WO2010132863A1 - Systèmes et procédés de traitement de co2 - Google Patents

Systèmes et procédés de traitement de co2 Download PDF

Info

Publication number
WO2010132863A1
WO2010132863A1 PCT/US2010/035041 US2010035041W WO2010132863A1 WO 2010132863 A1 WO2010132863 A1 WO 2010132863A1 US 2010035041 W US2010035041 W US 2010035041W WO 2010132863 A1 WO2010132863 A1 WO 2010132863A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbonate
precipitation
mixture
water
solution
Prior art date
Application number
PCT/US2010/035041
Other languages
English (en)
Inventor
Kyle Self
Kasra Farsad
Robert W. Elliott
Srikanth Bellur
Brian Curtis
Original Assignee
Calera Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Calera Corporation filed Critical Calera Corporation
Publication of WO2010132863A1 publication Critical patent/WO2010132863A1/fr

Links

Classifications

    • 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
    • B01D53/73—After-treatment of removed components
    • 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
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/60—Preparation of carbonates or bicarbonates in general
    • 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
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/604—Hydroxides
    • 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

  • Entity Small business concern.
  • the most concentrated point sources of carbon dioxide and many other atmospheric pollutants are energy-producing power plants, particularly power plants that produce their power by combusting carbon-based fuels (e.g., coal-fired power plants).
  • carbon-based fuels e.g., coal-fired power plants.
  • power plants utilizing carbon-based fuels are particularly attractive sites for technologies aimed at lowering emissions of carbon dioxide and other atmospheric pollutants.
  • the invention provides an apparatus for dewatering a mixture that includes a solid particulate composition and a supernatant solution in which the flue gas source is the flue gas stack of a power plant. In some embodiments, the invention provides an apparatus for dewatering a mixture that includes a solid particulate composition and a supernatant solution in which the flue gas source is the flue gas stack of a power plant and in which the flue gas enters the first connection at a temperature greater than 100 °F.
  • the liquid-solid separation apparatus comprises a baffle situated such that in operation the baffle deflects the precipitation reactor effluent such that precipitation product descends to a lower region of the liquid-solid separation apparatus and supernatant ascends and exits the liquid-solid separation apparatus.
  • the liquid-solid separation apparatus comprises a spiral channel configured to direct effluent from the precipitation reactor to flow in the spiral channel resulting in concentration of the precipitation product based on size and mass and production of a supernatant.
  • the waste gas stream further comprises SOx, NOx, heavy metals, VOCs, particulates, or a combination thereof.
  • Fig. IB provides a system of the invention comprising a processor and a treatment system, wherein the treatment system is configured to treat compositions from the processor.
  • Fig. ID provides a system of the invention comprising a processor and a treatment system, wherein supernatant from the treatment system may optionally be recirculated to the processor.
  • FIG. 4 provides a diagram of another embodiment of a low-voltage apparatus for producing hydroxide electrochemically.
  • Fig. 5 provides a schematic diagram of a CO 2 sequestration system or method according to some embodiments of the invention.
  • FIG. 7 provides a top-view schematic of an apparatus of one embodiment of the invention.
  • Fig. 10 provides a schematic diagram of a CO 2 sequestration system with an industrial plant according to some embodiments of the invention.
  • Fig. W4 provides carbonation profiles of two paste mixes.
  • Fig. W5 provides a TGA scan for 80% OPC/20% precipitation material.
  • Fig. W6 provides an overlay of XRD scans for 100% OPC.
  • Fig. W7 provides an overlay of XRD scans for 80% OPC/20% precipitation material.
  • the invention provides a method of CO 2 sequestration.
  • an amount of CO 2 may be removed or segregated from an environment, such as the Earth's atmosphere or a gaseous waste stream produced by an industrial plant, so that some or all of the CO 2 is no longer present in the environment from which the CO 2 was removed.
  • CO 2 sequestration removes CO 2 or prevents the release of CO 2 into the atmosphere from the combustion of fuel.
  • the CO 2 sequestered is in the form of a composition comprising carbonates, bicarbonates, or carbonates and bicarbonates.
  • the amount by weight of CO 2 that is sequestered by practicing the methods exceeds the amount by weight of CO 2 that is generated in practicing the methods by 1 to 100%, such as 5 to 100%, including 10 to 95%, 10 to 90%, 10 to 80%, 10 to 70%, 10 to 60%, 10 to 50%, 10 to 40%, 10 to 30%, 10 to 20%, 20 to 95%, 20 to 90%, 20 to 80%, 20 to 70%, 20 to 60%, 20 to 50%, 20 to 40%, 20 to 30%, 30 to 95%, 30 to 90%, 30 to 80%, 30 to 70%, 30 to 60%, 30 to 50%, 30 to 40%, 40 to 95%, 40 to 90%, 40 to 80%, 40 to 70%, 40 to 60%, 40 to 50%, 50 to 95%, 50 to 90%, 50 to 80%, 50 to 70%, 50 to 60% , 60 to 95%, 60 to 90%, 60 to 80%, 60 to 70%, 70 to 95%, 70 to 90%, 70 to 80%, 80 to 95%, 80 to 90%, and 90 to 95%.
  • the invention provides an aqueous-based method for processing a source of carbon dioxide (130) and producing a composition comprising carbonates, bicarbonates, or carbonates and bicarbonates, wherein the source of carbon dioxide comprises one or more additional components in addition to carbon dioxide.
  • the industrial source of carbon dioxide may be sourced, a source of proton- removing agents (140) may be sourced, and each may be provided to processor 110 to be processed (i.e., subjected to suitable conditions for production of the composition comprising carbonates, bicarbonates, or carbonates and bicarbonates).
  • the composition is produced in both the contactor and the reactor.
  • the contactor may produce an initial composition comprising bicarbonates and the reactor may produce the composition comprising carbonates, bicarbonates, or carbonates and bicarbonates from the initial composition.
  • methods of the invention may further comprise sourcing a source of divalent cations such as those of alkaline earth metals (e.g., Ca + , Mg + ).
  • the source of divalent cations may be provided to the source of proton-removing agents or provided directly to the processor.
  • the composition comprising carbonates, bicarbonates, or carbonates and bicarbonates may comprise an isolable precipitation material (e.g., CaCO 3 , MgCO 3 , or a composition thereof). Whether the composition from the processor comprises an isolable precipitation material or not, the composition may be used directly from the processor (optionally with minimal post-processing) in the manufacture of building materials.
  • an isolable precipitation material e.g., CaCO 3 , MgCO 3 , or a composition thereof.
  • compositions comprising carbonates, bicarbonates, or carbonates and bicarbonates directly from the processor (optionally with minimal post-processing) may be injected into a subterranean site as described in U.S. Provisional Patent Application No. 61/232,401, filed 7 August 2009, which application is incorporated herein by reference in its entirety.
  • a processor-produced composition of the invention comprises an isolable precipitation material or not
  • the composition may be directly provided to a treatment system of the invention for treatment (e.g., concentration, filtration, etc.).
  • the composition may be provided directly to the treatment system from a contactor, a reactor, or a settling tank of the processor.
  • a processor- produced composition that does not contain an isolable precipitation material may be provided directly to a treatment system for concentration of the composition and production of a supernatant.
  • a processor-produced composition comprising an isolable precipitation material may be provided directly to a treatment system for liquid-solid separation.
  • the processor-produced composition may be provided to any of a number of treatment system sub-systems, which sub-systems include, but are not limited to, dewatering systems, filtration systems, or dewatering systems in combination with filtration systems, wherein treatment systems, or a sub-systems thereof, separate supernatant from the composition to produce a concentrated composition (e.g., the concentrated composition is more concentrated with to respect to carbonates, bicarbonates, or carbonates and carbonates).
  • the invention provides a method for charging a solution with CO 2 from an industrial waste gas stream to produce a composition comprising carbonates, bicarbonates, or carbonates and bicarbonates.
  • the solution may have a pH ranging from pH 6.5 to pH 14.0 prior to charging the solution with CO 2 .
  • the solution may have a pH of at least pH 6.5, pH 7.0, pH 7.5, pH 8.0, pH 8.5, pH 9.0, pH 9.5, pH 10.0, pH 10.5, pH 11.0, pH 11.5 , pH 12.0, pH 12.5, pH 13.0, pH 13.5, or pH 14.0 prior to charging the solution with CO 2 .
  • the pH of the solution may be increased using any convenient approach including, but not limited to, use of proton- removing agents and electrochemical methods for effecting proton removal.
  • proton- removing agents may be used to increase the pH of the solution prior to charging the solution with CO 2 .
  • proton-removing agents include, but are not limited to, hydroxides (e.g., NaOH, KOH) and carbonates (e.g., Na 2 CO 3 , K 2 CO 3 ).
  • sodium hydroxide is used to increase the pH of the solution.
  • the invention provides a method for charging an alkaline solution (e.g., pH > pH 7.0) with CO 2 from an industrial waste gas stream to produce a composition comprising carbonates, bicarbonates, or carbonates and bicarbonates.
  • an alkaline solution e.g., pH > pH 7.0
  • CO 2 from an industrial waste gas stream
  • the composition resulting from charging the alkaline solution with CO 2 from an industrial waste source may be a slurry or a substantially clear solution (i.e., substantially free of precipitation material, such as at least 95% or more free) depending upon the cations available in the solution at the time the solution is charged with CO 2 .
  • the solution may, in some embodiments, comprise divalent cations such as Ca 2+ , Mg 2+ , or a combination thereof at the time the solution is charged with CO 2 .
  • the resultant composition may comprise carbonates, bicarbonates, or carbonates and bicarbonates of divalent cations (e.g. precipitation material) resulting in a slurry.
  • divalent cations e.g. precipitation material
  • Such slurries may comprise CaC ⁇ 3, MgC ⁇ 3, or a combination thereof.
  • the solution may, in some embodiments, comprise insufficient divalent cations to form a slurry comprising carbonates, bicarbonates, or carbonates and bicarbonates of divalent cations at the time the solution is charged with CO 2 .
  • the resultant composition may comprise carbonates, bicarbonates, or carbonates and bicarbonates in a substantially clear solution (i.e., substantially free of precipitation material, such as at least 95% or more free) at the time the solution is charged with CO 2 .
  • a substantially clear solution i.e., substantially free of precipitation material, such as at least 95% or more free
  • monovalent cations such as Na + , K + , or a combination thereof (optionally by addition of NaOH and/or KOH) may be present in the substantially clear solution at the time the solution is charged with CO 2 .
  • the composition resulting from charging such a solution with CO 2 may comprise, for example, carbonates, bicarbonates, or carbonates and bicarbonates of monovalent cations.
  • the invention provides a method for charging an alkaline solution (e.g., pH > pH 7.0) with CO 2 from an industrial waste gas stream to produce a composition comprising carbonates, bicarbonates, or carbonates and bicarbonates, wherein the composition is substantially clear (i.e., substantially free of precipitation material, such as at least 95% or more free).
  • the substantially clear composition may subsequently be contacted with a source of divalent cations (e.g., Ca 2+ , Mg 2+ , or a combination thereof) to produce a composition comprising carbonates, bicarbonates, or carbonates and bicarbonates of divalent cations resulting in a slurry.
  • a source of divalent cations e.g., Ca 2+ , Mg 2+ , or a combination thereof
  • such slurries may comprise CaC ⁇ 3, MgC ⁇ 3, or a combination thereof that may be treated as described herein.
  • an alkaline solution comprising NaOH e.g., NaOH dissolved in freshwater lacking significant divalent cations
  • a gas-liquid contactor with CO 2 from an industrial waste gas stream may be contacted in a gas-liquid contactor with CO 2 from an industrial waste gas stream to produce a composition comprising carbonates, bicarbonates, or carbonates and bicarbonates, wherein the composition is substantially clear due to a lack of precipitation material, which, in turn, is due to the lack of significant divalent cations.
  • the invention also provides aqueous-based methods of processing a source of carbon dioxide (130) and producing a composition comprising carbonates, bicarbonates, or carbonates and bicarbonates, wherein the source of carbon dioxide comprises one or more additional components in addition to carbon dioxide, and wherein at least a portion of treatment system supernatant is recirculated.
  • the supernatant may be used to wash compositions (e.g., precipitation material comprising CaC ⁇ 3 , MgC ⁇ 3 , or a combination thereof) of the invention.
  • the supernatant may be used to wash chloride from carbonate-based precipitation material.
  • at least a portion of the treatment system supernatant may be provided to an electrochemical system.
  • treatment system supernatant may be used to produce proton-removing agents or effect proton removal for processing carbon dioxide.
  • at least a portion of the supernatant from the treatment system may be provided to a different system or process.
  • Recirculation of treatment system supernatant is advantageous as recirculation provides efficient use of available resources; minimal disturbance of surrounding environments; and reduced energy requirements, which reduced energy requirements provide for lower carbon footprints for systems and methods of the invention.
  • a carbon dioxide-processing system of the invention is operably connected to an industrial plant (e.g., fossil fuel-fired power plant such as coal- fired power plant) and utilizes power generated at the industrial plant, reduced energy requirements provided by recirculation of treatment system supernatant provide for a reduced energy demand on the industrial plant.
  • a carbon dioxide-processing system not configured for recirculation i.e., a carbon-dioxide processing system configured for a once-through process such as that shown in Fig.
  • IB may have an energy demand on the industrial plant of at least 10% attributable to continuously pumping a fresh source of alkalinity (e.g., seawater, brine) into the system.
  • a fresh source of alkalinity e.g., seawater, brine
  • a 100 MW power plant e.g., a coal-fired power plant
  • a system configured for recirculation such as that shown in Fig. ID or Fig.
  • IE may have an energy demand on the industrial plant of less than 10%, such as less than 8%, including less than 6%, for example, less than 4% or less than 2%, which energy demand may be attributable to pumping make-up water and recirculating supernatant.
  • Carbon dioxide-processing systems configured for recirculation may, when compared to systems designed for a once-through process, exhibit a reduction in energy demand of at least 2%, such as at least 5%, including at least 10%, for example, at least 25% or at least 50%.
  • a carbon dioxide -processing system configured for recirculation consumes 9 MW of power for pumping makeup water and recirculating supernatant and a carbon dioxide-processing system designed for a once-through process consumes 10 MW attributable to pumping, then the carbon dioxide -processing system configured for recirculation exhibits a 10% reduction in energy demand.
  • the reduction in the energy demand attributable to pumping and recirculating may also provide a reduction in total energy demand, especially when compared to carbon dioxide -processing systems configured for once-through process.
  • recirculation provides a reduction in total energy demand of a carbon dioxide-processing system, wherein the reduction is at least 2%, such as at least 4%, including at least 6%, for example at least 8% or at least 10% when compared to total energy demand of a carbon dioxide-processing system configured for once-through process. For example, if a carbon dioxide-processing system configured for recirculation has a 15% energy demand and a carbon dioxide-processing system designed for a once-through process has a 20% energy demand, then the carbon dioxide-processing system configured for recirculation exhibits a 5% reduction in total energy demand.
  • a carbon dioxide-processing system configured for recirculation wherein recirculation comprises filtration through a filtration unit such as a nanofiltration unit (e.g., to concentrate divalent cations in the retentate and reduce divalent cations in the permeate), may have a reduction in total energy demand of at least 2%, such as at least 4%, including at least 6%, for example at least 8% or at least 10% when compared to a carbon dioxide -processing system configured for once-through process.
  • the energy demand of carbon dioxide -processing systems and methods of the invention may be further reduced by efficient use of other resources.
  • the energy demand of carbon dioxide-processing systems of the invention may be further reduced by efficient use of heat from an industrial source.
  • heat from the industrial source of carbon dioxide e.g., flue gas heat from a coal-fired power plant
  • a spray dryer may be used for spray drying the composition.
  • low-grade waste heat may be utilized by means of a heat exchanger to evaporatively spray dry the composition comprising the precipitation material.
  • utilizing heat from the industrial source of carbon dioxide for drying compositions of the invention allows for simultaneous cooling of the industrial source of carbon dioxide (e.g., flue gas from a coal- fired power plant), which enhances dissolution of carbon dioxide, a process which is inversely related to temperature.
  • the energy demand of carbon dioxide-processing systems of the invention may be further reduced by efficient use of pressure.
  • carbon dioxide- processing systems of the invention are configured with an energy recovery system.
  • the overall energy demand of the carbon dioxide -processing system may be less than 99.9%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 15%, 10%, 5%, or 3% when capturing and processing 70-90% of the carbon dioxide emitted from an industrial plant (e.g., coal-fired power plant).
  • an industrial plant e.g., coal-fired power plant
  • the overall energy demand of the carbon dioxide -processing system may be less than 30%, such as less than 20%, including less than 15%, for example, less than 10%, less than 5%, or less than 3% when capturing and processing 70-90% of the carbon dioxide emitted from an industrial plant (e.g., coal- fired power plant).
  • an industrial plant e.g., coal- fired power plant.
  • carbon dioxide -processing systems of the invention configured for recirculation, heat exchange, and/or pressure exchange may reduce the energy demand on power-providing industrial plants while maintaining carbon dioxide processing capacity.
  • recirculation and other methods described herein consume water as water may become part of a composition of the invention (e.g., precipitation material comprising, for example, amorphous calcium carbonate CaC(VH 2 O; nesquehonite MgC ⁇ 3 ⁇ 2H 2 O; etc.), may be vaporized by drying (e.g., spray drying) compositions of the invention, or lost in some other part of the process.
  • a composition of the invention e.g., precipitation material comprising, for example, amorphous calcium carbonate CaC(VH 2 O; nesquehonite MgC ⁇ 3 ⁇ 2H 2 O; etc.
  • drying e.g., spray drying
  • make-up water may be provided to account for water lost to processing carbon dioxide to produce compositions of the invention (e.g., spray-dried precipitation material).
  • make-up water amounting to less than 700,000 gallons per day may replace water lost to producing, for example, spray-dried precipitation material from flue gas from a 35 MWe coal-fired power plant.
  • Processes requiring only make-up water may be considered zero process water discharge processes.
  • that water may be sourced from any of the water sources (e.g., seawater, brine, etc.) described herein.
  • water may be sourced from the power plant cooling stream and returned to that stream in a closed loop system.
  • Processes requiring make-up water and additional process water are considered low process water discharge processes because systems and methods of the invention are designed to efficiently use resources.
  • the invention provides for contacting a volume of an aqueous solution with a source of carbon dioxide to produce a composition comprising carbonates, bicarbonates, or carbonates and bicarbonates, wherein the composition is a solution or slurry.
  • methods of the invention include contacting a volume of a divalent cation-containing aqueous solution with a source of CO 2 and subjecting the resultant solution to conditions that facilitate precipitation.
  • Divalent cations may come from any of a number of different sources of divalent cations depending upon availability at a particular location. Such sources include industrial wastes, seawater, brines, hard waters, rocks and minerals (e.g., lime, periclase, material comprising metal silicates such as serpentine and olivine), and any other suitable source.
  • waste streams from various industrial processes provide for convenient sources of divalent cations (as well as proton-removing agents such as metal hydroxides).
  • waste streams include, but are not limited to, mining wastes; ash (e.g., coal ash such as fly ash, bottom ash, boiler slag); slag (e.g. iron slag, phosphorous slag); cement kiln waste (e.g., cement kiln dust); oil refinery/petrochemical refinery waste (e.g. oil field and methane seam brines); coal seam wastes (e.g.
  • any of the divalent cations sources described herein may be mixed and matched for the purpose of practicing the invention.
  • material comprising metal silicates e.g., magnesium silicate minerals such as olivine, serpentine, etc.
  • any of the sources of divalent cations described herein for the purpose of practicing the invention.
  • a convenient source of divalent cations for preparation of compositions of the invention is water (e.g., an aqueous solution comprising divalent cations such as seawater or brine), which may vary depending upon the particular location at which the invention is practiced.
  • Suitable aqueous solutions of divalent cations include solutions comprising one or more divalent cations (e.g., alkaline earth metal cations such as Ca + and Mg + ).
  • the aqueous source of divalent cations comprises alkaline earth metal cations.
  • the alkaline earth metal cations include calcium, magnesium, or a mixture thereof.
  • the aqueous solution of divalent cations comprises calcium in amounts ranging from 50 to 50,000 ppm, 50 to 40,000 ppm, 50 to 20,000 ppm, 100 to 10,000 ppm, 200 to 5000 ppm, or 400 to 1000 ppm.
  • the aqueous solution of divalent cations comprises magnesium in amounts ranging from 50 to 40,000 ppm, 50 to 20,000 ppm, 100 to 10,000 ppm, 200 to 10,000 ppm, 500 to 5000 ppm, or 500 to 2500 ppm.
  • the ratio Of Ca 2+ to Mg 2+ (i.e., Ca 2+ :Mg 2+ ) in the aqueous solution of divalent cations is between 1 : 1 and 1 :2.5; 1 :2.5 and 1 :5; 1 :5 and 1 : 10; 1 :10 and 1 :25; 1 :25 and 1 :50; 1 :50 and 1 : 100; 1 : 100 and 1 : 150; 1: 150 and 1 :200; 1:200 and 1 :250; 1 :250 and 1 :500; 1 :500 and 1 : 1000, or a range thereof.
  • the ratio of Ca 2+ to Mg 2+ in the aqueous solution of divalent cations is between 1 : 1 and 1 :10; 1 :5 and 1 :25; 1: 10 and 1 :50; 1 :25 and 1 : 100; 1 :50 and 1 :500; or 1 : 100 and 1: 1000.
  • the ratio OfMg 2+ to Ca 2+ (i.e., Mg 2+ : Ca 2+ ) in the aqueous solution of divalent cations is between 1 : 1 and 1 :2.5; 1 :2.5 and 1 :5; 1 :5 and 1 : 10; 1 :10 and 1 :25; 1 :25 and 1 :50; 1 :50 and 1 : 100; 1 : 100 and 1 : 150; 1: 150 and 1 :200; 1 :200 and 1 :250; 1 :250 and 1 :500; 1:500 and 1 : 1000, or a range thereof.
  • the ratio of Mg + to Ca + in the aqueous solution of divalent cations is between 1 : 1 and 1 :10; 1 :5 and 1 :25; 1: 10 and 1 :50; 1 :25 and 1 : 100; 1 :50 and 1 :500; or 1 : 100 and 1 : 1000.
  • One or more components that are present in the source of divalent cations from which compositions of the invention (e.g., precipitation material) are prepared may be used to identify the source of divalent cations used.
  • source identifiers or markers
  • the source identifiers or markers that may be present in compositions of the invention include, but are not limited to, chlorine, sodium, sulfur, potassium, bromine, silicon, strontium, and the like. Such elements may be present in the compositions in any known valency. Any such source identifiers or markers may be present in small amounts ranging from, for example, 20,000 ppm or less, 2000 ppm or less, 200 ppm or less, or 20 ppm or less. In some embodiments, for example, the marker is strontium.
  • strontium may be incorporated into an aragonite lattice, and make up 10,000 ppm or less of the aragonite lattice, ranging in certain embodiments from 3 to 10,000 ppm, such as from 5 to 5000 ppm, including 5 to 1000 ppm, for example, 5 to 500 ppm or 5 to 100 ppm.
  • Source identifiers may vary depending upon the particular source of divalent cations (e.g., saltwater) employed to produce compositions of the invention.
  • the calcium carbonate content compositions of the invention may be 25% w/w or higher, such as 40% w/w or higher, including 50% w/w or higher, for example, 60% w/w or higher.
  • Such compositions have, in some embodiments, a calcium:magnesium ratio that is influenced by, and therefore reflects, the source of divalent cations from which the composition was produced.
  • the calcium:magnesium molar ratio ranges from 10: 1 to 1 :5 Ca:Mg, such as 5: 1 to 1 :3 Ca:Mg.
  • the composition is characterized by having a source identifying carbonate:hydroxide compound ratio, wherein this ratio ranges from, for example, 100 to 1 , 10 to 1 , or 1 to 1.
  • the aqueous solution of divalent cations may comprise divalent cations derived from freshwater, brackish water, seawater, or brine (e.g., naturally occurring brines or anthropogenic brines such as geothermal plant wastewaters, desalination plant waste waters), as well as other aqueous solutions having a salinity that is greater than that of freshwater, any of which may be naturally occurring or anthropogenic.
  • freshwater may be considered to have a salinity of less than 0.5 ppt (parts per thousand).
  • Brackish water may comprise more salt than freshwater, but not as much as salt as seawater.
  • Brackish water may be considered to have a salinity ranging from about 0.5 to about 35 ppt.
  • Seawater may be water from a sea, an ocean, or any other body of water that has a salinity ranging from about 35 to about 50 ppt.
  • Brine may have a salinity that is about 50 ppt or greater.
  • brine may be water saturated or nearly saturated with salt.
  • the water source from which divalent cations are derived is a mineral rich (e.g., calcium-rich and/or magnesium-rich) freshwater source.
  • the water source from which divalent cations are derived is a naturally occurring saltwater source selected from a sea, an ocean, a lake, a swamp, an estuary, a lagoon, a surface brine, a deep brine, an alkaline lake, an inland sea, or the like.
  • the water source from which divalent cations are derived is a surface brine.
  • the water source from which divalent cations are derived is a subsurface brine.
  • the water source from which divalent cations are derived is a deep brine.
  • the water source from which divalent cations are derived is a Ca-Mg-Na-(K)-Cl; Na-(Ca)-SO/r Cl; Mg-Na-(Ca)-SO/rCl; Na-C ⁇ 3-Cl; or Na-C ⁇ 3-SO/rCl brine.
  • the water source from which divalent cation are derived is an anthropogenic brine selected from a geothermal plant wastewater or a desalination wastewater.
  • Freshwater is often a convenient source of divalent cations (e.g., cations of alkaline earth metals such as Ca 2+ and Mg 2+ ). Any of a number of suitable freshwater sources may be used, including freshwater sources ranging from sources relatively free of minerals to sources relatively rich in minerals.
  • Mineral-rich freshwater sources may be naturally occurring, including any of a number of hard water sources, lakes, or inland seas. Some mineral-rich freshwater sources such as alkaline lakes or inland seas (e.g., Lake Van in Turkey) also provide a source of pH-modifying agents. Mineral-rich freshwater sources may also be anthropogenic.
  • a mineral-poor (soft) water may be contacted with a source of divalent cations such as alkaline earth metal cations (e.g., Ca 2+ , Mg 2+ , etc.) to produce a mineral-rich water that is suitable for methods and systems described herein.
  • Divalent cations or precursors thereof e.g. salts, minerals
  • divalent cations selected from Ca + and Mg + are added to freshwater.
  • monovalent cations selected from Na + and K + are added to freshwater.
  • freshwater comprising Ca + is combined with material comprising metal silicates, ash (e.g., fly ash, bottom ash, boiler slag), or products or processed forms thereof, including combinations of the foregoing, yielding a solution comprising calcium and magnesium cations.
  • material comprising metal silicates, ash e.g., fly ash, bottom ash, boiler slag
  • products or processed forms thereof including combinations of the foregoing, yielding a solution comprising calcium and magnesium cations.
  • some methods include preparing a source of divalent cations by adding one or more divalent cations (e.g., Ca + , Mg + , combinations thereof, etc.) to a source of water.
  • divalent cations e.g., Ca + , Mg + , combinations thereof, etc.
  • Sources of magnesium cations include, but are not limited, magnesium hydroxides, magnesium oxides, etc.
  • Sources of calcium cations include, but are not limited to, calcium hydroxides, calcium oxides, etc. Both naturally occurring and anthropogenic sources of such cations may be employed.
  • Naturally occurring sources of such cations include, but are not limited to mafic minerals (e.g., olivine, serpentine, periodotite, talc, etc.) and the like.
  • the amount of magnesium cation source that is added to the water may vary, e.g., depending upon the specific magnesium cation source and the initial water from which the CO 2 -charged water is produced. In certain embodiments, the amount of magnesium cation that is added to the water ranges from 0.01 to 100.0 grams/liter, such as from 1 to 100 grams/liter of water, including from 5 to 100 grams/liter of water, for example from 5 to 80 grams/liter of water, including from 5 to 50 grams/liter of water.
  • Increasing surface area by reducing particle size is one such method, which can be done by means well known in the art such as ball grinding and jet milling. Jet milling has the further advantage of destroying much of the crystal structure of the substance, enhancing solubility.
  • sonochemistry where intense sonication may be employed to increase reaction rates by a desired amount, e.g., 106 times or more.
  • the particles, with or without size reduction may be exposed to conditions which promote aqueous solution, such as exposure to an acid such as HCl, H 2 SO 4 , or the like; a weak acid or a base may also be used in some embodiments. See, e.g., U.S. Patent Application Publication Nos.
  • the methods and systems of the invention utilize serpentine as a mineral source.
  • Serpentine is an abundant mineral that occurs naturally and may be generally described by the formula OfX 2 ⁇ Si 2 O 5 (OH) 4 , wherein X is selected from the following: Mg, Ca, Fe + , Fe + , Ni, Al, Zn, and Mn, the serpentine material being a heterogeneous mixture consisting primarily of magnesium hydroxide and silica.
  • serpentine is used not only as a source of magnesium, but also as a source of hydroxide.
  • hydroxide is provided for removal of protons from water and/or adjustment of pH by dissolving serpentine; in these embodiments an acid dissolution is not ideal to accelerate dissolution, and other means are used, such as jet milling and/or sonication.
  • the length of time to dissolve the serpentine or other mineral is not critical, as once the process is started at the desired scale, and sufficient time has passed for appropriate levels of dissolution, a continuous stream of dissolved material may be maintained indefinitely. Thus, even if dissolution to the desired level takes days, weeks, months, or even years, once the process has reached the first time point at which desired dissolution has occurred, it may be maintained indefinitely.
  • the minerals may be used individually or in combination with each other as described in U.S. Patent Application Publication No. 2009/0301352, published 10 December 2009, which is incorporated herein by reference in its entirety. Additionally, the materials may be found in nature or may be manufactured.
  • an aqueous solution of divalent cations may be obtained from an industrial plant that is also providing a waste gas stream (e.g., combustion gas stream).
  • a waste gas stream e.g., combustion gas stream.
  • water-cooled industrial plants such as seawater-cooled industrial plants
  • water that has been used by an industrial plant for cooling may then be used as water for producing precipitation material. If desired, the water may be cooled prior to entering a precipitation system of the invention.
  • Such approaches may be employed, for example, with once-through cooling systems.
  • a city or agricultural water supply may be employed as a once-through cooling system for an industrial plant. Water from the industrial plant may then be employed for producing precipitation material, wherein output water has a reduced hardness and greater purity.
  • the aqueous solution of divalent cations may further provide proton-removing agents, which may be expressed as alkalinity or the ability of the divalent cation-containing solution to neutralize acids to the equivalence point of carbonate or bicarbonate.
  • Alkalinity (A ⁇ ) may be expressed by the following equation
  • a ⁇ [HCO 3 IT + 2[CO 3 2 IT + [B(OH) 4 IT + [OH] T + 2[PO 4 3 IT + [HPO 4 2 ] T + [SiO(OH) 3 ] T - [H + ] sws - [HSO 4 " ], wherein "T” indicates the total concentration of the species in the solution as measured. Other species, depending on the source, may contribute to alkalinity as well. The total concentration of the species in solution is in opposition to the free concentration, which takes into account the significant amount of ion pair interactions that occur, for example, in seawater.
  • the aqueous source of divalent cations may have various concentrations of bicarbonate, carbonate, borate, hydroxide, phosphate, biphosphate, and/or silicate, which may contribute to the alkalinity of the aqueous source of divalent cations.
  • Any type of alkalinity is suitable for the invention.
  • a source of divalent cations high in borate alkalinity is suitable for the invention.
  • the concentration borate may exceed the concentration of any other species in solution including, for example, carbonate and/or bicarbonate
  • the source of divalent cations has at least 10, 100, 500, 1000, 1500, 3000, 5000, or more than 5000 mEq of alkalinity.
  • the source of divalent cations has between 500 to 1000 mEq of alkalinity.
  • the water (such as salt water or mineral rich water) is not contacted with a source of CO 2 prior to subjecting the water to precipitation conditions.
  • the water will have an amount of CO 2 associated with it, e.g., in the form of bicarbonate ion, which has been obtained from the environment to which the water has been exposed prior to practice of the method.
  • Subjecting the water to precipitate conditions of the invention results in conversion of this CO 2 into a storage-stable precipitate, and therefore sequestration of the CO 2 .
  • Embodiments of these methods may be viewed as methods of sequestering CO 2 gas directly from the Earth's atmosphere.
  • Embodiments of the methods are efficient for the removal of CO 2 from the Earth's atmosphere. For example, embodiments of the methods are configured to remove CO 2 from saltwater at a rate of 0.025 M or more, such as 0.05 M or more, including 0.1 M or more per gallon of saltwater.
  • the invention provides for contacting a volume of an aqueous solution with a source of carbon dioxide to produce a composition comprising carbonates, bicarbonates, or carbonates and bicarbonates, wherein the composition is a solution or slurry.
  • the solution is a slurry comprising a precipitation material comprising carbonates, bicarbonates, or carbonates and bicarbonates.
  • the precipitation material is produced by subjecting the volume of the aqueous solution to precipitation conditions before, during, or after contact with the source of carbon dioxide.
  • the source Of CO 2 may be any convenient CO 2 source.
  • the source of CO 2 may be a gas, a liquid, a solid (e.g., dry ice), a supercritical fluid, or CO 2 dissolved in a liquid.
  • the CO 2 source is a gaseous CO 2 source such as a waste gas stream.
  • the gaseous CO 2 source may be substantially pure CO 2 or, as described in more detail below, comprise one or more components in addition to CO 2 , wherein the one or more components comprise one or more additional gases such as SOx (e.g., SO, SO 2 , SO3), NOx (e.g., NO, NO 2 ), etc., non-gaseous components, or a combination thereof.
  • the waste streams may further comprise VOC (volatile organic compounds), metals (e.g., mercury, arsenic, cadmium, selenium), and particulate matter comprising particles of solid (e.g., fly ash) or liquid suspended in the gas.
  • the gaseous CO 2 source may be a waste gas stream (e.g., exhaust) produced by an active process of an industrial plant.
  • the nature of the industrial plant may vary, the industrial plants including, but not limited to, power plants, chemical processing plants, mechanical processing plants, refineries, cement plants, steel plants, and other industrial plants that produce CO 2 as a by-product of fuel combustion or another processing step (e.g., calcination by a cement plant).
  • the gaseous CO 2 source may be flue gas from coal-fired power plant.
  • Waste gas streams comprising CO 2 include both reducing condition streams (e.g., syngas, shifted syngas, natural gas, hydrogen, and the like) and oxidizing condition streams (e.g., flue gas resulting from combustion).
  • Particular waste gas streams that may be convenient for the invention include oxygen- containing flue gas resulting from combustion (e.g., from coal or another carbon-based fuel with little or no pretreatment of the flue gas), turbo charged boiler product gas, coal gasification product gas, pre-combustion synthesis gas (e.g., such as that formed during coal gasification in power generating plants), shifted coal gasification product gas, anaerobic digester product gas, wellhead natural gas stream, reformed natural gas or methane hydrates, and the like.
  • waste gas streams may be produced from a variety of different types of industrial plants. Suitable waste gas streams for the invention include waste gas streams produced by industrial plants that combust fossil fuels (e.g., coal, oil, natural gas, propane, diesel), biomass, and/or anthropogenic fuel products of naturally occurring organic fuel deposits (e.g., tar sands, heavy oil, oil shale, etc.).
  • fossil fuels e.g., coal, oil, natural gas, propane, diesel
  • biomass e.g., tar sands, heavy oil, oil shale, etc.
  • a waste gas stream suitable for systems and methods of the invention is sourced from a coal-fired power plant, such as a pulverized coal power plant, a supercritical coal power plant, a mass burn coal power plant, a fluidized bed coal power plant.
  • the waste gas stream is sourced from gas or oil-fired boiler and steam turbine power plants, gas or oil-fired boiler simple cycle gas turbine power plants, or gas or oil-fired boiler combined cycle gas turbine power plants.
  • waste gas streams produced by power plants that combust syngas i.e., gas that is produced by the gasification of organic matter, for example, coal, biomass, etc. are used.
  • a line e.g., a duct, pipe, etc.
  • a line may be connected to the flue of the industrial plant such that gas leaving through the flue is conveyed to the appropriate location(s) of the C ⁇ 2 -processing system (e.g., processor or a component thereof, such as a gas-liquid contactor or gas-liquid- solid contactor).
  • the location of the gas conveyor on the industrial plant may vary, for example, to provide a waste gas stream of a desired temperature.
  • the flue gas may be obtained at the exit point of the boiler, gas turbine, kiln, or at any point of the power plant that provides the desired temperature.
  • the gas conveyor may be configured to maintain flue gas at a temperature above the dew point (e.g., 125 0 C) in order to avoid condensation and related complications.
  • Other steps may be taken to reduce the adverse impact of condensation and other deleterious effects, such as employing ducting that is stainless steel or fluorocarbon (such as poly(tetrafluoroethylene)) lined such the duct does not rapidly deteriorate.
  • waste gas streams may comprise carbon dioxide in an amount ranging from 40,000 ppm (4%) to 100,000 ppm (10%) depending on the waste gas stream (e.g., CO 2 from natural gas-fired power plants, furnaces, small boilers, etc.).
  • waste gas streams may comprise carbon dioxide in an amount ranging from 100,000 ppm (10%) to 150,000 ppm (15%) depending on the waste gas stream (e.g., CO 2 from coal-fired power plants, oil generators, diesel generators, etc.).
  • waste gas streams may comprise carbon dioxide in an amount ranging from 200,000 ppm (20%) to 400,000 ppm (40%) depending on the waste gas stream (e.g., CO 2 from cement plant calcination, chemical plants, etc.).
  • waste gas streams may comprise carbon dioxide in an amount ranging from 900,000 ppm (90%) to 1,000,000 ppm (100%) depending on the waste gas stream (e.g., CO 2 from ethanol fermenters, CO 2 from steam reforming at refineries, ammonia plants, substitute natural gas (SNG) plants, CO 2 separated from sour gases, etc.).
  • the concentration of CO 2 in a waste gas stream may be decreased by 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, 95% or more, 99% or more, 99.9% or more, or 99.99%.
  • at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, 99.9%, or 99.99% of the carbon dioxide may be removed from the waste gas stream.
  • the methods and systems of the invention are capable of absorbing 5% or more, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, 45% or more, 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, 95% or more, or 99% or more of the CO 2 in a gaseous source of CO 2 , such as an industrial source of CO 2 , e.g., flue gas from a power plant or waste gas from a cement plant.
  • a gaseous source of CO 2 such as an industrial source of CO 2 , e.g., flue gas from a power plant or waste gas from a cement plant.
  • the methods and systems of the invention are capable of absorbing 50% or more of the CO 2 in a gaseous source of CO 2 , such as an industrial source of CO 2 , e.g., flue gas from a power plant or waste gas from a cement plant.
  • a gaseous source of CO 2 such as an industrial source of CO 2 , e.g., flue gas from a power plant or waste gas from a cement plant.
  • a portion of the waste gas stream (i.e., not the entire gaseous waste stream) from an industrial plant may be used to produce compositions comprising carbonates, bicarbonates, or carbonates and bicarbonates.
  • the portion of the waste gas stream that is employed in producing compositions may be 75% or less, such as 60% or less, and including 50% and less of the waste gas stream.
  • most (e.g., 80% or more) of the entire waste gas stream produced by the industrial plant is employed in producing compositions.
  • 80% or more, such as 90% or more, including 95% or more, up to 100% of the waste gas stream (e.g., flue gas) generated by the source may be employed for producing compositions of the invention.
  • substantially 100% of the CO 2 contained in a flue gas, or a portion of the flue gas, from a power plant may be sequestered as a composition of the invention (e.g., precipitation material comprising one or more stable or metastable minerals).
  • a composition of the invention e.g., precipitation material comprising one or more stable or metastable minerals.
  • sequestration may be done in a single step or in multiple steps, and may further involve other processes for sequestering CO 2 (e.g., as the concentration of CO 2 is decreased in the flue gas, more energy-intensive processes that be prohibitive in energy consumption for removing all of the original CO 2 in the gas may become practical in removing the final CO 2 in the gas).
  • the gas entering the power plant may contain a concentration of CO 2 that is greater than the concentration of CO 2 in the flue gas exiting the plant, which flue gas has been treated by the processes and systems of the invention.
  • the methods and systems of the invention encompass a method comprising supplying a gas (e.g., atmospheric air) to a power plant, wherein the gas comprises CO 2 ; treating the gas in the power plant (e.g., by combustion of fossil fuel to consume O 2 ) to produce CO 2 , then treating exhaust gas to remove CO 2 ; and releasing the gas from the power plant, wherein the gas released from the power plant has a lower CO 2 content than the gas supplied to the power plant.
  • a gas e.g., atmospheric air
  • the gas released from the power plant contains at least 10% less CO 2 , or at least 20% less CO 2 , or at least 30% less CO 2 , or at least 40% less CO 2 , or at least 50% less CO 2 , or at least 60% less CO 2 , or at least 70% less CO 2 , or at least 80% less CO 2 , or at least 90% less CO 2 , or at least 95% less CO 2 , or at least 99% less CO 2 , or at least 99.5% less CO 2 , or at least 99.9% less CO 2 , than the gas entering the power plant.
  • the gas entering the power plant is atmospheric air and the gas exiting the power plant is treated flue gas.
  • methods and systems of the invention are also applicable to removing combustion gas components from less concentrated sources (e.g., atmospheric air), which contains a much lower concentration of pollutants than, for example, flue gas.
  • methods and systems encompass decreasing the concentration of CO 2 and/or additional components in atmospheric air by producing compositions of the invention.
  • the concentration of CO 2 in a portion of atmospheric air may be decreased by 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, 95% or more, 99% or more, 99.9% or more, or 99.99%.
  • Such decreases in CO 2 may be accomplished with yields as described herein, or with higher or lower yields, and may be accomplished in one processing step or in a series of processing steps.
  • the pH of the water that is contacted with the CO 2 source may vary.
  • the pH of the water that is contacted with the CO 2 source is acidic, such that the pH is lower than 7, such as 6.5 or lower, 6 or lower, 5.5 or lower, 5 or lower, 4.5 or lower, or 4 or lower.
  • the pH of the water may be neutral to slightly basic, by which is meant that the pH of the water may range from pH 7 to pH 9, such as pH 7 to pH 8.5, including pH 7.5 to pH 8.5.
  • the water such as alkaline earth metal ion-containing water (including alkaline solutions or natural saline alkaline waters) is basic when contacted with the CO 2 source, such as a carbon dioxide containing gaseous stream.
  • the CO 2 source such as a carbon dioxide containing gaseous stream.
  • the pH of the water is generally insufficient to cause precipitation of the storage-stable carbon dioxide sequestering product.
  • the pH may be 9.5 or lower, such as 9.3 or lower, including 9 or lower.
  • the pH as described above may be maintained at a substantially constant value during contact with the carbon dioxide containing gaseous stream, or the pH may be manipulated to maximize CO 2 absorption while minimizing base consumption or other means of removing protons, such as by starting at a certain pH and gradually causing the pH to rise as CO 2 continues to be introduced.
  • substantially constant is meant that the magnitude of change in pH during some phase of contact with the carbon dioxide source is 0.75 or less, such as 0.50 or less, including 0.25 or less, such as 0.10 or less.
  • the pH may be maintained at substantially constant value, or manipulated to maximize CO 2 absorption but prevent hydroxide precipitation without precipitation, using any convenient approach.
  • the pH is maintained at substantially constant value, or manipulated to maximize CO 2 absorption without precipitation, during CO 2 charging of the water by adding a sufficient amount of base to the water in a manner that provides the substantially constant pH.
  • Any convenient base or combination of bases may be adding, including but not limited to oxides and hydroxides, such as magnesium hydroxide, where further examples of suitable bases are reviewed below.
  • the pH may be maintained at substantially constant value, or manipulated to maximize CO 2 absorption, through use of electrochemical protocols, such as the protocols described below, so that the pH of the water is electrochemically maintained at the substantially constant value.
  • the invention provides for contacting a volume of an aqueous solution with a source of carbon dioxide to produce a composition comprising carbonates, bicarbonates, or carbonates and bicarbonates, wherein the composition is a solution or slurry.
  • a source of carbon dioxide to produce a composition comprising carbonates, bicarbonates, or carbonates and bicarbonates, wherein the composition is a solution or slurry.
  • compositions of the invention e.g., precipitation material comprising carbonates, bicarbonates, or carbonates and bicarbonates
  • protons are removed from various species (e.g. carbonic acid, bicarbonate, hydronium, etc.) in the aqueous solution to shift the equilibrium toward bicarbonate, carbonate, or somewhere in between. As protons are removed, more CO 2 goes into solution.
  • proton-removing agents and/or methods are used while contacting an aqueous solution with CO 2 to increase CO 2 absorption in one phase of the reaction, wherein the pH may remain constant, increase, or even decrease, followed by a rapid removal of protons (e.g., by addition of a base), which, In some embodiments, may cause rapid precipitation of precipitation material.
  • Protons may be removed from the various species (e.g. carbonic acid, bicarbonate, hydronium, etc.) by any convenient approach, including, but not limited to use of naturally occurring proton-removing agents, use of microorganisms and fungi, use of synthetic chemical proton-removing agents, recovery of waste streams from industrial processes, and using electrochemical means.
  • Naturally occurring proton-removing agents encompass any proton-removing agents found in the wider environment that may create or have a basic local environment.
  • Some embodiments provide for naturally occurring proton-removing agents including minerals that create basic environments upon addition to solution.
  • Such minerals include, but are not limited to, lime (CaO); periclase (MgO); iron hydroxide minerals (e.g., goethite and limonite); and volcanic ash. Methods for digestion of such minerals and rocks comprising such minerals are described in U.S. Patent Application No. 12/501,217, filed 10 July 2009, which is incorporated herein by reference in its entirety.
  • a subsurface brine comprising borate alkalinity provides a source of proton-removing agents.
  • a deep brine comprising carbonate alkalinity provides a source of proton-removing agents.
  • a deep brine comprising borate alkalinity provides a source of proton-removing agents.
  • naturally alkaline bodies of water include, but are not limited to surface water sources (e.g. alkaline lakes such as Mono Lake in California) and ground water sources (e.g. basic aquifers such as the deep geologic alkaline aquifers located at Searles Lake in California).
  • organisms are used to produce proton-removing agents, wherein the organisms (e.g., Bacillus pasteurii, which hydro lyzes urea to ammonia) metabolize a contaminant (e.g. urea) to produce proton-removing agents or solutions comprising proton-removing agents (e.g., ammonia, ammonium hydroxide).
  • organisms are cultured separately from the precipitation reaction mixture, wherein proton-removing agents or solution comprising proton-removing agents are used for addition to the precipitation reaction mixture.
  • naturally occurring or manufactured enzymes are used in combination with proton-removing agents to invoke precipitation of precipitation material.
  • Carbonic anhydrase which is an enzyme produced by plants and animals, accelerates transformation of carbonic acid to bicarbonate in aqueous solution.
  • carbonic anhydrase may be used to enhance dissolution of CO 2 and accelerate precipitation of precipitation material, as described in further detail herein.
  • Chemical agents for effecting proton removal generally refer to synthetic chemical agents that are produced in large quantities and are commercially available.
  • chemical agents for removing protons include, but are not limited to, hydroxides, organic bases, super bases, oxides, ammonia, and carbonates.
  • an organic base selected from pyridine, methylamine, imidazole, benzimidazole, histidine, and a phosphazene is used to remove protons from various species (e.g., carbonic acid, bicarbonate, hydronium, etc.) for preparation of compositions of the invention.
  • ammonia is used to raise pH to a level sufficient for preparation of compositions of the invention.
  • super bases suitable for use as proton- removing agents include sodium ethoxide, sodium amide (NaNH 2 ), sodium hydride (NaH), butyl lithium, lithium diisopropylamide, lithium diethylamide, and lithium bis(trimethylsilyl)amide.
  • Oxides including, for example, calcium oxide (CaO), magnesium oxide (MgO), strontium oxide (SrO), beryllium oxide (BeO), and barium oxide (BaO) are also suitable proton-removing agents that may be used.
  • Carbonates for use in the invention include, but are not limited to, sodium carbonate.
  • electrochemical methods may be used to produce caustic molecules (e.g., hydroxide) through, for example, the chlor-alkali process, or modification thereof (e.g., low-voltage modification).
  • Electrodes i.e., cathodes and anodes
  • a selective barrier such as a membrane
  • Electrochemical systems and methods for removing protons may produce by-products (e.g., hydrogen) that may be harvested and used for other purposes.
  • Additional electrochemical approaches that may be used in systems and methods of the invention include, but are not limited to, those described in U.S.
  • the methods of the invention allow large amounts of magnesium and, in some cases, calcium, to be added to the water used in some embodiments of the invention, increasing the amount of precipitate that may be formed per unit of water in a single precipitation step, allowing surprisingly high yields of carbonate-containing precipitate when combined with methods of dissolution of CO 2 from an industrial source in water, e.g., seawater or other saltwater source.
  • the precipitate comprises magnesium carbonate; in some embodiments the precipitate comprises calcium carbonate; in some embodiments, the precipitate comprises magnesium and calcium, and/or magnesium/calcium carbonates.
  • the ratio of magnesium to calcium in the precipitated material produced in a single precipitation step is at least 0.5: 1, or at least 1 : 1, or at least 2: 1, or at least 3: 1, or at least 4: 1, or at least 5: 1, or at least 6: 1, or at least 7: 1, or at least 8: 1, or at least 9: 1, or at least 10:1. In some embodiments the ratio of magnesium to calcium in the precipitated material produced in a single precipitation step is at least 2: 1.
  • the ratio of magnesium to calcium in the precipitated material produced in a single precipitation step is at least 4: 1. In some embodiments the ratio of magnesium to calcium in the precipitated material produced in a single precipitation step is at least 6: 1. In some embodiments, the precipitate contains calcium and magnesium carbonates, and contains components that allow at least a portion of the carbon in the carbonate to be traced back to a fossil fuel origin.
  • the temperature of the water may be adjusted to a value between 0°C and 30°C, such as to a value between 5°C and 25°C.
  • a given set of precipitation conditions may have a temperature ranging from 0 0 C to 100 0 C
  • the temperature may be adjusted in certain embodiments to produce the desired precipitate.
  • the temperature of the water may be raised using any convenient protocol. In some instances, the temperature is raised using energy generated from low or zero carbon dioxide emission sources, e.g., solar energy sources, wind energy sources, hydroelectric energy sources, geothermal energy sources, from the waste heat of the flue gas which can range up to 500 0 C, etc.
  • the pH of the water may range from 4 to 14 during a given precipitation process, in some instances the pH is raised to alkaline levels in order to produce the desired precipitation product.
  • the pH is raised to a level sufficient to cause precipitation of the desired CO 2 -sequestering product, as described above.
  • the pH may be raised to 9.5 or higher, such as 10 or higher, including 10.5 or higher.
  • the pH may be raised to a level that minimizes if not eliminates CO 2 production during precipitation.
  • the pH may be raised to a value of 10 or higher, such as a value of 11 or higher.
  • a source of an agent for removal of protons, during dissolution of CO 2 and/or during the precipitation step in which pH is raised may be a naturally occurring source.
  • the agent may comprise serpentine dissolved into aqueous solution, as described above.
  • the agent may comprise a natural body of highly alkaline water. Such bodies of water are well known and are sources of large amounts of alkalinity, e.g., Lake Van in Turkey has an average pH of 9.7-9.8.
  • fly ash, slag, cement waste, and other industrial wastes can provide sufficient alkalinity to remove at least a portion of the protons and/or provide a sufficient pH change for precipitation.
  • low-voltage electrochemical protocols are employed remove protons from the water, e.g. while CO 2 is dissolved and at the precipitation step.
  • low-voltage is meant that the employed electrochemical protocol operates at an average voltage of 2.0, 1.9, 1.8, 1.7, or 1.6 V or less, such as 1.5, 1.4, 1.3, 1.2, 1.1 V or less, such as 1.0 V or less, including 0.9V or less, 0.8V or less, 0.7V or less, 0.6V or less, 0.5V or less, 0.4V or less, 0.3V or less, 0.2V or less, or 0.1V or less.
  • electrochemical protocols that do not generate chlorine gas.
  • electrochemical protocols that do not generate oxygen gas are also of interest.
  • electrochemical protocols that do not generate hydrogen gas.
  • the electrochemical protocol is one that does not generate any gaseous by-byproduct.
  • ion-selective membranes a low-voltage system for producing hydroxide
  • the system and method make use of one or more ion-selective membranes (a low-voltage system for producing hydroxide), which are further described in International Patent Application No. PCT/US08/88242, filed 23 December 2008, titled “Low-Energy Electrochemical Hydroxide System and Method,” and International Patent Application No. PCT/US08/88246, filed 23 December 2008, titled “Low- Energy Electrochemical Proton Transfer System and Method,” each of which is incorporated herein by reference in its entirety.
  • a second set of methods and systems for removing protons from aqueous solution/producing hydroxide pertains to a low energy process for electrochemically preparing an ionic solution utilizing an ion exchange membrane in an electrochemical cell.
  • the system comprises an electrochemical system wherein an ion exchange membrane separates a first electrolyte from a second electrolyte, the first electrolyte contacting an anode and the second electrolyte contacting a cathode.
  • hydroxide ions form at the cathode and a gas does not form at the anode.
  • the system comprises an electrochemical system comprising a first electrolytic cell including an anode contacting a first electrolyte, and an anion exchange membrane separating the first electrolyte from a third electrolyte; and a second electrolytic cell including a second electrolyte contacting a cathode and a cation exchange membrane separating the first electrolyte from the third electrolyte; wherein on applying a voltage across the anode and cathode, hydroxide ions form at the cathode and a gas does not form at the anode.
  • the method comprises placing an ion exchange membrane between a first electrolyte and a second electrolyte, the first electrolyte contacting an anode and the second electrolyte contacting a cathode; and migrating ions across the ion exchange membrane by applying a voltage across the anode and cathode to form hydroxide ions at the cathode without forming a gas at the anode.
  • the method comprises placing a third electrolyte between an anion exchange membrane and a cation exchange membrane; a first electrolyte between the anion exchange and an anode; and second electrolyte between the cation exchange membrane and a cathode; and migrating ions across the cation exchange membrane and the anion exchange membrane by applying a voltage to the anode and cathode to form hydroxide ions at the cathode without forming a gas at the anode.
  • the methods and systems in various embodiments are directed to a low voltage electrochemical system and method for generating a solution of sodium hydroxide in an aqueous solution utilizing one or more ion exchange membranes wherein, a gas is not formed at the anode and wherein hydroxyl ions are formed at the cathode.
  • hydroxide ions are formed in an electrochemical process without the formation of oxygen or chlorine gas.
  • a solution of e.g., sodium hydroxide is formed in the solution around the cathode; concurrently, an acidified solution comprising hydrochloric acid is formed in the solution around the anode.
  • a gas such as chorine or oxygen does not form at the anode.
  • the sodium hydroxide solution is useable to sequester CO 2 as described herein, and the acidic solution is useable to dissolve calcium and magnesium bearing minerals to provide a calcium and magnesium ions for sequestering CO 2 , also as described herein.
  • the system is adaptable for batch and continuous processes as described herein.
  • the system includes an electrochemical cell wherein an ion exchange membrane (802, 824) is positioned to separate a first electrolyte (804) from a second electrolyte (806), the first electrolyte contacting an anode (808) and the second electrolyte contacting a cathode (810).
  • an anion exchange membrane (802) is utilized; in Fig. 3, a cation exchange membrane (824) is utilized.
  • the cell includes outlet port (818) for draining first electrolyte from the cell, and outlet port (820) for draining second electrolyte from the cell.
  • the inlet and outlet ports are adaptable for various flow protocols including batch flow, semi-batch flow, or continuous flow.
  • the system includes a duct (822) for directing gas to the anode; in various embodiments the gas comprises hydrogen formed at the cathode (810).
  • the voltage/current regulator is adaptable to increase or decrease the current or voltage across the cathode and anode in the system as desired.
  • second electrolyte (806) comprises sodium chloride
  • sodium ions migrate into the second electrolyte (806) from the first electrolyte (804) through the cation exchange membrane (824); protons form at the anode (808); and hydrogen gas forms at the cathode (810).
  • a gas e.g., oxygen or chlorine does not form at the anode (808).
  • second electrolyte (806) As hydroxide ions from the anode (810) and enter in to the second electrolyte (806) concurrent with migration of chloride ions from the second electrolyte, an aqueous solution of sodium hydroxide will form in second electrolyte (806). Consequently, depending on the voltage applied across the system and the flow rate of the second electrolyte (806) through the system, the pH of the second electrolyte is adjusted.
  • both the anode and the cathode comprise platinum, and the first and second electrolytes comprise a solution of sodium chloride.
  • 0.1 V to 1 V is applied across the anode and cathode the pH of the second electrolyte solution increased. Similar results are achievable with voltages of 0.1 V to 0.8 V; 0.1 V to 0.7 V; 0.1 V to 0.6 V; 0.1 V to 0.5 V; 0.1 V to 0.4 V; and 0.1 V to 0.3 V across the electrodes.
  • a volt of 0.6 V or less is applied across the anode and cathode; in another embodiment, a volt of 0.1 V to 0.6 V or less is applied across the anode and cathode; in yet another embodiment, a voltage of 0.1 to 1 V or less is applied across the anode and cathode.
  • hydrogen gas formed at the cathode (810) is directed to the anode (808) where, without being bound to any theory, it is believed that the gas is adsorbed and/or absorbed into the anode and subsequently forms protons at the anode.
  • an acidic solution comprising e.g., hydrochloric acid is obtained in the first electrolyte (804).
  • the system comprises an electrochemical cell including anode (808) contacting first electrolyte (804) and an anion exchange membrane (802) separating the first electrolyte from a third electrolyte (830); and a second electrolytic cell comprising a second electrolyte (806) contacting a cathode (880) and a cation exchange membrane (824) separating the first electrolyte from the third electrolyte, wherein on applying a voltage across the anode and cathode, hydrogen ions form at the cathode without a gas forming at the anode.
  • the system of Fig. 4 is adaptable for batch and continuous processes.
  • first electrolyte (804) and second electrolyte (806) comprise an aqueous salt solution comprising seawater, freshwater, brine, or brackish water or the like; and second electrolyte comprises a solution substantially of sodium chloride.
  • first (804) and second (806) electrolytes may comprise seawater.
  • the third electrolyte (830) comprises substantially sodium chloride solution.
  • first electrolyte (804) is in contact with the anode (808) and second electrolyte (806) is in contact with the cathode (810).
  • the third electrolyte (830), in contact with the anion and cation exchange membrane, completes an electrical circuit that includes voltage or current regulator (812).
  • the current/voltage regulator is adaptable to increase or decrease the current or voltage across the cathode and anode in the system as desired.
  • the system includes a duct (822) for directing gas to the anode; in various embodiments the gas is hydrogen formed at the cathode (810).
  • the gas is hydrogen formed at the cathode (810).
  • third electrolyte (830) comprises sodium chloride
  • chloride ions migrate into the first electrolyte (804) from the third electrolyte (830) through the anion exchange membrane (802); sodium ions migrate to the second electrolyte (806) from the third electrolyte (830); protons form at the anode; and hydrogen gas forms at the cathode.
  • a gas e.g., oxygen or chlorine does not form at the anode (808).
  • second electrolyte (806) as hydroxide ions from the cathode (810) enter into the solution concurrent with migration of sodium ions from the third electrolyte, increasingly an aqueous solution of sodium hydroxide will form in second electrolyte (806).
  • the pH of the solution will be adjusted. In one embodiment, when a volt of 0.1
  • V or less 0.2 V or less, 0.3 V or less, 0.4 V or less, 0.5 V or less, 0.6 V or less, 0.7 V or less, 0.8 V or less, 0.9 V or less, 1.0 V or less, 1.1 V or less, 1.2 V or less, 1.3 V or less, 01.4 V or less, 1.5 V or less, 1.6 V or less, 1.7 V or less, 1.8 V or less, 1.9 V or less, or 2.0 V or less or less is applied across the anode and cathode, the pH of the second electrolyte solution increased; in another embodiment, when a volt of 0.1 to 2.0 V is applied across the anode and cathode the pH of the second electrolyte increased; in yet another embodiment, when a voltage of 0.1 V to 1.0 V is applied across the anode and cathode the pH of the second electrolyte solution increased.
  • a volt of 0.6 volt or less is applied across the anode and cathode; in another embodiment, a volt of 0.1 V to 0.6 V or less is applied across the anode and cathode; in yet another embodiment, a voltage of 0.1 V to 1.0 V or less is applied across the anode and cathode.
  • first electrolyte (804) as proton form at the anode (808) and enter into the solution concurrent with migration of chloride ions from the third electrolyte to the first electrolyte, increasingly an acidic solution will form in first electrolyte (804).
  • the pH of the solution will be adjusted. In one embodiment, when a volt of 0.1 V or less, 0.2 V or less, 0.3 V or less, 0.4 V or less, 0.5 V or less, 0.6 V or less, 0.7 V or less, 0.8 V or less, 0.9 V or less, 1.0 V or less, 1.1 V or less, 1.2
  • V or less 1.3 V or less, 1.4 V or less, 1.5 V or less, 1.6 V or less, 1.7 V or less, 1.8 V or less, 1.9 V or less, or 2.0 V or less is applied across the anode and cathode, the pH of the second electrolyte solution increased; in another embodiment, when a volt of 0.1 V to 2.0 V is applied across the anode and cathode the pH of the second electrolyte increased; in yet another embodiment, when a voltage of 0.1 V to 1 V is applied across the anode and cathode the pH of the second electrolyte solution increased.
  • hydrogen gas formed at the cathode (810) is directed to the anode (808) where, without being bound to any theory, it is believed that hydrogen gas is adsorbed and/or absorbed into the anode and subsequently forms protons at the anode and enters the first electrolyte (804). Also, in various embodiments as illustrated in Figs. 2-4, a gas such as oxygen or chlorine does not form at the anode (808). Accordingly, as can be appreciated, with the formation of protons at the anode and migration of chlorine into the first electrolyte, hydrochloric acid is obtained in the first electrolyte (804).
  • the resulting solution can be used as the second electrolyte solution.
  • the hydrochloric acid can be used in place of, or in addition to, the acidified second electrolyte solution.
  • Embodiments described above produce electrolyte solutions enriched in bicarbonate ions and carbonate ions, or combinations thereof as well as an acidified stream.
  • the acidified stream can also find application in various chemical processes.
  • the acidified stream can be employed to dissolve calcium and/or magnesium rich minerals such as serpentine and olivine to create the electrolyte solution used in the reservoir 816.
  • Such an electrolyte solution can be charged with bicarbonate ions and then made sufficiently basic so as to precipitate carbonate compounds as described herein
  • Removal of the first proton produces bicarbonate and removal of the second produces carbonate, which may be precipitated as, e.g., a carbonate of a divalent cation, such as magnesium carbonate or calcium carbonate.
  • the removal of the two protons requires some process or combination of processes that typically require energy.
  • the source of renewable sodium hydroxide is typically the chloralkali process, which uses an electrochemical process requiring at least 2.8 V and a fixed amount of electrons per mole of sodium hydroxide. That energy requirement may be expressed in terms of a carbon footprint, i.e., amount of carbon produced to provide the energy to drive the process.
  • the invention includes forming a stable CO 2 -containing precipitate from a human-produced gaseous source of CO 2 , wherein the formation of the precipitate utilizes a process for removing protons from an aqueous solution in which a portion or all of the CO 2 of the gaseous source of CO 2 is dissolved, and wherein the CO 2 produced by the process of removing protons is less than 70% of the CO 2 removed from the gaseous source of CO 2 by the formation of precipitate.
  • This embodiment is useful in utilizing concentrated waters such as desalination brine, wherein the cation content is sufficiently high that addition of more Mg ions is difficult.
  • This embodiment is also useful in solutions of any concentration where two different products are desired to be produced - a primarily calcium carbonate material, and then a magnesium carbonate dominated material.
  • the yield of product from a given precipitation reaction may vary depending on a number of factors, including the specific type of water employed, whether or not the water is supplemented with divalent metal ions, the particular precipitation protocol employed, etc. In some instances, the precipitate protocols employed to precipitate the product are high yield precipitation protocols.
  • the amount of product produced for every liter of water ranges from 5 to 200 g, such as 10 to 100 g, including 20 to 100 g.
  • the yield of product may range from 5 to 20 g product per liter of water, such as 5 to 10, e.g., 6 to 8, g product per liter of water.
  • two or more reactors may be used to carry out the methods described herein.
  • the method may include a first reactor and a second reactor.
  • the first reactor is used for contacting the initial water with a magnesium ion source and for charging the initial water with CO 2 , as described above.
  • the water may be agitated to facilitate the dissolution of the magnesium ion source and to facilitate contact of the initial water with the CO 2 .
  • agitation of the CO 2 charged water is stopped, such that undissolved solids may settle by gravity.
  • the CO 2 charged water is then transferred from the first reactor to the second reactor. After transferring the CO 2 charged water to the second reactor, the step of carbonate precipitation may be performed, as described herein.
  • a multi-step process as described above, employing two or more reactors, as described above, can be used to carry out the methods described herein.
  • a first reactor is used for contacting the initial water with a magnesium ion source and for charging the initial water with CO 2 , as described above.
  • the CO 2 charged water is transferred from the first reactor to a second reactor for the carbonate precipitation reaction.
  • one or more additional steps of CO 2 charging and subsequent carbonate precipitation may be performed in the second reactor, as described above.
  • precipitation conditions can be used that favor the formation of particular morphologies of carbonate compound precipitates.
  • precipitation conditions can be used that favor the formation of amorphous carbonate compound precipitates over the formation of crystalline carbonate compound precipitates.
  • a precipitation facilitator may be added in addition to contacting the initial water with a magnesium ion source and charging the initial water with CO 2 , as described above.
  • the precipitation facilitator facilitates the formation of carbonate compound precipitates at lower pH's sufficient for nucleation, but insufficient for crystal formation and growth.
  • precipitation facilitators include, but are not limited to, aluminum sulfate (Al 2 SO/i)3.
  • composition which includes precipitated product and a mother liquor or supernatant solution (i.e., the remaining liquid from which the precipitated product was produced).
  • This composition may be a slurry of the precipitate and mother liquor or supernatant solution.
  • the precipitated product in sequestering carbon dioxide, is disposed of in some manner following its production.
  • the phrase "disposed of" means that the product is either placed at a storage site or employed for a further use in another product, i.e., a manufactured or man-made item, where it is stored in that other product at least for the expected lifetime of that other product.
  • this disposal step includes forwarding the slurry composition described above to a long-term storage site.
  • the storage site could be an above ground site, a below ground site or an underwater site.
  • the supernatant component of the slurry may naturally separate from the precipitate, e.g., via evaporation, dispersal, etc.
  • the resulting precipitated product may be separated from the supernatant component of the slurry. Separation of the precipitated product may be achieved using any of a number of convenient approaches. As detailed further herein, liquid-solid separators such as Epuramat's Extrem- Separator ("ExSep”) liquid-solid separator, Xerox PARC's spiral concentrator, or a modification of either of Epuramat's ExSep or Xerox PARC's spiral concentrator, are useful in some embodiments. Separation may also be achieved by drying the precipitated product to produce a dried precipitated product. Drying protocols of interest include filtering the precipitate from the mother liquor or supernatant solution to produce a filtrate and then air-drying the filtrate.
  • Drying protocols of interest include filtering the precipitate from the mother liquor or supernatant solution to produce a filtrate and then air-drying the filtrate.
  • air-drying may be at a temperature ranging from -70 to 120 0 C, as desired.
  • drying may include placing the slurry at a drying site, such as a tailings pond, and allowing the liquid component of the precipitate to evaporate and leave behind the desired dried product.
  • freeze-drying i.e., lyophilization
  • the precipitate is frozen, the surrounding pressure is reduced and enough heat is added to allow the frozen water in the material to sublime directly from the frozen precipitate phase to gas.
  • Yet another drying protocol of interest is spray drying, where the liquid containing the precipitate is dried by feeding it through a hot gas, e.g., where the liquid feed is pumped through an atomizer into a main drying chamber and a hot gas is passed as a co-current or counter-current to the atomizer direction.
  • the resultant precipitate may be disposed of in a variety of different ways, as further elaborated below.
  • the precipitate may be employed as a component of a building material, as reviewed in greater detail below.
  • the precipitate may be placed at a long-term storage site (sometimes referred to in the art as a carbon bank), where the site may be above ground site, a below ground site or an underwater site. Further details regarding disposal protocols of interest are provided below.
  • the resultant mother liquor or supernatant solution may also be processed as desired.
  • the mother liquor or supernatant solution may be returned to the source of the water, e.g., ocean, or to another location.
  • the mother liquor or supernatant solution may be contacted with a source of CO 2 , e.g., as described above, to sequester further CO 2 .
  • the mother liquor or supernatant solution may be contacted with a gaseous source of CO 2 in a manner sufficient to increase the concentration of carbonate ion present in the mother liquor or supernatant solution. Contact may be conducted using any convenient protocol, such as those described above.
  • the mother liquor or supernatant solution has an alkaline pH, and contact with the CO 2 source is carried out in a manner sufficient to reduce the pH to a range between 5 and 9, e.g., 6 and 8.5, including 7.5 to 8.2.
  • Dewatering is the separation of solids and liquid in mixtures of solids and liquids such as slurries and suspensions. Dewatering may be divided into three types by the methods employed: gravity separation, mechanical separation, and thermal separation. Dewatering may also be classified by the amount of solids present in the mixtures. Primary dewatering is a term used to describe the steps or methods used to obtain a mixture that is more concentrated in solids than the original mixture (e.g., up to and including 30 wt% solids).
  • Secondary dewatering is a term used to describe the steps or methods used to obtain a mixture that is more concentrated in solids than the original mixture, usually following primary dewatering, and resulting in a mixture greater than about 30wt% solids (e.g., 30wt%-90wt% solids). Steps or methods that result in mixtures that are more concentrated in solids than the original mixture such that the solids make up greater than 90wt% of the mixture may be referred to subsequent dewatering or final dewatering, depending on how many steps are included and if any further separation takes place. Dewatering of slurries and other mixtures of solids (e.g.
  • particles, colloids and liquid encompasses: activities to agglomerate or enlarge the solid particles in a mixture or slurry such as coagulation, flocculation, and growth of existing crystals; settling out of solids; physical separation of solids and liquid; and if required by the intended application, thermal removal of liquid from solids of a mixture or slurry.
  • Gravity separation of solids from liquid is one type of separation or dewatering. Gravity separation is characterized by utilizing the difference in the density or specific gravity of the solids and liquid. Settling out is the simplest form of gravity separation. The activities to agglomerate or enlarge the solid particles in a slurry or mixture allow for thickening or settling out of the solids in the liquid with less energy and/or time. Other methods that employ gravity include, but are not limited to, centrifugal separation, use of a hydrocyclone, use of a clarifier, use of a Lamella clarifier/thickener.
  • Mechanical separation is another type of solid- liquid separation or dewatering. Mechanical separation may indicate filtration methods or that a machine is used to separate solids from liquids in a mixture or slurry without exploiting the differences in density between the solids and liquids. Mechanical or physical separation methods that are described as filtration utilize a barrier through which the liquid and some solids may pass. A force may be applied to increase the flow rate of liquid through the barrier or filter. Filtration may be surface or depth filtration. Surface filtration occurs when a barrier, e.g. a sieve or wire mesh, prevents particles larger than the openings of the barrier from passing through and such particles are retained on the barrier surface.
  • a barrier e.g. a sieve or wire mesh
  • Depth filtration employs the thickness of a barrier in addition to the surface of the barrier with the intent of trapping solids in the voids within the thickness of the barrier and allowing the liquid in a mixture of solid particles and a liquid to pass.
  • surface filtration and depth filtration take place.
  • Filters may be characterized by the size of the smallest particle that may be stopped by the filter, by the permeability of the filter, and the amount of solids that accumulate in the filter and the rate of increased resistance to flow of liquid through the filter.
  • the flow of the mixture towards the barrier, and particularly the flow of the liquid portion of the mixture through the barrier may be facilitated by the application of a vacuum or pressure above the mixture.
  • the pressure may be applied by a solid implement, such as a plate or belt pressing upon a layer of the mixture, by a gas, or by hydraulic means in combination with a physical implement.
  • Filter aids are inert aids to separation. Filter aids act to either form a pre-coat on a coarse barrier or mix with the mixture to be separated so as to increase the permeability of the filter cake that forms, or in some cases to filter aids do both.
  • Suitable filter aid materials include diatomaceous earth, expanded perilitic rock, asbestos, cellulose, non- activated carbon, ashes, ground chalk, or a mixture thereof. In some cases, material that is cheap, waste, or otherwise rejected material is used a filter aid material.
  • droplets of slurry or other mixtures of solids and liquid are made by any suitable atomization technique, including, but not limited to use of: a pressure atomizer, a rotary atomizer, an air-assist atomizer, an airblast atomizer, or an ultrasonic atomizer or any combination thereof.
  • the droplets of solids and liquid are of average diameter from 5 ⁇ m to 500 ⁇ m.
  • the droplets of solids and liquid are of average diameter of greater than 500 ⁇ m, such as greater than 600 ⁇ m, such as greater than 700 ⁇ m, such as greater than 800 ⁇ m, such as greater than 900 ⁇ m, such as greater than 1 mm.
  • Dewatering methods may include primary, secondary, and final or subsequent dewatering.
  • dewatering methods of the invention include only primary dewatering.
  • primary dewatering may include methods or steps of gravity separation, mechanical separation, thermal evaporation or separation, or any combination thereof.
  • primary dewatering is followed by secondary dewatering, and during secondary dewatering methods or steps of gravity separation, mechanical separation, thermal evaporation or separation, or any combination thereof may be utilized.
  • secondary dewatering is preceded by primary dewatering and followed by final dewatering, and in final dewatering methods or steps of gravity separation, mechanical separation, thermal evaporation or separation, or any combination thereof may be used.
  • a mixture of a precipitated CCVsequestering carbonate compound composition characterized by having a 6 13 C value less than -10%o and the supernatant solution from which the CO 2 -sequestering carbonate compound composition was precipitated is dewatered to provide a dewatered C ⁇ 2 -sequestering carbonate compound composition of at least 20wt% solids and an effluent solution that includes the supernatant solution.
  • dewatering the mixture of a precipitated CO 2 - sequestering carbonate compound composition characterized by having a 6 13 C value less than -10%o and the supernatant solution from which the CCVsequestering carbonate compound composition was precipitated means to separate the carbonate compound composition from the supernatant solution such that a mixture with a higher concentration of carbonate compound composition results.
  • gravity separation, mechanical separation, thermal evaporation or separation, or any combination thereof may be used to dewater a mixture of a precipitated CO 2 -sequestering carbonate compound composition characterized by having a 6 13 C value less than -10%o and the supernatant solution from which the CO 2 -sequestering carbonate compound composition was precipitated.
  • the dewatered CCVsequestering carbonate compound composition and the effluent solution are processed after the separating step.
  • processing of the effluent solution includes adjusting the pH and/or chemical composition of the effluent solution so that it is suitable for release into an ocean, sea, river, other body of surface water, or a subterranean repository.
  • processing of the effluent solution includes subjecting the effluent solution to desalination methods or protocols.
  • the desalination methods or protocols include membrane protocols, distillation protocols, or a combination thereof.
  • the desalination methods or protocols include: a reverse osmosis protocol, a forward osmosis protocol, a nano-filtration protocol, a micro-filtration protocol, a pH adjusting protocol, a membrane distillation protocol, an electro-dialysis protocol, or a combination thereof.
  • processing of the effluent solution includes a reverse osmosis protocol, a forward osmosis protocol, a nano-filtration protocol, a micro- filtration protocol, a pH adjusting protocol, a membrane distillation protocol, a salt recovery protocol, a cation recovery protocol, an electro-dialysis protocol, or a combination thereof.
  • processing the C ⁇ 2 -sequestering carbonate compound composition includes particle size refining.
  • particle size refining may include reduction of the particle size through crushing, grinding, milling, or any combination thereof.
  • particle size refining may include agglomeration, sintering, or other enlarging of the particle into larger objects.
  • processing the C ⁇ 2 -sequestering carbonate compound composition includes the production of a building material that includes the CO 2 - sequestering carbonate compound composition such as a hydraulic cement, a cement, an aggregate, a supplementary cementitious material, a concrete or any combination thereof.
  • the building material that includes the CCVsequestering carbonate compound composition contains at least 25wt% of the CO 2 -sequestering carbonate compound composition.
  • the methods of the invention may be carried out at land or sea, e.g., at a land location where a suitable water is present at or is transported to the location, or in the ocean or other body of alkali-earth-metal- containing water, be that body naturally occurring or manmade.
  • a system is employed to perform the above methods, where such systems include those described below in greater detail.
  • the water of interest is one that includes calcium in amounts ranging from 50 ppm to 20,000 ppm, such as 200 ppm to 5000 ppm and including 400 ppm to 1000 ppm. Also of interest are waters that include magnesium in amounts ranging from 50 ppm to 40,000 ppm, such as 100 ppm to 10,000 ppm and including 500 ppm to 2500 ppm.
  • the water e.g., alkaline earth metal ion- containing water
  • saltwaters of interest include a number of different types of aqueous fluids other than fresh water, such as brackish water, sea water and brine (including man-made brines, for example geothermal plant wastewaters, desalination waste waters, etc., as well as naturally occurring brines as described herein), as well as other salines having a salinity that is greater than that of freshwater.
  • Brine is water saturated or nearly saturated with salt and has a salinity that is 50 ppt (parts per thousand) or greater.
  • Brackish water is water that is saltier than fresh water, but not as salty as seawater, having a salinity ranging from 0.5 to 35 ppt.
  • Seawater is water from a sea or ocean and has a salinity ranging from 35 to 50 ppt.
  • Freshwater is water that has a salinity of less than 5 ppt dissolved salts.
  • Saltwaters of interest may be obtained from a naturally occurring source, such as a sea, ocean, lake, swamp, estuary, lagoon, etc., or a man-made source, as desired.
  • the water may be obtained from the industrial plant that is also providing the gaseous waste stream.
  • water cooled industrial plants such as seawater cooled industrial plants
  • water that has been employed by the industrial plant may then be sent to the precipitation system and employed as the water in the precipitation reaction.
  • the water may be cooled prior to entering the precipitation reactor.
  • Such approaches may be employed, e.g., with once-through cooling systems.
  • a city or agricultural water supply may be employed as a once-through cooling system for an industrial plant.
  • the water from the industrial plant may then be employed in the precipitation protocol, where output water has a reduced hardness and greater purity.
  • such systems may be modified to include security measures, e.g., to detect tampering (such as addition of poisons) and coordinated with governmental agencies, e.g., Homeland Security or other agencies. Additional tampering or attack safeguards may be employed in such embodiments.
  • an industrial plant gaseous waste stream 30 is contacted with the water at precipitation step 20 to produce a CO 2 charged water (which may occur in a charging reactor in certain embodiments).
  • CO 2 charged water is meant water that has had CO 2 gas contacted with it, where CO 2 molecules have combined with water molecules to produce, e.g., carbonic acid, bicarbonate and carbonate ion.
  • Charging water in this step results in an increase in the "CO 2 content" of the water, e.g., in the form of carbonic acid, bicarbonate and carbonate ion, and a concomitant decrease in the amount of CO 2 of the waste stream that is contacted with the water.
  • the CO 2 charged water is acidic in some embodiments, having a pH of 6.0 or less, such as 4.0 or less, and including 3.0 and less.
  • the amount of CO 2 of the gas that is used to charge the water decreases by 85% or more, such as 99% or more as a result of this contact step, such that the methods remove 50% or more, such as 75% or more, e.g., 85% or more, including 99% or more of the CO 2 originally present in the gaseous waste stream that is contacted with the water.
  • the storage-stable product is precipitated at precipitation step 20.
  • Precipitation conditions of interest include those that modulate the physical environment of the water to produce the desired precipitate product.
  • the temperature of the water may be raised to an amount suitable for precipitation of the desired carbonate mineral to occur.
  • the temperature of the water may be raised to a value from 5 to 70 0 C, such as from 20 to 50 0 C and including 25 to 45°C.
  • a given set of precipitation conditions may have a temperature ranging from 0 to 100 0 C, the temperature may be raised in certain embodiments to produce the desired precipitate.
  • the pH of the water employed in methods may range from 5 to 14 during a given precipitation process
  • the pH is raised to alkaline levels in order to drive the precipitation of carbonate compounds, as well as other compounds, e.g., hydroxide compounds, as desired.
  • the pH is raised to a level which minimizes if not eliminates CO 2 production during precipitation, causing dissolved CO 2 , e.g., in the form of carbonate and bicarbonate, to be trapped in the carbonate compound precipitate.
  • the pH may be raised to 9 or higher, such as 10 or higher, including 11 or higher.
  • the pH of the water source e.g., alkaline earth metal ion-containing water
  • a pH raising agent may be employed, where examples of such agents include oxides (calcium oxide, magnesium oxide), hydroxides (e.g., potassium hydroxide, sodium hydroxide, brucite (Mg(OH) 2 , etc.), carbonates (e.g., sodium carbonate) and the like.
  • ash or slag in certain embodiments
  • one or more additional pH modifying protocols is employed in conjunction with the use of ash.
  • CO 2 charging and carbonate mineral precipitation may occur in the same or different reactors of the system. As such, charging and precipitation may occur in the same reactor of a system, e.g., as illustrated in Fig. 5 at step 20, according to certain embodiments of the invention. In yet other embodiments of the invention, these two steps may occur in separate reactors, such that the water is first charged with CO 2 in a charging reactor and the resultant CO 2 charged water is then subjected to precipitation conditions in a separate reactor. Further reactors may be used to, e.g., charge the water with desired minerals. [00194] Contact of the water with the source CO 2 may occur before and/or during the time when the water is subjected to CO 2 precipitation conditions.
  • embodiments of the invention include methods in which the volume of water is contacted with a source of CO 2 prior to subjecting the volume of water (e.g., alkaline earth metal ion-containing water) to mineral precipitation conditions.
  • Embodiments of the invention also include methods in which the volume of water is contacted with a source of CO 2 while the volume of water is being subjected to carbonate compound precipitation conditions.
  • Embodiments of the invention include methods in which the volume of water is contacted with a source of a CO 2 both prior to subjecting the volume of water (e.g., alkaline earth metal ion-containing water) to carbonate compound precipitation conditions and while the volume of water is being subjected to carbonate compound precipitation conditions.
  • the same water may be cycled more than once, wherein a first cycle of precipitation removes primarily calcium carbonate and magnesium carbonate minerals and leaves water to which metal ions, for example, alkaline earth metal ions, may be added, and that may have more CO 2 cycled through it, precipitating more carbonate compounds.
  • a first cycle of precipitation removes primarily calcium carbonate and magnesium carbonate minerals and leaves water to which metal ions, for example, alkaline earth metal ions, may be added, and that may have more CO 2 cycled through it, precipitating more carbonate compounds.
  • the water is not exceedingly alkaline, such that the water contacted with the CO 2 may have a pH of 10 or lower, such as 9.5 or lower, including 9 or lower and even 8 or lower.
  • the water that is contacted with the CO 2 is not a water that has first been made basic from an electrochemical protocol.
  • the water that is contacted with the CO 2 is not a water that has been made basic by addition of hydroxides, such as sodium hydroxide.
  • the water is one that has been made only slightly alkaline, such as by addition of an amount of an oxide, such as calcium oxide or magnesium oxide..).
  • the carbonate mineral precipitation station 20 may include any of a number of different components, such as temperature control components (e.g., configured to heat the water to a desired temperature), chemical additive components, e.g., for introducing chemical pH elevating agents (such as KOH, NaOH) into the water, electrolysis components, e.g., cathodes/anodes, etc, gas charging components, pressurization components (for example where operating the protocol under pressurized conditions, such as from 50-800 psi, or 100-800 psi, or 400 to 800 psi, or any other suitable pressure range, is desired) etc, mechanical agitation and physical stirring components and components to re-circulate industrial plant flue gas through the precipitation plant.
  • temperature control components e.g., configured to heat the water to a desired temperature
  • chemical additive components e.g., for introducing chemical pH elevating agents (such as KOH, NaOH) into the water
  • electrolysis components e.g., cathodes/anodes,
  • the precipitation product resulting from precipitation at step 20 may be separated from the precipitation station effluent at step 40 to produce separated precipitation product.
  • the separated precipitation product may also be a "wet dewatered precipitate.” Separation of the precipitation product from the precipitation station effluent is achieved using any of a number of convenient approaches, including draining (e.g., gravitational sedimentation of the precipitation product followed by draining), decanting, filtering (e.g., gravity filtration, vacuum filtration, filtration using forced air), centrifuging, pressing, or any combination thereof.
  • precipitation product is separated from precipitation station effluent by flowing precipitation station effluent against a baffle, against which supernatant deflects and separates from particles of precipitation product, which is collected in a collector.
  • precipitation product is separated from precipitation station effluent by flowing precipitation station effluent in a spiral channel separating particles of precipitation product and collecting the precipitation product in from an array of spiral channel outlets.
  • at least one liquid-solid separation apparatus is operably connected to the precipitation station such that precipitation station effluent may flow from the precipitation station to the liquid-solid separation apparatus (e.g., liquid-solid separation apparatus comprising either a baffle or a spiral channel).
  • the precipitation station effluent may flow directly to the liquid-solid separation apparatus, or the effluent may be pre -treated as described in more detail below.
  • Apparatus for dewatering mixtures of solids and liquids may employ one or more of the following types of separation: gravity (with or without chemical pre -treatment), mechanical, or thermal.
  • Grav separation refers to the evaporation off of the liquid portion of the mixture to increase the percentage of the mixture that is solids. Thermal separation may occur before gravity or mechanical separation as a pre-treatment step, or thermal separation may occur after gravity or mechanical separation to bring a mixture to a percent solids value that is suitable for the processing of the solids that is to follow.
  • Apparatus that utilize thermal separation apply heat or radiation to the mixture and drive off the liquid portion of the mixture from the solid portion.
  • the source of the heat or radiation include, but are not limited to: heat of the ambient air; flue gas heat; excess heat from geothermal power plant brines; heat from subterranean brines that are brought to the Earth's surface; solar heat; solar radiation; heat from power plant effluent water; subterranean gas heat; heat from burning municipal waste; heat from other waste sources; or any combination thereof.
  • Dewatering may be done in batch-wise or in continuous manners.
  • thermal separation may require little more than sufficient area for an evaporation pond.
  • Apparatus that employ thermal separation may employ more elements such as means for conveyance of the mixture of solid particles and liquid through a chamber or area where the temperature is sufficient to cause evaporation of the liquid, heat exchangers, means of introducing or elevating the temperature directly or indirectly, and means of mixing the mixture while evaporation takes place.
  • the evaporation may take place in a closed volume and condensing apparatus may be employed to recover the vaporized liquid.
  • Spray dryers atomize the mixture of solid particles and liquid and employ heated gas, e.g.
  • the temperature of the gas is typically above the boiling point of the liquid of the mixture.
  • the gas of elevated temperature may include industrial waste gas, such as flue gas.
  • the droplet size produced by the atomizing system of the spray dryer may produce droplets ranging in size from 10 to 500 microns in diameter.
  • the atomizing system of a spray drying apparatus may include nozzles, ultrasonic atomizers, and other suitable atomizing equipment that is compatible with the mixture in terms of the abrasiveness of the particles, the pH of the liquid, the temperature of the mixture and other variables that may influence the durability of the equipment.
  • Screw conveyors are used in applications where it is desirable to move liquids or slurries against gravity and in which pumping may not be an option.
  • Screw conveyor apparatus typically include a center shaft about which the screw turns and to which a motor is connected. The screw is encased in a housing. The housing of the conveyor is usually "u" shaped with material inputs and outlets either at the extremities or along the length of the conveyor.
  • a damp material or slurry i.e. a mixture of solid particles and a liquid
  • drying of the damp material or slurry may simultaneously occur due to the ambient conditions or because of applied heating, such as the application of heated air or the use of heat exchangers, and/or removal of liquid.
  • Gravity separation may also be referred to as settling.
  • gravity separation apparatus the Earth's gravity, gravity applied in the form of centripetal acceleration or centrifugal acceleration, or both are used to separate out solid particles from the surrounding liquid.
  • Apparatus that employ gravity separation include, but are not limited to: centrifuges; hydrocyclones; settlers; clarifiers; and a sludge bed clarifier. Gravity separation is typically made easier when the size of the solid particles is increased. Means of increasing the apparent size of particles suspended in a liquid in a mixture include coagulation, flocculation, and methods of crystal growth.
  • Crystal growth may be accelerated or enhanced by the introduction of seeds, nucleation sites, catalysts, agents which adjust the pH to favor growth of the desired crystal, agents which adjust the supersaturation of the solution to favor growth of the desired crystal, or any combination thereof.
  • Coagulation is a process by which small particles, usually colloidal in size (i.e. l ⁇ m or smaller in diameter), are brought together through the addition of electrolytes to the mixture of the solid particles and liquid, such that the electrolytes reduce the charges on the particles so that the particles may be in closer contact.
  • Flocculation is typically defined as a process whereby small particles or small groups of particles form large aggregates.
  • Flocculation usually occurs with the addition of a flocculant, which may be an electrolyte or a polyelectrolyte.
  • Electrolytes include, but are not limited to, NaCl, KCl, CaCl 2 , BaCl 2 , A1(NO 3 ) 3 , A1 2 (SO 4 ) 3 , K 2 SO 4 , K 2 CrO 4 , K 3 [Fe(CN) 6 ], K 4 [Fe(CN) 6 ], or combinations thereof.
  • Flocculants may be non-ionic, anionic, or cationic.
  • Monomers that may be used to make up the polyelectrolytes that are used as flocculants include, but are not limited to: acrylamide, sodium acrylate, and polyquarternary ester.
  • Nonionic polymers used as polyelectrolytes include, but are not limited to, are polyacrylamides and polyethylene oxide.
  • Anionic polymers used as polyelectrolytes include, but are not limited to, acrylamide co-polymer and polyacrylics.
  • Cationic polymers that may be used as polyelectrolytes include, but are not limited to, polyamines and acrylamide co-polymers.
  • gentle stirring to promote orthokinetic flocculation may be employed.
  • crystal growth, coagulation, and flocculation the formation of larger particles may allow the solids to settle out of the mixture more quickly and thus less time and/or less energy is needed to separate the solid particles from the liquid in the mixture.
  • the amount of material gravity settlers may be able to separate is often limited by the area of the apparatus.
  • Lamella clarifier/thickener may also be replaced by tube bundles, in which case the apparatus is called a "tube settler.”
  • the tubes in a tube settler may be of cross-sections other than rounds, e.g. square or U-shaped.
  • Lamella clarifiers and tube settlers may be used with electrostatic fields to enhance the separation of solids and liquids.
  • Electrophoresis may be used in conjunction with lamella or inclined tubes to hasten the settling time of particles in suspended in liquids.
  • Apparatus that employ forces other than the Earth's gravity include centrifuges and hydrocyclones.
  • Apparatus that employ mechanical separation include, but are not limited to: a filter press, a belt press, a vacuum drum, a separating conveyor belt, a vertical press, a centrifuge or hydrocyclone with a rigid perforated wall, and a spraying apparatus.
  • a spraying apparatus may not have a barrier as the other apparatus, however it is a mechanical means of separating the solid particles from the liquid as it forces droplets of the mixture through a volume of air or other gas. During the flight of the droplets through the gas, forces, e.g. frictional forces, separate the liquid from the solid particles.
  • Vibration intentionally applied or caused by the operation of the apparatus, may aid in the separation of liquid from a mixture of solid particles and a liquid by effectively shaking the liquid free of the solids.
  • Other sources of additional energy that may be used in mechanical separation systems include, but are not limited to, sound waves and radio waves.
  • a separating conveyor belt may be separating by utilizing a woven or porous belt that allows the liquid to be removed from the mixture in addition to taking advantage of vibration.
  • a vacuum drum is a rotating cylinder composed of a rigid, porous material, with a vacuum in the center of the apparatus that allows for surface and subsequently cake filtration. Washing of the cake may occur before the cake is removed from the drum by means of a knife or other similar cutting edge.
  • the dewatering apparatus of the invention comprises a gravity separation compartment and a mechanical separation compartment.
  • the gravity separation compartment is as described hereinabove and the mechanical separation compartment is as described hereinbelow.
  • the compartments are connected by any convenient means, e.g. conduit, piping and pumps, conveyor belt, screw conveyor, discrete containers (i.e. buckets) that are filled at one compartment to feed the other compartment or a combination thereof.
  • the dewatering apparatus of the invention comprises a mechanical separation compartment that includes at least one of: a filter press; a belt press; a vacuum drum; a separating conveyor belt; a vertical press; a spray drying apparatus, or a spraying system.
  • the dewatering apparatus of the invention includes a spray drying apparatus that is configured to operate at ambient temperature and at the relative humidity of the surrounding atmosphere.
  • the dewatering apparatus of the invention includes a spray drying apparatus that includes an inlet for gas at a temperature above ambient temperature.
  • the gas may be air, nitrogen, an inert gas, or industrial waste gas.
  • the dewatering apparatus of the invention includes a spray drying apparatus that includes an inlet for an industrial waste gas
  • the industrial waste gas may be effluent gas from the combustion of organic fuel, effluent gas from the burning of fossil fuel, effluent gas from calcinations processes, effluent gas from smelting processes or a combination thereof.
  • the dewatering apparatus of the invention comprises a thermal separation compartment, a gravity separation compartment, and a mechanical separation compartment.
  • the gravity and mechanical separation compartments are as described hereinabove and the thermal separation compartment may include: an oven, a furnace, a solar concentrator, a heat exchanger in contact with industrial waste gas at a temperature above ambient atmospheric temperature, a heat exchanger in contact with a geological brine at a temperature above ambient atmospheric temperature, a spray drying apparatus, one or more evaporation ponds or pools, a conveyance apparatus that allows direct exposure of the mixture to industrial waste gas at a temperature above that off the ambient atmosphere, or any combination thereof.
  • the dewatering apparatus of the invention comprises a thermal separation compartment, a gravity separation compartment, and a mechanical separation compartment
  • the compartments are the compartments are connected by any convenient means, e.g. conduit, piping and pumps, conveyor belt, screw conveyor, discrete containers (i.e. buckets) that are filled at one compartment to feed the other compartment or a combination thereof.
  • the dewatering apparatus of the invention includes thermal, gravity, and mechanical separation compartments
  • the mixture that is being dewatered may be directed to the compartments in any order as needed to obtain the desired dryness of the mixture, as indicated by the weight percent of the mixture that is solids.
  • Another alternative scenario is one in which the mixture may be initially provided to the gravity separation compartment where it is thickened until the mixture attains 20wt% solids, when it is provided to the mechanical separation compartment, through which the mixture passes more than once until the mixture is at least 60wt% solids, then the mixture is passed to the thermal separation compartment where it remains until the mixture is at least 90wt% solids.
  • the dewatering apparatus of the invention may be a screw apparatus that utilizes an enclosed housing with inlets for hot gas and outlets for cooler gas along the length of the housing, perpendicular to the length of the screw.
  • the hot gas contacts the material or slurry, causing some of the liquid to evaporate off.
  • the evaporated liquid and cooler gas leaves the housing of the screw conveyor and is further processed.
  • the material or slurry enters the screw apparatus with a percent solids (by weight) ranging from 10% to 45%.
  • the material leaving the apparatus may be from 45% to more than 90% solids by weight.
  • the material or slurry may be subjected to multiple passes through the screw apparatus to achieve the desired percent solids.
  • the dewatering apparatus of the invention may be a screw apparatus for dewatering a mixture of a synthetic, carbon dioxide sequestering carbonate compound composition and a supernatant solution that employs thermal separation that has connections that convey gas (e.g. flue gas, hot air) to a flue gas source and to a carbon dioxide sequestering apparatus and that employs a screw conveyor that allows for simultaneous movement of the mixture and exposure of the mixture to the flue gas.
  • the flue gas source is the flue gas stack of an industrial plant, such as a cement kiln, a fossil fuel burning power plant, an iron or steel smelting plant, or any other industrial plant with hot effluent gas.
  • the flue gas source is the flue gas stack of a power plant. In some embodiments of the apparatus of the invention, the flue gas source is the flue gas stack of a coal fired power plant. In some embodiments of the apparatus of the invention, the flue gas comprises carbon dioxide that enters the dewatering apparatus at a temperature greater than 100°F (37.78°C), such as greater than 110°F (43.33°C), such as greater than 120°F (48.89°C), such as greater than 130°F (54.44°C), such as greater than 140°F (60.0°C), such as greater than 150°F (65.56°C), such as greater than 160°F (71.11°C), such as greater than 170°F (76.67°C), such as greater than 180°F (82.22°C), such as greater than 190°F (87.78°C), such as greater than 200°F (93.33°C), such as greater than 210°F (98.89 "C), such as greater than 212
  • the gas leaving the dewatering screw apparatus is 10°F (5.56°C) less than the temperature of the flue gas entering the dewatering screw apparatus. In some embodiments, the gas leaving the dewatering screw apparatus is 20°F (11.11°C) less than the temperature of the flue gas entering the dewatering screw apparatus.
  • the drop in the gas temperature between the flue gas entering the dewatering screw apparatus and the gas leaving the dewatering screw apparatus is more than 20°F (11.11°C), such as more than 25°F, such as more than 30°F, such as more than 35°F, such as more than 40°F, such as more than 45°F, such as more than 50°F, such as more than 55°F, such as more than 60°F, such as more than 65°F, such as more than 70°F, such as more than 75°F, such as more than 80°F, such as more than 85°F, such as more than 90°F, such as more than 95°F, such as more than 100°F.
  • the dewatering apparatus of the invention may be a screw apparatus (e.g., Figs. 6-9) for dewatering a mixture of a synthetic, carbon dioxide sequestering carbonate compound composition and a supernatant solution that employs thermal separation that has connections that convey gas (e.g. flue gas, hot air) to a flue gas source and to a carbon dioxide sequestering apparatus and that employs a screw conveyor (e.g., Fig 7 (looking down on screw conveyor) and Fig. 8 (side view of screw conveyor)) that allows for simultaneous movement of the mixture and exposure of the mixture to the flue gas.
  • Fig. 6-9 for dewatering a mixture of a synthetic, carbon dioxide sequestering carbonate compound composition and a supernatant solution that employs thermal separation that has connections that convey gas (e.g. flue gas, hot air) to a flue gas source and to a carbon dioxide sequestering apparatus and that employs a screw conveyor (e.g., Fig 7 (looking down on screw conveyor
  • FIG. 6 shows the interaction of incoming precipitation material (1), hot flue gas (3), a screw drying apparatus (4), dried precipitation material (6) and the cooler flue gas (5).
  • the incoming precipitation material (1) is undergoes settling, optionally with precipitate growth (2) before feeding a slurry of precipitate material and supernatant solution to the screw drying apparatus.
  • the slurry may be fed to the screw drying apparatus in any convenient way, including using buckets, using pipes and pumps, using a belt conveyor, or a screw conveyor.
  • the screw drying apparatus (4) takes in hot flue gas (3) from a source such as, but not limited to, a flue stack from a coal burning power plant.
  • the flue gas is at a lower temperature (i.e. cooled flue gas (5)) that may be depleted in CO 2 and have an increased water or humidity content.
  • this cooled flue gas is released to the atmosphere.
  • this cooled flue gas is fed into the apparatus or system that creates the incoming precipitation material (7).
  • the precipitation material leaves the screw drying apparatus and goes to a system or station for further processing (6).
  • the screw drying apparatus may include multiple screw conveyors in series. Fig.
  • FIG 9 shows the inlet of damp solids or slurry that include precipitation solids (100) that is fed into the first screw conveyor through a conduit or other suitable conveyance means (110) such as a belt conveyor into the drying screw conveyor (400).
  • Flue gas from an industrial process is collected in a conduit (200) and conveyed into the drying screw conveyor through smaller conduits (210) that are present down the line of the drying screw conveyor.
  • the flue gas intimately contacts the precipitation material in the drying screw conveyor, the gas leaves through many conduits (310) along the length of the drying screw apparatus and is collected in larger conduits (300) for further processing.
  • the material may require further drying for the end use. In that case, the material may be passed to subsequent drying screw conveyors through an opening or conduit (500).
  • the first drying screw conveyor is located above the subsequent drying screw conveyors.
  • the material i.e. slurry or damp material
  • the material has the least percent solids at the top of the system or apparatus that includes multiple drying screw conveyors and has the most percent solids at the bottom or the system or apparatus where it is fed to further precipitate processing (510).
  • the material, or mixture of solid particles and liquid leaves the dewatering apparatus (e.g., screw apparatus) such that the mixture is at least 35wt% solids.
  • the dewatered mixture is at least 40wt% solids, such as at least 45wt% solids, such as at least 50wt% solids, such as at least 55wt% solids, such as at least 60wt% solids, such as at least 65wt% solids, such as at least 70wt% solids, such as at least 75wt% solids, such as at least 80wt% solids, such as at least 85wt% solids, such as at least 90wt% solids, such as at least 95wt% solids.
  • the mixture enters the dewatering apparatus at one level of solids and leaves the apparatus at a level of solids that is greater than upon entering the apparatus.
  • the dewatered mixture of solid particles and a liquid is at least 5wt% more solids than before the mixture entered the apparatus. In some embodiments, the dewatered mixture of solid particles and a liquid is at least 1 Owt% more solids than before the mixture entered the apparatus.
  • Liquid-solid separators such as Epuramat's Extrem-Separator (“ExSep”) liquid-solid separator, or a modification thereof, are useful in some embodiments for separation of the precipitation product from precipitation station effluent.
  • ExSep Epuramat's Extrem-Separator
  • Fig. 1 the related description in WO 2007/051640, published 10 May 2007, which is incorporated herein by reference.
  • the precipitation station effluent is introduced in the direction of gravity into a bath, in which precipitation product particles descend under the action of gravity and are removed from the lower region thereof. This removal of the precipitation product particles may be performed continuously or batch-wise.
  • Precipitation station effluent is particularly deflected in such a way that precipitation product particles (i.e., particles having a higher density than the water, which, generally, are to descend with the container continue their descending motion initiated by the precipitation station effluent pipe during the introduction in to the bath in a substantially undisturbed manner.
  • the deflection should not have the result that the precipitation product particles having higher density, that is, the precipitation product particles have an upwardly directed speed compound imposed on them during the deflection.
  • Such speed component should solely be imposed on the light water during the deflection so that as a result of the deflection at the baffle, the water receives the desired speed component for ascending in the bath.
  • the liquid-solid separation apparatus comprises an inlet operative to receive precipitation station effluent; a channel operative to allow flow of the precipitation station effluent, the channel being in a spiral configuration; a separating means for separating precipitation product from precipitation station effluent; and at least one outlet for precipitation product-depleted supernatant.
  • Liquid-solid separators such as Xerox PARC's spiral concentrator, or a modification thereof, are useful in some embodiments for separation of the precipitation product from precipitation station effluent.
  • Precipitation product is separated from the precipitation station effluent based on size and mass separation of precipitation product particles, which are made to flow in a spiral channel.
  • the inward directed transverse pressure field from fluid shear competes with the outward directed centrifugal force to allow for separation of precipitation product particles.
  • centrifugal force dominates and precipitation product particles move outward.
  • transverse pressure dominates and the precipitation product particles move inward.
  • the magnitudes of the two opposing forces depend on flow velocity, particle size, radius of curvature of the spiral section, channel dimensions, and viscosity of the precipitation station effluent.
  • a parallel array of outlets collects separated particles of precipitation product.
  • the required channel dimension is determined by estimating the transit time to reach the side -wall. This time is a function of flow velocity, channel width, viscosity, and radius of curvature. Larger particles of precipitation product may reach the channel wall earlier than the smaller particles which need more time to reach the side wall.
  • a spiral channel may have multiple outlets along the channel. This technique is inherently scalable over a large size range from sub- millimeter down to 1 micron.
  • liquid-solid separation apparatus or combinations thereof are capable of processing precipitation station effluent at 1000 L/min to 2,000,000 L/min, 5000 L/min to 2,000,000 L/min, 10,0000 L/min to 2,000,000 L/min, 20,000 L/min to 2,000,000 L/min, 25,000 L/min to 2,000,000 L/min, 50,000 L/min to 2,000,000 L/min, 100,000 L/min to 2,000,000 L/min, 250,000 L/min to 2,000,000 L/min, 500,000 L/min to 2,000,000 L/min, and 1,000,000 L/min to 2,000,000 L/min.
  • the resultant dewatered precipitate is then dried to produce a product, as illustrated at step 60 of Fig. 5. Drying can be achieved by air drying the filtrate. Where the filtrate is air dried, air drying may be at room or elevated temperature. In certain embodiments, the elevated temperature is provided by the industrial plant gaseous waste stream, as illustrated at step 70 of Fig. 10. In these embodiments, the gaseous waste stream (e.g., flue gas) from the power plant may be first used in the drying step, where the gaseous waste stream may have a temperature ranging from 30 to 700 0 C, such as 75 to 300 0 C.
  • the gaseous waste stream e.g., flue gas
  • the precipitate can be separated, washed, and dried in the same station for all processes, or in different stations for all processes or any other possible combination.
  • the precipitation and separation may occur in precipitation reactor 20, but drying and washing occur in different reactors.
  • precipitation, separation, and drying may occur all in the precipitation reactor 20 and washing occurring in a different reactor.
  • the separated precipitate may be further processed as desired.
  • the precipitate may then be transported to a location for long term storage, effectively sequestering CO 2 .
  • the precipitate may be transported and placed at long term storage sites, e.g., above ground, below ground, in the deep ocean, etc. as desired.
  • the dried product may be disposed of in a number of different ways.
  • the precipitate product is transported to a location for long term storage, effectively sequestering CO 2 in a stable precipitated product, e.g., as a storage-stable above ground CO 2 -sequestering material.
  • the precipitate may be stored at a long term storage site adjacent to the industrial plant and precipitation system.
  • the precipitate may be transported and placed at long term storage sites, e.g., above ground, below ground, etc. as desired, where the long term storage site is distal to the power plant (which may be desirable in embodiments where real estate is scarce in the vicinity of the power plant).
  • the precipitate may be transported in empty conveyance vehicles (e.g., barges, train cars, trucks, etc.) that were employed to transport the fuel or other materials to the industrial plant and/or precipitation plant.
  • conveyance vehicles used to bring fuel to the industrial plant, materials to the precipitation plant e.g., alkali sources
  • the composition is disposed of in an underwater location. Underwater locations may vary depending on a particular application.
  • any convenient protocol for transporting the composition to the site of disposal may be employed, and will necessarily vary depending on the locations of the precipitation reactor and site of disposal relative to each other, where the site of disposal is an above ground or below ground site disposal, etc.
  • a pipeline or analogous slurry conveyance structure is employed, where these approaches may include active pumping, gravitational mediated flow, etc., as desired.
  • the precipitate product is refined (i.e., processed) in some manner prior to subsequent use.
  • Refinement as illustrated in step 80 of Fig. 5 may include a variety of different protocols.
  • the product is subjected to mechanical refinement, e.g., grinding, in order to obtain a product with desired physical properties, e.g., particle size, etc.
  • the precipitate is combined with a hydraulic cement, e.g., as a supplemental cementitious material, as a sand, a gravel, as an aggregate, etc.
  • the mother liquor (i.e. supernatant solution) produced by the precipitation process may be employed to cool the power plant, e.g., in a once through cooling system.
  • heat picked up in the process may then be recycled back to precipitation plant for further use, as desired.
  • the initial water source may come from the industrial plant.
  • Such embodiments may be modified to employ pumping capacity provided by the industrial plant, e.g., to increase overall efficiencies.
  • the amount of carbon sequestered in the precipitate or even a downstream product that incorporates the precipitate, e.g., concrete may be determined, particularly where the CO 2 gas employed to make the precipitate is obtained from combustion of fossil fuels, e.g., coal.
  • Benefits of this isotopic approach include the ability to determine carbon content of pure precipitate as well as precipitate that has been incorporated into another product, e.g., as an aggregate or sand in a concrete, etc.
  • the quantification may be done by making a theoretical determination of the amount of CO 2 sequestered, such as by calculating the amount of CO 2 sequestered.
  • Standard information e.g., a predetermined amount of CO 2 sequestered per amount of product produced by a given reference process, may be used to readily determine the quantity of CO 2 sequestered in a given process that is the same or approximately similar to the reference process, e.g., by determining the amount produced and then calculating the amount of CO 2 that must be sequestered therein.
  • the processor may comprise a contactor such as a gas-liquid or a gas-liquid-solid contactor, wherein the contactor is configured for charging an aqueous solution or slurry with carbon dioxide to produce a carbon dioxide-charged composition, which composition may be a solution or slurry.
  • the contactor is configured to produce compositions from the carbon dioxide, such as from solvated or hydrated forms of carbon dioxide (e.g., carbonic acid, bicarbonates, carbonates), wherein the compositions comprise carbonates, bicarbonates, or carbonates and bicarbonates.
  • the processor may further comprise a reactor configured to produce compositions comprising carbonates, bicarbonates, or carbonates and bicarbonates from the carbon dioxide.
  • Systems such as that shown in Fig. 1C may further comprise a processor (110) comprising a contactor (112) (e.g., gas-liquid contactor, gas-liquid-solid contactor, etc.) and a reactor (114), wherein the processor is operably connected to each of a source of CO2-containing gas (130), a source of proton-removing agents (140), and a source of divalent cations (150).
  • a source of CO2-containing gas 130
  • a source of proton-removing agents 140
  • a source of divalent cations 150
  • Such systems of the invention are configured for aqueous-based processing of carbon dioxide from the source of carbon dioxide using both the source of proton-removing agents and the source of divalent cations, wherein the source of carbon dioxide comprises one or more additional components in addition to carbon dioxide.
  • treatment system may comprise a liquid-solid separator (122) or some other dewatering system configured to treat processor-produced compositions to produce supernatant and concentrated compositions (e.g., concentrated with respect to carbonates and/or bicarbonates, and any other co-products resulting from processing an industrial waste gas stream).
  • the treatment system may further comprise a filtration system, wherein the filtration system comprises at least one filtration unit configured for filtration of supernatant from the dewatering system, filtration of the composition from the processor, or a combination thereof.
  • the dewatering system, the filtration system, or a combination of the dewatering system and the filtration system may be configured to provide at least a portion of supernatant to the processor for processing carbon dioxide.
  • the treatment system may also be configured to provide at least a portion of supernatant to a washing system configured to wash compositions of the invention, wherein the compositions comprise precipitation material (e.g., CaC ⁇ 3, MgC ⁇ 3, or combinations thereof).
  • the processor of carbon dioxide-processing systems of the invention may be configured to receive treatment system supernatant in a contactor (e.g., gas-liquid contactor, gas-liquid-solid contactor), a reactor, a combination of the contactor and the reactor, or in any other unit or combination of units in the processor.
  • the carbon dioxide-processing system is configured to provide at least a portion of the supernatant to a system or process external to the carbon-dioxide processing system.
  • a system of the invention may be operably connected to a desalination plant such that the system provides at least a portion of treatment system supernatant to the desalination plant for desalination.
  • the invention provides a system for processing carbon dioxide as shown in Fig. IE, wherein the system comprises a processor (110) and a treatment system (120) configured for an aqueous-based process for processing carbon dioxide from a source of carbon dioxide (130) using a source of proton-removing agents (140), wherein the source of carbon dioxide comprises one or more additional components in addition to carbon dioxide, wherein the system further comprises an electrochemical system (160), and further wherein the processor, the treatment system, and the electrochemical system are operably connected for recirculating at least a portion of treatment system supernatant.
  • the system comprises a processor (110) and a treatment system (120) configured for an aqueous-based process for processing carbon dioxide from a source of carbon dioxide (130) using a source of proton-removing agents (140), wherein the source of carbon dioxide comprises one or more additional components in addition to carbon dioxide, wherein the system further comprises an electrochemical system (160), and further wherein the processor, the treatment system, and the electrochemical system are operably connected for recirculating
  • the dewatering system, the filtration system, or a combination of the dewatering system and the filtration system may be configured to provide at least a portion of treatment system supernatant to the processor for processing carbon dioxide.
  • the treatment system may also be configured to provide at least a portion of the treatment system supernatant to the electrochemical system, wherein the electrochemical system may be configured to produce proton-removing agents or effect proton removal.
  • the treatment system may also be configured to provide at least a portion of supernatant to a washing system configured to wash compositions of the invention, wherein the compositions comprise precipitation material (e.g., CaCO 3 , MgCO 3 , or combinations thereof).
  • the processor of carbon dioxide-processing systems of the invention may be configured to receive treatment system supernatant or an electrochemical system stream in a contactor (e.g., gas-liquid contactor, gas-liquid-solid contactor), a reactor, a combination of the contactor and the reactor, or in any other unit or combination of units in the processor.
  • a contactor e.g., gas-liquid contactor, gas-liquid-solid contactor
  • the carbon dioxide -processing system may be configured to provide at least a portion of the supernatant to a system (e.g., desalination plant) or process (e.g., desalination) external to the carbon- dioxide processing system.
  • Recirculation of treatment system supernatant is advantageous as recirculation provides efficient use of available resources; minimal disturbance of surrounding environments; and reduced energy requirements, which reduced energy requirements provide for lower (e.g., small, neutral, or negative) carbon footprints for systems and methods of the invention.
  • a carbon dioxide -processing system of the invention is operably connected to an industrial plant (e.g., fossil fuel-fired power plant such as coal-fired power plant) and utilizes power generated at the industrial plant, reduced energy requirements provided by recirculation of treatment system supernatant provide for a reduced energy demand on the industrial plant.
  • a carbon dioxide -processing system not configured for recirculation i.e., a carbon- dioxide processing system configured for a once- through process
  • a carbon- dioxide processing system configured for a once- through process such as that shown in Fig. IB
  • a 100 MW power plant e.g., a coal-fired power plant
  • a system configured for recirculation such as that shown in Fig. ID or Fig.
  • IE may have an energy demand on the industrial plant of less than 10%, such as less than 8%, including less than 6%, for example, less than 4% or less than 2%, which energy demand may be attributable to pumping make-up water and recirculating supernatant.
  • Carbon dioxide -processing systems configured for recirculation may, when compared to systems designed for a once-through process, exhibit a reduction in energy demand of at least 2%, such as at least 5%, including at least 10%, for example, at least 25% or at least 50%.
  • a carbon dioxide -processing system configured for recirculation consumes 9 MW of power for pumping make- up water and recirculating supernatant and a carbon dioxide-processing system designed for a once-through process consumes 10 MW attributable to pumping, then the carbon dioxide -processing system configured for recirculation exhibits a 10% reduction in energy demand.
  • the reduction in the energy demand attributable to pumping and recirculating may also provide a reduction in total energy demand, especially when compared to carbon dioxide -processing systems configured for once-through process.
  • recirculation provides a reduction in total energy demand of a carbon dioxide-processing system, wherein the reduction is at least 2%, such as at least 4%, including at least 6%, for example at least 8% or at least 10% when compared to total energy demand of a carbon dioxide-processing system configured for once-through process. For example, if a carbon dioxide-processing system configured for recirculation has a 15% energy demand and a carbon dioxide-processing system designed for a once-through process has a 20% energy demand, then the carbon dioxide-processing system configured for recirculation exhibits a 5% reduction in total energy demand.
  • a carbon dioxide-processing system configured for recirculation wherein recirculation comprises filtration through a filtration unit such as a nanofiltration unit (e.g., to concentrate divalent cations in the retentate and reduce divalent cations in the permeate), may have a reduction in total energy demand of at least 2%, such as at least 4%, including at least 6%, for example at least 8% or at least 10% when compared to a carbon dioxide -processing system configured for once-through process.
  • Fig. 10 provides a schematic of a system according to one embodiment of the invention.
  • system 100 includes water source 110.
  • water source 110 includes a structure having an input for water (e.g., alkaline earth metal ion-containing water), such as a pipe or conduit from an ocean, etc.
  • the input is in fluid communication with a source of sea water, e.g., such as where the input is a pipe line or feed from ocean water to a land based system or a inlet port in the hull of ship, e.g., where the system is part of a ship, e.g., in an ocean based system.
  • CO 2 source 130 Also shown in Fig. 10, is CO 2 source 130.
  • This system also includes a pipe, duct, or conduit, which directs CO 2 to system 100.
  • the gaseous waste stream employed in methods of the invention may be provided from the industrial plant to the site of precipitation in any convenient manner that conveys the gaseous waste stream from the industrial plant to the precipitation plant.
  • the waste stream is provided with a gas conveyer, e.g., a duct, which runs from a site of the industrial plant, e.g., a flue of the industrial plant, to one or more locations of the precipitation site.
  • the source of the gaseous waste stream may be a distal location relative to the site of precipitation, such that the source of the gaseous waste stream is a location that is 1 mile or more, such as 10 miles or more, including 100 miles or more, from the precipitation location.
  • the gaseous waste stream may have been transported to the site of precipitation from a remote industrial plant via a CO 2 gas conveyance system, e.g., a pipeline.
  • the industrial plant generated CO 2 containing gas may or may not be processed, e.g., remove other components, etc., before it reaches the precipitation site (i.e., a carbonate compound precipitation plant).
  • a portion of but less than the entire gaseous waste stream from the industrial plant may be employed in precipitation reaction.
  • the portion of the gaseous waste stream that is employed in precipitation may be 75% or less, such as 60% or less and including 50% and less.
  • substantially the entire gaseous waste stream produced by the industrial plant e.g., substantially all of the flue gas produced by the industrial plant, is employed in precipitation.
  • 80% or more, such as 90% or more, including 95% or more, up to 100% of the gaseous waste stream (e.g., flue gas) generated by the source may be employed during precipitation.
  • the gaseous waste stream may be one that is obtained from a flue or analogous structure of an industrial plant.
  • a line e.g., duct
  • the location of the source from which the gaseous waste stream is obtained may vary, e.g., to provide a waste stream that has the appropriate or desired temperature.
  • the flue gas may be obtained at the exit point of the boiler or gas turbine, the kiln, or at any point through the power plant or stack, that provides the desired temperature.
  • the flue gas is maintained at a temperature above the dew point, e.g., 125°C, in order to avoid condensation and related complications.
  • steps may be taken to reduce the adverse impact of condensation, e.g., employing ducting that is stainless steel, fluorocarbon (such as poly(tetrafluoroethylene)) lined, diluted with water and pH controlled, etc., so the duct does not rapidly deteriorate.
  • fluorocarbon such as poly(tetrafluoroethylene)
  • the CO 2 -containing gaseous stream may be pretreated or preprocessed (e.g., treated with H 2 O 2 ) prior to contacting it with water, e.g., alkaline earth metal-containing water (e.g., in a charging reactor).
  • Illustrative pretreatment or preprocessing steps may include: temperature modulation (e.g., heating or cooling), decompression, compression, incorporation of additional components (e.g., hydrate promoter gases), oxidation of various components to convert them to forms more amenable to sequestration in a stable form, and the like.
  • pretreatment of the gaseous waste stream improves the absorption of components of the CO 2 -containing gaseous stream into water, e.g., alkaline earth metal- containing water.
  • An exemplary pretreatment for improving absorption includes subjecting the CO 2 - containing gaseous stream to oxidizing conditions.
  • Precipitation reactor 120 may also contain design features that allow for the monitoring of one or more parameters such as internal reactor pressure, pH, precipitate particle size, metal-ion concentration, conductivity and alkalinity of the aqueous solution, and pCO 2 .
  • This reactor 120 may operate as a batch process or a continuous process.
  • the system further includes a drying station 160 for drying the precipitated carbonate mineral composition produced by the carbonate mineral precipitation station.
  • the drying station may include a filtration element, freeze drying structure, spray drying structure, etc as described more fully above.
  • the system may include a conveyer, e.g., duct, from the industrial plant that is connected to the dryer so that a gaseous waste stream (i.e., industrial plant flue gas) may be contacted directly with the wet precipitate in the drying stage.
  • Secondary dewatering may take place after primary dewatering (i.e., after dewatering the mixture or slurry to around 30wt% solids, or sometimes more, such as up to 35wt% 40wt%, 45wt%, etc. solids), and secondary dewatering may be used to effect greater separation of the solids from the liquid such that the secondary dewatered mixture or slurry comprises a greater wt% solids than primary dewatered mixture.
  • the secondary dewatered mixture or slurry may be greater than about 35wt% solids.
  • a secondary dewatering system may be configured to effect a secondary dewatered mixture or slurry comprising greater than 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt% 70wt%, 75wt%, 80wt%, 85wt% or 90% solids after secondary dewatering.
  • the secondary dewatered mixture is greater than about 90wt% solids.
  • the secondary dewatered mixture or slurry may be even greater than 90wt% solids depending upon the secondary dewatering system used. Further dewatering, which can be ternary, quaternary, etc.
  • Systems of the invention may include a carbonate precipitation apparatus that employs methods and apparatus discussed further herein to produce a mixture composed of a carbonate compound composition and a supernatant solution from reactants including, but not limited to, carbonates, bicarbonates, carbon dioxide, alkaline brines, sea water, alkaline aqueous solutions, and mixtures thereof.
  • the systems of the invention may include a refining station.
  • the refining station may include a carbonate compound refining station, a supernatant solution treatment system or both.
  • the carbonate compound refining station may include apparatus for decreasing or increasing the size of the carbonate compound materials provided by the dewatering systems.
  • the carbonate compound refining station may include a building materials fabrication system that includes systems and apparatus to provide at least one of supplementary cementitious material, pozzolan, aggregate, or cement.
  • the supernatant solution treatment system may include at least one of a pH adjustment system, a reverse osmosis apparatus, a nano- filtration apparatus, a forward osmosis apparatus, a micro-filtration apparatus, a membrane distillation apparatus, an electro-dialysis system, or a salt-recovery apparatus.
  • aspects of the invention include synchronizing the activities of the industrial plant and precipitation plant.
  • the activity of one plant may not be matched to the activity of the other.
  • the precipitation plant may need to reduce or stop its acceptance of the gaseous waste stream but the industrial plant may need to keep operating.
  • the plants may be configured to provide for continued operation of one of the co-located plants while the other reduces or ceases operation may be employed.
  • the precipitation plant may include emissions monitors to evaluate any gaseous emissions produced by the precipitation plant and to make required reports to regulatory agencies, both electronic (typically every 15 minutes), daily, weekly, monthly, quarterly, and annually.
  • gaseous handling at the precipitation plant is sufficiently closed that exhaust air from the precipitation plant which contains essentially all of the unused flue gas from the industrial plant is directed to a stack so that required Continuous Emissions Monitoring Systems can be installed in accordance with the statutory and regulatory requirements of the Country, province, state city or other political jurisdiction.
  • embodiments of the invention In addition to sequestering CO 2 , embodiments of the invention also sequester other components of industrial plant generated gaseous waste streams. For example, embodiments of the invention results in sequestration of at least a portion of one or more of NOx, SOx, VOC, Mercury and particulates that may be present in the waste stream, such that one or more of these products are fixed in the solid precipitate product.
  • precipitation system 100 In Fig. 10, precipitation system 100 is co-located with industrial plant 200. However, precipitation system 100 is not integrated with the industrial plant 200.
  • Suitable methods include, but are not limited to: thermogravimetric analysis (TGA), X-ray diffraction (XRD), X-ray fluorescence (XRF), coulometry, mass spectrometry, Raman spectroscopy, secondary electron analysis, and Fourier-transform infrared analysis (FT- IR).
  • TGA thermogravimetric analysis
  • XRD X-ray diffraction
  • XRF X-ray fluorescence
  • coulometry mass spectrometry
  • Raman spectroscopy Raman spectroscopy
  • secondary electron analysis secondary electron analysis
  • Fourier-transform infrared analysis FT- IR
  • a composition containing material that is the product of a carbon sequestration process is defined by the X-ray diffraction (XRD) pattern of the composition.
  • the XRD pattern shows the presence of ettringite for the composition containing material that is the product of a carbon sequestration process when the composition is first formed, but that aspect of
  • Precipitation material comprising magnesium carbonate, calcium carbonate, or combinations thereof is particularly useful.
  • Precipitation material may comprise two or more different carbonate compounds, three or more different carbonate compounds, four or more different carbonate compounds, five or more different carbonate compounds, etc., including non-distinct, amorphous carbonate compounds.
  • Precipitation material of the invention may comprise compounds having a molecular formulation X m (CO 3 ) B , wherein X is any element or combination of elements that can chemically bond with a carbonate group or its multiple and m and n are stoichiometric positive integers.
  • X may be an alkaline earth metal (elements found in column HA of the periodic table of elements) or an alkali metal (elements found in column IA of the periodic table of elements), or some combination thereof.
  • the precipitation material comprises dolomite (CaMg(CO 3 ) 2 ), protodolomite, huntite (CaMg 3 (COs)Zi), and/or sergeevite (Ca 2 Mg I i(CO3)i3*H 2 O), which are carbonate minerals comprising both calcium and magnesium.
  • the precipitation material comprises calcium carbonate in one or more phases selected from calcite, aragonite, vaterite, or a combination thereof.
  • the precipitation material comprises hydrated forms of calcium carbonate (e.g., Ca(CO 3 )- «H 2 O) where there are one or more structural waters in the molecular formula.) selected from ikaite (CaC ⁇ 3 ⁇ 6H 2 O), amorphous calcium carbonate (CaCO 3 ⁇ nH 2 O), monohydrocalcite (CaC ⁇ 3 ⁇ H 2 O), or combinations thereof.
  • the precipitation material comprises anhydrous amorphous calcium carbonate.
  • the precipitation material comprises magnesium carbonate, wherein the magnesium carbonate does not have any waters of hydration.
  • the amount by weight of calcium carbonate compounds in the precipitation material may exceed the amount by weight of magnesium carbonate compounds in the precipitation material.
  • the amount by weight of calcium carbonate compounds in the precipitation material may exceed the amount by weight magnesium carbonate compounds in the precipitation material by 5% or more, such as 10% or more, 15% or more, 20% or more, 25% or more, 30% or more.
  • the weight ratio of calcium carbonate compounds to magnesium carbonate compounds in the precipitation material ranges from 1.5 - 5 to 1, such as 2-4 to 1, including 2-3 to 1.
  • the amount by weight of magnesium carbonate compounds in the precipitation material may exceed the amount by weight of calcium carbonate compounds in the precipitation material.
  • the amount by weight of magnesium carbonate compounds in the precipitation material may exceed the amount by weight calcium carbonate compounds in the precipitation material by 5% or more, such as 10% or more, 15% or more, 20% or more, 25% or more, 30% or more.
  • the weight ratio of magnesium carbonate compounds to calcium carbonate compounds in the precipitation material ranges from 1.5 - 5 to 1, such as 2-4 to 1, including 2-3 to 1.
  • Adjusting major ion ratios during precipitation may influence the nature of the precipitation material.
  • Major ion ratios have considerable influence on polymorph formation. For example, as the magnesium:calcium ratio in the water increases, aragonite becomes the major polymorph of calcium carbonate in the precipitation material over low-magnesium calcite. At low magnesium:calcium ratios, low- magnesium calcite becomes the major polymorph.
  • compositions of the invention comprise calcium carbonate in the form of aragonite.
  • calcium may be replaced by a number of different metals including, but not limited to strontium, lead, and zinc, each of which, in one form or another, may be found in one or more starting materials (e.g., waste gas stream, source of proton-removing agents, source of divalent cations, etc.) of the invention.
  • Compositions may comprise, for example, mossottite, which is aragonite rich in strontium, or compositions may comprise a mixture of aragonite and strontianite (e.g., (Ca,Sr)CO 3 ).
  • Compositions may comprise, for example, tarnowitzite, which is aragonite rich in lead, or compositions may comprise a mixture of aragonite and cerussite (e.g., (Ca,Pb)CO 3 ).
  • Compositions may comprise, for example, nicholsonite, which is aragonite rich in Zn, or compositions may comprise a mixture of aragonite and smithsonite (e.g., (Ca,Zn)CU3).
  • Metals such as As, Ag, Ba, Be, Cd, Co, Cr, Cu, Hg, Mo, Ni, Pb, Se, Sb, Tl, V, and Zn may be provided by a waste gas stream, a source of proton-removing agents, a source of divalent cations, or a combination thereof.
  • Metals and other components found in such source e.g., waste gas streams, sources of proton-removing agents, sources of divalent cations
  • that do not form carbonates, bicarbonates, or carbonates and bicarbonates may be trapped in or adsorbed on precipitation material.
  • material containing certain leachable heavy metals may be classified as hazardous material if TCLP extracts have concentrations above threshold values for those heavy metals, which threshold values range from 0.2 mg/L (or ppm) for Hg and 100 mg/L for Ba. For example, if a TCLP analysis provides more than 0.2 mg/L mercury in an extract, then the material may be classified as hazardous material with respect to mercury. Likewise, if a TCLP analysis provides more than 100 mg/L barium in an extract, then the material may be classified as hazardous material with respect to barium. The 40 C.F.R.
  • ⁇ 261.24 includes, but is not limited to, As, Cd, Cr, Hg, and Pb, each of which might be found in waste gas streams resulting from combustion of fossil fuels (e.g., coal), and each of which, in one form or another, might be incorporated in compositions of the invention.
  • the list also includes a number of contaminants that might be present in industrial waste sources of divalent cations and/or proton-removing agents, which contaminants, in one form or another, might be incorporated in compositions of the invention.
  • fly ash which may be a source of divalent cations and/or proton-removing agents
  • fly ash which may be a source of divalent cations and/or proton-removing agents
  • red mud which may be a source of divalent cations and/or proton-removing agents
  • red mud might contain Cr, Ba, Pb, and/or Zn, each of which is found on the list in 40 C.F.R. ⁇ 261.24, and each of which, in one form or another, might be incorporated in compositions of the invention.
  • a composition of the invention comprises contaminants predicted not to leach into the environment by one or more tests selected from the group consisting of Toxicity Characteristic Leaching Procedure, Extraction Procedure Toxicity Test, Synthetic Precipitation Leaching Procedure, California Waste Extraction Test, Soluble Threshold Limit Concentration, American Society for Testing and Materials Extraction Test, and Multiple Extraction Procedure. Tests and combinations of tests may be chosen depending upon likely contaminants and storage conditions of the composition.
  • the composition may comprise As, Cd, Cr, Hg, and Pb (or products thereof), each of which might be found in a waste gas stream of a coal-fired power plant.
  • TCLP may be an appropriate test for solid and multiphasic compositions stored in the environment (e.g., built environment).
  • a composition of the invention comprises As, wherein the composition is predicted not to leach As into the environment.
  • a TCLP extract of the composition may provide less than 5.0 mg/L As indicating that the composition is not hazardous with respect to As.
  • a composition of the invention comprises Cd, wherein the composition is predicted not to leach Cd into the environment.
  • a TCLP extract of the composition may provide less than 1.0 mg/L Cd indicating that the composition is not hazardous with respect to Cd.
  • a TCLP extract of the composition may provide less than 5.0 mg/L Pb indicating that the composition is not hazardous with respect to Pb.
  • a composition of the invention may be non-hazardous with respect to a combination of different contaminants in a given test.
  • the composition may be non-hazardous with respect to all metal contaminants in a given test.
  • a TCLP extract of a composition may be less than 5.0 mg/L in As, 100.0 mg/L in Ba, 1.0 mg/L in Cd, 5.0 mg/mL in Cr, 5.0 mg/L in Pb, 0.2 mg/L in Hg, 1.0 mg/L in Se, and 5.0 mg/L in Ag.
  • compositions of the invention may effectively sequester CO 2 (e.g., as carbonates, bicarbonates, or a combinations thereof) along with various chemical species (or co-products thereof) from waste gas streams, industrial waste sources of divalent cations, industrial waste sources of proton-removing agents, or combinations thereof that might be considered contaminants if released into the environment.
  • Compositions of the invention incorporate environmental contaminants (e.g., metals and co-products of metals such as Hg, Ag, As, Ba, Be, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sb, Se, Tl, V, Zn, or combinations thereof) in a non-leachable form.
  • the invention provides a method of treating a waste gas stream comprising carbon dioxide and, optionally, any of a number of solid, liquid, or multiphasic waste streams, to produce a composition that provides a leachate in compliance with the TCLP protocol.
  • the composition provides less than 0.05 mg/L, 0.50 mg/L, 5.0 mg/L, 50 mg/L, or 500 mg/L As in the leachate provided by the TCLP procedure.
  • the composition provides less than 1.00 mg/L, 10.0mg/L, 100 mg/L, 1,000 mg/L, or 10,000 mg/L Ba in the leachate provided by the TCLP procedure.
  • the composition provides less than 0.01 mg/L, 0.10 mg/L, 1.0 mg/L, 10 mg/L, or 100 mg/L Cd in the leachate provided by the TCLP procedure.
  • the composition provides less than 0.05 mg/L, 0.50 mg/L, 5.0 mg/L, 50 mg/L, or 500 mg/L Pb in the leachate provided by the TCLP procedure.
  • the composition provides less than 0.002 mg/L, 0.02 mg/L, 0.20 mg/L, 2.0 mg/L, or 20 mg/L Hg in the leachate provided by the TCLP procedure.
  • the composition provides less than 0.01 mg/L, 0.10 mg/L, 1.0 mg/L, 10 mg/L, or 100 mg/L Se in the leachate provided by the TCLP procedure.
  • the composition provides less than 0.05 mg/L, 0.50 mg/L, 5.0 mg/L, 50 mg/L, or 500 mg/L Ag in the leachate provided by the TCLP procedure.
  • Such compositions of the invention, as described herein, are suitable for building products and the like.
  • Precipitation material which comprises one or more synthetic carbonates derived from industrial CO 2 , reflects the relative carbon isotope composition (8 13 C) of the fossil fuel (e.g., coal, oil, natural gas, or flue gas) from which the industrial CO 2 (from combustion of the fossil fuel) was derived.
  • the relative carbon isotope composition (8 13 C) value with units of %o (per mille) is a measure of the ratio of the concentration of two stable isotopes of carbon, namely 12 C and 13 C, relative to a standard of fossilized belemnite (the PDB standard).
  • the ⁇ 13 C value of the synthetic carbonate-containing precipitation material serves as a fingerprint for a CO 2 gas source.
  • the ⁇ 13 C value may vary from source to source (i.e., fossil fuel source), but the ⁇ 13 C value for composition of the invention generally, but not necessarily, ranges between -9%o to -35%o.
  • the ⁇ l3C value for the synthetic carbonate-containing precipitation material is between -l%o and -50%o, between -5%o and -40%o, between -5%o and -35%o, between -7%o and -40%o, between -7%o and -35%o, between -9%o and -40%o, or between -9%o and -35%o.
  • the ⁇ 13 C value for the synthetic carbonate-containing precipitation material is less than (i.e., more negative than) -3%o, -5%o, -6%o, -7%o, -8%o, -9%o, -10%o, -l l%o, -12%o, -13%o, -14%o, -15%o, -16%o, -17%o, -18%o, -19%o, -20%o, -21%o, -22%o, -23%o, -24%o, -25%o, -26%o, -27% «, -28% «, -29% «, -30% «, -31%«, -32%«, -33%«, -34% «, -35% «, -36% «, -37% «, -38%o, -39%o, -40%o, -41%o, -42%o, -43%o, -44%o, or -45%o, wherein the more negative the more negative the more negative
  • any suitable method may be used for measuring the ⁇ 13 C value, methods including, but no limited to, mass spectrometry or off-axis integrated- cavity output spectroscopy (off-axis ICOS).
  • compounds and materials comprising silicon, aluminum, iron, and others may also be prepared and incorporated within precipitation material with methods and systems of the invention. Precipitation of such compounds in precipitation material may be desired to alter the reactivity of cements comprising the precipitation material resulting from the process, or to change the properties of cured cements and concretes made from them.
  • the precipitation material comprises carbonates (e.g., calcium carbonate, magnesium carbonate) and silica in a carbonate:silica ratio between 1 : 1 and 1 : 1.5; 1 : 1.5 and 1 :2; 1 :2 and 1 :2.5; 1 :2.5 and 1 :3; 1 :3 and 1 :3.5; 1 :3.5 and 1 :4; 1 :4 and 1 :4.5; 1 :4.5 and 1 :5; 1 :5 and 1 :7.5; 1 :7.5 and 1 : 10; 1 : 10 and 1: 15; 1 : 15 and 1 :20, or a range thereof.
  • carbonates e.g., calcium carbonate, magnesium carbonate
  • silica in a carbonate:silica ratio between 1 : 1 and 1 : 1.5; 1 : 1.5 and 1 :2; 1 :2 and 1 :2.5; 1 :2.5 and 1 :3; 1 :3 and 1 :3.5; 1 :3.5 and 1 :4; 1
  • the precipitation material comprises carbonates and silica in a carbonate:silica ratio between 1: 1 and 1 :5, 1:5 and 1 : 10, or 1 :5 and 1 :20.
  • the precipitation material comprises silica and carbonates (e.g., calcium carbonate, magnesium carbonate) in a silica:carbonate ratio between 1 : 1 and 1 :1.5; 1 :1.5 and 1 :2; 1 :2 and 1 :2.5; 1 :2.5 and 1 :3; 1 :3 and 1 :3.5; 1 :3.5 and 1 :4; 1 :4 and 1 :4.5; 1 :4.5 and 1 :5; 1 :5 and 1 :7.5; 1 :7.5 and 1 : 10; 1 : 10 and 1: 15; 1 : 15 and 1 :20, or a range thereof.
  • silica and carbonates e.g., calcium carbonate, magnesium carbonate
  • the precipitation material comprises silica and carbonates in a silica:carbonate ratio between 1: 1 and 1 :5, 1:5 and 1 : 10, or 1 :5 and 1 :20.
  • precipitation material produced by methods of the invention comprises mixtures of silicon-based material and at least one carbonate phase.
  • the more rapid the reaction rate the more silica is incorporated with the carbonate-containing precipitation material, provided silica is present in the precipitation reaction mixture (i.e., provided silica was not removed after digestion of material comprising metal silicates).
  • Precipitation material may be in a storage-stable form (which may simply be air-dried precipitation material), and may be stored above ground under exposed conditions (i.e., open to the atmosphere) without significant, if any, degradation (or loss of CO 2 ) for extended durations.
  • the precipitation material may be stable under exposed conditions for 1 year or longer, 5 years or longer, 10 years or longer, 25 years or longer, 50 years or longer, 100 years or longer, 250 years or longer, 1000 years or longer, 10,000 years or longer, 1,000,000 years or longer, or even 100,000,000 years or longer.
  • a storage- stable form of the precipitation material may be stable under a variety of different environment conditions, for example, from temperatures ranging from -100 0 C to 600 0 C and humidity ranging from 0 to 100%, where the conditions may be calm, windy, or stormy.
  • the storage-stable form of the precipitation material undergoes little if any degradation while stored above ground under normal rainwater pH, the amount of degradation, if any, as measured in terms of CO 2 gas release from the product, does not exceed 5% per year, and in certain embodiments will not exceed 1% per year or 0.001% per year.
  • precipitation material provided by the invention does not release more than 1%, 5%, or 10% of its total CO 2 when exposed to normal conditions of temperature and moisture, including rainfall of normal pH for at least 1, 2, 5, 10, or 20 years, or for more than 20 years, for example, for more than 100 years.
  • the precipitation material does not release more than 1% of its total CO 2 when exposed to normal conditions of temperature and moisture, including rainfall of normal pH for at least 1 year.
  • the precipitation material does not release more than 5% of its total CO 2 when exposed to normal conditions of temperature and moisture, including rainfall of normal pH for at least 1 year.
  • the precipitation material does not release more than 10% of its total CO 2 when exposed to normal conditions of temperature and moisture, including rainfall of normal pH for at least 1 year. In some embodiments, the precipitation material does not release more than 1% of its total CO 2 when exposed to normal conditions of temperature and moisture, including rainfall of normal pH for at least 10 years. In some embodiments, the precipitation material does not release more than 1% of its total CO 2 when exposed to normal conditions of temperature and moisture including rainfall of normal pH for at least 100 years. In some embodiments, the precipitation material does not release more than 1% of its total CO 2 when exposed to normal conditions of temperature and moisture, including rainfall of normal pH for at least 1000 years.
  • any suitable surrogate marker or test that is reasonably able to predict such stability may be used.
  • an accelerated test comprising conditions of elevated temperature and/or moderate to more extreme pH conditions is reasonably able to indicate stability over extended periods of time.
  • a sample of the precipitation material may be exposed to 50, 75, 90, 100, 120, or 150 °C for 1, 2, 5, 25, 50, 100, 200, or 500 days at between 10% and 50% relative humidity, and a loss less than 1%, 2%, 3%, 4%, 5%, 10%, 20%, 30%, or 50% of its carbon may be considered sufficient evidence of stability of precipitation material of the invention for a given period (e.g., 1, 10, 100, 1000, or more than 1000 years).
  • any of a number of suitable methods may be used to test the stability of the precipitation material including physical test methods and chemical test methods, wherein the methods are suitable for determining that the compounds in the precipitation material are similar to or the same as naturally occurring compounds known to have the above specified stability (e.g., limestone).
  • CO 2 content of the precipitation material may be monitored by any suitable method, one such non-limiting example being coulometry.
  • Other conditions may be adjusted as appropriate, including pH, pressure, UV radiation, and the like, again depending on the intended or likely environment. It will be appreciated that any suitable conditions may be used that one of skill in the art would reasonably conclude indicate the requisite stability over the indicated time period.
  • the carbonate-containing precipitation material which serves to sequester CO 2 in a form that is stable over extended periods of time (e.g., geologic time scales), may be stored for extended durations, as described above.
  • the precipitation material if needed to achieve a certain ratio of carbonates to silica, may also be mixed with silicon-based material (e.g., from separated silicon-based material after material comprising metal silicates digestion; commercially available Si ⁇ 2 ; etc.) to form pozzolanic material.
  • silicon-based material e.g., from separated silicon-based material after material comprising metal silicates digestion; commercially available Si ⁇ 2 ; etc.
  • Pozzolanic materials of the invention are siliceous or aluminosiliceous materials which, when combined with an alkali such as calcium hydroxide (Ca(OH) 2 ), exhibit cementitious properties by forming calcium silicates and other cementitious materials.
  • precipitation material comprises metastable carbonate compounds that are more stable in salt water than in fresh water, such that upon contact with fresh water of any pH they dissolve and re-precipitate into other fresh water stable minerals.
  • the carbonate compounds are present as small particles, for example, with particle sizes ranging from 0.1 ⁇ m to 100 ⁇ m, 1 to 100 ⁇ m, 10 to 100 ⁇ m, 50 to 100 ⁇ m as determined by scanning electron microscopy (SEM).
  • particle sizes of the carbonate compounds range from 0.5 to 10 ⁇ m as determined by SEM.
  • the particles size exhibit a single modal distribution.
  • the particle sizes exhibit a bimodal or multi-modal distribution.
  • the particles have a high surface are ranging from, for example, 0.5 to 100 m /gm, 0.5 to 50 m /gm, or 0.5 to 2.0 m /gm as determined by Brauner, Emmit, & Teller (BET) Surface Area Analysis.
  • precipitation material may comprise rod-shaped crystals and/or amorphous solids.
  • the rod-shaped crystals may vary in structure, and in certain embodiments have a length to diameter ratio ranging from 500 to 1, 250 to 1, or 10 to 1.
  • the length of the crystals ranges from 0.5 ⁇ m to 500 ⁇ m, 1 ⁇ m to 250 ⁇ m, or 5 ⁇ m to 100 ⁇ m.
  • substantially completely amorphous solids are produced.
  • Spray-dried material e.g., precipitation material, silicon-based material, pozzolanic material, etc.
  • spray-dried material may have a consistent particle size (i.e., the spray-dried material may have a relatively narrow particle size distribution).
  • at least 50%, 60%, 70%, 80%, 90%, 95%, 97%, or 99% of the spray-dried material falls within ⁇ 10 microns, ⁇ 20 microns, ⁇ 30 microns, ⁇ 40 microns, ⁇ 50 microns, ⁇ 75 microns, ⁇ 100 microns, or ⁇ 250 microns of a given mean particle diameter.
  • Such spray-dried material may be used to manufacture cement, fine aggregate, mortar, coarse aggregate, concrete, and/or pozzolans of the invention; however, one of skill in the art will recognize that manufacture of cement, fine aggregate, mortar, coarse aggregate, concrete, and/or pozzolans does not require spray-dried precipitation material.
  • Air-dried precipitation material for example, may also be used to manufacture cement, fine aggregate, mortar, coarse aggregate, concrete, and/or pozzolans of the invention.
  • pozzolanic material has lower cementitious properties than ordinary Portland cement, but in the presence of a lime-rich media like calcium hydroxide, it shows better cementitious properties towards later day strength (> 28 days).
  • the pozzolanic reaction may be slower than the rest of the reactions which occur during cement hydration, and thus the short-term strength of concretes that include pozzolanic material of the invention may not be as high as concrete made with purely cementitious materials.
  • the mechanism for this display of strength is the reaction of silicates with lime to form secondary cementitious phases (calcium silicate hydrates with a lower C/S ratio), which display gradual strengthening properties usually after 7 days. The extent of the strength development ultimately depends upon the chemical composition of the pozzolanic material.
  • Increasing the composition of silicon-based material (optionally with added silica and/or alumina), especially amorphous silicon-based material, generally produces better pozzolanic reactions and strengths.
  • Highly reactive pozzolans such as silica fume and high reactivity metakaolin may produce "high early strength" concrete that increases the rate at which concrete comprising precipitation material of the invention gains strength.
  • Precipitation material comprising silicates and aluminosilicates may be readily employed in the cement and concrete industry as pozzolanic material by virtue of the presence of the finely divided siliceous and/or alumino-siliceous material (e.g., silicon-based material).
  • the siliceous and/or aluminosiliceous precipitation material may be blended with Portland cement, or added as a direct mineral admixture in a concrete mixture.
  • pozzolanic material comprises calcium and magnesium in a ratio (as above) that perfects setting time, stiffening, and long-term stability of resultant hydration products (e.g., concrete).
  • precipitation material comprises silica in which 10-20%, 20-30%, 30-40%, 40-50%, 50-60%, 60-70%, 70-80%, 80-90%, 90-95%, 95-98%, 98-99%, 99-99.9% of the silica has a particle size less than 45 microns (e.g., in the longest dimension).
  • siliceous precipitation material comprises aluminosilica in which 10-20%, 20-30%, 30-40%, 40-50%, 50-60%, 60-70%, 70-80%, 80-90%, 90-95%, 95-98%, 98-99%, 99-99.9% of the aluminosilica has a particle size less than 45 microns.
  • siliceous precipitation material comprises a mixture of silica and aluminosilica in which 10-20%, 20-30%, 30-40%, 40-50%, 50-60%, 60- 70%, 70-80%, 80-90%, 90-95%, 95-98%, 98-99%, 99-99.9% of the mixture has a particle size less than 45 microns (e.g., in the biggest dimension).
  • Pozzolanic material produced by the methods disclosed herein may be employed as a construction material, which material may be processed for use as a construction material or processed for use in an existing construction material for buildings (e.g., commercial, residential, etc.) and/or infrastructure (e.g., pavements, roads, bridges, overpasses, walls, levees, dams, etc.).
  • the construction material may be incorporated into any structure, the structures further including foundations, parking structures, houses, office buildings, commercial offices, governmental buildings, and support structures (e.g., footings for gates, fences and poles) is considered a part of the built environment.
  • the construction material may be a constituent of a structural or nonstructural component of such structure.
  • An additional benefit of using pozzolanic material as a construction material or in a construction material is that CO 2 employed in the process (e.g., CO 2 obtained from a waste gas stream) is effectively sequestered in the built environment.
  • pozzolanic material of the invention is employed as a component of a hydraulic cement (e.g., ordinary Portland cement), which sets and hardens after combining with water. Setting and hardening of the product produced by combining the precipitation material with cement and water results from the production of hydrates that are formed from the cement upon reaction with water, wherein the hydrates are essentially insoluble in water.
  • a hydraulic cement e.g., ordinary Portland cement
  • Such hydraulic cements, methods for their manufacture and use are described in co-pending U.S. Patent Application No. 12/126,776, filed on 23 May 2008, the disclosure of which application is incorporated herein by reference.
  • pozzolanic material blended with cement is between 0.5% and 1.0%, 1.0% and 2.0%, 2.0% and 4.0%, 4.0% and 6.0%, 6.0% and 8.0%, 8.0% and 10.0%, 10.0% and 15.0%, 15.0% and 20.0%, 20.0% and 30.0%, 30.0% and 40.0%, 40.0% and 50.0%, 50% and 60%, or a range thereof, pozzolanic material by weight.
  • pozzolanic material blended with cement is between 0.5% and 2.0%, 1.0% and 4.0%, 2.0% and 8.0%, 4.0% and 15.0%, 8.0% and 30.0%, or 15.0% and 60.0% pozzolanic material by weight.
  • pozzolanic material is blended with other cementitious materials or mixed into cements as an admixture or aggregate.
  • Mortars of the invention find use in binding construction blocks (e.g., bricks) together and filling gaps between construction blocks. Mortars of the invention may also be used to fix existing structure (e.g., to replace sections where the original mortar has become compromised or eroded), among other uses.
  • the pozzolanic material may be utilized to produce aggregates.
  • aggregate is produced from the precipitation material by pressing and subsequent crushing.
  • aggregate is produced from the precipitation material by extrusion and breaking resultant extruded material.
  • the solution was decanted and the solid product was recovered by either filter press or vacuum filtration. Additionally, the solution could be rinsed after the decant process; whereby water was added and the sample was filter pressed. Alternatively, water was added after initial vacuum filtration, stirred, and filtered again. Finally, the product was spray dried. The overall yield was 5 - 7 g/L of the original solution.
  • Example IB Liquid-Solid Separation
  • Precipitation reaction mixture is prepared as described above for Example IA.
  • Slurry comprising the precipitation product is produced in a reaction vessel (see Example IA), which, for the purpose of this example, is referred to as a precipitation station.
  • the slurry is provided to a liquid-solid separation apparatus as precipitation station effluent.
  • a precipitation station effluent pipe is used to provide the slurry to the liquid-solid separation apparatus and to direct slurry flow against a baffle, by which precipitation station effluent flow is deflected.
  • Heavier precipitation product particles continue their path of motion down (i.e., in the direction of gravity) the precipitation station effluent pipe to a collector while supernatant deflects, separates from precipitation product particles, and exits through the upper portion of the liquid-solid separation apparatus.
  • the resulting precipitation product is removed from the collector and dried to yield of calcium carbonate and magnesium carbonate hydrates.
  • Slurry comprising the precipitation product is produced in a reaction vessel (see Example IA), which, for the purpose of this example, is referred to as a precipitation station.
  • a precipitation station Following formation of precipitation product slurry (e.g., precipitation reaction mixture), the slurry is provided as precipitation station effluent to a liquid-solid separation apparatus, wherein the slurry is made to flow in a spiral channel. At the end of the spiral channel, a parallel array of outlets collects separated particles of precipitation product. The resulting precipitation product is removed from the collector and dried to yield calcium carbonate and magnesium carbonate hydrates.
  • precipitation product slurry e.g., precipitation reaction mixture
  • Paste samples of precipitation material were mixed according to ASTM standard C 305-06, standard practice for mixing of hydraulic pastes and mortars.
  • the first mix was of entirely OPC with a water to cement ratio of 0.55 by weight.
  • the second mix was 80% OPC and 20% precipitation material which, due to the consistency after mixing with a W/C ratio of .55, required a greater water to cement ratio of 0.70, see Table 2.
  • the pastes were poured onto metal slides to create slabs and then allowed to cure for 3 days in a curing chamber with a relative humidity of 98%. There were 5 slides total, each with a sample of 100% OPC mix and the 80/20 OPC-precipitation material mix.
  • the slides were then put into the QUV/se weathering chamber with the material facing inward to be exposed to the UV radiation and to provide the condensation surface (see apparatus of Fig. Wl).
  • the standard used for this experiment was ASTM Standard G154-06, Standard Practice for Operating Fluorescent Light Apparatus for UV Exposure of Nonmetallic Materials. The specific cycling of this standard is open ended, leaving the hours of exposure to be tailored to the total length of the experimental run and to the material being tested.
  • the device was cycled for 2000 total hours of exposure in intervals of 8 hours of UV followed by 4 hours of heat and vapor/condensation exposure, see Table 3. After every 100 hours of exposure the samples were rotated through the different positions in the machine to ensure an even irradiance was applied to each sample. The irradiance of the device was set to .78 W/m 2 from each of the bulbs, but often fluctuated down to .55 W/m and required constant recalibration. Temperature was controlled through a heating element in the water tank which cycled between 20 0 C and 40 0 C to create the vapor and condensation during the heating and cooling phase.
  • Samples were removed from the device at 500 hour intervals through a total exposure of 2000 hours (i.e., 500, 1000, 1500, and 2000 hours) and compared to a baseline at 0 hours of exposure.
  • the chamber was not sealed to the environment, letting in atmospheric air at standard pressure. Once the time intervals were reached, the material was tested through the analytical techniques (coulometry, thermogravimetric analysis, and X-ray diffraction) according to the testing schedule in Fig. W3.
  • Coulometry is a quantitative examination of the carbon content in the paste mixes. From the weathered slabs, material was removed from the surface and ground into a powder using a mortar and pestle. The powder was placed into a CM5230 Acidification Module (UIC, Inc.), where it was reacted in a series with perchloric and phosphoric acid. The resulting gas was isolated in N 2 where it was analyzed and outputted as % carbon by volume.
  • CM5230 Acidification Module UAC, Inc.
  • X-ray diffraction was done using a Rigaku Miniflex Diffractometer and analyzed using the software and databases associated with Jade 9 software, in addition to the database complied by Calera Corporation.
  • Material samples were prepared in the same way as in coulometry, using a mortar and pestle to create a powder from the surface of the weathered paste slabs. Aluminum sample dishes were then carefully prepared by filling with the powder and then leveled using a clean glass slide. Additional care was taken to create a random orientation of the powder grains by "chopping" the mounded powder before compacting to a level surface. This reduced the possibility of false intensity readings due to alignment of the powder grains. [00342] TGA
  • the phase After the initial hydration and curing (which formed the portlandite) the phase then reacted to form the carbonate and disappeared from both the TGA and XRD scans.
  • the time of exposure when the peaks disappeared was the same for both XRD and TGA; before 500 hours for the 100% OPC mixture and approximately close to 1000 hours for the mixture containing precipitation material.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Treating Waste Gases (AREA)

Abstract

L'invention concerne des systèmes et des procédés pour abaisser les niveaux de dioxyde de carbone et d'autres polluants atmosphériques. Des systèmes et procédés économiquement viables capables d'éliminer de vastes quantités de dioxyde de carbone et d'autres polluants atmosphériques de courants de déchets gazeux et de les séquestrer sous des formes stables au stockage sont également décrits.
PCT/US2010/035041 2009-05-14 2010-05-14 Systèmes et procédés de traitement de co2 WO2010132863A1 (fr)

Applications Claiming Priority (18)

Application Number Priority Date Filing Date Title
US17847509P 2009-05-14 2009-05-14
US61/178,475 2009-05-14
US17889909P 2009-05-15 2009-05-15
US61/178,899 2009-05-15
US18472609P 2009-06-05 2009-06-05
US61/184,726 2009-06-05
US22821009P 2009-07-24 2009-07-24
US61/228,210 2009-07-24
US23004209P 2009-07-30 2009-07-30
US61/230,042 2009-07-30
US23942909P 2009-09-02 2009-09-02
US61/239,429 2009-09-02
US25464009P 2009-10-23 2009-10-23
US61/254,640 2009-10-23
US30641210P 2010-02-19 2010-02-19
US61/306,412 2010-02-19
US31127510P 2010-03-05 2010-03-05
US61/311,275 2010-03-05

Publications (1)

Publication Number Publication Date
WO2010132863A1 true WO2010132863A1 (fr) 2010-11-18

Family

ID=43085367

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2010/035041 WO2010132863A1 (fr) 2009-05-14 2010-05-14 Systèmes et procédés de traitement de co2

Country Status (1)

Country Link
WO (1) WO2010132863A1 (fr)

Cited By (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7993500B2 (en) 2008-07-16 2011-08-09 Calera Corporation Gas diffusion anode and CO2 cathode electrolyte system
US8006446B2 (en) 2008-09-30 2011-08-30 Calera Corporation CO2-sequestering formed building materials
US8062418B2 (en) 2009-12-31 2011-11-22 Calera Corporation Methods and compositions using calcium carbonate
US8137444B2 (en) 2009-03-10 2012-03-20 Calera Corporation Systems and methods for processing CO2
US8333944B2 (en) 2007-12-28 2012-12-18 Calera Corporation Methods of sequestering CO2
US8357270B2 (en) 2008-07-16 2013-01-22 Calera Corporation CO2 utilization in electrochemical systems
US8470275B2 (en) 2008-09-30 2013-06-25 Calera Corporation Reduced-carbon footprint concrete compositions
US8491858B2 (en) 2009-03-02 2013-07-23 Calera Corporation Gas stream multi-pollutants control systems and methods
US8691175B2 (en) 2011-04-28 2014-04-08 Calera Corporation Calcium sulfate and CO2 sequestration
CN103995498A (zh) * 2013-07-18 2014-08-20 俞元洪 一种用于泥浆脱水固化施工装置的控制系统
US8834688B2 (en) 2009-02-10 2014-09-16 Calera Corporation Low-voltage alkaline production using hydrogen and electrocatalytic electrodes
US8857118B2 (en) 2007-05-24 2014-10-14 Calera Corporation Hydraulic cements comprising carbonate compound compositions
US8869477B2 (en) 2008-09-30 2014-10-28 Calera Corporation Formed building materials
US8906156B2 (en) 2009-12-31 2014-12-09 Calera Corporation Cement and concrete with reinforced material
US8936773B2 (en) 2011-04-28 2015-01-20 Calera Corporation Methods and compositions using calcium carbonate and stabilizer
US8999057B2 (en) 2011-09-28 2015-04-07 Calera Corporation Cement and concrete with calcium aluminates
US9061940B2 (en) 2008-09-30 2015-06-23 Calera Corporation Concrete compositions and methods
US9133581B2 (en) 2008-10-31 2015-09-15 Calera Corporation Non-cementitious compositions comprising vaterite and methods thereof
CN104927398A (zh) * 2014-06-10 2015-09-23 池州市富华粉体科技有限公司 一种活性轻质碳酸钙的制备方法
US9187834B2 (en) 2011-05-19 2015-11-17 Calera Corporation Electrochemical hydroxide systems and methods using metal oxidation
US9200375B2 (en) 2011-05-19 2015-12-01 Calera Corporation Systems and methods for preparation and separation of products
US9260314B2 (en) 2007-12-28 2016-02-16 Calera Corporation Methods and systems for utilizing waste sources of metal oxides
CN106044950A (zh) * 2016-07-22 2016-10-26 中南林业科技大学 一种盐碱水的正渗透处理系统及其处理方法
US9714406B2 (en) 2012-09-04 2017-07-25 Blue Planet, Ltd. Carbon sequestration methods and systems, and compositions produced thereby
WO2017200764A1 (fr) * 2016-05-19 2017-11-23 Lawrence Livermore National Security, Llc Membrane d'hydroxyde en fusion pour la séparation des gaz acides présents dans des émissions
US9828313B2 (en) 2013-07-31 2017-11-28 Calera Corporation Systems and methods for separation and purification of products
WO2018011567A1 (fr) * 2016-07-12 2018-01-18 The University Court Of The University Of Aberdeen Procédés et systèmes de capture et de conversion de dioxyde de carbone
US9880124B2 (en) 2014-11-10 2018-01-30 Calera Corporation Measurement of ion concentration in presence of organics
US9902652B2 (en) 2014-04-23 2018-02-27 Calera Corporation Methods and systems for utilizing carbide lime or slag
US9957621B2 (en) 2014-09-15 2018-05-01 Calera Corporation Electrochemical systems and methods using metal halide to form products
WO2018122666A1 (fr) * 2016-12-29 2018-07-05 Philip Morris Products S.A. Filtre d'article à fumer contenant du carbonate de magnésium amorphe
US10161050B2 (en) 2015-03-16 2018-12-25 Calera Corporation Ion exchange membranes, electrochemical systems, and methods
US10203434B2 (en) 2013-03-15 2019-02-12 Blue Planet, Ltd. Highly reflective microcrystalline/amorphous materials, and methods for making and using the same
US10236526B2 (en) 2016-02-25 2019-03-19 Calera Corporation On-line monitoring of process/system
US10266954B2 (en) 2015-10-28 2019-04-23 Calera Corporation Electrochemical, halogenation, and oxyhalogenation systems and methods
US10556848B2 (en) 2017-09-19 2020-02-11 Calera Corporation Systems and methods using lanthanide halide
US10590054B2 (en) 2018-05-30 2020-03-17 Calera Corporation Methods and systems to form propylene chlorohydrin from dichloropropane using Lewis acid
US10619254B2 (en) 2016-10-28 2020-04-14 Calera Corporation Electrochemical, chlorination, and oxychlorination systems and methods to form propylene oxide or ethylene oxide
US10847844B2 (en) 2016-04-26 2020-11-24 Calera Corporation Intermediate frame, electrochemical systems, and methods
CN112299418A (zh) * 2019-07-25 2021-02-02 深圳市太空微藻生物科技有限公司 一种制取二氧化碳的方法、装置以及应用该装置的螺旋藻水生植物养殖设备
CN112569773A (zh) * 2020-12-24 2021-03-30 南京圣创科技有限公司 一种增大脱硫浆液结晶粒径的方法和装置
US11377363B2 (en) 2020-06-30 2022-07-05 Arelac, Inc. Methods and systems for forming vaterite from calcined limestone using electric kiln
US11577965B2 (en) 2020-02-25 2023-02-14 Arelac, Inc. Methods and systems for treatment of lime to form vaterite
WO2024003575A1 (fr) * 2022-06-30 2024-01-04 Hydrophis Gas Ltd Procédé de séquestration de dioxyde de carbone et de minéraux à partir de déchets industriels
CN117365634A (zh) * 2023-11-21 2024-01-09 中国矿业大学 一种煤基固废与电厂烟气协同逐巷充填处置方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6620856B1 (en) * 1998-12-23 2003-09-16 Imerys Minerals, Limited Production of concentrated carbonate suspensions
US20090001020A1 (en) * 2007-06-28 2009-01-01 Constantz Brent R Desalination methods and systems that include carbonate compound precipitation
US20090081112A1 (en) * 2005-11-18 2009-03-26 Nordkalk Oyj Abp Process and apparatus for producing suspensions of solid matter

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6620856B1 (en) * 1998-12-23 2003-09-16 Imerys Minerals, Limited Production of concentrated carbonate suspensions
US20090081112A1 (en) * 2005-11-18 2009-03-26 Nordkalk Oyj Abp Process and apparatus for producing suspensions of solid matter
US20090001020A1 (en) * 2007-06-28 2009-01-01 Constantz Brent R Desalination methods and systems that include carbonate compound precipitation

Cited By (68)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8857118B2 (en) 2007-05-24 2014-10-14 Calera Corporation Hydraulic cements comprising carbonate compound compositions
US8333944B2 (en) 2007-12-28 2012-12-18 Calera Corporation Methods of sequestering CO2
US9260314B2 (en) 2007-12-28 2016-02-16 Calera Corporation Methods and systems for utilizing waste sources of metal oxides
US8357270B2 (en) 2008-07-16 2013-01-22 Calera Corporation CO2 utilization in electrochemical systems
US7993500B2 (en) 2008-07-16 2011-08-09 Calera Corporation Gas diffusion anode and CO2 cathode electrolyte system
US8894830B2 (en) 2008-07-16 2014-11-25 Celera Corporation CO2 utilization in electrochemical systems
US8869477B2 (en) 2008-09-30 2014-10-28 Calera Corporation Formed building materials
US8431100B2 (en) 2008-09-30 2013-04-30 Calera Corporation CO2-sequestering formed building materials
US8470275B2 (en) 2008-09-30 2013-06-25 Calera Corporation Reduced-carbon footprint concrete compositions
US9061940B2 (en) 2008-09-30 2015-06-23 Calera Corporation Concrete compositions and methods
US8603424B2 (en) 2008-09-30 2013-12-10 Calera Corporation CO2-sequestering formed building materials
US8006446B2 (en) 2008-09-30 2011-08-30 Calera Corporation CO2-sequestering formed building materials
US9133581B2 (en) 2008-10-31 2015-09-15 Calera Corporation Non-cementitious compositions comprising vaterite and methods thereof
US8834688B2 (en) 2009-02-10 2014-09-16 Calera Corporation Low-voltage alkaline production using hydrogen and electrocatalytic electrodes
US9267211B2 (en) 2009-02-10 2016-02-23 Calera Corporation Low-voltage alkaline production using hydrogen and electrocatalytic electrodes
US8491858B2 (en) 2009-03-02 2013-07-23 Calera Corporation Gas stream multi-pollutants control systems and methods
US8883104B2 (en) 2009-03-02 2014-11-11 Calera Corporation Gas stream multi-pollutants control systems and methods
US8137444B2 (en) 2009-03-10 2012-03-20 Calera Corporation Systems and methods for processing CO2
US9056790B2 (en) 2009-12-31 2015-06-16 Calera Corporation Methods and compositions using calcium carbonate
US8177909B2 (en) 2009-12-31 2012-05-15 Calera Corporation Methods and compositions using calcium carbonate
US8906156B2 (en) 2009-12-31 2014-12-09 Calera Corporation Cement and concrete with reinforced material
US8932400B2 (en) 2009-12-31 2015-01-13 Calera Corporation Methods and compositions using calcium carbonate
US8114214B2 (en) 2009-12-31 2012-02-14 Calera Corporation Methods and compositions using calcium carbonate
US8137455B1 (en) 2009-12-31 2012-03-20 Calera Corporation Methods and compositions using calcium carbonate
US8062418B2 (en) 2009-12-31 2011-11-22 Calera Corporation Methods and compositions using calcium carbonate
US8936773B2 (en) 2011-04-28 2015-01-20 Calera Corporation Methods and compositions using calcium carbonate and stabilizer
US9139472B2 (en) 2011-04-28 2015-09-22 Calera Corporation Methods and compositions using calcium carbonate and stabilizer
US8691175B2 (en) 2011-04-28 2014-04-08 Calera Corporation Calcium sulfate and CO2 sequestration
US9187834B2 (en) 2011-05-19 2015-11-17 Calera Corporation Electrochemical hydroxide systems and methods using metal oxidation
US9187835B2 (en) 2011-05-19 2015-11-17 Calera Corporation Electrochemical systems and methods using metal and ligand
US9200375B2 (en) 2011-05-19 2015-12-01 Calera Corporation Systems and methods for preparation and separation of products
US9957623B2 (en) 2011-05-19 2018-05-01 Calera Corporation Systems and methods for preparation and separation of products
US8999057B2 (en) 2011-09-28 2015-04-07 Calera Corporation Cement and concrete with calcium aluminates
US9714406B2 (en) 2012-09-04 2017-07-25 Blue Planet, Ltd. Carbon sequestration methods and systems, and compositions produced thereby
US10711236B2 (en) 2012-09-04 2020-07-14 Blue Planet, Ltd. Carbon sequestration methods and systems, and compositions produced thereby
US10203434B2 (en) 2013-03-15 2019-02-12 Blue Planet, Ltd. Highly reflective microcrystalline/amorphous materials, and methods for making and using the same
US11262488B2 (en) 2013-03-15 2022-03-01 Blue Planet Systems Corporation Highly reflective microcrystalline/amorphous materials, and methods for making and using the same
CN103995498A (zh) * 2013-07-18 2014-08-20 俞元洪 一种用于泥浆脱水固化施工装置的控制系统
US9828313B2 (en) 2013-07-31 2017-11-28 Calera Corporation Systems and methods for separation and purification of products
US10287223B2 (en) 2013-07-31 2019-05-14 Calera Corporation Systems and methods for separation and purification of products
US9902652B2 (en) 2014-04-23 2018-02-27 Calera Corporation Methods and systems for utilizing carbide lime or slag
CN104927398A (zh) * 2014-06-10 2015-09-23 池州市富华粉体科技有限公司 一种活性轻质碳酸钙的制备方法
US9957621B2 (en) 2014-09-15 2018-05-01 Calera Corporation Electrochemical systems and methods using metal halide to form products
US9880124B2 (en) 2014-11-10 2018-01-30 Calera Corporation Measurement of ion concentration in presence of organics
US10480085B2 (en) 2015-03-16 2019-11-19 Calera Corporation Ion exchange membranes, electrochemical systems, and methods
US10801117B2 (en) 2015-03-16 2020-10-13 Calera Corporation Ion exchange membranes, electrochemical systems, and methods
US10161050B2 (en) 2015-03-16 2018-12-25 Calera Corporation Ion exchange membranes, electrochemical systems, and methods
US10266954B2 (en) 2015-10-28 2019-04-23 Calera Corporation Electrochemical, halogenation, and oxyhalogenation systems and methods
US10844496B2 (en) 2015-10-28 2020-11-24 Calera Corporation Electrochemical, halogenation, and oxyhalogenation systems and methods
US10236526B2 (en) 2016-02-25 2019-03-19 Calera Corporation On-line monitoring of process/system
US11239503B2 (en) 2016-04-26 2022-02-01 Calera Corporation Intermediate frame, electrochemical systems, and methods
US10847844B2 (en) 2016-04-26 2020-11-24 Calera Corporation Intermediate frame, electrochemical systems, and methods
WO2017200764A1 (fr) * 2016-05-19 2017-11-23 Lawrence Livermore National Security, Llc Membrane d'hydroxyde en fusion pour la séparation des gaz acides présents dans des émissions
US10464015B2 (en) 2016-05-19 2019-11-05 Lawrence Livermore National Security, Llc Molten hydroxide membrane for separation of acid gases from emissions
WO2018011567A1 (fr) * 2016-07-12 2018-01-18 The University Court Of The University Of Aberdeen Procédés et systèmes de capture et de conversion de dioxyde de carbone
CN106044950A (zh) * 2016-07-22 2016-10-26 中南林业科技大学 一种盐碱水的正渗透处理系统及其处理方法
US10619254B2 (en) 2016-10-28 2020-04-14 Calera Corporation Electrochemical, chlorination, and oxychlorination systems and methods to form propylene oxide or ethylene oxide
WO2018122666A1 (fr) * 2016-12-29 2018-07-05 Philip Morris Products S.A. Filtre d'article à fumer contenant du carbonate de magnésium amorphe
US10556848B2 (en) 2017-09-19 2020-02-11 Calera Corporation Systems and methods using lanthanide halide
US10807927B2 (en) 2018-05-30 2020-10-20 Calera Corporation Methods and systems to form propylene chlorohydrin from dichloropropane using lewis acid
US10590054B2 (en) 2018-05-30 2020-03-17 Calera Corporation Methods and systems to form propylene chlorohydrin from dichloropropane using Lewis acid
CN112299418A (zh) * 2019-07-25 2021-02-02 深圳市太空微藻生物科技有限公司 一种制取二氧化碳的方法、装置以及应用该装置的螺旋藻水生植物养殖设备
US11577965B2 (en) 2020-02-25 2023-02-14 Arelac, Inc. Methods and systems for treatment of lime to form vaterite
US11377363B2 (en) 2020-06-30 2022-07-05 Arelac, Inc. Methods and systems for forming vaterite from calcined limestone using electric kiln
CN112569773A (zh) * 2020-12-24 2021-03-30 南京圣创科技有限公司 一种增大脱硫浆液结晶粒径的方法和装置
WO2024003575A1 (fr) * 2022-06-30 2024-01-04 Hydrophis Gas Ltd Procédé de séquestration de dioxyde de carbone et de minéraux à partir de déchets industriels
CN117365634A (zh) * 2023-11-21 2024-01-09 中国矿业大学 一种煤基固废与电厂烟气协同逐巷充填处置方法
CN117365634B (zh) * 2023-11-21 2024-05-10 中国矿业大学 一种煤基固废与电厂烟气协同逐巷充填处置方法

Similar Documents

Publication Publication Date Title
US20110277670A1 (en) Systems and methods for processing co2
US20120211421A1 (en) Systems and methods for processing co2
WO2010132863A1 (fr) Systèmes et procédés de traitement de co2
US9260314B2 (en) Methods and systems for utilizing waste sources of metal oxides
US8137444B2 (en) Systems and methods for processing CO2
US7754169B2 (en) Methods and systems for utilizing waste sources of metal oxides
AU2009260036B2 (en) Methods and systems for utilizing waste sources of metal oxides
AU2008278301B2 (en) Methods of sequestering CO2
CA2694971C (fr) Traitement du dioxyde de carbone au moyen d'une solution de recirculation
JP2012519076A (ja) ガス流複合汚染物質制御システムおよび方法
JP2011527664A (ja) 含金属シリケート材料からの炭酸塩含有組成物の製造
US20230285895A1 (en) Gaseous CO2 Capture Systems for Improving Capture Performance, and Methods of Use Thereof
Constanz et al. Methods of sequestering CO2
Farsad et al. Systems and methods for processing CO 2

Legal Events

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

Ref document number: 10775659

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10775659

Country of ref document: EP

Kind code of ref document: A1