EP3992265A1 - Procédé et installation de traitement des produits de produits crus à base de fischer-tropsch destinés à la fabrication de combustibles préformulés ou répondant aux normes - Google Patents

Procédé et installation de traitement des produits de produits crus à base de fischer-tropsch destinés à la fabrication de combustibles préformulés ou répondant aux normes Download PDF

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Publication number
EP3992265A1
EP3992265A1 EP20204893.0A EP20204893A EP3992265A1 EP 3992265 A1 EP3992265 A1 EP 3992265A1 EP 20204893 A EP20204893 A EP 20204893A EP 3992265 A1 EP3992265 A1 EP 3992265A1
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EP
European Patent Office
Prior art keywords
hydrogen
unit
fischer
fraction
chain
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP20204893.0A
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German (de)
English (en)
Inventor
Julian BAUDNER
Manuel SELINSEK
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Ineratec GmbH
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Ineratec GmbH
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Application filed by Ineratec GmbH filed Critical Ineratec GmbH
Priority to EP20204893.0A priority Critical patent/EP3992265A1/fr
Priority to AU2021370113A priority patent/AU2021370113A1/en
Priority to CA3195310A priority patent/CA3195310A1/fr
Priority to EP21798959.9A priority patent/EP4237513A1/fr
Priority to US18/034,264 priority patent/US20230383193A1/en
Priority to JP2023527289A priority patent/JP2023549739A/ja
Priority to CN202180073306.8A priority patent/CN116507704A/zh
Priority to PCT/EP2021/078508 priority patent/WO2022089955A1/fr
Publication of EP3992265A1 publication Critical patent/EP3992265A1/fr
Priority to CL2023001118A priority patent/CL2023001118A1/es
Withdrawn legal-status Critical Current

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    • 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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/34—Apparatus, reactors
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/026—Increasing the carbon monoxide content, e.g. reverse water-gas shift [RWGS]
    • 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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
    • 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
    • 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
    • C10G2400/04—Diesel oil
    • 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
    • C10G2400/08—Jet fuel

Definitions

  • the present invention relates to methods and systems for producing standard-compliant fuels, such as diesel or kerosene, by means of an integrated processing of the Fischer-Tropsch raw products (in particular oil and wax) using various process steps and corresponding systems.
  • standard-compliant fuels such as diesel or kerosene
  • Fischer-Tropsch synthesis (FTS) process used to produce hydrocarbons has been known for many decades.
  • a synthesis gas which mainly consists of carbon monoxide (CO) and hydrogen (H 2 )
  • CO carbon monoxide
  • H 2 hydrogen
  • a gas phase consisting of unreacted synthesis gas (mainly CO, H 2 ), short-chain hydrocarbons and volatile components of the by-products and CO 2 .
  • a hydrophobic phase of shorter-chain hydrocarbons that is liquid at ambient temperature and pressure (oil phase).
  • An aqueous phase consisting of the water of reaction that forms and the organic compounds dissolved in it.
  • Processes are known in which the wax and oil phases produced by the Fischer-Tropsch synthesis are processed by hydrogen treatment using what is known as hydrotreatment in refineries to form standardized fuel products such as petrol, diesel or kerosene.
  • WO 2007/031668 A1 describes a recirculation of gases from the upgrading unit into the Fischer-Tropsch reactor, the recycled gases are fed directly into the Fischer-Tropsch stage.
  • US 6,306,917 B1 describes the recirculation of the hydrotreatment gases in the synthesis gas production, with a purification of the gases being provided.
  • US 8,106,102 B2 describes the return of the hydrogen from the hydrotreatment to the Fischer-Tropsch stage.
  • WO 2004/096952 A1 describes the recycling of gases from treatment using separation stages.
  • a problem of the prior art is that decentralized, climate-neutral energy generation concepts are often based on direct on-site conversion to liquid and/or solid energy carriers with high energy densities for loss-reducing transport or intermediate storage of these renewable energies.
  • a fuel-oriented use of these climate-neutral energy sources then requires processing to standard-compliant fuels, which usually takes place in refineries.
  • conventional processing in refineries is based on very high throughputs, which means that only so-called co-processing of the decentralized Fischer-Tropsch products, which are limited in throughput, is possible. This only leads to the possibility of a climate-neutral admixture quota for the refinery product.
  • the object of the present invention was accordingly to provide methods and devices which no longer have the problems of the prior art, or at least only to a greatly reduced extent, or have new advantageous effects.
  • long-chain hydrocarbons is understood to mean hydrocarbons having at least 25 carbon atoms (C 25 ).
  • the long-chain hydrocarbons having at least 25 carbon atoms can be linear or branched. Usually the long chain hydrocarbons reach chains of about 100 carbon atoms. Even longer chains can be formed under special reaction conditions.
  • short-chain hydrocarbons means hydrocarbons having 5 to 24 carbon atoms (C 5 -C 24 ). The shorter-chain hydrocarbons having 5 to 24 carbon atoms can be linear or branched.
  • short-chain hydrocarbons means hydrocarbons having 1 to 4 carbon atoms (C 1 -C 4 ).
  • the short-chain hydrocarbons with 4 carbon atoms can be linear or branched.
  • wax phase is understood to mean that product phase of the Fischer-Tropsch synthesis which is characterized by long-chain hydrocarbons. In individual cases, minor amounts of other compounds of less than 10% by weight, in particular less than 5% by weight, can be present. This is known to the person skilled in the art and does not require any further explanation.
  • oil phase is understood to mean that product phase of the Fischer-Tropsch synthesis which is characterized by shorter-chain hydrocarbons. In individual cases, minor amounts of other compounds of less than 10% by weight, in particular less than 5% by weight, can be present. This is known to the person skilled in the art and does not require any further explanation.
  • standard-compliant fuels are understood to be fuels that can be used while complying with the respective legal standards, i.e. that meet the parameters of the respective standards. Depending on the currently applicable legal provisions, this may change.
  • such standards are EN 228 for gasoline, EN 590 or EN 15940 for diesel, and ASTM D7566 or ASTM D1566 for kerosene.
  • hydrotreatment unit is sometimes abbreviated to "HTE" for the sake of simplicity.
  • system and “device” are occasionally used synonymously.
  • a power-to-liquid (PtL) system or a power-to-liquid process in the narrower sense means a system or a process in which CO 2 is mixed with hydrogen, in particular electrolytically hydrogen obtained, is converted into the target products oil phase and wax phase, with a gas fraction with light, short-chain hydrocarbons (C 1 -C 4 ) and residual gases (CO, CO 2 , H 2 ) and an aqueous phase with dissolved oxygen-containing substances in addition to the target products Hydrocarbons (by-products including alcohols, organic acids) can occur.
  • this also includes the subsequent processing or processing unit of the wax and/or oil phase to produce standard-compliant fuels.
  • the term "consisting of” is to be interpreted in such a way that it refers to essential parts of a device or essential steps of a method. It goes without saying that common parts such as screws, pipe connectors, sleeves and so on can (or must) be present, even if they are not explicitly mentioned.
  • the present invention relates to methods and devices for producing standardized fuels, preferably gasoline (according to EN 228), diesel (according to EN 590 or EN 15940) and kerosene (according to ASTM D7566 or ASTM D1566), particularly preferably diesel or kerosene, by integrated processing the Fischer-Tropsch raw products (oil and wax) through various process steps.
  • standardized fuels preferably gasoline (according to EN 228), diesel (according to EN 590 or EN 15940) and kerosene (according to ASTM D7566 or ASTM D1566), particularly preferably diesel or kerosene, by integrated processing the Fischer-Tropsch raw products (oil and wax) through various process steps.
  • the synthesis gas as the starting point of the Fischer-Tropsch synthesis comes from the gasification of biomass, from synthesis gas production from fossil reactants (natural gas, oil, coal) or from electricity-based processes (conversion of electrolytically generated H 2 and CO 2 into storable ones Products).
  • the FT synthesis unit to be used in the present invention is generally based on two successive stages: an RWGS (reverse water-gas shift reaction) takes place in the first stage and the actual FT conversion takes place in the second.
  • RWGS reverse water-gas shift reaction
  • the synthesis gas obtained in the RWGS can also comprise CO 2 and CH 4 and possibly other impurities in addition to CO and H 2 or CO, H 2 O and H 2 .
  • the gas returned from the work-up contains C1 to C4 hydrocarbons in addition to hydrogen.
  • the mixture produced in the RWGS comprising CO and H 2 or CO, H 2 O and H 2 , is then fed into the FT unit as a reactant stream.
  • the FT product can be processed directly at the site of the FT synthesis unit to meet the standards fuels processed and thus a direct use can be realized.
  • this unit is procedurally coupled with the Fischer-Tropsch synthesis unit within the scope of the present invention and material utilization of the processing waste gas is realized in the Fischer-Tropsch synthesis unit.
  • the hydrogen feed of the Fischer-Tropsch unit can be reduced by this process control, since unreacted hydrogen from the processing plant reaches the inlet of the FT unit via a recycle.
  • the waste gases from the processing unit are fed into the synthesis gas production process in this connection. This counteracts the problem that a high proportion of H 2 is also required here in order to make carbon monoxide from the supplied CO 2 .
  • this synthesis gas production is effected by a reverse water gas shift reaction (RWGS).
  • RWGS reverse water gas shift reaction
  • the hydrogen is used in the present invention to produce synthesis gas in a RWGS.
  • recycled gases are added to the synthesis gas production.
  • purification is not necessary when the hydrotreatment gases are returned to the production of synthesis gas; in particular, no separation stages are necessary.
  • a special feature of the present invention is the direct introduction of the exhaust gas from the hydrotreatment into the RWGS.
  • the hydrotreatment unit comprises at least hydrocracking, hydrogenation and isomerization as different treatment steps in some embodiments. This enables the production of standardized fuels such as diesel or kerosene from the products discharged from a Fischer-Tropsch system.
  • a preferred embodiment of the present invention can be described as follows:
  • the wax phase discharged from the FT synthesis is conveyed into a storage tank of the hydrotreatment unit (HTE) and from there, together with metered hydrogen, is converted into shorter-chain hydrocarbons in a hydrocracking reactor.
  • HTE hydrotreatment unit
  • a separator arrangement which in preferred variants can be multi-stage, unreacted wax is separated off in a first hot separator. In preferred variants, this can be returned to the storage tank in the form of a wax recycle, as a result of which the wax fraction can be completely eliminated.
  • the short-chain hydrocarbons produced are separated from the remaining gas flow in a cold separator and conveyed to an oil storage tank at HTE.
  • the remaining gas stream comprising unreacted hydrogen and by-products of the cracking reaction, mainly short chain hydrocarbons such as methane and ethane, is fed to the HTE off-gas.
  • the oil phase discharged from the FT synthesis unit is also pumped into an oil storage tank at HTE, where it is mixed with the shorter-chain products of the hydrocracking reaction.
  • the mixed oil phase is then separated into the desired fractions in a separation unit. In a variant of the present invention, this separation is carried out by distillation. Internal recirculation to the HTE wax storage tank allows the long-chain portion of the oil phase resulting from the upper boiling end of the product fractions to be fed to the hydrocracker and thus also eliminated.
  • the light oil fraction resulting from the separation unit which is preferably composed of C5 to C10 hydrocarbons, can be removed from the HTE as crude gasoline, so-called naphtha, or within the HTE, preferably by additional processing steps such as, for example, and therefore preferably isomerization, to form higher-octane naphtha be processed.
  • a target fraction separated by the separation unit can also be processed in an isomerization and hydrogenation unit are processed to standard-compliant fuel. Due to the reaction, a large amount of hydrogen is required for this purpose.
  • the fuel can be separated from the gas phase in at least one downstream separator and the remaining gas stream, comprising unreacted hydrogen and by-products of the isomerization and hydrogenation unit, can be fed to the exhaust gas of the HTE.
  • the processes within the HTE include temperatures between 50 and 350° C., preferably between 100 and 300° C., pressures of up to 70 bar, in particular up to 50 bar, and are supported with precious metals, in particular platinum and/or palladium Alumina, or zeolites carried out.
  • precious metals in particular platinum and/or palladium Alumina, or zeolites carried out.
  • the synthesis unit and the work-up unit are in relatively close proximity to one another so that the hydrogen-containing gases produced in the work-up unit can be recirculated to the synthesis unit using apparatus.
  • a pipeline would also be suitable for this gas recirculation, although this would not adversely affect the hydrogen saving effect of the present invention, it would negate the advantages again due to the increased energy consumption.
  • the synthesis unit and processing unit are located on the same site, preferably in such a way that the return line must be less than 10 m long. It is particularly preferred if the synthesis unit and the processing unit are located directly next to one another at a distance of less than 1 m, or even in one housing.
  • the discharge device for product streams CO) originating from the Fischer-Tropsch synthesis can be configured or designed in various ways. It is possible to design these in such a way that all product flows can be derived. It is also possible that only individual product streams can be derived. And it is also possible that a part of the respective product streams is diverted and the rest is forwarded to the processing unit.
  • the discharge device can be configured, for example, as a flow diverter or as a plurality of flow diverters. Which part of which FT product is fed into the processing unit depends on which fuel is the target. It is quite possible that, for example, the oil phase already requires the requirements of a standard as a fuel.
  • the device of the present invention is accordingly arranged on a site, preferably in an apparatus complex, in particular in a housing.
  • the work-up unit comprises at least two, preferably at least three, in particular all four of the subunits mentioned.
  • the device of the present invention does not include a purification device for the gases that occur in the processing unit and are returned to the synthesis unit.
  • step III) can comprise the separation of the product obtained in step II) in a hot separator into a long-chain, waxy fraction, which is returned to Ia), and a shorter-chain, more oily fraction, and optionally further separation the shorter-chain fraction in a cold separator into a short-chain, oily fraction, and hydrogen, which is recovered.
  • step V) can also include the separation of the product obtained in step IV) in a first separation unit into a long-chain, waxy fraction, which is returned to Ia) and a shorter-chain, more oily fraction, and optionally a further separating the shorter-chain fraction in a second separation unit into a short-chain, oily product fraction, in particular naphtha, and a medium-chain fraction.
  • the separation in step VII) can be carried out in a cold separator.
  • the hydrogen obtained in steps III) and VII) can be recycled without further work-up, in particular without purification, and added to the feed hydrogen stream.
  • the returned gas stream can also include short-chain hydrocarbons, in particular C 1 to C 4 hydrocarbons.
  • the oil phase and the wax phase can be products of a Fischer-Tropsch synthesis.
  • the wax phase and the oil phase can also originate from a power-to-liquid process, preferably from a power-to-liquid process based on a Fischer-Tropsch synthesis.
  • processing unit of this embodiment can replace that of those described above with the sub-features C1), C2), C3) and C4).
  • C-C may comprise or consist of two separator units, wherein the first separator unit, preferably a hot separator unit, is configured to separate the product from unit C-B) into a long-chain, waxy fraction, and a shorter-chain, more oily fraction, and wherein the second separator unit, preferably a cold separator unit, is configured to separate the shorter chain fraction from the first separator unit into a short chain, oily fraction, and hydrogen.
  • the separator units are configured in such a way that the long-chain, waxy fraction from the first separator unit is returned to the wax phase.
  • C-E) can also comprise or consist of two separation units, a first separation unit being configured for separating the mixture obtained in mixing unit C-D) into a long-chain, waxy fraction and a shorter-chain, more oily fraction, and a second Separation unit is configured for further separation of fraction C-Eb) into a short-chain, oily product fraction, in particular naphtha, and a medium-chain fraction.
  • the separation units are configured in such a way that the long-chain, waxy fraction from the first separation unit is returned to the wax phase.
  • C-G can be configured as a separator, preferably a cold separator.
  • the work-up units are preferably configured in such a way that the hydrogen produced in CC) and CG) can be recycled without further work-up, in particular without purification, and either added to the reactant hydrogen stream or an RWGS plant without further work-up, or will.
  • a hydrogen feed line can be arranged in the Fischer-Tropsch synthesis unit between the RWGS stage and the Fischer-Tropsch stage in the device according to the invention.
  • the processing unit according to the invention is coupled to a power-to-liquid system, in particular to a power-to-liquid system based on a Fischer-Tropsch synthesis, in such a way that the wax phase and the oil phase from the products from the power-to-liquid plant.
  • An advantage of the present invention is that no purification of the gas is required in order to feed the gas mixture into the synthesis gas production.
  • An advantage of the present invention is that the hydrogen requirement necessary for a PtL plant and the total hydrogen requirement for both process steps, i.e. in the PtL process and the refining, are reduced.
  • a particular advantage of the present invention is that the specific setting of the parameters in the individual process steps or in the individual parts of the device makes it possible to produce fuels that conform to standards. How exactly the parameters are to be set in each case is known to the person skilled in the art on the basis of his general specialist knowledge and is carried out on the basis of the desired target products. It is particularly advantageous that within the scope of the present invention, one is not bound to existing standards, for example, but not exclusively to those mentioned above, but can react flexibly to changing standards and adapt the process and device parameters to the changed standards and to meet their requirements.
  • the present invention can therefore integrate the processing steps at the PtL site in order to reduce the overall requirement for hydrogen and enable direct production of standard-compliant fuels at the PtL site.
  • the hydrogen requirement required for the PtL system can thus be reduced by the H 2 management on which this invention is based, and the total requirement for hydrogen required for both process steps can be reduced.
  • a comparison of these data shows that from a total hydrogen requirement of 163.6 kg/h of hydrogen (127+36.6) per 1000 kg/h of CO 2 in the prior art, 27.3 kg/h have to be discharged and disposed of without being used of the present invention can be recycled and reused.
  • the present invention achieves a hydrogen saving of around 17%.
  • a CO 2 /H 2 mixture was provided and introduced into a Fischer-Tropsch synthesis unit, in which CO 2 and H 2 were initially converted into CO and H 2 in an RWGS reaction and then CO and H2 in a Fischer-Tropsch synthesis.
  • the supply of hydrogen was controlled during operation depending on the proportion of recycling gas; ie as the amount of recycling gas increases, correspondingly less hydrogen is metered in.
  • the corresponding amounts are in figure 4 shown, where the hydrogen supply is represented by a dashed line and the recycling stream by a dash-dot line (see also the legend of the figure 4 ).
  • the carbon dioxide supply was changed accordingly depending on the amount of the recycled gas.
  • the amount of carbon dioxide input is figure 4 represented by a dotted line.
  • the H 2 to CO ratio was determined by taking gas chromatographic measurements of the RWGS product stream.
  • the measured values obtained for the ratio of H 2 to CO are in figure 4 shown as dots.
  • FIG 1 shows schematically the present invention.
  • CO 2 and H 2 as feed gas A are converted into Fischer-Tropsch products in a synthesis unit 1 .
  • the synthesis unit 1 consists schematically of a RWGS 2 and the actual Fischer-Tropsch plant 3.
  • RWGS 2 CO 2 and H 2 are converted into synthesis gas, ie into CO and H 2 , including the by-products CO 2 and H 2 O may be present in the product gas.
  • CO and H 2 in turn are then converted into a gas phase product mixture B in the FT unit 3 consisting of unreacted synthesis gas (mainly CO, H2), short-chain hydrocarbons and volatile components of the by-products as well as CO 2 , a waxy solid at ambient temperature and pressure Phase of long-chain hydrocarbons (wax phase), a hydrophobic phase of shorter-chain hydrocarbons (oil phase) that is liquid at ambient temperature and ambient pressure and an aqueous phase of water of reaction that forms and therein dissolved organic compounds implemented.
  • This product mixture B (FT product) is then fed into the work-up unit 4.
  • This branched-off part C can include all of the four phases mentioned or also parts.
  • the FT product B can then be worked up in the work-up unit 4 by carrying out isomerization, cracking, hydrogenation and fractionation/separation.
  • hydrogen F is fed to the processing unit 4 .
  • At least one standard-compliant liquid fuel D is then discharged from the processing unit 4 .
  • the hydrogen-containing gas stream E obtained in the work-up unit 4, which may also contain C 1 -C 4 -hydrocarbons, is returned to the synthesis unit 1, in particular the RWGS unit 2 there, without further purification. Due to the recirculation of the hydrogen-comprising stream E, considerably less hydrogen is required than with a procedure according to the prior art.
  • Figure 2a shows the current state of the art.
  • the PtL site and the refinery are spatially separated from one another (symbolized by two dashed boxes, with the upper one representing the PtL site and the lower one representing the refinery).
  • the PtL site is shown in the upper box, to which a synthesis unit 1 is located accordingly figure 1 is located, and in the upper box the refinery, where a processing unit 4 is located accordingly figure 1 located.
  • Hydrogen A1 and carbon dioxide A2 are introduced into the synthesis unit and the products obtained are (among others) oil phase B1 and wax phase B2. These two phases B1 and B2 are worked up in the work-up unit 4 and the product D is obtained.
  • the PtL site also includes the processing unit 4 in addition to the synthesis unit 1, and this is not at another location, the refinery (symbolized by a large dashed box including both units).
  • This makes it possible to return the hydrogen produced in the processing unit 4 directly to the synthesis unit as a recycling stream E.
  • This has two enormous advantages: on the one hand, the amount of hydrogen required is reduced and, on the other hand, the hydrogen produced during processing does not have to be disposed of. Consequently, enormous ecological, economic and technical advantages are achieved.
  • a comparison of figures 2a and 2 B shows that from a total hydrogen requirement of 163.6 kg/h of hydrogen (127+36.6) per 1000 kg/h of CO 2 in the prior art, 27.3 kg/h have to be diverted unused and disposed of, which are recycled in the present invention and reused. In this respect, the present invention achieves a hydrogen saving of around 17%.
  • FIG 3 shows a possible variant of the processing of the FT products.
  • both the wax phase B2 and the oil phase B1 are temporarily stored in storage tanks ST2/ST1.
  • the oil phase B1 can (at any time) be subjected to degassing in the reservoir ST1 if this becomes necessary (not shown).
  • the wax phase B2, or a certain proportion thereof, is then fed into a hydrocracking reactor HC and reacted there with the supply of hydrogen from the hydrogen supply A1-II.
  • the product then goes into a warm separator HT, where it is separated and one phase is fed back into the storage tank ST2 and the other phase is fed further into a cold separator CT1.
  • separation takes place into a gas stream containing hydrogen, which is returned as recycling stream E, and a fraction, which is fed into the named storage tank ST1 for the oil phase B1.
  • the substance mixture is fed into a separation unit S1.
  • the bottom product obtained there is fed back into the storage tank ST2 for the wax phase and the top product is further fed into a further separation unit S2 directed.
  • their top product is discharged as naphtha, i.e. as product D1.
  • the bottom product of the second separation unit S2 is passed on into an isomerization reactor I, where it is reacted with the addition of hydrogen from the hydrogen feed A1-II.
  • figure 4 shows a graphic plot of the material flows according to example 2.

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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Industrial Gases (AREA)
EP20204893.0A 2020-10-30 2020-10-30 Procédé et installation de traitement des produits de produits crus à base de fischer-tropsch destinés à la fabrication de combustibles préformulés ou répondant aux normes Withdrawn EP3992265A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
EP20204893.0A EP3992265A1 (fr) 2020-10-30 2020-10-30 Procédé et installation de traitement des produits de produits crus à base de fischer-tropsch destinés à la fabrication de combustibles préformulés ou répondant aux normes
AU2021370113A AU2021370113A1 (en) 2020-10-30 2021-10-14 Methods and installation for the product preparation of fischer-tropsch-based raw products for producing preformulated fuels or fuels conforming to standards
CA3195310A CA3195310A1 (fr) 2020-10-30 2021-10-14 Procedes et installation pour la preparation de produits de produits bruts obtenus par procede de fischer-tropsch pour produire des carburants preformules ou des carburants conformes aux norme
EP21798959.9A EP4237513A1 (fr) 2020-10-30 2021-10-14 Procédés et installation pour la préparation de produits de produits bruts obtenus par procédé de fischer-tropsch pour produire des carburants préformulés ou des carburants conformes aux normes
US18/034,264 US20230383193A1 (en) 2020-10-30 2021-10-14 Process and installation for the product processing of fischer-tropsch based raw products for the production of pre-formulated fuels or standard-compliant fuels
JP2023527289A JP2023549739A (ja) 2020-10-30 2021-10-14 予備配合されたまたは規格に適合した燃料を製造するための、フィッシャー・トロプシュに基づく粗生成物の生成物ワークアップの方法および設備
CN202180073306.8A CN116507704A (zh) 2020-10-30 2021-10-14 用于生产预制或符合标准的燃料的费托基粗产物的产物加工的工艺和装置
PCT/EP2021/078508 WO2022089955A1 (fr) 2020-10-30 2021-10-14 Procédés et installation pour la préparation de produits de produits bruts obtenus par procédé de fischer-tropsch pour produire des carburants préformulés ou des carburants conformes aux normes
CL2023001118A CL2023001118A1 (es) 2020-10-30 2023-04-18 Proceso y planta para el procesamiento de productos de materias primas a base de fischer-tropsch

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EP21798959.9A Pending EP4237513A1 (fr) 2020-10-30 2021-10-14 Procédés et installation pour la préparation de produits de produits bruts obtenus par procédé de fischer-tropsch pour produire des carburants préformulés ou des carburants conformes aux normes

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WO2023222798A1 (fr) * 2022-05-19 2023-11-23 Totalenergies Onetech Procédé de production de combustible durable par l'intermédiaire du monoxyde de carbone
WO2024096929A3 (fr) * 2022-05-22 2024-08-08 Gti Energy Production d'hydrocarbures liquides à partir de dioxyde de carbone, en combinaison avec de l'hydrogène ou une source d'hydrogène

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US6306917B1 (en) 1998-12-16 2001-10-23 Rentech, Inc. Processes for the production of hydrocarbons, power and carbon dioxide from carbon-containing materials
WO2004096952A1 (fr) 2003-05-02 2004-11-11 Johnson Matthey Plc Production d'hydrocarbures par reformage a la vapeur et reaction de fischer-tropsch
WO2007031668A1 (fr) 2005-09-14 2007-03-22 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Reduction de taille d'une unite smr d'une unite gtl par utilisation de l'hydrogene d'un gaz residuaire
US8106102B2 (en) 2005-06-14 2012-01-31 Sasol Technology (Proprietary) Limited Process for the preparation and conversion of synthesis gas
US20130149767A1 (en) * 2011-12-07 2013-06-13 IFP Energies Nouvelles Process for the conversion of carbon-based material by a hybrid route combining direct liquefaction and indirect liquefaction in the presence of hydrogen resulting from non-fossil resources
DE102019200245A1 (de) * 2019-01-10 2020-07-16 Forschungszentrum Jülich GmbH Verfahren und Vorrichtung zur Herstellung von flüssigem Kraftstoff

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Publication number Priority date Publication date Assignee Title
US6306917B1 (en) 1998-12-16 2001-10-23 Rentech, Inc. Processes for the production of hydrocarbons, power and carbon dioxide from carbon-containing materials
WO2004096952A1 (fr) 2003-05-02 2004-11-11 Johnson Matthey Plc Production d'hydrocarbures par reformage a la vapeur et reaction de fischer-tropsch
US8106102B2 (en) 2005-06-14 2012-01-31 Sasol Technology (Proprietary) Limited Process for the preparation and conversion of synthesis gas
WO2007031668A1 (fr) 2005-09-14 2007-03-22 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Reduction de taille d'une unite smr d'une unite gtl par utilisation de l'hydrogene d'un gaz residuaire
US20130149767A1 (en) * 2011-12-07 2013-06-13 IFP Energies Nouvelles Process for the conversion of carbon-based material by a hybrid route combining direct liquefaction and indirect liquefaction in the presence of hydrogen resulting from non-fossil resources
DE102019200245A1 (de) * 2019-01-10 2020-07-16 Forschungszentrum Jülich GmbH Verfahren und Vorrichtung zur Herstellung von flüssigem Kraftstoff

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023222798A1 (fr) * 2022-05-19 2023-11-23 Totalenergies Onetech Procédé de production de combustible durable par l'intermédiaire du monoxyde de carbone
WO2024096929A3 (fr) * 2022-05-22 2024-08-08 Gti Energy Production d'hydrocarbures liquides à partir de dioxyde de carbone, en combinaison avec de l'hydrogène ou une source d'hydrogène

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CL2023001118A1 (es) 2023-11-17
EP4237513A1 (fr) 2023-09-06
AU2021370113A1 (en) 2023-06-22
CN116507704A (zh) 2023-07-28
CA3195310A1 (fr) 2022-05-05
US20230383193A1 (en) 2023-11-30
WO2022089955A1 (fr) 2022-05-05

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