Source: http://www.google.com/patents/US20100111810?dq=7,346,545
Timestamp: 2016-10-28 01:38:06
Document Index: 124040632

Matched Legal Cases: ['Application No. 61', 'Application No. 61', 'Application No. 61', 'in fine', 'Application No. 61', 'Application No. 61']

Patent US20100111810 - Non-cementitious compositions comprising co2 sequestering additives - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsNon-cementitious CO2 sequestering compositions are provided. The compositions of the invention include a CO2 sequestering additive, e.g., a CO2 sequestering carbonate composition. Additional aspects of the invention include methods of making and using the non-cementitious CO2 sequestering compositio...http://www.google.com/patents/US20100111810?utm_source=gb-gplus-sharePatent US20100111810 - Non-cementitious compositions comprising co2 sequestering additivesAdvanced Patent SearchTry the new Google Patents, with machine-classified Google Scholar results, and Japanese and South Korean patents.Publication numberUS20100111810 A1Publication typeApplicationApplication numberUS 12/609,491Publication dateMay 6, 2010Filing dateOct 30, 2009Priority dateOct 31, 2008Also published asCA2694980A1, CA2694980C, CN101925391A, EP2203241A1, EP2203241A4, EP2620207A2, EP2620207A3, US7829053, US20100239487, US20110240916, WO2010051458A1Publication number12609491, 609491, US 2010/0111810 A1, US 2010/111810 A1, US 20100111810 A1, US 20100111810A1, US 2010111810 A1, US 2010111810A1, US-A1-20100111810, US-A1-2010111810, US2010/0111810A1, US2010/111810A1, US20100111810 A1, US20100111810A1, US2010111810 A1, US2010111810A1InventorsBrent Constantz, Andrew Youngs, Joshua PattersonOriginal AssigneeBrent Constantz, Andrew Youngs, Joshua PattersonExport CitationBiBTeX, EndNote, RefManPatent Citations (98), Referenced by (48), Classifications (21), Legal Events (3) External Links: USPTO, USPTO Assignment, EspacenetNon-cementitious compositions comprising co2 sequestering additives
US 20100111810 A1Abstract
1. A non-cementitious composition comprising a CO2 sequestering additive, wherein the CO2 sequestering additive comprises carbon that was released in the form of CO2 from the combustion of fuel.
2. The non-cementitious composition according to claim 1, wherein the CO2 sequestering additive is a carbonate compound composition.
3. The non-cementitious composition according to claim 2, wherein the carbonate compound composition comprises a precipitate from an alkaline-earth metal-containing water.
4. The non-cementitious composition according to claim 3, wherein the alkaline-earth metal-containing water comprises CO2 derived from an industrial waste stream.
5. The non-cementitious composition of claim 1, wherein the composition is a paper product, polymeric product, lubricant, adhesive, rubber, chalk, asphalt product, paint, abrasive for paint removal, personal care product, ingestible product, animal ingestible product, agricultural product or environmental remediation product.
6-27. (canceled)
28. A method of producing a non-cementitious composition, the method comprising:
obtaining a CO2 sequestering additive, wherein the CO2 sequestering additive comprises carbon that was released in the form of CO2 from the combustion of fuel; and producing a non-cementitious composition comprising the CO2 sequestering additive. 29. The method according to claim 28, wherein the CO2 sequestering additive is a carbonate compound composition.
30. The method according to claim 29, wherein the carbonate compound composition comprises a precipitate from an alkaline-earth metal-containing water.
31. The method according to claim 30, wherein the alkaline-earth metal containing water comprises CO2 derived from an industrial waste stream.
32. The method of claim 28, wherein the non-cementitious composition is a paper product, polymeric product, lubricant, adhesive, rubber, chalk, asphalt product, paint, abrasive for paint removal, personal care product, ingestible product, animal ingestible product, agricultural product, soil amendment product, pesticide or environmental remediation product.
33-54. (canceled)
55. A method of sequestering carbon dioxide, the method comprising:
precipitating a CO2 sequestering carbonate compound composition from an alkaline-earth-metal-containing water, wherein the carbonate compound composition comprises carbon that was released in the form of CO2 from the combustion of fuel; and producing a CO2 sequestering additive comprising the carbonate compound composition; and producing a non-cementitious composition comprising the CO2 sequestering additive. 56. The method according to claim 55, wherein the alkaline-earth-metal-containing water is contacted to an industrial waste stream prior to the precipitating step.
[0001] This application claims the benefit of: U.S. Provisional Application No. 61/110,495, titled “NON-CEMENTITIOUS COMPOSITIONS COMPRISING CO2 SEQUESTERING ADDITIVES,” filed 31 Oct. 2008; U.S. Provisional Application No. 61/149,949, titled “NON-CEMENTITIOUS COMPOSITIONS COMPRISING CO2 SEQUESTERING ADDITIVES,” filed 4 Feb. 2009; and U.S. Provisional Application No. 61/181,250, titled, “COMPOSITIONS AND METHODS USING SUBSTANCES WITH NEGATIVE DELTA13C VALUES,” filed 26 May 2009, which applications are incorporated herein by reference.
[0012] Certain ranges are presented herein with numerical values being preceded by the term “about.” The term “about” is used herein to provide literal support for the exact number that it precedes, as well as a number that is near to or approximately the number that the term precedes. In determining whether a number is near to or approximately a specifically recited number, the near or approximating unrecited number may be a number which, in the context in which it is presented, provides the substantial equivalent of the specifically recited number.
[0015] It is noted that, as used herein and in the appended claims, the singular forms “a,” “an,” and “the” include plural references unless the context clearly dictates otherwise. It is further noted that the claims may be drafted to exclude any optional element. As such, this statement is intended to serve as antecedent basis for use of such exclusive terminology as “solely,” “only” and the like in connection with the recitation of claim elements, or use of a “negative” limitation.
[0018] Non-cementitious CO2 sequestering compositions are provided by the invention. By “CO2 sequestering composition” is meant that the composition contains carbon derived from a fuel used by humans, e.g., carbon having a fossil fuel origin. For example, CO2 sequestering compositions according to aspects of the present invention contain carbon that was released in the form of CO2 from the combustion of fuel. In certain embodiments, the carbon sequestered in a CO2 sequestering composition is in the form of a carbonate compound. Therefore, in certain embodiments, CO2 sequestering compositions according to aspects of the subject invention contain carbonate compounds where at least part of the carbon in the carbonate compounds is derived from a fuel used by humans, e.g., a fossil fuel. As such, production of compositions of the invention results in the placement of CO2 into a storage stable form, e.g., a stable component of a non-cementitious composition. Production of the CO2 sequestering compositions of the invention thus results in the prevention of CO2 gas from entering the atmosphere. The compositions of the invention provide for storage of CO2 in a manner such that CO2 sequestered (i.e., fixed) in the composition does not become part of the atmosphere. Compositions of the invention keep their sequestered CO2 fixed for substantially the useful life the composition, if not longer, without significant, if any, release of the CO2 from the composition. As such, where the compositions are consumable compositions, the CO2 fixed therein remains fixed for the life of the consumable, if not longer.
[0019] CO2 sequestering compositions of the invention include compositions that contain carbonates and/or bicarbonates, which may be in combination with a divalent cation such as calcium and/or magnesium, or with a monovalent cation such as sodium. The carbonates and/or bicarbonates may be in solution, in solid form, or a combination of solution and solid form, e.g., a slurry. The carbonates and/or bicarbonates may contain carbon dioxide from a source of carbon dioxide; in some embodiments the carbon dioxide originates from the burning of fossil fuel, and thus some (e.g., at least 10, 50, 60, 70, 80, 90, 95%) or substantially all (e.g., at least 99, 99.5, or 99.9%) of the carbon in the carbonates and/or bicarbonates is of fossil fuel origin, i.e., of plant origin. As is known, carbon of plant origin has a different ratio of stable isotopes (13C and 12C) than carbon of inorganic origin, and thus the carbon in the carbonates and/or bicarbonates, in some embodiments, has a δ13C of less than, e.g., −10%, or less than −15%, or less than −20%, or less than −35%, or less than −30%, or less than −35% as described in further detail herein below.
[0022] The carbonate compounds of the CO2 sequestering additives may be metastable carbonate compounds that are precipitated from a water, such as a salt-water, as described in greater detail below. The carbonate compound compositions of the invention include precipitated crystalline and/or amorphous carbonate compounds. Specific carbonate minerals of interest include, but are not limited to: calcium carbonate minerals, magnesium carbonate minerals and calcium magnesium carbonate minerals. Calcium carbonate minerals of interest include, but are not limited to: calcite (CaCO3), aragonite (CaCO3), vaterite (CaCO3), ikaite (CaCO3.6H2O), and amorphous calcium carbonate(CaCO3.nH2O). Magnesium carbonate minerals of interest include, but are not limited to: magnesite (MgCO3), barringtonite (MgCO3.2H2O), nesquehonite (MgCO3.3H2O), lanfordite (MgCO3.5H2O) and amorphous magnesium calcium carbonate (MgCO3.nH2O). Calcium magnesium carbonate minerals of interest include, but are not limited to dolomite (CaMgCO3), huntite (CaMg3(CO3)4) and sergeevite (Ca2Mg11(CO3)13.H2O). In certain embodiments, non-carbonate compounds like brucite (Mg(OH)2) may also form in combination with the minerals listed above. As indicated above, the compounds of the carbonate compound compositions are metastable carbonate compounds (and may include one or more metastable hydroxide compounds) that are more stable in saltwater than in freshwater, such that upon contact with fresh water of any pH they dissolve and re-precipitate into other fresh water stable compounds, e.g., minerals such as low-Mg calcite.
[0023] The CO2 sequestering additives of the invention are derived from, e.g., precipitated from, a water (as described in greater detail below). As the CO2 sequestering products are precipitated from a water, they may include one or more additives that are present in the water from which they are derived. For example, where the water is salt water, the CO2 sequestering products may include one or more compounds found in the salt water source. These compounds may be used to identify the solid precipitations of the compositions that come from the salt water source, where these identifying components and the amounts thereof are collectively referred to herein as a saltwater source identifier. For example, if the saltwater source is sea water, identifying compounds that may be present in the precipitated solids of the compositions include, but are not limited to: chloride, sodium, sulfur, potassium, bromide, silicon, strontium and the like. Any such source-identifying or “marker” elements would generally be present in small amounts, e.g., in amounts of 20,000 ppm or less, such as amounts of 2000 ppm or less. In certain embodiments, the “marker” compound is strontium, which may be present in the precipitated incorporated into the aragonite lattice, and make up 10,000 ppm or less, ranging in certain embodiments from 3 to 10,000 ppm, such as from 5 to 5000 ppm, including 5 to 1000 ppm, e.g., 5 to 500 ppm, including 5 to 100 ppm. Another “marker” compound of interest is magnesium, which may be present in amounts of up to 20% mole substitution for calcium in carbonate compounds. The saltwater source identifier of the compositions may vary depending on the particular saltwater source employed to produce the saltwater-derived carbonate composition. Also of interest are isotopic markers that identify the water source.
[0025] The compositions of the invention may be viewed as low-carbon footprint compositions. Low-carbon footprint compositions have a reduced carbon footprint as compared to corresponding compositions that lack the CO2 sequestering additive (where “corresponding” herein means the identical composition but for the presence of the CO2 sequestering additive of the invention). Using any convenient carbon footprint calculator, the magnitude of carbon footprint reduction of the compositions of the invention as compared to corresponding compositions that lack the CO2 sequestering additive may be 5% or more, such as 10% or more, including 25%, 50%, 75% or even 100% or more. In certain embodiments, the low-carbon footprint compositions of the invention are carbon neutral, in that they have substantially no, if any, calculated carbon footprint, e.g., as determined using any convenient carbon footprint calculator that is relevant for a particular composition of interest. Carbon neutral compositions of the invention include those compositions that exhibit a carbon footprint of 50 lbs CO2/cu yd material or less, such as 10 lbs CO2/cu yd material or less, including 5 lbs CO2/cu yd material or less, where in certain embodiments the carbon neutral compositions have 0 or negative lbs CO2/cu yd material, such as negative 1 or more, e.g., negative 3 or more lbs CO2/cu yd material. In some instances, the low carbon footprint compositions have a significantly negative carbon footprint, e.g., −100 or more lbs CO2/cu yd or less.
[0026] In certain embodiments compositions of the invention will contain carbon from fossil fuel; because of its fossil fuel origin, the carbon isotopic fractionation (δ13C) value of such compositions will be different from that of compositions containing inorganic carbon, e.g., limestone. As is known in the art, the plants from which fossil fuels are derived preferentially utilize 12C over 13C, thus fractionating the carbon isotopes so that the value of their ratio differs from that in the atmosphere in general; this value, when compared to a standard value (PeeDee Belemnite, or PDB, standard), is termed the carbon isotopic fractionation (δ13C) value. δ13C values for coal are generally in the range −30 to −20% and δ13C values for methane may be as low as −20% to −40% or even −40% to −80%. δ13C values for atmospheric CO2 are −10% to −7%, for limestone+3% to −3%, and for marine bicarbonate, 0%. Even if the non-cementitious material contains some natural limestone, or other source of C with a higher (less negative) δ13C value than fossil fuel, its δ13C value generally will still be negative and less than (more negative than) values for limestone or atmospheric CO2. In some embodiments, the non-cementitious material or product includes a CO2-sequestering additive comprising carbonates, bicarbonates, or a combination thereof, in which the carbonates, bicarbonates, or a combination thereof have a carbon isotopic fractionation (δ13C) value less than −5.00%. Compositions of the invention thus includes a non-cementitious material or product with a δ13C less than −10%, such as less than −12%, −14%, −16%, −18%, −20%, −22%, −24%, −26%, −28%, or less than −30%. In some embodiments the invention provides a non-cementitious material or product with a δ13C less than −10%. In some embodiments the invention provides a non-cementitious material or product with a δ13C less than −14%. In some embodiments the invention provides a non-cementitious material or product with a δ13C less than −18%. In some embodiments the invention provides a non-cementitious material or product with a δ13C less than −20%. In some embodiments the invention provides a non-cementitious material or product with a δ13C less than −24%. In some embodiments the invention provides a non-cementitious material or product with a δ13C less than −28%. In some embodiments the invention provides a non-cementitious material or product with a δ13C less than −30%. In some embodiments the invention provides a non-cementitious material or product with a δ13C less than −32%. In some embodiments the invention provides a non-cementitious material or product with a δ13C less than −34%. Such a non-cementitious materials or products may be carbonate-containing materials or products, as described above, e.g., a non-cementitious material or product with that contains at least 10, 20, 30, 40, 50, 60, 70, 80, or 90% carbonate, e.g., at least 50% carbonate w/w.
[0027] The relative carbon isotope composition (δ13C) value with units of % (per mil) is a measure of the ratio of the concentration of two stable isotopes of carbon, namely 12C and 13C, relative to a standard of fossilized belemnite (the PDB standard).
[0000] δ13C %=[(13C/12Csample−13C/12CPDB standard)/(13C/12CPDB standard)]�1000
Relative carbon isotope composition (δ
13C) values for carbon sources of interest.
δ13C Range [‰]
δ13C Average value [‰]
[0031] One difference between the carbon isotopes is in their mass. Any mass-discerning technique sensitive enough to measure the amounts of carbon we have can be used to find ratios of the 13C to 12C isotope concentrations. Mass spectrometry is commonly used to find δ13C values. Commercially available are bench-top off-axis integrated-cavity output spectroscopy (off-axis ICOS) instruments that are able to determine δ13C values as well. These values are obtained by the differences in the energies in the carbon-oxygen double bonds made by the 12C and 13C isotopes in carbon dioxide. The δ13C value of a carbonate precipitate from a carbon sequestration process serves as a fingerprint for a CO2 gas source, as the value will vary from source to source, but in most carbon sequestration cases δ13C will generally be in a range of −9% to −35%.
[0033] Precipitation material, which comprises one or more synthetic carbonates derived from industrial CO2, reflects the relative carbon isotope composition (δ13C) of the fossil fuel (e.g., coal, oil, natural gas, or flue gas) from which the industrial CO2 (from combustion of the fossil fuel) was derived. The relative carbon isotope composition (δ13C) value with units of % (per mille) is a measure of the ratio of the concentration of two stable isotopes of carbon, namely 12C and 13C, relative to a standard of fossilized belemnite (the PDB standard).
[0034] As such, the δ13C value of the CO2 sequestering additive serves as a fingerprint for a CO2 gas source. The δ13C value may vary from source to source (i.e., fossil fuel source), but the δ13C value for composition of the invention generally, but not necessarily, ranges between −9% to −35%. In some embodiments, the δ13C value for the CO2 sequestering additive is between −1% and −50%, between −5% and −40%, between −5% and −35%, between −7% and −40%, between −7% and −35%, between −9% and −40%, or between −9% and −35%. In some embodiments, the δ13C value for the CO2 sequestering additive is less than (i.e., more negative than) −3%, −5%, −6%, −7%, −8%, −9%, −10%, −11%, −12%, −13%, −14%, −15%, −16%, −17%, −18%, −19%, −20%, −21%, −22%, −23%, −24%, −25%, −26%, −27%, −28%, −29%, −30%, −31%, −32%, −33%, −34%, −35%, −36%, −37%, −38%, −39%, −40%, −41%, −42%, −43%, −44%, or −45%, wherein the more negative the δ13C value, the more rich the synthetic carbonate-containing composition is in 12C. Any suitable method may be used for measuring the δ13C value, methods including, but no limited to, mass spectrometry or off-axis integrated-cavity output spectroscopy (off-axis ICOS).
[0036] The present invention includes novel formulations which incorporate the CO2 sequestering composition into paper products. The term “paper products” is employed to refer to a thin material that is suitable for use in one or more of writing upon, printing upon or packaging and includes products commonly known as paper, card stock, and paperboard. Card stock is a type of paper that is thicker and more durable than paper but more flexible than paperboard (e.g., cardboard). Paper products of the invention are produced by pressing together moist fibers (e.g., cellulose, polymeric) in the form of a pulp composition and then drying the pressed fibers to form sheets of varying thickness. Paper products of the invention may be produced in accordance with traditional manufacturing protocols with the exception that an amount of the CO2 sequestering composition is employed. In producing paper products of the invention, an amount of the CO2 sequestering composition may be employed as a filler, absorbent or colorant to the pulp composition. By “colorant” is meant a compound that is able to impart a color to a product. Since the CO2 sequestering precipitate of the invention is inherently white in color, it is able to improve the white color of already white paper products, and lighten the color of paper products that are not white.
[0038] The density of paper products of the invention may vary greatly. The density of “paper” ranges from 100 kg/m3 to 1500 kg/m3, such as 250 kg/m3 to 1250 kg/m3, including 500 kg/m3 to 800 kg/m3. The density of “papercard” or “card stock” ranges from 1500 kg/m3 to 3000 kg/m3, such as 1700 kg/m3 to 2500 kg/m3, and including 2000 kg/m3 to 2250 kg/m3. The density of “paperboard” can be 3000 kg/m3 and denser, such as 3500 kg/m3 and denser, including 5000 kg/m3 and denser. The thickness of paper products the invention may also vary greatly. The thickness of “paper” ranges between 0.05 mm to 0.18 mm, such as 0.07 mm to 0.18 mm and including 0.1 mm to 0.15 mm. The thickness of “papercard” ranges between 0.18 mm to 0.25 mm, such as 0.18 mm to 0.2 mm and including 0.19 mm. The thickness of “paperboard” may be 0.25 mm and thicker, such as 0.3 mm and thicker, and including 1 mm and thicker. The weight of paper products of the invention may vary. By “weight” is meant the mass of paper product per unit area, usually measured in g/m2. The weight of “paper” may range between 20 g/m2 to 160 g/m2, such as 60 g/m2 to 150 g/m2 and including 80 g/m2 to 120 g/m2. The weight of “papercard” may range between 160 g/m2 to 500 g/m2, such as 175 g/m2 to 400 g/m2 and including 200 to g/m2 to 300 g/m2. The weight of “paperboard” may range from 500 g/m2 and heavier, such as 750 g/m2 and heavier and including 2000 g/m2 and heavier.
[0040] The present invention also includes novel formulations which incorporate the CO2 sequestering composition into polymeric products. The CO2 sequestering additive may be present in the polymeric product in various amounts, as desired, and may be present as fillers and/or other purposes. As such, the amount of CO2 sequestering additive in the polymeric composition may vary, and may be 1% by weight or more, such as 3% by weight or more, including 5% by weight or more. In certain embodiments, the polymeric products are plastics. The term “plastic” is used in its common sense to refer to a wide range of synthetic or semisynthetic organic solid materials suitable for the manufacture of industrial products (e.g., films, fibers, plates, tubes, bottles, boxes). Plastics may be polymers of high molecular weight, and may contain other substances to improve performance which may include but are not limited to acid scavengers, antimicrobial agents, antioxidants, antistatic agents, antifungal agents, clarifying agents, flame retardants, amine light stabilizers, UV absorbers, optical brighteners, photoselective additives, processing stabilizers, and the like. Plastics of the invention may be acrylics, polyesters, silicones, polyurethanes or halogenated plastics. Plastics of interest include, but are not limited to: polypropylenes (e.g., as employed in food containers, appliances, car bumpers), polystyrenes (e.g., as employed in packaging foam, food containers, disposable cups, plates, cutlery, CD and cassette boxes), high impact polystyrenes (e.g., as employed in fridge liners, food packaging, vending cups), acrylonitrile butadiene styrene (e.g., as employed in electronic equipment cases such as computer monitors, printers, keyboards), polyethylene terephthalates (e.g., as employed in carbonated drinks bottles, jars, plastic film, microwavable packaging), polyesters (e.g., as employed in fibers, textiles), polyamides (e.g., as employed in fibers, toothbrush bristles, fishing line, under-the-hood car engine mouldings), poly(vinyl chloride) (e.g., as employed in plumbing pipes and guttering, shower curtains, window frames, flooring), polyurethanes (e.g., as employed in cushioning foams, thermal insulation foams, surface coatings, printing rollers) polycarbonates (e.g., as employed in compact discs, eyeglasses, riot shields, security windows, traffic lights, lenses), polyvinylidene chloride (e.g., as employed in food packaging, saran), polyethylene (e.g., as employed in supermarket bags, plastic bottles) and polycarbonate/acrylonitrile butadiene styrene (e.g., as employed in car interior and exterior parts). Polymeric products, such as plastics, of the invention may be prepared in accordance with traditional manufacturing protocols for such compositions, with the exception that an amount of CO2 sequestering additive of the invention is employed. As such, an amount of the CO2 sequestering additive may be combined with other additives of the plastic precursor composition or feed, and then molded, cast, extruded into the final desired plastic product.
[0041] The present invention also includes novel formulations which incorporate the CO2 sequestering composition into lubricants. The CO2 sequestering composition may be present in the lubricants in various amounts, as desired, and may be present as fillers and/or other purposes. The amount of CO2 sequestering additive in the lubricant may vary, and may be 1% by weight or more, such as 3% by weight or more, including 5% by weight or more. The lubricating oil composition may be formulated for commercial purposes for use in internal combustion engines, such as gasoline and diesel engines, crankcase lubrication and the like. The oil (sometimes referred to as “base oil”) is an oil of lubricating viscosity and is the primary liquid constituent of a lubricant, into which additives and possibly other oils are blended to produce the final lubricant (herein “lubricating composition”). A base oil may be selected from natural (vegetable, animal or mineral) and synthetic lubricating oils and mixtures thereof. It may range in viscosity from light distillate mineral oils to heavy lubricating oils such as gas engine oil, mineral lubricating oil, motor vehicle oil, and heavy duty diesel oil. In some instances, the viscosity of the oil ranges from 2 to 30 mm2s−1, such as 5 to 20 mm2s−1 at 100� C.
[0044] In certain instances, the additive is a dispersant. A dispersant is an additive for a lubricant whose primary function is to hold solid and liquid contaminants in suspension, thereby passivating them and reducing engine deposits at the same time as reducing sludge depositions. Thus, for example, a dispersant maintains in suspension oil-insoluble substances that result from oxidation during use of the lubricant, thus preventing sludge flocculation and precipitation or deposition on metal parts of the engine. Dispersants are usually “ashless”, being non-metallic organic materials that form substantially no ash on combustion, in contrast to metal-containing, and hence ash-forming, materials. They comprise a long chain hydrocarbon with a polar head, the polarity being derived from inclusion of, e.g. an O, P or N atom. The hydrocarbon is an oleophilic group that confers oil-solubility, having for example 40 to 500 carbon atoms. Thus, ashless dispersants may comprise an oil-soluble polymeric hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed. Typically, the dispersants comprise amine, alcohol, amide, or ester polar moieties attached to the polymer backbone often via a bridging group. The ashless dispersant may be, for example, selected from oil-soluble salts, esters, amino-esters, amides, imides, and oxazolines of long chain hydrocarbon-substituted mono- and dicarboxylic acids or their anhydrides; thiocarboxylate derivatives of long chain hydrocarbons; long chain aliphatic hydrocarbons having a polyamine attached directly thereto, and Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine, such as described in U.S. Pat. No. 3,442,808. Dispersants include, for example, derivatives of long chain hydrocarbon-substituted carboxylic acids, examples being derivatives of high molecular weight hydrocarbyl-substituted succinic acid.
[0046] The present invention also includes novel formulations which incorporate the CO2 sequestering composition into adhesives. By “adhesives” is meant compounds that adhere to a substrate or bond two substrates together. Adhesives of the invention may be produced in accordance with traditional manufacturing protocols with the exception that an amount of the CO2 sequestering composition is employed. In producing adhesives of the invention, an amount of the CO2 sequestering composition may be employed as colorants, fillers, and to improve rheology and increase tensile strength.
[0047] The physical properties of adhesives of the invention may vary greatly depending upon the type of chemical system employed and the amount of the CO2 sequestering composition added. The viscosity may range from 1.0 cP to 750000 cP, such as 100 cP to 10000 cP, including 500 cP to 5000 cP, and including 1500 cP to 3000 cP. The effective temperature of the adhesive may range between −75� C. to 500� C., such as 0� C. to 200� C. and including 50� C. to 150� C. By “effective temperature” is meant the temperature range in which the adhesive shows no significant changes in its physical properties or utility (i.e., insignificant change in substrate bonding). The tensile strength of the adhesive may range from 0.1 MPa to 75 MPa, such as 10 MPa to 50 MPa and including 15 to 35 MPa. The elongation capacity of the adhesives may range from 1.0% to 150%, such as 40% to 100% and including 50% to 75%.
[0050] In some embodiments, adhesives of the invention may be liquid compositions which employ a solvent. Exemplary solvents may include, but are not limited to xylene, methanol, toluene, mineral spirits, acetone, butyl acetate, brominated solvents, mixtures thereof, among others. The amount of solvent comprises about 10% to 90% of the liquid composition, such as 50% to 75%, including 60% to 70%. The liquid composition may be applied by brushing, spraying, rolling, immersing the substrate into the composition, or any other convenient method for applying a coating to a surface. In some instances, depending on the amount of solvent, the liquid adhesive composition may be employed as a caulk or sealant. In other instances, the liquid adhesive composition may be dispensed using an aerosol sprayer by formulating the adhesive with a suitable propellant. Exemplary propellants include, but are not limited to fluorinated propellants such as HFCs, hydrocarbons such as propane, butane, isobutane, pentane, nitrogen, carbon dioxide and any compatible mixtures thereof. The amount of propellant may vary, ranging from 10% to 30%, such as 15% to 25%, including 15% to 20%. The composition, including the sprayable propellant may be packaged into an aerosol by any convenient protocol.
[0054] The present invention also includes novel formulations which incorporate the CO2 sequestering composition into rubber. The term “rubber” is used in its conventional sense to mean an elastic material of varying chemical composition which comprise long thread-like molecules and possess a flexibility in its molecular chain to allow for overall material flexing and coiling. Rubber of the invention may be produced in accordance with traditional manufacturing protocols with the exception that an amount of the CO2 sequestering composition is employed. In producing rubber of the invention, an amount of the CO2 sequestering composition may be employed as colorants, fillers and to improve workability of the raw rubber product. Rubber of the invention may be natural or synthetic. The term “natural” refers to rubber in the form of a hydrocarbon polymer of isoprene units derived from the milky colloidal suspension from the sap of a rubber tree or other such plants. Synthetic rubber may be derived from a number of different synthetic polymers including, but not limited to poly-styrene-butadiene, polyisobutylene, ethylene-propylene copolymer, polyneoprene, butadiene-acrylonitrile copolymer, fluoroelastomers, polyurethane, polysulfide, polyacrylate among others. Rubber of the invention may also include one or more additives, which include a vulcanizing agent, a vulcanization accelerator, a process oil, an anti-aging agent, an antioxidant and an anti-ozonant. In producing rubber of the invention, the components may be blended or mixed with the CO2 sequestering composition using any convenient protocol. Exemplary methods for blending the compositions include banbury mixers, sigman blade mixers, double-arm mixers, vortexing mixers, mixers that employ sonication, mixers that employ heavy agitation, among others. The rubber may be further shaped by rotary pressing, extruding, stamping, cutting, molding or any other convenient protocol into the final rubber product.
[0055] The present invention also includes novel formulations which incorporate the CO2 sequestering composition into chalk. The term “chalk” is used in its conventional sense to refer to a marking element usually in the form of a stick or block used for writing or drawing on a rough surface. Chalk in the present invention is a mixture of an amount of the CO2 sequestering composition with one or more thermosetting synthetic binders which is further processed into the form of sticks or blocks. Binders used in the production of chalk may be any conventional thermosetting synthetic binder. Exemplary binders include uncured epoxy, polyester, polyurethane or acrylic resins, or compatible mixtures thereof. Sticks or blocks of chalk are produced by forming a uniform mixture of the CO2 sequestering composition with the synthetic binder and pressing it under high pressure at room temperature. The procedure is preferably such that the mixture of components are processed in an extrusion press, cooled and crushed to a fine particle size, such as 100 microns or smaller, including 75 microns or smaller and preferably 60 microns or smaller. The pulverulent mixture of components obtained is then pressed at room temperature and under a pressure sufficient to consolidate the powder (e.g., 10-35 MPa) into sticks or blocks of chalky and friable consistency. Smaller sticks or blocks may also be cut from larger pre-pressed blocks. Colored chalk may also be produced using the above described method, with the exception that a colorant (i.e., dye) may be added to the CO2 sequestering composition and binder mixture.
[0056] The present invention also includes novel formulations which incorporate the CO2 sequestering composition into asphalt products. The term “asphalt” (i.e., bitumen) is used in its conventional sense to refer to the natural or manufactured black or dark-colored solid, semisolid or viscous material composed mainly of high molecular weight hydrocarbons derived from a cut in petroleum distillation after naptha, gasoline, kerosene and other fractions have been removed from crude oil.
[0057] The molecular composition of asphalt products may vary. Asphalt products of the invention may be composed of saturated and unsaturated aliphatic and aromatic compounds that possess functional groups that include, but are not limited to alcohol, carboxyl, phenolic, amino, thiol functional groups. In an exemplary embodiment, asphalt products may be 80% carbon by weight, 10% hydrogen by weight, 6% sulfur by weight, 3% total weight of oxygen and nitrogen; and may also include trace amounts of various metals such as iron, nickel and vanadium. The molecular weight of asphalt products may range from 0.2 kDa to 50 kDa, such as 1 kDa to 25 kDa, including 2 kDa to 10 kDa. Components of asphalts may be asphaltenes (i.e., high molecular weight compounds that are insoluble in hexane or heptane) or maltenes (i.e., lower molecular weight compounds that are soluble in hexane or heptane). The amount of asphaltenes in asphalt products may vary, ranging from 5% to 25% by weight, such as 10% to 20%, and including 12% to 15%. In some embodiments, asphalt products of the invention may also contain a polymeric additive to enhance workability, viscoelasticity, and strain recovery. Exemplary polymeric additives include polybutadiene, polyisoprene, ethylene/vinyl acetate copolymer, polyacrylate, polymethacrylate, polychloroprene, etc. Asphalt products of interest also include an amount of aggregate. Aggregate of the invention may be any convenient aggregate material. The aggregate material may be CO2 sequestering aggregates, for example as described in U.S. patent application Ser. No. 12/475,378, titled “ROCK AND AGGREGATE, AND METHODS OF MAKING AND USING THE SAME”; the disclosure of which is herein incorporated by reference.
[0059] The present invention also includes novel formulations which incorporate the CO2 sequestering composition into paint. By “paint” is meant any liquid, liquefiable, or mastic composition which, after application to a substrate in a thin layer, is converted to an opaque solid film. Paints may include one or more of the following components: pigments, binders, solvents and additives. Pigments are granular solids incorporated into the paint, e.g., to contribute color, toughness or simply to reduce the cost of the paint. Pigments of interest include natural and synthetic types. Natural pigments include various clays, calcium carbonate, mica, silicas, and talcs. Synthetic pigments include engineered molecules, calcined clays, blanc fix, precipitated calcium carbonate, and synthetic silicas. Hiding pigments, in making paint opaque, also protect the substrate from the harmful effects of ultraviolet light. Hiding pigments include titanium dioxide, phthalo blue, red iron oxide, and many others. Fillers are a special type of pigment that serve to thicken the film, support its structure and simply increase the volume of the paint. Fillers of interest include inert materials, such as talc, lime, baryte, clay, etc. Floor paints that will be subjected to abrasion may even contain fine quartz sand as a filler. Not all paints include fillers. On the other hand some paints contain very large proportions of pigment/filler and binder. The CO2 sequestering additive of the invention may be employed in place of all or some of the above pigment components in a given paint. The binder, or resin, is the actual film forming component of paint. The binder imparts adhesion, binds the pigments together, and strongly influences such properties as gloss potential, exterior durability, flexibility, and toughness. Binders of interest include synthetic or natural resins such as acrylics, polyurethanes, polyesters, melamine resins, epoxy, or oils, etc. Solvents of interest may be present, e.g., to adjust the viscosity of the paint. They may be volatile so as not to become part of the paint film. Solvents may be included to control flow and application properties, and affect the stability of the paint while in liquid state. Solvents of interest include water, e.g., water-based paints and organic solvents, e.g., aliphatics, aromatics, alcohols, and ketones. Organic solvents such as petroleum distillate, esters, glycol ethers, and the like find use. Additives of interest include additives to modify surface tension, improve flow properties, improve the finished appearance, increase wet edge, improve pigment stability, impart antifreeze properties, control foaming, control skinning, etc. Other types of additives include catalysts, thickeners, stabilizers, emulsifiers, texturizers, adhesion promoters, UV stabilizers, flatteners (de-glossing agents), biocides to fight bacterial growth, and the like.
[0061] The present invention also includes novel formulations which incorporate the CO2 sequestering composition into non-ingestible products. By “non-ingestible” is meant compounds that are not suitable for consumption. Of interest are novel non-ingestible formulations which incorporate the CO2 sequestering composition of the invention into personal care products. Personal care products of the invention are compositions intended for cleaning purposes or personal use such as for health and/or hygiene purposes. Personal care products may be products that relate to sun-care (e.g., sunscreens, sun-tan lotion, self tanning compositions, bronzers), baby-care (e.g., diapers, baby wipes, baby powder, diaper rash products), facial and body treatment (e.g., acne prevention wipes, acne treatment cream, facial cleansing soap and exfoliating soap, antiperspirants, deodorants, aftershave lotion, bath soap, bath wash, shaving cream, shaving gel, makeup removal, moisturizers, anti-wrinkle creams, lotions), foot-care (anti-itch cream, anti-fungal creams), oral-care (toothpaste, mouthwash), hair-care (shampoo, conditioner, hair spray, hair gel, mouse, colorants, depilatory treatments, hair bleach) and First Aid (bandages, antiseptic sprays, antibacterial gels). Another type of personal care product is cosmetics. Cosmetics of the invention are makeup products that include, but are not limited to mascara, eyeshadow, eyeliner, blush, concealer, foundation, face powder, lipstick, lip gloss, lip treatment, lipliner and nail polish. Another type of personal care product are cleaning products. Cleaning products of the invention are compounds used primarily in the removal of dirt, stains, impurities, microorganisms and the like. Cleaning products of the invention may be products that relate to laundry cleaners (e.g., laundry detergent, stain remover, fabric softener), dishwashing products (dishwashing liquid, dishwashing powders, dishwashing gels, rinse agents, fast-dry agents), room deodorizing products, bathroom cleaners (toilet, shower, marble, porcelain), powdered bleach, shoe polish and all-purpose cleaners.
[0063] In some embodiments, the CO2 sequestering composition of the invention may be employed in non-ingestible products as an abrasive. By “abrasive” is meant a compound that contains an amount of roughness which when used on a surface is able to abrade, smooth, buff, polish, grind and the like. The roughness of the abrasive may vary, depending on the particle sizes of the CO2 sequestering composition. In some instances, the particle sizes of the CO2 sequestering composition are small (≦0.5 micron) and may be incorporated into non-ingestible products where only a mild abrasive is desired (e.g., bathroom cleaners, baby wipes). In other instances, the particle sizes of the CO2 sequestering precipitate are large (≧5 micron) and may be incorporated into non-ingestible products where a strong abrasive is desired (e.g., bath soap, toothpaste). Exemplary non-ingestible products of the invention employing the CO2 sequestering composition as an abrasive include toothpaste, shoe polish, mouthwash, facial cleansing soaps, exfoliating products, acne prevention wipes, bath soap, bath wash, makeup remover, baby wipes, diaper rash products, bathroom cleaners, powdered bleach and all purpose cleaners. In some embodiments, the CO2 sequestering composition is employed as an abrasive for paint removal, such as in processes employing blasting techniques wherein the abrasive is suspended in a liquid and applied to a painted or coated surface. The CO2 sequestering composition may be used as an abrasive for paint removal in cases where the surfaces are delicate, such as lightweight metal and plastic surfaces, in some embodiments of the invention.
[0064] In other embodiments, the CO2 sequestering composition of the invention may be employed in non-ingestible products as an absorbent. By “absorbent” is meant a compound that possesses the capacity to absorb or soak up liquids (i.e., drying agent). Exemplary non-ingestible products of the invention employing the CO2 sequestering composition as an absorbent include eyeshadow, blush, concealer, foundation, face powder, sunscreen, sun-tan lotion, self tanning compositions, bronzers, baby powder, diaper rash products, deodorants and antiperspirants.
[0065] In other embodiments, the CO2 sequestering composition of the invention may be employed in non-ingestible products as an anticaking agent. By “anticaking agent” is meant a compound that prevents solid compositions from forming large aggregates (i.e., clumps) and facilitates a consistent granular or powdered composition. Exemplary non-ingestible products of the invention employing the CO2 sequestering composition as an anticaking agent include baby powder, foundation, face powder, blush, eyeshadow, diaper rash products, concealer, laundry detergent, dishwashing powder, rinse agents, fast-dry agents, room deodorizing powders, bathroom cleaners and powdered bleach.
[0066] In other embodiments, the CO2 sequestering composition of the invention may be employed in non-ingestible products as a buffering agent. By “buffering agent” is meant a compound that minimizes changes in pH. As such, the CO2 sequestering component may act to buffer any acidic or basic components traditionally used in formulations for these products or may be used to maintain a suitable pH during its use. Exemplary non-ingestible products of the invention employing the CO2 sequestering composition as a buffering agent include lip gloss, nail polish, sunscreens, sun-tan lotion, baby wipes, acne prevention wipes, acne treatment cream, facial cleansing soap and exfoliating soap, antiperspirants, deodorants, aftershave lotion, bath soap, bath wash, shaving cream, shaving gel, makeup removal, moisturizers, anti-wrinkle creams, anti-drying lotions, anti-itch cream, anti-fungal creams, conditioner, hair spray, hair gel, mouse, hair colorants, depilatory treatments, hair bleach, antiseptic sprays, antibacterial gels, laundry detergent, stain remover, teeth whitening agents, dishwashing liquid, dishwashing powders, dishwashing gels, rinse agents, fast-dry agents, bathroom cleaners and all-purpose cleaners.
[0067] In other embodiments, the CO2 sequestering composition of the invention may be employed in non-ingestible products as a filler. By “filler” is meant a non-reactive, solid ingredient used to dilute other solids, or to increase the volume of a product. In some instances, the CO2 sequestering composition may be used to dilute a potent active ingredient, which may be present in very small amounts, so that the product can be handled more easily. In other instances, the CO2 sequestering composition may be used to increase the volume of an expensive ingredient without disturbing the main function of the product. Exemplary non-ingestible products of the invention employing the CO2 sequestering composition as a filler include baby powder, foundation, face powder, blush, eyeshadow, diaper rash products, concealer, laundry detergent, dishwashing powder, rinse agents, fast-dry agents, room deodorizing powders, bathroom cleaners and powdered bleach.
[0068] In other embodiments, the CO2 sequestering composition of the invention may be employed in non-ingestible products as a colorant. By “colorant” is meant a compound that is able to impart a color to a product. Since the CO2 sequestering precipitate of the invention is inherently white in color, it is able to improve the white color of already white products, and lighten the color of those products that are not white. Exemplary non-ingestible products of the invention employing the CO2 sequestering composition as a filler include eyeshadow, blush, concealer, foundation, face powder, sunscreens, sun-tan lotion, self tanning compositions, bronzers, baby powder, acne treatment cream, facial cleansing soap, exfoliating soap, antiperspirants, deodorants, bath soap, bath wash, shaving cream, moisturizers, anti-wrinkle cream, teeth whitening agents, lotions, anti-inch cream, anti-fungal cream, toothpaste, shampoo, conditioner, hair mousse, hair colorants, laundry detergent, dishwashing powders and room deodorizing products.
[0069] In other embodiments, the CO2 sequestering composition of the invention may be employed in non-ingestible products as an opacifying agent. By “opacifying agent” is meant a substance that reduces the clear or transparent appearance of a product. The opacity of the non-ingestible product may vary depending on the particle sizes of the CO2 sequestering composition. For substantially opaque materials (e.g., anti-wrinkle cream), large particle sizes may be used (≧1 micron). For compositions where a less substantial opacity is desired, small particles may be used (≦0.5 micron). Exemplary non-ingestible products of the invention employing the CO2 sequestering composition as an opacifying agent include anti-wrinkle cream, bronzer, sun-tan lotion and self-tanning compositions.
[0070] In other embodiments, the CO2 sequestering composition of the invention may be employed in non-ingestible products as an oral-care agent. By “oral-care agent” is meant a compound that may be used to polish teeth, reduce oral odor or otherwise cleanse or deodorize the teeth and mouth. In addition to being a mild abrasive for polishing teeth, the CO2 sequestering composition, when incorporated in products used for oral hygiene, can buffer acids that facilitate tooth decay and provide a whitening component to oral-care products. Exemplary non-ingestible products of the invention employing the CO2 sequestering composition as an oral-care agent include toothpaste, teeth whitening agents and mouthwash.
[0071] In other embodiments, the CO2 sequestering composition of the invention may be employed in non-ingestible products as a UV-scattering agent. By “UV-scattering agent” is meant a compound that can sufficiently scatter UV light. Depending on the particle sizes of the CO2 sequestering precipitate, the amount of UV light (i.e., light having wavelengths≦380 nm) that is scattered and thus unavailable for absorption may vary. In some instances, the amount of UV light scattered may be 10% or more, including 25% or more, such as 50% or more. In some embodiments of the invention, the CO2 sequestering composition may be the only component used to protect against UV radiation. In other embodiments, the CO2 sequestering composition may be used in combination with conventional UV absorbing compositions to protect against UV radiation. Exemplary non-ingestible products of the invention employing the CO2 sequestering composition as a UV-scattering agent include sunscreen, face powder, blush and foundation.
[0072] The present invention also includes novel formulations which incorporate the CO2 sequestering composition into ingestible products. By “ingestible” is meant compositions that are taken orally, even though they may not be digested, where ingestibles are formulated for human consumption. Ingestibles of the invention may include food products, vitamins, nutritional supplements, pharmaceuticals and mineral fortified products.
[0076] In other embodiments, the CO2 sequestering composition of the invention may be employed in food products as an anti-caking agent. As described above, an anti-caking agent is used to prevent solid compositions from forming large aggregates (i.e., clumps) and facilitates a consistent granular or powdered composition. Exemplary food products of the invention employing the CO2 sequestering composition as an anti-caking agent include milk powders, baby formula, confectionary substances, sweetners and seasonings.
[0077] In other embodiments, the CO2 sequestering composition of the invention may be employed in food products as an emulsifier. By “emulsifier” is meant a substance that forms or maintains a uniform mixture of two or more immiscible phases. In some instances, the CO2 sequestering composition can be used to form a mixture of oil and water in food products. Exemplary food products of the invention employing the CO2 sequestering composition as an emulsifier include fat emulsions (e.g., salad dressings), broths and condiments.
[0079] In other embodiments, the CO2 sequestering composition of the invention may be employed in food products as a stabilizer. By “stabilizer” is meant a substance that facilitates a uniform dispersion of two or more immiscible substances. Exemplary food products of the invention employing the CO2 sequestering composition as a stabilizer include dairy based products, canned soups, milk substitutes, liquid whey and condiments.
[0080] Also of interest are novel ingestible formulations which incorporate the CO2 sequestering composition of the invention into vitamins, nutritional supplements and pharmaceuticals. Vitamins, nutritional supplements and pharmaceuticals of the invention may include any ingestible solids or liquids that are not food products (as described above) consumed for nutritional or medicinal purposes. In certain embodiments, the CO2 sequestering composition of the invention may be employed in vitamins, nutritional supplements and pharmaceuticals as buffering agents, fillers, anti-caking agents, colorants, and binders. By “binder” is meant a substance that is used to hold together ingredients of a compressed tablet or cake. Vitamins, nutritional supplements and pharmaceuticals of the invention may be in the form or a powder, syrup, liquid, tablet, capsule with powder filling, liquid-gel capsule and the like. Vitamins, nutritional supplements and pharmaceuticals may include, but are not limited to over-the-counter medications, behind-the-counter medications, prescription medications, liquid nutritional drinks, nutritional powders, weight-loss supplementals, mutivitamins, nutraceuticals, laxatives, antacids and the like. Traditional buffering agents, fillers, anti-caking agents, colorants and binders conventionally found in vitamins, nutritional supplements and pharmaceuticals may be substituted entirely or a certain amount removed and replaced by the CO2 sequestering compositions of the present invention.
[0082] In another exemplary embodiment, the CO2 sequestering composition of invention may be used for the mineral fortification of food products. By “mineral fortification” is meant the addition of minerals (e.g., calcium, magnesium) to food during production or processing. Food products of the invention may be fortified with minerals by substantially pure CO2 sequestering carbonate precipitate using any convenient protocol, such as for example mixing the CO2 sequestering composition with the food product. Depending on the type of food product, the amount of CO2 sequestering composition added may vary, ranging from 5 mg to 1500 mg, such as 10 mg to 500 mg and including 100 mg to 200 mg. Exemplary food products that may be fortified with CO2 sequestering compositions of the invention include, but are not limited to: baked goods (e.g., breads, cookies, biscuits, crackers, waffles, pancakes, cakes); bars (e.g., baked bars, breakfast bars, granola bars, energy bars); beverages (e.g., opaque beverages, both dairy and non-dairy); breakfast cereals; chewing gum; candies (e.g., opaque hard candies, chocolate, nougats, caramels, cream filled); frozen desserts (e.g., ice cream, frozen soy desserts, frozen yogurts); infant formulas; ingredient enrichment (e.g., flour, meals, grains, wheat, corn, rice, oats); liquid meals (e.g., replacement meals, special formulations for diabetic, diet or slimming drinks); milks; pastas (e.g., macaroni, spaghetti, noodles, couscous, ramen, instant noodles); powdered drink mixes (e.g., flavored milks, energy drinks, protein drinks); probiotics; soymilks; tofu; yogurts (e.g., bulk-fermented yogurts, drinkable yogurts, yogurt-based smoothies).
[0083] The present invention also includes novel formulations which incorporate the CO2 sequestering composition into animal ingestible products. By “animal ingestible” is meant compositions that are taken orally and are formulated for non-human (e.g., livestock, pets) consumption Animal Ingestible products of the invention may include but are not limited to animal food products, vitamins, nutritional supplements and pharmaceuticals for animal consumption. Of interest are novel animal-ingestible product formulations which employ the CO2 sequestering composition of the invention as buffering agents, fillers, anti-caking agents, colorants, emulsifiers, stabilizers and binders into food products, vitamins, nutritional supplements and pharmaceuticals formulated for animal consumption. Traditional buffering agents, fillers, anti-caking agents, colorants, emulsifiers, stabilizers and binders conventionally found in animal-ingestible products may be substituted entirely or a certain amount removed and replaced by the CO2 sequestering compositions of the present invention.
[0084] The present invention also includes novel formulations which incorporate the CO2 sequestering composition into agricultural products. By “agricultural products” is meant any composition that is employed in cultivating land, raising crops or vegetation, farming, and feeding, breeding, and raising livestock or any other activity associated therewith. Agricultural products of the invention may be soil amendment compositions (e.g., fertilizer, remediation), pest control (fungicides, insecticides) or nutritional and/or medicinal ingestible compositions for livestock (as detailed above). The CO2 sequestering composition of the invention may be added to traditional agricultural products as a supplement or entirely replace conventionally used agricultural products.
[0085] In some embodiments, the CO2 sequestering composition of the invention is a soil amendment. By “soil amendment” is meant a composition that aims to improve or remediate the desired properties of soil for agricultural usage. In some instances the soil amendment is a fertilizer to supply nutrients (e.g., calcium, magnesium) to the soil. In other instances, the soil amendment is a buffering agent to reduce changes to the pH of the soil. The CO2 sequestering composition of the invention may be contacted with the soil in the form of a slurry or a powder. The CO2 sequestering precipitate is either mixed with water prior to being dispensed onto the surface of the soil or is dispensed as a dry powder. Contacting the composition with the soil may be achieved using any convenient protocol. It may be gravity fed or pumped through hoses, spray nozzles or fixed sprayers to uniformly apply the composition. In other instances, the CO2 soil stabilization compositions of the invention may be poured from a reservoir or applied manually without the use of any industrial machinery. The composition may also be applied by releasing the composition at a depth within the soil by pumping the composition beneath the surface of the soil to be treated or by digging to a depth in the soil using conventional digging machinery and further applying the composition. The composition is then mixed into the soil. In any of the various treatments within the scope of the present invention, the soil may be mixed in situ or may be temporarily removed from the ground for mixing and then replaced. Mixing the soil with the CO2 sequestering composition may be accomplished using any convenient mixing equipment (e.g., rotary mixers, cement mixers, etc.). The prepared CO2-sequestering composition and soil mixture is then rotated and the entire mixture is blended in a uniform manner.
[0086] In other embodiments, the CO2 sequestering composition of the invention may be incorporated into pesticides. The term “pesticide” is used in its conventional sense to mean any compound that is used to eliminate, control or inhibit the proliferation of any organism which has characteristics that are regarded as injurious or unwanted. Pesticides of the invention may include those formulations used against insects, fungi, bacteria, rodents and the like. The CO2 sequestering composition may be employed in pesticides to improve the pesticide action or to aid in the application of the pesticide. For example, the CO2 sequestering composition may be employed as a water absorbent or as a granulating agent. In other instances, the composition may be employed as a crop-dusting filler to facilitate the uniform distribution of the pesticide on vegetation or crops. Pesticides of the invention may be prepared using any conventional protocol with the exception that an amount of the CO2 sequestering composition is added. The amount of CO2 sequestering additive in the pesticide may vary, and may be 1% by weight or more, such as 3% by weight or more, including 5% by weight or more, such as 25% by weight or more. The CO2 sequestrating composition may be incorporated into the pesticides during the formulation of the pesticide or may be subsequently added to the finished pesticide product. Incorporation of the composition into the pesticide may be accomplished by mixing the composition with the pesticide and rotating the mixture under agitation, vortex or sonication and blending into a uniform pesticide product.
[0087] The CO2 sequestering composition of the invention may also be employed in environmental remediation. By “environmental remediation” is meant the removal of pollution or contaminants from environmental media such as soil, groundwater, sediment or water for the general protection of human health and the environment.
[0089] In other embodiments, environmental remediation employing the CO2 sequestering composition of the invention is the neutralization of over-acidified water. By “acidified water” is meant a large body of water (e.g., pond, lake) that has a pH below 6.5 under ambient conditions and is often lower, such as 6.0 and including 5.0. The CO2 sequestering composition can be applied by any convenient protocol. In some instances, the composition is applied as a slurry or as a finely ground powder. Slurries are typically sprayed onto the water surface from boats or from stations located on the water, whereas powder is dispensed by helicopter or fixed-wing planes. The application of the CO2 sequestering composition may cause increases in pH that vary ranging from 1 to 4, including 2 to 4, such as 2.5 to 3.5. The amount of the CO2 sequestering composition applied to the acidified water may vary considerably (depending on the size and location of the body of water and the pH of the water) ranging from 0.1 kg to 100 kg or more, such as 1000 kg or more, including 10,000 kg or more.
[0091] A variety of different methods may be employed to prepare the CO2 sequestering additive of the compositions of the invention. CO2 sequestration protocols of interest include, but are not limited to, those disclosed in U.S. patent application Ser. Nos. 12/126,776, titled, “Hydraulic cements comprising carbonate compound compositions,” filed 23 May 2008; 12/163,205, titled “DESALINATION METHODS AND SYSTEMS THAT INCLUDE CARBONATE COMPOUND PRECIPITATION,” filed 27 Jun. 2008; and 12/486,692, titled “METHODS AND SYSTEMS FOR UTILIZING WASTE SOURCES OF METAL OXIDES” filed 17 Jun. 2009; 12/501,217, titled “PRODUCTION OF CARBONATE-CONTAINING COMPOSITIONS FROM MATERIAL COMPRISING METAL SILICATE,” filed 10 Jul. 2009; and 12/557,492, titled “CO2 COMMODITY TRADING SYSTEM AND METHOD,” filed 10 Sep. 2009; as well as International Application No. PCT/US08/88318, titled, “METHODS OF SEQUESTERING CO2,” filed 24 Dec. 2008; and PCT/US09/45722, titled “ROCK AND AGGREGATE, AND METHODS OF MAKING AND USING THE SAME,” filed 29 May 2009; as well as pending U.S. Provisional Patent Application Ser. Nos. 61/081,299; 61/082,766; 61/088,347; 61/088,340; and 61/101,631; the disclosures of which are herein incorporated by reference.
[0093] In certain embodiments, the water from which the carbonate precipitates are produced is a saltwater. In such embodiments, the carbonate compound composition may be viewed as a saltwater derived carbonate compound composition. As used herein, “saltwater-derived carbonate compound composition” means a composition derived from saltwater and made up of one or more different carbonate crystalline and/or amorphous compounds with or without one or more hydroxide crystalline or amorphous compounds. The term “saltwater” is employed in its conventional sense to refer to a number of different types of aqueous liquids other than fresh water, where the term “saltwater” includes brackish water, sea water and brine (including man-made brines, e.g., geothermal plant wastewaters, desalination waste waters, etc), 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. The saltwater source from which the mineral composition of the cements of the invention is derived may be a naturally occurring source, such as a sea, ocean, lake, swamp, estuary, lagoon, etc., or a man-made source. In certain embodiments, the saltwater source of the mineral composition is seawater.
[0098] Precipitation conditions of interest may vary. For example, the temperature of the water may be within a suitable range for the precipitation of the desired mineral to occur. In some embodiments, the temperature of the water may be in a range from 5 to 70� C., such as from 20 to 50� C. and including from 25 to 45� C. As such, while a given set of precipitation conditions may have a temperature ranging from 0 to 100� C., the temperature of the water may have to be adjusted in certain embodiments to produce the desired precipitate.
[0099] In normal sea water, 93% of the dissolved CO2 is in the form of bicarbonate ions (HCO3 −) and 6% is in the form of carbonate ions (CO3 −2). When calcium carbonate precipitates from normal sea water, CO2 is released. In fresh water, above pH 10.33, greater than 90% of the carbonate is in the form of carbonate ion, and no CO2 is released during the precipitation of calcium carbonate. In sea water this transition occurs at a slightly lower pH, closer to a pH of 9.7. While the pH of the water employed in methods may range from 5 to 14 during a given precipitation process, in certain embodiments 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. In certain of these embodiments, the pH is raised to a level which minimizes if not eliminates CO2 production during precipitation, causing dissolved CO2, e.g., in the form of carbonate and bicarbonate, to be trapped in the carbonate compound precipitate. In these embodiments, the pH may be raised to 10 or higher, such as 11 or higher.
[0104] In addition to comprising cations of interest and other suitable metal forms, waste streams from various industrial processes may provide proton-removing agents. Such waste streams include, but are not limited to, mining wastes; fossil fuel burning ash (e.g., combustion ash such as fly ash, bottom ash, boiler slag); slag (e.g. iron slag, phosphorous slag); cement kiln waste; oil refinery/petrochemical refinery waste (e.g. oil field and methane seam brines); coal seam wastes (e.g. gas production brines and coal seam brine); paper processing waste; water softening waste brine (e.g., ion exchange effluent); silicon processing wastes; agricultural waste; metal finishing waste; high pH textile waste; and caustic sludge. Mining wastes include any wastes from the extraction of metal or another precious or useful mineral from the earth. In some embodiments, wastes from mining are used to modify pH, wherein the waste is selected from red mud from the Bayer aluminum extraction process; waste from magnesium extraction from sea water (e.g., Mg(OH)2 such as that found in Moss Landing, Calif.); and wastes from mining processes involving leaching. For example, red mud may be used to modify pH as described in U.S. Provisional Patent Application No. 61/161,369, titled, “NEUTRALIZING INDUSTRIAL WASTES UTILIZING CO2 AND A DIVALENT CATION SOLUTION”, filed 18 Mar. 2009, which is hereby incorporated by reference in its entirety. Fossil fuel burning ash, cement kiln dust, and slag, collectively waste sources of metal oxides, further described in U.S. patent application Ser. No. 12/486,692, titled, “METHODS AND SYSTEMS FOR UTILIZING WASTE SOURCES OF METAL OXIDES,” filed 17 Jun. 2009, the disclosure of which is incorporated herein in its entirety, may be used in alone or in combination with other proton-removing agents to provide proton-removing agents for the invention. Agricultural waste, either through animal waste or excessive fertilizer use, may contain potassium hydroxide (KOH) or ammonia (NH3) or both. As such, agricultural waste may be used in some embodiments of the invention as a proton-removing agent. This agricultural waste is often collected in ponds, but it may also percolate down into aquifers, where it can be accessed and used.
[0105] Electrochemical methods are another means to remove protons from various species in a solution, either by removing protons from solute (e.g., deprotonation of carbonic acid or bicarbonate) or from solvent (e.g., deprotonation of hydronium or water). Deprotonation of solvent may result, for example, if proton production from CO2 dissolution matches or exceeds electrochemical proton removal from solute molecules. In some embodiments, low-voltage electrochemical methods are used to remove protons, for example, as CO2 is dissolved in the precipitation reaction mixture or a precursor solution to the precipitation reaction mixture (i.e., a solution that may or may not contain divalent cations). In some embodiments, CO2 dissolved in an aqueous solution that does not contain divalent cations is treated by a low-voltage electrochemical method to remove protons from carbonic acid, bicarbonate, hydronium, or any species or combination thereof resulting from the dissolution of CO2. A low-voltage electrochemical method operates at an average voltage of 2, 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 V or less, such as 0.9 V or less, 0.8 V or less, 0.7 V or less, 0.6 V or less, 0.5 V or less, 0.4 V or less, 0.3 V or less, 0.2 V or less, or 0.1 V or less. Low-voltage electrochemical methods that do not generate chlorine gas are convenient for use in systems and methods of the invention. Low-voltage electrochemical methods to remove protons that do not generate oxygen gas are also convenient for use in systems and methods of the invention. In some embodiments, low-voltage electrochemical methods generate hydrogen gas at the cathode and transport it to the anode where the hydrogen gas is converted to protons. Electrochemical methods that do not generate hydrogen gas may also be convenient. In some embodiments, electrochemical processes to remove protons do not generate a gas at the anode. In some instances, electrochemical methods to remove protons do not generate any gaseous by-byproduct. Electrochemical methods for effecting proton removal are further described in U.S. patent application Ser. No. 12/344,019, titled, “METHODS OF SEQUESTERING CO2,” filed 24 Dec. 2008; U.S. patent application Ser. No. 12/375,632, titled, “LOW ENERGY ELECTROCHEMICAL HYDROXIDE SYSTEM AND METHOD,” filed 23 Dec. 2008; International Patent Application No. PCT/US08/088,242, titled, “LOW ENERGY ELECTROMECHANICAL HYDROXIDE SYSTEM AND METHOD,” filed 23 Dec. 2008; International Patent Application No. PCT/US09/32301, titled, “LOW-ENERGY ELECTROCHEMICAL BICARBONATE ION SOLUTION,” filed 28 Jan. 2009; and International Patent Application No. PCT/US09/48511, titled, “LOW-ENERGY 4-CELL ELECTROCHEMICAL SYSTEM WITH CARBON DIOXIDE GAS,” filed 24 Jun. 2009, each of which are incorporated herein by reference in their entirety.
[0106] Low voltage electrochemical processes may produce hydroxide at the cathode and protons at the anode; where such processes utilize a salt containing chloride, e.g. NaCl, a product of the process will be HCl. In some embodiments of the invention, the HCL from a low-voltage electrochemical process as described herein may be used to make poly(vinyl chloride) (PVC). HCl from a low-voltage electrochemical process, e.g. a process that operates at a voltage of less than 2.0V, or less than 1.5V, or less than 1.0V, may be used in reactions well-known in the art to produce a vinyl chloride monomer. The vinyl chloride monomer may be used to produce poly(vinyl chloride) in some embodiments. In further embodiments, the PVC can be mixed with a carbonate precipitate formed by the methods described herein, e.g. a slightly wet carbonate precipitate, to form a building material. In some embodiments, the PVC/carbonate mixture may be extruded to form a slightly foamed profile, such as, e.g. a 2�4 or other lumber material. Carbonate/PVC lumber formed by such methods are thus encompassed by the invention. Such 1 umber may be CO2-sequestering because the carbonate in the lumber is a CO2-sequestering additive. In some embodiments, the amount of CO2 sequestering additive in the formed element comprising PVC is 5 wt % or more. In some embodiments, the amount of CO2 sequestering additive in the formed element comprising PVC is 10 wt % or more, 15 wt % or more, 20 wt % or more, 25 wt % or more, 30 wt % or more, 35 wt % or more, such as 40 wt % or more, 45 wt % or more, 50 wt %, 55 wt % or more, 60 wt % or more, such as up to 65 wt % or more. In some embodiments, the amount of CO2 sequestering additive in the formed element comprising PVC is 60 wt % or more. In some embodiments, the PVC and CO2 sequestering additive are mixed and formed in a screw extruder. In some embodiments, the formed element is injection molded. In some embodiments, the PVC is foamed to create a cellular structure that will hold anchoring devices such as nails and screws. In some embodiments, the formed element comprising PVC and CO2 sequestering additive is used to fabricate building elements that are flame resistant. In some embodiments, the formed element comprising PVC and CO2 sequestering additive is such that the amount of CO2 sequestering additive increases the finishability, i.e. ease of cutting and sanding, of the formed element. In some embodiments, the formed element comprising PVC and CO2 sequestering additive is such that the amount of CO2 sequestering additive enhances the coloring or appearance of the formed element. In some embodiments, the formed element comprising PVC and CO2 sequestering additive is such that the amount of CO2 sequestering additive gives stiffness to the formed element. In some embodiments, the CO2 sequestering additive is added to the PVC during the production of the PVC. In some such embodiments, the PVC can be derived from the CO2 sequestering methods of the invention.
[0107] Alternatively, electrochemical methods may be used to produce caustic molecules (e.g., hydroxide) through, for example, the chlor-alkali process, or modification thereof. Electrodes (i.e., cathodes and anodes) may be present in the apparatus containing the divalent cation-containing aqueous solution or gaseous waste stream-charged (e.g., CO2-charged) solution, and a selective barrier, such as a membrane, may separate the electrodes. 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. patent application Ser. No. 12/503,557, titled, “CO2 UTILIZATION IN ELECTROCHEMICAL SYSTEMS,” filed 15 Jul. 2009 and U.S. Provisional Application No. 61/091,729, titled, “LOW ENERGY ABSORPTION OF HYDROGEN ION FROM AN ELECTROLYTE SOLUTION INTO A SOLID MATERIAL,” filed 11 Sep. 2008, the disclosures of which are herein incorporated by reference.
[0114] The source of CO2 that is contacted with the volume of saltwater in these embodiments may be any convenient CO2 source. The CO2 source may be a liquid, solid (e.g., dry ice) or gaseous CO2 source. In certain embodiments, the CO2 source is a gaseous CO2 source. This gaseous CO2 is, in certain instances, a waste feed from an industrial plant. The nature of the industrial plant may vary in these embodiments, where industrial plants of interest include power plants (e.g., as described in further detail in International Application No. PCT/US08/88318, titled, “METHODS OF SEQUESTERING CO2,” filed 24 Dec. 2008, the disclosure of which is herein incorporated by reference), chemical processing plants, steel mills, paper mills, cement plants (e.g., as described in further detail in U.S. Provisional Application Ser. No. 61/088,340, the disclosure of which is herein incorporated by reference), and other industrial plants that produce CO2 as a byproduct. By waste feed is meant a stream of gas (or analogous stream) that is produced as a byproduct of an active process of the industrial plant. The gaseous stream may be substantially pure CO2 or a multi-component gaseous stream that includes CO2 and one or more additional gases. Multi-component gaseous streams (containing CO2) that may be employed as a CO2 source in embodiments of the subject methods include both reducing, e.g., syngas, shifted syngas, natural gas, and hydrogen and the like, and oxidizing condition streams, e.g., flue gases from combustion. Exhaust gases containing NOx, SOx, VOCs, particulates and Hg would commonly incorporate these compounds along with the carbonate in the precipitated product. Particular multi-component gaseous streams of interest that may be treated according to the subject invention include: oxygen containing combustion power plant flue gas, turbo charged boiler product gas, coal gasification product gas, shifted coal gasification product gas, anaerobic digester product gas, wellhead natural gas stream, reformed natural gas or methane hydrates, and the like.
[0116] The above protocol results in the production of a slurry of a CO2 sequestering precipitate and a mother liquor. Where desired, the compositions made up of the precipitate and the mother liquor may be stored for a period of time following precipitation and prior to further processing. For example, the composition may be stored for a period of time ranging from 1 to 1000 days or longer, such as 1 to 10 days or longer, at a temperature ranging from 1 to 40� C., such as 20 to 25� C.
[0120] The resultant dewatered precipitate may then be dried, as desired, to produce a dried product. Drying can be achieved by air drying the wet precipitate. Where the wet precipitate is air dried, air drying may be at room or elevated temperature. In yet another embodiment, the wet precipitate is spray dried to dry the precipitate, where the liquid containing the precipitate is dried by feeding it through a hot gas (such as the gaseous waste stream from the power plant), 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. Depending on the particular drying protocol of the system, the drying station may include a filtration element, freeze drying structure, spray drying structure, etc. Where desired, the dewatered precipitate product may be washed before drying. The precipitate may be washed with freshwater, e.g., to remove salts (such as NaCl) from the dewatered precipitate.
[0122] FIG. 1 provides a schematic flow diagram of a process for producing a CO2 sequestering product according to an embodiment of the invention. In FIG. 1, saltwater from salt water source 10 is subjected to carbonate compound precipitation conditions at precipitation step 20. As reviewed above, term “saltwater” is employed in its conventional sense to refer a number of different types of aqueous fluids other than fresh water, where the term “saltwater” includes brackish water, sea water and brine (including man-made brines, e.g., geothermal plant wastewaters, desalination waste waters, etc), as well as other salines having a salinity that is greater than that of freshwater. The saltwater source from which the carbonate compound composition of the cements of the invention is derived may be a naturally occurring source, such as a sea, ocean, lake, swamp, estuary, lagoon, etc., or a man-made source.
[0124] In the embodiment depicted in FIG. 1, the water from saltwater source 10 is first charged with CO2 to produce CO2 charged water, which CO2 is then subjected to carbonate compound precipitation conditions. As depicted in FIG. 1, a CO2 gaseous stream 30 is contacted with the water at precipitation step 20. The provided gaseous stream 30 is contacted with a suitable water at precipitation step 20 to produce a CO2 charged water. By CO2 charged water is meant water that has had CO2 gas contacted with it, where CO2 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 “CO2 content” of the water, e.g., in the form of carbonic acid, bicarbonate and carbonate ion, and a concomitant decrease in the pCO2 of the waste stream that is contacted with the water. The CO2 charged water is acidic, having a pH of 6 or less, such as 5 or less and including 4 or less. In certain embodiments, the concentration of CO2 of the gas that is used to charge the water is 10% or higher, 25% or higher, including 50% or higher, such as 75% or even higher. Contact protocols of interest include, but are not limited to: direct contacting protocols, e.g., bubbling the gas through the volume of water, concurrent contacting means, i.e., contact between unidirectionally flowing gaseous and liquid phase streams, countercurrent means, i.e., contact between oppositely flowing gaseous and liquid phase streams, and the like. Thus, contact may be accomplished through use of infusers, bubblers, fluidic Venturi reactor, sparger, gas filter, spray, tray, or packed column reactors, and the like, as may be convenient.
[0125] At precipitation step 20, carbonate compounds, which may be amorphous or crystalline, are precipitated. Precipitation conditions of interest include those that change the physical environment of the water to produce the desired precipitate product. For example, the temperature of the water may be raised to an amount suitable for precipitation of the desired carbonate compound(s) to occur. In such embodiments, the temperature of the water may be raised to a value from 5 to 70� C., such as from 20 to 50� C. and including from 25 to 45� C. As such, while a given set of precipitation conditions may have a temperature ranging from 0 to 100� C., the temperature may be raised in certain embodiments to produce the desired precipitate. In certain embodiments, the temperature is raised using energy generated from low or zero carbon dioxide emission sources, e.g., solar energy source, wind energy source, hydroelectric energy source, etc. While the pH of the water may range from 7 to 14 during a given precipitation process, in certain embodiments the pH is raised to alkaline levels in order to drive the precipitation of carbonate compound as desired. In certain of these embodiments, the pH is raised to a level which minimizes if not eliminates CO2 gas generation production during precipitation. In these embodiments, the pH may be raised to 10 or higher, such as 11 or higher. Where desired, the pH of the water is raised using any convenient approach. In certain embodiments, a pH raising agent may be employed, where examples of such agents include oxides, hydroxides (e.g., sodium hydroxide, potassium hydroxide, brucite), carbonates (e.g. sodium carbonate) and the like. The amount of pH elevating agent that is added to the saltwater source will depend on the particular nature of the agent and the volume of saltwater being modified, and will be sufficient to raise the pH of the salt water source to the desired value. Alternatively, the pH of the saltwater source can be raised to the desired level by electrolysis of the water.
[0133] Compositions of the invention find use in a variety of different applications, as reviewed above. The subject methods and systems find use in CO2 sequestration, particularly via sequestration in a variety of diverse man-made products. By “sequestering CO2” is meant the removal or segregation of CO2 from a gaseous stream, such as a gaseous waste stream, and fixating it into a stable non-gaseous form so that the CO2 cannot escape into the atmosphere. By “CO2 sequestration” is meant the placement of CO2 into a storage stable form, where the CO2 is fixed at least during the useful life of the composition. As such, sequestering of CO2 according to methods of the invention results in prevention of CO2 gas from entering the atmosphere and long term storage of CO2 in a manner that CO2 does not become part of the atmosphere.
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ClassificationC01B31/24Cooperative ClassificationY02P20/152, Y10T436/23, B01D2251/40, C04B26/02, B01D53/1418, C08K3/26, C01F5/24, C01B31/20, C01F11/18, B01D53/78, B01D2257/504European ClassificationC01B31/20, C04B26/02, C08K3/26, C01F5/24, C01F11/18, B01D53/14D, B01D53/78Legal EventsDateCodeEventDescriptionNov 4, 2009ASAssignmentOwner name: CALERA CORPORATION,CALIFORNIAFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:CONSTANTZ, BRENT;YOUNGS, ANDREW;PATTERSON, JOSHUA;REEL/FRAME:023469/0518Effective date: 20091102May 3, 2011CCCertificate of correctionApr 9, 2014FPAYFee paymentYear of fee payment: 4RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services