Ammonia-mediated carbon dioxide (CO2) separation method and system

Abstract

To provide a method and system for large-scale, feasible, and cost-effective carbon dioxide capture and sequestration. A method for sequestrating carbon dioxide (CO2) is provided. Aspects of the method include contacting a capture aqueous ammonia solution with a gaseous CO2 source under conditions sufficient to produce an aqueous ammonium carbonate solution 102. The aqueous ammonium carbonate solution is then mixed with a cation source 104 under conditions sufficient to produce a solid CO2-sequestering carbonate and an aqueous ammonium salt solution. The capture aqueous ammonia solution is then regenerated from the aqueous ammonium salt solution 106. Also provided is a system configured to carry out the method.

Description

Background Art

[0001] Carbon dioxide (CO2) is a naturally occurring compound that exists as a gas in the Earth's atmosphere. The sources of CO2 in the atmosphere are diverse and include humans and other organisms that produce CO2 during the process of respiration, as well as other natural sources such as volcanoes, hot springs, and geysers.

[0002] A further major source of atmospheric CO2 is industrial plants. Many types of industrial plants (including cement plants, oil refineries, steel mills, and power plants) burn various carbon-based fuels such as fossil fuels and synthesis gas. The fossil fuels used include coal, natural gas, petroleum, petroleum coke, and biofuels. The fuels also include those derived from tar sands, oil shale, coal liquefaction, and biofuels produced via coal gasification and synthesis gas.

[0003] The environmental impact of CO2 is an important concern. CO2 is generally regarded as a greenhouse gas. Due to the rapid increase in the concentration of atmospheric CO2 caused by human activities since the Industrial Revolution, anthropogenic CO2 is involved not only in global warming and climate change but also in the increase in the bicarbonate concentration in the oceans. The uptake of fossil fuel CO2 into the oceans is currently proceeding at approximately 1 million tons of CO2 per hour.

[0004] Due to concerns about anthropogenic climate change and ocean acidification, there is an urgent need to find large-scale, feasible, and cost-effective carbon capture and storage (CCS) methods. Generally, the CCS method separates pure CO2 from a flue gas stream containing multiple components, compresses this purified CO2, and finally injects it into an underground saline reservoir for geological isolation. These multiple steps are very energy and capital intensive.

Summary of the Invention

[0005] A method for separating carbon dioxide (CO2) is provided. Embodiments of this method include contacting an ammonia aqueous solution for recovery with a gaseous CO2 source under conditions sufficient to produce an ammonium carbonate aqueous solution. Next, the ammonium carbonate aqueous solution is mixed with a cation source under conditions sufficient to produce a solid carbonate for CO2 separation and an ammonium salt aqueous solution. Then, the ammonia aqueous solution for recovery is regenerated from the ammonium salt aqueous solution. A system configured to implement this method is also provided.

Brief Description of the Drawings

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[0007] A method for isolating carbon dioxide (CO2) is provided. Aspects of the method include contacting an aqueous ammonia solution for recovery with a gaseous CO2 source under conditions sufficient to produce an aqueous ammonium carbonate solution. Then, the aqueous ammonium carbonate solution is mixed with a cation source under conditions sufficient to produce a solid carbonate for CO2 isolation and an aqueous ammonium salt solution. Next, the aqueous ammonia solution for recovery is regenerated from the aqueous ammonium salt solution. Also provided is a system configured to implement the method.

[0008] Before explaining the present invention in more detail, it should be understood that the present invention is not limited to the specific embodiments described, and thus, naturally, it may change. Since the scope of the present invention is limited only by the appended claims, it should also be understood that the terms used in this specification are for the purpose of describing specific embodiments only and are not intended to be limiting.

[0009] When a range of values is presented, unless a different indication is explicitly given by the context, each value between the upper and lower limits of the range, down to one tenth of the unit of the lower limit, and any other stated value or intermediate value within the stated range is to be understood as being included within the present invention. The upper and lower limits of these smaller ranges may independently also be included within the respective smaller ranges and are also included within the present invention, subject to any specific exclusion of any limits within the stated range. Where the stated range includes one or both of the above limits, ranges excluding either or both of these included limits are also included within the present invention.

[0010] A particular range is presented in this specification with the term "about" prefixed to a numerical value. In this specification, the term "about" is used to provide literal support for the exact number that follows "about", as well as for numbers close to or approximately equal to the number that follows the term. In determining whether a number is close to or approximately equal to a specifically recited number, the unrecited number that is close or approximately equal may be a number that is substantially equivalent to the specifically recited number in the context in which the number is presented.

[0011] Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Any methods and materials similar to or equivalent to the methods and materials described herein can also be used in the practice or testing of embodiments of the present disclosure, but representative exemplary methods and materials are described below.

[0012] All publications and patents cited in this specification are hereby incorporated by reference as if each individual publication or patent was specifically and individually indicated to be incorporated by reference, and are incorporated by reference herein to disclose and describe the methods and / or substances in connection with which such publication is cited. The citation of any publication is for the purpose of showing that the disclosure of such publication was prior to the filing date of the present application and should not be construed as an admission that the present invention is not entitled to antedate such publication on the ground of prior invention. Further, the presented publication dates may be different from the actual publication dates, which may need to be independently verified.

[0013] Note that, in this specification and the appended claims, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. Further note that the claims may be drafted to exclude any optional element. Thus, this description is intended to serve as antecedent basis for the use of exclusive terms, such as "solely", "only", etc., or the use of "negative" limitations in connection with the recitation of claim elements.

[0014] Although it will be apparent to those skilled in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein can be readily separated from or combined with the features of any of several other embodiments without departing from the scope or spirit of the present invention, and has discrete elements and features. Any of the described methods can be performed in the order of the recited events or in any other order that is logically possible.

[0015] Method As summarized above, aspects of the present invention include a method for sequestering CO2 derived from a gaseous CO2 source. Thus, aspects of the present invention include a CO2 sequestration process, i.e., a process (method, protocol, etc.) for sequestering CO2. "Sequestration of CO2" means the removal or sequestration of a certain amount of CO2 from the environment, such as the Earth's atmosphere or an exhaust gas stream generated in an industrial plant, such that some or all of the CO2 is no longer present in the environment from which the CO2 was removed. The method for sequestering CO2 of the present invention sequesters CO2 by producing a substantially pure underground injectable CO2 product gas and a solid CO2 sequestration product with storage stability from a certain amount of CO2 such that the CO2 is sequestered. The solid CO2 sequestration product with storage stability incorporates a certain amount of CO2 into a storage-stable form, such as a storage-stable form on the ground or a storage-stable form in water, and is a storage-stable composition such that the CO2 no longer exists or cannot be a gas in the atmosphere. By sequestering CO2 according to the method of the present invention, it is possible to prevent CO2 gas from entering the atmosphere and to store CO2 over a long period of time in such a form that CO2 does not become part of the atmosphere.

[0016] As summarized above, aspects of the method include: a) contacting an aqueous ammonia solution for recovery with a gaseous CO2 source under conditions sufficient to produce an aqueous ammonium carbonate solution; b) mixing a cation source with the aqueous ammonium carbonate solution under conditions sufficient to produce a solid carbonate for CO2 sequestration and an aqueous ammonium salt solution; and c) regenerating the aqueous ammonia solution for recovery from the aqueous ammonium salt solution, for example, for continued use in further ammonia-mediated CO2 sequestration. Each of these aspects of the method will be further described in more detail below.

[0017] Recovery of CO2 Embodiments of the method include contacting an aqueous ammonia solution for recovery with a gaseous CO2 source (i.e., a CO2-containing gas) under conditions sufficient to produce an aqueous ammonium carbonate solution. The CO2-containing gas may be pure CO2 or, depending on the source, may be a mixture with one or more other gases and / or particulate components, for example, a multi-component gas (i.e., a multi-component gas stream). In certain embodiments, the CO2-containing gas is obtained from an industrial plant, for example, when the CO2-containing gas is an exhaust gas supply stream derived from an industrial plant. The industrial plant from which the CO2-containing gas can be obtained, for example, as an exhaust gas supply stream derived from the industrial plant, can be various plants. The industrial plants of interest may include, but are not limited to, power plants and industrial product manufacturing plants such as chemical and machining plants, oil refineries, cement plants, steel mills, etc., as well as other industrial plants that generate CO2 as a by-product of fuel combustion or other processing steps (such as firing by a cement plant). The supply streams of interest include gas streams generated in an industrial plant, for example, as secondary or incidental products of the processes carried out by the industrial plant.

[0018] In certain embodiments, the exhaust gas stream produced by an industrial plant that burns fossil fuels, such as coal, oil, natural gas, and synthetic fuel products from naturally occurring organic fuel deposits such as tar sands, heavy oils, oil shale, etc., is targeted. In certain embodiments, the power plant is a pulverized coal power plant, a supercritical coal power plant, a mass burn coal power plants, a fluidized bed coal power plant, a gas or oil fired boiler and steam turbine power plant, a gas or oil fired boiler simple cycle gas turbine power plant, and a gas or oil fired boiler combined cycle gas turbine power plant. In certain embodiments, the exhaust gas stream produced by a power plant that burns synthesis gas, i.e., a gas produced by gasification of an organic material such as coal, biomass, etc., is targeted. For example, in certain embodiments, such a power plant is an integrated gasification combined cycle (IGCC) power plant. In certain embodiments, the exhaust gas stream produced by a heat recovery steam generator (HRSG) plant is targeted. The exhaust gas stream targeted also includes the exhaust gas stream generated in a cement plant. Cement plants whose exhaust gas stream can be used in the method of the present invention include both wet process and dry process plants, and these plants may use a shaft kiln or a rotary kiln, and may be equipped with a pre - calciner. Each of these types of industrial plants may burn a single type of fuel or may burn two or more types of fuels sequentially or simultaneously. The exhaust gas stream targeted is the exhaust gas of the industrial plant, such as flue gas. "Flue gas" means a gas obtained from the combustion products of burning a fossil fuel or a biomass fuel and then led to a chimney (also known as the flue of an industrial plant).

[0019] The exhaust gas streams generated in cement plants are also suitable for the systems and methods of the present invention. The exhaust gas streams from cement plants include exhaust gas streams from both wet-process plants and dry-process plants, and these plants may use a shaft kiln or a rotary kiln, and may be equipped with a pre-calciner. Each of these industrial plants may burn a single type of fuel, or may burn two or more types of fuel sequentially or simultaneously. Other industrial plants such as smelters and oil refineries are also useful sources of exhaust gas streams containing carbon dioxide.

[0020] Industrial exhaust gas streams may contain carbon dioxide as a component derived from sources other than the main air, or, particularly in the case of coal-fired power plants, additional components (collectively sometimes referred to as non-CO2 pollutants), such as nitrogen oxides (NOx), sulfur oxides (SOx), and one or more additional gases. Additional gases and other components can include CO, mercury and other heavy metals, as well as particulate matter (e.g., from calcination and combustion processes). Additional non-CO2 pollutant components in the above gas streams can also include halides such as hydrogen chloride and hydrogen fluoride, fly ash, dust, and particulate matter such as metals containing arsenic, beryllium, boron, cadmium, chromium, chromium VI, cobalt, lead, manganese, mercury, molybdenum, selenium, strontium, thallium, and vanadium, as well as organic substances such as hydrocarbons, dioxins, and PAH compounds.In some embodiments, a suitable exhaust gas stream that can be processed has CO2 present in an amount of 200 ppm to 1,000,000 ppm, or 200 ppm to 500,000 ppm, or 200 ppm to 100,000 ppm, or 200 ppm to 10,000 ppm, or 200 ppm to 5,000 ppm, or 200 ppm to 2,000 ppm, or 200 ppm to 1,000 ppm, or 200 to 500 ppm, or 500 ppm to 1,000,000 ppm, or 500 ppm to 500,000 ppm, or 500 ppm to 100,000 ppm, or 500 ppm to 10,000 ppm, or 500 ppm to 5,000 ppm, or 500 ppm to 2,000 ppm, or 500 ppm to 1,000 ppm, or 1,000 ppm to 1,000,000 ppm, or 1,000 ppm to 500,000 ppm, or 1,000 ppm to 100,000 ppm, or 1,000 ppm to 10,000 ppm, or 1,000 ppm to 5,000 ppm, or 1,000 ppm to 2,000 ppm, or 2,000 ppm to 1,000,000 ppm, or 2,000 ppm to 500,000 ppm, or 2,000 ppm to 100,000 ppm, or 2,000 ppm to 10,000 ppm, or 2,000 ppm to 5,000 ppm, or 2,000 ppm to 3,000 ppm, or 5,000 ppm to 1,000,000 ppm, or 5,000 ppm to 500,000 ppm, or 5,000 ppm to 100,000 ppm, or 5,000 ppm to 10,000 ppm, or 10,000 ppm to 1,000,000 ppm, or 10,00 ppm to 500,000 ppm, or 10,000 ppm to 100,000 ppm, or 50,000 ppm to 1,000,000 ppm, or 50,000 ppm to 500,000 ppm, or 50,000 ppm to 100,000 ppm, or 100,000 ppm to 1,000,000 ppm, or 100,000 ppm to 500,000 ppm, or 200,000 ppm to 1,000 ppm including 200,000 ppm to 2,000 ppm, for example 180,000 ppm to 2,000 ppm, or 180,000 ppm to 10,000 ppm also including 180,000 ppm to 5,000 ppm.

[0021] Exhaust gas streams, particularly exhaust gas streams of various combustion gases, may contain one or more additional non-CO2 components, by way of example only, water, NOx (nitric oxide: NO and NO2), SOx (sulfur oxides: SO, SO2, and SO3), VOC (volatile organic compounds), mercury and other heavy metals, not limited thereto, and particulate matter (solid or liquid particles suspended in the gas). The temperature of the flue gas may also vary. In some embodiments, the temperature of the flue gas containing CO2 is 0°C to 2000°C, or 0°C to 1000°C, or 0°C to 500°C, or 0°C to 100°C, or 0°C to 50°C, or 10°C to 2000°C, or 10°C to 1000°C, or 10°C to 500°C, or 10°C to 100°C, or 10°C to 50°C, or 50°C to 2000°C, or 50°C to 1000°C, or 50°C to 500°C, or 50°C to 100°C, or 100°C to 2000°C, or 100°C to 1000°C, or 100°C to 500°C, or 500°C to 2000°C, or 500°C to 1000°C, or 500°C to 800°C, or 60°C to 700°C, etc., and includes 100°C to 400°C.

[0022] As summarized above, the ammonia aqueous solution for recovery is brought into contact with the gaseous CO2 source under conditions sufficient to produce an aqueous ammonium carbonate solution. The concentration of ammonia in the ammonia aqueous solution for recovery may vary, and in some cases, the ammonia aqueous solution for recovery contains ammonia (NH3) in a concentration range of 0.1 to 20.0 M, in some cases 0.1 to 5.0 M, for example in a concentration range of 0.1 to 4.0 M, for example 4.0 M, while in other cases it contains ammonia in a concentration range of 2 to 20 M, for example 4 to 20 M. The ammonia aqueous solution for recovery may optionally and appropriately contain water. The water that may constitute the ammonia aqueous solution for recovery includes, but is not limited to, fresh water, seawater, brine, produced water, and wastewater. The pH of the ammonia aqueous solution for recovery may vary, and in some cases, it is in the range of 10.0 to 13.5, for example, in the range of 10.0 to 13.0 including 10.5 to 12.5.

[0023] The CO2-containing gas may be contacted with the aqueous ammonia solution for recovery using an arbitrary and appropriate protocol, for example, as described above. For example, as the target contact protocol, a direct contact protocol, for example, bubbling the gas through a certain volume of aqueous medium, a cocurrent contact protocol, that is, contact between a gas-phase flow and a liquid-phase flow flowing in one direction, a countercurrent protocol, that is, contact between a gas-phase flow and a liquid-phase flow flowing in opposite directions, etc. may be mentioned, but it is not limited to these. When appropriate, the contact may be carried out by using an injector, a bubbler, a fluidized venturi reactor, a sparger, a gas filter, a spray, a tray, or a packed tower reactor, etc. This process may be a batch process or a continuous process.

[0024] In some cases, a gas-phase CO2 source is contacted with a liquid using a microporous membrane contactor. The target microporous membrane contactor includes a microporous membrane present in an appropriate housing, and this housing includes a gas outlet and a liquid outlet in addition to a gas inlet and a liquid inlet. This contactor is configured such that the gas and the liquid contact on opposite sides of this membrane in a form in which molecules dissolve from the gas into the liquid through the pores of the microporous membrane. This membrane can be configured in an arbitrary and appropriate form, and in some cases, this membrane is configured in a hollow fiber form. Examples of the form of the hollow fiber membrane reactor that may be used include those described in U.S. Patent Nos. 7,264,725, 6,872,240, and 5,695,545, but it is not limited to these, and the disclosure of this patent is incorporated herein by reference. In some cases, the microporous hollow fiber membrane contactor used is a Liqui-Cel (registered trademark) hollow fiber membrane contactor (Membrana, Charlotte, NC), and examples of the membrane contactor include a polypropylene membrane contactor and a polyolefin membrane contactor.

[0025] The contact between the liquid for recovery and the CO2-containing gas is carried out under conditions such that a substantial part of the CO2 present in the CO2-containing gas transfers into the solution, for example, to generate bicarbonate ions. The substantial part means 50% or more, including 10% or more, for example, 80% or more.

[0026] The temperature of the liquid for recovery in contact with the CO₂-containing gas may vary. In some cases, this temperature ranges from -1.4 to 100 °C, such as 20 to 80 °C and including 40 to 70 °C. In some cases, this temperature may range from -1.4 to 50 °C or higher, for example -1.1 to 45 °C or higher. In some cases, a lower temperature is used, and such temperature may range from -1.4 to 4 °C, for example -1.1 to 0 °C. In some cases, a higher temperature is used. For example, in some cases, the temperature of the liquid for recovery may be 25 °C or higher, for example 30 °C or higher, and in some embodiments, it may range from 25 to 50 °C, for example 30 to 40 °C.

[0027] The CO₂-containing gas and the liquid for recovery are brought into contact at a pressure suitable for generating a liquid filled with the desired CO₂. In some cases, the pressure of the contact conditions is selected such that the absorption of CO₂ is optimized, and such pressure may range from 1 atmosphere to 100 atmospheres, for example 1 to 50 atmospheres, for example 20 to 30 atmospheres or 1 to 10 atmospheres. When the contact is carried out at a place with a natural pressure of 1 atmosphere, the pressure may be increased to the desired pressure using any appropriate protocol. In some cases, the contact is carried out at a place where the optimal pressure exists, for example, a place below the surface of a water mass such as an ocean or a sea. In some cases, the contact between the CO₂-containing gas and the alkaline aqueous medium is carried out at a certain depth below the water surface (for example, the sea surface of the ocean), and this depth may, in some cases, range from 10 to 1000 meters, for example 10 to 100 meters. In some cases, the contact between the CO₂-containing gas and the liquid for CO₂ recovery is carried out at a pressure at which CO₂ is selectively absorbed from the CO₂-containing gas with respect to other gases in the CO₂-containing gas, such as N₂. In these cases, the pressure at which the CO₂-containing gas and the liquid for recovery come into contact may vary, and may be from 1 to 100 atmospheres (atm), for example 1 to 10 atmospheres, and including 20 to 50 atmospheres.

[0028] The gaseous CO2 source is contacted with the aqueous ammonia solution for recovery in a form sufficient to produce an aqueous ammonium carbonate solution. The aqueous ammonium carbonate solution can be diverse. In some cases, the aqueous ammonium carbonate solution contains at least one of ammonium carbonate and ammonium bicarbonate, and in some cases, it contains both ammonium carbonate and ammonium bicarbonate. The aqueous ammonium bicarbonate solution can also be regarded as a DIC-containing liquid. Therefore, when saturating the aqueous ammonia solution for recovery with CO2, the CO2-containing gas may be contacted with the CO2 recovery liquid under conditions sufficient to produce dissolved inorganic carbon (DIC) in the CO2 recovery liquid, that is, conditions sufficient to produce a DIC-containing liquid. DIC is represented by the formula DIC = [CO2 * + [HCO3 - + [CO3 2- (where [CO2 * is the sum of the carbon dioxide ([CO2]) concentration and the carbonic acid ([H2CO3]) concentration in the solution, [HCO3 - is the bicarbonate concentration (including ammonium bicarbonate), and [CO3 2- is the carbonate concentration (including ammonium carbonate).), which is the sum of the concentrations of inorganic carbon species. The DIC of this aqueous medium can be diverse. In some cases, it may be 10,000 ppm or more, including 5,000 ppm or more, for example, 15,000 ppm or more. In some cases, the DIC of this aqueous medium may be in the range of 7,500 - 15,000 ppm, including 5,000 - 20,000 ppm, for example, 8,000 - 12,000 ppm. The CO2 dissolved in the liquid can be diverse. In some cases, it is in the range of 1 - 35 mM, including 0.05 - 40 mM, for example, 25 - 30 mM. The pH of the resulting DIC-containing liquid can be various. In some cases, it may be in the range of 6 - 11, including 4 - 12, for example, 7 - 10, for example, 8 - 8.5.

[0029] In some cases where the gaseous CO2 source is a multi-component gas stream, the contacting is carried out in such a manner that CO2 is selectively absorbed by the CO2-absorbing aqueous medium. Selectively absorbed means that CO2 molecules preferentially transfer into solution relative to other molecules in the multi-component gas stream, such as N2, O2, Ar, CO, H2, CH4, etc.

[0030] If desired, the CO2-containing gas is contacted with the liquid for recovery in the presence of a catalyst that mediates the conversion of CO2 to bicarbonate (i.e., an absorption catalyst that is essentially heterogeneous or homogeneous). As the absorption catalyst, a catalyst that increases the rate of formation of bicarbonate ions from dissolved CO2 at a pH level in the range of 8 to 10 is targeted. The magnitude of the rate increase (compared to a control, for example, in the absence of the catalyst) can vary and, in some cases, is more than 2-fold, such as more than 5-fold, such as more than 10-fold, compared to an appropriate control. Further details regarding examples of suitable catalysts for such embodiments are described in U.S. Patent Application No. 14 / 636,043, the disclosure of which is incorporated herein by reference.

[0031] In some embodiments, the resulting aqueous ammonium carbonate solution is a two-phase liquid that contains droplets of a liquid condensed phase (LCP) in a bulk liquid, such as a bulk solution. The “liquid condensed phase” or “LCP” is a phase of a liquid solution that contains bicarbonate ions, and means a phase as described above in which the concentration of bicarbonate ions in the LCP phase is higher than the concentration in the surrounding bulk liquid. LCP droplets are characterized by the presence of a metastable bicarbonate-rich liquid precursor phase in which bicarbonate ions associate at a condensation concentration that exceeds the condensation concentration of the bulk solution and exist in an amorphous solution state. This LCP contains all of the components present in the bulk solution outside of the interface. However, the concentration of bicarbonate ions is higher than in the bulk solution. In these situations where LCP droplets are present, the LCP and the bulk solution may each contain ion pairs and pre-nucleation clusters (PNCs). These ions, when present, remain in their respective phases in the solution for a longer time compared to the ion pairs and PNCs in the solution. Further details regarding LCP-containing liquids are described in U.S. Patent Application No. 14 / 636,043, the disclosure of which is incorporated herein by reference.

[0032] Production of Solid Carbonates for CO2 Sequestration For example, following the production of an aqueous ammonium carbonate solution as described above, this aqueous ammonium carbonate solution is mixed with a cation source under conditions sufficient to produce a solid carbonate for CO2 sequestration and an aqueous ammonium salt solution. Cations of different valences can form solid carbonate compositions (e.g., in the form of carbonate minerals). In some cases, monovalent cations, such as sodium and potassium cations, may be used. In other cases, divalent cations, such as alkaline earth metal cations, e.g., calcium and magnesium cations, may be used. When cations are added to the aqueous ammonium carbonate solution, precipitation of carbonate solids, such as amorphous calcium carbonate when the divalent cation contains Ca 2+ can occur in a stoichiometric ratio of one carbonate species ion per cation.

[0033] In such cases, an optional and suitable cation source may be used. Examples of the cation source to be targeted include, but are not limited to, brine derived from water treatment facilities such as seawater desalination plants, brackish water desalination plants, groundwater recovery facilities, and drainage facilities that generate a concentrated stream of a solution with a high cation content. Natural sources such as natural seawater and geological brines, although not limited thereto, are also targeted as cation sources, and these may have various cation concentrations and can also provide a readily available cation source that induces the formation of carbonate solids from an aqueous ammonium carbonate solution. In some cases, the cation source may be the effluent from another step of the process, such as calcium salts (such as CaCl2) generated during the regeneration of ammonia from an aqueous ammonium salt solution.

[0034] The carbonate composition that is the product may be very diverse. The precipitate product may contain one or more different carbonate compounds, such as two or more different carbonate compounds, such as three or more different carbonate compounds, five or more different carbonate compounds, including amorphous carbonate compounds that cannot be clearly distinguished. The carbonate compound that is the precipitate product of the present invention may be a compound having the molecular formula X m (CO3) n wherein X is an element or combination of elements capable of chemically bonding to a carbonate group or multiple carbonate groups, and in certain embodiments, is an alkaline earth metal and not an alkali metal, and m and n are stoichiometric positive integers. These carbonate compounds may have the molecular formula X m (CO3) n ·H2O and may have one or more water of crystallization in the molecular formula. The amount of carbonate in the product may be 70% or more, including 40% or more, for example 80% or more, as measured by a coulometric method using the protocol described as coulometric titration.

[0035] The precipitated carbonate compound may contain many different cations such as ionic species of calcium, magnesium, sodium, potassium, sulfur, boron, silicon, strontium, and combinations thereof. Carbonate compounds of divalent metal cations, such as calcium carbonate compounds and magnesium carbonate compounds, are of interest. Specific carbonate compounds of interest include, but are not limited to, calcium carbonate minerals, magnesium carbonate minerals, and calcium magnesium carbonate minerals. Examples of 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). Examples of magnesium carbonate minerals of interest include magnesite (MgCO3), barringtonite (MgCO3·2H2O), nesquehonite (MgCO3·3H2O), ranfjordite (MgCO3·5H2O), hydro-magnesite, and amorphous calcium magnesium carbonate (MgCO3). Examples of calcium magnesium carbonate minerals of interest include dolomite ((CaMg)(CO3)2), huntite (Mg3Ca(CO3)4), and sergeevite (Ca2Mg 11 (CO3) 13 ·H2O), but are not limited to these. The carbonate compound of the product may contain one or more waters of hydration or may be an anhydride. In some cases, the amount expressed as the weight of the magnesium carbonate compound in the precipitate exceeds the amount expressed as the weight of the calcium carbonate compound in the precipitate. For example, the amount expressed as the weight of the magnesium carbonate compound in the precipitate may exceed the weight of the calcium carbonate compound in the precipitate by 5% or more, such as 10% or more, 15% or more, 20% or more, 25% or more, 30% or more. In some cases, the weight ratio of the magnesium carbonate compound to the calcium carbonate compound in the precipitate is in the range of 2 to 4 to 1, including, for example, 1.5 to 5 to 1, such as 2 to 3 to 1. In some cases, the precipitate may contain hydroxides such as, for example, divalent metal ion hydroxides such as calcium hydroxide and / or magnesium hydroxide.

[0036] Further details regarding the manufacture of the carbonate and the use of the carbonate so produced are presented in U.S. Application Nos. 14 / 112,495, 14 / 204,994, 14 / 214,129, 14 / 214,130, 14 / 636,043, and 14 / 861,996, and PCT Application No. US2015 / 054547, the disclosures of which are incorporated herein by reference.

[0037] In some cases, the manufacture of the carbonate is carried out in a continuous form, for example, as described in U.S. Application No. 14 / 877,766, the disclosure of this patent application being incorporated herein by reference. In some such cases, the manufacture of the carbonate may be carried out in the presence of a seed structure. A seed structure means a flowing liquid, for example, in a material generation zone, a solid structure or solid material present in the liquid before a divalent cation is introduced into the liquid. "With the aid of" means that the material is generated on or in at least one recess of the seed structure, such as pores, gaps, etc. In such cases, a composite structure of the carbonate material and the seed structure is generated. In some cases, the carbonate material as the product covers at least a part, if not all, of the surface of the seed structure. In some cases, the carbonate material as the product fills the recesses of the seed structure, such as pores, gaps, cracks, etc.

[0038] The seed structure may be widely diverse as desired. The term "seed structure" refers to any object on and / or in which the carbonate material, which is the product, is formed. The seed structure may, as desired, range from a single object to a particulate composition. When the seed structure is a single object, this seed structure may have various different shapes, which may be regular or irregular, and may have various different dimensions. Examples of the shapes include, but are not limited to, rod shape, mesh shape, massive shape, etc. A particulate composition composed of a plurality of particles, for example, a granular composition, is also within the scope. When the seed structure is a particulate composition, the dimensions of the particles may be diverse and, in some cases, are in the range of 0.01 to 1,000,000 μm, for example, 0.1 to 100,000 μm.

[0039] The seed structure may be composed of any suitable material or a plurality of materials. Examples of the materials include both the carbonate materials and non-carbonate materials as described above. The seed structure may be of natural origin, for example, natural sand, shell fragments derived from oyster shells, or other carbonate skeletal allochem, gravel, etc., or may be an artificial product, for example, crushed rock, crushed blast furnace slag, fly ash, cement kiln dust, red mud, etc. For example, the seed structure may be a particulate composition, for example, a granular composition such as sand coated with a carbonate material during the above-described process, such as a white carbonate material or a colored carbonate material.

[0040] In some cases, the seed structure may be, for example, coarse aggregate such as easily crushed Pleistocene coral rock obtained from tropical regions (e.g., Florida) that has low strength and cannot function as a concrete aggregate. In this case, the easily crushed coral rock can be used as the seed, and solid carbonate minerals for CO2 sequestration are deposited in the internal pores, whereby the coarse aggregate can pass the Los Angeles Rattler abrasion test and become suitable for use in concrete. When lightweight aggregate is desired, the deposit solution is allowed to penetrate only the outer surface, leaving the inner core relatively "hollow" to form a lightweight aggregate for use in lightweight concrete.

[0041] Manufacture of Materials from Carbonate Products for CO2 Sequestration The carbonate material that is the product may be further used, processed, and / or mixed with other compositions to produce materials for various end uses. In certain embodiments, the carbonate composition that is the product is refined (i.e., treated) in some form. Various different protocols can be mentioned as refinements. In certain embodiments, the product is subjected to mechanical refinement, such as grinding, to obtain a product having desired physical properties, such as particle size. In certain embodiments, the product is mixed with hydraulic cement as, for example, sand, gravel, aggregate, etc., and, for example, a final product, such as concrete or mortar, is manufactured.

[0042] Also, the formed building materials are also subject to the present invention. The formed building materials of the present invention can be very diverse. "Formed" means that an artificial structure has a defined physical shape, that is, it is shaped into a configuration, for example, molded, cast, cut, or manufactured by other methods. The formed building materials are different from amorphous building materials, for example, they do not have a defined and stable shape, and are different from particulate (e.g., powder) compositions that follow the shape of a container holding the building materials, such as a bag or other container. Exemplary formed building materials include, but are not limited to, bricks, plates, conduits, beams, washbasins, columns, drywall, etc. Further examples and details regarding the formed building materials are those described in U.S. Patent Application Publication No. 2011 / 0290156, the disclosure of which is incorporated herein by reference.

[0043] Also, non-cement manufactured products containing the products of the present invention as constituent components are also subject to the present invention. The non-cement manufactured products of the present invention can be very diverse. Non-cement means that the composition is not a hydraulic cement. Therefore, the composition is not a dry composition that hardens when mixed with a hardening fluid such as water to produce a stable product. Exemplary compositions include, but are not limited to, paper products, polymer products, lubricants, asphalt products, paints, cosmetics, toothpaste, deodorants, soaps, and personal care products such as shampoos, human edible products including both liquids and solids, agricultural products such as soil improvement products and animal feeds, etc. Further examples and details of the non-cement manufactured products are those described in U.S. Patent No. 7,829,053, the disclosure of which is incorporated herein by reference.

[0044] Aggregate As summarized above, the method and system of the present invention may be used, for example, to produce carbonate-coated aggregates for concrete and other applications. The carbonate-coated aggregates may be conventional aggregates or lightweight aggregates.

[0045] Aspects of the present invention include an aggregate composition for CO2 sequestration. The aggregate composition for CO2 sequestration includes a core and aggregate particles having a CO2 sequestration carbonate coating on at least a portion of the surface of the core. The CO2 sequestration carbonate coating is made of a CO2 sequestration carbonate material, such as described above. The CO2 sequestration carbonate materials present in the coatings of the coated particles of the aggregate composition of the present subject matter may vary. In some cases, the isotope profile of the core of the aggregate is different from the carbonate coating of the aggregate such that the aggregate has a carbonate coating having a first isotope profile and a core having a second isotope profile different from the first isotope profile.

[0046] In some cases, the carbonate material is a microcrystalline / amorphous carbonate material that is highly reflective. The microcrystalline / amorphous material present in the coatings of the present invention can be highly reflective. Since the material can be highly reflective, the total solar reflectance (TSR) value of the coating containing this material can be high. TSR can be measured using any suitable protocol, such as ASTM E1918 Standard Test Method for Measuring Solar Reflectance of Horizontal and Low-Sloped Surfaces in the Field (see also R. Levinson, H. Akbari, P. Berdahl, Measuring solar reflectance - Part II: review of practical methods, LBNL 2010). In some cases, the backsheet exhibits TSR values in the range of Rg;0 = 0.0 to Rg;0, = 1.0, for example, Rg;0, = 0.40 to Rg;0, = 0.98, for example, Rg;0, = 0.25 to Rg;0, = 0.99, measured using the protocol cited above.

[0047] In some cases, the coating containing the carbonate material is highly reflective to near-infrared (NIR) light, and in some cases, it is 10 - 99%, for example 50 - 99%. NIR light means light having a wavelength in the range of 700 nanometers (nm) to 2.5 mm. The NIR reflectance can be measured using any appropriate protocol, such as ASTM C1371-04a(2010)e1 Standard Test Method for Determination of Emittance of Materials Near Room Temperature Using Portable Emissometers (http: / / www.astm.org / Standards / C1371.htm) or ASTM G173-03(2012) Standard Tables for Reference Solar Spectral Irradiances: Direct Normal and Hemispherical on 37° Tilted Surface (http: / / rredc.nrel.gov / solar / spectra / am1.5 / ASTMG173 / ASTMG173.html). In some cases, the coating exhibits NIR reflectance values in the range of Rg;0 = 0.25 - Rg;0 = 0.99, including, for example, Rg;0 = 0.40 - Rg;0 = 0.98, measured using the protocols cited above, where Rg;0 = 0.0 - Rg;0 = 1.0.

[0048] In some cases, the carbonate coating is highly reflective to ultraviolet (UV) light, and in some cases, it is 10 - 99%, for example, 50 - 99%. UV light means light having a wavelength in the range of 400 nm to 10 nm. The UV reflectance can be measured using any appropriate protocol, such as ASTM G173 - 03(2012) Standard Tables for Reference Solar Spectral Irradiances: Direct Normal and Hemispherical on 37° Tilted Surface. In some cases, the material exhibits UV values in the range of Rg;0 = 0.25 - Rg;0 = 0.99, including, for example, Rg;0 = 0.4 - Rg;0 = 0.98, measured using the protocol cited above, where Rg;0 = 0.0 - Rg;0 = 1.0.

[0049] In some cases, the coating is highly reflective to visible light, and the reflectance of visible light can vary, and in some cases, it is in the range of 10 - 99%, for example, 10 - 90%. Visible light means light having a wavelength in the range of 380 nm to 740 nm. The visible light reflection characteristics can be measured using any appropriate protocol, such as ASTM G173 - 03(2012) Standard Tables for Reference Solar Spectral Irradiances: Direct Normal and Hemispherical on 37° Tilted Surface. In some cases, the coating exhibits visible light reflection characteristics in the range of Rg;0 = 0.25 - Rg;0 = 0.99, including, for example, Rg;0 = 0.4 - Rg;0 = 0.98, measured using the protocol cited above, where Rg;0 = 0.0 - Rg;0 = 1.0.

[0050] The materials that make up the carbonate component are, in some cases, amorphous or microcrystalline. When the material is microcrystalline, for example, the crystal diameter measured using Scherrer's equation applied to the FWHM of the X-ray diffraction pattern is small, and in some cases, it is 1000 microns or less in diameter, for example, 100 microns or less in diameter including 10 microns or less in diameter. In some cases, the crystal diameter ranges from 1000 μm to 0.001 μm in diameter, for example, 10 to 0.001 μm including 1 to 0.001 μm. In some cases, the crystal diameter is selected considering the wavelength(s) of the light to be reflected. For example, when light in the visible spectrum is to be reflected, the range of the crystal diameter of the material may be selected to be less than one-half of the "to be reflected" range so as to produce a photonic band gap. For example, when the range of the wavelength of the light to be reflected is 100 to 1000 nm, the crystal diameter of the material may be selected to be in the range of 50 nm or less, for example, 1 to 50 nm, for example, 5 to 25 nm. In some embodiments, the materials produced by the method of the present invention may include rod-shaped crystals and amorphous solids. The rod-shaped crystals may have various structures, and in certain embodiments, the ratio of the length to the diameter ranges from 500 to 1, for example, 10 to 1. In certain embodiments, the length of the crystal ranges from about 0.5 μm to about 500 μm, for example, 5 μm to 100 μm. In still other embodiments, a substantially completely amorphous solid is produced.

[0051] The density, porosity, and permeability of the coating material may vary depending on the application. Regarding the density, the density of the material may vary, but in some cases, the density is 5 g / cm 3 ~0.01 g / cm 3 , for example, 2.7 g / cm 3 ~0.4 g / cm 3 including 3 g / cm 3 ~0.3 g / cm 3is in the range. Regarding the porosity measured by gas surface adsorption measured by the BET method (Brown Emmett Teller (described, for example, in http: / / en.wikipedia.org / wiki / BET_theory, S. Brunauer, P. H. Emmett and E. Teller, J. Am. Chem. Soc., 1938, 60, 309. doi:10.1021 / ja01269a023)), in some cases, the porosity is 100 m 2 / g to 0.1 m 2 / g, for example, 40 m 2 / g to 1.5 m 2 / g including 60 m 2 / g to 1 m 2 / g. Regarding the permeability, in some cases, the permeability of the material is 0.1 to 100 darcies (measured using the protocol described, for example, in H. Darcy, Les Fontaines Publiques de la Ville de Dijon, Dalmont, Paris (1856)), for example, in the range of 1 to 10 darcies including 1 to 5 darcies. The permeability can also be characterized by evaluating the water absorption rate of the material. As measured by the water absorption rate protocol, for example, in some embodiments, the water absorption rate of the material is in the range of 0 to 25%, for example, 1 to 15% including 2 to 9%.

[0052] The hardness of the material may also vary. In some cases, the material exhibits a hardness of 5 or more, for example, 6 or more (measured using, for example, the protocol described in American Federation of Mineralogical Societies. “Mohs Scale of Mineral Hardness”), and in some cases, the hardness ranges from 3 to 8 Mohs, for example, 4 to 7 Mohs including 5 to 6 Mohs. The hardness can also be expressed from the perspective of the tensile strength measured using, for example, the protocol described in ASTM C1167. In such cases, the material may exhibit a compressive strength of 400 to 2000 N, for example, 500 to 1800 N including 100 to 3000 N.

[0053] In some embodiments, the carbonate material contains one or more contaminants, which are predicted not to leach into the environment by one or more tests selected from the group consisting of the Toxicity Characteristic Leaching Procedure, Extraction Procedure Toxicity Test, Synthetic Precipitation Leaching Procedure, California Waste Extraction Test, Soluble Threshold Limit Concentration, American Society for Testing and Materials Extraction Test, and Multiple Extraction Procedure. The tests and combinations of tests may be selected according to the possible contaminants of the composition and the storage conditions. For example, in some embodiments, the composition may contain As, Cd, Cr, Hg, and Pb (or their products), each of which may be present in the exhaust gas stream of a coal-fired power plant. The TCLP test for As, Ba, Cd, Cr, Pb, Hg, Se, and Ag may be a suitable test for the aggregates described herein. In some embodiments, the carbonate composition of the present invention contains As, and this composition is predicted not to leach As into the environment. For example, the As in the TCLP extract of this composition may be less than 5.0 mg / L, which indicates that this composition is not harmful with respect to As. In some embodiments, the carbonate composition of the present invention contains Cd, and this composition is predicted not to leach Cd into the environment. For example, the Cd in the TCLP extract of this composition may be less than 1.0 mg / L, which indicates that this composition is not harmful with respect to Cd. In some embodiments, the carbonate composition of the present invention contains Cr, and this composition is predicted not to leach Cr into the environment. For example, the Cr in the TCLP extract of this composition may be less than 5.0 mg / L, which indicates that this composition is not harmful with respect to Cr.In some embodiments, the carbonate composition of the present invention contains Hg, and this composition is predicted not to leach Hg into the environment. For example, the Hg in the TCLP extract of this composition may be less than 0.2 mg / L, which indicates that this composition is not harmful with respect to Hg. In some embodiments, the carbonate composition of the present invention contains Pb, and this composition is predicted not to leach Pb into the environment. For example, the Pb in the TCLP extract of this composition may be less than 5.0 mg / L, which indicates that this composition is not harmful with respect to Pb. In some embodiments, the carbonate composition and aggregate of the present invention may not be harmful with respect to different combinations of contaminants in a given test. For example, in a given test, this carbonate composition may not be harmful with respect to all metal contaminants. The TCLP extract of the composition may be, for example, less than 5.0 mg / L for As, less than 100.0 mg / L for Ba, less than 1.0 mg / L for Cd, less than 5.0 mg / mL for Cr, less than 5.0 mg / L for Pb, less than 0.2 mg / L for Hg, 1.0 mg / L for Se, and less than 5.0 mg / L for Ag. In fact, in the TCLP analysis of the composition of the present invention, most, if not all, of the metals being tested may be below the detection limit. In some embodiments, the carbonate composition of the present invention may not be harmful with respect to all (e.g., inorganic, organic, etc.) contaminants in a given test. In some embodiments, the carbonate composition of the present invention may not be harmful with respect to all contaminants in any combination of tests selected from the group consisting of Toxicity Characteristic Leaching Procedure, Extraction Procedure Toxicity Test, Synthetic Precipitation Leaching Procedure, California Waste Extraction Test, Soluble Threshold Limit Concentration, American Society for Testing and Materials Extraction Test, and Multiple Extraction Procedure.Accordingly, the carbonate composition and aggregate of the present invention can effectively sequester CO2 (e.g., as carbonate, bicarbonate, or a combination thereof) together with various chemical species (or their by-products) derived from exhaust gas streams, industrial waste sources of divalent cations, industrial waste sources of proton scavengers, or combinations thereof that may become contaminants when released into the environment. The compositions of the present invention incorporate environmental contaminants (e.g., metals and metal by-products such as Hg, Ag, As, Ba, Be, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sb, Se, Tl, V, Zn, or combinations thereof) in a non-leachable form.

[0054] The aggregate composition of the present invention includes a core region and particles having a carbonate coating for CO2 sequestration on at least a portion of the surface of the core. The coating may cover 90% or more, including 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 95% or more of the surface of the core. The thickness of the carbonate layer may vary as desired. In some cases, this thickness may range from 0.1 μm to 10 mm, for example, from 1 μm to 1000 μm including 10 μm to 500 μm.

[0055] The core of the coated particles of the aggregate composition described herein may be widely diverse. The core may be composed of any suitable and appropriate aggregate. Examples of suitable aggregates include natural mineral aggregates such as carbonate rocks, sand (e.g., natural silica sand), sandstone, gravel, granite, diorite, porphyry, basalt, etc., and synthetic aggregates such as industrial by-product aggregates, e.g., blast furnace slag, fly ash, municipal waste, and recycled concrete, but are not limited thereto. In some cases, the core contains a material different from the carbonate coating.

[0056] In some cases, the aggregate is a lightweight aggregate. In such cases, the core of the coated particle of the aggregate composition described herein may be widely diverse as long as the core is coated and provides the desired lightweight aggregate composition. The core may be composed of any optional and appropriate material. Examples of suitable aggregates include conventional lightweight aggregates such as lightweight aggregates of natural origin such as pumice, scoria, or crushed volcanic rock such as tuff, and synthetic materials such as heat-treated clay, shale, slate, diatomaceous earth, perlite, vermiculite, blast furnace slag, and fly ash, as well as non-conventional porous materials such as synthetic materials such as crushed coral, polymers, and low-density polymer materials, recycled waste such as wood, fibrous materials, cement kiln dust residues, recycled glass, various volcanic minerals, granite, silica-containing minerals, and ore tailings, but are not limited thereto.

[0057] The physical properties of the coated particles of the aggregate composition may vary. The density of the aggregate of the present invention may vary depending on the application for which the aggregate is to be used, for example, as long as the aggregate provides the desired properties for the building material in which the aggregate is used. In certain cases, the density of the aggregate particles is in the range of 1.1 to 5 g / cm³, for example, 1.3 to 3.15 g / cm³ including 1.8 g / cm³ to 2.7 g / cm³. Other particle densities in embodiments of the present invention may be, for example, in the range of 1.1 to 2.2 g / cm³ for lightweight aggregates, such as 1.2 to 2.0 g / cm³ or 1.4 to 1.8 g / cm³. In some embodiments, the present invention has a bulk density (unit weight) of 50 lb / ft 3 ~200 lb / ft 3 、or 75 lb / ft 3 ~175 lb / ft 3 、or 50 lb / ft 3 ~100 lb / ft 3 、or 75 lb / ft 3 ~125 lb / ft 3 、or lb / ft 3 ~115 lb / ft 3 、or 100 lb / ft 3 ~200 lb / ft 3 、or 125 lb / ft3 ~lb / ft 3 or 140 lb / ft 3 ~160 lb / ft 3 or 50 lb / ft 3 ~200 lb / ft 3 provides an aggregate in the range of. Some embodiments of the present invention are lightweight aggregates, for example, having a bulk density (unit weight) of 75 lb / ft 3 ~125 lb / ft 3 for example 90 lb / ft 3 ~115 lb / ft 3 In some cases, the weight of the lightweight aggregate is in the range of 50 - 1200 kg / m 3 for example 80 - 11 kg / m 3 is the range.

[0058] The hardness of the aggregate particles constituting the aggregate composition of the present invention may also vary. In certain cases, the hardness expressed in Mohs hardness is in the range of 1.0 - 9, for example, in the range of 1 - 7 including 1 - 6 or 1 - 5. In some embodiments, the Mohs hardness of the aggregate of the present invention is in the range of 2 - 5, or 2 - 4. In some embodiments, the Mohs hardness is in the range of 2 - 6. Other hardnesses such as Rockwell hardness, Vickers hardness, or Brinell hardness may also be used to characterize the aggregate of the present invention, and values equivalent to the Mohs hardness values may also be used to characterize the aggregate of the present invention. For example, a Vickers hardness grade of 250 corresponds to Mohs grade 3. Conversions between scales are known in the art.

[0059] The abrasion resistance of the aggregate may also be important for use on road surfaces, for example, when highly wear-resistant aggregates are useful to prevent surface abrasion. Abrasion resistance is related to, but not the same as, hardness. The aggregates of the present invention include, for example, aggregates having an abrasion resistance similar to that of natural limestone, or aggregates having an abrasion resistance superior to that of natural limestone, as well as aggregates having an abrasion resistance lower than that of natural limestone, as measured by methods accepted in the art such as ASTM C131-03. In some embodiments, the abrasion resistance of the aggregates of the present invention, as measured by ASTM C131-03, is less than 50%, or less than 40%, or less than 35%, or less than 30%, or less than 25%, or less than 20%, or less than 15%, or less than 10%.

[0060] The porosity of the aggregates of the present invention may also be within a specific range. As will be understood by those skilled in the art, in some cases, aggregates with a high porosity are desirable, in other cases, aggregates with a medium porosity are desirable, and in other cases, aggregates with a low or non-porous porosity are desirable. The porosity of the aggregates of some embodiments of the present invention, measured by water uptake after complete immersion for 60 minutes following oven drying and expressed as a percentage of the dry weight, may be in the range of 1 to 40%, for example 2 to 20%, or 2 to 10%, and further 3 to 9%, including 2 to 15%.

[0061] The sizes of the aggregate particles may vary. In some embodiments, the aggregate composition of the present invention may be a particulate composition that may be classified as fine particles or coarse particles. The fine aggregate according to an embodiment of the present invention is a particulate composition that substantially completely passes through a No. 4 sieve (ASTM C125 and ASTM C33). The average particle size of the fine aggregate composition according to an embodiment of the present invention ranges from 10 μm to 4.75 mm, for example, from 50 μm to 3.0 mm including 75 μm to 2.0 mm. The coarse aggregate of the present invention is a composition in which most remains on the No. 4 sieve (ASTM C125 and ASTM C33). The coarse aggregate composition according to an embodiment of the present invention is a composition having an average particle size in the range of 4.75 mm to 200 mm, for example, from 4.75 to 150 mm including 5 to 100 mm. As used herein, "aggregate" may also, in some embodiments, include sizes of 3 inches to 12 inches or even 3 inches to 24 inches, or more, for example 12 inches to 48 inches, or greater than 48 inches.

[0062] Concrete dry composite Also provided is a concrete dry composite that, when mixed with a suitable curing liquid (such as those described hereinafter), produces a curable composition that cures into concrete or mortar. The concrete dry composite described herein includes a certain amount of aggregate (such as those described above) and a cement such as a hydraulic cement. The term "hydraulic cement" is used in its conventional meaning and refers to a composition that cures after being mixed with water or a solution in which the solvent is water, such as a mixed solution. The curing of the product produced by mixing the concrete dry composite of the present invention with an aqueous liquid is due to the formation of a hydrate formed from the cement upon reaction with water, and this hydrate is essentially insoluble in water.

[0063] The aggregates of the present invention are used in place of conventional natural rock aggregates used in conventional concrete when mixed with pure Portland cement. In certain embodiments, other hydraulic cements of interest include blended Portland cement. The phrase "blended Portland cement" includes a hydraulic cement composition containing a Portland cement component and a significant amount of non-Portland cement component. When the cement of the present invention is a blended Portland cement, this cement contains a Portland cement component. The Portland cement component may be any optional and suitable Portland cement. As is known in the art, Portland cement is a powder composition produced by grinding Portland cement clinker (90% or more), a limited amount of calcium sulfate for controlling the setting time, and up to 5% of minor components (allowed by various standards). When the exhaust gas used to supply carbon dioxide to the above-described reaction contains SOx, sufficient sulfate may be present as calcium sulfate in the precipitated material, eliminating the need to add calcium sulfate as either cement or aggregate. As defined by European Standard EN197.1, "Portland cement clinker must be a hydraulic material composed of at least 2 / 3 calcium silicate (3CaO·SiO2 and 2CaO·SiO2) by mass, the balance consisting of aluminum and iron-containing clinker phases and other compounds. The ratio of CaO to SiO2 must be less than 2.0. The magnesium content (MgO) must not exceed 5.0% by mass." The concern regarding MgO is that brucite, magnesium hydroxide, may be formed in the later stage of the hardening reaction, which may lead to deformation, strength reduction, and cracking of the cement. Since brucite may be formed by MgO, brucite will not be formed in the case of magnesium carbonate-containing cement. In certain embodiments, the Portland cement component of the present invention is any Portland cement that meets the ASTM standards and the specifications of ASTM C150 (Types I - VIII) of the American Society for Testing and Materials (ASTM C150 - Standard Specification for Portland Cement).ASTM C150 includes eight types of Portland cement within its scope, each type having different properties and being specifically used according to those properties.

[0064] As hydraulic cement, carbonate-containing hydraulic cement is also targeted. Such carbonate-containing hydraulic cement, its manufacturing method and usage method are described in U.S. Patent No. 7,735,274, and the disclosure of this application is incorporated herein by reference.

[0065] In certain embodiments, the hydraulic cement may be a mixture of two or more different types of hydraulic cement, such as Portland cement and carbonate-containing hydraulic cement. In certain embodiments, the amount of the first cement in the mixture, for example Portland cement, ranges from 10 to 90% (w / w), for example, 30 to 70% (w / w) including 40 to 60% (w / w), for example, a mixture of 80% OPC (ordinary Portland cement) and 20% carbonate hydraulic cement.

[0066] In some cases, the CarbonStar rating (CSR) of the concrete dry composite composition and the concrete produced from this composition is lower than that of the control composition without the aggregates of the present invention. The CarbonStar rating (CSR) is a value that characterizes the embodied carbon (in the form of CaCO3) for any product, compared to the carbon intensity of the production of the product itself (i.e., in terms of CO2 generation). CSR is a measure based on the mass of embodied CO2 per unit of concrete. Among the three components in concrete, namely water, cement, and aggregates, cement is the most important factor that overwhelmingly contributes to CO2 emissions, with approximately a 1:1 mass ratio (1 ton of cement generates approximately 1 ton of CO2). Thus, if 1 cubic yard of concrete uses 600 pounds of cement, its CSR is 600. For 1 cubic yard of concrete according to an embodiment of the present invention, which contains 600 pounds of cement and in which at least a part of the aggregates is, for example, the carbonate-coated aggregates as described above, the CSR will be less than 600, and the CSR may be, for example, 500 or less, including 550 or less, 400 or less, 250 or less, 100 or less. In some cases, the CSR may be a negative value, for example, -500 or less, including -100 or less, -1000 or less. In some cases, the CSR of 1 cubic yard of concrete with 600 pounds of cement may be in the range of, for example, 500 to -5000, including -100 to -4000, such as -500 to -3000. To determine the CSR of a given 1 cubic yard of concrete containing the carbonate-coated aggregates of the present invention, the initial value of CO2 generated for the production of the cement component of 1 cubic yard of the concrete is determined. For example, if 1 cubic yard of the concrete contains 600 pounds of cement, an initial value of 600 is assigned to 1 cubic yard of the concrete. Next, the amount of the carbonate coating in 1 cubic yard of the concrete is determined.The molecular weight of the carbonate is 100 arbitrary units, and since 44% of the carbonate is CO2, multiply the amount of the carbonate film present in 1 cubic yard of the concrete by 0.44, subtract the resulting value from the initial value, and obtain the CSR for 1 cubic yard of concrete. For example, if 1 cubic yard of a given concrete mixture consists of 600 pounds of cement, 300 pounds of water, 1429 pounds of fine aggregate, and 1739 pounds of coarse aggregate, the weight of 1 cubic yard of concrete is 4068 pounds and the CSR is 600. If 10% of the total mass of the aggregates in this mixture is replaced with a carbonate film (such as the one described above), the amount of carbonate present in 1 cubic yard of the modified concrete is 317 pounds. Multiplying this value by 0.44 gives 139.5. Subtracting this number from 600 gives a CSR of 460.5.

[0067] Hardening composition The hardening compositions of the present invention, such as concrete and mortar, are produced by mixing hydraulic cement simultaneously with a certain amount of aggregate (fine aggregate for mortar, such as sand, and coarse aggregate with or without fine aggregate for concrete), and an aqueous liquid, such as water, or by pre-mixing the cement with the aggregate and then mixing the resulting dry components with water. The minimum size of the coarse aggregate selected for a concrete mixture using the cement composition of the present invention may be about 3 / 8 inch, and the size of this aggregate may vary, including a particle size distribution between these limits from the minimum value to 1 inch or more. The atomized aggregate is less than 3 / 8 inch in size, and here too, it may be stepped down to a finer size up to about the size of a 200-mesh sieve. Fine aggregate may be present in both the mortar and concrete of the present invention. The weight ratio of cement to aggregate in the dry components of the cement may vary, and in certain embodiments, it is in the range including 1:10 to 4:10, such as 2:10 to 5:10 and 55:1000 to 70:100.

[0068] To produce a hardenable composition, such as concrete, the liquid phase, such as an aqueous fluid, which is to be mixed with the dry components, can vary from pure water to water containing one or more solutes, additives, co-solvents, etc., as desired. The ratio of the dry components to the liquid phase mixed in the preparation of the hardenable composition can vary, and in certain embodiments, it is in the range of 2:10 to 7:10, for example, including 3:10 to 6:10, such as 4:10 to 6:10.

[0069] In certain embodiments, the cement may be used with one or more admixtures. Admixtures are compositions added to concrete to impart desirable properties that cannot be obtained in a basic concrete mixture, or to modify the properties of the concrete to make it easier to use, or to make it more suitable for a particular purpose or cost reduction. As is known in the art, an admixture is any material or composition other than hydraulic cement, aggregates, and water, and is used as a component of concrete or mortar to improve some property of the concrete or mortar or to reduce their cost. The amount of admixture used can vary depending on the nature of the admixture. In certain embodiments, the amount of these components is in the range of 1 to 50% w / w, for example, 2 to 10% w / w.

[0070] Examples of the admixtures of interest include finely divided mineral admixtures such as cementitious materials, pozzolans, pozzolanic and cementitious materials, and nominally inert materials. Examples of pozzolans include diatomaceous earth, milky white chart, clay, shale, fly ash, silica fume, and tuff, and pumice is part of the well-known pozzolans. Certain ground granulated blast furnace slag and high-calcium fly ash have both pozzolanic and cementitious properties. Examples of nominally inert materials can also include finely divided quartzite, dolomite, limestone, marble, granite, etc. Fly ash is defined in ASTM C618.

[0071] Other types of admixtures that may be used include plasticizers, accelerators, retarders, air-entrainers, foaming agents, water reducers, corrosion inhibitors, and pigments.

[0072] Thus, admixtures that may be used include curing accelerators, curing retarders, air-entraining agents, defoamers, alkali reactivity reducing agents, binder admixtures, dispersants, colorants, corrosion inhibitors, moisture-proof agents, gas generating agents, permeability reducing agents, pumping aids, shrinkage compensating agents, fungicides, bactericides, insecticides, viscoelasticity improvers, finely divided mineral admixtures, pozzolans, aggregates, wetting agents, strength improvers, water repellents, and any other concrete or mortar admixtures or additives, but are not limited thereto. Admixtures are well known in the art, and any desired admixtures of the types described above or any other desired types may be used at will and as appropriate. For example, reference is made to U.S. Patent No. 7,735,274, which is hereby incorporated by reference in its entirety.

[0073] In some cases, the curable composition is produced using an admixture of a bicarbonate-rich product (BRP), which may be in liquid or solid form, as described, for example, in U.S. Patent Application No. 14 / 112,495, published as U.S. Application Publication No. 2014 / 0234946, the disclosure of which is hereby incorporated by reference.

[0074] In certain embodiments, for example, when fiber-reinforced concrete is desired, the curable composition of the present invention includes cement used with fibers. The fibers may be made of zirconia-containing materials, steel, carbon, glass fibers, or synthetic materials such as polypropylene, nylon, polyethylene, polyester, rayon, high-strength aramid (i.e., Kevlar (registered trademark)), or mixtures thereof.

[0075] The components of the curable composition can be mixed using any appropriate and suitable protocol. Each material may be mixed during operation, or some or all of the materials may be premixed. Alternatively, a portion of the material may be mixed with water, with or without admixtures such as high-performance water reducers, and then the remaining materials may be mixed therewith. Any conventional device can be used as the mixing device. For example, a Hobart mixer, an inclined cylindrical mixer, an omnimixer, a Henschel mixer, a V-type mixer, and a Nauta mixer can be used.

[0076] Following the mixing of the components to produce a curable composition (e.g., concrete), in some cases, the curable composition, which was initially a fluid composition, subsequently cures after a predetermined time. The curing time can vary and, in certain embodiments, is in the range of 30 minutes to 48 hours, for example, 30 minutes to 24 hours including 1 hour to 4 hours.

[0077] The strength of the cured product can also vary. In certain embodiments, the strength of the cured cement may be in the range of 5 MPa to 70 MPa, for example, 10 MPa to 50 MPa including 20 MPa to 40 MPa. In certain embodiments, the cured product resulting from the cement of the present invention is extremely durable as measured using, for example, the test methods described in ASTM C1157.

[0078] Structure Aspects of the invention further include structures manufactured from the aggregates and curable compositions of the invention. Accordingly, further embodiments include artificial structures comprising the aggregates of the invention and methods for their manufacture. Accordingly, in some embodiments, the invention provides artificial structures comprising one or more of the aggregates described herein. The artificial structure may be any structure that may use aggregates, such as a building, a dam, a levee, a road, or any other artificial structure incorporating aggregates or rock. In some embodiments, the invention provides an artificial structure comprising the aggregates of the invention, such as a building, a dam, or a road, and in some cases, the aggregates may contain, for example, CO2 from the fossil fuel sources described above. In some embodiments, the invention provides a method for manufacturing a structure, which includes providing the aggregates of the invention.

[0079] Albedo improvement applications In some cases, the solid carbonate product may be used for albedo improvement applications. Albedo, i.e., the reflectance coefficient, refers to the diffuse reflectance or reflectivity of a surface. Albedo is defined as the ratio of the reflected radiation from the surface to the incident radiation on the surface. Albedo is a dimensionless ratio and may be expressed as a ratio or a percentage. Albedo is measured on a scale from zero for a surface that has no reflectivity of a completely black surface to 1 for a perfect reflection of a white surface. Albedo depends on the frequency of the radiation, but herein albedo is shown without reference to a specific wavelength and thus refers to the average value over the entire visible light spectrum, i.e., from about 380 to about 740 nm.

[0080] Since the methods of these embodiments are methods for improving the albedo of a surface, in some cases, by this method, an increase in albedo in the range of 0.9 or more, including 0.95 or more, including up to 1.0, such as 0.95 or more, 0.975 or more, 0.9 or more, 0.8 or more, 0.7 or more, 0.6 or more, 0.5 or more, 0.4 or more, 0.3 or more, 0.2 or more, 0.1 or more (compared to the albedo of the same surface not subjected to the method of the present invention, for example, an appropriate control) occurs. Therefore, aspects of the method include increasing the albedo of the surface in the range of 0.95 or more, including 0.975 or more, 0.9 or more, 0.8 or more, 0.7 or more, 0.6 or more, 0.5 or more, 0.4 or more, 0.3 or more, 0.2 or more, 0.1 or more, and up to about 1.0.

[0081] Aspects of the method include combining the surface to be treated with an effective amount of, for example, the highly reflective crystalline or amorphous material composition described above, in an amount effective to improve the albedo of the surface by a desired width such as the widths listed above. This material composition may be bound to the surface to be treated using any suitable and appropriate protocol. Thus, the material composition may be bound to the surface to be treated by incorporating the material into the material of the object having the surface to be modified. For example, if the surface to be treated is the surface of a building material such as a roof tile or a concrete mixture, the material composition may be mixed into the composition of the material such that the material composition is present on the surface of the object to be treated. Alternatively, for example, the material composition may be disposed on at least a portion of the surface to be treated by coating the surface with the composition. When the surface is coated with the material composition, the thickness of the film formed on the surface may vary and, in some cases, may be in the range of 2 mm to 20 mm, including 5 mm to 10 mm, including 0.1 mm to 25 mm. Applications in use as highly reflective pigments in other coating agents such as paints and solar panels are also contemplated.

[0082] The albedo of various surfaces may be improved. Target surfaces include surfaces of both artificial objects and objects of natural origin that face at least partially in an empty direction. Target artificial surfaces include roads, sidewalks, buildings and their components, such as roofs and their components (roofing sheets, roof granules, etc.) and sidewalls, runways, and other artificial structures, such as walls, dams, monuments, ornaments, etc., but are not limited thereto. Target surfaces of natural origin include surfaces of plants existing in both forested and non-forested areas, non-vegetated areas, water surfaces, such as lake surfaces, ocean surfaces, and sea surfaces, etc., but are not limited thereto.

[0083] For example, using the method described herein to form a carbonate layer on the surface of colored roof granules, the albedo of the colored granules can be easily increased. The thickness of the layer of carbonate material present on the surface of the colored roof granules can vary, but in some cases, the thickness ranges from 0.1 to 200 μm, for example, 5 to 100 μm, including 1 to 150 μm. By coating various different types of colored granules as described above, the reflectivity of the colored granules can be improved without substantially reducing the color of the colored granules, if at all. Examples of types of granules that may be coated with the carbonate layer described herein include roof granules.

[0084] Roof granules which can improve the reflectance of colored granules without substantially reducing the color of the colored granules, even if there is some color change, by coating with a carbonate layer. The roof granules may contain a core formed from a ground and sieved mineral material, which is then coated with one or more colored coating layers containing a binder in which one or more colored pigments such as appropriate metal oxides are dispersed. An inorganic binder may be used. The binder may be a soluble alkaline silicate, which is then insolubilized by heat or a chemical reaction, for example, by reaction between an acidic substance and the alkaline silicate, to form an insoluble colored coating on the mineral particles. The base particles used in the process for preparing the roof granules of the present invention can take several forms. The base particles may be inert core particles. The core particles may be chemically inert materials such as inert mineral particles, solid or hollow glass or ceramic spheres, or expanded glass or ceramic particles. Suitable mineral particles can be produced by a series of quarrying, grinding, and sieving operations and generally have a size intermediate between sand and gravel (i.e., between about U.S. mesh number 8 and U.S. mesh number 70). The average particle size of the core particles is from about 0.2 mm to about 3 mm, for example, from about 0.4 mm to about 2.4 mm. In particular, particles of appropriate size of natural origin substances such as talc, volcanic ash, granite, silica sand, chlorite, andesite, porphyry, marble, diorite, rhyolite, diabase, grey stone, quartz, slate, trap rock, basalt, and marine shells, as well as processed materials such as ceramic refractory clay and proppant, and recycled processed materials such as ground bricks, concrete, porcelain, and refractory clay can be used.Solid and hollow glass spheres are available, for example, from Potters Industries Inc., P.O. Box 840, Valley Forge, Pa. 19482-0840, as SPHERIGLASS® solid "A" glass sphere products, grade 1922 having an average particle size of 0.203 mm, product code 602578 having an average diameter of 0.59 mm, BALLOTTINI impact beads, product grade A having a diameter range of 600 to 850 micrometers (U.S. sieve size 20 to 30), and QCEL hollow spheres, product code 300 having an average particle size of 0.090 mm, etc. If desired, the glass spheres can be coated or treated with a suitable coupling agent to improve the adhesion of the internal coating composition to the binder. In the granules, the particles can be coated with a coating composition containing a binder and a pigment. The coating binder may be an inorganic material such as a metal silicate binder, for example, an alkali metal silicate such as sodium silicate.

[0085] Coating pigments that may be used include, but are not limited to, PC-9415 yellow, PC-9416 yellow, PC-9158 autumn gold, PC-9189 bright golden yellow, V-9186 iron-free chestnut brown, V-780 black, V0797 IR black, V-9248 blue, PC-9250 bright blue, PC-5686 turquoise, V-13810 red, V-12600 camouflage green, V12560 IR green, V-778 IR black, and V-799 black.

[0086] The methods described herein may also be used to produce frac sand. Frac sand is used in the oil and gas recovery industry to maintain porous voids in fractured geological structures to maintain the integrity of the geological fracture. Using the methods described herein, coated substrates and processed sand having an adjustable surface coating that can contribute to the buoyancy of the sand in a fluid stream may be produced. Using the methods described herein, the surface of the sand is effectively designed to maintain a buoyancy above average in the fluid flow when the fracturing fluid is pumped into the geological fracture site under very high pressure, and a substrate having a carbonate material (crystalline or amorphous) in a dense regular pattern form or an irregular pattern form may be produced. In some cases, the method produces a product that, when contacted with a second medium, reacts as an expansive cement and provides voids for gas and fluid to flow from the surrounding geological structure, and includes a crystalline or amorphous but unreacted cementitious coating compound. This wide range of properties can be activated by close contact with a fluid or gas, continuous fluid contact, or other magnetic or acoustic activation supplied from the geological surface.

[0087] The methods of using the carbonate precipitation compounds described herein in the various applications described above, including albedo improvement applications, and the compositions produced thereby are further described in U.S. Application Nos. 14 / 112,495 and 14 / 214,129, the disclosures of which are incorporated herein by reference.

[0088] Ammonia regeneration As described above, by mixing a cation source with an aqueous ammonium carbonate solution, a solid carbonate for CO2 separation and an aqueous ammonium salt solution are produced. The produced aqueous ammonium salt solution may vary with respect to the nature of the anion of the ammonium salt, and specific ammonium salts that may be present in the aqueous ammonium salt solution include, but are not limited to, ammonium chloride, ammonium acetate, ammonium sulfate, ammonium nitrate, and the like.

[0089] Aspects of the present invention may further include, in addition to the production of carbonate, regenerating the aqueous ammonia solution for recovery from the aqueous ammonium salt solution, for example, as described above. The regeneration of the aqueous ammonia solution for recovery means treating the aqueous ammonium salt solution in a manner sufficient to generate a certain amount of ammonia from the aqueous ammonium salt solution. The proportion of the introduced ammonium salt converted to ammonia during this regeneration step may vary and, in some cases, may be in the range of 20 to 80%, for example, 35 to 55%.

[0090] Ammonia may be regenerated from the aqueous ammonium salt solution in this regeneration step using any suitable regeneration protocol. In some cases, a distillation protocol is used. Any suitable distillation protocol may be used, but in some embodiments, the distillation protocol used involves heating the aqueous ammonium salt solution in the presence of a source of an alkaline component to produce a gaseous ammonia / water product, which is then condensed to produce a liquid aqueous ammonia solution for recovery.

[0091] The source of the alkaline component may vary as long as it is sufficient to convert the ammonium in the aqueous ammonium salt solution to ammonia. Any suitable source of the alkaline component may be used.

[0092] Examples of the source of the alkali component that may be used in this playback step include chemical agents. Examples of the chemical agents that may be used as the source of the alkali component include, but are not limited to, hydroxides, organic bases, superbases, oxides, and carbonates. Examples of the hydroxides include chemical species that provide hydroxide anions in a solution, including sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH)2), or magnesium hydroxide (Mg(OH)2). Organic bases are generally nitrogen-containing bases that are carbon-containing molecules, including primary amines such as methylamine, secondary amines such as diisopropylamine, tertiary amines such as diisopropylethylamine, aromatic amines such as aniline, pyridine, imidazole, and benzimidazole, and various forms thereof. Examples of the superbases suitable for use as a proton remover include sodium ethoxide, sodium amide (NaNH2), sodium hydride (NaH), butyllithium, lithium diisopropylamide, lithium diethylamide, and lithium bis(trimethylsilyl)amide. For example, oxides including calcium oxide (CaO), magnesium oxide (MgO), strontium oxide (SrO), beryllium oxide (BeO), and barium oxide (BaO) are also suitable proton removers that may be used.

[0093] The silica source is also a target as the alkali component source. The silica source may be pure silica, or a composition containing silica in combination with other compounds, such as inorganic substances, as long as the silica source is sufficient to impart the desired alkalinity. In some cases, the silica source is a silica source of natural origin. Examples of silica sources of natural origin include rocks containing silica, which may be in the form of sand or larger rocks. When the silica source is a larger rock, in some cases, the rock is crushed, its size is reduced, and its surface area is increased. The silica source composed of components in the range of 0.1 mm to 500 cm, including the longest dimension in the range of 0.01 mm to 1 meter, such as 1 mm to 100 cm, such as 1 mm to 50 cm, is the target. The silica source may be surface-treated, if desired, to increase the surface area of the silica source. Various different silica sources of natural origin may be used. Examples of the target silica sources of natural origin include ultramafic rocks such as komatiite, picrite basalt, kimberlite, lamproite, and kanranite; mafic rocks such as basalt, diabase (coarse-grained basalt), and porphyry; intermediate rocks such as andesite and diorite; intermediate calc-alkaline rocks such as quartz andesite and granodiorite; and igneous rocks including felsic rocks such as rhyolite, aplite-pegmatite, and granite, but are not limited thereto. Artificial silica sources are also the target. Examples of artificial silica sources include mining wastes, fossil fuel combustion ashes, slags such as iron slag, phosphorus slag, cement kiln wastes, oil refinery / petrochemical plant wastes such as oil field and methane layer brines, coal seam wastes such as gas production brines and coal seam brines, paper processing wastes, water softening such as ion exchange spent brines, silicon processing wastes, agricultural wastes, metal finishing wastes, high pH fiber wastes, and caustic sludge, but are not limited thereto. Mining wastes include wastes derived from the extraction of earth-derived metals or other valuable or useful inorganic substances. Examples of the target wastes include mining-derived wastes used to increase the pH, including red mud derived from the Bayer aluminum extraction process; for example, wastes derived from magnesium extraction from seawater in Moss Landing, California; and wastes derived from other mining processes involving leaching.In the process of burning fossil fuels such as in a coal-fired power plant, often ash rich in silica is generated. In some embodiments, the combustion of fossil fuels, such as ash from a coal-fired power plant, such as fly ash, such as ash discharged from a chimney, and bottom ash are provided as a silica source. Further details regarding the silica source and its use are described in U.S. Provisional Application No. 14 / 112,495, filed Oct. 17, 2013, the disclosure of which is incorporated herein by reference.

[0094] In embodiments of the present invention, the ash is used as a source of alkali components. In certain embodiments, using coal ash as the ash is also contemplated. The coal ash used in the present invention refers to the residue generated from the combustion of pulverized anthracite, lignite, bituminous coal, or sub-bituminous coal in a power plant boiler or coal combustion furnace, such as a chain grate boiler, a cyclone boiler, and a fluidized bed boiler. Such coal ash includes fly ash, which is fine particulate fossil coal ash carried from the furnace by exhaust gas or flue gas, and bottom ash, which accumulates as agglomerates at the bottom of the furnace.

[0095] Fly ash is generally very heterogeneous and contains a mixture of glassy particles having various distinguishable crystalline phases such as quartz, mullite, and various iron oxides. Fly ash of interest includes F-type and C-type fly ash. The F-type and C-type fly ash mentioned are defined by CSA standard A23.5 and ASTM C618. The main difference between these classifications is the content of calcium, silica, alumina, and iron in the ash. The chemical properties of fly ash are greatly affected by the chemical composition of the coal being burned (i.e., anthracite, bituminous coal, and lignite). The fly ash of interest contains a significant amount of silica (silicon dioxide, SiO2) (both amorphous and crystalline) and lime (calcium oxide, CaO, magnesium oxide, MgO).

[0096] When harder and older anthracite and bituminous coal are burned, generally F-type fly ash is produced. F-type fly ash essentially has pozzolanic properties and has a lime (CaO) content of less than 10%. Fly ash produced by burning newer lignite or sub-bituminous coal has, in addition to pozzolanic properties, a certain degree of self-adhesion. In the presence of water, C-type fly ash hardens over time and gains strength. The lime (CaO) content of C-type fly ash is generally 20% or more. The contents of alkali and sulfate (SO4) are generally higher in C-type fly ash.

[0097] Fly ash material solidifies while suspended in the exhaust gas and is recovered using various methods, such as an electrostatic precipitator or filter bags. Since the particles solidify while suspended in the exhaust gas, fly ash particles are generally spherical and range in size from 0.5 μm to 100 μm. The fly ash of interest includes those containing at least about 80% by weight of particles less than 45 microns. In certain embodiments of the present invention, the use of highly alkaline fluidized bed combustor (FBC) fly ash is also contemplated.

[0098] In embodiments of the present invention, the use of bottom ash is also contemplated. Bottom ash is formed as agglomerates in a coal combustion boiler from the combustion of coal. Such a combustion boiler may be a wet boiler or a dry boiler. Bottom ash is quenched in water when produced in a wet or dry boiler. This quenching results in agglomerates 90% of which are in the particle size range of 0.1 mm to 20 mm, and the bottom ash agglomerates have a wide distribution of agglomerate sizes within this range. The main chemical components of bottom ash are silica and alumina, and include small amounts of oxides of Fe, Ca, Mg, Mn, Na, and K, as well as sulfur and carbon.

[0099] In certain embodiments, the use of volcanic ash as ash is also contemplated. Volcanic ash consists of small tephra, i.e., fragments of crushed rock and glass produced by volcanic eruptions with a diameter of less than 2 millimeters.

[0100] In one embodiment of the present invention, cement kiln dust (CKD) is used as an alkali component source. The properties of the fuel from which the ash and / or CKD are derived, and the means of burning the fuel will affect the chemical composition of the ash and / or CKD obtained. Thus, based on the chemical composition of the ash and / or CKD, this ash and / or CKD may be used as part or the only means for adjusting the pH, and various other components may be used together with the specific ash and / or CKD.

[0101] In a particular embodiment of the present invention, slag is used as an alkali component source. The slag may be used as a single pH adjuster or in combination with one or more additional pH adjusters such as ash. Slag is generated from metal processing and may contain calcium and magnesium oxides as well as iron, silicon, and aluminum compounds. In certain embodiments, using slag as a pH adjusting substance provides additional advantages by introducing reactive silicon and alumina into the precipitate product. Examples of the slag of interest include, but are not limited to, blast furnace slag from iron refining, slag from electric arc or blast furnace treatment of steel, copper slag, nickel slag, and phosphorus slag.

[0102] As described above, in certain embodiments, ash (or slag in certain embodiments) is used as the sole method of adjusting the pH of water to the desired level. In still other embodiments, one or more additional pH adjustment protocols are used in combination with the use of ash.

[0103] In certain embodiments, the use of other waste materials, such as demolished or recycled concrete or mortar, as an alkali component source is also contemplated. When used, the concrete will dissolve, releasing sand and aggregate, which may, if desired, be recycled to the carbonate-forming portion of the process.

[0104] In certain embodiments, an inorganic alkali component source is also targeted. In such cases, the inorganic alkali component source that contacts the aqueous ammonium salt solution can be various, and examples of the inorganic alkali component source that is targeted include, but are not limited to, the silicates, carbonates, fly ash, slag, lime, cement kiln dust, etc. described above. In some cases, the inorganic alkali component source includes, for example, the rocks described above.

[0105] In these embodiments, the temperature at which the aqueous ammonium salt solution is heated can be various, but in some cases, the temperature ranges from 25 to 200 °C, for example, 25 to 185 °C. The heat used to provide the desired temperature can be obtained from any and appropriate supply sources including waste heat sources such as steam, flue gas waste heat, etc.

[0106] Distillation can be carried out at any pressure. When distillation is carried out at atmospheric pressure, the temperature at which distillation is carried out can be various, and in some cases, it ranges from 50 to 120 °C, for example, 60 to 100, for example, 70 to 90 °C. In some cases, distillation is carried out at a pressure lower than atmospheric pressure. The pressure in such embodiments can be various, but in some cases, the pressure lower than atmospheric pressure ranges from 1 to 14 psig, for example, 2 to 6 psig. When distillation is carried out at a pressure lower than atmospheric pressure, distillation can be carried out at a lower temperature compared to the embodiment carried out at atmospheric pressure. In such cases, the temperature can be various as desired, but in some embodiments where a pressure lower than atmospheric pressure is used, the temperature ranges from 15 to 60 °C, for example, 25 to 50 °C. In the embodiment of a pressure lower than atmospheric pressure, it is also targeted to use, if not all, at least a part of the waste heat as the heat used during distillation. Examples of the waste heat source that can be used in such cases include flue gas, the absorption heat generated by CO2 recovery and the resulting formation of ammonium carbonate, and coolant (such as those derived from the same-site CO2-containing gas supply sources of, for example, the power plants, factories, etc. described above), and combinations thereof, but are not limited thereto.

[0107] The regeneration of the ammonia aqueous solution for recovery may also be carried out using an electrolysis-mediated protocol in which a direct current is introduced into an ammonium salt aqueous solution to regenerate ammonia. Any suitable electrolysis protocol may be used. Examples of electrolysis protocols that can be adapted for the regeneration of ammonia from an ammonium salt aqueous solution include those derived from the electrolysis systems described in U.S. Patent Application Publication Nos. 2006 / 0185985 and 2008 / 0248350, and PCT Patent Application Publication No. WO2008 / 018928 (the disclosure of this application is incorporated herein by reference), and one or more components thereof may be used.

[0108] The resulting recovered ammonia water for regeneration may vary, for example, depending on the specific regeneration protocol used. In some cases, the recovered ammonia water for regeneration contains ammonia (NH3) at a concentration in the range of 4 to 20 M, for example, 12.0 to 16.0 M. The pH of the ammonia aqueous solution for recovery may vary and in some cases is in the range of 10.0 to 13.0, for example, 10.0 to 12.5.

[0109] In some cases, the method further includes contacting the recovered ammonia water for regeneration, for example, with the gaseous CO2 source described above, under conditions sufficient to produce an ammonium carbonate aqueous solution. In other words, the method may include recycling the regenerated ammonia to the process. In such cases, the recovered ammonia water for regeneration may be used as the sole recovered liquid, or may be mixed with another liquid, such as makeup water, to produce a recovered ammonia water suitable for use as a CO2 recovery liquid. Any suitable water may be used when mixing the regenerated ammonia water with additional water. The water that can be used to produce the recovered ammonia water includes, but is not limited to, fresh water, seawater, brine, produced water, and wastewater.

[0110] Recycling In some cases, the method may include recycling one or more reaction components from one stage of the process to another stage of the process. For example, as described above, the regenerated aqueous ammonia solution may be recycled to the CO2 recovery stage. The cation salts and / or aggregates generated during ammonia regeneration may be recycled to the carbonate formation stage. The waste heat generated in one stage, for example CO2 recovery, may be used in another stage, for example ammonia regeneration described above. This is a non-limiting example of an embodiment in which recycling is carried out.

[0111] Production of pure CO2 gas One or more stages of the method may result in the production of CO2. For example, during the production of solid carbonate from aqueous ammonium carbonate, up to 1 mole of CO2 may be produced per 2 moles of ammonium bicarbonate. Alternatively or in addition, the ammonia regeneration step may produce off-gas CO2. In such cases, although CO2 may be produced, the net amount of CO2 in the carbonate compound is sequestered as part of the overall process. Any CO2 produced may be a substantially pure CO2 product gas, which may be sequestered by injection into a geological subsurface location, as described in more detail below. Thus, this process is an effective CO2 sequestration process. The phrase "substantially pure" means that the product gas is pure CO2 or a CO2-containing gas with limited amounts of other non-CO2 components.

[0112] Following the production of the CO2 product gas in the related embodiment, an aspect of the present invention may include injecting the product CO2 gas into a geological subsurface location to isolate the CO2. Injection means introducing or placing the CO2 product gas into a geological subsurface location. The geological subsurface locations can be various and include both underground locations and deep-sea locations. Examples of the target underground locations include fossil fuel reservoirs such as oil fields, gas fields, and unmineable coal seams, brine reservoirs such as salt-bearing layers and salt-filled basalt layers, deep aquifers, porous formations such as partially or completely depleted oil or gas layers, salt caverns, sulfur caverns, and sulfur domes, and various other underground formations.

[0113] In some cases, prior to injection into the geological subsurface location, the CO2 product gas may be pressurized. To perform such pressurization, the gaseous CO2 may be compressed in one or multiple stages, and if desired, the accompanying water may then be cooled and condensed. Subsequently, the moderately pressurized CO2 may be further dried by conventional methods such as using molecular sieves if desired, and sent to a CO2 condenser that cools and liquefies the CO2. Then, this CO2 may be efficiently pumped at a minimum output to the pressure required to send the CO2 into the depth within the formation where CO2 injection is desired or into the deep sea. Alternatively, the CO2 may be compressed through a series of stages and discharged as a supercritical fluid at a pressure comparable to the pressure required for injection into the formation or the deep sea. If desired, the CO2 may be transported from the production site to the subsurface formation by, for example, pipelines, railways, trucks, or other appropriate protocols.

[0114] In some cases, the CO2 product gas is used in an enhanced oil recovery (EOR) protocol. Enhanced oil recovery (abbreviated as EOR) is a general term for techniques that increase the amount of crude oil that can be extracted from an oil field. Enhanced oil recovery is also called improved recovery or tertiary recovery. In the EOR protocol, the CO2 product gas is injected into an underground crude oil accumulation, i.e., a reservoir.

[0115] The production and sequestration of CO2 gas is further described in U.S. Application No. 14 / 861,996, the disclosure of which is incorporated herein by reference.

[0116] Alkali enrichment In some cases, the method further includes subjecting an aqueous ammonium carbonate solution to a membrane-mediated protocol, such as an alkali enrichment protocol that includes contacting a first and a second liquid on opposite sides of a membrane. In such cases, the membrane may be a cationic membrane or an anionic membrane. Further details regarding alkali enrichment protocols, such as membrane-mediated alkali enrichment protocols, are described in U.S. Patent Application No. 14 / 636,043, the disclosure of which is incorporated herein by reference. In some such cases, the method includes contacting an aqueous ammonia solution for recovery with a gaseous CO2 source in a reactor that combines recovery and alkali enrichment, the reactor comprising, for example, a hollow fiber membrane component that is a core having a plurality of hollow fibers, an alkali enrichment membrane component that surrounds the hollow fiber membrane component and defines a first liquid flow path in which the hollow fiber membrane component is present, and a housing configured to house the alkali enrichment membrane component and the hollow fiber membrane component, the housing being configured to define a second liquid flow path between the alkali enrichment membrane component and the inner surface of the housing. In such cases, the alkali enrichment membrane component may be configured as a cylinder, and the hollow fiber membrane component may be axially disposed within the cylinder. In such cases, the housing may be configured as a cylinder in which the housing and the alkali enrichment membrane component share a central axis.

[0117] System Aspects of the invention further include a system for sequestering CO2 from a gaseous CO2 source by a protocol as described above. The system is an apparatus comprising, for example, functional modules or reactors operably coupled in a form sufficient to implement the method of the invention as described above. Aspects of such a system include a CO2 gas / aqueous ammonia solution for recovery module, a carbonate production module, and an aqueous ammonia solution for recovery regeneration module.

[0118] In some cases, the CO2 gas / ammonia aqueous solution module for recovery comprises a hollow fiber membrane. In some cases, the system is operably coupled to a gaseous CO2 source. As described above, the gaseous CO2 source may be a multi-component gas stream such as flue gas.

[0119] The carbonate production module is operably coupled to the CO2 gas / ammonia aqueous solution module for recovery. Some module embodiments comprise a continuous reactor configured to produce a carbonate material for CO2 sequestration. If the system comprises a continuous reactor (i.e., a flow-through reactor), the system comprises a reactor in which material is retained in the flowing stream within the reactor, and reactants (e.g., divalent cations, bicarbonate-rich aqueous liquids, etc.) are continuously supplied to the reactor and exit as a continuous stream of product. Thus, the continuous reactor component of the system is not a batch reactor. A given system may comprise, for example, the continuous reactor described herein, more particularly in combination with one or more additional components described hereinafter.

[0120] In some embodiments, the continuous reactor of the present system includes a flowing aqueous liquid, such as an aqueous ammonium carbonate solution, and a divalent cation introduction device configured to introduce divalent cations into the flowing aqueous liquid at an introduction position, and a site for generating a non-slurry and solid-phase carbonate material for CO2 isolation, which is disposed at a distance from the divalent cation introduction device. The flowing aqueous liquid may be present in a continuous reactor that may be optionally and appropriately configured, and may be a moving, for example, the above-mentioned flow of the aqueous liquid. The continuous reactor of interest includes a liquid inlet and a liquid discharge outlet, and the inlet and the outlet are arranged relative to each other such that liquid continuously moves or flows into or out of the reactor. The reactor may have an arbitrary and appropriate structure, and in some cases, the length of the reactor, along which the liquid flows, may be longer than the dimension of any given cross-section of the reactor. The inlet is at the first end of the reactor, and the outlet is at the second end of the reactor. The volume of the reactor may vary, and in some cases, it is in the range of 10 L to 1,000,000 L, for example, 1,000 L to 100,000 L.

[0121] The continuous reactor of interest further includes a divalent cation introduction device configured to introduce divalent cations into the flowing aqueous liquid at an introduction position. Any optional and appropriate introduction device may be used, and this introduction device may be a liquid-phase introduction device or a solid-phase introduction device depending on the nature of the divalent cation source. In some cases, this introduction device may be arranged at a position that is substantially the same as, if not completely the same as, the inlet for the liquid containing the bicarbonate-rich product. Alternatively, this introduction device may be arranged at a distance downstream from the inlet. In such a case, the distance between the inlet and the introduction device may vary, and in some embodiments, it is in the range of 1 cm to 10 m, for example, 10 cm to 1 m. This introduction device may be operably coupled to a divalent cation source or reservoir.

[0122] The continuous reactor of interest also includes a site for producing a solid-phase carbonate material for CO2 isolation that is not a slurry. This site is a zone or region of the continuous reactor where a solid-phase carbonate material for CO2 isolation that is not a slurry is produced as a result of the reaction of a divalent cation with bicarbonate ions in a liquid containing a bicarbonate-rich product. The reactor may be configured to produce any of the above-described solid-phase carbonate materials for CO2 isolation that are not slurries at the production site. In some cases, the production site is located at a distance from the divalent cation introduction position. This distance may vary, but in some cases, the distance between the divalent cation introduction device and the material production site is in the range of 1 cm to 10 m, for example, 10 cm to 1 m.

[0123] The production site may include one or more seed structures such as those described above. In such cases, the reactor may be configured to contact the seed structure in an immersed or non-immersed format as described above. In the non-immersed format, the flowing liquid may exist on the surface of the seed structure, for example, as layers of various thicknesses, but a gas, such as air, separates at least two portions of the seed structure, for example, two different types of particles that are not immersed in the liquid.

[0124] In an embodiment of the present system, further details regarding such a reactor that may be used as a carbonate production module are described in U.S. Application No. 14 / 877,766, the disclosure of which is incorporated herein by reference.

[0125] The ammonia aqueous solution regeneration module for recovery may be various as long as it is configured to generate ammonia from an ammonium salt aqueous solution by, for example, distillation or electrolysis as described above. In some cases, the regeneration module will be configured to produce a pressure lower than atmospheric pressure as described above, and as a result, this module will include one or more components for producing a pressure lower than atmospheric pressure, such as a pump. In some cases, the regeneration module is operably coupled to a heat source, such as steam, and / or one or more waste heat sources, such as those described above. In some embodiments, the regeneration module includes a source of an alkaline component, such as the inorganic alkaline source described above.

[0126] In some cases, the system is configured to recycle the regenerated ammonia aqueous solution for recovery to, for example, the CO2 gas / ammonia aqueous solution module for recovery as described above.

[0127] In some cases, the present system and the modules of the present system are industrial-scale systems, and an industrial-scale system means that the system is configured to process a composition (e.g., gas, liquid, etc.) with an industrial-scale amount / volume of input. For example, the present system and the modules of the present system, such as the CO2 contactor module, carbonate generation module, ammonia regeneration module, etc., are configured to process a liquid with an industrial-scale amount of 10,000 gallons per day or more, for example, 1,000 gallons per day or more, for example, 25,000 gallons per day or more, and in some cases, the present system and the modules of the present system are configured to process 1,000,000,000 gallons per day or less, for example, 500,000,000 gallons per day or less. Similarly, the present system and the modules of the present system, such as the CO2 contactor module, etc., are configured to process a gas with an industrial-scale amount of 25,000 cubic feet per hour or more, for example, 100,000 cubic feet per hour or more, for example, 25,000 cubic feet per hour or more including 250,000 cubic feet per hour or more, and in some cases, the present system and the modules of the present system are configured to process 500,000,000 cubic feet per hour or less, for example, 100,000,000 cubic feet per hour or less.

[0128] In some embodiments, the system may be in fluid connection with an aqueous medium source, e.g., a natural or artificial aqueous medium source, and may be located at the same site as the location where the CO2 separation protocol is implemented. The present system may be on land or at sea. The system may be a land-based system, for example, in a coastal area close to a seawater source, or may be in an inland location if water is piped from a saltwater source, e.g., the ocean, to the present system. Alternatively, the system may be an aquatic system, i.e., a system that exists on or in water. Such a system may, if desired, exist on a ship, on an ocean platform, etc. In certain embodiments, the system may be located at an arbitrary and appropriate location, for example, at the same location as an industrial plant, such as a power plant.

[0129] FIG. 1 shows a schematic diagram of a system according to an embodiment of the present invention. As shown in FIG. 1, the system 100 includes a CO2 gas / ammonia aqueous solution for recovery module 102, a carbonate generation module 104, and a recovered ammonia aqueous solution regeneration module 106. The system 100 is configured such that the CO2-containing gas 108 from the source 109 (e.g., the flue gas of a power plant at the same site) is mixed with the ammonia aqueous solution recovery liquid in the CO2 gas / ammonia aqueous solution for recovery module 102 so that the ammonium carbonate aqueous solution 110 is generated, and then the ammonium carbonate aqueous solution 110 is conveyed to the carbonate generation module 104 fluidically coupled thereto. In the carbonate generation module 104, the ammonium carbonate aqueous solution 110 is mixed with the cation source 112 under conditions sufficient to generate the solid carbonate 114 for CO2 separation and the ammonium salt aqueous solution 116. Then, the ammonium salt aqueous solution 116 is conveyed to the recovered ammonia aqueous solution regeneration module 106 fluidically coupled thereto, where it is heated, for example, by steam from the steam source 120 in the presence of the inorganic alkali component source 118. Then, the regenerated ammonia aqueous solution 122 is conveyed to the CO2 gas / ammonia aqueous solution for recovery module 102 fluidically coupled thereto.

[0130] FIG. 2 shows a schematic diagram of a system according to an embodiment of the present invention, in which ammonia regeneration is carried out at a pressure lower than atmospheric pressure and all heat is provided by a waste heat source. As shown in FIG. 2, the system 200 includes a CO2 gas / ammonia aqueous solution for recovery module 202, a carbonate production module 204, and an ammonia aqueous solution for recovery regeneration module 206. The system 200 is configured such that a CO2-containing gas from a source 208 (e.g., a flue of a power plant) is mixed with an ammonia aqueous solution recovery liquid in the CO2 gas / ammonia aqueous solution for recovery module 202 so that an ammonium carbonate aqueous solution 210 is generated, and then the ammonium carbonate aqueous solution 210 is conveyed to the carbonate production module 204 fluidically coupled thereto. In the carbonate production module 204, the ammonium carbonate aqueous solution 210 is mixed with a cation source 212 under conditions sufficient to produce a solid carbonate 214 for CO2 separation and an ammonium salt aqueous solution 216. The ammonium salt aqueous solution 216 is then conveyed to the ammonia aqueous solution for recovery regeneration module 206 fluidically coupled thereto, where it is heated in the presence of an inorganic alkali component source 218. The waste heat cooling system, flue gas 208, and CO2 gas / ammonia aqueous solution for recovery module 202 of the power plant 220 at the same site are used as a heat source for the regeneration module 206. The regenerated ammonia aqueous solution 222 is then conveyed to the CO2 gas / ammonia aqueous solution for recovery module 202 fluidically coupled thereto.

[0131] In some cases, the CO2 gas / ammonia aqueous solution module for recovery includes a reactor that combines recovery and alkali enrichment. The reactor includes a core hollow fiber membrane component (for example, the component including a plurality of hollow fiber membranes), an alkali enrichment membrane component that surrounds the core hollow fiber membrane component and defines a first liquid flow path where the core hollow fiber membrane component is present, and a housing configured to house the alkali enrichment membrane component and the core hollow fiber membrane component, the housing being configured to define a second liquid flow path between the alkali enrichment membrane component and the inner surface of the housing. In some cases, the alkali enrichment membrane component is configured as a cylinder, and the hollow fiber membrane component is arranged axially within the cylinder. In some cases, the housing is configured as a cylinder in which the housing and the alkali enrichment membrane component share a central axis. Embodiments of the present invention further include, for example, a reactor that combines recovery and alkali enrichment as described above.

[0132] In some cases, the protocol described above is carried out using a system of one or more shipping - capable modular units configured for use in the sequestration of CO2, such as described in PCT Application No. US2016 / 024338, the disclosure of which is incorporated herein by reference. The modular unit aspects include a support, such as a housing or base, with one or more of a CO2 gas / liquid contactor subunit, a carbonate formation subunit, an alkali enrichment subunit, a water softening subunit, a cation recovery subunit, a heat exchange subunit, a reverse osmosis subunit, a nanofiltration subunit, a microfiltration subunit, an ultrafiltration subunit, and a purified CO2 recovery subunit. The modular units configured for use in the present invention may include, for example, an ammonia regeneration unit as described above. A system composed of one or more such modular units is also provided. The systems disclosed herein include large - scale production systems in which individual modular units house only one or a plurality of given subunits, such as a CO2 gas / liquid contactor subunit, a carbonate formation subunit, an alkali enrichment subunit, a water softening subunit, a cation recovery subunit, a heat exchange subunit, a reverse osmosis subunit, a nanofiltration subunit, a microfiltration subunit, an ultrafiltration subunit, and a purified CO2 recovery subunit. Aspects of the invention include larger assemblies of a number of individual modular units, which may be combined and have one or a number of individual modular units including a CO2 gas / liquid contactor subunit, a carbonate formation subunit, an alkali enrichment subunit, a water softening subunit, a cation recovery subunit, a heat exchange subunit, a reverse osmosis subunit, a nanofiltration subunit, a microfiltration subunit, an ultrafiltration subunit, and a purified CO2 recovery subunit. Also provided is a method of using the unit / system in a CO2 sequestration protocol.

[0133] The following examples are provided for illustration and not limitation.

Example

[0134] I. Recovery of CO2 with Aqueous Ammonia Solution A. Materials and Methods The experiment was carried out in a batch by contacting a synthetic flue gas with approximately 25 gallons of a 0.5 M NH3 (about 1 wt% NH3) recovery solution in a single (one unit) 2.5×8 Liqui-Cel membrane contactor (membrane surface area of 1.4 m 2 ). A back pressure of 25 psig was applied, and the recovery solution was pumped through the gas phase side (volume = 0.15 L) of the contactor at a flow rate of 0.5 g / min (gpm) (1.9 L / min (lpm)). The synthetic flue gas was flowed in countercurrent through the liquid phase side (volume = 0.40 L) of the contactor. The gas inlet concentration was in the range of 5 - 50% CO2 (the balance was made up with air), the inlet volume was 10 - 40 slpm (air + CO2), and the inlet pressure was 2 - 20 psig. During data collection, the recovery solution was flowed through the membrane contactor only once, and the CO2 concentration (%, inlet and outlet), O2 concentration (%, inlet and outlet), gas volume (slpm, air and CO2), gas pressure (psig, inlet and outlet), liquid flow rate (gpm, inlet), liquid pressure (psig, inlet and outlet), liquid pH (outlet), liquid temperature (°C, outlet), and liquid conductivity (mS / cm, outlet) were recorded.

[0135] The outlet liquid (after contact with the synthetic flue gas) was collected in a separate tank and combined. The combined outlet liquid was used as a new inlet recovery solution to repeat the experiment, which enabled verification of recovery solutions with different pH values.

[0136] B. Results The plots in Figure 3 demonstrate CO2 absorption from the synthetic flue gas, which depends on the pH of the 0.5 M NH3 (about 1 wt% NH3) recovery solution and the gas volume entering the single (one unit) 2.5×8 Liqui-Cel membrane contactor. It is expected that by using a larger membrane contactor (larger surface area, longer residence time, etc.), the rate of CO2 absorption will increase significantly.

[0137] II. Mineral Formation The following shows that an ammonium bicarbonate solution can be used as a carbon-containing solution in the formation of carbonate minerals when it comes into contact with hard water (cation source).

[0138] A. Materials and Methods 200 ml of ACS reagent grade ammonium bicarbonate was mixed with 200 ml of ACS reagent grade CaCl2 (0.5 M) and a metathesis reaction was carried out. This solution was reacted while gently stirring with a stirrer under open atmosphere. After 5 minutes, this solution was filtered through a Buchner funnel, the resulting precipitate was collected and dried overnight at 75 °C.

[0139] The obtained substance was observed by scanning electron microscope (SEM) and Fourier transform infrared analysis (FTIR). The FTIR spectrum was recorded using a Nicolet IS-10 manufactured by Thermo-Fisher equipped with a HeNe laser and a high-speed recovery deuterated triglycine sulfate (DTGS) detector. The scan was collected on a germanium ATR crystal at a resolution of 16 and an optical speed of 0.4747. The SEM image was recorded using a Hitatchi TM-3030 benchtop model.

[0140] B. Results Precipitation occurred by the above-described reaction, which was separated from the supernatant and identified as calcite (peak identifiers 871 cm -1 , 714 cm -1 ) by both crystal habit (Figure 4A) and Fourier transform infrared analysis. Furthermore, this supernatant was identified as ammonium chloride (peak identifiers 1100 cm as NH3 -1 , 1450 cm as NH4Cl -1 ).

[0141] The experiment was further repeated and the CaCl2 solution was titrated into the NH4HCO3 solution in the presence of silica sand. By this reaction, a separate film similar to the film produced using NaHCO3 as a carbon-containing reactant was obtained.

[0142] III. Coating Process A. Materials and Methods 0.25 M of CaCl2 was added in a metathesis reaction format to either an equal volume of 0.5 M of NaHCO3 or 0.5 M of Na2CO3 and analyzed immediately after mixing. The results indicate the existence of two distinct pathways towards calcium carbonate formation, namely, the well-known pathway named Reaction 2 (the carbonate pathway from CaCl2 (aqueous solution) and Na2CO3 (aqueous solution) at high pH), and another pathway named Reaction 1 (the bicarbonate pathway from CaCl2 (aqueous solution) in NaHCO3 (aqueous solution) at neutral pH).

[0143] FTIR spectra were recorded using a Nicolet IS-10 from Thermo-Fisher equipped with a HeNe laser and a fast recovery deuterated triglycine sulfate (DTGS) detector. Scans were collected on a germanium ATR crystal at a resolution of 16 and an optical speed of 0.4747. Samples for FTIR were prepared by adding 0.25 M of CaCl2 (Sigma, lot number BCBL2738 and deionized water) to 0.5 M of NaHCO3 (Aqua Solutions, lot number 319302 and deionized water). 20 μl was pipetted onto the ATR crystal and the reaction was recorded in a time-resolved format using a macro applied to Omnic 9.2 software. Spectra were recorded at 0, 10, 20, 1800 seconds.

[0144] pH was recorded in a time-resolved format using an OrionStar A215 pH meter equipped with an Orion 8157BNUMD Ross Ultra pH / ATC probe. While adding 0.25 M CaCl2 solution (Sigma, lot number BCBL2738 and deionized water) to 0.5 M NaHCO3 solution (AquaSolutions, lot number 319302 and deionized water) and 0.5 M of Na2CO3 (Sigma, lot number SLBD98664), sampling was done every 3 seconds and data was recorded using StarCom 1.0.

[0145] The dissolved inorganic carbon (DIC) content of the solution and solid carbonate samples was measured by acid titration and coulometry using a CM150 carbon analysis system (UIC, Inc.). Generally, the samples were titrated with 2N H2PO4 (Sigma Aldrich). However, to detect the CO2 generated by the reaction of CaCl2 (Sigma Aldrich) and NaHCO3 (Aqua Solutions), the samples were not titrated with H2PO4 because CO2 would be liberated from CaCO3 upon titration with H2PO4. Instead, the CaCl2 solution was titrated with the NaHCO3 solution. This allowed for the quantification of CO2 by coulometry. Subsequently, any solids formed in the reaction were isolated, dried, and analyzed by FTIR to confirm that their composition was CaCO3. All analyses using the CM150 system were performed at 40 °C.

[0146] B. Results Time-resolved Fourier transform infrared spectra (FTIR) of Reaction 1 at 0 s, 10 s, 30 s, and 30 min after mixing show the v3 (1400 cm -1 ), v1 (1087 cm -1 ), v2 (877 cm -1 ), and v4 (714 cm -1 ) infrared active vibration modes of calcite. The v3, which is the asymmetric C–O stretching vibration of the carbonate bond, is seen to be shifted by bidentate, resulting in a characteristic calcite peak, suggesting that calcium carbonate is formed via a bicarbonate pathway similar to that proposed for natural formation. The v1, which is the symmetric carbonate vibration mode, is related to the free carbonate available in the structure. The v2, which is the out-of-plane bending vibration, and v4, which is the in-plane bending vibration, are at 877 cm -1 and 714 cm -1It is identified by. It can be seen that the FTIR spectrum identifies that the CaCO3 (calcite) formed by LCP reactions 1 and 2. The final products of both pathways seem to be the same. In the static images of nanoparticle tracking analysis (NTA) of 0.25 M NaHCO3, droplets of a liquid condensate phase rich in bicarbonate are seen. The static image of NTA of reaction 1 immediately after mixing visualizes the chemical pathway of the low-pH reaction (reaction 1) driven by LCP with respect to the time-resolved format of part A, i.e., the conventional high-pH reaction (reaction 2). The yields of reaction 1 with respect to reaction 2, measured by DIC analysis, measured for CaCO3 and CO2. This result reinforces that reactions 1 and 2 have different pathways due to the difference in the generation of CO2 (expected for reaction 1). The pH response by the time-resolved method of the dump reaction of reaction 1 shows an initial decrease in pH, which is probably due to the removal of bicarbonate. The pH response by the time-resolved method of the dump reaction of reaction 1 shows little decrease in pH, suggesting that carbonate is consumed during mineral formation and that the carbonate is buffered by bicarbonate. During the reaction of carbonate formation, a liquid condensate phase (LCP) occurs in the presence of calcium ions, which serves as a nucleus to form CaCO3. As the CaCO3 precipitation proceeds, dehydration of the reaction product occurs, as judged by the decrease in the δO-H vibration peak. According to the FTIR spectrum, this structure was initially hydrated and amorphous as reported previously, showing broad peaks in the observed range. However, the gradual appearance of sharp peaks as the reaction progresses is at 1400 cm -1 (v3, asymmetric CO3), 1087 cm -1 (v1, symmetric CO3), 877 cm -1 (v2, out-of-plane band of CO3), and 714 cm -1 (v4, in-plane band of CO3), which is related to the development of the crystal structure of the carbonate polymorph and indicates the formation of the calcite phase. This specific reaction is called reaction 1 in the main report and is compared with reaction 2, the conventional CaCO3 precipitation pathway. Reaction 1: CaCl2 (aqueous solution) + 2NaHCO3 (aqueous solution) ⇔ CaCO3 (solid) + 2NaCl (aqueous solution) + H2O (liquid) + CO2 (gas) Reaction 2: CaCl2 (aqueous solution) + Na2CO3 (aqueous solution) ⇔ CaCO3 (solid) + 2NaCl (aqueous solution) The products as a result of Reaction 1 and Reaction 2 are the same. The yields of CO2 and CaCO3 are 90% and 80% respectively, and the stoichiometry and chemical pathway of Reaction 1 were confirmed. The pH was also measured in a time-resolved format, and it was suggested that Reaction 1 occurs at a lower pH compared to the conventional Reaction 2. This is directly related to the LCP formation mechanism because Ca 2+ tends to interact with HCO3 - and precipitation reaction can occur at neutral pH. In either case, the initial pH decreases somewhat due to the start of CaCO3 precipitation.

[0147] IV. Treatment of Hard Water Solutions with high concentrations of divalent ions, such as calcium (Ca 2+ ), magnesium (Mg 2+ ), etc., for use as hard water in the coating process described above, are produced from seawater or other saline or brine sources using existing water treatment technologies such as nanofiltration (NF) or reverse osmosis (RO).

[0148] A. Materials and Methods Current seawater (28,500 ppm TDS), calcium chloride (CaCl2, 5,500 ppm TDS), etc. were treated with small pieces of various commercially available NF and RO membrane elements with a diameter of 4 inches (12.57 square inches). The membrane permeate flux (gallons / ft 2 ·day, GFD) was adjusted by a valve in the concentrate stream of a flat plate test system. Samples of the permeate were analyzed by ion chromatography and / or conductivity probe to measure the ion rejection rate of a given membrane. The system pressure (psig) during screening was also recorded.

[0149] B. Results The inventors were able to successfully verify the permeation of monovalent ions and the rejection of divalent ions by using artificial seawater as a feed solution and a commercially available NF membrane. The inventors verified that there are commercially available NF membranes (e.g., TS40 (TriSep) and ESNA1-LF2 (Hydranautics)) that can achieve calcium ion rejection of over 80% in a CaCl2 solution.

[0150] V. Ammonia reforming by geomass A. Ammonia reforming Different types of biomass, such as high surface area carbonates or solid silicates, fly ash, slag, bottom ash, economizer ash, red mud, and other wastes are heated in the presence of back-end process water containing ammonium salts to regenerate ammonia gas (NH3) from ammonium salts (NH4 + ). This is carried out in a recovery column similar to those used in the industrially developed Solvay process.

[0151] Ammonia reforming regenerates a reactive recovery solution for contact with flue gas and ultimately absorbs gaseous CO2 in an aqueous solution to convert it to bicarbonate ions (HCO3 - ). Ammonia (NH3) is converted to ammonium (NH4 + ) in the CO2 recovery process described above, while NH4 + is converted back to NH3 in the ammonia reforming process described above. In other words, NH3 is not consumed in any part of the processes described above. NH3 simply facilitates the sequestration of gaseous CO2 into HCO3 - in an aqueous solution, and then HCO3 - mineralizes to carbonate (CO3 2- ) in the coating process described above.

[0152] Ammonia (NH3) is regenerated by heating an aqueous ammonium salt solution, such as ammonium chloride (NH4Cl), ammonium acetate (NH4OAc), etc., in the presence of diomas fine powder, such as limestone, fly ash, slag, basalt, etc., and is reused, for example, in the CO2 absorption process at the front end of the carbon recovery and mineral formation protocol shown in Figure 1.

[0153] 1. Materials and Methods 5 - 20 mL of an ammonium salt solution (0.5 M, saturated) was added to a sample container containing diomas fine powder (2 - 10 g), and the container was heated to 30 - 150 °C for 15 - 126 minutes. During heating, a low flow rate of air (pre-washed with 8 M KOH solution) was passed through the suspension. All the volatilized ammonia gas (NH3) was trapped as ammonium (NH4 + ) in an acid scrubber (5 mL of 1 M HCl). Then, the NH 4+ in the acid scrubber was quantified by ion chromatography, and the "NH3 reforming yield (%)" in the following figures represents the measured amount of NH4 + from ion chromatography divided by the theoretical yield of NH3 (based on the amount and concentration of ammonium salt added to the diomas fine powder).

[0154] 2. Results The regeneration of ammonia (NH3) from ammonium salts was verified in many systems where the diomas fine powder, ammonium salts and their concentrations, reaction temperature, and reaction time were varied. As further shown in Figure 4, after heating for only 30 minutes, an ammonia reforming yield exceeding 40% was observed at a low temperature of 75 °C.

[0155] As shown in Figure 4, ammonia (NH3) reforming was carried out with different types of diomas, such as fly ash, CaCO3, basalt, etc., as ammonium (NH4 +)It is carried out by heating in the presence of a salt solution, such as ammonium chloride (NH4Cl), ammonium acetate (NH4OAc), ammonium nitrate (NH4NO3), etc. The bar graph (left vertical axis) shows the experimental yield of NH3 reforming, while the line graph (right vertical axis) shows the concentration of the recovered NH3 in the reformed solution. What these two sets of data show is that although the NH3 reforming yield is low in some cases (for example, 10% for CaCO3 diomas), the concentration of NH3 recovered in the same system can be very high (for example, 415 mM), and an effective CO2 recovery solution for removing CO2 from flue gas is produced.

[0156] As shown in Figure 5, the NH3 reforming yield in the absence of any diomas is relatively significantly low. The exception is ammonium bicarbonate (NH4HCO3), in which case 30% of NH3 is produced in the presence of heat, but undesirable CO2 is also generated from this system. In short, this graph shows the advantage of diomas in advancing the NH3 reforming process. Figure 6 shows data verifying the NH3 reforming from NH4Cl at 75 °C in the presence of various types of diomas. This result demonstrates that NH3 reforming can occur at low temperatures in the presence of common types of diomas, such as fly ash, CaCO3, and basalt.

[0157] B. Further studies using various types of diomas 1. Studies were conducted to evaluate the ability of recycled concrete / mortar to act as an alkaline component diomas source for ammonia reforming. Figure 7 shows a plot of "diomas alkaline component (mmol) versus time (min)" for various basalts and recycled concrete / mortar diomas, where 1 M HCl was titrated into a suspension of 0.25 g of diomas in a saturated ammonium chloride solution at 70 °C until a pH of 3.30 was maintained. This data represents the rate of release of the alkaline component from the diomas when it comes into contact with a fresh ammonium chloride solution.

[0158] 2. In addition to other materials, a study was conducted to evaluate the ability of recycled concrete / mortar to act as an alkali component geothermal source for ammonia modification. The bar graph in Figure 8 shows the sodium (Na + ), potassium (K + ), calcium (Ca 2+ ), and magnesium (Mg 2+ ) leached from these materials when various geothermal materials were mixed with a 2M ammonium chloride solution at room temperature for 10 minutes. The "ion concentration in the reforming solution (mmol / L)" is shown, where CKD = cement kiln dust and CCR = coal combustion residue. The remaining solid was separated by filtration, and the filtrate, i.e., the "reforming solution", was analyzed by ion chromatography. These data demonstrate the ability of various materials to act as a source of Ca 2+ for producing solid carbonate materials.

[0159] C. Ammonia Modification by Vacuum Distillation A study was conducted to evaluate the effect on ammonia modification at pressures lower than atmospheric pressure. The graph in Figure 9 shows the concentrations (mol / L) of calcium and alkali components measured by ion chromatography and acid titration, respectively, in the reformer liquid after being modified in the presence of arc furnace steelmaking slag. Higher calcium ion concentrations and lower alkali component concentrations were observed in the reformer liquid of the test using vacuum compared to the test without using vacuum (labeled "55 °C, no vacuum"). The control tests "55 °C, no slag" and "55 °C, water" showed minimal reactions.

[0160] VI. Various Representative Systems A. 2MW Coal-Fired Power Plant FIG. 7 is a diagram of a system according to an embodiment of the present invention suitable for use in a 2MW coal-fired power plant. The specific parameters outlined in this process diagram are based on the CO2 recovery rate. For a 50% recovery, this corresponds to approximately 2,250 pounds of CO2 per hour or approximately 390 moles of CO2 per minute. For example, the U.S. EPA has reported that the average CO2 emissions from coal-fired power plants in the United States are 2,249 pounds of CO2 per hour per MW (see the website at the address with "www." prefixed to "epa.gov / energy"). Assuming operation 24 hours a day, 7 days a week and 50% CO2 recovery, the following is obtained.

[0161]

Number

[0162] In other words, the parameters for the flows in the figure, such as temperature, concentration, volume, flow rate, etc., correspond to the treatment of approximately 2,250 pounds of CO2 per hour by a 2MW demonstration power plant.

[0163] The related chemical pathways implemented in the system shown in FIG. 10 are as follows. Step 1: CO2 + NH3 + H2O → NH4HCO3 Step 2: 2NH4HCO3 + CaCl2 → CaCO3 + 2NH4Cl + H2CO3 Step 3: NH4Cl + diomas (clay-based alkaline minerals, i.e., CaO, CaOH2, CaCO3, MgO, MgOH2, etc.) → NH3 + hard water

[0164] B. Further 2MW Coal-Fired Power Plant System FIGS. 11A, 11B, and 11C show system diagrams for three different 2MW coal-fired power plants. Generally speaking, · The process change is centered around the output periphery of the reformer and its front-end CO2 recovery section by Geomas. · The temperature is shown for specific cases. · An open system with a storage tank operating semi - continuously with options for recycling also minimizes the cooling load. · Increasing the concentration of the reactant throughout minimizes the heating load in the reformer. Individually, · Figure 11A increases the concentration of NH3 coming from the reformer, which in turn decreases the volume of steam and the energy required for heating. · Figure 11B re - introduces a secondary contactor section for absorbing the NH3 gas coming from the reformer. · Figure 11C presents premixing the NH3 gas from the reformer with the flue gas from the slip stream before entering the contactor for CO2 absorption.

[0165] C. 10MW Coal - Fired Power Plant Figure 12 shows an example of a system according to an embodiment of the present invention suitable for use in a 10MW coal - fired power plant. It shows the estimated mass flow balance of a process that removes 50% of the carbon dioxide from a 10MW slip stream of the flue gas of the coal - fired power plant. A total of 14,643 kg / hr of low - pressure steam and 3176 gallons / minute of cooling water are used. The difference between the inlet temperature and the outlet temperature of the cooling water is 10°C. The flue gas is assumed to be 12 wt% carbon dioxide and enter at about 105°F.

[0166] D. 10MW Coal - Fired Power Reformer with a Vacuum Ammonia Reformer Figure 13 shows the overall mass flow diagram of a system incorporating three proposed in-plant power and cooling water reduction techniques. As shown in Figure 13, by operating the reformer continuously under vacuum, thus reducing the operating temperature of the reformer (to about 70°F in this example) and increasing the electrical pump load of the reformer, the heat of the flue gas (H1), the absorption heat (H2), and the heat of the recirculating water used in this example for coal power generation (H3) can be utilized. This is due to the fact that increasing the degree of vacuum for reforming results in a lower temperature at which the reformer can operate. With this configuration, the required amount of steam (zero in this case compared to Figure 12) and the required amount of cooling water (reduced by about 33% in this case compared to Figure 12) are significantly reduced / eliminated. Further, the recirculating water in this coal-fired power plant may be cooled to a temperature close to the reformer temperature. This simultaneously causes the heat required for reforming to be supplied to the process, the required amount of steam to decrease, and the temperature of the recirculating water to drop, enabling the parent coal-fired power plant to use the recirculating water further.

[0167] Notwithstanding the appended claims, the disclosure described herein is also defined by the following appendices. 1. A method for separating CO2 from a gaseous CO2 source, comprising: a) contacting an ammonia aqueous solution for recovery with the gaseous CO2 source under conditions sufficient to produce an aqueous ammonium carbonate solution; b) mixing a cation source with the aqueous ammonium carbonate solution under conditions sufficient to produce an aqueous solution of a carbonate for CO2 separation and an ammonium salt; c) regenerating the ammonia aqueous solution for recovery from the aqueous ammonium salt solution; and separating CO2 from the gaseous CO2 source. 2. The method according to appendix 1, wherein the ammonia aqueous solution for recovery contains ammonia at a concentration in the range of 4.0 to 20.0 M. 3. The method according to appendix 1 or 2, wherein the gaseous CO2 source is a multi-component gas stream. 4. The method according to appendix 3, wherein the gaseous CO2 source is flue gas. ​ 5. The method according to appendix 4, wherein the flue gas is obtained from an industrial source.

[0168] 6. The method according to any one of appendices 1 to 5, wherein the gaseous CO2 source is contacted with the aqueous ammonia solution for recovery using a membrane contactor. 7. The method according to appendix 6, wherein the membrane contactor is a hollow fiber membrane contactor. 8. The method according to any one of appendices 1 to 7, wherein the aqueous ammonium carbonate solution contains at least one of ammonium carbonate and ammonium bicarbonate. 9. The method according to any one of appendices 1 to 8, wherein the aqueous ammonium carbonate solution contains both ammonium carbonate and ammonium bicarbonate. 10. The method according to any one of appendices 1 to 9, wherein the regeneration of the aqueous ammonia solution for recovery from the aqueous ammonium salt solution includes distillation.

[0169] 11. The method according to appendix 10, wherein the distillation is carried out at a pressure lower than atmospheric pressure. 12. The method according to appendix 11, wherein the pressure lower than atmospheric pressure is in the range of 1 to 14 psig. 13. The method according to any one of appendices 10 to 12, wherein the distillation includes heating the aqueous ammonium salt solution in the presence of a source of inorganic alkali components. 14. The method according to appendix 13, wherein the source of inorganic alkali components includes silicate, carbonate, fly ash, slag, lime, or cement kiln dust. 15. The method according to appendix 13, wherein the source of inorganic alkali components includes rock.

[0170] 16. The method according to any one of appendices 10 to 15, wherein the distillation uses waste heat. 17. The method according to appendix 16, wherein the waste heat is supplied from a source selected from the group consisting of flue gas, absorption heat generated by step (a), and coolant, and combinations thereof. 18. The method according to any one of appendices 1 to 9, wherein the regeneration of the aqueous ammonia solution for recovery from the aqueous ammonium salt solution includes electrolysis. 19. The method according to any one of appendices 1 to 18, further comprising contacting the regenerated recovered aqueous ammonia solution with a gaseous CO2 source under conditions sufficient to produce an aqueous ammonium carbonate solution. 20. The method according to any one of appendices 1 to 19, wherein the cation source comprises an alkaline earth metal cation.

[0171] 21. The method according to appendix 20, wherein the cation source is a divalent cation source. 22. The method according to appendix 21, wherein the divalent cation comprises an alkaline earth metal cation. 23. The divalent alkaline earth metal cation is Ca 2+ and Mg 2+ and is selected from the group consisting of those and combinations thereof, according to the method of appendix 22. 24. The mixing step (b) comprises introducing the cation source into the flowing aqueous ammonium carbonate solution under conditions sufficient to form a solid carbonate in the flowing aqueous ammonium carbonate solution that is non-slurry for CO2 isolation, according to the method of any one of appendices 20 to 23. 25. The method according to appendix 24, wherein the solid carbonate for CO2 isolation is a particulate composition.

[0172] 26. The method according to appendix 24, comprising forming the solid carbonate for CO2 isolation with the aid of a seed structure. 27. The method according to appendix 26, wherein the solid carbonate for CO2 isolation is formed on at least one of the surface or recess of the seed structure. 28. The method according to any one of appendices 1 to 27, further comprising manufacturing a building material from the material of the solid carbonate for CO2 isolation. 29. The method according to appendix 28, wherein the building material comprises an aggregate. 30. The method according to appendix 29, wherein the seed structure is a porous, permeable aggregate that will be filled with the solid carbonate for CO2 isolation to produce a solid aggregate with lower porosity and higher density compared to the seed structure.

[0173] 31. The method according to appended claim 30, wherein the filled aggregate is filled to a greater extent at the outer edge than inside, and lightweight aggregate is produced by making new aggregate have a lower density in the inner region compared to the outer edge. 32. The method according to appended claim 28, wherein the building material includes roof granules. 33. A CO2 isolation system comprising a CO2 gas / ammonia aqueous solution for recovery module, a carbonate generation module, and an ammonia aqueous solution regeneration module for recovery. 34. The system according to appended claim 33, wherein the CO2 gas / ammonia aqueous solution for recovery module comprises a hollow fiber membrane. 35. The system according to appended claim 33 or 34, which is operably coupled to a gaseous CO2 source.

[0174] 36. The system according to any one of appended claims 33 to 35, wherein the gaseous CO2 source is a multi-component gas stream. 37. The system according to appended claim 36, wherein the gaseous CO2 source is flue gas. 38. The system according to any one of appended claims 33 to 37, wherein the ammonia aqueous solution regeneration module for recovery is configured to generate an ammonia aqueous solution for recovery by distillation. 39. The system according to appended claim 38, wherein the ammonia aqueous solution regeneration module for recovery is configured to generate ammonia for recovery by distillation at a pressure lower than atmospheric pressure. 40. The system according to appended claim 38 or 39, wherein the ammonia aqueous solution regeneration module for recovery is operably coupled to a waste heat source.

[0175] 41. The system according to any one of appended claims 38 to 40, wherein the ammonia aqueous solution regeneration module for recovery comprises an inorganic alkali source. 42. The system according to any one of appended claims 33 to 37, wherein the ammonia aqueous solution regeneration module for recovery is configured to generate an ammonia aqueous solution for recovery by electrolysis. 43. The system according to any one of Appendices 33 to 42, configured to recycle the aqueous ammonia solution for regeneration and recovery to the CO2 gas / aqueous ammonia solution module for recovery.

[0176] The invention described above has been described in some detail by way of illustration and examples for the purpose of clarity of understanding. However, it will be readily apparent to those skilled in the art that, in light of the teachings of the present disclosure, specific changes and modifications can be made to these without departing from the spirit or scope of the appended claims.

[0177] Therefore, the foregoing is merely illustrative of the principles of the present invention. It will be understood by those skilled in the art that, although not explicitly described or shown herein, various configurations that embody the principles of the present invention and are within its spirit and scope can be devised. Further, all language representing the examples and conditions described herein is intended primarily to assist the reader in understanding the principles and concepts of the present invention, which are the contribution of the inventors to the advancement of the art, and should not be construed as limited to such specifically described examples and conditions. Further, all descriptions of the principles, aspects, and embodiments of the present invention, as well as the specific examples thereof, are intended to encompass both their structural equivalents and functional equivalents.

[0178] Furthermore, such equivalents are intended to include both currently known equivalents and equivalents developed in the future, i.e., any developed elements that perform the same function regardless of structure. Therefore, the scope of the present invention is not intended to be limited to the exemplary embodiments shown and described herein. Rather, the scope and spirit of the present invention are embodied by the appended claims.

[0179] Cross-reference to related applications This application claims the benefit of U.S. Provisional Application No. 62 / 313,613, filed Mar. 25, 2016, and U.S. Provisional Application No. 62 / 451,506, filed Jan. 27, 2017, under 35 U.S.C. § 119(e), the disclosures of which are hereby incorporated by reference in their entireties.

Claims

1. Gaseous CO ２ CO derived from the source ２ is an isolation method, a) contacting the aqueous ammonia solution for recovery with a gaseous CO ２ source under conditions sufficient to produce an aqueous ammonium carbonate solution; and b) CO ２ Mixing a cation source with the aqueous ammonium carbonate solution under conditions sufficient to produce an aqueous solution of an isolation carbonate and an ammonium salt, and c) regenerating the aqueous ammonia solution for recovery from the aqueous ammonium salt solution; d) said CO ２ manufacturing building materials from the carbonate for isolation comprising: said regenerating includes distillation by heating the aqueous ammonium salt solution in the presence of an inorganic alkali component source; said distillation uses waste heat supplied from a source selected from the group consisting of flue gas, the heat of absorption generated by step (a), a coolant derived from an industrial plant which is a source of CO2-containing gas at the same site, and combinations thereof; The gaseous CO ２ CO derived from the source ２ Isolation method

2. The gaseous CO ２ source is a multi-component gas stream, the method according to claim 1.

3. The gaseous CO ２ source is flue gas, the method according to claim 2.

4. contacting the gaseous CO source with the aqueous ammonia solution for recovery using a membrane contactor, the method according to any one of claims 1 to 3. ２ ​

5. The method according to any one of claims 1 to 4, wherein said distillation is carried out at a pressure lower than atmospheric pressure.

6. Under conditions sufficient to produce an aqueous ammonium carbonate solution, contacting the regenerated recovered aqueous ammonia solution with a gaseous CO ２ source, the method according to any one of claims 1 to 5, further comprising.

7. The method according to any one of claims 1 to 6, wherein said cation source includes divalent cations of alkaline earth metals.

8. The divalent cation of the alkaline earth metal is Ca ２＋ and Mg ２＋ The method according to claim 7, which is selected from the group consisting of and combinations thereof.

9. The step (b) of mixing is to introduce the cation source into the flowing aqueous ammonium carbonate solution under conditions sufficient to form a solid carbonate as a non-slurry for isolation in the flowing aqueous ammonium carbonate solution. ２ The method according to any one of claims 1 to 8, comprising introducing the cation source into the flowing aqueous ammonium carbonate solution under conditions sufficient to form a solid carbonate as a non-slurry for isolation in the flowing aqueous ammonium carbonate solution.

10. The CO mentioned above ２ The method according to claim 9, wherein the solid carbonate for isolation is a particulate composition.

11. CO ２ a gas / ammonia aqueous solution module for recovery, and The foregoing CO ２ A solid carbonate production module operably coupled to the CO gas / ammonia aqueous solution module for recovery, and configured to produce an aqueous ammonia solution for recovery, the solid carbonate generation module and the CO ２ an aqueous ammonia solution regeneration module operably coupled to the gas / aqueous ammonia solution module for recovery, a building material manufacturing module configured to manufacture building materials from solid carbonate and operably coupled to the solid carbonate production module comprising: the production of the aqueous ammonia solution for recovery includes distillation including heating the aqueous ammonium salt solution in the presence of an inorganic alkali component source; said distillation uses waste heat supplied from a source selected from the group consisting of flue gas, the heat of absorption generated by the contact of the aqueous ammonia solution for recovery with the CO2 gas, a coolant derived from an industrial plant which is a source of CO2-containing gas at the same site, and combinations thereof; Gaseous CO ２ CO derived from the source ２ isolation system.

12. Recycled ammonia aqueous solution is recycled to the CO ２ The isolation system according to claim 11, which is configured to recycle the gas / recycled ammonia aqueous solution module.

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