Methods and compositions for carbon dioxide sequestration

Abstract

The present invention relates to a method for capturing carbon dioxide and permanently sequestering it in the form of Group II metal carbonates. The invention involves the production of HCl by reacting a material comprising magnesium chloride hydrate with water vapor. The HCl generated from this process is used to leach Group II mineral salts from a variety of different materials including minerals and industrial wastes. The leached Group II mineral salts are used to capture carbon dioxide by forming Group II mineral carbonates.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 174,977, filed April 14, 2021, which is incorporated by reference in its entirety.

[0002] FIELD OF THEINVENTION The present invention relates generally to the reduction of atmospheric carbon dioxide, and more specifically to carbon dioxide capture and sequestration. [Background technology]

[0003] background The ongoing warming of the planet due to the presence and production of greenhouse gases such as carbon dioxide makes the capture and permanent sequestration of carbon dioxide by economical means imperative.

[0004] Carbon capture and storage (CCS) has the potential to significantly reduce greenhouse gas emissions from industries that rely on combustion processes, such as power plants and cement manufacturing facilities. Unfortunately, capturing carbon dioxide via CCS is energy intensive due to the thermal energy requirements and the need to compress the captured carbon dioxide for underground storage. This energy demand can reduce effective power output from power generating units by more than 20%.

[0005] Gas companies use amine scrubbing to separate carbon dioxide from methane, and very similar methods can be used to remove carbon dioxide from flue gas. A major problem with amine scrubbing is that regeneration of the amine solution and subsequent compression of the carbon dioxide is very energy intensive. As a result, installing an amine-based carbon capture unit on a power plant reduces its efficiency by as much as 35%.

[0006] An alternative CCS method involves the oxy-combustion process, in which coal is burned in the presence of pure oxygen to produce carbon dioxide and water as combustion products. The CO2 is then captured by condensing the water from the carbon dioxide / water mixture. The pure oxygen used in oxy-combustion is obtained from an energy-intensive air separation process in which air is cryogenically cooled to a liquid form and the pure oxygen is distilled from the nitrogen in the liquid air.

[0007] Given our reliance on fossil fuels, the widespread deployment of CCS is essential to reduce greenhouse gases and control global warming. While some companies are focused on finding alternative CCS methods, a great deal of research is focused on improving the efficiency of current carbon capture processes. Summary of the Invention

[0008] overview It is an object of the present invention to provide a method for carbon dioxide absorption and sequestration that overcomes many of the shortcomings of the prior art. The inventors have identified a method for the production of mineral ion salts that can be used to sequester carbon dioxide in the form of mineral ion carbonates. The mineral ion salts can be obtained from different sources, including industrial wastes and various geological silicate minerals.

[0009] Some embodiments of the disclosure are directed to methods of using waste materials to sequester carbon dioxide. In some embodiments, the methods include reacting magnesium chloride hydrate-containing material with steam to generate hydrochloric acid and magnesium hydroxide, contacting a gas stream containing carbon dioxide with the magnesium hydroxide to obtain a partially or fully carbonated fluid, contacting the waste with hydrochloric acid and optionally water to leach mineral ion salts from the waste into a brine or slurry, recovering the mineral ion salts from the brine or slurry, and reacting the partially or fully carbonated fluid with mineral ion salts to sequester carbon dioxide in the form of mineral ion carbonate. In some embodiments, the partially or fully carbonated fluid is a mixture of Mg(OH)x (HCO3) y where x+y=2. In some embodiments, the mineral ion carbonate comprises precipitated calcium carbonate (PCC). In some embodiments, the mineral ion carbonate further comprises lower value mixed carbonates.

[0010] Some embodiments of the disclosure are directed to methods of using geological silicate minerals to sequester carbon dioxide. In some embodiments, the methods include reacting a magnesium chloride hydrate-containing material with water vapor to generate hydrochloric acid and magnesium hydroxide, contacting a gas stream containing carbon dioxide with the magnesium hydroxide to obtain a partially or fully carbonated fluid, contacting the geological silicate mineral with hydrochloric acid and optionally water to leach mineral ion salts from the geological silicate mineral into a brine or slurry, recovering the mineral ion salts from the brine or slurry, and reacting the partially or fully carbonated fluid with the mineral ion salts to sequester carbon dioxide in the form of mineral ion carbonate. In some embodiments, the partially or fully carbonated fluid is a mixture of Mg(OH) x (HCO3) y where x+y=2. In some embodiments, the mineral ion carbonate comprises precipitated calcium carbonate. In some embodiments, the mineral ion carbonate further comprises lower value mixed carbonates.

[0011] In some embodiments, the mineral ion salt comprises at least one Group II metal cation. In some embodiments, the Group II metal cation is a calcium cation. In some embodiments, the Group II metal cation is a magnesium cation. In some embodiments, the waste is an industrial waste. In some embodiments, the industrial waste is selected from the group consisting of stone, concrete, steel slag, biomass fuel production slag, and waste coal fly ash.

[0012] In some embodiments, the carbon dioxide is a component of a flue gas stream. In some embodiments, the carbon dioxide is atmospheric carbon dioxide. In some embodiments, the step of contacting the waste with hydrochloric acid is carried out at ambient temperature. In some embodiments, the step of contacting the waste with hydrochloric acid is carried out at a temperature greater than ambient temperature. In some embodiments, the step of contacting the waste with hydrochloric acid is carried out at ambient pressure.

[0013] In some embodiments, the step of contacting the waste with hydrochloric acid does not involve mechanical agitation or grinding of solids. In some embodiments, the step of contacting the waste with hydrochloric acid involves mechanical agitation or grinding of solids. In some embodiments, the step of contacting the waste with hydrochloric acid further comprises recirculating liquid to increase contact of the waste with the hydrochloric acid.

[0014] In some embodiments, the step of contacting the geological silicate mineral with hydrochloric acid is carried out at ambient temperature. In some embodiments, the step of contacting the geological silicate mineral with HCl is carried out at a temperature greater than ambient temperature. In some embodiments, the step of contacting the geological silicate mineral with hydrochloric acid is carried out at ambient pressure. In some embodiments, the step of contacting the geological silicate mineral with hydrochloric acid is carried out at a pressure greater than ambient pressure.

[0015] In some embodiments, the step of contacting the geological silicate mineral with hydrochloric acid does not involve mechanical agitation or grinding of solids. In some embodiments, the step of contacting the geological silicate mineral with hydrochloric acid involves mechanical agitation or grinding of solids. In some embodiments, the step of contacting the geological silicate mineral with hydrochloric acid further comprises recirculating liquid to increase contact of the geological silicate mineral with the hydrochloric acid.

[0016] In some embodiments, the mineral ion salts present in the brine or slurry are recovered. In some embodiments, the brine or slurry is transferred to a settling tank. In some embodiments, the solids in the brine or slurry are allowed to settle to the bottom of the settling tank. In some embodiments, the brine or slurry is transferred to an evaporation pond. In some embodiments, the liquid in the brine or slurry is allowed to evaporate. In some embodiments, solar energy and / or naturally occurring wind power is used to increase the evaporation rate. In some embodiments, non-renewable energy is not used to increase the evaporation rate. In some embodiments, no energy is provided to the evaporation pond to increase the evaporation rate.

[0017] In some embodiments, the mineral ion salt comprises at least one Group II metal cation. In some embodiments, the Group II metal cation is a calcium cation. In some embodiments, the Group II metal cation is a magnesium cation. In some embodiments, the geological silicate mineral is selected from the group consisting of olivine, forsterite, pyrope, spessartine, grossular, ferrochromite, hydrogrossular, norbergite, chondrodite, humite, clinohumite, datolite, titanite, anhydrite, lawsonite, axite, sericite, epidote, sulphurite, tanzanite, clinochromite, allanite, dreissite, vesuvianite, paopgoite, tourmaline, osumilite, cordierite, sekaninite, eudialyte, millarite, enstatite, pigeonite, diopside, sulphurite ... The mineral is selected from the group consisting of augite, proxferroite, wollastonite, schismatic, anthophyllite, cummingtonite, tremolite, actinolite, amphibole, glaucophane, sodalite, antigorite, chrysophyllite, lizardite, talc, illite, montmorillonite, chlorite, vermiculite, sepiolite, palygorskite, biotite, phlogopite, nacre, glauconite, oligoclase, andespar, anorthite, anorthite, nepheline, lazurite, erionite, chabazite, heulandite, stilbite, scolecite, mordenite, clinoenstatite, and combinations thereof.

[0018] It is specifically contemplated that any limitation discussed with respect to one embodiment of the invention may apply to any other embodiment of the invention. Furthermore, any composition of the invention may be used in any method of the invention, and any method of the invention may be used to produce or utilize any composition of the invention.

[0019] Other objects, features and advantages of the present invention will become apparent from the following detailed description. It should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. [Brief description of the drawings]

[0020] [Figure 1] FIG. 1 is a block diagram of a carbon dioxide sequestration process according to some embodiments of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] Detailed Description The present invention relates to a method for capturing carbon dioxide and permanently sequestering it in the form of metal carbonates. The invention involves the production of HCl by reacting a material comprising magnesium chloride hydrate with water vapor. The HCl generated from this process is used to leach mineral salts from a variety of different materials including minerals and industrial wastes. The leached mineral salts are used to capture carbon dioxide by forming carbonate salts of the mineral salt cations.

[0022] Of the many mineral salts available, Group II salts are generally used for CO2 capture. The Group II metals calcium and magnesium are relatively abundant in various geological deposits and industrial wastes around the world. Abundant calcium- and magnesium-containing minerals and wastes provide relatively inexpensive feedstocks for CO2 sequestration chemicals.

[0023] A.Definition As used herein, the term "carbonate" or "carbonate product" generally refers to a carbonate salt [CO3] 2- The term is thus defined as a mineral component that contains both carbonate / bicarbonate mixtures and species that contain only carbonate ions. The terms "bicarbonate" and "bicarbonate products" generally refer to the bicarbonate base [HCO3]. 1- Thus, the term encompasses both carbonate / bicarbonate mixtures and species containing only bicarbonate ions.

[0024] As used herein, "Ca / Mg" refers to either Ca only, Mg only, or a mixture of both Ca and Mg. The ratio of Ca to Mg can range from 0:100 to 100:0, including, for example, 1:99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, and 99:1. x Ca (1-x) " and "Ca x Mg (1-x) The symbols "Group II" and "Group 2" are synonymous. The terms "Group II" and "Group 2" are used interchangeably. Magnesium chloride hydrate refers to any hydrate, including but not limited to hydrates having 2, 4, 6, 8, or 12 equivalents of water per equivalent of magnesium chloride. Depending on the context, the abbreviation "MW" means either molecular weight or megawatts. The abbreviation "PFD" is a process flow chart. The abbreviation "Q" is heat (or heat load), and heat is a type of energy. It does not include any other type of energy.

[0025] As used herein, the term "sequestration" is used generally to refer to techniques or actions whose partial or total effect is to remove CO2 from a point source and store it in some form so as to prevent it from returning to the atmosphere. Use of this term does not exclude any of the described embodiments from being considered "sequestration" techniques.

[0026] When used in conjunction with the term "comprising" in the claims and / or specification, the use of the words "a" or "an" may mean "one," but is also consistent with the meanings of "one or more," "at least one," and "one or more."

[0027] Throughout this application, the term "about" is used to indicate that a value includes the inherent variation of error for the device, method employed to determine the value, or variation that exists among the study subjects.

[0028] The terms "comprise," "have," and "include" are open-ended linking verbs. Any form or tense of one or more of these verbs, such as "comprises," "comprising," "has," "having," "includes," and "including," are also open-ended. For example, any method that "comprises," "has," or "includes" one or more steps is not limited to having only those one or more steps, but also encompasses other unlisted steps.

[0029] The above definitions take precedence over any conflicting definitions in any of the documents incorporated herein by reference. However, the fact that a particular term is defined should not be taken to indicate that any undefined term is indefinite. Rather, all terms used are believed to describe the invention in terms that allow one skilled in the art to understand the scope and practice the invention.

[0030] B. Sequestration of CO2 using Group II salts leached from geological minerals or industrial wastes 1 shows a simplified process flow diagram illustrating a schematic exemplary embodiment of the apparatus and method of the present disclosure. This diagram is provided for illustrative purposes only, and thus only illustrates certain aspects of the present invention, and is not intended to limit the scope of the claims in any way.

[0031] A method for recovering carbon dioxide is disclosed herein. Referring to Figure 1, the method involves a first step of reacting magnesium chloride hydrate-containing material 20 with water vapor 10 in a reactor 25 to generate HCl 30 and Mg(OH)240. The magnesium chloride hydrate-containing material 20 may contain magnesium chloride in the dihydrate, tetrahydrate, hexahydrate, octahydrate, dodecahydrate, or other hydrated forms. Decomposition of the magnesium chloride hydrate produces Mg(OH)240 and HCl 30. This internally generated HCl 30 may be in the form of HCl gas, an aqueous solution of HCl, or a gaseous solution of HCl in water vapor.

[0032] A gas stream containing carbon dioxide 50 is contacted with Mg(OH)240 to obtain a partially or fully carbonated fluid 110. The partially or fully carbonated fluid 110 is the reaction product of Mg(OH)240 and carbon dioxide 50, which is Mg(OH) x (HCO3) y where x+y=2.

[0033] The HCl 30 is sent to a reactor 35 where it contacts the industrial waste 40 and / or the geological silicate mineral 50. Water 80 in liquid or gas form can be optionally provided to the reactor 35. The contact of the HCl 30 with the industrial waste 60 and / or the geological silicate mineral 70 can be carried out at normal pressure. Alternatively, the contact of the HCl 30 with the industrial waste 60 and / or the geological silicate mineral 70 can be carried out at a pressure higher than normal pressure. The contact of the HCl 30 with the industrial waste 60 and / or the geological silicate mineral 70 can be carried out at normal temperature. Alternatively, the contact of the HCl 30 with the industrial waste 60 and / or the geological silicate mineral 70 can be carried out at a temperature higher than normal temperature. The concentration of the HCl 30 in the reactor 35 can be controlled by adjusting the conditions in the reactor 25 and / or by adjusting the time and / or rate at which the HCl 30 is provided to the reactor 35. By controlling the HCl concentration in reactor 35, chloride incorporation into the various SiO composites can be controlled or avoided.

[0034] The HCl 30 and the industrial waste 60 and / or geological silicate minerals 70 may be reacted in the reactor 35 without mechanical agitation or grinding of the solids. The HCl 30 and the industrial waste 60 and / or geological silicate minerals 70 in the reactor 35 may be subjected to mechanical agitation and / or grinding of the solids. Liquid in the reactor 35 may be recirculated to increase contact of the HCl 30 with the industrial waste 60 and / or geological silicate minerals 70.

[0035] Contact of the HCl 30 with the industrial waste 60 and / or geological silicate minerals 70 causes the HCl 30 to react with the industrial waste 60 and / or geological silicate minerals 70 and leach mineral ion salts from the waste into a brine or slurry 90. The brine or slurry 90 is recovered, which contains the mineral ion salts from the industrial waste 60 and / or geological silicate minerals 70. The mineral ion salts present in the brine or slurry 90 may be in solution, in solid form, or a combination of solution and undissolved solids.

[0036] The mineral ion salts 100 present in the brine or slurry 90 are recovered. Various methods can be used to aid in the recovery of the mineral ion salts 100 present from the brine or slurry 90. The brine or slurry 90 can be transferred to a settling tank. The solids in the brine or slurry 90 can be allowed to settle to the bottom of the settling tank. Alternatively, a sand filter can be used to remove the solids from the brine or slurry 90. The brine or slurry 90 can be transferred to an evaporation pond where the liquid in the brine or slurry 90 is evaporated. Solar energy and / or naturally occurring wind power can be utilized to increase the evaporation rate. In some embodiments, non-renewable energy is not used to increase the evaporation rate. In some embodiments, no energy is provided to the evaporation pond to increase the evaporation rate. The brine or slurry 70 can be transferred to an evaporation system. The evaporation system can be a single, double, or triple effect evaporation system.

[0037] The mineral ion salt 100 is Mg(OH) present in a partially or fully carbonated fluid 110. x (HCO3) y to sequester the carbon dioxide in the form of mineral ion carbonate 120. EXAMPLES

[0038] C. Working Example The following examples are included to demonstrate preferred embodiments of the invention. Those skilled in the art should recognize that the techniques disclosed in the following examples represent techniques found by the inventors to work well in the practice of the invention, and thus may be considered to constitute preferred modes for its practice. However, those skilled in the art should recognize in light of this disclosure that many changes can be made to the specific embodiments disclosed and still obtain the same or similar results without departing from the spirit and scope of the invention.

[0039] Example 1 Evaluation of materials for the generation of PCC Three industrial waste test materials (blast furnace slag, biomass slag, coal fly ash) were tested for the production of precipitated calcium chloride (PCC, a precipitated mineral ion salt). The study was conducted to evaluate the use of raw-unamended brine from the three test sources. Various conditions were tested to test the settling process across a wide range of processing conditions. Process control of settling temperature, change in volume of precipitated salt relative to the uptake liquor, and pH control of the uptake liquor conditions can be used to enhance the precipitation selectivity of calcium salts relative to magnesium and iron salts contained in the raw test materials.

[0040] The test materials were contacted with hydrochloric acid in a recirculating bath to produce brines and the solids were filtered after dissolution. The brines were analyzed using SEM / ICP to determine the chemical composition of the dissolved salts. The results, provided in Table 1 below, demonstrate that brines with high calcium content can be obtained from hydrochloric acid dissolution of various industrial wastes. These high calcium brines can be used to produce PCC or can be used directly in carbon dioxide sequestration processes.

[0041] (Table 1) Salt solution composition index TIFF2024515621000001.tif39160

[0042] Example 2 Waste Melting and CO2 Capture A sample of MgCl2 hydrate-containing material was reacted with water vapor in a decomposition reactor to generate aqueous Mg(OH)2 and HCl gas. A mixture of unreacted water vapor and gaseous HCl was collected as aqueous HCl. This solution was diluted to a concentration of 15% and the resulting solution was used to dissolve coal fly ash and biomass slag waste. The waste dissolution process involved adding each waste to the HCl solution in a separate reactor and monitoring the reaction temperature. Additional water was added to dilute or reliquefy the dissolution reactants. Because the biomass slag dissolution reaction involves the evolution of water vapor and loss of moisture, water was added to compensate for the water loss. Table 2 below shows the temperatures, volumes, and masses for the various waste-dissolution experimental runs.

[0043] Table 2. Waste dissolution run specifications TIFF2024515621000002.tif94160

[0044] Once the materials were thoroughly mixed and optionally reliquefied with water, the resulting brine and slurry were allowed to stand for 30 minutes to complete any remaining reactions. During this period, the temperature of the brine / slurry began to drop to ambient temperature and the pH of the slurry was measured using a calibrated pH meter. Aqueous NH4OH was added to low pH samples (<3.5) to raise the pH to ≧6. Once the slurry had cooled to ambient temperature, the solids were filtered from the slurry to obtain a cake and filtrate. In some aspects, the brine generated from the dissolution of waste materials disclosed above can be used directly without filtration.

[0045] A stream of gaseous CO2 was bubbled through an aqueous Mg(OH)2 solution generated from the decomposition of MgCl2 hydrate with water vapor to obtain a carbonation solution containing Mg(HCO3)2. The carbonation solution was combined with the brine or filtrate produced above to obtain a product containing calcium carbonate (solid) and MgCl2 in solution. The product was filtered to separate precipitated calcium carbonate (PCC) from the MgCl2 solution. Inductively Coupled Plasma (ICP) analysis was performed on PCC collected from runs 7 and 8 in Table 2. The cation composition is shown in Table 3 below.

[0046] (Table 3) Calcium carbonate ICP analysis TIFF2024515621000003.tif87160

[0047] The results in Table 3 above demonstrate that high purity calcium carbonate can be obtained by utilizing HCl generated from the decomposition of magnesium chloride hydrate-containing materials. HCl was used to dissolve various waste materials to obtain a brine or slurry with high calcium content. Magnesium hydroxide generated from the decomposition of magnesium chloride hydrate-containing materials was carbonated with carbon dioxide gas, and the resulting carbonated solution was combined with the waste-derived brine or slurry to obtain a magnesium chloride solution containing precipitated calcium carbonate. The method disclosed herein provides a novel means to recycle various waste materials and utilize them as a key component for environmentally conscious sequestration of carbon dioxide gas. The method can be extended to the use of geological silicate minerals as waste substitutes.

Claims

1. A method for sequestering carbon dioxide using waste materials or geological silicate minerals, comprising the steps of: reacting a magnesium chloride hydrate containing material with water vapor to generate HCl and Mg(OH)2; A gas stream containing carbon dioxide and Mg(OH) 2 to obtain a partially or fully carbonated fluid comprising Mg(OH)x(HCO3)y, where x+y=2; contacting the waste material or geological silicate mineral with HCl and optionally water to leach mineral ion salts from the waste material or geological silicate mineral into a brine or slurry; recovering the mineral ion salts from the brine or slurry; and reacting the partially or fully carbonated fluid with the mineral ion salts to sequester carbon dioxide in the form of mineral ion carbonates, including calcium carbonate. A method comprising:

2. 2. The method of claim 1, wherein the mineral ion salt comprises calcium and / or magnesium cations.

3. The method of claim 1, wherein the waste material is selected from the group consisting of stone, concrete, steel slag, biomass fuel production slag, and waste coal fly ash.

4. The geological silicate mineral is selected from the group consisting of olivine, forsterite, pyrope, spessartine, grossular, ferrochromite, hydrogrossular, norbergite, chondrodite, humite, clinohumite, datolite, titanite, anhydrite, lawsonite, axonite, schizopyrite, epidote, schizopyrite, tanzanite, clinopyroxene, allanite, draisite, vesuvianite, papagoite, tourmaline, osumilite, cordierite, sekanilite, eudialyte, miralite, enstatite, pigeonite, diopside, ferropyroxene, augite, proxfite, and schizopyroxene.

2. The method of claim 1, wherein the fluoride is selected from the group consisting of proxferroite, wollastonite, anthophyllite, cummingtonite, tremolite, actinolite, amphibole, glaucophane, sodalite, antigorite, chrysotile, lizardite, talc, illite, montmorillonite, chlorite, vermiculite, sepiolite, palygorskite, biotite, phlogopite, nacreous mica, glauconite, oligoclase, andesite, anorthite, anorthite, nepheline, lazurite, erionite, chabazite, heulandite, stilbite, scolecite, mordenite, clinoenstatite, and combinations thereof.

5. 2. The method of claim 1, wherein the carbon dioxide is atmospheric carbon dioxide or is a component of a flue gas stream.

6. 2. The method of claim 1, wherein the carbon dioxide is atmospheric carbon dioxide.

7. 10. The method of claim 1, wherein the step of contacting the waste material with HCl is carried out at ambient temperature.

8. 10. The method of claim 1, wherein the step of contacting the waste material with HCl is carried out at atmospheric pressure.

9. 10. The method of claim 1, wherein the step of contacting the waste material with HCl does not involve mechanical agitation or grinding of the solids.

10. 10. The method of claim 1, wherein the step of contacting the waste material with HCl further comprises recirculating the liquid to increase contact of the waste material with HCl.

11. 10. The method of claim 1, further comprising the steps of transferring the brine or slurry to a settling tank and allowing solids in the brine or slurry to settle to the bottom of the settling tank.

12. 10. The method of claim 1, further comprising the steps of transferring the brine or slurry to an evaporation pond and evaporating the liquid in the brine or slurry.

13. 13. The method of claim 12, wherein solar energy and / or naturally occurring wind power is utilized to increase the evaporation rate.

14. 13. The method of claim 12, wherein no non-renewable energy is used to increase the evaporation rate.

15. 13. The method of claim 12, wherein no energy is provided to the evaporation pond to increase the evaporation rate.

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