[go: up one dir, main page]

WO2025219656A1 - Production de gaz de synthèse - Google Patents

Production de gaz de synthèse

Info

Publication number
WO2025219656A1
WO2025219656A1 PCT/FI2025/050197 FI2025050197W WO2025219656A1 WO 2025219656 A1 WO2025219656 A1 WO 2025219656A1 FI 2025050197 W FI2025050197 W FI 2025050197W WO 2025219656 A1 WO2025219656 A1 WO 2025219656A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
calcination
reduction
carbon
gas stream
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/FI2025/050197
Other languages
English (en)
Inventor
Eemeli Tsupari
Sampsa VUORI
Juho KAUPPINEN
Cyril BAJAMUNDI
Esko Salo
Aki HÄMÄLÄINEN
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.)
VTT Technical Research Centre of Finland Ltd
Original Assignee
VTT Technical Research Centre of Finland Ltd
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 VTT Technical Research Centre of Finland Ltd filed Critical VTT Technical Research Centre of Finland Ltd
Publication of WO2025219656A1 publication Critical patent/WO2025219656A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/002—Horizontal gasifiers, e.g. belt-type gasifiers
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/28—Moving reactors, e.g. rotary drums
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
    • C01D1/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/02—Oxides or hydroxides
    • C01F11/04—Oxides or hydroxides by thermal decomposition
    • C01F11/06—Oxides or hydroxides by thermal decomposition of carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/02—Magnesia
    • C01F5/06—Magnesia by thermal decomposition of magnesium compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2/00—Lime, magnesia or dolomite
    • C04B2/10—Preheating, burning calcining or cooling
    • 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
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/0073—Selection or treatment of the reducing gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00121—Controlling the temperature by direct heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
    • B01J6/001—Calcining
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
    • B01J6/008—Pyrolysis reactions
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00017—Aspects relating to the protection of the environment
    • C04B2111/00019—Carbon dioxide sequestration
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/095—Exhaust gas from an external process for purification
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0966—Hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0969—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1659—Conversion of synthesis gas to chemicals to liquid hydrocarbons

Definitions

  • the present invention relates to a process for producing synthesis gas by utilizing the carbon dioxide (CO2)-containing stream obtained from a calcination of a carbonate-containing raw material, and to the further uses of said synthesis gas.
  • CO2 carbon dioxide
  • the present invention thus relates to a process for producing synthesis gas, by first producing carbon monoxide (CO) or a CO-containing gas mixture from a stream containing carbon dioxide (CO2) obtained from the calcination of a carbonate-containing raw material, among others, by utilizing Reactions (1) and (2) and subsequently contacting the CO-containing gas mixture further with a hydrogencontaining gas to produce synthesis gas.
  • CO carbon monoxide
  • CO2 carbon dioxide
  • CO2 carbon dioxide
  • the produced CO has a high energy content, with almost twice the energy content compared to utilized carbonaceous material.
  • the new process decreases the consumption of conventional fuels, and it cuts down the carbon emissions of fuel combustion.
  • the process provides a new technology, wherein limestone can be utilized in the production of synthesis gas.
  • the process also eliminates the need for high pressures and extreme temperatures in the production of carbon monoxide and synthesis gas.
  • the optional electric calcination offers a cost-effective solution for the calcination and for capturing CO2 by decreasing the consumption of energy from burning fossil fuels, while eliminating emissions of e.g. carbon and carbon dioxide from thermal energy production.
  • the new process provides new resource efficient alternatives and enhances the process sustainability by decreasing the need for external energy supply.
  • FIGURES 1 and 2 illustrate process configurations encompassed by the present invention
  • Fig. 1 illustrating the alternative of combining the reduction with the calcination
  • Fig. 2 illustrating the alternative of carrying out a separate reduction of the CO2-containing gas stream obtained from a heat treatment step.
  • FIGURE 3 illustrates a process configuration incorporating some preferred embodiments of the below description, showing for example the optional addition of further reagents (e.g. O2, H2, CH4, and steam) to either the calcination or the reduction step, or both, as well as using dotted lines to show the optional recovery of the CCh-containing gas stream, and to show the optional use of the CO-containing gas stream as dilution gas to enhance calcination.
  • further reagents e.g. O2, H2, CH4, and steam
  • FIGURE 4 illustrates a process configuration according to an embodiment of the invention, where the synthesis gas is further converted into hydrocarbons.
  • FIGURE 5 illustrates the high CO2 concentrations which can be achieved by electrically heated calcination reactor, as a function of the pressure.
  • FIGURE 6 is a graph showing the contents of a typical CO-containing gas stream obtained in a reduction reaction carried out in accordance with the invention by using three different carbonaceous materials having different reactivities.
  • synthesis gas encompasses a mixture of gaseous and possibly liquid components including carbon monoxide (CO) and hydrogen (H2). Typically, it contains also carbon dioxide (CO2) and methane (CH 4 ).
  • gas streams or “gas mixtures” are mentioned, it is typically referred to wet gas or humid gas saturated with liquid vapor.
  • the present invention thus relates to a process for producing synthesis gas, by first producing a carbon monoxide (CO)-containing gas mixture by calcining a raw material containing carbonates, to produce carbon dioxide (CO 2 ), obtaining a gas stream containing carbon dioxide (CO2) from the calcination, and reacting the CCh-containing gas stream with a carbonaceous material to cause a reduction of the CO2 into CO, the process being characterized by subsequently contacting an obtained CO-containing gas mixture with a hydrogen-containing gas to produce synthesis gas.
  • CO carbon monoxide
  • the raw material is typically a material containing carbonates, preferably containing the carbonates in the form of calcium carbonate (CaCOs), calcium magnesium carbonate (CaMgfCChE), magnesium carbonate (MgCOs), lithium carbonate (Li2CO3), potassium carbonate (K2CO3), or sodium carbonate (Na2CO3), or a mixture of two or more of these, most suitably being a mineral raw material, such as limestone or dolomite, or a calcium carbonate -containing fraction obtained from chemical pulping of wood materials.
  • CaCOs calcium carbonate
  • CaMgfCChE calcium magnesium carbonate
  • MgCOs magnesium carbonate
  • Li2CO3 lithium carbonate
  • K2CO3 potassium carbonate
  • Na2CO3 sodium carbonate
  • any known calcination equipment can be used in the process, such as a fluidized bed reactor, shaft furnace, flash calciner or rotary kiln, but a preferred option is to carry out the calcination described herein in a rotary kiln.
  • the calcination is typically carried out in a hollow cylindrical device with two ends.
  • the hollow cylindrical device is configured to be rotated around an axis of rotation.
  • the axis of rotation is typically orientated horizontally or substantially horizontally.
  • the term ’’axis orientated horizontally means an axis that is orientated perpendicular to a gravity vector or perpendicular to the normal on the surface of the Earth.
  • the term ’’axis orientated substantially horizontally means an axis that is tilted a few degrees, for example less than 10 degrees, from the axis that is orientated perpendicular to a gravity vector or perpendicular to the normal on the surface of the Earth.
  • a feed end is fixed at a higher level than a discharge end.
  • the material carried through the kiln will gradually move from the feed end to the discharge end when the device is rotated.
  • the material is distributed over an inner surface of the cylindrical device by the rotation.
  • the rotational speed of the hollow cylindrical device may be, for example, in the range between 0.1 and 10 revolutions per minute (rpm).
  • the rotational speed may be adjustable.
  • the feed inlet is positioned at the feed end of the device that is fixed at a higher level than the discharge end at which the outlet for the solid product is positioned.
  • the calcination step carried out in said rotary kiln will thus take place during a time interval that is determined by the time it takes for the material to move from the feed end of the hollow cylindrical device to the discharge end.
  • the heating can be applied using electrical heating equipment or a fuel-powered burner, or a combination of these, the heating equipment preferably positioned by the discharge end of the substantially horizontal rotary kiln. Heating of the cavity within the hollow cylindrical device typically takes place by increasing a wall temperature of the rotatable hollow cylindrical device.
  • the heating system may be capable of adjusting the temperature within the cavity, for example in a range between 150 °C and 1600 °C.
  • the calcination is at least partly achieved via electrical heating. It may, however, also be carried out entirely by electrical heating.
  • Said calcination step can optionally be followed by one or more further heat treatment steps, preferably one or two.
  • a further heat treatment step might be e.g. a sintering step or a clinkering step.
  • Such subsequent heat treatment steps are typically heated at least partly by combustion.
  • the temperature used in the calcination step is typically >750 °C, preferably 750 - 1100 °C, more preferably 900 - 1100 °C, and, generally, the calcinations are operated at a pressure that is close to atmospheric pressure, typically at a slight overpressure level of 0.0001 to 0.5 bar, but electric calcination can also be operated at a slight vacuum, which facilitates the calcination reaction.
  • the calcination reaction occurs within the range of -0.5 to 2 bar pressure, preferably 0.0001 - 0.5 bar.
  • calcination is followed by one or more further heat treatment steps
  • their temperatures can naturally be different from the temperatures of the other heat treatment steps, such as achieved by operating each heat treatment step at a higher temperature than the previous one.
  • a preferred alternative is to operate a further heat treatment step at a temperature of 1000 - 1600 °C, more preferably 1200 - 1500 °C, and most suitably 1300
  • the duration of each of the calcination and other heat treatment steps typically ranges from few seconds to days, e.g. from 2 seconds to 20 days, or from 5 seconds to 10 days, partly based on the temperature and on the rate of energy transfer, which are significantly influenced by the type of equipment and process. Further, the selected raw material has an influence.
  • the residence time in a rotary kiln could be 1 - 30 h, or 6 - 24 h, while the residence time in a fluid bed reactor could be as low as seconds, and the residence time in a shaft kiln could be as long as 12 - 50 h, or 16 - 48 h.
  • a preheating step is carried out, e.g. to pre-dry the raw material before the above-described calcination, which pre-heating step can be carried out at a lower temperature than the calcination, such as a temperature of 150 - 800 °C, preferably 200 - 750 °C, and more preferably 600 - 750 °C.
  • the calcination is carried out in the presence of oxygen (see the further reagents of Figs. 3 and 4), preferably in the form of oxygen gas (O2), thus resulting in a higher quality for the CO2 in the resulting gas stream, among others reducing the concentration of nitrogen (N2) in the calcination, while also lowering the CO2 content in the reaction zone, thus favouring the production of products in the calcination reaction.
  • oxygen can for example be oxygen produced by electrolysis from water using Reaction (3),
  • the oxygen can optionally be produced at the same site of the present process.
  • a further option is to recirculate a fraction of the CO-containing gas mixture to the calcination, which will also reduce the CCh-contcnt in the calcination zone, thus favouring the production of products in the calcination reaction, as mentioned above for the additional oxygen supply.
  • a mixture of oxygen gas and steam is used in the calcination.
  • the calcination produces both a calcined solid product, e.g. in the form of calcium oxide (CaO) and a gas stream containing CO2 and further off-gases.
  • the gas stream is utilized in the following reduction step, although a fraction thereof can be separated and utilized elsewhere, such as in other processes or in other steps of the herein described process.
  • One preferred alternative is to utilize the separated fraction of off-gases by recirculating it back to the calcination.
  • This gas stream obtained as an intermediate product from the calcination is rich in CO2, typically containing >50 vol-% CO2, or more than 70 vol-%, or even more than 90 vol-% (see Fig. 5), while it preferably contains 85 - 95 vol-% CO2. Further, it may contain carbon monoxide (CO), oxygen (O2), hydrogen (H2), nitrogen (N2), and/or steam (H2O), and traces of other gases as further off-gases.
  • CO carbon monoxide
  • O2 oxygen
  • H2
  • the gas stream containing carbon dioxide (CO2), obtained from the calcination, can be recovered (see Figs. 2-4) before reacting it with the carbonaceous material in a separate process step, i.e. a separate reduction step.
  • This recovery may take place e.g. by separating the gaseous fraction from the solid product via a gas outlet in the heat treatment unit.
  • these units form an integrated sequence of units.
  • the gas stream is recovered, it is preferably fed to the reduction step directly, or it may be purified or concentrated before taking part in the reduction step.
  • the reduction may be carried out in a reduction unit that is separate from the heat treatment unit(s), these units form an integrated sequence of units.
  • the temperature of the stream containing CO2 may even be sufficient to provide an optimal reduction step without further heating, particularly if no separate step for concentrating the CO2 of the stream has been carried out.
  • the stream containing CO2 can be heated separately, preferably to a temperature of >900 °C, more preferably 900 - 1500 °C, before taking part in any further reactions, such as the reduction step.
  • This alternative may also be applied when a low temperature has been applied in the calcination, such as a temperature below 900 °C, or a temperature below 800 °C.
  • the reduction step can be carried out at a pressure that is close to atmospheric pressure, or at slightly adjusted pressure, more typically at a pressure in the range of -1 - 10 bar, preferably 0 - 2 bar.
  • the gas stream can be contacted with one or more catalysts, such as nickel, calcium oxide, magnesium oxide, zinc oxide, or aluminium oxide, preferably in catalytic amounts, before further reactions.
  • either the CCh-containing gas stream, or a fraction of off gases separated therefrom, or a combination of one of these streams with added gaseous streams is purified to increase the CO2 content of this gas stream, and/or to remove undesired components, such as excess oxygen, nitrogen or sulphur dioxide.
  • This purification can take place e.g. by washing, scrubbing, cooling or drying the gas stream, or by a combination of two or more such techniques, and preferably results in a CO2 concentration of >85 vol-%.
  • the gas stream containing carbon dioxide (CO2), obtained from the calcination can be used as such in the reduction step, without recovery (see Fig. 1).
  • the heat generated in the calcination can be utilized also for this reduction reaction.
  • the heat of the reduction reaction may be at least partly achieved by electrical heating, or alternatively entirely by electrical heating.
  • a temperature of 900 - 1500 °C may be used, more preferably 900 - 1100 °C, and most suitably 950-1050 °C.
  • the reduction reaction will begin immediately in the solid material feed end of the heat treatment unit, or in the area of the heat treatment unit that is close to the feed end/area.
  • the reduction reaction might be complete or essentially complete by the time the solid material reaches the discharge end, or the reaction might be completed or essentially completed at the discharge end, where the heating possibly is most efficient.
  • This alternative is particularly suitable for embodiments, where the heating takes place by electric heating.
  • the CCh-containing stream is reacted to produce a CO-containing gas mixture, optionally generating also activated carbon.
  • This reduction step utilizes a carbonaceous reagent, which preferably is in the form of char, charcoal, coke, petroleum coke or biochar, or a hydrocarbon or acid or alcohol thereof, preferably in the form of methane (CH4), ethylene (C2H4), propylene (C3H6), butenes (C4H8), or formic acid, or methanol (CH3OH), or a mixture of hydrocarbons.
  • a mixture of carbon and hydrocarbon(s) can be used in the reduction reaction, or a biomass, such as wood chips, or a combination of any of these.
  • the optional biomass is preferably formed of wood chips or other crude or dried biomass, thus preferably excluding refined carbon products.
  • the carbonaceous reactant used in the reduction step contains carbon, preferably in the form of char, charcoal, coke, or petroleum coke, or biochar or activated carbon, and/or it contains a hydrocarbon, preferably in the form of methane (CH4), ethylene (C2H4), propylene (C3H6), butenes (C4H8), or formic acid, or methanol (CH3OH), more preferably in the form of methane (CH4), ethylene (C2H4), propylene (ChHe), or butenes (C4H8), which are advantageous in that they lack oxygen in their structures, or a mixture of hydrocarbons, or it contains a biomass or a woody biomass, such as wood chips, or a combination of any of these.
  • a hydrocarbon preferably in the form of methane (CH4), ethylene (C2H4), propylene (C3H6), butenes (C4H8), or formic acid, or methanol (CH3OH), more
  • the carbonaceous reactant is formed of one or more carbons or one or more hydrocarbons, or it is formed of a mixture of carbon(s) and hydrocarbon(s), or it is a combination of any of these, more preferably being formed of carbon(s) or a mixture of carbon(s) and hydrocarbon(s), the carbon(s) particularly selected from char and/or biochar.
  • the carbonaceous reactant is selected from a mixture of one or more carbons and one or more hydrocarbons, each preferably selected from the above lists, more preferably with the content of carbons in the carbonaceous reactant being 30-100 w-%, more preferably 50-90 w-%.
  • biochar is intended to cover all carbon materials obtained from biomaterials, i.e. conventional biochar, as well as biocoke and biocharcoal, and torrefied biomass.
  • the potential sources of the include both fresh biomass and waste materials, with waste materials being a preferred option particularly when aiming for an ecological improvement.
  • the stream containing CO2 can be used in the reduction step with only the carbonaceous reagent, and thus without further additives, but can, in an embodiment, also be reacted in the presence of steam (see the further reagents of Figs. 3 and 4), preferably in the form of superheated steam, thus providing a further means for heating, while also resulting in a gas stream containing hydrogen.
  • the stream containing CO2 is reacted in the presence of oxygen gas (O2) (see the further reagents of Figs. 3 and 4), for example oxygen produced by electrolysis, e.g., at the same site of the present process.
  • oxygen gas for example oxygen produced by electrolysis, e.g., at the same site of the present process.
  • the oxygen will facilitate the heating of the reduction step, but will also take part in the reactions to produce carbon monoxide, via Reaction (4)
  • a further alternative is again to use a mixture of oxygen gas and steam.
  • the stream containing CO2 is reacted in the presence of a hydrogen-containing gas (see the further reagents of Figs. 3 and 4), which can be either separately added hydrogen, or hydrogen carried to the reaction with the gas stream or with another added stream, such as the above-mentioned steam, or it can be hydrogen produced by electrolysis (see Reaction (3)), e.g., at the same site of the present process.
  • the hydrogen in the reduction reaction will provide among others the further advantage of lowering the CO pressure in the reduction, whereby production of CO will be favoured in Reactions (1) and (2). Further, the hydrogen will adjust the CO/H ratio to favour the production of a desired synthesis gas, or to produce methane or methanol, as specified below.
  • the stream containing CO2 is reacted with the carbonaceous material in the presence of added CO2, e.g. used to initiate the reduction reaction.
  • the CCh-containing gas stream with one or more catalysts, such as nickel, calcium oxide, magnesium oxide, zinc oxide, or aluminium oxide, to the reduction reaction.
  • the catalyst is typically added as a solid material, e.g. a fixed bed or a coating, in the reduction unit, or it may be added to the carbonaceous material or the stream containing CO2 before reacting into a CO- containing product gas mixture.
  • any solid reagents and materials are premixed with the carbonaceous material before the reduction reaction takes place, while any gaseous reagents and materials are premixed with the CCh-containing gas stream.
  • a CO-containing gas mixture is obtained as an intermediate product, preferably having a CO content of more than 60 vol-%, more preferably more than 70 vol- %, or even more than 80 vol-% (see Fig. 6).
  • This gas mixture may, in addition to carbon monoxide, contain e.g. unreacted carbon dioxide, as well as hydrogen (H2) and other common gaseous components, such as oxygen (O2), nitrogen (N2), ethylene (C2H4), methane (CH4), ethane (C2H6) and/or sulphur dioxide (SO2), typically in trace amounts, such as in a combined content of the O2, N2, C2H4, CH4, C2H6 and SO2 of less than 10 vol- % (see Fig.
  • the CO-containing gas mixture will typically contain a more complex mixture of components, such as the mentioned ethylene, methane and ethane.
  • activated carbon can be generated.
  • the obtained CO-containing gas mixture is optionally recovered.
  • a fraction of this intermediate product can be used further, e.g., as a fuel in energy production or in other high-temperature processes, such as calcinations, and it may be utilized as a carbon source in such processes, or in the manufacture of synthetic fuels, chemicals or plastics, or alternatively as a diluting gas for calcination (see Fig. 3), to adjust the contents of materials during calcination, e.g. to reduce recarbonization, to facilitate calcination at lower temperatures, and to adjust the quality of the calcined product.
  • a further option is to return the synthesis gas or a fraction thereof, containing unreacted CO2, or unreacted CO2 separated from this fraction, to the reduction step.
  • the CO-containing gas mixture is contacted further with a hydrogen-containing gas to produce synthesis gas.
  • the hydrogen-containing gas can, again, be either separately added hydrogen, or hydrogen carried to the reaction with the gas stream or with another added stream, such as the above-mentioned steam or a methane stream or a mixture of these, or it can be hydrogen produced by electrolysis, e.g., at the same site of the present process.
  • the step of producing synthesis gas takes place on the same site as the calcination step and the reduction step, merely in a separate reaction unit or reaction zone.
  • the hydrogen production can take place at the same site, e.g. by electrolysis.
  • the herein described process thus results in synthesis gas, which typically contains carbon monoxide (CO), hydrogen (H2), unreacted carbon dioxide (CO2), and methane (CH4), and traces of other unreacted components from the CO-containing gas mixture.
  • the synthesis gas can be further used as a fuel in energy production or in other high-temperature processes, or as a hydrogen or carbon source in such processes, or in the manufacture of synthetic fuels, chemicals or plastics. Further, it can be used as a reducing agent to convert iron ore into sponge iron.
  • the iron ore for this optional conversion is typically in the form of hematite (Fe20s) or magnetite (Fc ⁇ Ch).
  • the invention also relates to the further conversion of the synthesis gas into hydrocarbon products or their alcohols (see Fig. 4), wherein the synthesis gas or the remaining unreacted CO-containing gas mixture with the hydrogen-containing gas mixture is reacted further in conditions that produce hydrocarbons, such as methane (CFU), ethylene (C2H4), propylene (C3H6), butenes (C4H8), or formic acid (HCOOH), methanol (CH3OH), or higher alkanes, higher olefins, synthetic gasoline, diesel fuel, kerosene or waxes and lubricants.
  • CFU methane
  • ethylene C2H4
  • propylene C3H6
  • butenes C4H8
  • HCOOH formic acid
  • CH3OH methanol
  • suitable conditions include using a pressure of 1 - 10 bar and a temperature of 300 - 400 °C
  • suitable conditions include a pressure of 50 - 80 bar and a temperature of 200 - 300 °C.
  • Said higher alkanes and higher olefins may include for example nonane, nonene, decane, decene, or further alkanes or olefins having > 10 carbon atoms.
  • the waxes may, in turn, be polyethylene waxes, or paraffin waxes, or other commonly used waxes, while the lubricants may be polyolefin-based lubricants or similarly other commonly used lubricants.
  • the further conversion of the synthesis gas into hydrocarbons is optimized to obtain a product rich in methane and/or methanol.
  • This is preferably achieved by utilizing conditions of methanation (3H2 + CO CH4 + H2O) and/or methanol formation (CO + 2H2 CH3OH), respectively.
  • the methanation reaction utilizes a H2/CO molecular ratio of 3 : 1 and is typically catalyzed by a nickel catalyst, while the methanol synthesis utilizes a H2/CO ratio of 2: 1 and is typically catalyzed by a copper catalyst.
  • the conditions that produce hydrocarbons may, for example, involve varying the temperature or the pressure of the conversion reaction, or using one or more catalysts, such as iron, cobalt, nickel, and ruthenium-based catalysts, such as Ru/TiCh or Ni/AhCh, or alternatively biocatalysts.
  • catalysts such as iron, cobalt, nickel, and ruthenium-based catalysts, such as Ru/TiCh or Ni/AhCh, or alternatively biocatalysts.
  • a calcination of a calcium carbonate (CaCCh) material (limestone, containing 97 % CaCCF) was carried out in electrically heated rotary kiln at 1000 °C, and a solid product of calcium oxide (CaO) was obtained, as well as a gaseous product containing mainly carbon dioxide (CO2), obtained from the carbonate and released as its own gas stream.
  • Fig. 5 illustrates the CO2 content in an offgas from calcination reactor operated as described herein, as a function of the pressure.
  • the gaseous product was collected, purified and carried to a reduction unit.
  • the carbon dioxide in the gaseous product was reduced with the help of a carbonaceous material fed into the reaction.
  • the reaction requires energy, which can be transferred to the reaction with the heat of the gaseous product fed into it, but in the present example, the reduction unit was further heated by resistors.
  • the CO2- containing gaseous stream was combined with various carbon materials, providing different test results. The contents of gaseous products were continually measured. Three different carbon materials were used, being char coal produced from different natural raw materials, char coal 1 being obtained by pyrolysis from wood chips and having the highest reactivity, char coal 2 being obtained by pyrolysis from bark waste, and char coal 3 being obtained by pyrolysis from a digestate originating from biowaste.
  • the present invention is useful for producing synthesis gas, which can be further converted into hydrocarbon products.
  • the synthesis gas can be used e.g. as a fuel in energy production or in other high-temperature processes, such as calcinations, and it may also be utilized as a carbon source in such processes.
  • the synthesis gas can be used as a reducing agent to convert iron ore into sponge iron.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Thermal Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Ceramic Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Structural Engineering (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

La présente invention propose un procédé de production d'un gaz de synthèse, par production d'un premier monoxyde de carbone (CO) à partir d'un flux contenant du dioxyde de carbone (CO2), obtenu à partir de la calcination d'une matière première contenant du carbonate, puis mise en contact d'un gaz produit contenant du CO obtenu avec un gaz contenant de l'hydrogène pour produire un gaz de synthèse.
PCT/FI2025/050197 2024-04-18 2025-04-17 Production de gaz de synthèse Pending WO2025219656A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20245494 2024-04-18
FI20245494A FI131724B1 (en) 2024-04-18 2024-04-18 Producing synthesis gas

Publications (1)

Publication Number Publication Date
WO2025219656A1 true WO2025219656A1 (fr) 2025-10-23

Family

ID=95560473

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI2025/050197 Pending WO2025219656A1 (fr) 2024-04-18 2025-04-17 Production de gaz de synthèse

Country Status (2)

Country Link
FI (1) FI131724B1 (fr)
WO (1) WO2025219656A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011061299A1 (fr) * 2009-11-20 2011-05-26 Rv Lizenz Ag Conversion thermochimique de matériaux carbonés, en particulier pour la production d'énergie sans émissions
WO2014053847A1 (fr) * 2012-10-04 2014-04-10 Rockfuel Innovations Limited Système et procédé de production de monoxyde de carbone
WO2015015161A1 (fr) 2013-07-30 2015-02-05 Cogent Heat Energy Storage Systems Ltd Procédé de génération d'énergie
EP2883940A1 (fr) * 2012-08-09 2015-06-17 Wuhan Kaidi Engineering Technology Research Institute Co., Ltd. Procédé et dispositif pour la gazéification d'une biomasse par cyclisation de dioxyde de carbone sans oxygène
US20230151286A1 (en) * 2019-11-25 2023-05-18 Wormser Energy Solutions, Inc. Char Preparation System and Gasifier for All-Steam Gasification with Carbon Capture

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11623863B2 (en) * 2017-12-12 2023-04-11 Carbon Engineering Ltd. Air-to-syngas systems and processes
CN109437604B (zh) * 2018-11-13 2020-09-25 北京科技大学 利用甲烷重整实现烧成石灰显热回收及尾气利用的方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011061299A1 (fr) * 2009-11-20 2011-05-26 Rv Lizenz Ag Conversion thermochimique de matériaux carbonés, en particulier pour la production d'énergie sans émissions
EP2883940A1 (fr) * 2012-08-09 2015-06-17 Wuhan Kaidi Engineering Technology Research Institute Co., Ltd. Procédé et dispositif pour la gazéification d'une biomasse par cyclisation de dioxyde de carbone sans oxygène
WO2014053847A1 (fr) * 2012-10-04 2014-04-10 Rockfuel Innovations Limited Système et procédé de production de monoxyde de carbone
WO2015015161A1 (fr) 2013-07-30 2015-02-05 Cogent Heat Energy Storage Systems Ltd Procédé de génération d'énergie
US20230151286A1 (en) * 2019-11-25 2023-05-18 Wormser Energy Solutions, Inc. Char Preparation System and Gasifier for All-Steam Gasification with Carbon Capture

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JIANG PENG ET AL: "A thermodynamic view on the in-situ carbon dioxide reduction by biomass-derived hydrogen during calcium carbonate decomposition", CHINESE JOURNAL OF CHEMICAL ENGINEERING, CHEMICAL INDUSTRY PRESS, BEIJING, CN, vol. 68, 19 January 2024 (2024-01-19), pages 231 - 240, XP087550983, ISSN: 1004-9541, [retrieved on 20240119], DOI: 10.1016/J.CJCHE.2023.12.017 *

Also Published As

Publication number Publication date
FI20245494A1 (en) 2025-10-19
FI131724B1 (en) 2025-10-20

Similar Documents

Publication Publication Date Title
Fermoso et al. Sorption enhanced catalytic steam gasification process: a direct route from lignocellulosic biomass to high purity hydrogen
AU2014214982B2 (en) Methods for fuel conversion
RU2412226C2 (ru) Способ получения и конверсии синтез-газа (варианты)
CN102838116B (zh) 一种焦炉煤气与二氧化碳制一氧化碳的方法
Iordanidis et al. Autothermal sorption-enhanced steam reforming of bio-oil/biogas mixture and energy generation by fuel cells: concept analysis and process simulation
CN103242134A (zh) 一种生活垃圾热解气化净化方法
JP6304856B2 (ja) 改良型三塔式循環流動層によるバイオマスのガス化方法
CN102585947A (zh) 一种由煤制备含甲烷的气体的方法及设备
Devasahayam Catalytic actions of MgCO3/MgO system for efficient carbon reforming processes
Armbrust et al. Calcium looping cycle for hydrogen production from biomass gasification syngas: experimental investigation at a 20 kWth dual fluidized-bed facility
WO2020023452A1 (fr) Procédés et systèmes de production d'hydrogène de grande pureté avec capture de co2 à partir de biomasse et de déchets biogènes
Liu et al. CO2 capture and utilization through isothermal carbonation-calcination looping integrated with MSW pyrolysis volatile reforming
Vamvuka et al. Enhanced H2 gas production from steam gasification of a winery waste through CO2 capture by waste concrete fines and use of alkali catalysts
CN102259835B (zh) 一种基于熔融盐特性的粗合成气净化提质方法
Hernández-Fontes et al. Enhanced hydrogen production via assisted biomass gasification using lithium manganate as a bifunctional material
CN110982558B (zh) 一种基于化学链技术的煤或生物质气化直接制备氢气和一氧化碳的方法
CN105883851A (zh) 一种新型气化与热解耦合煤气多联产工艺
WO2025219656A1 (fr) Production de gaz de synthèse
JP2024546495A (ja) バイオマスガス化からのメタノール
JP2022511116A (ja) 蒸気／ｃｏ２改質による水素及びｆｔ生成物の製造
US12161969B2 (en) Redox reaction facilitated carbon dioxide capture from flue gas and conversion to carbon monoxide
KR102173505B1 (ko) 유동층 반응기를 이용한 메탄 생산 방법
WO2025219657A1 (fr) Conversion de dioxyde de carbone formé pendant des traitements thermiques en composants appropriés destinés à être utilisés en tant que combustible
CN107021876B (zh) 应用于石油石化行业的ccus系统及工艺方法
Lu et al. Effects of B-site substitution of SrFe2O4 oxygen carrier on the biomass chemical looping gasification performance

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 2025722270

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2025722270

Country of ref document: EP

Effective date: 20251021

ENP Entry into the national phase

Ref document number: 2025722270

Country of ref document: EP

Effective date: 20251021

ENP Entry into the national phase

Ref document number: 2025722270

Country of ref document: EP

Effective date: 20251021

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 25722270

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2025722270

Country of ref document: EP

Effective date: 20251021

ENP Entry into the national phase

Ref document number: 2025722270

Country of ref document: EP

Effective date: 20251021