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WO2025219077A1 - Traitement de l'eau dans des procédés « power-to-liquid » - Google Patents

Traitement de l'eau dans des procédés « power-to-liquid »

Info

Publication number
WO2025219077A1
WO2025219077A1 PCT/EP2025/058948 EP2025058948W WO2025219077A1 WO 2025219077 A1 WO2025219077 A1 WO 2025219077A1 EP 2025058948 W EP2025058948 W EP 2025058948W WO 2025219077 A1 WO2025219077 A1 WO 2025219077A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
rwgs
synthesis
wastewater
electrolysis
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.)
Pending
Application number
PCT/EP2025/058948
Other languages
German (de)
English (en)
Inventor
Tim BÖLTKEN
Peter Pfeifer
Frieder Graeter
Sebastian Fischer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ineratec GmbH
Original Assignee
Ineratec GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ineratec GmbH filed Critical Ineratec GmbH
Publication of WO2025219077A1 publication Critical patent/WO2025219077A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
    • 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
    • C07C29/152—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 characterised by the reactor used
    • 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
    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C25B1/042—Hydrogen or oxygen by electrolysis of water by electrolysis of steam
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/081—Supplying products to non-electrochemical reactors that are combined with the electrochemical cell, e.g. Sabatier reactor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/061—Methanol production
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis

Definitions

  • the present invention relates to improved or simplified water treatment in power-to-liquid systems or processes, in particular in the conversion of CO2 to hydrocarbons comprising a reverse water gas shift reaction for the production of synthesis gas.
  • the separated aqueous phase therefore primarily contains alcohols, but also carboxylic acids, which can be explained by the oxygen present in the reaction mixture, either in the CO or CO2, as well as by the oxidizing effect of water.
  • carboxylic acids which can be explained by the oxygen present in the reaction mixture, either in the CO or CO2, as well as by the oxidizing effect of water.
  • methanol synthesis it is the product itself, along with higher-value alcohols, that is contaminated; in Fischer-Tropsch synthesis, these are more likely undesirable side reactions, which can lead to the product water being contaminated with concentrations ranging from a few milligrams to a few grams per liter (e.g., 20 mg - 2 g).
  • concentrations ranging from a few milligrams to a few grams per liter (e.g., 20 mg - 2 g).
  • concentrations ranging from a few milligrams to a few grams per liter (e.g., 20 mg - 2 g).
  • the loading of the reaction water is typically lower than with iron-based catalysts; ruthenium-based catalysts probably behave similarly.
  • FT Fischer-Tropsch synthesis
  • the gases hydrogen and carbon monoxide, and especially carbon dioxide dissolve in the reaction water. The latter is responsible for the formation of carbonic acid and thus a very low pH value of the water.
  • wastewater treatment processes that can be used to make this water suitable for electrolysis include membrane distillation, reverse osmosis, and distillation. All of these processes require energy and therefore reduce the net yield of stored energy in the synthetic fuels.
  • CA 3047846 Al describes a process of converting CO2 and H2 via rWGS and FT, whereby water formed from the rWGS is used to slak lime The resulting product water is not recycled into the actual power-to-liquid (PtL) process.
  • KR 101152666 Bl and US 9,199,890 B2 disclose the use of separated water from the synthesis and from a subsequent treatment step of the liquid synthesis product in a reformer to generate synthesis gas. Product water from the combustion of undesirable byproducts is also recycled into the reforming process.
  • KR 20150104819 A discloses the use of water from the synthesis and hydrotreatment processes in the production of synthesis gas by reforming natural gas (methane); here, no electrolysis is required and the steam is fed into the reforming process.
  • AU 2003203442 B2 discloses the use of a combination of a rWGS stage and autothermal reforming of natural gas.
  • the resulting CO2 is recycled, with a portion of the hydrogen required for carbon dioxide reduction coming from the reforming of the resulting naphtha. There is no information on water management.
  • US 8,506,910 B2 discloses the recycling of collected water from an RWGS reactor, a subsequent methanol or dimethyl ether synthesis, and a subsequent gasoline synthesis from the methanol/dimethyl ether intermediate to the electrolysis unit.
  • the required water quality is not disclosed.
  • the different qualities of the water from the various steps are not described in detail.
  • WO 2010/112982 A1 describes a process for the conversion of CO2 and H2 via rWGS and FT in which CO2 is recycled to the RWGS and water is recycled to produce hydrogen.
  • rWGS reverse water gas shift
  • the process concept is usually as follows: Demineralized water is subjected to electrolysis, followed by rWGS, to which the CO2 is added.
  • wastewater is generated on the one hand, and CO as a product on the other, which is fed into the synthesis of valuable materials (for example, methanol synthesis or Fischer-Tropsch synthesis). There, in addition to the valuable product, wastewater is also generated.
  • rWGS In rWGS, according to the reaction equation CO2 + H2 CO + H2O, water is also produced from the hydrogen used to reduce carbon dioxide. With an excess of hydrogen, synthesis gas (a mixture of CO and H2 ) is produced, which can significantly accelerate the Fischer-Tropsch reaction or the formation of methanol, or which, for example, enables the Fischer-Tropsch reaction in the case of cobalt catalysts. Water (hereinafter also referred to as accompanying water) is often used in the feed of the rWGS to prevent the undesirable formation of carbon, see, for example, WO 2019/048236 Al.
  • the object of the present invention was therefore to overcome the disadvantages of the prior art described above and to provide devices and methods which no longer have these problems or at least only to a considerably lesser extent.
  • ambient temperature means a temperature of 20°C. Unless otherwise stated, temperatures are in degrees Celsius (°C).
  • the present invention relates, in a first essential aspect, to a device for converting CO2 to hydrocarbons comprising a reverse water gas shift reaction for producing synthesis gas, the device comprising:
  • At least one device for treating the supplied water comprising at least one reverse osmosis device, and optionally a first ion exchange unit and/or a second ion exchange unit;
  • At least one electrolysis device preferably selected from a water electrolysis unit or a steam electrolysis unit, which electrolyzes the demineralized water coming from the water treatment device, comprising separate outlets for the oxygen produced and the hydrogen produced;
  • At least one rWGS device downstream of the electrolysis which comprises i) in addition to the hydrogen supply line, at least one further supply line for the carbon base containing CO2, ii) at least one further supply line for water vapor, iii) at least one outlet line for the gaseous rWGS product, and iv) at least one waste water outlet line for condensed associated water and reaction water;
  • At least one synthesis device downstream of the rWGS device which comprises i) in addition to the supply line for the gaseous rWGS product, at least one outlet for the synthesis product, and ii) at least one waste water outlet;
  • an evaporator unit may be provided according to B); where the respective rWGS devices and synthesis devices are assigned heating devices for the respectively discharged wastewater, which are configured to degas the respective wastewater at pressures of less than 6 bar, and preferably more than 0.3 bar, and each comprise exhaust gas outlets; the device has a return line for the heated wastewater originating from the at least one synthesis device into the at least one rWGS device; and the device has a return line for the heated wastewater originating from the at least one rWGS device a) partly into the device for treating the supplied water, in particular the reverse osmosis device, and b) partly into the at least one rWGS device.
  • the heat required to heat the wastewater is obtained by the heating device at least partially, preferably entirely, from the waste heat of the at least one synthesis device. This is preferably achieved through the use of heat exchangers.
  • the heating devices are configured to heat the respective wastewater to at least 50°C, in particular at least 70°C and at most 100°C.
  • the heating device can also be assigned an evacuation device in its exhaust line to promote degassing. The maximum permissible temperature during heating then results from the vapor pressure of the water. Through this heating, gases dissolved in the respective wastewater are expelled and can then be discharged as exhaust gas. In particular, CO2 is thus expelled and the CO2 content in the wastewater is significantly reduced. In addition, hydrogen and carbon monoxide are outgassed. Volatile dissolved components of hydrocarbons and alcohols from the synthesis wastewater, which can be problematic for side reactions in the rWGS device, can also be removed in this way.
  • the various exhaust gas outlets are combined and combined into a single exhaust gas line. While this is a preferred variant because it simplifies the connection to other systems, this measure is not absolutely necessary.
  • the at least one synthesis device is configured either to carry out a Fischer-Tropsch synthesis or to carry out a methanol synthesis, preferably including dehydrogenated secondary products, such as preferably dimethyl ether or olefins or oxymethylene ether or aromatics, in particular dimethyl ether or olefins.
  • the present invention relates to a process for converting CO? to hydrocarbons comprising a reverse water gas shift reaction for generating synthesis gas, in particular in a device according to the present invention as described above, wherein the process comprises the following steps: a) supplying water, in particular process water; b) treating the supplied water at least by means of reverse osmosis, and optionally by means of a first ion exchanger unit and/or a second ion exchanger unit; c) electrolyzing the demineralized water coming from the water treatment, preferably by means of a water electrolysis unit or a steam electrolysis unit and separately discharging the oxygen produced and the hydrogen produced; d) carrying out an rWGS downstream of the electrolysis, comprising i) supplying hydrogen and supplying carbon base containing CO 2 , ii) supplying water vapor, iii) discharging the gaseous rWGS product, and iv) discharging the waste water, in particular from condensed associated
  • the heat required to heat the waste water is obtained at least partially, preferably completely, from the waste heat of the at least one synthesis.
  • the respective wastewater is heated, in addition to the pressure reduction, to at least 50°C, in particular at least 70°C and at most 100°C.
  • the various exhaust gases are combined and combined to form a single overall exhaust gas, which is preferred but not absolutely necessary.
  • the at least one synthesis is either a Fischer-Tropsch synthesis or a methanol synthesis, preferably including dehydrated secondary products.
  • the demineralized water coming from the water treatment device or water treatment system is preferably demineralized and free of impurities.
  • the carbon base preferably comprises CO2, which can originate from biomass fermentation or gasification, as well as from its removal from industrial processes or the air.
  • the carbon base consists essentially of CO2 and is supplied in particular in gaseous form. Essentially, in this context, means at least 90 vol.%.
  • the heated wastewater originating from the synthesis or synthesis device is low in hydrocarbon contamination (HC) and has a greatly reduced CO2, H2 , and CO content, particularly at the target temperature and optionally reduced pressure.
  • HC hydrocarbon contamination
  • CO2, H2 , and CO content particularly at the target temperature and optionally reduced pressure.
  • deionized water from other sources can optionally be metered into the rWGS device as additional accompanying water.
  • the term "low in” in this context particularly preferably means a reduction in hydrocarbon contamination of >90% compared to the content before the synthesis or synthesis device.
  • the wastewater originating from the rWGS or rWGS device is generally free of HC, since the catalysts used there generally allow reforming of the HC components at high temperatures in the presence of associated water.
  • the CO2, H2 , and CO content are significantly reduced.
  • the reduction in CO2 and CO content allows for use in electrolysis.
  • Contaminants introduced through recirculation, such as particles or inorganic foreign ions, are advantageously retained in reverse osmosis. Therefore, recirculation to reverse osmosis is the preferred option.
  • the present invention relates to the use of the device according to the invention for power-to-liquid processes.
  • accompanying water is added as steam to the reactant mixture in the rWGS reactor stage to avoid soot/carbon formed via CO decomposition, Boudouard equilibrium, or the Bosch reaction, or to avoid HC decomposition reactions, even though this adversely affects the equilibrium position.
  • the addition of accompanying water is an integral component of the present invention.
  • the rWGS unit primarily removes residual HC components from the synthesis wastewater, making the purification suitable for water electrolysis.
  • the molar ratio of steam to carbon in carbon-containing components is referred to as the S/C (steam-to-carbon) ratio and is at least 0.2, but typically between 0.5 and a maximum of about 1.2.
  • the CO2 conversion under elevated pressure is typically below 50%. Therefore, the CO2 not converted in the RWGS is recycled either before or after synthesis. This means that twice as much CO2 passes through the RWGS unit as CO2 is produced.
  • the water demand in the RWGS is at least as high as the hydrocarbon-contaminated (HC) product water generated from the synthesis unit, starting at an S/C ratio of 0.5.
  • This product water can thus be used 100% as accompanying water for steam generation for the RWGS feed, because gas components that could cause undesirable parameter deviations in the RWGS are expelled beforehand.
  • HC hydrocarbon-contaminated
  • the HC components contained in the water are converted almost completely (>98%) in a single pass.
  • the water condensed from the rWGS is composed of two parts accompanying water vapor and one part reaction water, a single water molecule passes through the rWGS reactor on average twice, meaning the condensate can be considered free of HC components.
  • the resulting excess rWGS condensate can be used to produce demineralized water, preferably bypassing at least the first stage of ion exchange. For this purpose, only gas must be expelled, in principle similar to the process after the FT reactor. Waste heat can also be utilized here.
  • the present invention differs from the prior art in particular by a combination of the following features, which is not known from the prior art:
  • the synthesis wastewater passes through the rWGS reactor twice due to the recycling of the degassed rWGS wastewater together with the degassed synthesis wastewater, which reduces both the water demand of the PtL overall process as well as the need for accompanying water in the rWGS unit.
  • the devices and methods according to the invention therefore enable significantly more efficient operation compared to the prior art. This is because it makes it possible to remove organic substances from water from the synthesis process without requiring additional expenditures for reducing BOD/COD. At the same time, a significant amount of process water for electrolysis is saved, thus increasing overall process efficiency and significantly reducing the amount of salt required for ion exchange. For applications in water-scarce regions or in offshore plants for the purpose of producing PtL products, a significantly reduced water requirement also represents an energy saving, where salt water would otherwise have to be converted into process water.
  • the process water requirement for removing the BOD/COD in the synthesis water is reduced by at least 30%, or without discharge up to a maximum of 70%, preferably a maximum of 66%, depending on the water feed point in the raw water treatment process.
  • the person skilled in the art can, insofar as these are not explicitly described in this description, determine the exact design of the devices described, such as size, wall thicknesses, materials, etc., to suit the reaction conditions envisaged for a specific reaction within the scope of his general technical knowledge.
  • the individual parts of the devices are operatively connected to one another in a customary and known manner.
  • Figure 1 shows a highly schematically illustrated preferred variant of a device according to the invention. It shows a device for converting CO2 to hydrocarbons comprising a reverse water gas shift reaction for Production of synthesis gas.
  • the water supply enters from the top left, with process water or tap water being used in particular.
  • This water enters a device for treating the supplied water, comprising, in the example shown, a first ion exchange unit IT-1, a reverse osmosis device U/O, and a second ion exchange unit IT-2 (the variant comprising IT-1, U/O, IT-1 is a preferred variant according to the invention).
  • the demineralized water VE-W which is preferably free of impurities (demineralized and free of impurities means, in particular, below the usual detection limits; demineralized water is preferably understood in the usual context), enters an electrolysis device EL, which is preferably a water electrolysis unit or a steam electrolysis unit (combinations are also possible).
  • an electrolysis device EL which is preferably a water electrolysis unit or a steam electrolysis unit (combinations are also possible).
  • the demineralized water VE-W coming from the water treatment device is electrolyzed.
  • the hydrogen produced is, at least in part, fed into an rWGS device rW, which comprises at least one outlet for the rWGS product and at least one wastewater outlet AW-r.
  • the outlet for the rWGS product is designed as a direct reactant feed line for a synthesis device SV connected downstream of the rWGS device rW, so that the rWGS product is fed via this line into the synthesis device SV, which comprises at least one outlet for the synthesis product SP and at least one wastewater outlet AW-S.
  • a detailed design of the connection between the RWGS and synthesis unit can also include pressure increase via a compressor and associated further condensation, as well as heat exchangers or other units.
  • the heat exchangers can also be understood as components of the respective units; the precise design of the units can be understood as independent of the design according to the invention.
  • the device comprises a supply line for carbon base KB, which in the illustration shown leads into the supply line of the rWGS unit.
  • both the rWGS device rW and the synthesis device SV are each assigned a heating device EV for the respective discharged wastewater.
  • the respective discharged water is heated to at least 50°C, preferably at least 70°C, via the heating devices EV. in particular at least 70°C and at most 100°C, heated to expel volatile components, in particular CO2, if necessary under reduced pressure.
  • the device has a return line for the heated wastewater AW-SV originating from the synthesis device SV into the rWGS device rW, and a return line for the heated wastewater AW-rW originating from the rWGS device rW.
  • the return of the heated wastewater AW-rW originating from the rWGS device rW is divided so that a portion is returned to the reverse osmosis device U/O, and a portion is returned to the rWGS device rW. The division is made according to the water requirement in the rWGS device.
  • a dashed arrow illustrates that additional deionized water can optionally be metered into the rWGS device rW as accompanying water VE-W-B, if desired or necessary.
  • This figure also shows that the exhaust gas lines from the EV heating devices are combined, resulting in a single exhaust gas stream.
  • a portion of the degassed synthesis water, or ideally a portion of the degassed rWGS wastewater can be diverted to prevent the accumulation of particles or foreign ions. Since the rWGS wastewater is very clean, diverting it is advantageous.
  • all units shown can consist of multiple modules, especially reactors.
  • SV synthesis device especially methanol synthesis device or Fischer-T ropsch synthesis device
  • Example Degassing of a FT wastewater by heating at 50°C and ambient pressure
  • the following table shows various degassing scenarios. At 50°C, the majority of the components were reduced by more than 90% compared to pure expansion at a separation temperature of 5°C in a cold trap. By further reducing the pressure to 0.3 bar, this reduction could be further increased by around 75%. Thus, by heating, an order of magnitude less CO, H2, and CO2, as well as C1-C8 hydrocarbons, were found in the wastewater from the FT. Starting from this, the concentrations in the liquid phase could be reduced again to one-third by reducing the pressure to negative pressure, so that ultimately only about 3-4 mol% of the normal substance concentrations were contained (reference condition 5°C and ambient pressure). This provided accompanying water for the rWGS reactor, and the risk of side reactions was greatly reduced. The remaining 3-4 mol% were converted in the rWGS by reforming.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Metallurgy (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Combustion & Propulsion (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention concerne un traitement amélioré de l'eau dans des systèmes et des procédés « power-to-liquid » (transformation d'électricité en hydrogène liquide), en particulier dans la conversion de CO2 en hydrocarbures, comprenant une réaction de conversion inverse eau-gaz pour produire un gaz de synthèse.
PCT/EP2025/058948 2024-04-17 2025-04-02 Traitement de l'eau dans des procédés « power-to-liquid » Pending WO2025219077A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102024110837.1 2024-04-17
DE102024110837.1A DE102024110837A1 (de) 2024-04-17 2024-04-17 Wasseraufbereitung in Power-to-Liquid-Prozessen

Publications (1)

Publication Number Publication Date
WO2025219077A1 true WO2025219077A1 (fr) 2025-10-23

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PCT/EP2025/058948 Pending WO2025219077A1 (fr) 2024-04-17 2025-04-02 Traitement de l'eau dans des procédés « power-to-liquid »

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DE (1) DE102024110837A1 (fr)
WO (1) WO2025219077A1 (fr)

Citations (9)

* Cited by examiner, † Cited by third party
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US6693138B2 (en) 2002-04-09 2004-02-17 Chevron U.S.A. Inc. Reduction of carbon dioxide emissions from Fischer-Tropsch GTL facility by aromatics production
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