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WO2010097449A1 - Procédé pour la séquestration de dioxyde de carbone - Google Patents

Procédé pour la séquestration de dioxyde de carbone Download PDF

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Publication number
WO2010097449A1
WO2010097449A1 PCT/EP2010/052439 EP2010052439W WO2010097449A1 WO 2010097449 A1 WO2010097449 A1 WO 2010097449A1 EP 2010052439 W EP2010052439 W EP 2010052439W WO 2010097449 A1 WO2010097449 A1 WO 2010097449A1
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Prior art keywords
carbon dioxide
magnesium
aqueous
calcium
pressure
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English (en)
Inventor
Harold Boerrigter
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Publication of WO2010097449A1 publication Critical patent/WO2010097449A1/fr
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    • 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
    • C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
    • 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
    • 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
    • B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
    • 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
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the present invention provides a process for carbon dioxide sequestration.
  • Background of the invention The rising carbon dioxide concentration in the atmosphere due to the increased use of energy derived from fossil fuels potentially may have a large impact on the global climate. Thus there is an increasing interest in measures to reduce the carbon dioxide concentration emissions to the atmosphere.
  • the first intermediate reaction also referred to as leaching, frees the magnesium ions from the mineral, following:
  • a disadvantage of this process is that only one mole of carbon dioxide is captured from the carbon dioxide- comprising gas per mole of magnesium and/or calcium ions, see reaction 1. Therefore, large amounts of mineral are required and in practice the carbon dioxide-comprising gas is provided at high pressure and with high carbon dioxide partial pressure, ideally even pure carbon dioxide .
  • EP 1836127 a process for preparing pure magnesium or calcium carbonate is disclosed.
  • the overall mineralisation reaction is separated into the two intermediate steps, however this is only done to allow removal of the solids from the aqueous bicarbonate solution after leaching. Although the intermediate leaching step and precipitation step separated, they are performed under generally the same conditions.
  • the present invention provides a process for sequestration of carbon dioxide comprising: a. an aqueous slurry comprising magnesium or calcium- comprising silicate particles under low temperature and low pressure conditions to obtain an aqueous bicarbonate solution; b.
  • An advantage of the process according to the invention is that up to twice the amount of carbon dioxide may captured from the carbon dioxide-comprising gas compared to the amount of carbon dioxide, which is mineralised. In addition, a high-pressure concentrated carbon dioxide-comprising gas may be obtained.
  • a further advantage is that there is no need to provide the carbon dioxide-comprising gas to the process at high pressure nor is there a need to provide a carbon dioxide-comprising gas comprising high carbon dioxide partial pressures. Therefore, there is no need to pre- treat, e.g. by upstream amine absorption processes the carbon dioxide-comprising gas prior to applying the process according to the invention.
  • the present invention provides a process for the sequestration of carbon dioxide by reacting the carbon dioxide with a mineral, typically a silicate mineral, to form a carbonate.
  • a mineral typically a silicate mineral
  • Suitable silicate minerals may have different structures.
  • silicates may be composed of orthosilicate monomers, i.e. the orthosilicate ion SiOzp " which has a tetrahedral structure.
  • Orthosilicate monomers form oligomers by means of 0-Si-O bonds at the polygon corners.
  • the Q s notation refers to the connectivity of the silicon atoms.
  • the value of superscript s defines the number of nearest neighbour silicon atoms to a given Si.
  • Orthosilicates also referred to as nesosilicates, are silicates which are composed of distinct orthosilicate tetrathedra that are not bonded to each other by means of
  • 0-Si-O bonds Q ⁇ structure
  • Other structures include chain silicates, also referred to as inosilicates, which might be single chain (SiC ⁇ " as unit structure, i.e. a structure) .
  • sheet silicate hydroxides also referred to as phyllosilicates, which have a sheet structure ( ⁇ p) n .
  • orthosilicates or chain silicates can be relatively easy reacted with carbon dioxide to form carbonates and can thus suitably be used for carbon dioxide sequestration.
  • magnesium or calcium orthosilicates suitable for mineral carbonation are olivine, in particular forsterite, and monticellite .
  • suitable chain silicates are minerals of the pyroxene group, in particular wollastonite .
  • the more abundantly available magnesium or calcium silicate hydroxide minerals, for example serpentine, are sheet silicates and are more difficult to convert into carbonates, i.e. the reaction times for carbonation are much longer. Such sheet silicate hydroxides need to undergo a heat treatment or activation at elevated temperatures prior to the reaction with carbon dioxide.
  • the serpentine mineral is at least partly converted into its corresponding ortho- or chain silicate mineral, silica and water.
  • the activation of silicate hydroxide minerals may include a conversion of part of the silicate hydroxide minerals into an amorphous sheet silicate hydroxide mineral derived compound.
  • a carbon dioxide-comprising stream is contacted with an aqueous slurry comprising magnesium or calcium-comprising silicate particles.
  • the carbon dioxide partial pressure in the carbon dioxide-comprising gas that is contacted with the aqueous slurry is at least 0.01 bar, more preferably the carbon dioxide partial pressure is in the range of from 0.01 bar to 0.5, even more preferably 0.1 bar to 0.2 bar at Standard Temperature and Pressure conditions of 0 0 C and 1 bar.
  • Such carbon dioxide partial pressures allow for the direct capture of carbon dioxide from dilute carbon dioxide-comprising gases, without the need for a pre-treatment of the dilute gas in order to increase the carbon dioxide partial pressure.
  • step (a) of the process according to the invention the carbon dioxide-comprising gas stream is contacted with the aqueous slurry comprising magnesium or calcium-comprising silicate particles, magnesium and or calcium ions are leached from the mineral and an aqueous bicarbonate solution is formed following reaction (Ia) .
  • Reference herein to leaching is to a conversion of the silicate mineral wherein at least part of the magnesium of calcium is removed from the mineral and dissolved in the aqueous medium as magnesium or calcium cations.
  • Reference herein to the extent of leaching is to the mole% of magnesium and/or calcium leached from the mineral, based on the total number of moles of magnesium and/or calcium present in the original mineral.
  • references herein to an aqueous bicarbonate solution is to a solution comprising dissolved bicarbonate anions and dissolved cations of metals, which were originally part of the mineral provided to the process by the aqueous slurry comprising magnesium or calcium-comprising silicate particles, wherein the moles of dissolved bicarbonate anions in the aqueous bicarbonate solution is equal to or more than twice the moles of the mentioned metal cations in the aqueous bicarbonate solution.
  • step (a) the carbon dioxide-comprising gas stream is contacted with the aqueous slurry comprising magnesium or calcium-comprising silicate particles under low temperature and low carbon dioxide partial pressure conditions.
  • the carbon dioxide-comprising gas stream is contacted with the aqueous slurry comprising magnesium or calcium-comprising silicate particles at a temperature in the range of from 1 to 100 0 C, more preferably 10 to 60 0 C, even more preferably 15 to 50 0 C and at a carbon dioxide partial pressure in the range of from 0.01 to 35 bara, more preferably 0.05 to 25 bara, even more preferably 0.1 to 10 bara.
  • step (a) the solubility of the bicarbonate is maximised, and thus as a consequence so is the extent of leaching which may be achieved. Due to the low carbon dioxide partial pressure requirements there is no need to pressurise the carbon dioxide-comprising gas prior to contacting it with the aqueous slurry. It will be appreciated that in case the temperature of the carbon dioxide-comprising gas is to high it can advantageously be cooled by heat-exchange with another process stream.
  • an electrolyte is added to the aqueous slurry in order to improve the formation of the bicarbonate and the leaching of metal ions from the mineral and improve precipitation in the later stages of the process.
  • sodium or potassium bicarbonate is provided to the aqueous slurry and/or optionally to the aqueous bicarbonate solution, preferably in an amount as to obtain a sodium or potassium bicarbonate concentration of 1 mol or less per litre of the aqueous medium, i.e. not including solids.
  • the magnesium or calcium-comprising silicate particles may have any suitable size, preferably the particles have an average particle size in the range of from 0.1 ⁇ m to 5 cm, more preferably 0.5 to 500 ⁇ m.
  • Reference herein to average diameter is to the volume medium diameter D(v,0.5), meaning that 50 volume% of the particles have an equivalent spherical diameter that is smaller than the average diameter and 50 volume% of the particles have an equivalent spherical diameter that is greater than the average diameter.
  • the equivalent spherical diameter is the diameter calculated from volume determinations, e.g. by laser diffraction measurements.
  • the mineral particles In order to reach optimal leaching of the magnesium and/or calcium cations from the mineral particles it is preferred that the mineral particles have an average particle size of 50 ⁇ m or less, more preferably 15 ⁇ m or less .
  • the preferred particle size may be obtained by any suitable process for reducing the size of particles.
  • the process for reducing the particle size is a mechanical process, further referred to as grinding. Examples of grinding processes are for instance dry or wet grinding. Reference herein to wet grinding is to grinding in the presence of a suitable grinding fluid. Dry grinding of mineral to obtain particles of such small dimensions, however, is difficult, requires significantly more power and may require additional safety measure due to the formation of dust particles.
  • the mineral grinding is performed by wet grinding, preferably using an aqueous medium as grinding fluid.
  • the mineral may by dry grinded to an average particle size of approximately 500 ⁇ m and subsequently, after addition of the aqueous medium, wet grinded to the desired final average particle diameter.
  • step (a) the magnesium or calcium-comprising silicate particles are treated to reduce the average particle size to an average particle size in the range of from 0.1 to 50 ⁇ m, even more preferably of from 0.5 to 15 ⁇ m.
  • the treatment for reducing the average particle size will be grinding, or wet grinding as the mineral is provided to step (a) in the form of an aqueous slurry.
  • step (a) the aqueous slurry of magnesium or calcium-comprising silicate particles is contacted with carbon dioxide-comprising gas for in the range of from 1 to 60 minutes, preferably 10 to 30 minutes.
  • carbon dioxide-comprising gas for in the range of from 1 to 60 minutes, preferably 10 to 30 minutes.
  • at least 35 mol%, more preferably at least 40 mol% of magnesium and calcium cations present in the mineral is leached and dissolved in the aqueous medium to form an aqueous bicarbonate solution, based on the total amount of magnesium and calcium cations present in the mineral prior to step (a) .
  • the carbon dioxide content in the carbon dioxide-depleted gas is at most 50%, more preferably at most 30% of the carbon dioxide content in the carbon dioxide-comprising gas, based on the carbon dioxide content in the carbon dioxide-comprising gas.
  • an aqueous bicarbonate solution comprising dissolved magnesium and/or calcium bicarbonate, as part of the aqueous slurry.
  • the aqueous bicarbonate solution may also comprise dissolved carbon dioxide.
  • the composition of the aqueous slurry changes and will typically comprise an aqueous bicarbonate solution, residual magnesium or calcium-comprising silicate mineral particles and silica. It will be appreciated that at least part of the silica may be deposited in or on the residual mineral particles.
  • the aqueous slurry obtained from step (a), i.e. the aqueous slurry comprising the aqueous bicarbonate solution, residual magnesium or calcium-comprising silicate mineral particles and silica is further referred to as the treated slurry.
  • the mineral comprises of iron cations it may be advantageous to subject the treated slurry to an iron separation process.
  • One effect of grinding the mineral comprising iron to a particle size below approximately 20 ⁇ m is that the iron is released form the mineral may suitably be removed from the treated slurry using any suitable separation process, preferably a magnetic separation.
  • An advantage of such a separation of iron clusters is that the iron can be used for other purposes and additionally the quantity of the solid effluent, which needs to be disposed of, is reduced.
  • the aqueous bicarbonate solution is pressurised to a pressure above atmospheric pressure.
  • the aqueous bicarbonate solution is pressurised to a pressure in the range of from 20 to 200 bara, preferably of from 50 to 150 bara.
  • the aqueous bicarbonate solution may first be separated from the treated slurry this is not necessary.
  • the aqueous bicarbonate solution is provided to step (b) in the form of the treated slurry obtained from step (a) .
  • Pressurising the aqueous bicarbonate solution provides significant advantages compared to pressurising any gaseous stream, such as a carbon dioxide-comprising stream. Pressurizing liquid or liquid slurry streams requires significantly less energy and can be accomplished using compact devices such a for instance a liquid or liquid slurry pump.
  • the pressurised aqueous bicarbonate solution is subsequently heated to induce bicarbonate decomposition.
  • the dissociation products are solid magnesium or calcium carbonate, carbon dioxide and water.
  • the pressurised aqueous bicarbonate solution is heated to a temperature in the range of from 120 0 C or higher, preferably 140 0 C or higher.
  • the predominantly formed carbonates are magnesite (in case of magnesium) and calcite and aragonite (in case of calcium) .
  • hydromagnesite or nesquehonite in case of magnesium
  • hydrocalcite in case of calcium
  • the latter carbonates have significant amounts of water incorporated in their crystal structure, which leads to a higher weight of the precipitated carbonate material, and thus may lead to increased transportation and storage or disposal cost. It should be noted that some hydrocalcite, hydromagnesite and/or nesquehonite may be formed during the heating of the pressurised aqueous bicarbonate solution when the temperature is still low.
  • the pressurised aqueous bicarbonate solution may be heated by any suitable means for heating liquids or liquid slurries.
  • the pressurised aqueous bicarbonate solution is heated or at least pre-heated by heat exchange with other stream in the process, such as the carbon dioxide-comprising gas or carbon dioxide- depleted gas of step (a) .
  • the heat of an optional mineral activation process as described herein below, for e.g. serpentine mineral may be used to heat the pressurised aqueous bicarbonate solution.
  • carbon dioxide is formed.
  • the heated, pressurised aqueous bicarbonate solution is preferably maintained at elevated pressure and elevated temperature for an extended time period.
  • the heated, pressurised aqueous bicarbonate solution is maintained at elevated pressure and temperature for a time period of at least 1 minute, more preferably at least 20 minutes.
  • the elevated pressure is above atmospheric pressure, more preferably is the range of from 20 to 200 bara, preferably of from 50 to 150 bara. Additionally, it is preferred that the elevated pressure is approximately equal to the pressure of the heated, pressurised aqueous bicarbonate solution, i.e. with in a range of from 10 bar below to 10 bar above the pressure of the heated, pressurised aqueous bicarbonate solution.
  • the elevated temperature is a temperature above at which the aqueous slurry is contacted with the carbon dioxide-comprising gas in step (a) . More preferably the elevated temperature is a temperature in the range of from 120 0 C or higher, preferably 140 0 C or higher.
  • the elevated temperature is approximately equal to the temperature of the heated, pressurised aqueous bicarbonate solution, i.e. with in a range of from 20 0 C below to 20 0 C above the temperature of the heated, pressurised aqueous bicarbonate solution.
  • the pressurised aqueous bicarbonate solution is heated and/or the heated, pressurised aqueous bicarbonate solution is maintained at elevated pressure and elevated pressure under a carbon dioxide-comprising atmosphere.
  • the partial pressure of the carbon dioxide in the atmosphere influences the formation of carbonates.
  • the pressurised aqueous bicarbonate solution is heated and/or the heated, pressurised aqueous bicarbonate solution is maintained at elevated pressure and elevated pressure under a carbon dioxide-comprising atmosphere with the partial pressure of carbon dioxide of at least 1 bara, more preferably the partial pressure of carbon dioxide is in the range of from 1 to 200 bara, even more preferably of from 20 to 150 bara. Most preferred is an essentially pure carbon dioxide atmosphere, not taking steam into account.
  • the carbon-dioxide atmosphere will automatically be formed during the dissociation of the bicarbonate.
  • the thus formed carbon dioxide atmosphere is essentially pure and will have a pressure equal to the pressure of the heated, pressurized aqueous bicarbonate solution.
  • At least part of the pressurised carbon dioxide can be withdrawn from the process in the form of a high-pressure carbon dioxide stream.
  • the carbon dioxide partial pressure in the high pressure carbon dioxide stream is, while again excluding the presence of steam, in the range of from 0.5 bar to 1, even more preferably 0.9 bar to 1 bar, still more preferably 0.95 to 1 bar at Standard Temperature and Pressure conditions of 0 0 C and 1 bar.
  • the high- pressure carbon dioxide stream consists of essentially pure carbon dioxide, not taking steam into account.
  • This high-pressure carbon dioxide steam can be further used.
  • the high-pressure carbon dioxide stream may be used in enhanced oil recovery applications or in chemical synthesis processes using carbon dioxide.
  • the high-pressure carbon dioxide stream is particularly suitable for sub-surface carbon dioxide storage . If desired additional carbon dioxide can be added to the atmosphere initially, preferably this additional carbon dioxide is carbon dioxide withdrawn form the process via the high-pressure carbon dioxide stream. Maintenance of the heated, pressurized aqueous bicarbonate solution at elevated temperatures and pressures may be done separately from the heating of the pressurized solution in step (c) .
  • step (c) by first heating the pressurised aqueous bicarbonate solution in a heat exchanger and subsequently providing the heated, pressurised to a separate unit.
  • the maintenance of the heated, pressurized aqueous bicarbonate solution at elevated temperatures and pressures is combined with the heating of the pressurized solution in step (c) .
  • Suitable reactors units include for instance tubular flow reactor units or high-pressure reactor vessel units.
  • a batch-wise or semi- continuously operated autoclave is used.
  • a bicarbonate-depleted aqueous effluent is obtained from step (c) .
  • This effluent typically comprises solid magnesium carbonate and/or calcium carbonate, silica and residual mineral, e.g. in the form of an aqueous slurry.
  • This aqueous slurry may still be at elevated temperature. Therefore, the effluent can be used for instance to heat or preheat the pressurised aqueous bicarbonate solution. This may be done using any suitable means for heat exchange, including a heat exchanger.
  • the effluent of step (c) can suitably be further treated by filtration, preferably at high pressure.
  • the solid residue obtained after filtration may be disposed of in any suitable way.
  • the solid residue is fist dried, e.g. by contacting it with the carbon dioxide- comprising gas or carbon dioxide-depleted gas of step (a) .
  • the heat of an optional mineral activation process as described herein below, for e.g. serpentine mineral may be used to dry the solid residue.
  • the liquid filtrate obtained after filtration may be further treated to remove, if any, electrolyte and can be disposed of or recycled to step (a) of the process. Any magnesium and/or calcium-comprising silicate mineral may be used.
  • the magnesium and/or calcium- comprising silicate mineral may for example be a mixed silicate-oxide compound and/or a mixed silicate-oxide- hydroxide compound.
  • the magnesium and/or calcium- comprising silicate mineral may be in its hydrated form.
  • Reference herein to magnesium or calcium-comprising silicate is to silicates comprising magnesium, calcium or both. Silicates comprising magnesium are preferred due to their abundances in nature. Part of the magnesium or calcium may be replaced by other metals, for example iron, aluminium or manganese.
  • magnesium and/or calcium silicate minerals are natural occurring calcium or magnesium silicate minerals, e.g. wollastonite, olivine, sepiolite or serpentine, and industrial waste streams such as steel slag, paper bottom ash, or coal fly ash.
  • the magnesium and/or calcium-comprising silicate mineral is a magnesium-comprising silicate mineral, more preferably olivine or serpentine.
  • Serpentine is most preferred due to its natural abundance. Serpentine is a general name applied to several members of a polymorphic group of minerals having comparable molecular formulae, i.e. (Mg, Fe) 3Si2U5 (OH) 4 or
  • Serpentine with a high magnesium content i.e. serpentine that has no Fe or deviates little from the composition Mg3Si2 ⁇ 5 (OH) 4 is preferred since a possible resulting mineral after activation is has a chemical composition resembling an olivine, which has the composition Mg2Si ⁇ 4 and can sequester more carbon dioxide than olivine with a substantial amount of magnesium replaced by iron.
  • Olivine is a general name applied to several members of a polymorphic group of minerals having comparable molecular formulae, i.e. Mg2Si ⁇ 4 or (Mg, Fe) 2Si ⁇ 4, depending on the iron content.
  • sheet silicate minerals such as serpentine require a heat treatment or activation prior to being contacted with the carbon dioxide- comprising gas.
  • Activation of serpentine minerals for mineralisation purposes has been described in for instance EP1951424. In EP1951424, the activation is performed by contacting the mineral with hot synthesis gas. However, it will be appreciated that also other hot gasses may be used such as for instance hot flue gas.
  • such an activation is performed in a fluidized bed reactor, in particular in a fluidized bed reactor, wherein a combustible fuel is provided together with a molecular oxygen-comprising gas, for instance natural gas and air, and the combustible gas is combusted inside the fluidized bed.
  • a combustible fuel is provided together with a molecular oxygen-comprising gas, for instance natural gas and air, and the combustible gas is combusted inside the fluidized bed.
  • the sheet silicate mineral e.g. serpentine
  • the sheet silicate mineral is provided to the activation process in the form of particles having an average particle size in the range of from 100 to 750 ⁇ m, more preferably 200 to 500 ⁇ m.
  • Such particles are especially suitable when the activation is performed in a fluidized bed reactor.
  • Such particles sizes may be conveniently obtained by crushing the raw mineral. Crushing is a relatively simple method that does not require a high energy input. Additionally, there is no direct need to add significant amounts if any of liquids, in that sense crushing is comparable to a dry grinding process. The presence of additional components such as liquids during the activation of the mineral is disadvantageous, as these components require additional energy to be heated.
  • the activated mineral particle size can be further reduced by dry of wet grinding, preferably wet grinding, more preferably wet grinding during step (a) of the process according to the invention, as described herein above.
  • the aqueous slurry which is contacted with the carbon dioxide-comprising gas in step (a) of the process according to the invention, may be any suitable aqueous slurry comprising an aqueous medium, preferably water, and solid material particles.
  • the solid material is a material at least comprising a magnesium and/or calcium silicate.
  • the solid material comprises at least 50 wt%, more preferably 75 wt% more preferably more than 90 wt% of magnesium and/or calcium silicate, based on the total weight of the solid material.
  • Other components comprised in the solid material may include for instance sand, clay, metal oxides, metal hydroxides or one or more metal carbonates, such as magnesium carbonate or calcium carbonate.
  • the aqueous slurry suitably contains up to 60 wt% of solid material, based on the total weight of the aqueous slurry, preferably 10 to 50 wt%.
  • the aqueous slurry may, for example, be formed by mixing magnesium or calcium- comprising silicate particles with the aqueous medium.
  • the carbon dioxide-comprising gas may be pure carbon dioxide or a mixture of carbon dioxide with one or more other gases.
  • the carbon dioxide is a dilute carbon dioxide-comprising gas. It is an advantage of the present invention that such dilute carbon dioxide- comprising gases may be used without the need to for pre- treatment, i.e. pre-concentrating (for instance by an amine absorption process) , pre-pressurising or preheating.
  • suitable dilute carbon dioxide- comprising gases include flue gas, synthesis gas or the effluent of a water-gas-shift process.
  • Reference herein to synthesis gas is to a gas comprising at least hydrogen, carbon monoxide and optionally carbon dioxide.
  • the carbon monoxide content of synthesis gas may be reduced by a water-gas-shift process wherein carbon monoxide is converted with water to hydrogen and carbon dioxide .
  • Suitable sequestration alternative include landfill, sub-surface storage onshore or offshore, i.e. deep ocean sequestration.
  • the mineral is a magnesium based mineral as, contrary to calcium bicarbonate, the ocean water are typically not saturated with magnesium carbonate.
  • FIG 1 a schematic representation is given an embodiment of a carbon dioxide sequestration process according to the invention. It will be appreciated that features described in the embodiment of Figure 1 may also be used alone or in combination with any other feature in the process according to the invention.
  • aqueous slurry comprising magnesium and/or calcium silicate particles 100 and carbon dioxide-comprising gas 105 are provided to contactor 110.
  • contactor 110 aqueous slurry comprising magnesium and/or calcium silicate particles 100 and carbon dioxide-comprising gas 105 are contacted and optionally the magnesium and/or calcium silicate particles are in-situ grinded to a smaller particle size.
  • Carbon dioxide-depleted gas 115 exits contactor 110 and may be released in to the atmosphere or may be further processed, e.g. in the case of synthesis gas.
  • An aqueous bicarbonate solution is withdrawn from contactor 110 in the form of treated slurry 120.
  • Treated slurry 120 may optionally be provided to a separator (not show) to remove iron particles.
  • the magnesium and/or calcium comprising silicate mineral comprises iron and the mineral is grinding below 20 ⁇ m iron clusters present in the mineral may be liberated and these may be recovered by magnetic separation.
  • Treated slurry 120 is pressurised in slurry pump 125 and pressurised treated slurry 130 exists slurry pump 125.
  • Pressurised treated slurry 130 is subsequently provided to reactor 135, wherein pressurised treated slurry 130 is heated under pressure in the presence of carbon dioxide atmosphere 140.
  • reactor 135 may consist of a slurry heater 135a connected in series to vessel 135b. If desired, carbon dioxide can be retrieved from reactor 135 or vessel 135b via line 145. Bicarbonate depleted aqueous effluent 150 of reactor 135 can be disposed of or further treated.

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Abstract

La présente invention concerne un procédé pour la séquestration de dioxyde de carbone comprenant : (a) la mise en contact d'un flux gazeux comportant du dioxyde de carbone avec une bouillie aqueuse comportant du magnésium ou comportant des particules de silicate comportant du calcium dans des conditions de basse température et de basse pression pour obtenir une solution aqueuse de bicarbonate ; (b) la mise sous pression de la solution aqueuse de bicarbonate à une pression supérieure à la pression atmosphérique ; et (c) le chauffage de la solution aqueuse sous pression pour induire une décomposition de bicarbonate, la formation de magnésium et/ou du carbonate de calcium solide et la formation de dioxyde de carbone de haute pression.
PCT/EP2010/052439 2009-02-27 2010-02-25 Procédé pour la séquestration de dioxyde de carbone Ceased WO2010097449A1 (fr)

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WO2012028418A1 (fr) 2010-09-02 2012-03-08 Novacem Limited Procédé intégré pour la production de compositions contenant du magnésium
EP2623467A1 (fr) * 2012-02-03 2013-08-07 Omya Development AG Procédé pour la préparation d'une solution aqueuse comprenant au moins un carbonate d'hydrogène alcalin à la terre et son utilisation
EP2623466A1 (fr) * 2012-02-03 2013-08-07 Omya Development AG Procédé pour la préparation d'une solution aqueuse comprenant au moins un carbonate d'hydrogène alcalin à la terre et son utilisation
CN111683732A (zh) * 2018-02-08 2020-09-18 矿物碳化国际有限公司 矿物碳酸化的集成方法
CN113149212A (zh) * 2021-04-22 2021-07-23 四川绵阳岷山实业集团有限公司 一种放射状碳酸钙生物填料、制备方法及其污水处理中的应用
EP4442351A1 (fr) * 2023-04-06 2024-10-09 Hochschule Weihenstephan-Triesdorf Biotechnologie und Bioinformatik Procédé et système de séquestration de dioxyde de carbone à partir d'un mélange gazeux source
US12129749B1 (en) 2023-07-26 2024-10-29 Saudi Arabian Oil Company Methods for removing carbon dioxide from natural gas
WO2025175338A1 (fr) * 2024-02-19 2025-08-28 Mineral Carbonation International Pty Ltd Produits de carbonate de magnésium

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Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012028418A1 (fr) 2010-09-02 2012-03-08 Novacem Limited Procédé intégré pour la production de compositions contenant du magnésium
EA026157B1 (ru) * 2012-02-03 2017-03-31 Омиа Интернэшнл Аг Способ получения водного раствора, содержащего по меньшей мере один гидрокарбонат щелочно-земельного металла, и его применение
US10221077B2 (en) 2012-02-03 2019-03-05 Omya International Ag Process for the preparation of an aqueous solution comprising at least one earth alkali hydrogen carbonate and its use
WO2013113805A1 (fr) * 2012-02-03 2013-08-08 Omya Development Ag Procédé pour la préparation d'une solution aqueuse comprenant au moins un carbonate d'hydrogène alcalino-terreux et son utilisation
WO2013113807A1 (fr) * 2012-02-03 2013-08-08 Omya Development Ag Procédé pour la préparation d'une solution aqueuse comprenant au moins un carbonate d'hydrogène alcalino-terreux et son utilisation
AU2013214263B2 (en) * 2012-02-03 2015-11-12 Omya International Ag Process for the preparation of an aqueous solution comprising at least one earth alkali hydrogen carbonate and its use
AU2013214265B2 (en) * 2012-02-03 2016-06-09 Omya International Ag Process for the preparation of an aqueous solution comprising at least one earth alkali hydrogen carbonate and its use
EP2809619B1 (fr) 2012-02-03 2016-09-28 Omya International AG Procédé pour la préparation d'une solution aqueuse comprenant au moins un carbonate d'hydrogène alcalin à la terre et son utilisation
EP2809618B1 (fr) 2012-02-03 2016-11-23 Omya International AG Procédé pour la préparation d'une solution aqueuse comprenant au moins un carbonate d'hydrogène alcalin à la terre et son utilisation
EP2623466B1 (fr) 2012-02-03 2017-03-29 Omya International AG Procédé pour la préparation d'une solution aqueuse comprenant au moins un carbonate d'hydrogène alcalin à la terre et son utilisation
EP2623467A1 (fr) * 2012-02-03 2013-08-07 Omya Development AG Procédé pour la préparation d'une solution aqueuse comprenant au moins un carbonate d'hydrogène alcalin à la terre et son utilisation
EP2623466A1 (fr) * 2012-02-03 2013-08-07 Omya Development AG Procédé pour la préparation d'une solution aqueuse comprenant au moins un carbonate d'hydrogène alcalin à la terre et son utilisation
US11235982B2 (en) 2012-02-03 2022-02-01 Omya International Ag Process for the preparation of an aqueous solution comprising at least one earth alkali hydrogen carbonate and its use
EA026927B1 (ru) * 2012-02-03 2017-05-31 Омиа Интернэшнл Аг Способ получения водного раствора, содержащего по меньшей мере один гидрокарбонат щелочно-земельного металла, и его применение
US11235981B2 (en) 2012-02-03 2022-02-01 Omya International Ag Process for the preparation of an aqueous solution comprising at least one earth alkali hydrogen carbonate and its use
US11235980B2 (en) 2012-02-03 2022-02-01 Omya Iniernational Ag Process for the preparation of an aqueous solution comprising at least one earth alkali hydrogen carbonate and its use
CN111683732A (zh) * 2018-02-08 2020-09-18 矿物碳化国际有限公司 矿物碳酸化的集成方法
CN113149212A (zh) * 2021-04-22 2021-07-23 四川绵阳岷山实业集团有限公司 一种放射状碳酸钙生物填料、制备方法及其污水处理中的应用
EP4442351A1 (fr) * 2023-04-06 2024-10-09 Hochschule Weihenstephan-Triesdorf Biotechnologie und Bioinformatik Procédé et système de séquestration de dioxyde de carbone à partir d'un mélange gazeux source
WO2024208737A1 (fr) * 2023-04-06 2024-10-10 Hochschule Weihenstephan-Triesdorf Biotechnologie Und Bioinformatik Procédé et système de séquestration de dioxyde de carbone à partir d'un mélange de gaz source
US12129749B1 (en) 2023-07-26 2024-10-29 Saudi Arabian Oil Company Methods for removing carbon dioxide from natural gas
WO2025175338A1 (fr) * 2024-02-19 2025-08-28 Mineral Carbonation International Pty Ltd Produits de carbonate de magnésium

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