WO2025207367A1 - Procédés de production de gaz industriels et de capture d'oxyde de carbone à l'aide de matériaux contenant du fer ferreux - Google Patents

Procédés de production de gaz industriels et de capture d'oxyde de carbone à l'aide de matériaux contenant du fer ferreux

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Publication number
WO2025207367A1
WO2025207367A1 PCT/US2025/020368 US2025020368W WO2025207367A1 WO 2025207367 A1 WO2025207367 A1 WO 2025207367A1 US 2025020368 W US2025020368 W US 2025020368W WO 2025207367 A1 WO2025207367 A1 WO 2025207367A1
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Prior art keywords
ferrous iron
mixture
iron
containing mixture
ferrous
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English (en)
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David Tew
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Step Function LLC
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Step Function LLC
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    • 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/06—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents
    • C01B3/061—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents by reaction of water with metal oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • 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
    • C01F11/18—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
    • C01F5/24—Magnesium carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/20—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/24—Hydrocarbons
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present disclosure relates to methods for producing climatepositive industrial gases, such as hydrogen (H 2 ), methane (CH 4 )from ferrous iron-containing materials, such as ultramafic minerals and industrial wastes, through material oxidation and carbonation, while recovering valuable trace metals and producing construction materials.
  • the process disclosed yields multiple value streams while helping to mitigate the environmental challenges associated with reactive industrial wastes, such as metal slags and mine tailings.
  • the methods are based on oxidizing ferrous cations (Fe 2+ ) to ferric cations (Fe 3+ ) (and potentially other cations) in the presence of water (H2O) and carbon dioxide (CO 2 ).
  • Hydrocarbon fuels have historically played a crucial role in global industrial development, providing essential energy for transportation, heating, and industrial processes.
  • the environmental impact of fossil fuel emissions necessitates a transition to climate-neutral - or positive - energy sources.
  • Hydrogen (H 2 ) is a critical component of synthetic fuels, yet current production methods primarily rely on fossil fuels, resulting in significant carbon dioxide (CO 2 ) emissions.
  • CO 2 carbon dioxide
  • the process may involve mixing a ferrous iron-containing material with water and, in some examples, reaction accelerants.
  • the mixture may be mechanically and chemically deoxygenated and heated to 100-300°C to initiate material dissolution and the subsequent oxidation of ferrous cations (Fe 2+ ) to ferric cations (Fe 3+ ) while reducing and generating hydrogen (from water) and/or methane (from water and carbon dioxide if carbon dioxide is introduced into the ferrous iron-containing mixture).
  • carbon dioxide may be added after recovering hydrogen.
  • Carbon dioxide may be injected at a high pressure (e.g., about 200 bar) post-oxidation to facilitate mineralization, using the exothermic reaction to maintain a favorable temperature (e.g., 100-300°C).
  • metal complexing/chelating reagents are added to bind trace metals such as nickel (Ni), copper (Cu), cobalt (Co), and platinum group metals (PGMs) for recovery.
  • a method for producing an industrial gas using a ferrous iron- containing material comprising: combining the ferrous iron- containing material with water form a ferrous iron-containing mixture, wherein the ferrous iron-containing material and, subsequently, the ferrous iron- containing mixture comprise ferrous cations (Fe2+); maintaining the ferrous iron-containing mixture for an operating period at one or more processing conditions selected from the group consisting of an operating temperature range, an operating pressure range, an operating acidity (pH) level, and an operating catalyst concentration, wherein maintaining the ferrous iron- containing mixture for the operating period at the one or more processing conditions causes the ferrous cations (Fe2+) to oxidize into ferric cations (Fe3+) while releasing the industrial gas; and collecting the industrial gas from the ferrous iron-containing mixture thereby forming a ferric iron-containing mixture, wherein carbon dioxide is introduced to one or both of: (a) the ferrous iron-containing mixture, together with the water, such that the ferric iron
  • Clause 6 The method of clause 1, further comprising, after collecting the industrial gas from the ferrous iron-containing mixture and forming the ferric iron-containing mixture, introducing carbon dioxide into the ferric iron- containing mixture thereby forming the carbonated mixture.
  • ferrous iron-containing material further comprises one or more elements selected from the group consisting of silicon, aluminum, calcium, and magnesium.
  • Clause 8 The method of clause 7, wherein the carbonated mixture further comprises one or more carbonates selected from the group consisting of calcium carbonate (CaCO 3 ), manganese carbonate (MnCO 3 ), and magnesium carbonate (MgCO 3 ).
  • Clause 14 The method of clause 1, wherein forming the ferrous iron- containing mixture comprises exposing the ferrous iron-containing mixture to electromagnetic radiation in a microwave-to-ultraviolet range.
  • Clause 20 The method of clause 1, wherein the carbon dioxide is introduced at a pressure of between 5 and 300 bar.
  • Clause 23 The method of clause 1, wherein the industrial gas comprises separating hydrogen from additional recovered gas.
  • Clause 26 The method of clause 25, wherein the chelating agent is selected from the group consisting of ammonia, ethylenediaminetetraacetic acid, sulfuric acid, cyanide, and an oxime-based extractant.
  • the chelating agent is selected from the group consisting of ammonia, ethylenediaminetetraacetic acid, sulfuric acid, cyanide, and an oxime-based extractant.
  • Clause 27 The method of clause 1 further comprising recovering heat from at least one of the ferric iron-containing mixture and the carbonated mixture and using that heat to raise the temperature of the ferrous iron- containing mixture.
  • Clause 28 The method of clause 1 further comprising drying the carbonated mixture to recover the carbonated mixture.
  • FIG. 1 is a block diagram illustrating various materials (starting, intermediate, and resulting materials) that are involved in producing industrial gases and sequestering carbon dioxide using ferrous iron-containing materials, in accordance with some examples.
  • FIG. 2B is a schematic illustration of a system for producing industrial gases and sequestering carbon dioxide using a simultaneous introduction of water and carbon dioxide to ferrous iron-containing materials, in accordance with some examples.
  • FIG. 3 is a process flowchart of a method for producing industrial gases and sequestering carbon dioxide using ferrous iron-containing materials, in accordance with some examples.
  • FIG. 4A is a plot illustrating concentration profiles of various materials as a function of time during hydrogen production.
  • FIG. 4B is a plot illustrating the cumulative hydrogen output as a function of time during hydrogen production.
  • FIG. 4C is a plot illustrating concentration profiles of various materials as a function of time during carbon dioxide sequestration.
  • FIG. 4D is a plot illustrating the cumulative amount of carbon dioxide that is sequestered as a function of time during carbon dioxide sequestration.
  • geologic sources of hydrogen have recently been identified as potential opportunities for the provision of (at least) climate-neutral hydrogen at globally-relevant scales. These opportunities include 1) the recovery of hydrogen that has been produced over geologic time-scales and trapped in naturally occurring reservoirs (i.e., white hydrogen), and 2) the production of hydrogen on-demand via the leveraging of the chemical potential of ferrous-iron rich (e.g., ultramafic) minerals (i.e., orange hydrogen).
  • the concurrent scope economies include the realization of multiple value streams from the same minerals via the concurrent sequestration of carbon dioxide, the recovery of remaining valuable metals, and the use of the resulting carbonate minerals as construction products.
  • Methods for producing industrial gases e.g., hydrogen, ammonia, and/or methane
  • ferrous iron-containing materials e.g., olivine, copper slag
  • Ferrous iron-containing materials and other like materials may be collectively referred to as reducing materials.
  • hydrogen is produced (with varied reaction kinetics).
  • Carbon dioxide may be added later, in a separate operation (after collecting hydrogen).
  • methane and hydrogen may both be produced, e.g., at the same time.
  • the relative amounts of methane and hydrogen may depend on the relative amounts of water and carbon dioxide as well as process conditions (e.g., temperature, catalysts, composition of the ferrous iron-containing materials).
  • various carbonates e.g., ferrous carbonate
  • the types of carbonates may depend on the composition of the ferrous iron-containing materials.
  • these materials may comprise one or more of the following cations: manganese, calcium, and magnesium. These cations may also be converted into carbonates.
  • ferrous iron-containing materials e.g., copper (Cu), cobalt (Cu), nickel (Ni), gold (Au), silver (Ag), the rare earth elements (REEs), and platinum group metals (PGMs)
  • Cu copper
  • cobalt Cu
  • Ni nickel
  • Au gold
  • Au silver
  • Au rare earth elements
  • PGMs platinum group metals
  • various chelating agents may be used to facilitate the recovery of valuable trace metals adding significant economic benefits.
  • the process provides cost-effective hydrogen, ammonia, and/or methane production, carbon dioxide sequestration, resource recovery, and the like. More specifically, these methods and systems utilize abundant ferrous iron-containing waste and natural materials and leverage natural processes to produce hydrogen at low cost. The carbon dioxide sequestration enhances environmental benefits while producing valuable carbonate-based materials. Overall, this process addresses the need for climate-neutral hydrogen production and offers a sustainable pathway to mitigating the environmental impact of carbon emissions while providing economic benefits through resource recovery and industrial applications.
  • a process may yield approximately 1 kg of hydrogen (H 2 ) and sequester about 1 tonne of carbon dioxide (CO 2 ) per tonne of natural olivine generating about 2 tonnes of mixed carbonates.
  • H 2 hydrogen
  • CO 2 carbon dioxide
  • the mineral carbonates resulting from the process are more chemically stable than the reactive raw materials.
  • Such reactive stability may be attractive from an environmental standpoint, as they may be less likely to leach dangerous trace elements (e.g., arsenic - As) into the environment.
  • FIG. 1 is a block diagram illustrating various materials (starting, intermediate, and resulting materials) that are involved in producing industrial gases and sequestering carbon dioxide using ferrous iron-containing materials, in accordance with some examples.
  • a ferrous iron-containing material 250 is used as a reducing agent.
  • the ferrous iron-containing material 250 is combined with one or more non-iron salts 255, various examples of which are described below. It should be noted that these non-iron salts 255 may exist in the form or in addition to non-ferrous components 254, further described below.
  • the ferrous iron-containing material 250 comprises at least ferrous cations 253 (that are later oxidized to ferric cations 265).
  • the ferrous iron-containing material 250 may also include nonferrous components 254, such as silicon, aluminum, calcium, and/or magnesium.
  • the carbonated mixture 266 (formed at the end of the overall process) further comprises one or more carbonates selected from the group iron carbonate (FeCO 3 ), calcium carbonate (CaCO 3 ), manganese carbonate (MnCO 3 ), and magnesium carbonate (MgCO 3 ).
  • the ferrous iron-containing material 250 is formed from particles with an average diameter of less than 1 centimeter, less than 10 millimeters, or even less than 1 millimeter. Smaller particles have a larger surface-to-volume ratio and, therefore, help with improving reaction kinetics.
  • Ferrous iron-containing material 250 may be also referred to as ferrous iron-rich materials in which iron content is at least about 5% by weight, at least 10% by weight, or even at least 20% by weight.
  • an additive 261 e.g., an oxidation additive
  • a dissolution agent may be added to the ferrous iron-containing mixture 262.
  • the dissolution agent may be an acid (e.g., carbonic acid (H 2 CO 3 ), hydrochloric acid (HCI), sulfuric acid (H 2 SO 4 ), nitric acid (HNO3)) for adjusting the acidity of the ferrous iron-containing mixture 262 as further described below.
  • an additive 261 may be a deoxygenation additive. It has been found that controlling the reduction potential (e.g., oxygen fugacity (Eh)) of the mixture impacts the kinetics of hydrogen production.
  • various steps may be used to either remove oxygen (e.g., from the mixtures and/or environment) or prevent it from entering the system - including the reuse of a portion of the oxygen-poor solution (forming the ferric iron-containing mixture 264) departing the oxidation reactor 210.
  • two separate water loops are used, e.g., (1) one oxygen-poor loop for the oxidation reactor 210 and (2) one carbon-dioxide rich loop for the carbonation reactor 234. A portion of the oxygen-poor water may be transferred into the carbonation reactor 234 to carry the solid reactants.
  • the remaining portion of the oxygen-poor water (as large as possible) stays in the oxidation reactor 210.
  • This oxygen-poor water will also contain dissolved salts that can be reused in the oxidation reactor 210 (e.g., helping to minimize the need for additional salt).
  • the salt concentration in the oxygen-poor water may be 5-200 g of salt per kg of water or more, specifically, 10- 100 g salt / kg water.
  • the reduction potential of the soluation (a measure of the concentration of oxygen) in reduction potential of the carbon-dioxide-rich water may be >0 mV.
  • an additive 261 may be an accelerant, such as sodium chloride (NaCI), nickel chloride hexahydrate (NiCI 2 *6H2O), potassium chloride (KCI), copper chloride (CuCI 2 ).
  • NaCI sodium chloride
  • NiCI 2 *6H2O nickel chloride hexahydrate
  • KCI potassium chloride
  • CuCI 2 copper chloride
  • the amount of the additive 261 in either one of the ferrous iron-containing mixture 262, ferric iron-containing mixture 264, or carbonated mixture 266 is 0.1-20% by weight, or more specifically, 1-10% by weight.
  • an industrial gas 272 is generated and collected.
  • the industrial gas 272 may contain hydrogen (H 2 ), ammonia (NH 3 ), methane (CH ), and/or potentially higher hydrocarbons (such as propane and butane), including alcohols (such as methanol).
  • the composition of the industrial gas 272 depends on the composition of the ferrous iron-containing mixture 262 and the processing conditions.
  • a chelating agent 284 is added to one or more of the ferrous iron-containing mixture 262, ferric iron-containing mixture 264, and carbonated mixture 266 to recover one or more metal components, which may be selected from the group consisting of copper (Cu), cobalt (Cu), nickel (Ni), gold (Au), silver (Ag), the rare earth elements (REEs), and the platinum group metals (PGMs).
  • Some examples of chelating agents 284 include but are not limited to ammonia (NH 3 ), ethylenediaminetetraacetic acid (CI O HI 6 N 2 O 8 ), sulfuric acid (H 2 SO 4 ), sodium cyanide (NaCN), and oxime-based extractants.
  • the carbonated mixture 266 comprises carbonate minerals 290, e.g., iron carbonate (FeCO 3 ).
  • carbonate minerals 290 further comprise one or more of calcium carbonate, and magnesium carbonate.
  • the carbonated mixture 266 may also comprise trace metals 298, some of which may be recovered using chelating agents 284.
  • the carbonated mixture 266 may comprise the remaining water 260 (unreacted water), which may be recovered (e.g., filtered) and reused.
  • FIG. 2A is a schematic illustration of a system 200 for producing industrial gases 272 and sequestering carbon dioxide 280 using the sequential introduction of water 260 and carbon dioxide 280 to ferrous iron-containing materials 250, in accordance with some examples.
  • system 200 may comprise a mixing tank 208, an oxidation reactor 210, and a carbonization reactor 234.
  • a mixing tank 208 may be used as an oxidation reactor 210 and even as a carbonization reactor 234.
  • the functionality may be provided by different reagents added to the tank.
  • the ferric iron-containing mixture 264 may be transferred to the carbonization reactor 234 where the ferric iron-containing mixture 264 is combined with carbon dioxide 280 (from a carbon dioxide storage 232) to form the carbonated mixture 266.
  • carbonation reaction (as well as other reactions) may be exothermic.
  • the carbonated mixture 266 may pass through the heat exchanger 209 to transfer some of this generated heat to the ferrous iron-containing mixture 262.
  • the carbonated mixture 266 may then be passed through a water separator 240 to recover the carbonate minerals 290.
  • Water 260 or, more specifically, water solution 292 may be further processed to recover various additional materials 294 from water solution 292 (while the remaining water 260 may be recycled).
  • FIG. 2B is a schematic illustration of another example of a system 200 for producing industrial gases 272 and sequestering carbon dioxide 280 using the simultaneous introduction of water 260 and carbon dioxide 280 to ferrous iron- containing materials 250, in accordance with some examples.
  • a mixing tank 208 may be used to combine water 260, carbon dioxide 280, and ferrous iron-containing materials 250 and remove the industrial gas 272 (into the gas storage 222).
  • the industrial gas 272 may comprise methane.
  • the carbonated mixture 266 may be produced directly from the ferrous iron-containing mixture 262. Water 260 and/or various additional materials 294 may be recovered from the carbonated mixture 266 in a manner similar to the one described above with reference to FIG. 2A.
  • FIG. 2C is a schematic illustration of a system 200 for underground production of industrial gases 272 and sequestering carbon dioxide 280, in accordance with some examples.
  • water 260 and carbon dioxide 280 are pumped underground (e.g., using an injection well) to an underground area containing the ferrous iron-containing material 250.
  • additional materials e.g., catalysts
  • Water 260 and carbon dioxide 280 react with the ferrous iron-containing material 250 and form a carbonated mixture 266 while releasing industrial gas 272, which is carried (e.g. using a production well) to gas storage 222.
  • FIG. 3 is a process flowchart of method 300 for producing industrial gases 272 and sequestering carbon dioxide 280 using ferrous iron-containing materials 250, in accordance with some examples.
  • ferrous iron-containing materials 250 and systems 200 for processing these materials are described above.
  • Method 300 comprises (block 310) combining the ferrous iron- containing material 250 with water 260 to form a ferrous iron-containing mixture 262.
  • carbon dioxide 280 is introduced (block 311) into the ferrous iron-containing mixture 262 (e.g., to generate methane) and form a carbonated mixture 266 directly from the ferrous iron-containing mixture 262.
  • non-iron-containing reactive species includeinclude but are not limited to magnesium ortho-silicate/forsterite (Mg 2 SiO4) and calcium ortho- silicate/la mite (Ca 2 SiO4).
  • Mg 2 SiO4 magnesium ortho-silicate/forsterite
  • Ca 2 SiO4 calcium ortho- silicate/la mite
  • Magnesium and/or calcium-containing materials have some carbon dioxide (CO 2 ) sequestration value as will now be explained in more detail.
  • methane (CH 4 ) production and carbon dioxide (CO 2 ) sequestration may be performed in a single step using ferrous iron-containing materials.
  • olivine a mixture of fayalite and forsterite
  • water a mixture of fayalite and forsterite
  • carbon dioxide a specific example of such a reaction between olivine (a mixture of fayalite and forsterite), water, and carbon dioxide is presented below.
  • fayalite (Fe 2 SiO 4 ) and forsterite (Mg 2 SO 4 ) react with water and carbon dioxide to a yield mixture contaiing the carbonated minerals magnesite (MgCO 3 ) and siderite (FeCO 3 ) in addition to methane (CH 4 ).
  • MgCO 3 carbonated minerals magnesite
  • FeCO 3 siderite
  • methane methane
  • more carbon dioxide is sequestered than would be generated in the combustion of the produced methane.
  • calcium oxides were contained within the initial ferrous iron- contain mixture, calcium carbonate (CaCCh) would also be a reaction product.
  • the mass ratio of the water 260 added to the ferrous iron-containing material 250 to form the ferrous iron-containing mixture 262 is between 0.1 and 10 or, more specifically, between 0.25 and 2 (relative to the total weight of the ferrous iron-containing mixture 262).
  • the amount of water needs to be sufficient to dissolve the ferrous iron-containing minerals and oxidize most of the resulting ferrous cations 253 (Fe 2+ ).
  • the mass ratio of the carbon dioxide 280 added to the ferrous iron-containing material 250 to form ferrous iron- containing mixture 262 is between 0.1 and 10 or, more specifically, between 0.25 and 2.
  • ferrous iron-containing material 250 and, subsequently, the ferrous iron-containing mixture 262 comprise ferrous cations 253 (Fe 2+ ).
  • ferrous cations (Fe 2+ ) 253 are used as reducing agents to recover hydrogen (from water) and/or methane (from a combination of water and carbon dioxide), e.g., by oxidizing the ferrous cations 253 (Fe 2+ ) to ferric cations 265 (Fe 2+ ).
  • (block 310) forming the ferrous iron-containing mixture 262 comprises (block 312) introducing an additive 261 to the ferrous iron-containing material 250 and water 260 (while forming the ferrous iron- containing mixture 262).
  • the ferrous iron-containing mixture 262 may comprise a catalytic oxidation-enhancing additive.
  • additives 261 are within the scope, e.g., sodium-containing additive, aluminum- containing additive, iron-containing additive, copper-containing additive, nickel- containing additive, magnetite, chromite, platinum group metals, and potentially microorganisms.
  • (block 310) forming the ferrous iron-containing mixture 262 comprises (block 313) adjusting the acidity (pH) of the ferrous iron- containing mixture 262 to between 1 and 5 pH or, more specifically, to 2 to 4 pH.
  • the acidic pH levels will help to accelerate the dissolution of the ferrous- iron containing material 250 into the ferrous iron-containing mixture 262, thereby accelerating the production of industrial gases 272.
  • adjusting the acidity (pH) of the ferrous iron-containing mixture 262 may comprise adding, to the ferrous iron-containing mixture 262, one or acids selected from the group consisting of carbonic acid (H 2 CO 3 ), hydrochloric acid (HCI), nitric acid (HNO 3 ), and sulfuric acid (H 2 SO 4 ).
  • HCI carbonic acid
  • HNO 3 hydrochloric acid
  • SO 4 sulfuric acid
  • the basic pH levels will help to accelerate the production of industrial gases from the ferrous iron containing mixture 262.
  • adjusting the acidity (pH) of the ferrous- iron containing mixture 262 may comprise adding, to the ferrous iron- containing mixture, one or more bases selected from the group consisting of sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide Ca(OH) 2 , and magnesium hydroxide Mg(OH) 2 .
  • bases selected from the group consisting of sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide Ca(OH) 2 , and magnesium hydroxide Mg(OH) 2 .
  • NaOH sodium hydroxide
  • KOH potassium hydroxide
  • Ca(OH) 2 calcium hydroxide
  • Mg(OH) 2 magnesium hydroxide
  • (block 310) forming the ferrous iron-containing mixture 262 comprises (block 314) heating the ferrous iron-containing mixture 262 to at least 100°C or, more specifically, to at least 200°C, e.g., 100-300°C. Heating increases the reaction kinetics thereby speeding up the process of generating the industrial gas 272. However, at the same time, higher temperature decreases the hydrogen yield and the degree of reaction exothermicity.
  • the ferrous iron containing mixture 262 will be contained in an oxidation reactor 210 and maintained at approximately the saturation pressure of water for the reaction temperature. However, the pressure may increase ( ⁇ 10%) as the industrial gases 272 are being generated, if they are not immediately removed from the oxidation reactor 210. Hence, during the reaction, most of the water will remain in liquid form.
  • the heating may be achieved by heating a mixing tank 208 and/or by heating incoming reagents (e.g., water 260, ferrous iron-containing material 250, and/or carbon dioxide 280).
  • incoming reagents e.g., water 260, ferrous iron-containing material 250, and/or carbon dioxide 280.
  • the ferrous iron-containing material 250 may be supplied as a ⁇ 1100 °C molten slag when combined with the water 260, as the molten slag leaves the furnace/smelter.
  • the reaction kinetics are extremely fast, preheating the water and carbon dioxide may not be necessary, and the achievement of complete mixing and full reaction will be more achievable.
  • the industrial gas 272 can be generated in close proximity to the furnace/smelter, thereby enabling the use of the produced gas as a supplement to the fuel being supplied to the furnace or smelter and reducing the amount of fresh fuel consumed.
  • Method 300 may proceed with (block 340) collecting the industrial gas 272 from the ferrous iron-containing mixture 262 thereby forming a ferric iron- containing mixture 264.
  • the industrial gas 272 may comprise hydrogen and/or methane.
  • industrial gas 272 may comprise additional recovered gases 274 that may be later separated (block 344) from hydrogen and methane.
  • the industrial gas 272 is generated by reducing hydrogen (from water) and/or carbon (from carbon dioxide).
  • combining the ferrous iron-containing material 250 with the water 260 further comprises (block 311) introducing carbon dioxide 280 into the ferrous iron-containing mixture 262 (i.e., combining the ferrous iron-containing material 250 with the carbon dioxide 280).
  • the ferrous iron-containing mixture 262 comprises both the water 260 and the carbon dioxide 280.
  • method 300 further comprises (block 350) introducing carbon dioxide 280 into the ferric iron-containing mixture 264 thereby forming the carbonated mixture 266. More specifically, carbon dioxide 280 is introduced into the ferric iron-containing mixture 264 after collecting the industrial gas 272 from the ferrous iron-containing mixture 262 (and forming the ferric iron-containing mixture 264).
  • (block 340) collecting the industrial gas 272 comprises (block 342) separating hydrogen and/or methane from additional recovered gas 274.
  • this separation process is performed using one or more techniques selected from the group consisting of a passive hydrogen- permeable membrane and an active electrochemical device.
  • method 300 further comprises (block 380) drying the carbonated mixture 266 to recover the carbonated mineral mixture.
  • a batch system may comprise a single reactor that is sequentially used to produce fuel and then sequester carbon dioxide.
  • the weight of ferrous iron-containing material is 500 weight units, which can be scaled/adapted based on the operating scales of actual systems. Weight units are used here to illustrate the proportions of different materials.
  • the amount of water may be 500-1000 weight units.
  • Water may be in a deoxygenated form (e.g., water processed using thermal degassing, vacuum degassing, and/or nitrogen purging). 20-40 weight units of additives (e.g., sodium chloride (NaCI)) and 0-10 weight units of Ni, Cu, or Al-containing salts may be added.
  • additives e.g., sodium chloride (NaCI)
  • 0-10 weight units of Ni, Cu, or Al-containing salts may be added.
  • an acid e.g., H2SO4
  • a base e.g., sodium hydroxide NaOH
  • an acidic pH is believed to be helpful from a waste/mineral dissolution (kinetic) standpoint, while a basic pH is believed to be helpful from a hydrogen production (yield) standpoint.
  • the reactor may be closed and any air trapped in the reactor is evacuated with a vacuum pump in an effort to remove as much reactive oxygen as possible to facilitate the production of hydrogen.
  • the sealed reactor may be then heated to between 200 and 300 °C. The pressure increases with the increasing water saturation pressure.
  • the sealed reactor is stirred periodically (e.g., for 1-10 minutes each hour) and may be maintained at a constant temperature for durations of between several hours and several days. During this time, the ferrous iron-containing material dissolves into the aqueous solution, releasing ferrous (Fe +2 ) iron. If most dissolved and gaseous oxygen has been removed from the system, the dissolved ferrous iron will react with water (instead of oxygen).
  • ferrous (Fe +2 ) iron oxidizes to ferric (Fe +3 ) iron in the form of magnetite (Fe 3 O 4 ) and/or hematite (Fe 2 O 3 ), while the hydrogen cations (H + ) from water are reduced to hydrogen gas (H 2 ).
  • the reactor is cooled down to ambient temperature, and the produced gas is removed.
  • the first reactor will be sized such that the slurry stream entering at the specified flow rate has a residence time of the desired duration (i.e., minutes to hours) before departing to ensure that an adequate amount of the solid material reacts with the aqueous solution.
  • the gaseous fuel products will be removed from the reactor as they are produced.
  • FIG. 4A is a plot illustrating concentration profiles of various materials as a function of time during hydrogen production.
  • the process involved combining forsterite (about 0.6 moles) and fayalite (0.08 moles) with water (2.1 moles).
  • Forsterite (Mg2SiO4) comprising Mg 2+ cations is a magnesium-rich olivine constituent.
  • Fayalite (Fe 2 SiO ) comprising ferrous cations (Fe 2+ ) is an iron-rich olivine constinuent.
  • the reactor was maintained at a temperature of 200 °C by removing the heat of the reaction from the adiabatic reactor, and the pressure increased from ⁇ 15 bar to ⁇ 16 bar as the industrial gas 272 (hydrogen in this case) was produced.
  • the amount of forsterite and fayalite remaining was less than 0.02-0.03 moles, while the amount of lizardite (Mg 3 Si 2 O5(OH) 4 ) produced was over 0.3 moles.
  • the amount of brucite (Mg(OH) 2 ) produced was over 0.2 moles.
  • ⁇ 0.04 moles of magnetite (Fe 3 O 4 ) were produced.
  • the following is a representation of the reactions (presented in the unbalanced form):
  • FIG. 4B is a plot illustrating hydrogen output as a function of time during hydrogen production, presented in the above-referenced test. About 50% of recoverable hydrogen was recovered in half a day, while more than 70% of the recoverable hydrogen was recovered in the first full day.

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Abstract

L'invention concerne des procédés de production de gaz industriels (par exemple, de l'hydrogène, de l'ammoniac et/ou du méthane) à l'aide de matériaux contenant du fer ferreux (par exemple, l'olivine) tout en séquestrant simultanément le dioxyde de carbone. Le procédé peut consister à mélanger un matériau contenant du fer ferreux avec de l'eau et, dans certains exemples, un accélérateur de réaction. Le mélange peut être chauffé à 100 jusqu'à 300 °C pour initier l'oxydation de cations ferreux (Fe2+) en cations ferriques (Fe3+) tout en réduisant l'hydrogène (provenant de l'eau) et/ou le méthane (provenant de l'eau et du dioxyde de carbone, lorsque du dioxyde de carbone est introduit dans le mélange contenant du fer ferreux). Dans certains exemples, le dioxyde de carbone peut être ajouté ultérieurement (après récupération d'hydrogène) pour former des carbonates. Plus particulièrement, le dioxyde de carbone peut être injecté à une pression élevée (par exemple, environ 200 bars) après l'oxydation pour faciliter la minéralisation, à l'aide de la réaction exothermique afin de maintenir une température favorable. Dans certains exemples, des réactifs de complexation/chélation de métal sont ajoutés pour lier des métaux à l'état de trace, tels que le nickel, le cuivre, le cobalt et les métaux du groupe du platine pour la récupération.
PCT/US2025/020368 2024-03-26 2025-03-18 Procédés de production de gaz industriels et de capture d'oxyde de carbone à l'aide de matériaux contenant du fer ferreux Pending WO2025207367A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100120104A1 (en) * 2008-11-06 2010-05-13 John Stuart Reed Biological and chemical process utilizing chemoautotrophic microorganisms for the chemosythetic fixation of carbon dioxide and/or other inorganic carbon sources into organic compounds, and the generation of additional useful products
US20120159841A1 (en) * 2009-09-08 2012-06-28 The Ohio State University Research Foundation Synthetic fuels and chemicals production with in-situ co2 capture
US20210214517A1 (en) * 2018-06-05 2021-07-15 Oxford University Innovation Limited Process
US20240042374A1 (en) * 2020-12-25 2024-02-08 Tohoku University Carbon dioxide fixation method, carbon dioxide recovery method, carbon dioxide fixation device and environmentally friendly industrial facility
US20240076962A1 (en) * 2021-08-05 2024-03-07 Cenovus Energy Inc. Carbon dioxide or hydrogen sulfide sequestration in a subterranean reservoir using sorbent particles

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100120104A1 (en) * 2008-11-06 2010-05-13 John Stuart Reed Biological and chemical process utilizing chemoautotrophic microorganisms for the chemosythetic fixation of carbon dioxide and/or other inorganic carbon sources into organic compounds, and the generation of additional useful products
US20120159841A1 (en) * 2009-09-08 2012-06-28 The Ohio State University Research Foundation Synthetic fuels and chemicals production with in-situ co2 capture
US20210214517A1 (en) * 2018-06-05 2021-07-15 Oxford University Innovation Limited Process
US20240042374A1 (en) * 2020-12-25 2024-02-08 Tohoku University Carbon dioxide fixation method, carbon dioxide recovery method, carbon dioxide fixation device and environmentally friendly industrial facility
US20240076962A1 (en) * 2021-08-05 2024-03-07 Cenovus Energy Inc. Carbon dioxide or hydrogen sulfide sequestration in a subterranean reservoir using sorbent particles

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