WO2023164154A1 - Carbon dioxide-capturing cement compositions and related methods - Google Patents
Carbon dioxide-capturing cement compositions and related methods Download PDFInfo
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- WO2023164154A1 WO2023164154A1 PCT/US2023/013853 US2023013853W WO2023164154A1 WO 2023164154 A1 WO2023164154 A1 WO 2023164154A1 US 2023013853 W US2023013853 W US 2023013853W WO 2023164154 A1 WO2023164154 A1 WO 2023164154A1
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- 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
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- B01D—SEPARATION
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/005—Geopolymer cements, e.g. reaction products of aluminosilicates with alkali metal hydroxides or silicates
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- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/047—Zeolites
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- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
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- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/0016—Granular materials, e.g. microballoons
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- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
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- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/30—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing magnesium cements or similar cements
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
- C04B40/0042—Powdery mixtures
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- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/02—Selection of the hardening environment
- C04B40/0231—Carbon dioxide hardening
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- B01D2253/106—Silica or silicates
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- B01D—SEPARATION
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- B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
- B01D2253/1124—Metal oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
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Definitions
- Carbon dioxide emissions continue to make worse the problems of global warming and other negative environmental impacts. Some challenges include extreme weather events and health hazards caused by increase carbon dioxide levels in the atmosphere and these challenges become more prevalent every day.
- One way to reduce carbon dioxide emissions is by utilizing renewable energy sources that are climate friendly, instead of the conventional fuel burning energy sources. Unfortunately, the adaptation of these technologies and the advancement of these technologies have not increased at a fast enough rate to reduce the total amount of carbon dioxide within the atmosphere. Accordingly, improved techniques for mitigating carbon dioxide levels are desired.
- cement compositions that can capture carbon dioxide are generally described.
- the cement composition may replace conventional cement compositions in concrete.
- the subject matter of the present disclosure involves, in some cases, interrelated products, alternative solutions to a particular problem, and/or a plurality of different uses of one or more systems and/or articles.
- a concrete admixture comprising a first plurality of particles comprising a pozzolanic material, and a second plurality of particles comprising a metal oxide, wherein the concrete admixture is capable of enhancing the absorption of carbon dioxide of a cement composition or a concrete composition.
- a cement composition comprising a first material comprising a pozzolanic material; a second material comprising silica and/or carbonate compound; and a metal oxide.
- a cement composition is described, the composition comprising a first material comprising a porous inorganic material; a second material comprising silica; and a third material comprising a metal oxide.
- a cement composition comprising a first material comprising a porous inorganic material; a second material comprising a carbonate compound; and a metal oxide.
- a cement composition comprising a first material comprising a porous material; a second material comprising a silica and/or a carbonate compound.
- a method for preparing a concrete mixture comprising combining a first plurality of particles comprising a first material comprising a porous inorganic material with a second plurality of particles comprising a second material comprises silica or a carbonate compound, wherein the first plurality of particles and/or the second plurality of particles has an average particle size of less than or equal to 100 microns.
- a method of capturing carbon dioxide comprising capturing carbon dioxide from an ambient environment using a material comprising a cement composition, the cement composition comprising a first material comprising a porous inorganic material; a second material comprising silica and/or a carbonate compound; and a third material comprising a metal oxide.
- the material is or comprises concrete.
- a method of forming a concrete composition comprising combining a concrete admixture comprising a first plurality of particles comprising a pozzolanic material and a second plurality of particles comprising a metal oxide with one or more concrete-forming materials to form a mixture; curing the mixture to form the concrete.
- a method of capturing carbon dioxide comprising adsorbing or absorbing carbon dioxide from an ambient environment with concrete, the concrete comprising a concrete admixture comprising a first plurality of particles comprising a pozzolanic material and a second plurality of particles comprising a metal oxide.
- FIG. l is a schematic diagram illustrating a process for preparing and transporting concrete, according to some embodiments.
- FIG. 2 is a diagram depicting carbon dioxide, according to some embodiments.
- FIG. 3 is a diagram comparing carbon dioxide capture of some compositions described herein relative to certain existing concretes, according to some embodiments
- FIG. 4 is a plot that depicts that temperature change over 5 days of four different cement compositions where the control sample and the sample with glass and zeolite experienced a peak temperature change of 16 °F while the sample with zeolites and shells experienced a peak change of 18.5 °F, according to some embodiments;
- FIG. 5 is a table that depicts that the maximum carbon dioxide absorption of various cementitious formulations after 3 days, 7 days, and 28 days, according to some embodiments;
- FIG. 6 is a gas chromatograph depicting the relative absorption rates of CO2 for a sample of commercially available cementitious materials and a sample of the carbon- capturing cement compositions as described herein, according to some embodiments;
- FIG. 7 is an x-ray diffraction spectrum depicting the variations in crystal structure between a zeolite sample and a sample of the cement compositions described herein, according to some embodiments;
- FIG. 8 is a schematic diagram showing loading of a first material, a second, and a third material into a grinding apparatus, where the materials may be further enhanced, e.g., via fracturing and/or heating, according to some embodiments;
- FIG. 9 is a schematic diagram illustrating the process CO2 absorption into an inventive cement composition, followed by mineralization the carbon dioxide into a carbonate; according to some embodiments;
- FIG. 10 is a schematic diagram of a concrete mixture comprising an inventive cement composition, according to some embodiments.
- FIG. 11 is a schematic illustrating the mining of materials to packing of inventive cement compositions, according to some embodiments.
- FIG. 12 is a schematic diagram of concrete comprising the inventive cement compositions repairing a crack to the concrete, according to some embodiments;
- FIGS. 13A-13B show microscopic images comparing mortar without a concrete admixture and mortar that includes a concrete admixture, according to some embodiments.
- FIG. 14 is a graph comparing a control sample without a concrete admixture with two formulations that include a concrete admixture, according to some embodiments.
- compositions that can capture carbon dioxide from an ambient environment, such as the surrounding atmosphere or air.
- This disclosure also describes methods for capturing carbon dioxide using cement and/or concrete compositions.
- the inventive compositions may comprise materials that are capable of capturing carbon dioxide from the atmosphere and may also result in incorporating the carbon dioxide into the material itself (e.g., via mineralization of the carbon dioxide into one or more materials of the composition, such as a carbonate-containing compound).
- These compositions can form concrete, which can be incorporated into numerous structures, including roads, bridges, streets, buildings, and the like, resulting in structures that can sequester carbon dioxide directly from the atmosphere and thus reduce the impact of carbon dioxide in the environment.
- inventive compositions described herein may supplement or, at least partially, replace conventional concrete or components that make up concrete (e.g., cement, concrete aggregates).
- Conventional concrete preparations include mixing cement, mineral aggregates, and water, forming the mixture as desired, and allowing the mixture to harden into concrete.
- the uptake of carbon dioxide by these conventional concretes is minimal, if any, making them ineffective for carbon capture.
- manufacturing conventional concretes also release carbon dioxide, further limiting conventional concretes as carbon-capturing technologies.
- concrete can be prepared that sequesters carbon dioxide from the surrounding environment.
- the compositions and methods described herein can result in concrete compositions that significantly reduce carbon dioxide from its surroundings and may also result in less carbon dioxide emission during the concrete manufacturing process.
- the cement and/or concrete compositions may become stronger (e.g., increased mechanical strength) as the materials of the compositions capture carbon dioxide and trap (e.g., mineralize) it (e.g., as a carbonate-containing compound) within the concrete.
- the ability to produce carbon-capturing concrete can turn sidewalks, buildings, and other structures into carbon negative sinks for sequestering carbon dioxide from the atmosphere.
- compositions, and methods described herein may maintain or increase the structural integrity and/or strength of cement when compared to other certain existing concrete compositions. This is because the compositions described herein may increase in strength as they capture carbon dioxide from the ambient surroundings. Other advantages are described below.
- the cement compositions may comprise a mixture of materials (e.g., a first material, a second material, a third material), which may form an admixture that can be added to concreteforming materials as described in more detail below.
- the mixture of materials can replace conventional cements (e.g., portland cement, original portland cement) in concrete compositions, resulting in a concrete that can sequester carbon dioxide from the surrounding environment.
- the carbon dioxide-capturing compositions e.g., cements, concretes
- the cement compositions include a first material.
- the first material comprises one or more zeolites. In some embodiments, the first material comprises basalt. In some embodiments, the first material comprises a pozzolanic material. In some embodiments, the first material comprises a zeolite, a basalt, and/or a pozzolanic material. Details regarding these materials and other materials are described in more detail below.
- the first material may be present in a cement and/or concrete composition at a particular amount.
- a weight percentage of the first material within the cement and/or concrete composition is greater than or equal to 5 wt%, greater than or equal to 10 wt%, greater than or equal to 20 wt%, greater than or equal to 30 wt%, greater than or equal to 40 wt%, greater than or equal to 50 wt%, greater than or equal to 60 wt%, greater than or equal to 70 wt%, greater than or equal to 80 wt%, or greater than or equal to 90 wt%.
- the weight percentage of the first material within the cement and/or concrete composition is less than or equal to 90 wt%, less than or equal to 80 wt%, less than or equal to 70 wt%, less than or equal to 60 wt%, less than or equal to 50 wt%, less than or equal to 40 wt%, less than or equal to 30 wt%, less than or equal to 20 wt%, less than or equal to 10 wt%, or less than or equal to 5 wt%. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 5 wt% and less than or equal to 80 wt%). Other ranges are possible.
- the remaining percentage may be another material (e.g., a second material, a third material, concrete-forming material).
- the first material may comprise one or more zeolites.
- the one or more zeolites can each be a porous zeolite with the same or different composition.
- the zeolites comprise a honeycomblike lattice structure.
- the zeolites are porous materials comprising aluminosilicates.
- the zeolite comprises clinoptilolite.
- the zeolite is a naturally occurring zeolite.
- the zeolite is a synthetic zeolite.
- the zeolites can capture or sequester carbon dioxide via molecular binding (e.g., absorption, absorption, non-covalent interactions, covalent interactions) within pores of the zeolite.
- the carbon dioxide upon binding to the zeolite, the carbon dioxide may be converted to a carbonate compound (e.g., calcium carbonate) via carbonization of the first material or another material (e.g., a second material, a third material) in the composition.
- one or more zeolites may comprise a particular amount of the first material and/or the cement composition.
- a weight percentage of zeolite is greater than or equal to 5 wt%, greater than or equal to 10 wt%, greater than or equal to 20 wt%, greater than or equal to 30 wt%, greater than or equal to 50 wt%, greater than or equal to 60 wt%, greater than or equal to 65 wt%, greater than or equal to 70 wt%, greater than or equal to 75 wt%, greater than or equal to 80 wt%, greater than or equal to 85 wt%, or greater than or equal to 90 wt%.
- a weight percentage of zeolite is less than or equal to 90 wt%, less than or equal to 85 wt%, less than or equal to 80 wt%, less than or equal to 75 wt%, less than or equal to 70 wt%, less than or equal to 65 wt%, less than or equal to 60 wt%, less than or equal to 50 wt%, less than or equal to 30 wt%, less than or equal to 20 wt%, less than or equal to 10 wt%, or less than or equal to 5 wt%. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 5 wt% and less than or equal to 90 wt%). Other ranges are possible.
- the remaining percentage may be another zeolite, another first material, and/or some other material (e.g., a second material, a third material).
- the zeolite may be a porous zeolite.
- the zeolite (or some other first material) may have a particular porosity.
- the porosity of the zeolite (or some other first material) is greater than or equal to 20%, greater than or equal to 30%, greater than or equal to 50%, greater than or equal to 60%, greater than or equal to 70%, or greater than or equal to 80%.
- the porosity of the zeolite (or some other first material) is less than or equal to 80%, less than or equal 70%, less than or equal to 60%, less than or equal to 50%, less than or equal to 30%, or less than or equal to 20%. Combinations of the above referenced ranges are also possible (e.g., greater than or equal to 20% and less than or equal to 80%). Other ranges are possible.
- the one or more zeolites each have a particular average pore size.
- the zeolite has an average pore diameter of less than 1,000 pm, less than 750 pm, less than 500 pm, less than 250 pm, less than 100 pm, less than 50 pm, less than 25 pm, less than 20 pm, less than 10 pm, less than 1 pm, less than 750 nm, less than or equal to 500 nm, less than or equal to 250 nm, less than or equal to 100 nm, or less than or equal to 50 nm.
- the zeolite has an average pore diameter of greater than or equal to 50 nm, greater than or equal to 100 nm, greater than or equal to 200 nm, greater than or equal to 250 nm, greater than or equal to 500 nm, greater than or equal to 750 nm, greater than or equal to 1 qm, greater than or equal to 5 qm, greater than or equal to 10 qm, greater than or equal to 20 qm, greater than or equal to 25 qm, greater than or equal to 50 qm, greater than or equal to 100 qm, greater than or equal to 250 qm, greater than or equal to 500 qm, greater than or equal to 750 qm, or greater than or equal to 1,000 qm. Combinations of the foregoing ranges are also possible (e.g., greater than or equal to 50 nm and less than or equal to 1,000 qm). Other ranges are possible as this disclosure is not so limited.
- the first material comprises a basalt.
- Basalts may comprise a fine-grained (e.g., grain sizes less than 1000 qm) rock formed from volcanic activity, which may also comprise a columnar structure.
- basalts may comprise iron and/or magnesium compounds.
- basalts comprise silica (e.g., SiCh) and/or alkali metal oxides (e.g., Na2O and K2O).
- the basalt may be present in the first material or the cement composition with a particular amount.
- a weight percentage of basalt within the first material and/or the cement composition is greater than or equal to 5 %wt, greater than or equal to 10 %wt, greater than or equal to 15 %wt, greater than or equal to 20 %wt, greater than or equal to 25 %wt, greater than or equal to 30 %wt, or greater than or equal to 35 %wt.
- the weight percentage of basalt within the first material and/or the cement composition is less than or equal to 35 %wt, less than or equal to 30 %wt, less than or equal to 25 %wt, less than or equal to 20 %wt, less than or equal to 15 %wt, less than or equal to 10 %wt, or less than or equal to 5 %wt. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 5 %wt or less than or equal to 35 %wt). Other ranges are possible.
- the remaining percent can be remaining first material (e.g., zeolite, basalt) and/or some other material of the composition (e.g., a second material, a third material).
- the first material comprises a pozzolanic material.
- Pozzolanic materials may comprise naturally derived materials and/or industrially produced material comprising a sili con-containing and/or aluminum-containing compounds that may react with calcium hydroxide when exposed to water.
- the pozzolanic material comprises or is derived from volcanic ash.
- the pozzolanic material comprises silicon-containing volcanic ash, fly ash, silica fume, metakaolin, slag, and/or vitrified calcium aluminosilicate.
- the pozzolanic material may comprise diatomaceous earth, clays, rice hull ash, calcined fullers earth, calcined diatomite, uncalcined diatomite, zeolitic trass, and/or calcined clay.
- the pozzolanic material comprises olivine, serpentine, basalts, wollastonite, calcium carbonate, and/or metal organic frameworks (MOFs).
- the pozzolanic material comprises a mafic mineral (e.g., olivine, serpentine, wollastonite) and/or an ultramafic mineral.
- a cement composition or concrete admixture comprises a particular amount of pozzolanic material.
- the cement composition or concrete admixture has a weight percentage of pozzolanic material of greater than or equal to 50 wt%, greater than or equal to 60 wt%, greater than or equal to 70 wt%, greater than or equal to 80 wt%, or greater than or equal to 90 wt%.
- the cement composition or concrete admixture has a weight percentage of less than or equal to 90 wt%, less than or equal to 80 wt%, less than or equal to 70 wt%, less than or equal to 60 wt%, or less than or equal to 50 wt%.
- the cement compositions may also comprise a second material.
- the second material increases the mineralization capacity of carbon dioxide within the cement and/or concrete composition. It should be understood that the second material (e.g., the material that increases the mineralization capacity of carbon dioxide within the cement and/or concrete composition) is optional. In some embodiments, the second material is not present.
- the second material may comprise a variety of materials.
- the second material comprises waste glass.
- the second material comprises silica.
- the second material comprises carbonate-containing compounds, such as calcium carbonate.
- the second material comprises waste glass, silica, and/or carbonate-containing compounds. Details regarding these materials are described below.
- the second material may be present in a cement and/or concrete composition with a particular amount.
- a weight percentage of the second material within the cement and/or concrete composition is greater than or equal to 10 %wt, greater than or equal to 15 %wt, greater than or equal to 20 %wt, greater than or equal to 25 %wt, greater than or equal to 30 %wt, greater than or equal to 35 %wt, greater than or equal to 40 %wt, or greater than or equal to 50 %wt.
- the weight percentage of the second material within the cement and/or concrete composition is less than or equal to 50 %wt, less than or equal to 40 %wt, less than or equal to 35 %wt, less than or equal to 30 %wt, less than or equal to 25 %wt, less than or equal to 20 %wt, less than or equal to 15 %wt, or less than or equal to 10 %wt. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 10 %wt and less than or equal to 50 %wt). Other ranges are possible.
- the remaining percentage can be another material (e.g., a first material, a third material) as described elsewhere herein.
- the second material comprises waste glass.
- Waste glass may comprise discarded glass from other processes (e.g., recycled glass from consumer outputs, disposed of glass from industrial and/or construction sites).
- waste glass is an amorphous material comprising silica (SiCh), calcium carbonate (CaCCh), and/or sodium carbonate (TsfeCCh).
- waste glass is an amorphous material further comprising aluminum oxide, quicklime (CaO), magnesia (MgO), potassium oxide (K2O), and/or sodium oxide (Na2O).
- waste glass comprises greater than or equal to 3%, greater than or equal to 6%, greater than or equal to 9%, greater than or equal to 12%, greater than or equal to 15%, greater than or equal to 18%, greater than or equal to 21%, greater than or equal to 24%, greater than or equal to 27%, or greater than or equal to 30% of the second material or of the cement and/or concrete composition. In some embodiments, waste glass comprises less than or equal to 30%, less than or equal to 27%, less than or equal to 24%, less than or equal to 21%, less than or equal to 18%, less than or equal to 15%, less than or equal to 12%, less than or equal to 9%, less than or equal to 6%, or less than or equal to 3%. Combinations of the above-referenced ranges are also possible. Other ranges are possible.
- the second material comprises a carbonate-containing compound.
- the carbonate-containing compound comprises calcium carbonate (CaCOs), sodium carbonate (NazCO,), and/or potassium carbonate (K2CO3).
- the calcium-containing compound comprises magnesium carbonate (MgCCh).
- Cement and/or concrete compositions may also comprise a third material.
- the third material may alter the pore size of other materials in the mixture (e.g., the pore size of the first material, the pore size of the second material). In embodiments, in which the second material is not present, it should be understood that the composition may include the first material and third material but not the second material as described herein.
- the third material may also improve the overall compressive strength of the cement composition and/or the resulting concrete and may also reduce water loss (and/or shrinking as a result of water loss) of the cement composition and/or the resulting concrete.
- the third material may comprise a variety of material.
- the third material comprises a metal oxide, such as a transition metal oxide.
- the metal oxide comprises titanium dioxide (TiCh). Additional non-limiting examples of metal oxides include zirconium oxide, hafnium oxide, zinc oxide, and/or iron oxide. Other metal oxides are possible as this disclosure is not so limited.
- the metal oxide can be present within a cement composition or concrete admixture in an amount of greater than or equal to 10 wt%, greater than or equal to 20 wt%, greater than or equal to 30 wt%, greater than or equal to 40 wt%, or greater than or equal to 50 wt% and/or less than or equal to 50 wt%, less than or equal to 40 wt%, less than or equal to 30 wt%, less than or equal to 20 wt%, or less than or equal to 10 wt%. Combinations of the foregoing ranges are possible. Of course, other ranges are possible as this disclosure is not so limited.
- the third material may be present in a cement and/or concrete composition at a particular amount.
- a weight percentage of the third material within the cement and/or concrete composition is greater than or equal to 0.1 %wt, greater than or equal to 0.5 %wt, greater than or equal to 1 %wt, greater than or equal to 2 %wt, greater than or equal to 3 %wt, greater than or equal to 4 %wt, greater than or equal to 5 %wt, or greater than or equal to 10 %wt.
- the weight percentage of the third material within the cement and/or concrete composition is less than or equal to 10 %wt, less than or equal to 5 %wt, less than or equal to 4 %wt, less than or equal to 3 %wt, less than or equal to 2 %wt, less than or equal to 1 %wt, less than or equal to 0.5 %wt, or less than or equal to 0.1 %wt. Combinations of the abovereferenced ranges are also possible (e.g., greater than or equal to 0.1 %wt and less than or equal to 10 %wt). Other ranges are possible.
- the remaining percentage may be another material (e.g., a first material, a second material) as described elsewhere herein.
- the third material comprises titanium dioxide.
- titanium dioxide is crystalline and may promote the uptake of carbon dioxide.
- the diameter (e.g., the average diameter) of the titanium dioxide particles may be greater than or equal to 0.5 nm, greater than or equal to 1 nm, greater than or equal to 25 nm, greater than or equal to 50 nm, greater than or equal to 100 nm, greater than or equal to 250 nm, greater than or equal to 500 nm, greater than or equal to 1 pm, greater than or equal to 25 pm, greater than or equal to 100 pm, greater than or equal to 250 pm, or greater than or equal to 500 pm.
- the diameter of the titanium dioxide particles is less than or equal to 500 pm, less than or equal to 250 pm, less than or equal to 100 pm, less than or equal to 25 pm, less than or equal to 1 pm, less than or equal to 500 nm, less than or equal to 250 nm, less than or equal to 100 nm, less than or equal to 50 nm, less than or equal to 25 nm, less than or equal to 1 nm, or less than or equal to 0.5 nm. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0.5 nm and less than or equal to 500 pm). Other ranges are possible.
- the first material, the second material, and/or the third material may be present within a cement composition (or some other mixture of these materials) each as a plurality of particles.
- a mixture e.g., an admixture
- a cement composition comprises a (first) plurality of particles comprising a first material (e.g., a zeolite, a pozzolanic material), a (second) plurality of particles comprising a second material (e.g., a carbonate compound), and a (third) plurality of particles comprising a third material.
- a cement composition comprises a (first) plurality of particles comprising a first material, optionally a (second) plurality of particles comprising the second material, and a (third) plurality of particles comprising titanium oxide.
- first first plurality of particles comprising a first material
- second second plurality of particles comprising the second material
- third third plurality of particles comprising titanium oxide.
- a plurality of particles e.g., a first plurality of particles, a second plurality of particles
- an average particle size (e.g., diameter) is less than or equal to 1000 pm, less than or equal to 750 pm, less than or equal to 500 pm, less than or equal to 250 pm, less than or equal to 100 pm, less than or equal to 50 pm, less than or equal to 20 pm, less than or equal to 10 pm, or less than or equal to 1 pm. In some embodiments, an average particle size is greater than or equal to 1 pm, greater than or equal to 20 pm, greater than or equal to 50 pm, greater than or equal to 100 pm, greater than or equal to 250 pm, greater than or equal to 500 pm, greater than or equal to 750 pm, or greater than or equal to 1,000 pm. Combinations of the above-reference ranges are also possible (e.g., greater than or equal to 1 pm and less than or equal to 1,000 pm). Other ranges are possible.
- any one of the first, the second, and/or the third material may be obtained from conventional mining processes or may be the waste of conventional mining processes.
- FIG. 11 illustrates a process of gathering materials to packaging.
- the cement compositions can comprise a mixture of the first material(s) (and mixtures thereof), the second material, and/or the third material.
- cement is used in production of concrete, and concrete compositions may comprise the same or different composition as the cement composition used to prepare the concrete composition. Accordingly, descriptions regarding cement compositions as described herein may also be applicable to the resulting concrete.
- mixtures of first material, the second material, and/or the third material form admixtures that can be added to existing cement and/or concrete compositions.
- a mixture comprises a first material (e.g., a pozzolanic material) and a third material (e.g., titanium dioxide) and does not comprise a second material.
- a mixture comprises the second and third material, and does not comprise the first material.
- the mixture comprises the first material and, optionally, the second material and/or the third material. In some such embodiments, this mixture can be an admixture that can be added to existing cement and/or concrete mixtures.
- the admixture comprises solid particles, rather than a liquid, which may aid handling of the concrete admixture or the resulting concrete. In some such embodiments, the admixture enhances the ability of the existing cement and/or concrete composition to absorb carbon dioxide.
- a liquid which may aid handling of the concrete admixture or the resulting concrete.
- the admixture enhances the ability of the existing cement and/or concrete composition to absorb carbon dioxide.
- the cement compositions comprising a first material, a second material, and/or a third material may be used to form concrete (e.g., concrete compositions, concrete mixtures).
- concrete e.g., concrete compositions, concrete mixtures.
- concrete-forming materials include pastes that can bind cement and/or concrete materials together to form solid concrete (e.g., after curing the concrete mixture).
- concrete e.g., a concrete composition, a concrete mixture
- first material, the second material, and/or the third material is greater than or equal to 0.01 wt%, greater than or equal to 0.05 wt%, greater than or equal to 0.1 wt%, greater than or equal to 1 wt%, greater than or equal to 2 wt%, greater than or equal to 3 wt%, greater than or equal to 5 wt%, greater than or equal to 10 wt%, or greater than or equal to 15 wt% of the total weight of the concrete composition.
- the first material, the second material and/or the third material is less than or equal to 15 wt%, less than or equal to 10 wt%, less than or equal to 5 wt%, less than or equal to 3 wt%, less than or equal to 2 wt%, less than or equal to 1 wt%, less than or equal to 0.1 wt%, less than or equal to 0.05 wt%, or less than or equal to 0.01 wt% of the total weight of the concrete composition. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0.01 wt% and less than or equal to 15 wt%). Other ranges are possible.
- the remaining balance for the total weight of the concrete composition may be another of the first material, the second material, and/or the third material, and/or one or more concrete-forming materials (e.g., concrete aggregates, paste, water, sand).
- the cement composition (e.g., comprising a first material, a second material, and/or a third material) may comprise particles of a particular particle size.
- an average particle dimension e.g., diameter
- an average particle dimension is less than or equal to 1000 pm, less than or equal to 750 pm, less than or equal to 500 pm, less than or equal to 250 pm, less than or equal to 100 pm, less than or equal to 50 pm, less than or equal to 20 pm, less than or equal to 10 pm, or less than or equal to 1 pm.
- an average particle dimension is greater than or equal to 1 pm, greater than or equal to 20 pm, greater than or equal to 50 pm, greater than or equal to 100 pm, greater than or equal to 250 pm, greater than or equal to 500 pm, greater than or equal to 750 pm, or greater than or equal to 1,000 pm. Combinations of the abovereference ranges are also possible (e.g., greater than or equal to 1 pm and less than or equal to 1,000 pm). Other ranges are possible.
- the combination of materials can adsorb carbon dioxide. While carbon dioxide is, overall, a non-polar molecular, the two double-bonded oxygens in carbon oxide provides positive character to the carbon of the carbon dioxide. It is believed that a negatively charged (and/or partially negatively charged) species within the materials (e.g., the first material, the second material, and/or the third material), such as oxygen atoms within a zeolite and/or pozzolanic material may attract the positive character of the carbon of carbon dioxide, and may, in some embodiments, facilitate further reactions of the carbon dioxide, such as mineralization into a carbonate-containing compound. FIG. 9 is a schematic representation of such a process.
- FIG. l is a schematic illustration showing the gathering and processing of materials (e.g., a first material, a second material, a third material).
- materials e.g., a first material, a second material, a third material.
- the materials may be mined and further micronized such that the particle size of the materials is at or below a micron scale.
- the cement composition may then be mixed and transported, for example, to an end user.
- the end user may then construct materials from the cement, where the resulting cement and/or concrete can capture carbon dioxide from the ambient environment and mineralize the carbon dioxide directly into the concrete.
- the concrete may improve in physical properties, such as mechanical strength as it captures and mineralizes carbon dioxide from the surrounding environment.
- the method comprises incorporating (e.g., mixing) the first material and the second material.
- the first material and/or the second material may each comprise a plurality of particles (e.g., a plurality of particles of the first material, a plurality of particles of the second material) and incorporating may include grinding and mixing of the particles to below a certain particle dimension (e.g., less than or equal to 1000 microns).
- a variety of grinding techniques may be used. Non-limiting examples of grinding techniques including mortar and pestle and/or ball milling (including planetary ball milling).
- grinding a material e.g., a first material, a second material
- grinding reduces the particle size (e.g., below 100 pm in average particle size).
- reducing the particle size of the material(s) increases the surface area of the material(s) so that the material(s) have more exposure to carbon dioxide.
- grinding may increase the porosity of the material.
- grinding may heat the material (e.g., by at least 1 °C, by at least 5 °C, by at least 10 °C).
- a high energy ball mill/grinder reduces the particle size the first material, the second material, and/or the third material to less than or equal to 100 microns in average particle dimension.
- the adsorption surface area of the materials may be increased, increasing the ability to capture carbon dioxide.
- high energy ball milling/grinding may result in local hot spots while grinding which may make amorphous (e.g., from a crystalline or crystalline state) at least portions of the first material, the second material and/or the third material, which may increase the absorption and/or reactivity towards carbon dioxide.
- the method comprises reducing in size the first material, the second material, and/or the third material to particles having an average diameter of less than or equal to 100 microns.
- the size reduction can be achieved via grinding, crushing, granulating, pulverizing, and/or other methods capable of reducing clinker or other cementitious products into a fine powder.
- the method comprises adding the mixture of the first material, the second material, and the third material to a concrete-forming composition to form a concrete mixture.
- the concrete mixture may further comprise concrete aggregates, and/or OPC.
- the concrete mixture is free of portland cement or OPC.
- a concrete composition comprises a cement composition as described elsewhere herein and further comprises one or more concrete-forming materials (e.g., concrete aggregates, paste, water).
- the method further comprises curing the concrete mixture by hydrating the mixture with water.
- the mixture is hydrated, calcium-silicate hydrate forms within the mixture which may result in an increase in strength.
- the method comprises capturing carbon dioxide with the mixture. Atmospheric carbon dioxide may be adsorbed, absorbed, trapped, and/or captured into the cured concrete mixture.
- the cement composition can capture carbon dioxide a particular amount of carbon dioxide.
- the cement composition before capturing in an amount of carbon dioxide may be 100 kg, and, after capturing carbon dioxide, the composition may weight 102 kg, such that 2 kg of carbon dioxide was captured (i.e., 2 wt% relative to the mass of the composition prior to capturing carbon dioxide).
- the composition captures greater than or equal to 0.1 wt%, greater than or equal to 0.2 wt%, greater than or equal to 0.3 wt%, greater than or equal to 0.5 wt%, greater than or equal to 1 wt%, greater than or equal to 2 wt%, greater than or equal to 3 wt%, greater than or equal to 4 wt%, or greater than or equal to 5 wt%, relative to the composition before it captured any carbon dioxide.
- the composition captures less than or equal to 5 wt%, less than or equal to 4 wt%, less than or equal to 3 wt%, less than or equal to 2 wt%, less than or equal to 1 wt%, less than or equal to 0.5 wt%, less than or equal to 0.3 wt%, less than or equal to 0.2 wt%, or less than or equal to 0.1 wt%. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0.1 wt% and less than or equal to 5 wt%). Other ranges are possible.
- the compositions can capture a particular amount of carbon dioxide.
- the compositions are capable of capturing an amount of carbon dioxide greater than or equal to 0.1 wt%, greater than or equal to 1 wt%, greater than or equal to 2 wt%, greater than or equal to 3 wt%, greater than or equal to 4 wt%, or greater than or equal to 5 wt% relative to the mass of the composition prior to capturing carbon dioxide.
- the compositions are capable of capturing an amount of carbon dioxide less than or equal to 5 wt%, less than or equal to 4 wt%, less than or equal to 3 wt%, less than or equal to 2 wt%, less than or equal to 1 wt%, or less than or equal to 0.1 wt% relative to the mass of the composition prior to capturing carbon dioxide. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 1 wt% and less or equal to 5 wt% relative to the mass of the composition prior to capture carbon dioxide). Other ranges are possible.
- the concrete may react with carbon dioxide (e.g., the carbon dioxide reacts with at least one component of the composition).
- the carbon dioxide may absorb and/or adsorb onto and/or into at least one component of the mixture (e.g., within a pore of the first material of the mixture).
- water is added to the mixture to facilitate and/or promote curing.
- the method comprises mixing the mixture with portland cement (e.g., OPC) and/or other cementitious materials.
- portland cement e.g., OPC
- the method may exclude portland cement while including other cementitious materials and/or concrete-forming materials (e.g., concrete aggregates, paste, water).
- the mixture comprises microorganisms that help promote and/or catalyze the mineralization of carbon dioxide (e.g., within the pores of a first material of the cement or concrete mixture).
- microorganisms in the mixture comprise bacteria of that Bacillus strain which may promote and/or accelerate the mineralization process of carbon dioxide (e.g., within the pores or a first material).
- the present invention may capture carbon dioxide directly from air within the concrete composition.
- One application of some embodiments described herein is to provide users with a concrete mixture that improves compressive strength while actively attracting, capturing, and/or mineralizing atmospheric carbon dioxide.
- Various embodiments may provide users with a process that provides negative emission technology with pozzolanic properties that may replace at least 5%, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, or at least 60% of cement (e.g., portland cement) in the concrete production process.
- cement e.g., portland cement
- a typical concrete may require 100 kg of conventional (e.g., portland) cement, and the inventive cement compositions described herein may allow at least 60% of this conventional cement to be replaced.
- the concrete process may also comprise a gathering process, a mixing process, and a distribution process. Many of these components allow for the process to create a concrete composition that can reduce the amount of carbon dioxide from the surrounding environment.
- the present technology may be a negative emission technology with pozzolanic properties that replaces a portion of traditional OPC cement to produce a concrete that can capture and store carbon dioxide emissions.
- Waste glass and zeolite can be used due to their natural pozzolanic properties that aid in formation of concrete. Waste glass also helps mitigate the additional water for curing, as well as balance out the densities in the concrete caused by the other materials.
- the waste glass can be augmented or replaced with a carbonate-containing compound, such as calcium carbonate.
- a carbonate-containing compound such as calcium carbonate.
- the calcium carbonate material may aid in the increase of strength of the cured cement mixture over time.
- the concrete mixture can be created in many proportions and main materials can be slightly altered as desired by the user.
- the mixing process then takes the gathered materials and combines each one to create a concrete mixture as shown in FIG. 2. Once all the raw materials are properly ground up, each may be added to a mixture that includes a ready -mix concrete solution.
- the mixture process uses 69-87% zeolite and basalt, 12-30% waste glass and/or calcium carbonate, and 1-3% titanium dioxide.
- the basalt can be augmented or replaced by an amount of zeolite used within the composition.
- some basalt levels may improve the rate of carbon dioxide mineralization from the industry standard of hundreds to thousands of years to just a few years, greatly increasing the carbon dioxide capture efficacy of the concrete composition.
- microorganisms e.g., bacteria
- the bacillus bacteria may act as a catalyst of mineralizing the carbon dioxide into the concrete structure (e.g., as a carbonate), forming, in some cases, a precipitated calcium carbonate sediment.
- the cement and resulting concrete compositions can be used to fabricate carbon- capturing objects.
- the cement and/or resulting concrete compositions are suited for capturing carbon dioxide from the ambient environment or from the atmosphere.
- the compositions can be formed into a variety of shapes and sizes suitable for a variety of purposes, including construction materials, buildings, sidewalks, roads, bridges, and the like. In some cases, the compositions can be formed into artistic articles such as monuments and/or statues.
- the cement compositions may at least partially replace portland cement in concrete mixtures, shown in FIG. 10; however, in other embodiments, the cement compositions can be further mixed with portland cement.
- the inventive cement compositions described herein or concrete comprising the inventive cement compositions described herein may be “self- healing,” in that physical damage (e.g., cracks, breaks, tears) in the material may repair itself spontaneously (i.e., without the input of more than ambient surroundings).
- physical damage e.g., cracks, breaks, tears
- concrete comprising an inventive cement composition has had damage done to its surface, forming a crack.
- carbon dioxide is captured (i.e., by the inventive cement composition), it may mineralize within the cement forming, e.g., calcium carbonate filaments within the crack that may reduce the structural impact of the crack on the concrete as a whole.
- the following example describes a cement composition that can sequester environmental carbon dioxide into calcium carbonate.
- Sample 1 and Sample 3 represent two existing compositions, acting as comparisons and comprising commercially available cementitious materials. Specifically, Sample 1 and Sample 3 comprise Buzzi -Greencastle T1(M4476) and a composition according to the present disclosure comprising 86.5 wt% zeolites, 13 wt% waste glass, and 0.5 wt% TiCh. Sample 2 and Sample 4 represent two carbon-capturing cement compositions are described elsewhere herein. Sample 2 and Sample 4 have been incorporated into concrete composition at amounts of 20 wt% and 5 wt%, respectively.
- the compressive strength of each sample was tested after 4 days, 7 days, and 28 days. After 4 days, Sample 2 had a higher compressive strength than both comparison samples, while Sample 4 had a higher compressive strength than Sample 1 and 97% of the compressive strength of Sample 3. After 7 days, Sample 2 had a higher compressive strength than Sample 1 and 89% of the compressive strength of Sample 3, while Sample 4 had a higher compressive strength than Sample 1 and 96.9% of the compressive strength of Sample 3. After 28 days, Sample 2 had a higher compressive strength than both control samples, while Sample 4 had a higher compressive strength than Sample 1 and 98% of the compressive strength of Sample 3. Therefore, the construction material described herein has comparable compressive strength and/or greater compressive strength than the control samples described above. As a result, the articles described herein may be considered as a suitable replacement for certain existing methods such as OPC.
- the rate of carbon dioxide uptake was also measured via gas chromatography.
- a sample of the composition (labeled as “136881.1” in FIG. 4) was spiked with increasing amounts of carbon dioxide, but a CO2 peak was not observed as shown in FIG. 4, indicating the sample was absorbing carbon dioxide.
- a control concrete sample comprised of Buzzi -Greencastle T1 was also spiked with carbon dioxide, and the spectrum did show a carbon dioxide peak indicating less absorption of carbon dioxide.
- the rate of carbon dioxide uptake is observed to be higher for inventive compositions relative to the commercially available sample.
- the increased mass of calcium carbonate was also measured to determine the degree of sequestration that has occurred. Without wishing to be bound by any particular theory, it is believed the captured CO2 chemically reacts with calcium hydroxide to form calcium carbonate. Powder samples of the construction material and control samples were treated with 18 mL of 0.5 N HC1 and diluted with 100 mL H2O. A portion of the HC1 is consumed when it reacts with the calcium carbonate in each sample. After each sample was stirred for at least one hour, each sample was back-titrated with 1 N NaOH to determine the amount of HC1 that was consumed by the sample. It was then possible to determine the total carbonate content of the sample to examiner carbon dioxide mineralization, and this procedure was verified on a sample of pure calcium carbonate. The inventive cement compositions had 1.19x more CaCCh content than would have been predicted based on the pure calcium carbonate comparison sample
- X-ray diffraction data shown in FIG. 5 depicts the crystal structure of a test sample of the inventive cement compositions and a control sample comprising zeolite. An increase in the area of the calcite and dolomite peaks were observed in the test sample relative to the control sample.
- the following example compares slag without a concrete admixture to two samples including a concrete admixture.
- the carbon-capturing ability of mortar formed without the addition of a concrete admixture was compared to the carbon-capturing ability of two formulations that included a concrete admixture capable of enhancing carbon dioxide uptake by the same mortar.
- a reference to “A and/or B,” when used in conjunction with open-ended language such as “comprising” can refer, in one embodiment, to A without B (optionally including elements other than B); in another embodiment, to B without A (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.
- the phrase “at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements.
- This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase “at least one” refers, whether related or unrelated to those elements specifically identified.
- “at least one of A and B” can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.
- embodiments may be embodied as a method, of which various examples have been described.
- the acts performed as part of the methods may be ordered in any suitable way. Accordingly, embodiments may be constructed in which acts are performed in an order different than illustrated, which may include different (e.g., more or less) acts than those that are described, and/or that may involve performing some acts simultaneously, even though the acts are shown as being performed sequentially in the embodiments specifically described above.
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Abstract
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Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US18/841,322 US20250161874A1 (en) | 2022-02-25 | 2023-02-24 | Carbon dioxide-capturing cement compositions and related methods |
| EP23760702.3A EP4482805A4 (en) | 2022-02-25 | 2023-02-24 | Carbon dioxide-trapping cement compositions and associated processes |
| MX2024010404A MX2024010404A (en) | 2022-02-25 | 2024-08-23 | Carbon dioxide-capturing cement compositions and related methods |
| US18/939,355 US20250269325A1 (en) | 2022-02-25 | 2024-11-06 | Carbon dioxide-capturing cement compositions and related methods |
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| US17/894,990 US20230271134A1 (en) | 2022-02-25 | 2022-08-24 | Carbon dioxide-capturing cement compositions and related methods |
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| US17/934,667 US11931693B2 (en) | 2022-02-25 | 2022-09-23 | Carbon dioxide-capturing cement compositions and related methods |
| US17/934,667 | 2022-09-23 |
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| US18/939,355 Continuation-In-Part US20250269325A1 (en) | 2022-02-25 | 2024-11-06 | Carbon dioxide-capturing cement compositions and related methods |
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| EP4251586A1 (en) | 2021-12-23 | 2023-10-04 | Graymont Western Canada Inc. | Lime-based cement extender compositions, and associated systems and methods |
| US11986769B1 (en) | 2022-12-12 | 2024-05-21 | Greencraft Llc | Carbon mineralization using hyaloclastite, volcanic ash and pumice mineral and an alkaline solution, cement and concrete using same and method of making and using same |
| AU2023409369B2 (en) * | 2022-12-20 | 2025-08-14 | Graymont Western Canada Inc. | Systems and methods for storing and mineralizing carbon dioxide with lime |
| WO2026032349A1 (en) * | 2024-08-08 | 2026-02-12 | Formwork Io Limited | Building materials for atmospheric carbon-dioxide sequestration and capture and production methods thereof |
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| US20210221694A1 (en) * | 2020-01-17 | 2021-07-22 | Leonard Tim Sperry, III | Processes for manufacturing a material |
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| US4065544A (en) * | 1970-05-11 | 1977-12-27 | Union Carbide Corporation | Finely divided metal oxides and sintered objects therefrom |
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| EP2331929B1 (en) * | 2008-09-12 | 2018-11-14 | MTS Systems Corporation | Autopilot system for use in a wind tunnel |
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| NL2002282C2 (en) * | 2008-12-03 | 2010-06-07 | A & G Holding | Pozzolanic binder composition. |
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| US20110277670A1 (en) * | 2010-05-14 | 2011-11-17 | Kyle Self | Systems and methods for processing co2 |
| CA2821776C (en) | 2010-12-15 | 2016-08-23 | Carboncure Technologies Inc. | Carbon dioxide sequestration in concrete articles |
| US10273187B2 (en) * | 2013-03-24 | 2019-04-30 | Trevor Cyril Waters | Metal oxide activated cement |
| KR101575791B1 (en) * | 2013-06-21 | 2015-12-09 | 서울특별시 | Soil Concrete Composition |
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| EP4482805A4 (en) | 2026-04-01 |
| US20230271882A1 (en) | 2023-08-31 |
| US20240261729A1 (en) | 2024-08-08 |
| CL2024002527A1 (en) | 2025-05-09 |
| MX2024010404A (en) | 2025-02-10 |
| EP4482805A1 (en) | 2025-01-01 |
| US20230271135A1 (en) | 2023-08-31 |
| US11931693B2 (en) | 2024-03-19 |
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