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

Abstract

To provide a method and a system that regenerate an aqueous capture ammonia in aqueous capture ammonia mediated carbon dioxide CO2 sequestration.SOLUTION: A method according to the present invention includes contacting an aqueous capture ammonia 122 with a gaseous source 108 of CO2 under conditions sufficient to produce an aqueous ammonium carbonate 110. The aqueous ammonium carbonate 110 is then combined with a cation source 112 under conditions sufficient to produce a solid CO2 sequestering solid carbonate 114 and an aqueous ammonium salt 116. The aqueous capture ammonia 122 is then regenerated from the aqueous ammonium salt 116. Also provided are systems configured to perform the methods.SELECTED DRAWING: Figure 1

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 CO2 in the atmosphere is industrial plants. Many types of industrial plants (including cement plants, oil refineries, ironworks, 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 CO2 in the atmosphere since the Industrial Revolution as a result of human activities, anthropogenic CO2 is involved not only in global warming and climate change but also in the increase in the bicarbonate concentration in the ocean. The uptake of fossil fuel CO2 into the ocean is currently proceeding at about 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 sequestering carbon dioxide (CO2) is provided. One aspect of this method involves contacting a recovery ammonia aqueous solution with a gaseous CO2 source under conditions sufficient to produce an ammonium carbonate aqueous solution. The ammonium carbonate aqueous solution is then mixed with a cation source under conditions sufficient to produce a solid carbonate and an ammonium salt aqueous solution for CO2 sequestering. The recovery ammonia aqueous solution is then regenerated from the ammonium salt aqueous solution. A system configured to carry out this method is also provided. [Brief explanation of the drawing]

[0006] [Figure 1] This is a schematic diagram of a system relating to one embodiment of the present invention. [Figure 2] This is a schematic diagram of a system according to one embodiment of the present invention, in which ammonia regeneration is carried out at a pressure lower than atmospheric pressure and all the heat is supplied by a waste heat source. [Figure 3] As described in the examples below, this graph shows the carbon dioxide absorption rate (%), which depends on the gas capacity (standard liters per minute, SLPM), for a single pass through one hollow fiber membrane contactor (surface area 1.4 m2) with a CO2 gas concentration ranging from 5% to 50% (air supplemented as the remainder), using a 0.5 M NH3 solution. [Figure 4] This graph shows the results of the ammonia reforming study described in the examples below. [Figure 5] This graph shows the results of the ammonia reforming study described in the examples below. [Figure 6] This graph shows the results of the ammonia reforming study described in the examples below. [Figure 7] This graph shows the results of the ammonia reforming study described in the examples below. [Figure 8] This graph shows the results of the ammonia reforming study described in the examples below. [Figure 9] This graph shows the results of the ammonia reforming study described in the examples below. [Figure 10]This is a diagram of a system according to one embodiment of the present invention, suitable for use in a 2MW coal-fired power plant. [Figure 11A] This diagram shows a system according to various embodiments of the present invention, suitable for use in a 2MW coal-fired power plant. [Figure 11B] This diagram shows a system according to various embodiments of the present invention, suitable for use in a 2MW coal-fired power plant. [Figure 11C] This diagram shows a system according to various embodiments of the present invention, suitable for use in a 2MW coal-fired power plant. [Figure 12] This is a diagram of a system according to one embodiment of the present invention, suitable for use in a 10MW coal-fired power plant. [Figure 13] This is a diagram of a system according to one embodiment of the present invention, suitable for use in a 10MW coal-fired power plant, in which the ammonia regenerator is operated under reduced pressure / low temperature using waste heat. [Modes for carrying out the invention]

[0007] A method for sequestering carbon dioxide (CO2) is provided. One aspect of this method involves contacting a recovery ammonia aqueous solution with a gaseous CO2 source under conditions sufficient to produce an ammonium carbonate aqueous solution. The ammonium carbonate aqueous solution is then mixed with a cation source under conditions sufficient to produce a solid carbonate and an ammonium salt aqueous solution for CO2 sequestering. The recovery ammonia aqueous solution is then regenerated from the ammonium salt aqueous solution. A system configured to carry out this method is also provided.

[0008] Before describing the present invention in more detail, it should be understood that the present invention is not limited to the specific embodiments described and, therefore, may vary. It should also be understood that the scope of the present invention is limited only by the appended claims, and that the terms used herein are intended solely to describe, and not to limit, specific embodiments.

[0009] When a range of values ​​is presented, unless otherwise explicitly indicated by the context, each value between the upper and lower limits of that range, up to one-tenth of the lower limit, and any other stated or intermediate values ​​within the stated range should be understood to be included within the present invention. The upper and lower limits of these smaller ranges may be independently included within those smaller ranges and are also included within the present invention, provided that any limits within the stated ranges are specifically excluded. If the stated ranges include one or both of the limits, ranges that do not include one or both of these limits are also included within the present invention.

[0010] Certain ranges are presented herein with the term “approximately” preceding the numerical value. In this specification, the term “approximately” is used to provide literal support for the exact number that follows it, as well as for any number that is close to or nearly equal to it. In determining whether a number is close to or nearly equal to a specifically stated number, the close or nearly equal unstated number may be substantially equivalent to the specifically stated number in the context in which the number is shown.

[0011] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which the present invention pertains. Any methods and substances similar to or equivalent to those described herein may also be used in carrying out or testing embodiments of the present disclosure, but representative examples of methods and substances are listed below.

[0012] All publications and patents referenced herein are incorporated herein by reference, just as each individual publication or patent is indicated to be specifically and individually incorporated by reference, and are incorporated herein by reference to disclose and describe the methods and / or substances for which such publications are referenced in connection therewith. Any reference to a publication is intended to indicate that the disclosure in such publication predates the filing date of this application and should not be construed as an admission that the present invention does not qualify as prior to such publication on the grounds of prior art. Furthermore, the publication dates presented may differ from the actual publication dates, which may need to be verified by the user.

[0013] In this specification and the attached claims, the singular forms "a," "an," and "the" refer to multiple subjects unless the context clearly indicates otherwise. Furthermore, it should be noted that the claims may be constructed to exclude any optional element. Therefore, this statement is intended to serve as an antecedent basis for the use of exclusive terms such as "alone" or "only," or for the use of "negative" limitations, in relation to the enumeration of elements in the claims.

[0014] As will be apparent to those skilled in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has distinct elements and features that can be readily separated from or combined with any of the features of several other embodiments without departing from the scope or spirit of the invention. Any described method may be carried out in the order of events described or in any other logically possible order.

[0015] method As summarized above, aspects of the present invention include a method for sequestering CO2 from a gaseous CO2 source. Therefore, aspects of the present invention include a CO2 sequestering process, i.e., a process (method, protocol, etc.) for sequestering CO2. "CO2 sequestering" means the removal or sequestering of a certain amount of CO2 from an environmental source, such as the Earth's atmosphere or exhaust gas flows generated at an industrial plant, such that some or all of the CO2 no longer exists in the environment from which the CO2 has been removed. The CO2 sequestering method of the present invention sequesters CO2 by producing a substantially pure, underground-injectable CO2 product gas and a storage-stable solid CO2 sequestering product from a certain amount of CO2, such that the CO2 is sequestered. The storage-stable solid CO2 sequestering product is a composition that incorporates a certain amount of CO2 into a storage-stable form, such as a form that is storage-stable on land or in water, such that the CO2 no longer exists as an atmospheric gas or cannot be an atmospheric gas. The CO2 sequestration method of the present invention prevents CO2 gas from entering the atmosphere and enables long-term storage of CO2 in a manner that prevents CO2 from becoming part of the atmosphere.

[0016] As summarized above, embodiments of the present method include: a) contacting a recovery aqueous ammonia solution 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 recovery aqueous ammonia solution from the aqueous ammonium salt solution for continued use, for example, in further ammonia-mediated CO2 sequestration. Each of these embodiments of the present method will be described in more detail below.

[0017] CO2 capture Embodiments of this method include contacting a recovery aqueous ammonia solution 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, 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 originating from the industrial plant. An industrial plant from which the CO2-containing gas can be obtained, for example, as an exhaust gas supply stream originating from the industrial plant, may be a variety of plants. Target industrial plants include, but are not limited to, power plants, chemical and machining plants, refineries, cement plants, steel mills, and other industrial plants that generate CO2 as a by-product of fuel combustion or other processing steps (such as firing by cement plants), as well as industrial product manufacturing plants. The target supply flows include gas flows generated in industrial plants, for example, gas flows as by-products or accidental by-products of processes carried out by the industrial plant.

[0018] In certain embodiments, the scope includes exhaust gas flows produced by industrial plants that burn fossil fuels, such as coal, petroleum, and natural gas, as well as artificial fuel products from naturally occurring organic fuel deposits such as tar sands, heavy oil, and oil shale. In certain embodiments, the power plants are pulverized coal power plants, supercritical coal power plants, mass-burn coal power plants, fluidized-bed coal power plants, gas or oil combustion boiler and steam turbine power plants, gas or oil combustion boiler simple cycle gas turbine power plants, and gas or oil combustion boiler combined cycle gas turbine power plants. In certain embodiments, the scope includes exhaust gas flows produced by power plants that burn synthesis gas, i.e., gas produced by the gasification of organic materials such as coal and biomass, for example, in certain embodiments such as gasification combined cycle (IGCC) plants. In certain embodiments, the scope includes exhaust gas flows produced by heat recovery steam generator (HRSG) plants. Other examples of exhaust gas flows included are those generated in cement plants. Cement plants whose exhaust gas flow can be used in the method of the present invention include both wet process and dry process plants, which may use shaft kilns or rotary kilns and may be equipped with pre-firing equipment. Each of these types of industrial plants may burn a single type of fuel or two or more fuels sequentially or simultaneously. The exhaust gas flow in question is the exhaust gas of an industrial plant, for example, flue gas. "Flue gas" means gas obtained from combustion products of burning fossil fuels or biomass fuels and then led to a chimney (also known as an industrial plant flue).

[0019] Exhaust gas flows generated at cement plants are also suitable for the system and method of the present invention. Exhaust gas flows from cement plants include those from both wet-process and dry-process plants, which may use shaft kilns or rotary kilns and may be equipped with pre-firing devices. Each of these industrial plants may burn a single type of fuel, or two or more fuels sequentially or simultaneously. Other industrial plants, such as smelters and oil refineries, are also useful sources of exhaust gas flows containing carbon dioxide.

[0020] Industrial exhaust gas flows may contain carbon dioxide as a component originating from sources other than the primary air, or, particularly in the case of coal-fired power plants, further components (sometimes collectively referred to as non-CO2 pollutants), such as nitrogen oxides (NOx), sulfur oxides (SOx), and one or more additional gases. Further gases and other components may include CO, mercury, and other heavy metals, as well as dust particles (e.g., from calcination and combustion processes). Further non-CO2 pollutant components in the gas flows may also include halides such as hydrogen chloride and hydrogen fluoride, fly ash, dust, and particulate matter such as metals including 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, suitable exhaust gas flows that can be processed are 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 ppm 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 500ppm~10,000ppm, or 500ppm~5,000ppm, or 500ppm~2,000ppm, or 500ppm~1,000ppm, or 1,000ppm~1,000,000ppm, or 1,000ppm~500,000ppm, or 1,000ppm~100,000ppm, or 1,000ppm~10,000ppm, or 1,000ppm~5,000ppm, or 1,000ppm~2,000ppm, or 2,000ppm~1,000,000ppm, or 2,000ppm~500,000ppm m, or 2000ppm~100,000ppm, or 2000ppm~10,000ppm, or 2000ppm~5,000ppm, or 2000ppm~3000ppm, or 5000ppm~1,000,000ppm, or 5000ppm~500,000ppm, or 5000ppm~100,000ppm, or 5000ppm~10,000ppm, or 10,000ppm~1,000,000ppm, or 10,000ppm~500,000ppm, or 10,000ppm~100,000ppm, and It contains CO2 present in amounts of 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 2,000 ppm, including 200,000 ppm to 2,000 ppm, for example, 180,000 ppm to 2,000 ppm, or 180,000 ppm to 5,000 ppm, including 180,000 ppm to 10,000 ppm.

[0021] The exhaust gas flow, particularly the exhaust gas flow of various combustion gases, may contain one or more additional non-CO2 components, such as, but not limited to, water, NOx (nitrous oxide: NO and NO2), SOx (sulfur oxide: SO, SO2, and SO3), VOCs (volatile organic compounds), heavy metals such as mercury, and particulate matter (solid or liquid particles suspended in the gas). The flue gas temperature may also vary. In some embodiments, the temperature of the flue gas containing CO2 includes 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 500°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 100°C to 400°C.

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

[0023] The CO2-containing gas may be brought into contact with the ammonia aqueous solution for recovery using any and appropriate protocol, as described above. Examples of contact protocols include, but are not limited to, direct contact protocols, such as bubbling the gas through a certain volume of aqueous medium; parallel contact protocols, i.e., contact between a gas phase flow and a liquid phase flow flowing in one direction; and counter-flow protocols, i.e., contact between a gas phase flow and a liquid phase flow flowing in opposite directions. Contact may be carried out using an injector, bubbler, fluid venturi reactor, spurger, gas filter, spray, tray, or packed column reactor, where appropriate. This process may be a batch process or a continuous process.

[0024] In some cases, a microporous membrane contactor is used to bring a gaseous CO2 source into contact with a liquid. The microporous membrane contactor in question comprises a microporous membrane located in a suitable housing, the housing comprising a gas outlet and a liquid outlet in addition to a gas inlet and a liquid inlet. The contactor is configured such that the gas and liquid come into contact on opposite sides of the membrane in such a way that molecules dissolve from gas to liquid through the pores of the microporous membrane. The membrane can be made of any and suitable form, and in some cases, the membrane is made of hollow fibers. Examples of hollow fiber membrane reactors that may be used include, but are not limited to, those described in U.S. Patents 7,264,725, 6,872,240, and 5,695,545, the disclosures of which are incorporated herein by reference. In some cases, the microporous hollow fiber membrane contactor used is the Liqui-Cel® hollow fiber membrane contactor (Membrana, Charlotte, NC), and examples of membrane contactors include polypropylene membrane contactors and polyolefin membrane contactors.

[0025] Contact between the recovery liquid and the CO2-containing gas is carried out under conditions such that a substantial portion of the CO2 present in the CO2-containing gas is transferred into the solution, generating, for example, bicarbonate ions. A substantial portion means 50% or more, including 10% or more, for example, 80% or more.

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

[0027] CO2-containing gas and recovery liquid are brought into contact at a pressure suitable for producing a liquid filled with the desired amount of CO2. In some cases, the pressure of the contact conditions is selected to optimize CO2 absorption, and such pressure may be in the range of 1 to 100 atmospheres, e.g., 1 to 50 atmospheres, e.g., 20 to 30 atmospheres, or 1 to 10 atmospheres. When contact is made in a location with natural atmospheric pressure of 1 atmosphere, the pressure may be increased to the desired pressure using an optional and appropriate protocol. In some cases, contact is made in a location where the optimal pressure exists, e.g., below the surface of a body of water such as an ocean or sea. In some cases, contact between the CO2-containing gas and the alkaline aqueous medium is made at a depth below the water surface (e.g., the ocean surface), and this depth may be in some cases in the range of 10 to 1000 meters, e.g., 10 to 100 meters. In some cases, contact between the CO2-containing gas and the CO2 recovery liquid is made at a pressure at which CO2 is selectively absorbed from the CO2-containing gas in relation to other gases in the CO2-containing gas, e.g., N2. In these cases, the pressure at which the CO2-containing gas and the recovery liquid come into contact can vary, ranging from 1 to 100 atmospheres (atm), for example, from 1 to 10 atmospheres and from 20 to 50 atmospheres.

[0028] A gaseous CO2 source is brought into contact with the ammonia recovery solution in a form sufficient to produce an ammonium carbonate solution. The ammonium carbonate solution can be diverse, in some cases containing at least one of ammonium carbonate and ammonium bicarbonate, and in some cases containing both ammonium carbonate and ammonium bicarbonate. The ammonium bicarbonate solution can also be considered a DIC-containing liquid. Therefore, when saturating the ammonia recovery solution with CO2, the CO2-containing gas may be brought into contact with the CO2 recovery liquid under conditions sufficient to produce dissolved inorganic carbon (DIC) in the CO2 recovery liquid, i.e., sufficient to produce a DIC-containing liquid. DIC is given by the formula DIC = [CO2] * ]+[HCO3 - ]+[CO3 2- ](wherein, [CO2 * [HCO3] is the sum of the carbon dioxide ([CO2]) concentration and carbonic acid ([H2CO3]) concentration in the solution. - ] is the bicarbonate concentration (including ammonium bicarbonate), and [CO3 2- ] is the carbonate concentration (including ammonium carbonate). ) is the total concentration of inorganic carbon species. The DIC of this aqueous medium may vary, and in some cases 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 to 15,000 ppm, including 5,000 to 20,000 ppm, for example, 8,000 to 12,000 ppm. The CO2 dissolved in the liquid may vary, and in some cases may be in the range of 1 to 35 mM, including 0.05 to 40 mM, for example, 25 to 30 mM. The pH of the resulting DIC-containing liquid may vary, and in some cases may be in the range of 6 to 11, including 4 to 12, for example, 7 to 10, for example, 8 to 8.5.

[0029] In some cases where the gaseous CO2 source is a multi-component gas stream, contact occurs in a manner that the CO2 is selectively absorbed by the CO2-absorbing aqueous medium. Selective absorption means that CO2 molecules preferentially move into the solution over other molecules in the multi-component gas stream, such as N2, O2, Ar, CO, H2, and CH4.

[0030] If desired, the CO2-containing gas is brought into contact with the recovery liquid 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). The absorption catalyst is one that increases the rate of bicarbonate ion formation from dissolved CO2 at pH levels in the range of 8 to 10. The magnitude of the rate increase (e.g., compared to a control without the catalyst) can vary and in some cases is more than 2 times, e.g. more than 5 times, e.g. more than 10 times, compared to a suitable 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 ammonium carbonate aqueous solution is a two-phase liquid containing droplets of a liquid condensate phase (LCP) in a bulk liquid, such as a bulk solution. The "liquid condensate phase," or "LCP," refers to a phase of liquid solution containing bicarbonate ions, where the concentration of bicarbonate ions in the LCP phase is higher than that in the surrounding bulk liquid, as described above. The LCP droplet is characterized by the presence of a metastable, bicarbonate-rich liquid precursor phase, where bicarbonate ions associate to a condensate concentration exceeding that of the bulk solution and exist in an amorphous solution state. This LCP contains all the components present in the bulk solution outside the interface, except that 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 contain ion pairs and pre-nucleation clusters (PNCs), respectively. These ions, if present, remain in their respective phases for longer periods compared to ion pairs and PNCs in the solution. Further details relating to LCP-containing liquids are described in U.S. Patent Application No. 14 / 636,043, 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 valencies can form a solid carbonate composition (e.g., in the form of a carbonate mineral). 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, such as calcium and magnesium cations, may be used. When cations are added to the aqueous ammonium carbonate solution, the divalent cations become Ca 2+ A precipitate of a carbonate solid, such as amorphous calcium carbonate when it contains cations, can be formed at a stoichiometric ratio of 1 carbonate species ion per cation.

[0033] In such cases, an optional and appropriate cation source may be used. Examples of the target cation source include, but are not limited to, brines derived from water treatment facilities such as seawater desalination plants, brackish water desalination plants, groundwater recovery facilities, and drainage facilities that generate concentrated streams of solutions with 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 accessible cation sources that induce the formation of carbonate solids from aqueous ammonium carbonate solutions. In some cases, the cation source may be the effluent from another step of the process, for example, calcium salts (such as CaCl2) generated during the regeneration of ammonia from aqueous ammonium salt solutions.

[0034] The carbonate composition that is the product may be very diverse. The precipitate product may contain one or more different carbonate compounds, for example, two or more different carbonate compounds, for example, 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 a combination of elements that can chemically bond 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 structural waters present 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 compounds may contain many different cations, such as calcium, magnesium, sodium, potassium, sulfur, boron, silicon, strontium, and combinations thereof. The focus is on carbonate compounds of divalent metal cations, such as calcium carbonate compounds and magnesium carbonate compounds. Specific carbonate compounds included are, but are not limited to, calcium carbonate minerals, magnesium carbonate minerals, and calcium-magnesium carbonate minerals. Calcium carbonate minerals included are, but are not limited to, calcite (CaCO3), aragonite (CaCO3), vaterite (CaCO3), iquite (CaCO3·6H2O), and amorphous calcium carbonate (CaCO3). The magnesium carbonate minerals covered include magnesite (MgCO3), barringtonite (MgCO3·2H2O), neskehonite (MgCO3·3H2O), ranfordite (MgCO3·5H2O), hydromagnesite, and amorphous magnesium calcium carbonate (MgCO3). The calcium magnesium carbonate minerals covered include dolomite (CaMg)(CO3)2), hanthite (Mg3Ca(CO3)4), and sergeevite (Ca2Mg 11 (CO3) 13 Examples include, but are not limited to, H2O. The carbonate compound of the product may contain one or more waters of hydration, or it may be anhydrous. In some cases, the amount of magnesium carbonate compound in the precipitate, expressed by weight, exceeds the amount of calcium carbonate compound in the precipitate. For example, the amount of magnesium carbonate compound in the precipitate, expressed by weight, may exceed the weight of calcium carbonate compound in the precipitate by 5% or more, e.g., 10%, 15%, 20%, 25%, or 30% or more. In some cases, the weight ratio of magnesium carbonate compound to calcium carbonate compound in the precipitate is in the range of 2 to 4:1, including 1.5 to 5:1, e.g., 2 to 3:1. In some cases, the precipitate may contain hydroxides such as divalent metal ion hydroxides, e.g., calcium hydroxide and / or magnesium hydroxide.

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

[0037] In some cases, the production of carbonates is carried out in a continuous form, for example, as described in U.S. Patent Application No. 14 / 877,766, the disclosure of which is incorporated herein by reference. In some such cases, the production of carbonates may be carried out in the presence of a seed structure, the seed structure meaning a solid structure or solid material present in a flowing liquid, for example, in a material formation area, before the introduction of divalent cations into the liquid. "With the help of" means that the material is formed on or in at least one recess of the seed structure, for example, a pore, a gap, etc. In such cases, a composite structure of the carbonate material and the seed structure is formed. In some cases, the carbonate material, which is the product, covers all, if not part, of the surface of the seed structure. In some cases, the carbonate material, which is the product, fills recesses of the seed structure, for example, pores, gaps, cracks, etc.

[0038] The seed structure may be broadly diverse as desired. The term "seed structure" is used to refer to any object on which the carbonate material product is formed and / or within it. The seed structure may range from a single object to a particulate composition as desired. If the seed structure is a single object, it may have a variety of different shapes, whether fixed or irregular, and a variety of different dimensions. Examples of shapes include, but are not limited to, rod-shaped, mesh-shaped, and lump-shaped. Particulate compositions consisting of multiple particles, such as granular compositions, are also included. If the seed structure is a particulate composition, the particle dimensions may vary, in some cases ranging from 0.01 to 1,000,000 μm, for example, from 0.1 to 100,000 μm.

[0039] The seed structure may consist of any and appropriate materials or a combination of materials. The materials in question include both carbonate materials and non-carbonate materials as described above. The seed structure may be of natural origin, such as naturally occurring sand, oyster shell fragments, or other carbonate skeleton allochem, gravel, etc., or it may be an artificial material, such as crushed rock, crushed blast furnace slag, fly ash, cement kiln dust, red clay, etc. For example, the seed structure may be a particulate composition, such as a white carbonate material or a colored carbonate material, or a granular composition, such as sand coated with a carbonate material during the process, as described above.

[0040] In some cases, the seed structure may be a coarse aggregate, such as a brittle Pleistocene coral rock obtained from tropical regions (e.g., Florida), which has low strength and cannot function as concrete aggregate. In this case, brittle coral rock can be used as seed, and solid carbonate minerals for CO2 sequestration are deposited in the internal pores, so that the coarse aggregate can pass the Los Angeles Rattler abrasion test and is suitable for use in concrete. If a lightweight aggregate is desired, it can be made into a lightweight aggregate for use in lightweight concrete by impregnating only the outer surface with a deposit solution, leaving the inner core relatively "hollow".

[0041] Manufacturing of materials from carbonate products for CO2 sequestration. The carbonate material product may be further used, manipulated, and / or mixed with other compositions to produce materials for various end uses. In certain embodiments, the carbonate composition product is refined (i.e., processed) in some form. Various different protocols can be used for refinement. 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, such as sand, gravel, or aggregate, to produce, for example, a final product, such as concrete or mortar.

[0042] Formed building materials are also covered. The formed building materials of the present invention may be very diverse. "Formed" means that an artificial structure has been given a defined physical shape, i.e., a structure, for example, molded, cast, cut, or otherwise manufactured. Formed building materials are different from amorphous building materials, such as particulate (e.g., powder) compositions that do not have a defined and stable shape but conform to the shape of a container that holds the building material, such as a bag or other container. Examples of formed building materials include, but are not limited to, bricks, boards, conduits, beams, washbasins, columns, and dry-construction walls. Further examples and details relating to formed building materials are described in U.S. Patent Publication No. 2011 / 0290156, the disclosures of which are incorporated herein by reference.

[0043] The present invention also covers non-cementary products containing the product of the present invention as a component. Non-cementary products of the present invention can be very diverse. Non-cementary means that the composition is not a hydraulic cement. Therefore, the composition is not a dry composition that hardens to produce a stable product when mixed with a hardening fluid such as water. 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, products for human ingestion including both liquids and solids, soil conditioners, and agricultural products such as animal feed. Further examples and details of non-cementary products are 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 aggregate for concrete and other applications. The carbonate-coated aggregate may be conventional aggregate or lightweight aggregate.

[0045] Aspects of the present invention include a CO2 sequestration aggregate composition. The CO2 sequestration aggregate composition 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 consists of, for example, a CO2 sequestration carbonate material as described above. The CO2 sequestration carbonate material present in the coating of the coated particles of the aggregate composition of this subject may vary. In some cases, the isotopic profile of the aggregate core is different from the carbonate coating of the aggregate such that the aggregate has a carbonate coating having a first isotopic profile and a core having a second isotopic profile different from the first isotopic profile.

[0046] In some cases, the carbonate material is a highly reflective microcrystalline / amorphous carbonate material. The microcrystalline / amorphous material present in the coating of the present invention can be highly reflective. Because the material can be highly reflective, the total surface reflectance (TSR) value of the coating containing this material can be high. TSR can be measured using any and appropriate 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 shows TSR values ​​in the range of Rg;0,=0.25 to Rg;0,=0.99, including Rg;0,=0.40 to Rg;0,=0.98, measured using the protocol cited above, for example.

[0047] In some cases, coatings containing carbonate materials are highly reflective to near-infrared (NIR) light, ranging from 10 to 99%, for example, 50 to 99%. NIR light refers to light with wavelengths in the range of 700 nanometers (nm) to 2.5 mm. NIR reflectance can be measured using any and 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 to Rg;0=0.99, including Rg;0=0.40 to Rg;0=0.98, measured using, for example, the protocol cited above.

[0048] In some cases, carbonate coatings are highly reflective to ultraviolet (UV) light, ranging from 10 to 99%, for example, 50 to 99%. UV light refers to light with wavelengths in the range of 400 nm to 10 nm. UV reflectance can be measured using any and 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 to Rg;0=0.99, including Rg;0=0.4 to Rg;0=0.98, measured using the protocol cited above, for example.

[0049] In some cases, the coating is highly reflective to visible light, and the visible light reflectance can vary, in some cases ranging from 10 to 99%, for example, from 10 to 90%. Visible light refers to light with wavelengths in the range of 380 nm to 740 nm. Visible light reflectance can be measured using any and 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 reflectance in the range of Rg;0=0.25 to Rg;0=0.99, including Rg;0=0.4 to Rg;0=0.98, as measured using the protocol cited above, for example.

[0050] The materials constituting the carbonate component are, in some cases, amorphous or microcrystalline. When the material is microcrystalline, the crystal diameter, measured using Scherrer's formula applied to the FWHM of the X-ray diffraction pattern, is small, and in some cases is less than 1000 microns in diameter, for example, less than 100 microns in diameter, including less than 10 microns in diameter. In some cases, the crystal diameter is in the range of 10 to 0.001 μm, for example, 1 to 0.001 μm, including 1000 μm to 0.001 μm in diameter. In some cases, the crystal diameter is selected considering the wavelength(s) of light to be reflected. For example, if light in the visible spectrum is to be reflected, the crystal diameter range of the material may be selected to be less than half of the "reflected" range to create a photonic band gap. For example, if the wavelength range of light to be reflected is 100 to 1000 nm, the crystal diameter of the material may be selected to be less than 50 nm, for example, in the range of 1 to 50 nm, for example, 5 to 25 nm. In some embodiments, the material 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 length to diameter is in the range of 500 to 1, for example, 10 to 1. In certain embodiments, the length of the crystals is in the range of about 0.5 μm to about 500 μm, for example, 5 μm to 100 μm. In yet 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 density, the density of the material may vary, but in some cases the density is 5 g / cm³. 3 ~0.01 g / cm³ 3 For example, 2.7 g / cm³ 3 ~0.4g / cm 3 Contains 3g / cm³ 3 ~0.3g / cm 3This is within the range. Regarding porosity measured by gas surface adsorption measured by the BET method (Brown Emmett Teller (see, for example, http: / / en.wikipedia.org / wiki / BET_theory, S. Brunauer, PH Emmett and E. Teller, J. Am. Chem. Soc., 1938, 60, 309. doi:10.1021 / ja01269a023), porosity is, in some cases, 100m 2 / g~0.1m 2 / g, for example, 40m 2 / g~1.5m 2 60mg containing / g 2 / g~1m 2 The range may be in the order of / g. With respect to permeability, in some cases the permeability of the material may be in the range of 1 to 10 darcy, including, for example, 1 to 5 darcy, and is measured using the protocol described, for example, H. Darcy, Les Fontaines Publiques de la Ville de Dijon, Dalmont, Paris (1856). Permeability can also be characterized by evaluating the water absorption rate of the material. As measured by the water absorption rate protocol, for example, the water absorption rate of the material is in the range of 1 to 15%, including, for example, 2 to 9%, and is measured using the protocol described, for example, H. Darcy, Les Fontaines Publiques de la Ville de Dijon, Dalmont, Paris (1856).

[0052] The hardness of the material may vary. In some cases, the material exhibits a Mohs scale of 5 or higher, including 3 or more Mohs (measured using the protocol described, for example, American Federation of Mineralogical Societies, “Mohs Scale of Mineral Hardness”), and the hardness is in some cases in the range of 4 to 7 Mohs, including 3 to 8 Mohs (for example, 5 to 6 Mohs). Hardness can also be expressed in terms of tensile strength, measured using the protocol described, for example, ASTM C1167. In such cases, the material may exhibit a compressive strength of 400 to 2000 N, including 100 to 3000 N (for example, 500 to 1800 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 depending on the potential 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 flow of a coal-fired power plant. TCLP tests for As, Ba, Cd, Cr, Pb, Hg, Se, and Ag may be appropriate tests for the aggregates described herein. In some embodiments, the carbonate composition of the present invention contains As, which is predicted not to leach As into the environment. For example, the As content of the TCLP extract of this composition may be less than 5.0 mg / L, indicating that this composition is not harmful in terms of As. In some embodiments, the carbonate composition of the present invention contains Cd, and this composition is not expected to leach Cd into the environment. For example, the Cd content of the TCLP extract of this composition may be less than 1.0 mg / L, indicating that this composition is not harmful in terms of Cd. In some embodiments, the carbonate composition of the present invention contains Cr, and this composition is not expected to leach Cr into the environment. For example, the Cr content of the TCLP extract of this composition may be less than 5.0 mg / L, indicating that this composition is not harmful in terms of Cr.In some embodiments, the carbonate composition of the present invention contains Hg, and this composition is not expected to leach Hg into the environment. For example, the Hg content of the TCLP extract of this composition may be less than 0.2 mg / L, indicating 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 not expected to leach Pb into the environment. For example, the Pb content of the TCLP extract of this composition may be less than 5.0 mg / L, indicating 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, this carbonate composition may not be harmful with respect to all metal contaminants in a given test. The TCLP extract of the composition may contain, 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 / L for Cr, less than 5.0 mg / L for Pb, less than 0.2 mg / L for Hg, less than 1.0 mg / L for Se, and less than 5.0 mg / L for Ag. In practice, in 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.Therefore, the carbonate compositions and aggregates of the present invention can effectively sequestrate CO2 (for example, as carbonates, bicarbonates, or combinations thereof) along with various chemical species (or their by-products) derived from exhaust gas flows, industrial waste sources of divalent cations, industrial waste sources of proton scavenging agents, or combinations thereof, which may become pollutants if released into the environment. The compositions of the present invention incorporate environmental pollutants (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-leaching form.

[0054] The aggregate composition of the present invention comprises 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 of the core surface, 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, and 95% or more. The thickness of the carbonate layer may vary as desired. In some cases, this thickness may be in the range of 1 μm to 1000 μm, for example, 0.1 μm to 10 mm, including 10 μm to 500 μm.

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

[0056] In some cases, the aggregate is lightweight aggregate. In such cases, the core of the coated particles of the aggregate composition described herein may be broadly diverse, as long as the core is coated and gives the desired lightweight aggregate composition. The core may be composed of any and appropriate material. Examples of suitable aggregates include, but are not limited to, conventional lightweight aggregates, such as naturally occurring lightweight aggregates such as pumice, slag, or fractured volcanic rocks 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 unconventional porous materials, such as synthetic materials such as fractured coral, polymers, and low-density polymer materials, recycled waste such as wood, fibrous materials, cement kiln dust residue, recycled glass, various volcanic minerals, granite, silica-containing minerals, and ore scrap.

[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 in which the aggregate will be used, for example, insofar as the aggregate provides the desired properties to the building material in which it will be used. In certain cases, the density of the aggregate particles is in the range of 1.3 gm / cc to 3.15 gm / cc, including 1.8 gm / cc to 2.7 gm / cc. Other particle densities in embodiments of the present invention may be in the range of 1.1 to 2.2 gm / cc, for example, 1.2 to 2.0 g / cc or 1.4 to 1.8 g / cc, for lightweight aggregates. In some embodiments of the present invention, the bulk density (unit weight) is 50 lb / ft. 3 ~200lb / ft 3 , or 75 lb / ft 3 ~175 lb / ft 3 , or 50 lb / ft 3 ~100lb / ft 3 , or 75 lb / ft 3 ~125 lb / ft 3 , or lb / ft 3 ~115 lb / ft 3 , or 100 lb / ft 3 ~200lb / ft 3 , or 125 lb / ft3 ~lb / ft 3 , or 140 lb / ft 3 ~160 lb / ft 3 , or 50 lb / ft 3 ~200lb / ft 3 The present invention provides aggregates within the range of [specified range]. Some embodiments of the present invention provide lightweight aggregates, for example, with a bulk density (unit weight) of 75 lb / ft 3 ~125 lb / ft 3 For example, 90 lb / ft 3 ~115 lb / ft 3 The aggregate is provided. In some cases, the weight of the lightweight aggregate is 50-1200 kg / m 3 For example, 80-11 kg / m 3 It is within the range.

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

[0059] The abrasion resistance of aggregates can also be important for use on road surfaces, for example, when highly abrasion-resistant aggregates are useful to prevent surface abrasion. Abrasion resistance is related to, but not identical to, hardness. The aggregates of the present invention include, for example, aggregates whose abrasion resistance is similar to that of natural limestone, or aggregates whose abrasion resistance is superior to that of natural limestone, as well as aggregates whose abrasion resistance is 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 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%, as measured by ASTM C131-03.

[0060] The porosity of the aggregate of the present invention may also be within a specific range. As those skilled in the art will understand, in some cases, aggregates with high porosity are desirable; in other cases, aggregates with moderate porosity are desirable; and in other cases, aggregates with low porosity or no porosity are desirable. The porosity of the aggregates of some embodiments of the present invention, measured by water absorption after oven drying followed by complete immersion for 60 minutes and expressed as a percentage of dry weight, may be in the range of 1 to 40%, for example, 2 to 20%, or 2 to 15%, including 2 to 10% and even 3 to 9%.

[0061] The aggregate particles may vary in size. The aggregate compositions of the present invention are particulate compositions that may be classified as fine-grained or coarse-grained in some embodiments. The fine aggregates according to embodiments of the present invention are particulate compositions that pass through a fourth sieve (ASTM C125 and ASTM C33) almost completely. The average particle size of the fine aggregate compositions according to embodiments of the present invention is in the range of 50 μm to 3.0 mm, including 10 μm to 4.75 mm, for example, 75 μm to 2.0 mm. The coarse aggregates of the present invention are compositions that mostly remain on the fourth sieve (ASTM C125 and ASTM C33). The coarse aggregate compositions according to embodiments of the present invention are compositions with an average particle size in the range of 4.75 to 150 mm, including 4.75 mm to 200 mm, for example, 5 to 100 mm. In this specification, “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 larger.

[0062] Dry concrete composite Furthermore, a concrete dry composite is also provided that, when mixed with an appropriate hardening liquid (such as those described later), produces a hardening composition that hardens into concrete or mortar. The concrete dry composite described herein contains a certain amount of aggregate (for example, as described above) and cement such as hydraulic cement. The term "hydraulic cement" is used in its conventional sense and refers to a composition that hardens after being mixed with water or a solution in which the solvent is water, such as a mixed solution. The hardening of the product produced by mixing the concrete dry composite of the present invention with an aqueous liquid is due to the formation of hydrates formed from cement during the reaction with water, and these hydrates are essentially insoluble in water.

[0063] The aggregate of the present invention, when mixed with pure Portland cement, is used as a substitute for conventional natural rock aggregate used in conventional concrete. In certain embodiments, other hydraulic cements subject to consideration include mixed Portland cement. The term "mixed Portland cement" includes hydraulic cement compositions containing Portland cement components and significant amounts of non-Portland cement components. When the cement of the present invention is mixed Portland cement, this cement contains Portland cement components. The Portland cement components may be any and appropriate 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 to control the hardening time, and up to 5% of trace components (as permitted by various standards). If the exhaust gas used to supply carbon dioxide to the aforementioned reaction contains SOx, sufficient sulfate may be present in the precipitated material as calcium sulfate, eliminating the need to add calcium sulfate as either cement or aggregate. As defined by European standard EN197.1, "Portland cement clinker is a hydraulic material that must consist of at least two-thirds by mass of calcium silicate (3CaO·SiO2 and 2CaO·SiO2) and the remainder consisting of an aluminum and iron-containing clinker phase 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 magnesium hydroxide, or brusite, may form later in the hardening reaction, leading to deformation, strength reduction, and cracking of the cement. Since brusite can be formed by MgO, brusite will not form in the case of magnesium carbonate-containing cement. In certain embodiments, the Portland cement components of the present invention are any Portland cement that meets the ASTM standard and the specifications of the American Society for Testing and Materials C150 (Types I-VIII) (ASTM C150 - Standard Specifications for Portland Cement).ASTM C150 encompasses eight types of Portland cement, each with different properties, which are used specifically for their respective purposes.

[0064] As a type of hydraulic cement, carbonate-containing hydraulic cement is also included. Such carbonate-containing hydraulic cement, its manufacturing method and method of use are described in U.S. Patent No. 7,735,274, which 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, is in the range of 30-70% (w / w), including 10-90% (w / w), for example, 40-60% (w / w), for example, a mixture of 80% OPC (ordinary Portland cement) and 20% carbonate hydraulic cement.

[0066] In some cases, the CarbonStar grade (CSR) of a concrete-dried composite composition, and of concrete produced from this composition, is lower than that of a control composition without aggregate in the present invention. The CarbonStar grade (CSR) is a value that characterizes the embodied carbon (in the form of CaCO3) for any given product, compared to the carbon concentration of the product's production itself (i.e., in terms of CO2 emissions). CSR is a metric based on the embodied mass of CO2 per unit of concrete. Of the three components in concrete, namely water, cement, and aggregate, cement is the most important factor, contributing overwhelmingly to CO2 emissions, in a ratio of approximately 1:1 by mass (1 ton of cement generates approximately 1 ton of CO2). Therefore, if 1 cubic yard of concrete uses 600 pounds of cement, its CSR is 600. Concrete according to an embodiment of the present invention in one cubic yard, comprising 600 pounds of cement, wherein at least a portion of the aggregate in the concrete is, for example, carbonate-coated aggregate as described above, will have a CSR of less than 600, and the CSR may be, for example, 500 or less, including, for example, 400 or less, for example, 250 or less, for example, 100 or less, and in some cases, the CSR may be a negative value, including, for example, -100 or less, for example, -100 or less, for example, -500 or less, and in some cases, the CSR of one cubic yard of concrete with 600 pounds of cement may be in the range of -100 to -4000, including, for example, 500 to -5000, for example, -500 to -3000. To determine the CSR of a given concrete containing carbonate-coated aggregate of the present invention in one cubic yard, the initial value of CO2 generated for the production of the cement component of the concrete in one cubic yard is determined. For example, if one cubic yard of concrete contains 600 pounds of cement, an initial value of 600 is assigned to one cubic yard of concrete. Next, the amount of carbonate coating in one cubic yard of concrete is determined.Since the molecular weight of carbonate is 100 arbitrary units and 44% of carbonate is CO2, the amount of carbonate film present in 1 cubic yard of the above concrete is multiplied by 0.44, and the resulting value is subtracted from the initial value to obtain the CSR for 1 cubic yard of concrete. For example, if a given concrete mixture in 1 cubic yard 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 aggregate in this mixture is replaced with a carbonate film (for example, as described above), the amount of carbonate present in 1 cubic yard of modified concrete becomes 317 pounds. Multiplying this value by 0.44 gives 139.5. Subtracting this value from 600 gives a CSR of 460.5.

[0067] curable composition The curable compositions of the present invention, such as concrete and mortar, are produced by simultaneously mixing hydraulic cement with a certain amount of aggregate (fine aggregate for mortar, e.g., sand; coarse aggregate with or without fine aggregate for concrete) and an aqueous liquid, e.g., water, or by pre-mixing cement with aggregate and then mixing the resulting dry component with water. The minimum size of coarse aggregate selected for concrete mixtures using the cement composition of the present invention may be about 3 / 8 inch, and the size of this aggregate may vary from the minimum to 1 inch or more, including particle size variations between these limits. Micronized aggregate is less than 3 / 8 inch in size and may be further graded to finer sizes, 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 component of cement may vary, and in certain embodiments, ranges from 1:10 to 4:10, e.g., 2:10 to 5:10 and 55:100 to 70:100.

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

[0069] In certain embodiments, cement may be used with one or more admixtures. Admixtures are compositions added to concrete to impart desirable properties to the concrete that cannot be obtained with the 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 to reduce costs. As is known in the art, admixtures are any material or composition other than hydraulic cement, aggregate, and water, and are used as components of concrete or mortar to improve some property of the concrete or mortar, or to reduce their costs. The amount of admixture used may vary depending on the properties of the admixture. In certain embodiments, the amounts of these components are in the range of 1 to 50% w / w, for example, 2 to 10% w / w.

[0070] The admixtures covered include cementitious materials, pozzolanes, pozzolanic and cementitious materials, and nominally inert materials, as well as finely milled mineral admixtures. Examples of pozzolanes include diatomaceous earth, milky chert, clay, shale, fly ash, silica fume, and tuff, with pumice being a well-known example of a pozzolane. Certain crushed blast furnace granulated slags and high-calcium fly ash possess both pozzolanic and cementitious properties. Examples of nominally inert materials include finely milled fossilized quartz ore, dolomite, limestone, marble, and granite. 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-reducing agents, corrosion inhibitors, and pigments.

[0072] Thus, the admixtures covered include, but are not limited to, hardening accelerators, hardening retarders, air-entraining agents, defoamers, alkali reactivity reducers, binding admixtures, dispersants, colorants, corrosion inhibitors, moisture-proofing agents, gas generators, permeability reducers, pumping aids, shrinkage compensators, fungicides, fungicides, insecticides, viscoelastic modifiers, micronized mineral admixtures, pozzolanes, aggregates, wetting agents, strength enhancers, water repellents, and any other concrete or mortar admixtures or additives. Admixtures are well known in the art, and any and appropriate admixtures of the above types or any other desired types may be used. For example, see U.S. Patent No. 7,735,274, which is incorporated herein by reference in its entirety.

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

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

[0075] The components of the curable composition can be mixed using any and appropriate protocol. Each material may be mixed during the process, or some or all of the materials may be pre-mixed. Alternatively, some of the materials may be mixed with water containing or without admixtures such as high-performance water-reducing agents, and then the remaining materials may be mixed with this. Any conventional mixing apparatus can be used. For example, Hobart mixers, inclined cylindrical mixers, Omni mixers, Henschel mixers, V-type mixers, and Nauter mixers can be used.

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

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

[0078] structure Aspects of the present invention further include structures manufactured from the aggregates and curable compositions of the present invention. Accordingly, further embodiments include artificial structures containing the aggregates of the present invention and methods for manufacturing them. Accordingly, in some embodiments, the present invention provides an artificial structure containing one or more types of aggregates described herein. This artificial structure may be any structure that may use aggregates, such as a building, a dam, a dike, a road, or any other artificial structure incorporating aggregates or rocks. In some embodiments, the present invention provides an artificial structure containing the aggregates of the present invention, for example, a building, a dam, or a road, and in some cases, this aggregate may contain, for example, CO2 derived from the fossil fuel sources described above. In some embodiments, the present invention provides a method for manufacturing a structure, which includes providing the aggregates of the present invention.

[0079] Albedo improvement applications In some cases, solid carbonate products may be used for albedo enhancement applications. Albedo, or reflectance coefficient, refers to the diffuse reflectance or reflectivity of a surface. Albedo is defined as the ratio of reflected radiation from a surface to incident radiation onto that surface. Albedo is a dimensionless ratio and may be expressed as a ratio or a percentage. Albedo is measured on a scale from zero, where a completely black surface has no reflectivity, to 1, where a white surface has perfect reflectivity. Although albedo depends on the frequency of radiation, in this specification, albedo is expressed without mentioning a specific wavelength and therefore 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 the methods result in an albedo increase of 0.05 or more, for example, 0.1 or more, 0.2 or more, 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, and up to 0.0, including 0.95 or more (compared to an appropriate control, e.g., the albedo of the same surface not subjected to the methods of the present invention) with a width of 0.95 or more, for example, 0.1 or more, for example, 0.2 or more, for example, 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, and up to about 1.0.

[0081] Embodiments of this method include bonding a target surface with an amount effective in improving the surface albedo by a desired width, such as the widths listed above, such as the highly reflective microcrystalline or amorphous material composition described above. This material composition may be bonded to the target surface using any and appropriate protocol. Thus, the material composition may be bonded to the target surface by incorporating the material into the material of the object having the surface to be modified. For example, if the target surface is the surface of a building material such as roof tiles or concrete mixtures, the material composition may be mixed into the material composition such that the material composition is present on the target surface of the object. Alternatively, the material composition may be placed on at least a portion of the target surface by, for example, coating the target 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 0.1 mm to 25 mm, for example, 5 mm to 10 mm. Applications as a highly reflective pigment in paints and other coatings such as solar panels are also included.

[0082] The albedo of various surfaces may be improved. Target surfaces include, but are not limited to, surfaces of both artificial and naturally occurring objects that are at least partially facing the sky. Target artificial surfaces include, but are not limited to, roads, walkways, buildings and their components, such as roofs and their components (roofing slabs, roofing granules, etc.) and side walls, runways, and other artificial structures, such as walls, dams, monuments, and ornaments. Target naturally occurring surfaces include, but are not limited to, plant surfaces in both forested and non-forested areas, non-vegetated areas, and water surfaces, such as lake surfaces, ocean surfaces, and sea surfaces.

[0083] For example, the albedo of a colored granule can be easily increased by the method described herein, which involves generating a carbonate layer on the surface of the colored roof granule. The thickness of the carbonate material layer present on the surface of the colored roof granule may vary, but in some cases, the thickness is in the range of 1 to 150 μm, including 0.1 to 200 μm, for example, 5 to 100 μm. By coating various different types of colored granules as described above, the reflectivity of the colored granule can be improved, for example, without substantially reducing the color of the colored granule, if any. An example of the type of granule that may be coated with the carbonate layer described herein is roof granule.

[0084] Roofing granules, which can be coated with a carbonate layer to improve the reflectivity of colored granules without substantially reducing the color of the colored granules, if any, may be some, may include a core formed from crushed and sieved mineral material, the core being subsequently coated with one or more colored film layers containing a binder in which one or more colored pigments, such as suitable metal oxides, are dispersed. An inorganic binder may be used. The binder may be a soluble alkaline silicate, which is then insoluble by heat or chemical reaction, for example, by a reaction between an acidic substance and the alkaline silicate, resulting in an insoluble colored film on the mineral particles. The base particles used in the process of preparing the roofing 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 foamed glass or ceramic particles. Suitable mineral particles can be produced by a series of quarrying, crushing, and sieving operations, and are generally of an intermediate size between sand and gravel (i.e., between US mesh number approximately 8 and US mesh number 70). The average particle size of the core particles is approximately 0.2 mm to approximately 3 mm, for example, approximately 0.4 mm to approximately 2.4 mm. In particular, particles of appropriate size from naturally occurring materials such as talc, volcanic sludge, granite, silica sand, green stone, andesite, porphyry, marble, syenite, rhyolite, diorite, greystone, quartz, slate, trapeze, basalt, and marine shells can be used, as well as processing materials such as ceramic refractory clay and propane, and recycled processing materials such as crushed bricks, concrete, porcelain, and refractory clay.Solid and hollow glass spheres are available, for example, from Potters Industries Inc., PO Box 840, Valley Forge, Pa. 19482-0840, including SPHERIGLASS® solid "A" glass spheres, grade 1922 with an average particle size of 0.203 mm, product code 602578 with an average diameter of 0.59 mm, BALLOTTINI impact beads, product grade A with a diameter range of 600-850 micrometers (US sieve diameter 20-30), and QCEL hollow spheres, product code 300 with an average particle size of 0.090 mm. If desired, the glass spheres may be coated or treated with an appropriate coupling agent to improve adhesion of the internal coating composition to the binder. In granules, particles may 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] Applicable coated pigments include, but are not limited to, PC-9415 Yellow, PC-9416 Yellow, PC-9158 Autumn Gold, PC-9189 Bright Golden Yellow, V-9186 Iron 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 method described herein may also be used to produce fract sand. Frax sand is used in the oil and gas recovery industry to maintain porous voids in fractured geological structures in order to preserve the integrity of the geological fracture. Using the method described herein, coated substrates and processed sands having surface coatings that can be adjusted for the purpose, which can contribute to the buoyancy of the sand in a fluid flow may be produced. Using the method described herein, substrates having carbonate material (crystalline or amorphous) in a tightly regular or irregular pattern form may be produced, in which the surface of the sand is effectively designed to maintain above-average buoyancy in a fluid flow when the fracking fluid is pumped into the geological fracture site under very high pressure. In some cases, the method produces a product containing a crystalline or amorphous, but unreacted, cementitious coating compound, in which the material reacts as an expansive cement, providing voids for the flow of gases and fluids from the surrounding geological structure. These broad properties can be activated by close contact with a fluid or gas, sustained fluid contact, or activation by other magnetic or sonic waves supplied from a geological surface.

[0087] The uses of the carbonate precipitate compounds described herein in the various applications described above, including albedo improvement applications, and the compositions produced thereby, are further described in U.S. applications No. 14 / 112,495 and No. 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 sequestration and an aqueous ammonium salt solution are produced. The resulting aqueous ammonium salt solution may vary in properties of the ammonium salt anion, 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, and ammonium nitrate.

[0089] Embodiments of the present invention may further include, in addition to the production of carbonates, the regeneration of a recoverable ammonia aqueous solution from an ammonium salt aqueous solution, as described above. Regeneration of the recoverable ammonia aqueous solution means treating the ammonium salt aqueous solution in a manner sufficient to generate a certain amount of ammonia from it. The proportion of the ammonium salt added that is converted to ammonia during this regeneration step may vary, and in some cases may be in the range of 20-80%, for example, 35-55%.

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

[0091] The alkaline component source may be varied, as long as it is sufficient to convert the ammonium in the ammonium salt aqueous solution to ammonia. Any and appropriate alkaline component source may be used.

[0092] Chemical agents can be used as alkali sources in this regeneration step. These include, but are not limited to, hydroxides, organic bases, superbases, oxides, and carbonates. Hydroxides include sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH)2), or magnesium hydroxide (Mg(OH)2), which yield hydroxide anions in solution. Organic bases are generally carbon-containing molecules that are nitrogen-containing bases, including primary amines such as methylamine, secondary amines such as diisopropylamine, tertiary amines such as diisopropylethylamine, aromatic amines such as aniline, heterocyclic aromatic compounds such as pyridine, imidazole, and benzimidazole, and various forms thereof. Suitable superbases for use as proton removal agents include sodium ethoxide, sodium amide (NaNH2), sodium hydride (NaH), butyllithium, lithium diisopropylamide, lithium diethylamide, and lithium bis(trimethylsilyl)amide. For example, oxides containing calcium oxide (CaO), magnesium oxide (MgO), strontium oxide (SrO), beryllium oxide (BeO), and barium oxide (BaO) are also suitable proton removal agents that may be used.

[0093] Silica sources are also considered as alkali sources. The silica source may be pure silica, or it may be a composition containing silica in combination with other compounds, such as inorganic substances, as long as it is sufficient to impart the desired alkalinity. In some cases, the silica source is a naturally occurring silica source. Examples of naturally occurring silica sources include silica-containing rocks, which may be in the form of sand or larger rocks. When the silica source is a larger rock, in some cases, this rock is crushed, reducing its size and increasing its surface area. Silica sources consisting of components with longest dimensions ranging from 0.01 mm to 1 meter, e.g., 1 mm to 100 cm, e.g., 1 mm to 50 cm, and 0.1 mm to 500 cm are considered. The silica source may be surface-treated, if desired, to increase its surface area. Various different naturally occurring silica sources may be used. Natural silicon sources covered include, but are not limited to, ultramafic rocks such as komatiite, picritite basalt, kimberlite, lamproite, and peridotite; mafic rocks such as basalt, diorite (coarse-grained basalt), and gabbro; neutral rocks such as andesite and diorite; neutral felsic rocks such as quartz andesite and granite diorite; and igneous rocks including felsic rocks such as rhyolite, aplite pegmatite, and granite. Artificial silica sources are also covered. Artificial silica sources include mining waste, fossil fuel combustion ash, slag, such as iron slag and rinse slag, cement kiln waste, refinery / petrochemical plant waste, such as oil field and methane bed brine, coal seam waste, such as gas production brine and coal seam brine, paper processing waste, water softening, such as ion exchange wastewater, and silicon processing waste. Examples of such waste include, but are not limited to, agricultural waste, metal finishing waste, high-pH fiber waste, and caustic sludge. Mining waste includes waste resulting from the extraction of earth-derived metals or other valuable or useful inorganic materials. Examples of such waste include mining waste used to increase pH, including red mud from the Bayer aluminum extraction process; waste from magnesium extraction into seawater in Moss Landing, California, for example; and waste from other mining processes involving leaching.In processes that burn fossil fuels, such as coal-fired power plants, silica-rich ash is often generated. In some embodiments, ash from the combustion of fossil fuels, such as coal-fired power plants, such as fly ash, such as ash discharged from chimneys, and bottom ash, are provided as silica sources. Further details relating to silica sources and their use are described in U.S. Provisional Application No. 14 / 112,495, filed October 17, 2013, the disclosure of which is incorporated herein by reference.

[0094] In embodiments of the present invention, ash is used as an alkaline component source. In certain embodiments, coal ash may be used as the ash. The coal ash used in the present invention refers to the residue produced from the combustion of crushed anthracite, lignite, briquette, or subbriquette in a power plant boiler or coal combustion furnace, such as a chain grate boiler, cyclone boiler, or fluidized bed boiler. Examples of such coal ash include fly ash, which is finely pulverized 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 with various identifiable crystalline phases, such as quartz, mullite, and various iron oxides. The types of fly ash in question are 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 lies in the calcium, silica, alumina, and iron content in the ash. The chemical properties of fly ash are greatly influenced by the chemical composition of the coal being burned (i.e., anthracite, cyanite, and lignite). The fly ash in question contains substantial amounts of silica (silicon dioxide, SiO2) (both amorphous and crystalline) and lime (calcium oxide, CaO, magnesium oxide, MgO).

[0096] When harder, older anthracite and tungsten coal are burned, F-type fly ash is generally produced. F-type fly ash essentially possesses pozzolanic properties and has a calcium (CaO) content of less than 10%. Fly ash produced by burning newer lignite or tungsten coal possesses pozzolanic properties as well as some degree of self-adhesiveness. In the presence of water, C-type fly ash hardens and gains strength over time. The calcium (CaO) content of C-type fly ash is generally 20% or more. Alkali and sulfate (SO4) content is generally higher in C-type fly ash.

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

[0098] Embodiments of the present invention also include the use of bottom ash. Bottom ash is formed as agglomerates in a coal-fired boiler from the combustion of coal. Such a combustion boiler may be a wet boiler or a dry boiler. When bottom ash is produced in a wet or dry boiler, it is rapidly cooled in water. This rapid cooling produces 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 size within this range. The main chemical components of bottom ash are silica and alumina, with 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 covered. Volcanic ash consists of small tephra, i.e., small fragments of 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 alkaline component source. The properties of the fuel from which the ash and / or CKD are derived, and the means of combustion of the fuel, will affect the chemical composition of the resulting ash and / or CKD. Therefore, based on the chemical composition of the ash and / or CKD, this ash and / or CKD may be used as part of or solely as a means of adjusting the pH, and various other components may be used together with the specific ash and / or CKD.

[0101] In certain embodiments of the present invention, slag is used as an alkaline component source. The slag may be used alone as a 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 adjuster offers further advantages by introducing reactive silicon and alumina into the precipitate product. Examples of suitable slags include, but are not limited to, blast furnace slag derived from iron smelting, slag derived from electric arc or blast furnace processing of steel, copper slag, nickel slag, and rind slag.

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

[0103] In certain embodiments, other waste materials, such as demolished or recycled concrete or mortar, may also be used as the alkali source. If used, the concrete will dissolve, releasing sand and aggregate, which may be recycled into the carbonate-generating portion of the process, if desired.

[0104] In certain embodiments, inorganic alkali sources are also included. In such cases, the inorganic alkali source that comes into contact with the ammonium salt aqueous solution may be varied, and examples of such inorganic alkali sources include, but are not limited to, the silicates, carbonates, fly ash, slag, lime, and cement kiln dust mentioned above. In some cases, the inorganic alkali source includes, for example, the rocks mentioned above.

[0105] In these embodiments, the temperature at which the ammonium salt aqueous solution is heated may vary, but in some cases the temperature is in the range of 25 to 200°C, for example, 25 to 185°C. The heat used to give the desired temperature may be obtained from any and appropriate source, including exhaust heat sources such as steam and flue gas exhaust heat.

[0106] Distillation may be carried out at any pressure. When distillation is carried out at atmospheric pressure, the temperature at which distillation is carried out may vary, in some cases ranging from 50 to 120°C, for example from 60 to 100°C, or for example from 70 to 90°C. In some cases, distillation is carried out at a pressure lower than atmospheric pressure. The pressure in such embodiments may vary, but in some cases the pressure lower than atmospheric pressure is in the range of 1 to 14 psig, for example from 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 embodiments where it is carried out at atmospheric pressure. In such cases, the temperature may vary as desired, but in some embodiments where a pressure lower than atmospheric pressure is used, the temperature is in the range of 15 to 60°C, for example from 25 to 50°C. In embodiments with a pressure lower than atmospheric pressure, it is also possible to use waste heat for some, if not all, of the heat used during distillation. Examples of waste heat sources that may be used in such cases include, but are not limited to, flue gas, absorbed heat generated by CO2 recovery and the resulting production of ammonium carbonate, and coolants (such as those originating from CO2-containing gas sources in the same location as the aforementioned power plants and factories), and combinations thereof.

[0107] The regeneration of the recovered ammonia aqueous solution may also be carried out using an electrolysis-mediated protocol, which involves introducing a direct current into the ammonium salt aqueous solution to regenerate ammonia. Any optional and appropriate electrolysis protocol may be used. Examples of electrolysis protocols that can be adapted to the regeneration of ammonia from ammonium salt aqueous solutions may use one or more components derived from the electrolysis systems described in U.S. Patent Applications Publication Nos. 2006 / 0185985 and 2008 / 0248350, and PCT Application Publication No. WO2008 / 018928 (the disclosures of which are incorporated herein by reference).

[0108] The recovered ammonia solution may vary depending, for example, on the specific recovery protocol used. In some cases, the recovered ammonia solution contains ammonia (NH3) at concentrations ranging from 4 to 20 M, for example, 12.0 to 16.0 M. The pH of the recovered ammonia solution may vary, in some cases ranging from 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 with, for example, the gaseous CO2 source described above, under conditions sufficient to produce an aqueous ammonium carbonate solution. In other words, the method may include recycling the recovered ammonia into the process. In such cases, the recovered ammonia water may be used as the sole recovery liquid, or it may be mixed with another liquid, such as makeup water, to produce recovered ammonia water suitable for use as a CO2 recovery liquid. When the recovered ammonia water is mixed with additional water, any and appropriate water may be used. The water from which recovered ammonia water can be produced includes, but is not limited to, fresh water, seawater, brine, generated water, and wastewater.

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

[0111] Production of pure CO2 gas One or more steps of this method may result in the generation of CO2. For example, during the production of a solid carbonate from an aqueous ammonium carbonate solution, up to 1 mole of CO2 may be produced for every 2 moles of ammonium bicarbonate. Alternatively, in addition, waste CO2 may be produced by the ammonia regeneration step. In such cases, CO2 may be produced, but the overall process sequesters a net amount of CO2 in the carbonate compound. Any CO2 produced may be substantially pure CO2 product gas, which may be sequestered by injection into a geological subsurface location, as will be described in more detail later. Thus, this process is an effective CO2 sequestering process. The term "substantially pure" means that the product gas is either 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 embodiments thereof, aspects of the present invention may include injecting the product CO2 gas into a geological subsurface location to sequestrate the CO2. Injection means introducing or placing the CO2 product gas into a geological subsurface location. The geological subsurface location may vary and include both subsurface and deep-sea locations. The subsurface locations in question include a variety of different subsurface formations, such as fossil fuel reservoirs, e.g., oil fields, gas fields, and unextractable coal seams; brine reservoirs, e.g., saline and salt-filled basalt layers; deep aquifers; porous formations such as partially or completely depleted oil or gas seams; salt cavities, sulfur cavities, and sulfur domes.

[0113] In some cases, the CO2 product gas may be pressurized prior to injection into a location below the geological surface. To achieve such pressurization, the gaseous CO2 may be compressed in one or more stages, and any accompanying water may be cooled and condensed as desired. The moderately pressurized CO2 may then be further dried, if desired, by conventional methods such as the use of molecular sieves, and sent to a CO2 condenser to cool and liquefy the CO2. This CO2 may then be efficiently pumped at minimum power to the pressure required to deliver the CO2 to the depth in the geological formation or deep sea where CO2 injection is desired. Alternatively, the CO2 may be compressed through a series of steps and discharged as a supercritical fluid at a pressure comparable to the pressure required for injection into the geological formation or deep sea. If desired, the CO2 may be transported from the production site to the subsurface geological formation, for example, by pipeline, rail, truck, or other appropriate protocol.

[0114] In some cases, CO2 product gas is used in the Enhanced Oil Recovery (EOR) protocol. Enhanced oil recovery (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, CO2 product gas is injected into underground crude oil reservoirs.

[0115] The production and sequestration of CO2 gas is further described in U.S. Patent 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, which involves contacting first and second liquids on opposite sides of a membrane. In such cases, the membrane may be a cationic or anionic membrane. Further details relating to alkali enrichment protocols, such as the membrane-mediated alkali enrichment protocol, 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 combining recovery and alkali enrichment, the reactor comprising a core hollow fiber membrane component having, for example, a plurality of hollow fiber membranes; an alkali enrichment membrane component surrounding the hollow fiber membrane component and defining a first liquid channel in which the hollow fiber membrane component exists; and a housing configured to house the alkali enrichment membrane component and the hollow fiber membrane component, the housing configured to define a second liquid channel between the alkali enrichment membrane component and the inner surface of the housing. In such a case, the alkali-enriched membrane component may be configured as a cylindrical object, and the hollow fiber membrane component is arranged axially within the cylindrical object. In such a case, the housing may be configured as a cylindrical object in which the housing and the alkali-enriched membrane component share a central axis.

[0117] system A further aspect of the present invention includes a system for sequestering CO2 from a gaseous CO2 source by the protocol described above. The system is an apparatus comprising, for example, functional modules or reactors, such as those described above, which are coupled in a manner sufficient to carry out the method of the present invention as described above. An aspect of such a system comprises a CO2 gas / recovery ammonia aqueous solution module, a carbonate generation module, and a recovery ammonia aqueous solution regeneration module.

[0118] In some cases, the CO2 gas / recovery ammonia aqueous solution module includes 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] A carbonate generation module is operably coupled to a CO2 gas / recovery ammonia aqueous solution module. Some module embodiments include a continuous reactor configured to produce a carbonate material for CO2 sequestration. When the system includes a continuous reactor (i.e., a flow-through reactor), the system includes a reactor in which the material is held in a flow through the reactor, and a reactant (e.g., a divalent cation, a bicarbonate-rich aqueous liquid) is continuously supplied to the reactor, exiting as a continuous flow of product. Therefore, the continuous reactor component of the system is not a batch reactor. A given system may include, for example, the continuous reactor described herein, in combination with one or more further components, more specifically as described below.

[0120] In some embodiments, the continuous reactor of the system comprises a flowing aqueous liquid, for example, an aqueous solution of ammonium carbonate; a divalent cation introduction device configured to introduce divalent cations into the flowing aqueous liquid at an introduction point; and a portion located at a distance from the divalent cation introduction device, which generates a non-slurry, solid-phase CO2 sequestration carbonate material. The flowing aqueous liquid is a moving stream of the aqueous liquid, for example, the above-mentioned liquid, which may be present in the continuous reactor, which may be configured as appropriate. The continuous reactor in question comprises a liquid inlet and a drain outlet, which are arranged relative to each other so that the liquid moves or flows continuously 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 dimensions of any given cross-section of the reactor, with the inlet at a first end of the reactor and the outlet at a second end of the reactor. The reactor volume can vary, and in some cases range from 10 L to 1,000,000 L, for example, from 1,000 L to 100,000 L.

[0121] The continuous reactor in question is a divalent cation introduction device, further comprising an introduction device configured to introduce divalent cations into a flowing aqueous liquid at the introduction point. An optional and appropriate introduction device may be used, which may be a liquid-phase or solid-phase introduction device depending on the properties of the divalent cation source. In some cases, the introduction device may be located substantially, if not entirely, in the same location as the inlet for the liquid containing the bicarbonate-rich product. Alternatively, the introduction device may be located at a distance downstream from the inlet. In such cases, the distance between the inlet and the introduction device may vary, in some embodiments ranging from 1 cm to 10 m, for example, from 10 cm to 1 m. The introduction device may be operably coupled to the divalent cation source or reservoir.

[0122] The continuous reactor in question also includes a section for producing a solid-phase CO2 sequestration carbonate material in a non-slurry state. This section is a region or area of ​​the continuous reactor where a solid-phase CO2 sequestration carbonate material is produced in a non-slurry state as a result of the reaction of a divalent cation with a liquid bicarbonate ion containing a bicarbonate-rich product. The reactor may be configured to produce a solid-phase CO2 sequestration carbonate material in any of the non-slurry states described above at the production site. In some cases, the production site is located at a distance from the divalent cation introduction site. 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 comprise seed structures (or more) as described above. In such cases, the reactor may be configured to bring the seed structures into contact in an immersed or non-immersed form, as described above. In the non-immersed form, the flowing liquid may be present on the surface of the seed structures, for example, as layers of varying thicknesses, while a gas, such as air, separates at least two parts of the seed structures, for example, two different types of particles, which are not immersed in the liquid.

[0124] Further details relating to such reactors, which may be used as carbonate-producing modules in embodiments of this system, are described in U.S. Patent Application No. 14 / 877,766, the disclosure of which is incorporated herein by reference.

[0125] The ammonia aqueous solution regeneration module for recovery may vary, as long as it is configured to produce 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 generate a pressure lower than atmospheric pressure, as described above, and as a result, the module will include one or more components for generating a pressure lower than atmospheric pressure, such as a pump. In some cases, the regeneration module will be 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 will include an alkaline component source, such as the inorganic alkali source described above.

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

[0127] In some cases, the System and its modules are industrial-scale systems, meaning that the system is configured to process industrial-scale quantities / volumes of input compositions (e.g., gases, liquids, etc.). For example, the System and its modules, such as the CO2 contactor module, carbonate generation module, ammonia regeneration module, etc., are configured to process industrial-scale quantities of liquid, such as 10,000 gallons / day or more, including, for example, 25,000 gallons / day or more, and in some cases, the System and its modules are configured to process 1,000,000,000 gallons / day or less, for example, 500,000,000 gallons / day or less. Similarly, the System and its modules, such as the CO2 contactor module, are configured to process industrial-scale quantities of gas at a rate of 25,000 cubic feet / hour or more, such as 100,000 cubic feet / hour or more, including 250,000 cubic feet / hour or more. In some cases, the System and its modules are configured to process 500,000,000 cubic feet / hour or less, such as 100,000,000 cubic feet / hour or less.

[0128] In some embodiments, the system may be fluidly connected to an aqueous medium source, e.g., a naturally occurring or artificial aqueous medium source, and may be located in the same location where the CO2 sequestration protocol is implemented. The system may be located on land or at sea. The system may be a land-based system, for example, in a coastal area near a seawater source, or in an inland location if water is supplied to the system via piping from a saltwater source, e.g., the ocean. Alternatively, the system may be a water-based system, i.e., a system located on or underwater. Such a system may be located on a ship, on an offshore platform, etc., if desired. In certain embodiments, the system may be located in any and appropriate location, e.g., in the same location as an industrial plant, e.g., a power plant.

[0129] Figure 1 shows a schematic diagram of a system according to one embodiment of the present invention. As shown in Figure 1, the system 100 comprises a CO2 gas / ammonia aqueous solution recovery module 102, a carbonate generation module 104, and an ammonia aqueous solution recovery regeneration module 106. The system 100 is configured such that CO2-containing gas 108 from a supply source 109 (e.g., flue gas from a power plant at the same location) is mixed with ammonia aqueous solution recovery liquid in the CO2 gas / ammonia aqueous solution recovery module 102, and then the ammonium carbonate aqueous solution 110 is transported to the hydrodynamically coupled carbonate generation module 104. In the carbonate generation module 104, the ammonium carbonate aqueous solution 110 is mixed with a cation source 112 under conditions sufficient to produce a solid carbonate 114 for CO2 sequestration and an ammonium salt aqueous solution 116. The ammonium salt aqueous solution 116 is then transported to a hydrodynamically coupled recovery ammonia aqueous solution regeneration module 106, where it is heated, for example, by steam from a steam source 120, in the presence of an inorganic alkaline component source 118. The regenerated ammonia aqueous solution 122 is then transported to a hydrodynamically coupled CO2 gas / recovery ammonia aqueous solution module 102.

[0130] Figure 2 shows a schematic diagram of a system according to one embodiment of the present invention, in which ammonia regeneration is carried out at a pressure lower than atmospheric pressure and all heat is supplied by a waste heat source. As shown in Figure 2, the system 200 comprises a CO2 gas / ammonia aqueous solution recovery module 202, a carbonate generation module 204, and an ammonia aqueous solution recovery regeneration module 206. The system 200 is configured such that CO2-containing gas from a supply source 208 (e.g., a power plant flue) is mixed with ammonia aqueous solution recovery liquid in the CO2 gas / ammonia aqueous solution recovery module 202 so as to produce an ammonium carbonate aqueous solution 210, and then the ammonium carbonate aqueous solution 210 is transported to the hydrodynamically coupled carbonate generation module 204. In the carbonate generation 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 sequestration and an ammonium salt aqueous solution 216. The ammonium salt aqueous solution 216 is then transported to a hydrodynamically coupled recovery ammonia aqueous solution regeneration module 206, where it is heated in the presence of an inorganic alkaline component source 218. The waste heat cooling system, flue gas 208, and CO2 gas / recovery ammonia aqueous solution module 202 of the power plant 220 located at the same site are used as heat sources for the regeneration module 206. The regenerated ammonia aqueous solution 222 is then transported to a hydrodynamically coupled CO2 gas / recovery ammonia aqueous solution module 202.

[0131] In some cases, the CO2 gas / recovery ammonia aqueous solution module comprises a reactor combining recovery and alkali enrichment, the reactor comprising a core hollow fiber membrane component (for example, a component comprising a plurality of hollow fiber membranes), an alkali enrichment membrane component surrounding the core hollow fiber membrane component and defining a first liquid flow path in which the core hollow fiber membrane component exists, and a housing configured to house the alkali enrichment membrane component and the core hollow fiber membrane component, the housing 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 cylindrical object, and the hollow fiber membrane component is arranged axially within the cylindrical object. In some cases, the housing is configured as a cylindrical object sharing a central axis with the housing and the alkali enrichment membrane component. Embodiments of the present invention further include, for example, a reactor combining recovery and alkali enrichment as described above.

[0132] In some cases, the protocols described above are carried out using a system of one or more shippable modular units configured for use in CO2 sequestration, as described, for example, in PCT application US2016 / 024338 (the disclosure of which is incorporated herein by reference). The configuration of the unit comprises a support, such as a housing or base, accompanied by one or more of the following: a CO2 gas / liquid contactor subunit, a carbonate generation 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. A modular unit configured for use in the present invention may include, for example, an ammonia regeneration unit as described above. Systems comprising one or more such modular units are also provided. The systems disclosed herein include high-yield systems in which individual modular units house one or more given subunits, such as a CO2 gas / liquid contactor subunit, a carbonate generation 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 present invention include larger assemblies of many individual modular units that are combined and may have one or more individual modular units containing a CO2 gas / liquid contactor subunit, a carbonate generation 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. Methods of using the units / systems in CO2 sequestration protocols are also provided.

[0133] The following examples are provided for illustrative purposes only and are not limiting. [Examples]

[0134] I. CO2 recovery using ammonia solution A. Materials and Methods The experiment involved a single (1 unit) 2.5 × 8 Liqui-Cel film contactor (1.4 m 2 The process was carried out in batches where approximately 25 gallons of a 0.5 M NH3 (approximately 1 wt% NH3) recovery solution was brought into contact with the synthesized flue gas within the membrane surface area. 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 synthesized flue gas was flowed countercurrently through the liquid phase side (volume = 0.40 L) of the contactor. The gas inlet concentration ranged from 5 to 50% CO2 (the remainder was supplemented with air), the inlet volume was 10 to 40 slpm (air + CO2), and the inlet pressure was 2 to 20 psig. During data collection, the recovery solution was passed through the membrane contactor only once, and the following parameters were recorded: 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).

[0135] The outlet liquid (after contact with the synthesized flue gas) was collected in a separate tank and combined into one. The combined outlet liquid was then used as a new inlet recovery solution, and the experiment was repeated, allowing for the verification of recovery solutions with different pH levels.

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

[0137] II. Mineral Formation The following demonstrates that 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 double decomposition reaction was carried out. This solution was reacted with gentle stirring using a stirrer under open air. After 5 minutes, the solution was filtered through a Buchner funnel, the resulting precipitate was collected, and dried overnight at 75°C.

[0139] The obtained material was observed using a scanning electron microscope (SEM) and Fourier transform infrared analysis (FTIR). FTIR spectra were recorded using a Thermo-Fisher Nicolet IS-10 equipped with a HeNe laser and a fast-recovering deuterated triglycine sulfate (DTGS) detector. Scanning was performed on a germanium ATR crystal at a resolution of 16 and an optical velocity of 0.4747. SEM images were recorded using a Hitachi TM-3030 benchtop model.

[0140] B. Results The reaction described above produces a precipitate, which is separated from the supernatant. This precipitate is then analyzed using both crystal habit (Figure 4A) and Fourier transform infrared analysis to determine the calcite (peak identifier 871cm²). -1 , 714cm -1 ) was identified. Furthermore, this supernatant was analyzed using ammonium chloride (peak identifier NH3 at 1100 cm³). -1 , NH4Cl as 1450cm -1 ) was identified as such.

[0141] Further experiments were repeated, and a CaCl2 solution was titrated in an NH4HCO3 solution in the presence of silica sand. This reaction yielded a separate coating similar to the one produced using NaHCO3 as the carbon-containing reagent.

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

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

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

[0145] The dissolved inorganic carbon (DIC) content of solution and solid carbonate samples was measured by acid titration and coulometry using a CM150 carbon analysis system (UIC, Inc.). Generally, samples were titrated with 2N H2PO4 (Sigma Aldrich). However, to detect CO2 generated in the reaction between CaCl2 (Sigma Aldrich) and NaHCO3 (Aqua Solutions), titration with H2PO4 would liberate CO2 from CaCO3. Therefore, instead of titrating with H2PO4, the CaCl2 solution was titrated with the NaHCO3 solution. This allowed for the quantitative determination of CO2 by coulometry. Subsequently, all solids produced in the reaction were isolated, dried, and analyzed by FTIR to confirm their composition as CaCO3. All analyses using the CM150 system were performed at 40°C.

[0146] B. Results The time-resolved Fourier transform infrared (FTIR) spectra of reaction 1 at 0 seconds, 10 seconds, 30 seconds, and 30 minutes after mixing show the v3 (1400 cm⁻¹) infrared active vibrational mode of calcite. -1 ), v1 (1087cm -1 ), v2 (877cm -1 ), and v4 (714cm -1 The asymmetric CO stretching vibration of the carbonate bond, v3, is observed to be shifted by a bidentate, giving rise to a characteristic calcite peak, which suggests that calcium carbonate is formed via a bicarbonate pathway similar to that proposed for its natural formation. The symmetric carbonate vibration mode, v1, relates to the free carbonates available in the structure. The out-of-plane bending vibration, v2, and the in-plane bending vibration, v4, are 877 cm², respectively. -1 and 714cm -1It is identified by the following. The FTIR spectrum identifies it as CaCO3 (calcite) formed by LCP reactions 1 and 2. The final products of both pathways appear to be identical. The still image of the nanoparticle tracking analysis (NTA) of 0.25 M NaHCO3 shows droplets of a bicarbonate-rich liquid condensate phase. The still image of the NTA of reaction 1 immediately after mixing is measured in time-resolved form of part A, i.e., it visualizes the chemical pathway of the LCP-driven low-pH reaction (reaction 1) compared to the conventional high-pH reaction (reaction 2). The yields of CaCO3 and CO2 measured by DIC analysis for reaction 1 compared to reaction 2. This result reinforces the idea that reactions 1 and 2 have different pathways due to the difference in CO2 generation (which is expected for reaction 1). The time-resolved pH response of the dump reaction of reaction 1 shows an initial decrease in pH, which is probably due to the removal of bicarbonate. The time-resolved pH response of the dump reaction in reaction 1 showed almost no decrease in pH, suggesting that the carbonate is consumed during mineral formation and buffered by the bicarbonate. During the carbonate formation reaction, a liquid condensate phase (LCP) is formed in the presence of calcium ions, which acts as a nucleus for CaCO3 formation. CaCO3 precipitation proceeds, and dehydration of the reaction product occurs, as indicated by the decrease in the δO-H oscillation peak. According to the FTIR spectrum, this structure was initially hydrated and amorphous, as previously reported, and showed a broad peak over the observed range. However, the gradual appearance of a sharp peak as the reaction progresses suggests that at 1400 cm⁻¹ -1 (v3, asymmetric CO3), 1087cm -1 (v1, symmetric CO3), 877 cm -1 (v2, CO3 out-of-plane band), and 714cm -1 As can be seen from the increase in (v4, in-plane band of CO3), this is related to the development of the carbonate polymorphic crystal structure and indicates the formation of a calcite phase. This particular reaction is referred to as reaction 1 in the main report and is compared with reaction 2, which is 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 resulting from Reaction 1 and Reaction 2 are identical. The yields of CO2 and CaCO3 were 90% and 80%, respectively, confirming the stoichiometry and chemical pathway of Reaction 1. pH was also measured in a time-resolved format, suggesting that Reaction 1 occurs at a lower pH compared to the conventional Reaction 2. This is because Ca 2+ is HCO3 - It tends to interact with other molecules, and the precipitation reaction can occur at a neutral pH, thus directly relating to the LCP formation mechanism. In either case, the initial pH decreases slightly due to the initiation of CaCO3 precipitation.

[0147] IV. Treatment of hard water For use as hard water in the coating process described above, a high concentration of divalent ions, such as calcium (Ca 2+ ), magnesium (Mg 2+ Solutions containing such substances 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 various commercially available NF and RO membrane elements in 4-inch (12.57 square inch) diameter pieces. Membrane permeation flux (gallons / ft) was measured. 2 The concentration flow (GFD) of the plate test system was regulated by a valve. The ion exclusion rate of a given membrane was measured by analyzing the permeate sample by ion chromatography and / or conductivity probe. The system pressure (psig) during screening was also recorded.

[0149] B. Results The inventors successfully verified the permeation of monovalent ions and the exclusion of divalent ions using artificial seawater as the supply solution and commercially available NF membranes. The inventors also verified the existence of commercially available NF membranes (e.g., TS40 (TriSep) and ESNA1-LF2 (Hydranautics)) that can achieve more than 80% calcium ion exclusion in CaCl2 solutions.

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

[0151] Ammonia reforming involves regenerating a reactive recovery solution for contact with flue gas, and finally absorbing gaseous CO2 in an aqueous solution to form bicarbonate ions (HCO3). - ) is converted to ammonium (NH4) in the CO2 recovery process described above. + ) transforms into NH4 + It is converted back to NH3 in the ammonia reforming process described above. In other words, NH3 is not consumed in any part of the process described above. NH3 is simply HCO3 in an aqueous solution of gaseous CO2. - Promote isolation to HCO3 - In the coating process described above, carbonate (CO3 2- ) forms minerals.

[0152] Ammonia (NH3) can be regenerated by heating an aqueous solution of ammonium salts, such as ammonium chloride (NH4Cl) or ammonium acetate (NH4OAc), in the presence of geomass fine powders, such as limestone, fly ash, slag, or basalt, and reused in a CO2 absorption process at the front end of a carbon recovery and mineral formation protocol, such as the one shown in Figure 1.

[0153] 1. Materials and Methods 5-20 mL of ammonium salt solution (0.5 M, saturated) was added to a sample container containing geomass fine powder (2-10 g), and the container was heated at 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 volatile ammonia gas (NH3) was removed in an acid scrubber (5 mL of 1 M HCl) and ammonium (NH4) was removed. + It was then captured as NH in the acid scrubber. 4+ The NH4 was quantified by ion chromatography, and the "NH3 modification yield (%)" in the following figure is calculated by dividing the NH4 by the theoretical yield of NH3 (based on the amount and concentration of ammonium salt added to the geomass fine powder) from the ion chromatography. + This represents the measured quantity.

[0154] 2.Results The regeneration of ammonia (NH3) from ammonium salts was investigated in numerous systems with varying concentrations of geomass fine powder, ammonium salt, and their respective reaction temperatures and reaction times. As further shown in Figure 4, an ammonia reforming yield of over 40% was observed at a low temperature of 75°C after heating for only 30 minutes.

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

[0156] As shown in Figure 5, the NH3 reforming yield is relatively significantly lower in the absence of any geomass. The exception is ammonium bicarbonate (NH4HCO3), in which case 30% 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 geomass in advancing the NH3 reforming process. Figure 6 shows data verifying NH3 reforming from NH4Cl at 75°C in the presence of various types of geomass. These results demonstrate that NH3 reforming can occur at low temperatures in the presence of common types of geomass, such as fly ash, CaCO3, and basalt.

[0157] B. Further investigations using various types of geomass 1. A study was conducted to evaluate the ability of recycled concrete / mortar to act as a geomass source of alkaline components for ammonia modification. Figure 7 shows a plot of "geomass alkaline component (mmol) per time (minutes)" for various basalt and recycled concrete / mortar geomasses. 1 M HCl was titrated into a suspension of 0.25 g of geomass 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 alkaline components from the geomass upon contact with a fresh ammonium chloride solution.

[0158] 2. In addition to other materials, studies were conducted to evaluate the ability of recycled concrete / mortar to act as an alkaline geomass source for ammonia modification. The bar graph in Figure 8 shows the amount of sodium (Na) leached from various geomass materials when they were mixed with a 2M ammonium chloride solution at room temperature for 10 minutes. + ), potassium (K + ), calcium (Ca 2+ ), and magnesium (Mg 2+ The ion concentration (mmol / L) in the reforming solution 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 are used to produce Ca for various materials and solid carbonate materials. 2+ It demonstrates the ability to act as a source.

[0159] C. Ammonia reforming by vacuum distillation A study was conducted to evaluate the effect of pressures lower than atmospheric pressure on ammonia reforming. The graph in Figure 9 shows the concentrations (mol / L) of calcium and alkali components in the reformer solution after reforming in the presence of arc furnace steelmaking slag, as measured by ion chromatography and acid titration, respectively. The reformer solution in the vacuum test showed higher calcium ion concentrations and lower alkali component concentrations compared to the test without vacuum (labeled "55°C, no vacuum"). The control tests, "55°C, no slag" and "55°C, water," showed minimal reaction.

[0160] VI. Various Representative Systems A. 2MW Coal-fired Power Plant Figure 7 shows a diagram of a system according to one 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 capture rate. At 50% capture, 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 reports 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 "epa.gov / energy" preceded by "www."). Assuming 24 hours of operation, 7 days a week and 50% CO2 capture, the following applies:

[0161]

number

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

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

[0164] B. Further 2MW coal-fired power plant systems Figures 11A, 11B, and 11C show system diagrams for three different 2MW coal-fired power plants. In general, The process changes primarily focus on the geomass reformer and the output to the CO2 capture section at its front end. • The temperature shown is for a specific case. An open system with a semi-continuous storage tank, with recycling options, also minimizes the cooling load. • Increasing the concentration of the reagent throughout the process minimizes the heating load in the reformer. Individually, Figure 11A shows that increasing the concentration of NH3 coming from the reformer reduces the volume of steam and the energy required for heating. Figure 11B shows the reintroduction of the secondary contactor compartment to absorb NH3 gas coming from the reformer. Figure 11C illustrates the premixing of NH3 gas from the reformer with flue gas from the slipstream before it enters the contactor for CO2 absorption.

[0165] C. 10MW Coal-fired Power Plant Figure 12 shows an example of a system according to one embodiment of the present invention suitable for use in a 10 MW coal-fired power plant. It shows the estimated mass flow balance of a process that removes 50% of carbon dioxide from a 10 MW slipstream of flue gas in a coal-fired power plant. A total of 14,643 kg / hr of low-pressure steam and 3,176 gallons / min of cooling water are used. The difference between the inlet and outlet temperatures of the cooling water is 10°C. The flue gas is assumed to be 12 wt% carbon dioxide and enters at approximately 105°F.

[0166] D. 10MW coal-fired power plant reformer with reduced-pressure ammonia reformer Figure 13 shows the overall mass flow diagram of a system incorporating three proposed in-house power and cooling water reduction techniques. As shown in Figure 13, by operating the reformer continuously under vacuum, thus lowering the reformer's operating temperature (approximately 70°F in this example), and increasing the reformer's electric pump load, the heat of the flue gas (H1), absorbed heat (H2), and the heat of the recirculated water for the coal-fired power plant in this example (H3) can be utilized. This is because increasing the vacuum level for reforming allows the reformer to operate at a lower temperature. This configuration significantly reduces / eliminates the steam requirement (to zero in this case compared to Figure 12) and the cooling water requirement (approximately 33% reduction in this case compared to Figure 12). Furthermore, the temperature of the recirculated water in this coal-fired power plant may be lowered to a temperature close to the reformer temperature. This simultaneously ensures that the heat necessary for reforming is supplied to the process, reducing the amount of steam required, lowering the temperature of the recirculated water, and allowing the parent coal-fired power plant to use more of the recirculated water.

[0167] Notwithstanding the attached claims, the disclosures described herein are also defined by the following annotations: 1. A method for sequestering CO2 derived from a gaseous CO2 source, a) Contacting the ammonia aqueous solution to be recovered with a gaseous CO2 source under conditions sufficient to generate an ammonium carbonate aqueous solution, b) Mixing the cation source and the ammonium carbonate aqueous solution under conditions sufficient to generate a carbonate and ammonium salt aqueous solution for CO2 sequestration, c) Regenerating the ammonia aqueous solution for recovery from the ammonium salt aqueous solution. Includes, A method for isolating CO2 derived from the aforementioned 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 gaseous CO2 source is a multi-component gas stream, as described in Appendix 1 or 2. 4. The gaseous CO2 source is flue gas, as described in Appendix 3. 5. The method described in Appendix 4, wherein the flue gas is obtained from an industrial source.

[0168] 6. The method according to any one of the appendices 1 to 5, wherein the gaseous CO2 source is brought into contact with the ammonia aqueous solution for recovery using a membrane contactor. 7. The membrane contactor is a hollow fiber membrane contactor, as described in Appendix 6. 8. The ammonium carbonate aqueous solution comprises at least one of ammonium carbonate and ammonium bicarbonate, as described in any of Appendix 1 to 7. 9. The ammonium carbonate aqueous solution is provided according to any one of the methods described in Appendix 1 to 8, wherein the aqueous solution contains both ammonium carbonate and ammonium bicarbonate. 10. The method according to any one of the appendices 1 to 9, wherein the recovery aqueous ammonia solution is regenerated from the aqueous ammonium salt solution, including 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 described in 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 the appendices 10 to 12, wherein the distillation comprises heating the aqueous solution of the ammonium salt in the presence of an inorganic alkaline component source. 14. The inorganic alkali component source is the method according to Appendix 13, wherein the inorganic alkali component source includes silicates, carbonates, fly ash, slag, lime, or cement kiln dust. 15. The inorganic alkaline component source is the method described in Appendix 13, including rock.

[0170] 16. The distillation is carried out using waste heat, according to any of the methods described in Appendix 10 to 15. 17. The method according to Appendix 16, wherein the exhaust heat is supplied from a source selected from the group consisting of flue gas, absorbed heat generated by process (a), coolant, and combinations thereof. 18. The method according to any one of the appendices 1 to 9, wherein the recovery aqueous ammonia solution is regenerated from the ammonium salt aqueous solution, including electrolysis. 19. The method according to any one of the appendices 1 to 18, further comprising contacting the regenerated recovered ammonia aqueous solution with a gaseous CO2 source under conditions sufficient to produce an ammonium carbonate aqueous solution. 20. The cation source comprises an alkaline earth metal cation, as described in any of the methods described in Appendix 1 to 19.

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

[0172] 26. The method according to Appendix 24, comprising generating the CO2 sequestration solid carbonate with the help of a species structure. 27. The method according to Appendix 26, wherein the solid carbonate for CO2 sequestration is generated on or in at least one of the surface of the seed structure or in a recess. 28. The method according to any one of the appendices 1 to 27, further comprising manufacturing a building material from the material of the solid carbonate for CO2 sequestration. 29. The building material includes aggregate, as described in Appendix 28. 30. The method according to Appendix 29, wherein the seed structure is a porous, permeable aggregate that is filled with the CO2 sequestration solid carbonate in order to produce a solid aggregate that is less porous and denser than the seed structure.

[0173] 31. The method according to Appendix 30, wherein the filled aggregate is filled to a greater extent at the outer edge than at the interior, and new aggregate is added to produce lightweight aggregate with a lower density in the interior region compared to the outer edge. 32. The building material is the method described in Appendix 28, including roofing granules. 33. CO2 gas / ammonia aqueous solution module for recovery, Carbonate generation module, A recovery ammonia aqueous solution regeneration module and A CO2 isolation system that incorporates the following features, derived from a gaseous CO2 source. 34. The CO2 gas / ammonia aqueous solution recovery module comprises a hollow fiber membrane, as described in Appendix 33. 35. The system described in Appendix 33 or 34, operably coupled to a gaseous CO2 source.

[0174] 36. The system described in any of appendices 33 to 35, wherein the gaseous CO2 source is a multi-component gas flow. 37. The system described in Appendix 36, wherein the gaseous CO2 source is flue gas. 38. The system according to any one of the appendices 33 to 37, wherein the recovery aqueous ammonia regeneration module is configured to generate the recovery aqueous ammonia by distillation. 39. The system as described in Appendix 38, wherein the recovery ammonia aqueous solution regeneration module is configured to generate recovery ammonia by distillation at a pressure lower than atmospheric pressure. 40. The system according to Appendix 38 or 39, wherein the recovery ammonia aqueous solution regeneration module is operably coupled to a heat source.

[0175] 41. The recovery ammonia aqueous solution regeneration module is equipped with an inorganic alkali source, as described in any of the appendices 38 to 40. 42. The system according to any one of the appendices 33 to 37, wherein the recovery ammonia aqueous solution regeneration module is configured to generate the recovery ammonia aqueous solution by electrolysis. 43. A system according to any one of the appendices 33 to 42, configured to recycle the ammonia aqueous solution for recycling into the CO2 gas / ammonia aqueous solution for recycling module.

[0176] While the invention described above has been explained in some detail with illustrations and examples to clarify its understanding, it will be readily apparent to those skilled in the art that certain changes and modifications can be made to them in light of the teachings of this disclosure 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. Those skilled in the art will understand that they can devise various configurations that embody the principles of the present invention and fall within its spirit and scope, even if they are not explicitly described or shown herein. Furthermore, all examples and conditions described herein should be interpreted as not being limited to such specifically detailed examples and conditions, and are primarily intended to assist the reader in understanding the principles and concepts of the present invention, which represent the inventors' contribution to the advancement of the art. Moreover, all descriptions of the principles, aspects, and embodiments of the present invention, as well as specific examples thereof, are intended to encompass both their structural and functional equivalents.

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

[0179] Cross-reference of related applications This application claims priority to U.S. Provisional Application No. 62 / 313,613 filed March 25, 2016 and U.S. Provisional Application No. 62 / 451,506 filed January 27, 2017, pursuant to Section 119(e) of the U.S. Patent Act, the disclosures of these applications are incorporated herein by reference.

Claims

1. Gaseous CO ２ CO2 derived from the source ２ A method of isolation, a) Under conditions sufficient to generate an aqueous ammonium carbonate solution, the ammonia solution for recovery is converted to gaseous CO2. ２ To bring it into contact with the source, b) CO ２ Mixing the cation source and the ammonium carbonate aqueous solution under conditions sufficient to generate the sequestering carbonate and ammonium salt aqueous solution, c) Regenerating the ammonia aqueous solution for recovery from the ammonium salt aqueous solution. It includes, The process of regenerating the ammonia aqueous solution for recovery from the ammonium salt aqueous solution includes electrolysis. The aforementioned gaseous CO ２ CO2 derived from the source ２ A method to isolate it.

2. The method according to claim 1, wherein the ammonia aqueous solution for recovery contains ammonia at a concentration in the range of 0.1 to 20.0 M.

3. The aforementioned gaseous CO ２ The method according to claim 1, wherein the source is a multi-component gas flow.

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

5. The method according to claim 4, wherein the flue gas is obtained from an industrial source.

6. Contacting the gaseous CO source with the ammonia aqueous solution for recovery using a membrane contactor, the method according to claim 1. ２ The method according to claim 1, wherein the gaseous CO source is contacted with the ammonia aqueous solution for recovery using a membrane contactor.

7. The method according to claim 6, wherein the membrane contactor is a hollow fiber membrane contactor.

8. The method according to claim 1, wherein the aqueous solution of ammonium carbonate contains at least one of ammonium carbonate and ammonium bicarbonate.

9. The method according to claim 1, wherein the aqueous solution of ammonium carbonate contains both ammonium carbonate and ammonium bicarbonate.

10. Under conditions sufficient to generate an ammonium carbonate aqueous solution, the regenerated recovered ammonia aqueous solution is converted to gaseous CO2. ２ The method according to claim 1, further comprising bringing it into contact with a source.

11. The method according to claim 1, wherein the cation source includes an alkaline earth metal cation.

12. The method according to claim 11, wherein the cation source is a source of divalent cations.

13. The method according to claim 12, wherein the divalent cation includes an alkaline earth metal cation.

14. The alkaline earth metal cation is Ca ２＋ and Mg ２＋ The method according to claim 13, selected from the group consisting of, and combinations thereof.

15. The aforementioned CO ２ The method according to claim 1, further comprising manufacturing a building material from a material of isolation carbonate.

16. The method according to claim 15, wherein the building material includes aggregate.

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