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WO2015154887A1 - Procédé et système d'activation de minéraux de silicate minéral - Google Patents

Procédé et système d'activation de minéraux de silicate minéral Download PDF

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Publication number
WO2015154887A1
WO2015154887A1 PCT/EP2015/025018 EP2015025018W WO2015154887A1 WO 2015154887 A1 WO2015154887 A1 WO 2015154887A1 EP 2015025018 W EP2015025018 W EP 2015025018W WO 2015154887 A1 WO2015154887 A1 WO 2015154887A1
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Prior art keywords
reaction
solid
magnesium
mixture
silicate
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Michael Priestnall
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Cambridge Carbon Capture Ltd
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Cambridge Carbon Capture Ltd
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Priority claimed from GB1306559.4A external-priority patent/GB2515995A/en
Application filed by Cambridge Carbon Capture Ltd filed Critical Cambridge Carbon Capture Ltd
Priority to ES15723131T priority Critical patent/ES2824676T3/es
Priority to CN201580030663.0A priority patent/CN106573197B/zh
Priority to DK15723131.7T priority patent/DK3129125T3/da
Priority to EP15723131.7A priority patent/EP3129125B1/fr
Priority to US15/303,208 priority patent/US9963351B2/en
Publication of WO2015154887A1 publication Critical patent/WO2015154887A1/fr
Anticipated expiration legal-status Critical
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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
    • C01F11/02—Oxides or hydroxides
    • C01F11/12—Oxides or hydroxides from silicates
    • 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
    • C01F5/14—Magnesium hydroxide
    • 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
    • C01F5/14—Magnesium hydroxide
    • C01F5/22—Magnesium hydroxide from magnesium compounds with alkali hydroxides or alkaline- earth oxides or 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
    • 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
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/12—Methods and means for introducing reactants
    • B01D2259/126—Semi-solid reactants, e.g. slurries
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • 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 disclosure relates to methods of producing activated mineral silicate for use in sequestrating Carbon Dioxide, for example from flue-gas, by utilizing a process which involves digestion of metal mineral Silicates. Moreover, the present disclosure also relates to systems for executing aforesaid methods.
  • a key principle of mineral Carbonation is also known as “mineral sequestration technology", wherein sequestration of Carbon Dioxide (CO2) is achieved by capturing Carbon Dioxide (CO2) in a form of stable mineral Carbonates.
  • Such sequestration employs a process which is an exothermic reaction of a metal Oxide and Carbon Dioxide (CO2) to form stable Carbonate materials as provided in a reaction formula (1 ): wherein M is a metal, preferably an alkaline earth metal such as Calcium or Magnesium.
  • Magnesium or Calcium Silicate minerals such as Olivine, wollastonite, and Serpentine.
  • the Carbonation reactions of these minerals are as follows:
  • CaSiOs + CO2 CaCOs + S1O2 + 90 kJ mol-1 CO2 (4)
  • step (a) reacting the metal hydroxide product of step (a) with at least one of the alkali-metal carbonate and the alkali-metal bicarbonate produced in step (b) to produce a carbonate of the metal formerly contained in the metal silicate of step (a).
  • the alkali-metal hydroxide is in aqueous solution which limits the maximum reaction temperature to the vapour pressure of the aqueous solution at the pressure under which the reaction is carried out. A low reaction temperature limits the reaction rate at atmospheric pressure, while use of a pressurised vessel increases process costs.
  • Alkali-metal hydroxides, such as NaOH and KOH, used in steps (1 ) and (2) are energy-intensive and expensive chemicals to manufacture.
  • alkali-metal hydroxide, additional to that used in step (1 ), is used to react with Carbon Dioxide.
  • the present invention seeks to provide an improved method of activation of magnesium silicate minerals by conversion to magnesium hydroxide.
  • This present embodiment of the invention allows for a method of large scale industrial use and continuous carbonation without advanced pressure chambers or equipment.
  • a method for activation of magnesium silicate minerals by conversion to magnesium hydroxide is provided, which method comprising:
  • an embodiment of the method includes the liquid slurry of step c being separated into solid and aqueous solution phase products.
  • an embodiment of the method includes reacting any of the aqueous phases at atmospheric pressure with a gas comprising 0.04%-100% CO2.
  • an embodiment of the method includes mixing the solid phase product with water and reacted at atmospheric pressure with a gas comprising 0.04%-100% CO 2 .
  • an embodiment of the method includes air or flue gas as the gas in the reaction. This allows for a very simple and cost effective solution utilizing what is available at the site of operation.
  • an embodiment of the method includes using a hydroxide or a carbonate of sodium or a potassium as the alkali metal compound in the reaction.
  • an embodiment of the method includes a serpentine or an olivine rock as the magnesium silicate mineral in the reaction. Further optionally the method includes heating the unpressurised vessel in step (b) to a temperature in the range 140C-220C.
  • an embodiment of the method as claimed in claims 1 characterized in that the method includes continuously adding the magnesium silicate mineral and alkali metal compound of step (a) together allowing continuous reacting thereof under the conditions of step (b) and further continuously removing the product of step (b).
  • an embodiment of the method includes the molar ratio of substantially 2 moles of alkali metal per mole of silicon in the mixture.
  • an embodiment seeks to provide a system for activation of magnesium silicate minerals by conversion to magnesium hydroxide; wherein the system includes a first reaction chamber which is operable to receive a Silicate-based material and an alkaline compound, and a blending apparatus for blending contents of the first reaction chamber to produce a mixture therein as claimed in any of the preceding method above.
  • an embodiment of the invention includes a system for activation of magnesium silicate minerals by conversion to magnesium hydroxide, wherein the system is operable to execute sequestration by Carbon Dioxide (CO2).
  • CO2 Carbon Dioxide
  • an embodiment seeks to provide an improved method of sequestrating Carbon Dioxide (CO2).
  • the further embodiment of the invention also seeks to provide a system for sequestrating Carbon Dioxide (CO2).
  • embodiments of the present invention provide a method of sequestrating Carbon Dioxide (CO2) which comprises: (a) reacting an alkaline earth silicate-based material with an alkali metal compound to form a mixture comprising a hydroxide of the alkaline earth, wherein the alkali metal is selected from sodium and/or potassium, and wherein the alkaline earth is selected from magnesium and/or calcium; and preferably wherein no water is added to the reaction mixture and no more than two moles of alkali-metal (in the alkali-metal compound) are added per mole of silicon (in the alkaline earth silicate).
  • CO2 Carbon Dioxide
  • the method includes reacting the mixture in (b) at a pressure of less than the vapour pressure of water at the temperature of reaction, for example at ambient atmospheric pressure. This allows for a capacity for large scale industrial use and continuous carbonation without advanced pressure chambers or equipment.
  • the mixture is in a stoichiometric molar ratio between Si in the Silicate-based material and the alkali metal in the alkaline compound in a range of 1 :1 to 1 :2.
  • the mixture is in a form of an aqueous solution with the molality of >30 molar of alkaline compound per litre water (H2O).
  • the method includes using flue gases with less than 50 vol% Carbon Dioxide (CO2) as part of a gas mixture for carbonation.
  • the reaction of the mixture is executed at an ambient pressure and at a reaction temperature of circa 180 °C. This has significant benefit over disclosed prior art.
  • the Carbonation of Silicates is an exothermic reaction, but kinetically slow, which requires high energy consuming conditions, thus influencing costs and environmental impact of the reaction.
  • an alkaline compound, Sodium Hydroxide is optionally used while executing the method, thereby providing significant improvement over prior art, and using the alkaline compound in a much more economical and efficient manner.
  • the method includes carrying out reactions in an unpressurised continuous mode to achieve substantially complete conversion of Magnesium Silicate to Magnesium Hydroxide, and carbonation of Magnesium Hydroxide.
  • embodiments of the present invention provide a system for sequestrating Carbon Dioxide (CO2), wherein a first reaction chamber is arranged to receive a Silicate-based material and an alkaline compound, wherein a blending arrangement is provided for the first reaction chamber to produce a mixture of the Silicate-based material and the alkaline compound therein.
  • CO2 Carbon Dioxide
  • Embodiments of the present invention substantially eliminate the aforementioned problems in the prior art, wherein:
  • FIG. 1 is an illustration of a flow chart of a digestion Step 1 involving alkaline digestion of Serpentine or Olivine to convert them to Brucite and Silica;
  • FIG. 2 is an illustration of a flow chart of a Carbonation step 2 involving direct Carbonation of Brucite, namely Magnesium Hydroxide, with flue-gas to form Magnesium Carbonate;
  • FIG. 3a and 3b are illustrations of XRD patterns of selected samples, wherein solid products from dissolution of Dunite, namely a form of Olivine, using Sodium Hydroxide (NaOH) solution of concentration in a range of 15 to 40 mol/kg (left), and using Sodium Hydroxide (NaOH) solution of concentration 50 mol/kg (right) solutions.
  • FIG. 4a and 4b are illustrations of TG (4a) and DTG (4b) curves of selected samples: solid products from dissolution of Dunite at a temperature of 180° C for 6 hours with different concentrations of Sodium Hydroxide (NaOH) solution;
  • FIG.5 is a graph wherein there are shown M g (OH)2 concentrations in solid products based on TG results: Dunite dissolved at a temperature of 180 °C with different concentrations of Sodium Hydroxide (NaOH) solution, namely measured as moles of NaOH per kg of water.
  • FIG. 6 is an illustration of XRD patterns of solid products from dissolution of Dunite at 180 °C with Sodium Hydroxide (NaOH) solution having a molar concentration of 40 mol/kg solution, for different temporal durations
  • FIG. 7a and 7b are illustrations of TG (7a) and DTG (7b) curves of solid products from dissolution of Dunite at a temperature of 180° C with Sodium Hydroxide (NaOH) solution having a molar concentration of 40 mol/kg for different temporal durations
  • FIG. 6 is an illustration of XRD patterns of solid products from dissolution of Dunite at 180 °C with Sodium Hydroxide (NaOH) solution having a molar concentration of 40 mol/kg solution, for different temporal durations
  • FIG. 7a and 7b are illustrations of TG (7a) and DTG (7b) curves of solid products from dissolution of Dunite at a temperature of 180° C with Sodium Hydroxide (NaOH) solution having a molar concentration of 40
  • FIG. 8 is a graph in which there is shown Magnesium Hydroxide Mg(OH)2 concentration in solid products based on TG results: Dunite dissolved at a temperature of 180° C with a molar concentration of Sodium Hydroxide (NaOH) solution being 40 mol/kg for different durations;
  • FIG. 1 1 a and 1 1 b are illustrations showing Brucite quantification with Rietveld Refinement and TGA (FIG. 1 1 a), wherein Forsterite and Brucite concentrations were obtained via Rietveld Refinement QPA of selected samples (FIG. 1 1 b).
  • FIG. 12a and 12b depict experimental data concerning the removal of CO2 by means of Brucite powder in aqueous suspension, specifically the resulting CO2 level for a monitored exit gas after processing.
  • an underlined number is employed to represent an item over which the underlined number is positioned or an item to which the underlined number is adjacent.
  • a non-underlined number relates to an item identified by a line linking the non-underlined number to the item.
  • the non- underlined number is used to identify a general item at which the arrow is pointing.
  • FIG. 1 there is shown an embodiment of digestion system and process 100, wherein there occurs alkaline digestion of a Silicate-based material, preferably an alkaline earth silicate and more specifically a naturally occurring feedstock containing magnesium or calcium silicate, such as Serpentine, Olivine, Dunite, and/or Wollastonite 101.
  • the process 100 results in reaction products being generated, namely a conversion to Brucite and Silica in a case of Olivine 101 being a feed mineral employed.
  • Olivine 101 is fed into a stirred reactor 102 together with an alkali 103 and heat is provided from a heat source 104.
  • the alkali is beneficially selected from a mineral Hydroxide.
  • a preferable alkali used is Sodium Hydroxide (NaOH).
  • the reaction mixture of the digestion process 100 comprises a stoichiometric ratio between the soluble silicate- based material and the solid hydroxide of the alkaline earth compound of about 1 :2.
  • This stoichiometric ratio aims to minimise the input of the alkaline compound, such as Sodium Hydroxide (NAOH), into the initial reaction mixture. This limits the regeneration of Sodium Hydroxide (NaOH) from carbonates at the end of the reaction, which is costly and time consuming.
  • the reaction mixture is preferably in an aqueous solution during reaction, but it would favourably also be in a non-aqueous mixture.
  • the reaction mixture is a solid-state dry mixture of a powder of the alkaline-earth silicate and the alkali-metal compound, in the stoichiometric ratio of one mole of silicon, namely in the silicate, per two moles of alkali-metal.
  • Solid alkali-metal compounds such as NaOH, KOH and Na2COs, have high melting points, namely 318 °C, 406 °C and 851 °C, respectively.
  • Using an aqueous system, such as taught by Blencoe would therefore be expected to be essential to achieving mixing and reaction at temperatures below 300 °C.
  • Dunite can also be used to yield Mg(OH)2 via solid state reaction, with a preferable ratio of Dunite to NaOH in a mole ratio of 1 :2, at a temperature around 180 °C.
  • results of experiments, as provided in FIGs. 3a, 3b, 5, with aqueous NaOH and Olivine show that minimum reaction conditions of a temperature of 180 °C and a NaOH concentration of 40mol/kg are substantially required to form magnesium hydroxide; this aqueous system requires a pressure vessel to reach a required reaction temperature.
  • aqueous NaOH and Olivine show that minimum reaction conditions of a temperature of 180 °C and a NaOH concentration of 40mol/kg are substantially required to form magnesium hydroxide; this aqueous system requires a pressure vessel to reach a required reaction temperature.
  • the products of reaction, containing no excess NaOH, are a solidified glass which is substantially less caustic than in the aqueous process and are therefore much safer to handle;
  • the intial step (a) can be conducted at a pressure slightly below the vapour pressure of pure water for the temperature of that step.
  • Blencoe does not claim a preferred temperature or pressure or aqueous solution composition for that initial step (a), but in a table of experimental results shows that all reactions in which serpentine or olivine are converted to a major phase of brucite are done in aqueous solution in a pressure vessel at a temperature of 200C and pressure ⁇ 15atm.
  • One experiment conducted at a temperature of 22C and 1 atm pressure for 72hrs results in conversion to a minor phase of brucite; subsequent additional reaction at 200C and ⁇ 15bar then converts substantially to brucite with a minor residual phase of serpentine.
  • the preferred alkali 103 for this digestion process is beneficially Sodium Hydroxide or Potassium Hydroxide, together with water (H2O). It is also possible to use Sodium Carbonate, Sodium Bicarbonate, Potassium Carbonate and Potassium Bicarbonate as the alkali for the digestion process.
  • the heat source 104 is employed to raise a temperature of the digestion process, whilst stirring of the mixture is implemented, to a temperature of less than 250 °C, and for a temporal period of less than 6 hours.
  • a preferred range of temperature is from 140 °C to 220 °C.
  • the reaction can be best performed with the temperature being less than 200 °C, and most preferentially at around 180 °C, throughout the process, as shown in the results FIG. 4 to FIG. 8.
  • the digestion vessels used are most suitably Teflon (PTEE) to withstand hot-conc-NaOH with the maximum operating temperature usually specified at 220°C.
  • PTEE Teflon
  • Magnesium silicate mineral feedstocks have been showing excellent results for this process.
  • Other alkaline earth silicates such as calcium silicate and wollastonite are also suited for the preferred process.
  • This digestion process is preferably carried out at a pressure of less than 20 Bar, wherein 1 Bar corresponds to nominal atmospheric pressure at sea-level.
  • the reaction can be more preferably carried out at a pressure less than 10 Bar.
  • the reaction can be further more preferably be carried out at pressure conditions lower than the vapour pressure of pure water at the temperature of reaction.
  • Continuous operation is generally recognised by process engineers as preferable to batch operations because:
  • reaction parameters such as temperature, pH and reactant concentrations are easier to maintain at fixed optimum levels
  • FIG.2 there is provided an illustration of the details of a Carbonation process 200 as also depicted in equations 206 and 207.
  • the Brucite (MgOh ) powder 205 is fed into a continuous reactor 201 , together with a flue-gas 204.
  • the decarbonised flue gas 202 and Magnesium Carbonate (MgCOs) powder 203 are the reaction products of this Carbonation process 200.
  • Mg(OH)2 (Brucite) powder is provided as added to water to form an aqueous suspension which is then used at ambient temperature and pressure to scrub CO2 from a gaseous mixture of nitrogen (N2) and CO2.
  • N2 gaseous mixture of nitrogen
  • the scrubbing process using wet-Brucite which simultaneously removes the CO2 from the gas mixture and converts the Brucite to magnesium carbonates.
  • Substantial removal and conversion can be achieved such that most, if not all, of the CO2 is taken out of the gas mixture and most, if not all, of the Brucite is converted.
  • a gas mixture of (nitrogen) N2 containing 4-5% CO2 (carbon dioxide, cylinder pre-mix) was bubbled continuously at a fixed flow-rate (around 2.25 litres/minute) through a fixed circulating volume (around 10 litres) of water (pre- saturated before the experiment with 5%CO-N2) containing a suspension of magnesium hydroxide powder (0.871 mol, 50.8 grams).
  • the CO2 concentration in the exit gas was initially zero (as it was totally removed by reaction with Brucite) and was monitored as the suspended Brucite particles were consumed in the reaction to form dissolved magnesium bicarbonate. Periodic samples of the circulating liquid were taken to monitor change in pH and magnesium ion concentration.
  • Gas flow rate was measured by calibrated glass tube rotammeter at a fixed 2.25 litres/minute (atmospheric pressure).
  • Concentration of CO2 was measured using a calibrated inline infrared datalogger (range: 0-5%CO2 measured to nearest 0.25%).
  • Temperature was ambient, in a range of 9.5-1 1 °C.
  • Solution pH was in a rangeof pH 8.2-8.9.
  • the DGC reactor provides a large and dynamic interfacial area between gas bubbles and circulating liquid.
  • CO2 dissolves from the gas (g) into the liquid (I) phase (or aqueous phase, aq) and reactions occur with the suspended Brucite particles (solid phase being labelled as s):
  • Results show that for the first 3.5 hours of the 12hour experimental period, removal of CO2 from the inlet 5%C02-N2 gas mixture was 100%. Over the first 6hrs (first day), CO2 removal averaged 93% and over the full 12hours averaged 62%. Results show unequivocally that a Brucite-water suspension can fully scrub CO2 from dilute gas mixtures.
  • Olivine 101 is mixed with NaOH 103 and water 106 in a mole ratio in the range of 1 :(1 -6):(0-5).
  • the mixture is reacted at 180°C- 220°C in a stirred PTFE vessel at a pressure ⁇ 10bar to produce a solid mixture 102.
  • Cooling and removal of resulting solid reaction mixture from reaction vessel is followed by separation of Brucite powder from the reaction mixture by dissolving the soluble fraction of the reaction mixture in water and filtering the resulting suspension 108.
  • the Brucite powder 205 is dispersed in water and a flue-gas 204 containing CO2 sparged into the Brucite dispersion to form a dispersion of magnesium carbonate 203 and to remove CO2 from the flue-gas 202.
  • Carbon Dioxide (CO2) directly from low-Carbon Dioxide (CO2) flue-gases at a less than ca 50vol% Carbon Dioxide (CO2).
  • This flue-gas mixture is used for the carbonation step and more typically 3-25vol% Carbon Dioxide (CO2) has also been used during carbonation.
  • This is much more cost effective than using previously captured and separated pure Carbon Dioxide (CO2) which often also is pressurised.
  • CCS Carbon Capture and Storage
  • flue gases can be treated directly without expensive separation of CO2 or pressurisation;
  • the use of magnesium hydroxide directly in unpressurised aqueous carbonation also enables the carbonation step to be more easily separated from the earlier steps of the overall process, and to be performed at a different time and place.
  • embodiments of the present disclosure are operated in a substantially unpressurized manner at pressures in a range of 0.5 Bar to 10.0 Bar, more optionally in a range of 0.8 Bar to 5.0 Bar, and yet more optionally in a range of 0.9 Bar to 2.0 Bar.
  • pressurized in contradistinction, refers to pressures, for example, in excess of 20 Bar, in excess of 50 Bar, or even in excess of 100 Bar.
  • the first steps of the process in which a mined magnesium silicate mineral is converted into magnesium hydroxide can be carried out at the mine site, while, without a need for elevated temperatures or pressures for reaction, the final step in which CO2 in flue-gas reacts with aqueous magnesium hydroxide, can be carried out at a distant source of CO2 emissions, such as a power station or on board a ship.
  • magnesium hydroxide compared with magnesium silicate or the reaction mixture, magnesium hydroxide, having a lower molar mass and being able to react more completely with CO2, has a much higher CO2 sequestration capacity, namely tonnes of CO2 stored per tonne of magnesium hydroxide that is carbonated; this means that less material needs to transported and used to sequester the same mass of CO2 and, therefore, less energy and cost is expended in transport and handling tasks.
  • magnesium hydroxide powder is replaced with magnesium silicate powder in water slurry, it is surprisingly found, pursuant to the present disclosure, that it is also possible to achieve substantial direct aqueous-phase carbonation of Serpentine and Olivine powders, and substantial scrubbing of CO2 from ambient pressure flue gas.
  • Serpentine and Olivine and other related magnesium silicate minerals such as chrysotile, lizardite, antigorite, and forsterite are composed of alternating crystal layers of magnesium oxide/hydroxide and silica. It is believed that the mechanism by which the magnesium silicate mineral dissolution and carbonation is possible under such mild conditions is that a suitable pH in the range of pH8 to pH9 is maintained by the addition of CO2, such that successive crystal layers of magnesium hydroxide dissolve directly into solution to form a solution of magnesium bicarbonate. In this pH range, carbonate ion concentration in solution is orders or magnitude lower than bicarbonate ion concentration and the formation of passivating solid magnesium carbonate phases on the surface of magnesium silicate particles is therefore avoided.
  • magnesium silicate mineral powders are much cheaper as feedstocks for carbonation than magnesium hydroxide, or thermally or chemically activated magnesium silicate mineral powers;
  • Nickel and Iron and other minor elemental constituents typically present in magnesium silicate minerals and wastes may be released in the process and can potentially be economically recovered from solution or by purification of the solid products.
  • the efficiency of this entire process as illustrated in FIG. 1 and FIG.2 has been analysed through various scalability experiments, wherein it has been found that, for the Magnesium-mineral Silicates, the alkaline treatment is attractive as the associated Carbonation reaction is chemically favorable at a higher pH resulting in a higher reaction rate:
  • Mg(OH)2 Magnesium Hydroxide (Mg(OH)2) was produced by using either a solution of Sodium Hydroxide (NaOH) having a molar concentration of 50 mol/kg for a temporal duration of 6 hours (73 wt%), or by using a solution of Sodium Hydroxide (NaOH) having a molar concentration of 40 mol/kg for a temporal duration of 18 and 24 hours (79 - 80 wt%).
  • NaOH Sodium Hydroxide
  • the TGA analyses results were found to be in accordance with the qualitative XRD results and with the Rietveld Refinement Quantitative Phase Analysis.
  • compacted Dunite powder can be heated in a sealed vessel at a temperature around 180 °C, preferably for around six hours, to produce a product comprising Brucite.
  • the Olivine and/or Serpentine is a Magnesium mineral which are suitable feedstock materials due to their high content of Magnesium (Mg) and wide abundance and large concentration in mineralogical sites.
  • a method of sequestrating Carbon Dioxide (CO2) as outlined above further includes reacting the mixture in (b) at a pressure of less than the vapour pressure of pure water at the temperature of reaction
  • a method of sequestrating Carbon Dioxide (CO2) as outlined above further includes using the mixture with a stoichiometric ratio between the Si in the alkaline earth silicate-based material and the alkali metal in the alkaline compound in a range of 1 :1 to 1 :2.
  • a method of sequestrating Carbon Dioxide (CO2) as outlined above includes using the mixture in a form of an aqueous solution with the molality of >30 molar of alkaline compound per litre water (H2O).
  • a method of sequestrating Carbon Dioxide (CO2) as outlined above includes reacting the mixture at ambient atmospheric pressure.
  • a method of sequestrating Carbon Dioxide (CO2) as outlined above includes executing the reaction at a temperature of ca 180 °C.
  • a method of sequestration Carbon Dioxide (CO2) as outlined above includes using flue gases with less than 50vol% Carbon Dioxide (CO2) as part of a gas mixture for carbonation.
  • a method of sequestrating Carbon Dioxide (CO2) as outlined above includes carrying out reactions in an unpressurised continuous mode to achieve substantially complete carbonation of the Magnesium Hydroxide or Magnesium silicate.
  • a system for sequestrating Carbon Dioxide (CO2) wherein the system includes a first reaction chamber which is operable to receive a Silicate- based material and an alkaline compound, and a blending apparatus for blending contents of the first reaction chamber to produce a mixture therein.
  • CO2 Carbon Dioxide
  • the system for sequestrating Carbon Dioxide (CO2) as described above is operable to execute the method outlined above method of sequestrating Carbon Dioxide (CO2).
  • the compound in the reaction may be selected from any one or combination of Hydroxide, Carbonate, and/or Bicarbonate as would be suitable to the person skilled in the art.
  • Expressions such as “including”, “comprising”, “incorporating”, “consisting of”, “have”, “is” used to describe and claim the present invention are intended to be construed in a non-exclusive manner, namely allowing for items, components or elements not explicitly described also to be present.
  • Reference to the singular is also to be construed to relate to the plural.
  • Numerals included within parentheses in the accompanying claims are intended to assist understanding of the claims and should not be construed in any way to limit subject matter claimed by these claims.

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Abstract

L'invention concerne un procédé d'activation de minéraux de silicate de magnésium par conversion en hydroxyde de magnésium pour la séquestration de dioxyde de carbone (CO2). Le procédé comprend le chauffage d'un mélange solide-solide à sec d'un matériau à base de silicate alcalino-terreux et d'un composé de métal alcalin à une température inférieure à 300°C pour former un produit solide comprenant essentiellement un mélange d'hydroxyde de magnésium et de silicate de métal alcalin, le matériau à base de silicate comprenant un minéral du type Olivine ou Serpentine d'origine naturelle et un silicate de métal alcalin. Le procédé selon l'invention comprend une dissolution ultérieure du produit solide dans une solution aqueuse pour former une boue liquide aqueuse alcaline comprenant des produits en phase solide et aqueuse et la réaction de la phase solide ainsi formée avec du dioxyde de carbone (CO2), produisant un carbonate métallique. Le procédé fournit un processus qui a présenté une très bonne rentabilité et un très bon rendement énergétique dans la production d'hydroxyde de magnésium et la séquestration de CO2 par carbonatation minérale.
PCT/EP2015/025018 2013-04-10 2015-04-10 Procédé et système d'activation de minéraux de silicate minéral Ceased WO2015154887A1 (fr)

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ES15723131T ES2824676T3 (es) 2014-04-10 2015-04-10 Método de activación de minerales de silicato mineral
CN201580030663.0A CN106573197B (zh) 2014-04-10 2015-04-10 活化硅酸盐矿物质的方法和体系
DK15723131.7T DK3129125T3 (da) 2014-04-10 2015-04-10 Fremgangsmåde til aktivering af mineralske silicatmineraler
EP15723131.7A EP3129125B1 (fr) 2014-04-10 2015-04-10 Procédé d'activation de minéraux de silicate minéral
US15/303,208 US9963351B2 (en) 2014-04-10 2015-04-10 Method and system of activation of mineral silicate minerals

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GB1306559.4A GB2515995A (en) 2013-04-10 2013-04-10 Method and system of sequestrating carbon dioxide
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GB1406520.5A GB2516141B (en) 2013-04-10 2014-04-10 Activation of mineral silicate minerals by conversion to magnesium hydroxide

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CN106396810A (zh) * 2016-09-10 2017-02-15 上海大学 一种利用蛇纹石制备硅镁复合肥的方法
CN106396746A (zh) * 2016-09-10 2017-02-15 上海大学 一种活化碱熔法制备蛇纹石制备硅镁钾硫复合肥的方法
WO2018053497A1 (fr) * 2016-09-19 2018-03-22 The Turstees Of Columbia University In The City Of New York Procédés et systèmes de production de matériaux à base de silicate activé à l'aide d'énergie et de matériaux durables
US9963351B2 (en) 2014-04-10 2018-05-08 Cambridge Carbon Capture Ltd Method and system of activation of mineral silicate minerals
CN111346600A (zh) * 2020-03-24 2020-06-30 中国科学院上海应用物理研究所 一种基于正硅酸钠和碳酸盐协同作用的co2捕获方法
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

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CN105158439A (zh) * 2015-08-24 2015-12-16 中国地质科学院岩溶地质研究所 一种碳酸盐岩储层溶蚀过程模拟试验装置
FR3077008B1 (fr) * 2018-01-25 2023-10-06 Brgm Procede et dispositif de capture et/ou de liberation d'especes anioniques assiste par electrolyse
CN115838261B (zh) * 2022-12-01 2024-07-30 太原理工大学 一种利用烟气活化固碳后煤矸石及碱性矿渣制备注浆材料的方法

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US9963351B2 (en) 2014-04-10 2018-05-08 Cambridge Carbon Capture Ltd Method and system of activation of mineral silicate minerals
CN106365915A (zh) * 2016-09-10 2017-02-01 上海大学 一种利用蛇纹石制备硅镁磷钾复合肥的方法
CN106396810A (zh) * 2016-09-10 2017-02-15 上海大学 一种利用蛇纹石制备硅镁复合肥的方法
CN106396746A (zh) * 2016-09-10 2017-02-15 上海大学 一种活化碱熔法制备蛇纹石制备硅镁钾硫复合肥的方法
WO2018053497A1 (fr) * 2016-09-19 2018-03-22 The Turstees Of Columbia University In The City Of New York Procédés et systèmes de production de matériaux à base de silicate activé à l'aide d'énergie et de matériaux durables
CN109923068A (zh) * 2016-09-19 2019-06-21 纽约市哥伦比亚大学理事会 使用可持续能量和材料生产活化硅酸盐基材料的方法和系统
US11242261B2 (en) 2016-09-19 2022-02-08 The Trustees Of Columbia University In The City Of New York Methods and systems for producing activated silicate based materials using sustainable energy and materials
US20220127151A1 (en) * 2016-09-19 2022-04-28 The Trustees Of Columbia University In The City Of New York Methods and systems for producing activated silicate based materials using sustainable energy and materials
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
CN111346600A (zh) * 2020-03-24 2020-06-30 中国科学院上海应用物理研究所 一种基于正硅酸钠和碳酸盐协同作用的co2捕获方法

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