WO2011061198A1 - Procédé de production d'hydrocarbures, en particulier d'essence, à partir de gaz de synthèse - Google Patents

Procédé de production d'hydrocarbures, en particulier d'essence, à partir de gaz de synthèse Download PDF

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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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Prior art keywords
converter
methanol
type
synthesis
catalyst
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PCT/EP2010/067606
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German (de)
English (en)
Inventor
Joachim Engelmann
Genrikh Falkevich
Rashit Temirbulatovich Sarsenov
Original Assignee
Chemieanlagenbau Chemnitz Gmbh
Sapr - Neftekhim Llc.
Too Techno Trading Ltd.
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Application filed by Chemieanlagenbau Chemnitz Gmbh, Sapr - Neftekhim Llc., Too Techno Trading Ltd. filed Critical Chemieanlagenbau Chemnitz Gmbh
Priority to EA201200731A priority Critical patent/EA021044B1/ru
Priority to AU2010320947A priority patent/AU2010320947B2/en
Priority to CA2780483A priority patent/CA2780483C/fr
Priority to CN201080052110.2A priority patent/CN102686540B/zh
Publication of WO2011061198A1 publication Critical patent/WO2011061198A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516—Multisteps
    • C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1022—Fischer-Tropsch products
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Definitions

  • the invention relates to a process for the production of hydrocarbons, in particular gasoline, from non-hydrocarbon compounds, in particular from synthesis gas, which contains carbon monoxide and hydrogen.
  • Synthesis gas which is primarily a mixture of carbon monoxide and hydrogen, can be generated from various readily available solid and gaseous sources of carbon and hydrogen.
  • the hydrocarbon raw material synthesized based on synthesis gas and the motor fuels are real alternatives to petroleum hydrocarbons and sometimes better in quality. Therefore, the effectiveness of the technology for converting synthesis gas into hydrocarbons has been a current problem for many years.
  • synthesis gas gas can be produced in two stages: first, the synthesis of oxygen compounds (eg methanol or dimethyl ether or a mixture of both compounds), then the conversion of the oxygen compounds on a zeolite-containing catalyst into a mixture hydrocarbons.
  • oxygen compounds eg methanol or dimethyl ether or a mixture of both compounds
  • US Pat. No. 6,191,175 discloses a process for the preparation of methanol or dimethyl ether. For this purpose, first, the synthesis of methanol from synthesis gas, which is preheated in a first reactor. The reaction product is optionally mixed with synthesis gas and reacted again in a second reactor, which also serves either the methanol synthesis or the synthesis of dimethyl ether. In order to achieve high product capacities, the process is preferably conducted adiabatically.
  • US 5,908,963 discloses a process for the preparation of dimethyl ether.
  • the product may contain up to 20% by weight of methanol and up to 20% by weight of water.
  • synthesis gas is converted into a gas mixture of dimethyl ether, methanol and water in one or more reactors.
  • the catalysts used have both a methanol synthesis activity and the ability to dehydrate methanol.
  • the gas mixture is separated by means of several distillation and washing steps to obtain pure dimethyl ether.
  • the product of the first stage may be passed directly to the second or it may be separated, for example the water is separated (with or without methanol) and H 2 and carbon monoxide (unreacted synthesis gas ), which (possibly after discharge of C0 2 ) are recycled to the first stage.
  • the prior art proposes processes of conversion of oxygen compounds to hydrocarbons which overcomes the problem by maintaining a degree of conversion of the raw material at a level of more than 99%. to solve.
  • the separated from the final product water is led away from the plant and fed to the biological or biochemical purification.
  • US 4,814,535 (1989) discloses a method of producing gasoline from oxygenated compounds having a number from 1 to 4 carbon atoms.
  • the conversion of the raw material is maintained at a level of 99.9% by the temperature at the inlet to the reactor is gradually increased and the raw material flow is reduced. If the degree of conversion falls below 99.9%, the supply of raw materials is interrupted.
  • US 4,523,046 (1985) discloses a method of producing gasoline from methanol.
  • the catalyst is arranged in individual beds and upon contact of the raw material with the catalyst bed, a degree of conversion of the raw material of practically 100% is achieved. When reducing the degree of conversion of the raw material is passed to the next catalyst bed.
  • No. 5,602,289 uses a gas which is mixed together from two gas streams (C 2 -hydrocarbons and C 3+ -hydrocarbons) returned to the reactor as diluting component.
  • the partial pressure of the water including the water which has formed in the reaction of the conversion of the methanol in the reactor, is less than 2.2 atm.
  • the limitation of the partial pressure for water vapor is due to the known effect of the irreversible deactivation of the zeolite in the presence of water vapor.
  • the composition of the diluting component is given in this preferred case by a ratio of the C 2 -C hydrocarbons / C 3+ hydrocarbons in the limits between 1/3 and 3/1 and a hydrogen content between 10 and 50% mol.
  • the object of the invention is the development of an economical and simplified process of the production of gasoline hydrocarbons from synthesis gas and a simple plant scheme with simplified technological stages.
  • the aim is also to achieve a high Benzselektekt technically with high gasoline quality and the provision of a waste-free technology without environmentally harmful by-products.
  • the production of hydrocarbons is effected by the conversion of a CO- and H2-containing gas mixture (also referred to below as synthesis gas)
  • R 1 are alkyl groups having a carbon number of 1 to 5
  • R is hydrogen, alkyl and alkoxy groups having a carbon number of 1 to 5
  • Isoparaffins branched saturated aliphatic hydrocarbons having at least 5 carbon atoms
  • synthesis gas is separated from the first and / or second product stream and is at least partially recycled as recycle gas into the first converter
  • the aqueous phase containing the compound R-O-R is added either for purification or first for rectification.
  • the rectification is followed by a
  • Type R-O-R to 5 which is added for purification. Which in any case
  • the converters of the synthesis of compounds of the type R-O-R and the synthesis of gasoline with removal of the heat of the exothermic reaction from the reaction zone have heat transfer surfaces through which the heat of reaction is transferred to a boiling heat carrier.
  • the heat carrier (or its vapors) condenses in a cooling zone, which preferably contains boiling water for generating water vapor. The condensate flows back to the heat of reaction zone (principle of the "heat pipe").
  • the reactions in the converters of the synthesis of compounds of type R -OR and the synthesis of gasoline are preferably carried out under approximately isothermal conditions in which the temperature difference ( ⁇ ) within the catalyst bed does not exceed 40 K, preferably at a ⁇ of 10-20 K, more preferably at a ⁇ of less than 5 K.
  • the heat of reaction is preferred for generating water vapor with a
  • the process according to the invention for the production of gasoline from synthesis gas involves the contact of the synthesis gas with the catalyst in the first converter (converter of the synthesis of oxygen-containing compounds) under the conditions of the synthesis of Compounds of the type R 1 -0-R2.
  • the term "compound of the type R 1 -O-R 2" denotes - with R 1 - alkyl radicals having 1 to 5 C atoms, - with R 2 - hydrogen, alkyl and alkoxy radicals with
  • Whether methanol or a mixture of methanol and dimethyl ether (DME) or other compounds of the type R 1 -O-R 2 are produced in the first step is controlled in particular by the catalysts used.
  • DME dimethyl ether
  • catalysts known from the prior art which are customarily used for the synthesis of methanol (for example zinc-chromium oxide catalysts, copper-based catalysts with additions of zinc oxide and / or aluminum oxide, combinations of copper and rare earth metals, copper oxide / zinc oxide). Catalysts and copper oxide / zinc oxide / chromium oxide catalysts and others) are used.
  • the product stream of the converter of the synthesis of compounds of the type R 1 -O-R 2 is preferably cooled with subsequent separation of the liquid and gaseous phase in the separator.
  • the (complete) product stream from the methanol synthesis converter is introduced directly into the second gasoline synthesis converter without separation.
  • the unreacted components of the synthesis gas (CO, H 2 , CO 2 , nitrogen and others) are preferably partially incorporated in the first converter of the synthesis of
  • Recycled compounds of the type R 1 -OR 2 are mixed with the used gas mixture used, which contains CO and H 2 , and partly unreacted synthesis gas in the converter of the synthesis of gasoline to suppress the reaction of decomposition of the compounds Type R 1 -OR 2 fed. At the same time it is preferably discharged to another part of the process, to avoid the accumulation of inert components.
  • the feeding of a part of unreacted components of the synthesis gas into the converter of the gasoline synthesis is realized with a volume flow at the inlet to the gasoline synthesis converter, which has a partial pressure of hydrogen of not less than 0.07 MPa and CO of not less than 0.08 MPa guaranteed.
  • Compounds of the type R 1 -OR 2 preferably contain at least partly a protonated zeolite (eg HZSM-5), preferably from the group of the pentasils.
  • 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.
  • a water vapor stable catalyst can be obtained by modification with Group Ib elements. It is also possible to use combinations of silicon dioxide with oxides of metals (gallium oxide and / or indium oxide) (US Pat. No.
  • the feedstock fed into the second converter is either the entire first
  • the partial pressure of the steam in the starting material of the gasoline synthesis converter is particularly advantageously below 0.3 MPa (advantageous distinguishing feature).
  • the process in the gasoline synthesis converter is carried out particularly advantageously at a partial pressure of the hydrogen of at least 0.07 MPa and at a partial pressure of the carbon monoxide of at least 0.008 MPa (advantageous distinguishing feature).
  • the process according to the invention is characterized in that the contact of the starting material with the catalyst takes place in the second converter in the presence of hydrogen and carbon monoxide. This advantageously the selectivity of the implementation of
  • a coolable converter with almost isothermal conditions in the reaction zone with a heat transfer area of over 40 m 2 / m 3 catalyst is preferably used, the volume of the circulating gas is, based on 1 m 3 catalyst less than 150 m 3 .
  • the heat of reaction is preferably used to generate water vapor at a pressure of up to 22 MPa. This is also a distinguishing feature of the invention, which together with features of claim 1 allows to obtain a high gasoline quality at a selectivity of more than 83, preferably more than 86. By selectivity is meant here the yield of gasoline, based on the hydrocarbon portion of the reacted methanol.
  • the conversion of the compound of the type R 1 -O-R 2 (preferably of the methanol and optionally of the dimethyl ether) in the gasoline synthesis converter is more than 85% and less than 99.5% for methanol and more than 92% and less 99.8% for dimethyl ether.
  • the incomplete conversion of the compound of the type R 1 -O-R 2 is an essential distinguishing feature of the invention, which allows the selectivity of the process (yield of the gasoline fraction, based on the hydrocarbon content of the reacted
  • the product contains gasoline synthesis
  • This "dry” gas contains mainly gaseous substances (short-chain hydrocarbons (Q-C 2 ), CO, CO 2 and H 2 and other components of the synthesis gas).
  • the product of the gasoline synthesis is cooled and separated into unstable gasoline, an aqueous phase and the uncondensed gas components.
  • the separation is preferably carried out by a physical phase separation in a three-phase separator.
  • the uncondensed gas constituents contain components of synthesis gas, light hydrocarbons (Ci and C 2 ), traces of heavier hydrocarbons. This circulating gas is, at least partially in the converter of gasoline synthesis and / or in the
  • Converter of the synthesis of compounds of the type R -O-R returned.
  • the volume of the circulating gas in the converter of the gasoline synthesis can advantageously be set, the partial pressure of the methanol and the water.
  • the liquid phase in the three-phase separator forms, due to the difference in density, a phase interface between hydrocarbons containing the gasoline hydrocarbons and water.
  • the lower density liquid gasoline hydrocarbons collects above the phase interface, while the aqueous phase settles at the bottom.
  • the liquid hydrocarbons separated in the three-phase separator contain the gasoline hydrocarbons which are preferably passed to a rectification column in which, if necessary, preferably components of the heavy gasoline (Durolfr potentially) and head gases - mainly C 3 -C 4 - hydrocarbons and radicals of C 1 -C 2 - Hydrocarbons (short-chain hydrocarbons) and synthesis gas components are separated. With a permissible content of durene in the gasoline hydrocarbons, the heavy fuel gas is not separated.
  • the obtained stable gasoline fraction with a necessary saturated steam pressure below 500 - 700 mm QS (depending on the required gasoline grade) is either commercial gasoline or forms the basis for the production of commercial gasoline with an octane number of 92 - 98 (RON).
  • the water separated in the three-phase separator contains methanol.
  • the methanol content of the water depends on the degree of methanol conversion in the gasoline synthesis, as a rule it is more than 3% by mass and less than 30% by mass.
  • Compounds of the type R 1 -OR 2 are initially separated in a rectification column due to the different boiling temperatures in fractions, of which one fraction is mainly methanol or another compound of the type R 1 -OR 2 with a low content of water (concentrated methanol) and the other fraction contains water with a small content of methanol (contaminated water).
  • the concentrated methanol or optionally dimethyl ether or another compound of the type R 1 -OR 2 is preferably returned to the converter of the gasoline synthesis.
  • the contaminated water still contains a residual content of methanol (usually at most 5% by mass) or another compound of the type R 1 OR 2 .
  • Method is catalytically decomposed methanol and optionally another compound of the type R 1 -OR 2 by contact with a catalyst (steam reforming or catalytic decomposition) into hydrogen and gaseous carbon oxides.
  • a catalyst steam reforming or catalytic decomposition
  • the water is separated after cooling, by condensation, from the generated oxides of carbon (CO and C0 2 ) and hydrogen.
  • the carbon oxides and the hydrogen can be advantageously mixed with the synthesis gas and in the process of synthesis of compounds of the type
  • R 1 -O-R 2 are recycled. After the separation of the gases, chemically purified water is advantageously obtained, with subsequent degassing of the water.
  • the contact of the methanol-containing water with the catalyst is preferably carried out at a temperature below 380 ° C, more preferably below 350 ° C and preferably above 200 ° C.
  • the contact of the water containing a compound of the type R 1 -OR 2 (preferably methanol, optionally dimethyl ether) with the catalyst is preferably realized at a pressure which allows the generated components of the synthesis gas in the first converter directly or with the help of a cycle compressor in the first converter to initiate.
  • This pressure corresponds to the sum of the reaction pressure for the synthesis of the compounds of the Type R 1 -0-R 2 and the pressure loss between exit of the product of the catalytic methanol decomposition and entry of the feedstock in the converter of the methanol synthesis.
  • the residual content of the R 1 -O-R 2 type chemical compound in the water may also be removed by a biological purification process.
  • the biologically purified water can be introduced into the sewage network.
  • the biological purification requires a methanol content in the water of less than 0.2-1 mass%, obtaining such a concentration by the rectification involves high energy expenditure or it is a large dilution of the contaminated water required with pure water, which also increases the cost of biological purification.
  • the use of the catalytic purification of the water of compounds of the type R x -O-R is another advantageous distinguishing feature, since it allows to control the process conditions in the gasoline synthesis converter with relatively little effort, the degree of conversion of the compounds of the type R 1 -OR 2, thereby achieving a high selectivity and quality of the products.
  • the invention also provides a system for carrying out the method according to the invention.
  • This attachment contains:
  • At least one separator which is suitable, petroleum hydrocarbons from a
  • R (preferably methanol) in CO and H 2 to catalyze.
  • the above-mentioned components are preferably connected in series, i. H. the first converter is connected directly or indirectly to the second converter so that at least part of the product flow from the first converter is introduced into the second converter.
  • the second converter is connected to the separator c.), So that the product stream from the second converter into the separator c.) Is passed.
  • the separator c.) Is indirectly connected to the third converter so that the water which was separated in the separator c.) And contains the chemical compound of the type R 1 -OR 2, if necessary, after a prior distillative separation of the main amount of the
  • connection of the type R 1 -OR 2 is passed to the third converter.
  • the separator c.) also has a connection with the second converter, which allows the short-chain hydrocarbons and the other components of the gas phase of the separator c.) To be returned to the input into the second converter.
  • the system preferably contains a connection line from the third converter to the first converter, which makes it possible to introduce CO and H 2 formed in the third converter into the first converter.
  • the system contains an additional separator for separating the product stream from the first converter.
  • the additional separator preferably has a connection line to the first converter, which makes it possible to introduce separated CO and H 2 in the separator into the first converter.
  • This (additional) separator preferably also has a first connection line to the second converter, which makes it possible to feed chemical compounds of the type R 1 -OR 2, if necessary after separation of at least part of the water, into the second converter and a second one Connecting line to the second converter, which makes it possible, if necessary, to introduce at least a portion of the gas stream containing CO and H 2 , in the second converter.
  • the first converter in the system is connected directly to the second converter by a stream, so that the complete product stream from the first converter without separation into the second converter is initiated.
  • the separator c. Preferably has a connection line to the first converter, which allows the dry gas (unreacted CO and H 2 and short-chain hydrocarbons) to be returned to the first converter.
  • the second product stream is separated into hydrocarbons containing gasoline hydrocarbons, gas and water.
  • the water which contains the unreacted chemical compound of the type R 1 -O-R 2 is preferably introduced into a separator (c.) Downstream of the apparatus (preferably a rectification column), which contains the
  • R 1 -OR 2 compound is not completely removed from the water.
  • the additional device therefore also has a connection line to the third converter which makes it possible to supply the still contaminated water to the third converter,
  • Known catalysts can be used for the decomposition of the compound of the type R-O-R (preferably of the methanol and, if appropriate, of the DME).
  • R-O-R preferably of the methanol and, if appropriate, of the DME.
  • An overview is provided in the article by Klabunowski E.I. a. "Catalysts of the conversion of methanol into synthesis gas” (Catalysis in the industry, 2004, N. 6, p 3-9) given, as well as the catalysts of steam reforming of CO, the catalysts of methanol synthesis and other catalysts.
  • a converter of any type can be used, preferably a fixed-bed flow-through converter of a granulated catalyst.
  • the converter used in step d.) Is hereafter called water purification converter.
  • converter is used synonymously with reactor in the description of the invention.
  • the converters used in step a.) And / or step b.) are preferably flow-through reactors in which the catalyst is introduced as a fixed bed.
  • the first and / or the second converter are cooled.
  • the cooling is preferably carried out by indirect evaporation cooling.
  • the reaction procedure in step a.) And / or step b.) Takes place as nearly as possible isothermally.
  • the converters are preferably designed so that they allow a direct and complete removal of the heat of reaction generated in the catalyst bed and thus allow a reaction at an approximately constant temperature in the volume of the reaction space.
  • the heat of reaction dissipated by the cooling in the first and / or second reactor can be used to advantage for the production of water vapor.
  • the first converter methanol synthesis and optionally DME synthesis
  • the first converter preferably has a ratio of the heat transfer area to the catalyst volume of not less than 50
  • water vapor having a pressure of not less than 0.6 MPa and not more than 4 MPa is preferably produced.
  • the second converter (gasoline synthesis) preferably has a ratio of the heat transfer area to the catalyst volume of not less than 40 m 2 / m 3 and not more than 200 m 2 / m 3 .
  • water vapor having a pressure of not less than 3.0 MPa and not more than 22 MPa is preferably produced.
  • the heat of reaction removed by the generated steam can advantageously be used to produce a refrigerant which can be used for the product separation after step a) and / or after step b).
  • the synthesis gas used in the process can be obtained from a wide variety of starting materials.
  • the source materials may be of fossil or biological origin (eg coal, biomass, natural gas or biogas).
  • the ratio of CO to H 2 in the synthesis gas depends on the starting materials used for the preparation and on the production process.
  • the syngas usually also contains inert components (such as N 2 and water).
  • the synthesis gas is preferably purified of catalyst poisons (sulfur compounds, nitrogen compounds) and foreign substances, dried and, if necessary, compressed.
  • the ratio of H 2 / CO in the synthesis gas is preferably not less than 2.
  • a large yield of methanol (DME), based on C in CO is obtained.
  • the yield of methanol (DME) decreases and the yield of C0 2 increases .
  • Step b.) The conversion of compounds of the type R 1 -OR 2 on a zeolite catalyst into a mixture of hydrocarbons takes place.
  • the compounds of the type R 1 - OR which are produced in the first stage may be passed as a whole product stream from the first converter to the second stage or be separated from the product of the first converter in any variant and then added to the second stage.
  • Unreacted synthesis gas is preferably selected from the product of the first converter or separated from the product of the second converter and in the first converter for the synthesis of
  • the synthesis gas can be used advantageously as a crude mixture, but is preferably dried and compressed if necessary and heated in admixture with the cycle gas to a temperature which is close to the reaction temperature, heated, for.
  • recuperator heat exchangers and / or heaters steamer heaters, stoves and / or electric heaters
  • first converter in the figures - block I
  • R 1 -O-R 2 (methanol and optionally dimethyl ether) passed.
  • contact is made with the catalyst of the methanol synthesis or with the catalyst of the methanol synthesis and the catalyst of the dehydration of methanol to dimethyl ether (DME).
  • DME dimethyl ether
  • Copper-containing catalysts are preferably used at a temperature up to 260 ° C and a pressure up to 6 MPa.
  • the reaction of CO and H 2 to form methanol is exothermic with a heat effect of 90.73 kJ / mole of methanol. Therefore, an isothermal cooling converter is preferably used in step a.). It is capable of reducing the required volume of cycle gas and performing the synthesis under optimum conditions, with concomitant reduction in the formation of byproducts, increased yield of methanol, catalyst life extension, and generation of medium pressure water vapor for use as an energy source.
  • the product from the converter of the synthesis of the compounds of the type R 1 -O-R 2 is preferably cooled in heat exchangers by preheating the raw material stream (synthesis gas).
  • the product stream may preferably be separated into a gas product and a condensate.
  • the product is preferably cooled in the air cooler and in the water cooler, and in the presence of dimethyl ether in the product, even using deep cold.
  • the organic components and the water are condensed.
  • the condensate (crude ethanol, water content up to 20% or mixture of dimethyl ether, methanol and water) is separated in the separator.
  • the gas product from the separator is unreacted synthesis gas, a portion of which is returned to the first converter for mixing with the starting syngas for complete conversion.
  • the separator may also be followed by a rectification column for separating off the water from the mixture with the organic components, since the Presence of water in the feed to the second converter to convert the
  • the separated compounds of the type R 1 -OR 2 (methanol or methanol / DME mixture) or the product stream from the first converter (block I) is fed into the second converter (in the figures - block III) of the synthesis of gasoline, where it prefers with the recycle stream of methanol (stream 11 in Figures 1 + 2) from the block V, with the recycle stream of the light hydrocarbon gas (stream 7 in Fig. 1) from the block IV and the stream of unreacted synthesis gas (Stream 5 on Fig. 1) from the separator (block II) is mixed.
  • the mixed stream is preferably heated in the recuperator - heat exchangers and in the heater and fed into the converter for gasoline synthesis.
  • the presence of hydrogen and carbon monoxide in the process of the invention in the zone of the reaction of methanol (and optionally dimethyl ether) reduces, at least in part, the undesired decomposition of methanol into hydrogen and carbon monoxide in step b.).
  • the partial pressure of the hydrogen is preferably higher than 0.07 MPa and the partial pressure of the carbon monoxide higher than 0.008 MPa.
  • hydrogen and carbon monoxide are mixed with the methanol previously separated from the first product stream (and optionally dimethyl ether), or the first product stream containing unreacted synthesis gas is passed directly into the second converter.
  • the hydrogen and the carbon monoxide serve as diluting components in the second converter, i. H. they dilute the educt (methanol and possibly DME).
  • the dilution of the methanol (of the methanol + of the DME) in the feed stream to the second converter must be such that the partial pressure of the methanol is less than 0.5 MPa and that of the water is less than 0.3 MPa.
  • the product from the converter of the gasoline synthesis is preferably cooled in recuperator heat exchangers, wherein preferably the starting material of the converter (methanol and possibly DME), if possible in admixture with circulating gas, is heated.
  • the cooled stream is preferably added to the second separator (in Figures Block IV) to separate the Converted converter product of gasoline synthesis.
  • the petrol hydrocarbons condense, part of the light ones
  • Hydrocarbons the unreacted compounds of the type R 1 -O-R 2 and water.
  • the separator are preferably 1. the water, which unreacted compounds of the type
  • R 1 -OR 2 contains, 2. the gasoline hydrocarbons and 3. the gaseous phase, which contain hydrogen, carbon oxides and light hydrocarbons (mainly up to 4 carbon atoms, predominantly methane and C 2 -C 4 hydrocarbons) resulting from the conversion of methanol form, separated.
  • a portion of the gas phase is mixed with a portion of the CO and H 2 -containing gases from the first separator (in the block II) and preferably as diluting components to the feedstock (methanol and possibly DME) in the converter of the gasoline synthesis.
  • the condensate of the gasoline hydrocarbons from the separator c.) Is preferably heated and led to the stabilizing column, in the light overhead gases (short-chain hydrocarbons, essentially propane, propylene, butane, butylene, as well as methane, ethane, ethylene and H 2 ) from the stable gasoline (Stream 8 on the pictures) are separated. Possibly.
  • the C 3 -C 4 -hydrocarbons can be separated off as liquid fraction C 3 -C 4 .
  • heavy fuel (stream 9 in the figures) in the stabilizing column or in an additional column can be separated.
  • aqueous phase (stream 10 in the figures) from the separator c.) Can be used as a variant in a rectification column (block V in Fig. 1 + 2) and then to the converter of water purification (block VI in Fig. 1 + 2) be directed.
  • a rectification column block V in Fig. 1 + 2
  • the converter of water purification block VI in Fig. 1 + 2
  • Rectification column the concentration of the compound of the type R 1 -O-R 2 (stream 11 in Figs. 1 + 2) takes place.
  • This recycle stream is directed to the block of gasoline synthesis.
  • the water obtained in the bottom of the column, which contains residual contents of R 1 -O-R 2, is passed to the converter for water purification.
  • the aqueous phase from the separator c.) Can also be added directly to the water purification.
  • Fig. 1 shows the block diagram for a preferred production process of gasoline from synthesis gas according to the inventive method with separation of the recycle stream of the synthesis gas from the product of the converter of the synthesis of compounds of the type R 1 -OR 2 and the catalytic decomposition of the methanol in the water following the removal by distillation of the main amount of methanol from the process water.
  • Figure 2 shows the block diagram for a preferred synthetic gasoline synthesis process of the present invention with direct introduction of the product stream from the first converter to the second converter and separation of the recycle stream of the synthesis gas from the product of the gasoline synthesis converter and the catalytic decomposition of the methanol in the water after the separation by distillation of the main amount of methanol from the process water.
  • synthesis gas 1 whose major components hydrogen and carbon monoxide in a ratio depending on the method of production but which also contains inert components is purified of catalyst poisons and impurities, compressed as necessary, and injected into the first converter (block I ) of the synthesis of compounds of the type
  • R 1 -O-R 2 is fed, where it is mixed with the cycle gas 3.
  • the resulting mixture is preheated to the reaction temperature in recuperator heat exchangers and heaters (steam and / or electric heaters, ovens) and in the converter of the synthesis of
  • Conducted compounds of the type R 1 -O-R2 In the preparation of the compounds of the type R 1 - O-R, the contact with the catalyst of the methanol synthesis or with the catalyst of the methanol synthesis and the catalyst of the dehydration of methanol to dimethyl ether.
  • the use of copper-containing catalysts at a temperature of up to 260 ° C and a pressure of up to 8 MPa is preferred, but it can also zinc-chromium catalysts, which at a temperature of up to 360 ° C and to work at a pressure of more than 8 MPa.
  • the product from the converter of the synthesis of compounds of the type R 1 -O-R 2 is cooled in heat exchangers by the raw material stream is preheated, as well as in the air and water cooler, in the presence of dimethyl ether in the product is also deep
  • the condensate (crude ethanol, water content up to 20% or mixture of dimethyl ether, methanol and water) is separated in the separator (block II).
  • the gas product from the separator is unreacted synthesis gas, part of which (stream 3) is passed to mix with the starting syngas for more complete conversion of the feedstock.
  • Separator separated compounds of the type R 1 -OR 2 4 are reacted with the recycle stream of methanol 11 from block V, the recycle stream 7 of the light Hydrocarbon gases from the second separator (block IV) and the stream 5 of the unreacted synthesis gas from block II, preferably gas product from the separator, mixed.
  • the components are preferably heated in recuperator heat exchangers and / or in heaters and fed into the gasoline synthesis converter.
  • the conversion of the compounds of the type R 1 -O-R 2 (methanol and optionally DME) in the second converter (block III) is preferably kept below 99.5%.
  • the product of the gasoline synthesis converter contains the hydrocarbons (especially gasoline hydrocarbons) produced in the reaction of the compounds of type R 1 -O-R 2 and unreacted
  • Both converters are preferably cooled converters.
  • the first converter has a heat transfer area of at least 50 m 2 per 1 m 3 of catalyst at a flow rate of the recycle gas of less than 150 real m 3 / m 3 catalyst.
  • the heat transfer surface is at least 40 m 2 per 1 m 3 of catalyst at a flow rate of the circulating gas of gasoline synthesis of less than 150 real m 3 / m 3 catalyst.
  • the steam generated in the cooling of the converter is, as described above, used to produce a refrigerant by means of an absorption refrigerator, in steam heaters for preheating the feed streams of the first converter and as bottom heating of the column for product separation.
  • the product from the converter of gasoline synthesis (block III) is cooled in the recuperator heat exchangers, whereby the feed material of the converter is heated, furthermore it is cooled in coolers. In the process of cooling, condensation of the petroleum hydrocarbons and of the water takes place.
  • the cooled stream 6 is transferred to the separator c.) (Block IV) for separation of the reactor product of gasoline synthesis.
  • the separator c.) 1. the methanol-containing water 10, 2. the petrol hydrocarbon phase 8 + 9 and 3. the gas phase 7, which contains hydrogen, carbon oxides and light hydrocarbons, which form in the conversion of methanol, separated.
  • the recycle stream of the light hydrocarbon gas 7 is mixed in the highlighted case with a portion of the CO and H 2 -containing gases 5 from the first separator (Block II) to form a diluting component for the feedstock of the synthesis of
  • the aqueous phase 10 from the separator is added to the block V to concentrate the
  • block V of the concentration of the compounds of the type R 1 -O-R 2 the enrichment of the methanol in the head is realized in a rectification column and the recycle stream of methanol 11 is obtained, which is conveyed to block III of the gasoline synthesis.
  • the gas Ström 13 is obtained from the decomposition of the methanol - carbon oxides and hydrogen, which is the first converter (block I) is supplied. It is obtained chemically purified water 14, which is used for the replenishment of the system of the recooling water, the system of steam generation and for other purposes.
  • Fig. 2 The manufacturing process shown in Fig. 2 is a simplified variant of the method shown in Fig. 1 and differs from this in particular in the following point:
  • the product of the first converter (block I) is heated in heat exchangers and / or heaters and passed directly, without prior separation, to the converter (block III) of the gasoline synthesis.
  • recycled cycle gas 3 (here from block IV) can also be added here again.
  • the product from the first converter essentially corresponds in its composition to the product from the process on FIG. 1.
  • the conversion of the compound of the type R 1 -O-R 2 is preferably kept below 99.5%.
  • the product from the gasoline synthesis converter is also preferably cooled first in the recuperator heat exchangers and in coolers.
  • the partially cooled stream 6 is fed into the block IV of the separation of the products of the gasoline synthesis converter, where condensation of the gasoline hydrocarbons and the water takes place due to the cooling in the coolers.
  • the water 10 which contains unreacted compounds of the type R 1 -O-R 2, deposited and the gasoline hydrocarbon phase and the gas phase are separated.
  • the gas product from the separator consists mainly of unreacted synthesis gas and light hydrocarbons, part of which (stream 3) is recycled to the first converter (block I) for mixing with the starting syngas for more complete conversion of the feedstock.
  • the water formed in the converter of gasoline synthesis contains here, depending on the degree of conversion, usually between 3.5% and 40% methanol (and possibly DME). There is therefore a purification of the water in a rectification column (block V) and then in a separate converter of water purification (block VI) by catalytic decomposition of the methanol into hydrogen and carbon oxides (these gases are recycled as an admixture to the synthesis gas in the process -. see description of Fig. 1).
  • the hydrocarbon condensate from the separator (block IV) is passed to the stabilization column (block IV), in which the gasoline 8 is separated.
  • the stabilization column (block IV), in which the gasoline 8 is separated.
  • From the unstable petroleum hydrocarbons heavy fuel 9 can be separated in a stabilizing column or an additional column.
  • the water phase 10 from the separator is in the block V of the enrichment of the
  • Type R 1 -OR 2 compounds and then fed to the water purification converter (block VI).
  • block V of the concentration of the compounds of the type R x -O-R the enrichment of the methanol in the top part is realized in a rectification column and a recycle stream of this methanol 11 is obtained, which is returned to the block III of the gasoline synthesis.
  • the methanol-containing water stream is preferably conveyed through the recuperator heat exchangers and / or preheaters, where it is heated to the required reaction temperature, and then fed to the converter for water purification, where contact with the catalyst for decomposition of the methanol in Hydrogen and carbon oxides is realized.
  • the product from the water purification converter is preferably cooled in recuperator heat exchangers and an air cooler. Subsequently, the gas phase is separated from the condensate in a separator. The thereby separated gases of decomposition of the methanol 13 emerge from the separator and are passed for mixing with the crude synthesis gas in the first converter (block I).
  • the purified water is conveyed to the degasifier column. It is obtained chemically purified water 14, which is used for the replenishment of the system of the recooling water, the system of steam generation and for other purposes.
  • the converters are cooled indirectly.
  • the water absorbs the heat from a heat carrier, which in turn dissipates the heat from the reaction zone.
  • the water leaves blocks I and III as steam.
  • Fig. 3 shows a block diagram of the TIGAS process.
  • Synthesis gas is mixed with cycle gas containing unreacted components of the synthesis gas and light hydrocarbons, and enters the reactor of synthesis of methanol + DME with a bifunctional catalyst consisting of a catalyst component of methanol synthesis and a catalyst component of dehydration of methanol ,
  • the resulting mixture of methanol + DME + water and components of the unreacted synthesis gas is added to the gasoline synthesis stage where conversion of the methanol and DME to hydrocarbons occurs on a zeolite-containing catalyst.
  • the product mixture is then separated into gasoline, an aqueous phase which is put to purification, a C3-C4 fraction and gas, part of which as a circulation gas is led to the stage of synthesis of oxygen compounds. All stages are performed at approximately the same pressure in the range of 50-100 bar.
  • the yield of oxygen compounds based on CH 2 in the synthesis gas, is 94%.
  • the yield of gasoline is 73.34, based on CH 2 in the synthesis gas without taking into account losses in the product separation, etc ..
  • examples of different variants of the process execution according to the invention are listed.
  • the volume flow of the synthesis gas is: 738.3 m (i.N.) / h.
  • MEGAMAX 700 ® components CuO, ZnO, A1 2 0 3
  • SMA-2 zeolite-containing catalyst from Südchemie
  • the operating conditions in the converter of the synthesis of compounds of the type R 1 -O-R 2 are temperatures in the range of 210 to 260 ° C and pressures in the range of 50 to 55 MPa.
  • the volume of the catalyst is 0.46 m, the heat exchange surface in the reaction zone is 30 m.
  • the pressure of the generated water vapor is 1.8 MPa.
  • Example 2 In the converter of gasoline synthesis in Examples 2 to 4 is a pressure of 7 bar and in Example 5, a pressure of 45 bar before.
  • the temperature of the process is in the range of 310 to 430 ° C in the reaction regime and in the range of 280 to 500 ° C in the regeneration regime.
  • converters of methanol synthesis and gasoline synthesis are cooled. Converters with a heat transfer area of 60 m 2 / m 3 of catalyst are used.
  • the reactions in the converters of the synthesis of methanol and the synthesis of gasoline are carried out under approximately isothermal conditions in which the temperature difference within the catalyst bed is below 5 K.
  • Example 2 differ by a different choice of application of individual distinguishing features of the invention.
  • Example 2
  • the synthesis gas production facility is mainly similar to the scheme shown in Figure 1 and includes: one block (Block I) of synthesis of methanol from synthesis gas, one block (Block II) of methanol separation from the product stream of Block I, one block (Block III) the synthesis of gasoline from crude methanol, one block (Block IV) of the fractionation with removal of the product gasoline, one block (Block V) of the separation of methanol from the process water.
  • the synthesis gas production plant is mainly similar to the one shown in Fig. 1 and includes: one block of the synthesis of methanol from synthesis gas (block I), one block (block II) of the separation of methanol from the product stream of block I, one block (Block III) the synthesis of gasoline from crude methanol, one block (Block IV) of the fractionation with removal of the product gasoline, one block (Block V) of the separation of methanol from the process water.
  • the synthetic gas production facility corresponds to the scheme of Figure 1 and includes: a block (Block I) of the synthesis of methanol from synthesis gas, a block (Block II) of the separation of methanol from the product stream of Block I, a block ( Block III) of the synthesis of gasoline from crude methanol, one block (block IV) of the fractionation with removal of the product gasoline, one block (block V) of the separation of methanol from the process water, one block (block VI) of the water purification of methanol.
  • the synthetic gas production facility is as shown in Figure 2 and includes: one block (block I) of synthesis of methanol from synthesis gas, one block (block III) of the synthesis of gasoline without methanol separation from the product stream of block I. , one block (block IV) of the fractionation with removal of the product gasoline, one block (block V) of the separation of methanol from the process water, one block (block VI) of the water purification of methanol Table 5.1.
  • V - block of concentration of compounds of the type R 1 -O-R 2 (preferred

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Abstract

Procédé de production d'hydrocarbures sous forme d'essence, par conversion de gaz de synthèse, pour obtenir un composé contenant oxygéné, tel que du méthanol et/ou du diméthyléther, dans un premier convertisseur, et par conversion supplémentaire en hydrocarbures dans un second convertisseur. Ledit procédé est en particulier caractérisé en ce que le gaz de synthèse non entré en réaction est renvoyé dans le premier convertisseur et en ce que les hydrocarbures légers et les constituants non entrés en réaction du gaz de synthèse sont prélevés du flux de produit du second convertisseur et renvoyés dans le premier ou dans le second convertisseur. Le renvoi de ces constituants permet le réglage de pressions partielles, en particulier du méthanol dans le second convertisseur, ce qui améliore la qualité du produit. Pour améliorer encore la qualité du produit, ledit processus est mené de préférence dans des conditions isothermes et dans des conditions de conversion non complète.
PCT/EP2010/067606 2009-11-17 2010-11-16 Procédé de production d'hydrocarbures, en particulier d'essence, à partir de gaz de synthèse WO2011061198A1 (fr)

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EA201200731A EA021044B1 (ru) 2009-11-17 2010-11-16 Способ получения углеводородов, в особенности бензина, из синтез-газа
AU2010320947A AU2010320947B2 (en) 2009-11-17 2010-11-16 Method for generating hydrocarbons, in particular gasoline, from synthesis gas
CA2780483A CA2780483C (fr) 2009-11-17 2010-11-16 Procede de production d'hydrocarbures, en particulier d'essence, a partir de gaz de synthese
CN201080052110.2A CN102686540B (zh) 2009-11-17 2010-11-16 从合成气中生产烃特别是汽油的方法

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DE102009046790A DE102009046790B9 (de) 2009-11-17 2009-11-17 Verfahren zur Erzeugung von Kohlenwasserstoffen, insbesondere Benzin, aus Synthesegas
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DE102018103552A1 (de) 2018-02-16 2019-08-22 Chemieanlagenbau Chemnitz Gmbh Verfahren und Anlage zur Herstellung eines synthetischen Benzins
WO2023214001A1 (fr) 2022-05-06 2023-11-09 Totalenergies Onetech Procédé d'obtention d'hydrocarbures, et installation associée
WO2023214014A1 (fr) 2022-05-06 2023-11-09 Totalenergies Onetech Procédé de fabrication d'un carburéacteur comprenant une étape de conversion d'un flux d'alcool dans un lit fluidisé, carburéacteur et installation associés
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DE102018103552A1 (de) 2018-02-16 2019-08-22 Chemieanlagenbau Chemnitz Gmbh Verfahren und Anlage zur Herstellung eines synthetischen Benzins
WO2019158687A1 (fr) 2018-02-16 2019-08-22 Chemieanlagenbau Chemnitz Gmbh Procédé et installation de production d'une essence synthétique
DE102018103552B4 (de) 2018-02-16 2024-01-25 Cac Engineering Gmbh Verfahren und Anlage zur Herstellung eines synthetischen Benzins
WO2023214001A1 (fr) 2022-05-06 2023-11-09 Totalenergies Onetech Procédé d'obtention d'hydrocarbures, et installation associée
WO2023214014A1 (fr) 2022-05-06 2023-11-09 Totalenergies Onetech Procédé de fabrication d'un carburéacteur comprenant une étape de conversion d'un flux d'alcool dans un lit fluidisé, carburéacteur et installation associés
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FR3135263A1 (fr) 2022-05-06 2023-11-10 Totalenergies Onetech Procédé de fabrication d’un carburéacteur comprenant une étape de conversion d’un flux d’alcool dans un lit fluidisé, carburéacteur et installation associés
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EA201200731A1 (ru) 2012-10-30
DE102009046790B9 (de) 2013-05-08
DE102009046790B4 (de) 2012-05-16
CA2780483C (fr) 2013-03-05

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