned to the converter of the gasoline synthesis. The contaminated water contains a residual content of methanol (usually max. 5 Ma.-%) or another compound of the type R ^ OR 2.

To remove the residual methanol from the contaminated water of fiction, modern

Process, methanol is decomposed and optionally another compound of the type R 1 -OR 2 by the contact with a catalyst (steam reforming or catalytic decomposition) into hydrogen and gaseous carbon oxides catalytically. The water is separated after cooling, by condensation of the generated oxides of carbon (CO and C0 2) and hydrogen. The carbon oxides and hydrogen can advantageously be mixed with the synthesis gas and in the process of synthesis of compounds of type

R 1 is -OR 2 are returned. After the separation of gases, is advantageously obtained chemically purified water 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 which (if necessary, preferably methanol, dimethyl ether) comprises a compound of the type R 1 -OR 2, with the catalyst is preferably implemented at a pressure, which allows the components of the synthesis gas produced in the first converter directly or initiate using a cycle compressor in the first converter. This pressure corresponds to the sum of the reaction pressure for the synthesis of compounds of the type R 1 -0-R 2 and the pressure loss between the outlet of the product of the catalytic methanol decomposition and entry of the feedstock into the converter, the methanol synthesis.

Alternatively, the residual content of the chemical compound of the type R 1 -OR 2 can be removed in the water by a biological purification process. The biologically treated water can be discharged into the sewage network.

However, it must be considered that the biological purification of water in a methanol content of less than 0.2 - 1 requires Mass.-%, obtaining a concentration by rectification is associated with high energy demands, or it is a great dilution of the contaminated water required with pure water, which increases the cost of the biological treatment.

The use of the catalytic purification of the water of compounds of type R x -0- R is a further advantageous distinguishing feature, since it allows to control the process conditions in the converter of the gasoline synthesis of relatively low cost, the degree of conversion of compounds of the type R 1 -OR 2 to decrease, thereby achieving a high selectivity and quality of the products.

Investment:

The invention is also a plant for implementing the inventive method.

This facility includes:

a. To catalyze) at least one first converter, containing a catalyst, which is suitable for the reaction of CO with H 2 (to the chemical compound of the type R 1 -OR 2 preferably methanol),

b. ) To catalyze at least one second converter, which contains a catalyst, which is suitable for the conversion of the chemical compound of the type R 1 -OR 2 in hydrocarbons,

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

separate product stream comprising petroleum hydrocarbons and chemical

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

contains traces of CO and aliphatic hydrocarbons,

d. ) At least a third converter, which contains a catalyst, which is suitable for the reaction of the chemical compound contained in the water of the type R x -0-

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

The above components are preferably connected in series, that is, the first converter is connected to directly or indirectly to the second converter, that at least a part of the product stream from the first converter to the second converter is initiated. The second converter is connected to the separator c.) So that the product stream from the second converter into the separator c.) Is conducted. In this case), the separator c. Indirectly connected to the third converter, so that the water which has been separated in the separator c.), And contains the chemical compound of the type R 1 -OR 2, wherein need for a prior distillative separation of the bulk of of the

Compound of the type R 1 -OR 2 is geleitetet to the third converter. The separator c.) Is also due to a connection to the second converter, which allows the short-chain hydrocarbons and the other components of the gas phase of the separator c.) To the input to the second converter. Preferably, the plant includes a third connection line from the converter to the first converter, which enables to initiate formed in the third converter CO and H 2 in the first converter.

To carry out the variant of the process with separation of the first product stream, the plant comprises an additional separator for separating the product stream from the first converter. In this case, preferably, the additional separator has a connecting line to the first converter, which enables to initiate separated in the separator CO and H 2 in the first converter. This (additional) Separator preferably also includes a first connecting line to the second converter, which allows chemical compounds of the type R 1 -OR 2, feeding when necessary after removal of at least a portion of the water in the second converter and a second , optionally at least includes connecting line to the second converter, which allows a portion of the gas stream containing CO and H 2 introduced to the second converter.

To carry out the model with the direct introduction of the (complete) the first product stream in the second converter of the first converter in the system is directly connected to the second converter by a material flow, so that the entire product stream from the first converter without separation in the second converter is initiated. In this case, preferably, the separator c.) A connecting line to the first converter, which makes it possible, due to the dry gas (unreacted CO and H 2 as well as short-chain hydrocarbons) in the first converter.

In either case, a separation of the second product stream into hydrocarbons petroleum hydrocarbons, gas and water takes place included. The water containing unreacted chemical compound of the type R 1 -OR 2 is preferred (in a separator c.) Downstream device preferably a rectification column) containing the

is possibility (if necessary, DME and preferably methanol) to separate a product with a high content of compound of the type R 1 -OR 2 in water which can be added again to the starting material of the second converter. Therefore, this separator c.) downstream device preferably has a connection line for returning the separated concentrated solution of the chemical compound of the type R 1 -OR 2 in the water in the second converter on. This additional apparatus is the

Compound of the type R 1 -OR 2, however, is not completely removed from the water. therefore, the additional device also has a connecting 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 type R is -OR disassembled.

1 2

For the decomposition of the compound of the type R -OR (preferably the methanol and possibly the DME) can be used known catalysts, an overview in the article of Klabunowski EI including "catalysts of the conversion of methanol into synthesis gas" (catalysis in industry, 2004 N. 6, pp 3-9), where, as well as the catalysts of steam reforming of CO, the catalysts of the methanol synthesis and other catalysts.

In step d.) A converter of any type can be used, is preferably a Durchströmkonverter fixed bed of a granulated catalyst. The converter used in step d.) Is hereinafter referred to as converter water purification.

The organization of a continuous process of production of synthetic gasoline from synthesis gas are preferably not one, but two converters used: a converter works in a mode of reaction, the second converter operates in a mode of regeneration of the catalyst.

The term converter is used synonymously in the description of the invention with the reactor. The converters used in step a.) And / or step b.) Are preferred Durchströmreaktoren, in which the catalyst is introduced as a fixed bed.

the first and / or second converters are preferably cooled. The cooling is preferably carried out by indirect evaporative cooling. . The reaction is carried out in step a.) And / or step b) is approximately isothermal as possible. The converters are preferably designed such that they allow direct and complete removal of the reaction heat produced in the catalyst bed and thus allow the reaction at approximately constant temperature in the volume of the reaction space.

The heat removed by the cooling in the first and / or second reactor reaction heat can be advantageously used for the generation of steam.

The first converter (methanol synthesis, and DME synthesis, if necessary) preferably has a ratio of heat transfer area to the catalyst volume of not less than 50

2 3

m In and not more than 400 m 2 / m 3. With the discharged in the first converter heat of reaction is preferably water vapor at a pressure of not less than 0.6 MPa and generates not more than 4 MPa.

The second converter (gasoline synthesis) preferably has a ratio of 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 discharged in the second converter heat of reaction is preferably water vapor at a pressure of not less than 3.0 MPa and generates not more than 22 MPa.

The heat dissipated by the generated steam heat of reaction can be advantageously used for production of a refrigerant which can be used for product separation according to step a.) And / or after step b.).

The synthesis gas used in the process can be obtained from various starting materials. The starting materials can 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 used to prepare starting materials and the production method. The synthesis gas typically contains also inert components (such as N 2 and water). The synthesis gas is preferably purified of catalyst poisons (sulfur compounds, nitrogen compounds), and foreign matter, dried and, when 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 obtained. With a smaller ratio, the yield is reduced to methanol (DME), and it increases the yield of C0. 2

The individual process steps of the method according to the invention are described with reference to preferred embodiments:

Gasoline from synthesis gas is generated in two steps. In step a), the synthesis of

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

Step b.) The conversion of the compounds of the type R 1 -OR 2 at a zeolite catalyst in a mixture of hydrocarbons. The compounds of the type R 1 - OR, which are generated in the first stage may be passed from the first converter to the second stage, or are separated from the product of the first converter in any variant, and then added to the second stage as the entire product stream.

From the product of the first converter can take dimethyl ether are separated as starting material for the second stage of methanol and, including a mixture with water. Unreacted synthesis gas is preferably separated from the product of the first converter or from the product of the second converter and the first converter for the synthesis of

Compounds of the type R 1 -OR 2 recirculated.

The synthesis gas can be advantageously used as a crude mixture, but is preferably dried and compressed at need and mixed with the recycle gas to a temperature which is close to the reaction temperature, heated, for example. As in recuperative heat exchangers and / or heaters (steam heaters, stoves, and / or electric) and the first converter (in the figures - Block I) for the synthesis of compounds of type

R 1 -OR 2 (methanol and optionally dimethyl ether) passed. In the preparation of compounds of the type R 1 -OR 2 of the contact with the catalyst for methanol synthesis or with the catalyst of the methanol synthesis catalyst and the dehydration of methanol to dimethyl ether (DME) is carried out.

For methanol synthesis in step a.) Preferably copper-containing catalysts are 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 having a heat effect of 90.73 kJ / mol of methanol. Therefore,.) Is preferably used an isothermal converter cooling in step a. This is able to reduce the required volume of the recycle gas and carry out the synthesis under optimum conditions, with a corresponding reduction of the formation of by-products, an increased yield of methanol, an extension of the duration of the catalyst and the generation of medium pressure - Water steam for use as an energy source.

The product from the converter of the synthesis of compounds of the type R 1 -OR 2 is preferably cooled in heat exchangers by the material flow (synthesis gas) is preheated. As a variant, the product stream can preferably be separated into a gas product and a condensate. For this, the product preferably in air coolers and water coolers, and in the presence of dimethyl ether in the product, even using deep cold, cool. The organic components and water are condensed. The condensate (crude methanol, water content to 20% and mixture of dimethyl ether, methanol and water) is deposited in the separator. The product gas from the separator is unconverted synthesis gas, part of which is returned to the first converter for mixing with the starting synthesis gas conversion is complete.

As a variant, the separator can be followed by a rectification column for separating the water from the mixture with the organic components, since the presence of water in the feed material for the second converter for converting the

Compounds of the type R 1 -OR 2 in hydrocarbons, the irreversible deactivation of the zeolite catalyst used in the second converter accelerated. 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 in the second converter - fed (on the pictures III Block) synthesizing gasoline, where they preferentially with the recycle stream of the methanol (stream 11 in the figures 1 + 2) from the block V, the gas with the recycle stream of light hydrocarbon (stream 7 in Fig. 1) from the block IV and the stream of unreacted synthesis gas (stream 5 in Fig. 1) is mixed from the separator (block II). The mixed stream is preferably in the recuperator - heat exchangers and heaters and fed into the converter for gasoline synthesis.

The presence of hydrogen and carbon monoxide in the inventive method in the zone of the reaction of methanol (and optionally dimethyl ether) is reduced, at least in part, the undesirable decomposition of methanol to hydrogen and carbon monoxide in Step b.). Thus, the selectivity of the formation of hydrocarbons is advantageously increased. The partial pressure of hydrogen is preferably higher than 0.07 MPa and the partial pressure of carbon monoxide is greater than 0.008 MPa. In order that the required effect is achieved either hydrogen and carbon monoxide with the previously separated methanol from the first product stream (and optionally dimethyl ether) were mixed, or the first product stream containing still unreacted synthesis gas is passed directly to the second converter. The hydrogen and carbon monoxide are used in the second converter as a diluting component, that is, they dilute the starting material (and optionally methanol DME). The dilution of the methanol (the methanol + 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 water is less than 0.3 MPa.

The product from the converter to the gasoline synthesis is preferred in recuperator - cooled heat exchangers, wherein preferably the feed of the converter (methanol and DME, if necessary), it is possible in a mixture with the circulating gas is heated. The cooled stream is preferred for the second separator transferred (in the figures block IV) to separate the converter product of the gasoline synthesis. On cooling in the recuperator and in the coolers, the petroleum hydrocarbons condense a portion of the light

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

R contains from 1 -OR 2, 2. the petroleum hydrocarbons and 3. the gas phase containing hydrogen, carbon oxides and light hydrocarbons (mainly to 4 carbon atoms, predominantly methane and C 2 -C 4 - hydrocarbons), which is in the conversion of methanol forming, separately. A portion of the gas phase with a portion of CO - mixed-containing gases from the first separator (in the figures Block II), and preferred as the diluent components to the feed (methanol and optionally DME) recycled to the converter of the gasoline synthesis - and H 2.

The condensate of petroleum hydrocarbons from the separator c.) Is preferably heated and passed to the stabilization column in which the light overhead gases (short-chain hydrocarbons, substantially propane, propylene, butane, butylene, and also methane, ethane, ethylene and H 2) from the stable gasoline (stream 8 on the pictures) are separated. Possibly. the C 3 -C 4 may - hydrocarbons are separated as a liquid fraction C 3 -C 4 alkyl. From the petroleum hydrocarbons which are fed into the stabilization column, also naphtha can (stream 9 on the pictures) are separated in the stabilizing column or in an additional column.

The aqueous phase (stream 10 on the pictures) from the separator c.) Can (as a variation in a rectification column block V on Fig. 1 + 2) and then (to the converter, the water cleaning block VI on Fig. 1 + 2) are conducted. In the

Rectification column takes place, the concentration of the compound of the type R 1 -OR 2 (stream 11 to the Fig. 1 + 2). This recycle stream is fed into the block of the gasoline synthesis. The water obtained in the bottom of the column, which contains residual contents of R 1 -OR 2 is passed to the converter water purification. The aqueous phase from the separator c.) Can also be added directly to the water purification.

Based on the figures below two preferred variants of the method according to the invention are explained in detail.

Fig. 1 shows the block diagram for a preferred manufacturing process of gasoline from synthesis gas by the inventive process 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 methanol in water in connection to the distillative separation of the main amount of methanol from the process water.

Fig. 2 shows the block diagram for a preferred manufacturing process of gasoline from synthesis gas by the inventive process with a 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 converter of the gasoline synthesis and the catalytic decomposition of the methanol in the water after the distillative separation of the main amount of methanol from the process water.

In Fig. 1, synthesis gas 1, the principal components hydrogen and carbon monoxide in a ratio that depends on the method of their production, but which also contains inert components, purified of catalyst poisons and admixtures, compressed at need, and (in the first converter block I ) of the synthesis of compounds of type

R 1 is -OR fed 2 where it is mixed with the recycle gas. 3 The resulting mixture is preheated to the reaction temperature in the recuperator -Wärmetauschern and heaters (vapor and / or Elektroerhitzern, ovens) and in the converter of the synthesis

Compounds of the type R 1 -O-R2 conducted. In the preparation of compounds of the type R 1 - OR of the contact with the catalyst for methanol synthesis or with the catalyst of the methanol synthesis catalyst and the dehydration of methanol to dimethyl ether takes place. In the synthesis of methanol, the use of copper-containing catalysts at a temperature of up to 260 ° C and a pressure of up to 8 MPa is preferred, but it can also zinc chromium catalysts at a temperature of up to 360 ° C and will be working at a pressure of more than 8 MPa, is used.

The product from the converter of the synthesis of compounds of the type R 1 -OR 2 is cooled in heat exchangers by the raw material stream is preheated, and also deep in the air and water cooler, in the presence of dimethyl ether in the product is for cooling

Refrigerant used, the compounds of the type R 1 -OR 2 and water condense. The condensate (crude methanol, water content to 20% and mixture of dimethyl ether, methanol and water) in the separator (Block II) is deposited. The product gas from the separator is unreacted synthesis gas, part of which (stream 3) is passed to be mixed with the output of syngas for complete conversion of the raw material. the in

Separator separated compounds of the type R 1 -OR 2 4 (methanol and optionally DME) are mixed with the recycle stream of the methanol 11 in block V, the recycle stream 7 of the light hydrocarbon gases from the second separator (Block IV) and the flow 5 of the non- reacted synthesis gas from block II, preferably the product gas from the separator are mixed. The components are after mixing, preferably in recuperator - heated in heaters and fed into the converter of the gasoline synthesis heat exchangers and / or.

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

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

Both converters (block I and III) are preferably cooled converter. 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 the gasoline synthesis of below 150 real m 3 / m 3 catalyst. The steam generated in cooling the converter is as described above, to produce a refrigerant by means of an absorption refrigerating machine used in steam heaters for preheating the feed currents of the first converter and the bottom heating of the column for product separation.

The product from the converter to the gasoline synthesis (Block III) is in the recuperator - cooled heat exchangers, wherein the feedstock of the converter is heated further, it is cooled in coolers. In the process of cooling a condensation of petroleum hydrocarbons and water takes place. The cooled stream 6) (Block IV) for separating the reactor product of the gasoline synthesis is transferred to the separator. C. are 1. In the separator c.), the methanol-containing water 10, 2. the gasoline hydrocarbon phase 8 + 9 and 3. the gas phase 7 containing hydrogen, carbon oxides and light hydrocarbons formed during the conversion of methanol, separated.

The recycle stream of light hydrocarbon gas 7 is in the highlighted case with part of the CO - and H 2 - mixed gases containing 5 from the first separator (Block II), a diluent component for the starting material in the synthesis of

to obtain compounds of the type R 1 -OR. 2 The hydrocarbon condensate (including C 5+ - hydrocarbons) 6 from the separator (Block IV) is performed to stabilize column (Block IV), in which the light overhead gases are separated from the stable gasoline 7. 8 For the unstable petroleum hydrocarbons may also naphtha 9 are separated in a stabilization or an additional column.

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

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

Water purification of compounds of the type R 1 -OR 2 conducted. The water contains here, depending on the degree of conversion, usually between 3.5% and 30 Mass.- Mass.-%

Compounds of the type R 1 -OR. 2

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

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

. The manufacturing process shown in Figure 2 is a simplified variant of the method illustrated in Figure 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 directly fed without prior separation, to the converter (Block III) of the gasoline synthesis.

As a diluent component of the oxygen-containing feedstock recirculated recycle gas may here also be added 3 (Block IV from here).

Here, too, the synthesis gas is mixed with 1 prior to or at the feed into the first converter in addition to the circulating gas 3 is additionally hydrogen and carbon monoxide 13 which is formed in the converter of the catalytic water purification (block VI). The product from the first converter corresponds in its composition is substantially the product of the method in FIG. 1.

To obtain a maximum high gasoline quality (low proportion of heavy gasoline), the conversion of the compound of the type R 1 -OR 2 (optionally methanol and DME) preferably below 99.5%.

The product from the converter of gasoline synthesis is preferably cooled again first in the recuperative heat exchangers and coolers. The partially cooled stream 6 is fed into the block IV of the separation of the products of the converter of the gasoline synthesis, where by the cooling in the coolers takes place condensation of the petroleum hydrocarbons and water. In the separator, the water 10 containing unreacted compounds of the type R 1 -OR 2 is deposited and the gasoline hydrocarbon phase and the gas phase will be separated. The product gas from the separator is composed mainly of unreacted synthesis gas, and light hydrocarbons, a portion thereof (stream 3) (block I) is recycled for mixing with the output of syngas for complete conversion of the raw material in the first converter.

The water formed in the converter of the gasoline synthesis here contains, depending on the degree of conversion, usually between 3.5% and 40% methanol (and optionally DME). therefore, it is carried out 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 (where these gases are recycled as an additive to synthesis gas in the process - see description of Fig. 1).

The hydrocarbon condensate from the separator (Block IV) is performed to stabilize column (Block IV), in which the gasoline is separated. 8 For the unstable petroleum hydrocarbons may also naphtha 9 are separated in a stabilization column or an additional column.

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

Compounds of the type R 1 -OR 2, and then fed into the converter of water purification (block VI). In block V the concentration of the compounds of type R x R -0- enrichment of the methanol is realized in the head part in a rectification column and there is obtained a recycle stream 11 of this methanol that is returned in block III the gasoline synthesis. The bottom product of the column - the water 12 containing 5% of methanol 2-5 is fed (block VI) in the converter of water purification.

In block VI cleaning the methanol-containing stream of water is preferably promoted, where it is heated to the required reaction temperature by the recuperative heat exchanger and / or preheater and then fed into the converter water purification, where the contact with the catalyst of the decomposition of methanol in hydrogen and carbon oxides is realized.

The product from the converter of water purification is preferably cooled in recuperative heat exchangers and air coolers. Subsequently, the gas phase is separated from the condensate in a separator. The separated gases thereby the decomposition of the methanol 13 exit the separator, and (Block I) are passed to be mixed with the raw synthesis gas in the first converter. The purified water is conveyed to the degasifier. It is chemically obtain purified water 14, which is used to refill the rear of the cooling water system, the system of steam generation and for other purposes.

By the Fig. 1 and 2 shown the converters are water cooled indirectly. The water absorbs the heat from a heat transfer medium, which in turn transfers heat from the reaction zone. The water leaves block I and III as steam.

In the following the invention is further illustrated with a comparative example and 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", conducted 1987th

On Fig. 3 is a block diagram of the process TIGAS is illustrated.

Synthesis gas is mixed with recycle gas, which contains unreacted components of the synthesis gas and light hydrocarbons and enters the reactor, the synthesis of methanol + DME with a bifunctional catalyst which comprises a catalyst component of the methanol synthesis and a catalyst component of the dehydration of methanol, a , The resulting mixture of methanol + DME + water and of components of the unreacted synthesis gas is added to the gasoline synthesis step where the conversion of methanol and DME is taking place on a zeolite catalyst into hydrocarbons. The product mixture is then dissolved in benzene, an aqueous phase, which is given for cleaning, a C3-C4 fraction and gas, a part of which is passed as a circulating gas to the stage of synthesis of oxygen compounds separated. All stages are at an approximately equal pressure in the range of 50 - carried out bar 100th

There is synthesis gas containing H 2: CO = used. 3

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

Overall, the yield of gasoline 73.34, based on CH 2 in the synthesis gas without taking into account losses in product separation, etc .. In addition, examples of different variants of the process execution according to the invention are listed weight.

Here, a real synthesis gas with the following composition, in percent by volume, used: CO - 21.91; H 2-61.16; C0 2 to 6.38; CH 4 to 1.83; H 2 0 to 8.72.

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

For the synthesis of methanol from synthesis gas, a catalyst Südchemie with the label MEGAMAX 700 ® (components CuO, ZnO, A1 2 0 3) and for the synthesis of gasoline from methanol, a zeolite-containing catalyst Südchemie called SMA-2 used.

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

is located in the converter of the gasoline synthesis in Examples 2 to 4, 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 the methanol synthesis and gasoline synthesis are cooled. It will converter having a heat transfer area of 60 m 2 / m 3 of catalyst used.

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

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

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

The plant of production of synthetic gasoline mainly corresponds to the scheme on Fig 1 and consists of:. A block (Block I) the synthesis of methanol from synthesis gas, one block (Block II) the removal of methanol from the product stream of the block I, a block (block III) the synthesis of gasoline from crude methanol, a block (block IV), fractionating with separation of the product gasoline, one block (block V) the separation of methanol from the process water.

In contrast with the scheme in Fig. 1, however, the block of water purification of methanol is not in operation. In the complex also absent in contrast to Fig. 1, the flows 5, 13 and 14, ie in the block III of the stream 5 is not given.

Table 2.1. Material balance of the plant

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

99%

Synthesis gas from the block in 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 CH2 of the methanol, ** based on CH 2 of the synthesis gas. Table 2.2. Characterization of the currents in the chart on Fig. 1

example 3

The plant of production of synthetic gasoline mainly corresponds to the scheme on Fig 1 and consists of:. A block of the synthesis of methanol from synthesis gas (Block I), a block (Block II) separation of the methanol from the product stream of the block I, a block (block III) the synthesis of gasoline from crude methanol, a block (block IV), fractionating with separation of the product gasoline, one block (block V) the separation of methanol from the process water.

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

Regimen with generation of catalyst selectivity of conversion of the conversion of synthetic gasoline from gasoline synthesis: methanol: the (CO + C0 2) in

Crude methanol without the block SMA-2 99% conversion of methanol: water purification from methanol 94.2% in petrol:

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 the currents in the chart on Fig. 1

Physical Properties Composition of the streams [Mass.-]

the material flows

T [U C] P Massenstro 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 to 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 3.49 486.2 2.15 34.32 0.16 to 53.19 6.69

8 40.4 79.2 0.70 - - - - 0.01 2.97 97.02

9 45.4 0.60 18.2 - - - - - - 100.00

10 0.40 5.0 180.9 - - 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 plant of production of synthetic gasoline corresponds to the scheme on Fig 1 and consists of:. A block (Block I) the synthesis of methanol from synthesis gas, one block (Block II) separation of the methanol from the product stream of the block I, a block ( block III) the synthesis of gasoline from crude methanol, a block (block IV), fractionating with separation of the product gasoline, one block (block V) the removal of methanol from the process water, a block (block VI) of water purification from methanol.

Table 4.1. Material balance of the plant

Regime generating catalyst the conversion of the selectivity of the conversion of methanol synthesis of synthetic gasoline conversion of (CO + C0 2) in gasoline from crude methanol ". , ,, "" "Methanol to gasoline, methanol

9 I / 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 the currents in the chart on Fig. 1

example 5

The plant of production of synthetic gasoline corresponds to the scheme on Figure 2 and includes:. A block (Block I) the synthesis of methanol from synthesis gas, one block (Block III) synthesizing gasoline without removal of methanol from the product stream of the block I , a block (block IV), fractionating with separation of the product gasoline, one block (block V) the removal of methanol from the process water, a block (block VI) of water purification from methanol Table 5.1. Material balance of the plant

Regimen with production of catalyst, the conversion of selectivity of the conversion of synthetic gasoline from gasoline synthesis: methanol: conversion of (CO + C0 2) in the flow of methanol to 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 the currents in the chart on Fig. 2

Physical properties of composition of the streams, Mass.-%

the material flows

TP MassenH 2 CO CO 2 H 2 0 CH 3 OH C 1 -C 4 5+ c current [

[° C] [MPa]

kg / h]

1 60.0 5.70 329.5 11.68 58.17 26.61 0.76 to 2.78 -

2 117.5 4.35 2263 6.01 7.46 39.23 1.37 11.77 32.56 1.6

3 29.9 4.9 1,931.7 6.94 8.59 44.88 0.04 to 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 79.9 0.70 - - - - 0.01 3.07 96.92

9 45.4 0.60 16.9 - - - - - - 100,000 0.40 5.0 181.2 - - 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 to 100.0 - - - 0

LIST OF REFERENCE NUMBERS

On the pictures and the text, the following terms are used:

1 - output synthesis gas

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

3 - recycle gas (synthesis gas recycled from the Block II or IV in the block I)

4 - crude methanol (or starting material of the compounds of the type R 1 -OR 2)

5 - Circulating gas (synthesis gas, which is given by the Block II in the block III)

6 - product of the block of the gasoline synthesis

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

8 - petrol

9 - naphtha

10 - Process water

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

containing waste water, the compounds of the type R 1 -OR 2 (preferably methanol) - 12

13 - gases to 2 (in the separation of compounds of the type R 1 -OR preferably

form methanol)

14 - Chemically purified water

15 - Gas

16 - C3-C4 fraction

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

II - block of separation of the first separator

III - block of synthesis of gasoline to the second converter

IV - block of separation with the second separator and the stabilization of the unstable column

gasoline

V - block of the concentration of the compounds of the type R 1 -OR 2 (preferably

Methanol) in a rectification column from the process water

VI - block the catalytic water purification of compounds of the type R 1 -OR 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 generate a first product stream
- at least one chemical compound of the type R 1 -O-R 2 (where R 1 - alkyl groups having a carbon number of 1 to 5 and
R - hydrogen, alkyl and alkoxy groups having a carbon number of 1 to 5), wherein the chemical compound of the type R 1 -OR 2 is preferably methanol and / or dimethyl ether, as well as
- unreacted components of synthesis gas,
contains
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, to produce a product stream comprising
- petroleum hydrocarbons, including up to 45 degree. -% of aromatic compounds contained therein to 1 degree. -% benzene and not less than 40% Mass.- isoparaffins
- Q-Gr hydrocarbons, which are preferably formed in an amount of not more than 17 Mass.- (converted to C in the unreacted methanol and / or, when necessary, in the unreacted dimethyl ether),
- unreacted compound of the type R 1 -OR 2,
- and also did not react components of the synthesis gas contains,
wherein synthesis gas from the first and / or second product stream is separated and is partially recycled to minimum as recycle gas into the first converter, c.) separation of the product of the second converter, wherein the unstable gasoline is stabilized by known methods, wherein
i. ) A gasoline fraction from which at need a fraction containing durene, is separated off,
ii. ) A fraction of C3-C4 hydrocarbons
iii. ) A gas stream containing light hydrocarbons and unreacted
contains components of the synthesis gas, and
iv. ) Contains an aqueous phase, the unreacted compound of the type R 1 -OR 2, preferably methanol and / or dimethyl ether,
be obtained
wherein the guest current iii.) is partially returned to minimum in the second converter and / or in the first converter as a circulating gas,
and the aqueous phase iv.) directly to the purification of the compound of the type R x R -0- or is first added to the rectification by the rectification wherein a
Separating into a concentrated solution of the compound of the type R 1 -OR 2
(Preferably not less than 75%) and one with the compound of the type R 1 -OR 2 polluted water (preferably containing compound of the type R 1 -OR 2 to 5%) occurs, which is applied for cleaning.
2. The method according to claim 1, characterized in that the feedstock of the second converter a partial pressure of hydrogen of more than 0.07 MPa, a partial pressure of the oxides of carbon of greater than 0.008 MPa, a partial pressure of the compound of the type R 1 -OR 2 (preferably methanol and / or of the dimethyl ether) of less than 0.5 MPa and a water partial pressure of less than 0.3 MPa.
3. The method according to claim 1 or 2, characterized, in that the conversion of
Compound of the type R 1 -OR 2 (preferably methanol) in step b.) Is 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 % by weight.
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 nearly isothermal conditions, which through the heat of reaction by the heat transfer surface at a ratio of heat transfer area to the volume of the catalyst of not less be 50 m 2 / m 3 achieved.
5. The method according to claim 4, characterized in that is produced by the discharged from the first converter heat of reaction steam at a pressure of up to 4 MPa, wherein the volume of the recycle gas which did not react contains components of the synthesis gas, and which in the first converter is fed, not real 150 m 3, relative to 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 in the second converter takes place under nearly isothermal conditions, which through the heat of reaction by the heat transfer surface at a ratio of heat transfer area to the volume of the catalyst of not less be 40 m 2 / m 3 achieved.
7. The method according to claim 6, characterized in that steam is generated at a pressure of up to 22 MPa by discharged from the second converter heat of reaction, and the volume of the circulating gas stream iii), which light hydrocarbons of the product stream of the second converter, and also unreacted components of the synthesis gas contains a value to 150 real m 3, relative to 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 this, purified water and the 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
Compound of the type R 1 -OR 2 (preferably methanol) contaminated water with the catalyst at a pressure is carried out which allows to introduce the generated components of the synthesis gas in the first converter directly or by means of a circulating 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 to the second converter for adjusting the partial pressures of hydrogen and oxides of carbon, in particular carbon monoxide, is fed.
11. Installation for carrying out the method according to any one of claims 1 to 10 comprising:
e. To catalyze) at least one first converter, containing a catalyst, which is suitable for the reaction of CO with H 2 (to the chemical compound of the type R 1 -OR 2 preferably methanol),
f. ) To catalyze at least one second converter, which contains a catalyst, which is suitable for the conversion of the chemical compound of the type R 1 -OR 2 in hydrocarbons,
G. ) At least one separator which is suitable petroleum hydrocarbons from a
separate product stream comprising petroleum hydrocarbons and chemical
Compounds of the type R 1 -OR 2, water and gas, which short-chain hydrocarbons, the synthesis gas components, compounds of the type R 1 -
contains traces of CO and aliphatic hydrocarbons,
H. ) At least a third converter, which contains a catalyst, which is suitable for the reaction of the chemical compound contained in the water of the type R x -0-
R (preferably methanol) 2 to catalyze in CO and H.
12. Plant according to claim 11, characterized in that it includes an additional separator for separating the product stream from the first converter, wherein the additional separator has a connecting line to the first converter, which makes it possible in the separator separated CO and H 2 first in the initiate converter, whereby the (additional) separator preferably has a first connection line to the second converter includes, which allows chemical compounds of the type
R 1 is -OR 2, contains H 2, optionally together with 0 to feed in the second converter and a second connecting line to the second converter, which makes it possible to feed, if necessary, 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 entire product stream from the first converter to the second converter is introduced, the separator c.) Is preferably a connecting line to the first converter contains, which makes it possible to feed unreacted CO and H 2 as well as short-chain hydrocarbons in the first converter.
14. Installation according to one of claims 11 to 13, characterized in that it comprises at least one of the following additional ingredients: i. ) A connecting line from the third converter to the first converter, which makes it possible, formed in the third converter CO and H 2 introduced to the first converter, and / or ii. ) A separator c.) Downstream device that the separation
1 2
the compound of the type R is -OR allows, said plant a connection line for returning the separated chemical
1 2
Compound of the type R is -OR in the second converter contains and / or iii. ) Devices for removing the heat of reaction in the first and / or second
Converter, which preferably enable the generation of steam, wherein the devices for dissipating the heat of reaction in the first converter preferably has a ratio of heat exchange area to catalyst volume of
2 3
In at least 50 m and in the second converter is preferably a ratio of
2 3
having heat exchange area to catalyst volume of at least 40 m Im.
PCT/EP2010/067606 2009-11-17 2010-11-16 Method for generating hydrocarbons, in particular gasoline, from synthesis gas WO2011061198A1 (en)

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JP6116801B2 (en) 2012-01-17 2017-04-19 三菱重工業株式会社 System or method for producing a gasoline
RU2544241C1 (en) * 2014-01-22 2015-03-20 Общество С Ограниченной Ответственностью "Новые Газовые Технологии-Синтез" Method of producing aromatic hydrocarbons from natural gas and apparatus therefor
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