Method for carbon dioxide storage utilizing carbon dioxide sequestration in an anhydrite-rich formation
12460513 ยท 2025-11-04
Assignee
Inventors
- Isah Mohammed (Dhahran, SA)
- Dhafer Abdullah AL SHEHRI (Dhahran, SA)
- Abubakar Isah (Dhahran, SA)
- Mohamed Mahmoud (Dhahran, SA)
Cpc classification
C01P2002/70
CHEMISTRY; METALLURGY
International classification
Abstract
A method for carbon dioxide (CO.sub.2) storage includes injecting a brine solution into a subterranean anhydrite-rich formation, then injecting carbon dioxide into the subterranean anhydrite-rich formation and reacting the carbon dioxide with the subterranean anhydrite-rich formation to form one or more minerals thereby sequestering the carbon dioxide in the subterranean anhydrite-rich formation. The temperature in the subterranean anhydrite-rich formation is from 300 Kelvin (K) to 365 K and the pressure in the subterranean anhydrite-rich formation is from 90 bar to 120 bar.
Claims
1. A method of carbon dioxide storage, comprising: injecting a brine solution into a subterranean anhydrite-rich formation, wherein the subterranean anhydrite-rich formation is anhydrous and free of hydrocarbons; injecting carbon dioxide into the subterranean anhydrite-rich formation; reacting the carbon dioxide with the subterranean anhydrite-rich formation in the presence of the brine solution to form one or more minerals thereby sequestering the carbon dioxide in the subterranean anhydrite-rich formation, wherein a temperature in the subterranean anhydrite-rich formation is from 300 to 365 K, wherein a pressure in the subterranean anhydrite-rich formation is from 90 to 120 bar, wherein the brine solution comprises sodium chloride, calcium chloride, magnesium chloride, sodium bicarbonate, and sodium sulfate, wherein the brine solution comprises ionic concentrations of Na.sup.+ in a range from 5,000 to 50,000 parts per million (ppm), Ca.sup.2+ in a range from 100 to 1,500 ppm, Mg.sup.2+ in a range from 500 to 5,000 ppm, SO.sub.4.sup.2 in a range from 1,000-9,000 ppm, Cl.sup. in a range from 10,000-70,000 ppm, and HCO.sub.3.sup. in a range from 10-500 ppm, and wherein a mineral content of the subterranean anhydrite-rich formation after the reacting comprises 80 to 90 weight percent (wt. %) anhydrite, 1 to 5 wt. % calcite, 5 to 10 wt. % dolomite, 1 to 5 wt. % scapolite, 0.1 to 1 wt. % quartz; 0.1 to 1 wt. % feldspar, and 0.1 to 1 wt. % siderite.
2. The method of claim 1, wherein after the reacting the subterranean anhydrite-rich formation has a greater than 150 wt. % increase in total carbon compared to an initial amount of total carbon in the subterranean anhydrite-rich formation before the reacting wherein the reaction time is 15 days; wherein the subterranean anhydrite-rich formation has a gas porosity of 0.5 to 5% and a gas permeability of 0.05 to 0.1 mD; wherein the carbon dioxide is injected into the subterranean anhydrite-rich formation as a supercritical fluid; and wherein the brine solution and carbon dioxide are injected into the subterranean anhydrite-rich formation through tubing present in one or more boreholes that extend from the surface into the subterranean anhydrite-rich formation.
3. The method of claim 2, wherein after the reacting the subterranean anhydrite-rich formation has a greater than 160% increase in total carbon compared to an initial amount of total carbon in the subterranean anhydrite-rich formation before the reacting wherein the reaction time is 15 days.
4. The method of claim 3, wherein after the reacting the subterranean anhydrite-rich formation has a greater than 170% increase in total carbon compared to an initial amount of total carbon in the subterranean anhydrite-rich formation before the reacting wherein the reaction time is 15 days.
5. The method of claim 1, wherein the temperature is from 315 to 350 K.
6. The method of claim 5, wherein the temperature is from 325 to 340 K.
7. The method of claim 1, wherein the pressure is from 95 to 115 bar.
8. The method of claim 7, wherein the pressure is from 100 to 110 bar.
9. The method of claim 1, wherein the one or more minerals formed by reacting the carbon dioxide with the anhydrite-rich formation are selected from the group consisting of calcite, siderite, and feldspar.
10. The method of claim 1, wherein reacting the carbon dioxide with the anhydrite-rich formation forms calcite and a final calcite concentration of the anhydrite-rich formation is at least 1 wt. % greater than an initial calcite concentration of the anhydrite-rich formation before the reacting.
11. The method of claim 1, wherein reacting the carbon dioxide with the anhydrite-rich formation forms dolomite and a final dolomite concentration of the anhydrite-rich formation is at least 1 wt. % less than an initial dolomite concentration of the anhydrite-rich formation before the reacting.
12. The method of claim 1, wherein a dissolution of anhydrite in the presence of supercritical CO.sub.2 increases an availability of calcium, facilitating mineral trapping of CO.sub.2.
13. The method of claim 1, further comprising: injecting a barium chloride solution into the subterranean anhydrite-rich formation after the injecting the brine solution, wherein the barium chloride reacts with the subterranean anhydrite-rich formation to precipitate barium sulfate and barium carbonate, and wherein the concentration of barium chloride in the subterranean anhydrite-rich formation after the injecting the barium chloride solution is in a range from 0.01 to 0.1 M.
14. The method of claim 13, wherein after reacting the carbon dioxide with the anhydrite-rich formation, the subterranean anhydrite-rich formation has a greater than 240 wt. % increase in total carbon compared to an initial amount of total carbon in the subterranean anhydrite-rich formation before the reacting wherein the reaction time is 15 days.
15. The method of claim 14, wherein after reacting the carbon dioxide with the anhydrite-rich formation, the subterranean anhydrite-rich formation has a greater than 250 wt. % increase in total carbon compared to an initial amount of total carbon in the subterranean anhydrite-rich formation before the reacting wherein the reaction time is 15 days.
16. The method of claim 15, wherein after reacting the carbon dioxide with the anhydrite-rich formation, the subterranean anhydrite-rich formation has a greater than 260% increase in total carbon compared to an initial amount of total carbon in the subterranean anhydrite-rich formation before the reacting wherein the reaction time is 15 days.
17. The method of claim 13, wherein reacting the carbon dioxide with the anhydrite-rich formation forms one or more minerals selected from the group consisting of calcite, siderite, feldspar, and barite.
18. The method of claim 17, wherein a final calcite concentration of the anhydrite-rich formation is at least 1.5 wt. % greater than an initial calcite concentration of the anhydrite-rich formation before the reacting.
19. The method of claim 17, wherein a final dolomite concentration of the anhydrite-rich formation is at least 2 wt. % less than to an initial dolomite concentration of the anhydrite-rich formation before the reacting.
20. The method of claim 17, wherein a final barite concentration of the anhydrite-rich formation is at least 0.5 wt. % greater than an initial barite concentration of the anhydrite-rich formation before the reacting.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) A more complete appreciation of this disclosure and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:
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DETAILED DESCRIPTION
(81) In the drawings, like reference numerals designate identical or corresponding parts throughout the several views. Further, as used herein, the words a, an and the like generally carry a meaning of one or more, unless stated otherwise.
(82) Furthermore, the terms approximately, approximate, about, and similar terms generally refer to ranges that include the identified value within a margin of 20%, 10%, or preferably 5%, and any values therebetween.
(83) As used herein, the term brine solution or brine refers to a concentrated aqueous solution of salts, primarily sodium chloride (NaCl), but may also include other salts such as calcium chloride (CaCl.sub.2)), magnesium chloride (MgCl.sub.2), sodium bicarbonate (NaHCO.sub.3), and sodium sulfate (Na2SO.sub.4). This may be a man-made solution which mimics the ionic composition of seawater or a naturally sourced seawater or brackish water. Brine is utilized in various applications, including subsurface carbon mineralization processes, where it interacts with geological formations to facilitate carbon dioxide (CO.sub.2) storage.
(84) As used herein, the term subterranean anhydrite refers to a naturally occurring mineral form of calcium sulfate (CaSO.sub.4) that is found in underground geological formations. Anhydrite is typically characterized by its lack of water in its crystal structure, distinguishing it from gypsum, which contains water. Subterranean anhydrite is often formed in arid environments through evaporation and is commonly associated with sedimentary rock formations. In the context of carbon dioxide (CO.sub.2) storage, subterranean anhydrite can play a role in mineralization processes, as it has the potential to react with injected CO.sub.2 and brine solutions to facilitate the transformation of CO.sub.2 into stable carbonate minerals, thus contributing to long-term CO.sub.2 sequestration.
(85) As used herein, the term subterranean anhydrite-rich formation refers to a geological structure characterized by a presence of anhydrite (CaSO.sub.4) within its composition. This formation typically consists of layers of anhydrite interspersed with other minerals and rock types, often found in sedimentary basins or evaporite sequences. Subterranean anhydrite-rich formations are of particular interest in geological studies related to carbon dioxide (CO.sub.2) storage, as they provide a reactive medium for carbon mineralization. When CO.sub.2 is injected into these formations, it can interact with the anhydrite and brine solutions present, facilitating the transformation of CO.sub.2 into stable carbonate minerals. The unique properties of anhydrite, including its chemical reactivity and ability to undergo dissolution and precipitation processes, make these formations valuable for effective long-term CO.sub.2 sequestration strategies.
(86) As used herein, the term gas permeability refers to the ability of a porous material, such as rock or sediment, to allow the passage of gases through its interconnected pore spaces. It is a property that influences the movement and flow of gases, including carbon dioxide (CO.sub.2), within geological formations. Gas permeability is typically measured in units of Darcy or millidarcy (mD) and is influenced by factors such as pore size, pore shape, rock texture, and the degree of saturation of the material.
(87) As used herein, the term gas porosity refers to the volume percentage of a rock or sediment that is filled with gas. Gas porosity is measured as a percentage (%) and is equal to the percentage of the volume contained within the rock or sediment that is currently occupied by gas.
(88) As used herein, the term calcite refers to a naturally occurring mineral form of calcium carbonate (CaCO.sub.3), characterized by its crystalline structure and typically appearing in a range of colors, including white, colorless, or shades of yellow, brown, or gray. Calcite is one of the most abundant minerals in the Earth's crust and is commonly found in sedimentary rocks, such as limestone and marble. It plays a role in various geological and biological processes, including carbon cycling and the formation of carbonate rocks. In the context of carbon dioxide (CO.sub.2) storage and mineralization, calcite is of particular interest as it can form through the reaction of CO.sub.2 with calcium-bearing minerals, facilitating the long-term sequestration of CO.sub.2 in solid mineral form.
(89) As used herein, the term siderite refers to a naturally occurring mineral composed of iron carbonate (FeCO.sub.3). It typically appears as a brownish or yellowish mineral, often forming in sedimentary environments or as a result of hydrothermal processes. Siderite is prevalent in various geological contexts, particularly in iron ore deposits and as a secondary mineral in some sedimentary rocks. In the context of carbon mineralization and carbon dioxide (CO.sub.2) storage, siderite can form through the reaction of CO.sub.2 with iron-bearing minerals, thereby facilitating the conversion of gaseous CO.sub.2 into stable carbonate minerals. This transformation is important for long-term carbon sequestration strategies, as siderite is relatively stable and can help immobilize CO.sub.2 within geological formations.
(90) As used herein, the term feldspar refers to a group of abundant rock-forming minerals that are primarily composed of aluminosilicates of potassium, sodium, and calcium. Feldspar minerals are classified into three main types: orthoclase (potassium feldspar), plagioclase (sodium and calcium feldspar), and microcline. They typically appear in a range of colors, including white, pink, gray, or green, and are characterized by their crystalline structure and two-dimensional cleavage. Feldspar is a major component of many igneous, metamorphic, and sedimentary rocks, and it plays a role in the geological processes that lead to the formation of soil and other minerals. In the context of carbon dioxide (CO.sub.2) storage and mineralization, feldspar can react with CO.sub.2 and other fluids, contributing to the long-term sequestration of carbon by facilitating the formation of stable carbonate minerals.
(91) Aspects of this disclosure are directed to a method for carbon dioxide sequestration in an anhydrite rich formation. Anhydrite, with its chemically reactive properties, facilitates efficient mineralization of CO.sub.2 into stable carbonate minerals, thereby immobilizing carbon in a solid form and preventing its release back into the atmosphere. This process not only enhances the long-term storage capacity of the geological formation but also reduces the risks of leakage associated with traditional CO.sub.2 storage methods. Overall, the method of present disclosure represents a promising approach to addressing the pressing challenge of global warming while simultaneously leveraging existing geological resources.
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(93) At step 52, the method 50 includes injecting a brine solution into a subterranean anhydrite-rich formation. Subterranean anhydrite-rich formations are geological structures characterized by the presence of anhydrite, a calcium sulfate mineral that typically forms in arid environments through the evaporation of seawater or saline water bodies. Anhydrite-rich layers have unique physical and chemical properties, which include low permeability and high mechanical strength. This makes them effective seals for hydrocarbons and other fluids, allowing for the formation of reservoirs beneath them. Anhydrite formations often form a caprock on other rock formations and can be near hydrocarbon basins, however, these anhydrite formations are typically substantially free of hydrocarbons. Anhydrite is typically found in extensive layered deposits and sedimentary basins that are formed when large volumes of sea water have been evaporated, often interbedded other minerals including gypsum, halite, and limestone. These sedimentary accumulations can be hundreds of feet thick and cover large areas. Also, anhydrite can form in tidal flat sediments and shorelines from sea water evaporation. Anhydrite formations are also typically substantially free from water before the introduction of brine, although they can be found near formations that contain water and is often found near water-containing gypsum. In one or more embodiments, the anhydrite formations used herein will be free from hydrocarbons. Additionally, these formations can serve as ideal candidates for carbon dioxide storage because their impermeability minimizes the risk of leakage, making them suitable for carbon capture and storage (CCS) initiatives. Furthermore, the geological stability and structural integrity of anhydrite-rich formations can also facilitate enhanced oil recovery techniques, making them valuable in both environmental and economic contexts. Overall, these formations play a role in energy resource management and environmental sustainability.
(94) Suitable examples of subterranean rocks rich in anhydrite include, but are not limited to, sandstone, basalt, limestone, dolomite, shale, gabbro, peridotite, granite, serpentinite, marl, quartzite, chalk, carbonates, mudstone, siltstone, rhyolite, diorite, tuff, conglomerate, breccia, phyllite, schist, gneiss, amphibolite, and slate.
(95) In some embodiments, the primary mineral content of the subterranean anhydrite-rich formation includes 80-90 wt. %, preferably 82-88 wt. %, preferably 84-86 wt. %, preferably 85.4 wt. % anhydrite; 1-5 wt. %, preferably 2-4 wt. %, preferably 2.2 wt. % calcite; 5-10 wt. %, preferably 6-9 wt. %, preferably 7-8 wt. %, preferably 7.8 wt. % dolomite; 1-5 wt. %, preferably 2-4 wt. %, preferably 3-4 wt. %, preferably 3.7 wt. % scapolite; 0.1-1 wt. %, preferably 0.1-0.5 wt. %, preferably 0.2 wt % quartz; 0.1-1 wt. %, preferably 0.1-0.5 wt. %, preferably 0.3 wt. % aragonite, 0.1-1 wt. %, preferably 0.1-0.5 wt. %, preferably 0.2 wt % feldspar, and 0.1-1 wt. %, preferably 0.1-0.5 wt. %, preferably 0.1 wt % siderite.
(96) Injecting brine solution into an anhydrite-rich subterranean formation serves a role in investigating the interactions between CO.sub.2 and brine, particularly in the context of carbon storage. In some embodiments, the brine solution may have different salts including, but not limited to, potassium chloride (KCl), calcium sulphate (CaSO.sub.4), magnesium sulphate (MgSO.sub.4), lithium chloride (LiCl), strontium chloride (SrCl.sub.2), and sodium thiosulfate (Na.sub.2S.sub.2O.sub.3). In some embodiments, the brine solution may be a naturally sourced sea water or brackish water. In some embodiments, the brine solution may be formulated. In a preferred embodiment, the brine solution comprises five salts: sodium chloride (NaCl), calcium chloride (CaCl.sub.2), magnesium chloride (MgCl.sub.2), sodium bicarbonate (NaHCO.sub.3), and sodium sulfate (Na.sub.2SO.sub.4). In some embodiments, the brine water includes, by mass, ions of, Na.sup.+: 5,000-50,000 parts per million (ppm), more preferably 15,000-20,000 ppm, more preferably 16,000-19,500 ppm, more preferably 17,000-19,000 ppm, and yet more preferably 18,300; Ca.sup.2+: 100-1,500 ppm, more preferably 500-1,000 ppm more preferably 600-700 ppm, more preferably 625-675 ppm and yet more preferably 650 ppm; Mg.sup.2+: 500-5,000 ppm, more preferably 1,000-4000 ppm, more preferably 1,500-3,000 ppm more preferably 1,800-2,500 ppm, and yet more preferably 2,110 ppm; SO.sub.4.sup.2: 1,000-9,000 ppm, more preferably 3,000-7,000 ppm, more preferably 4,000-6,000 ppm, more preferably 3,800-4,600 ppm, and yet more preferably 4,290 ppm; Cl.sup.: 10,000-70,000 ppm, more preferably 20,000-50,000 ppm, more preferably 25,000-40,000 ppm more preferably 25,000-37,000 ppm, and yet more preferably 32,200 ppm; and HCO.sub.3.sup.: 10-500 ppm, more preferably 50-400 ppm, more preferably 75-300 ppm, more preferably 100-150 ppm, and yet more preferably 120 ppm.
(97) In some embodiments, the primary mineral content of the subterranean anhydrite-rich formation treated with CO.sub.2-saturated brine includes 80-90 wt. %, preferably 82-88 wt. %, preferably 84-86 wt. %, preferably 85.1 wt. % anhydrite; 1-5 wt. %, preferably 2-4.5 wt. %, preferably 4.1 wt. % calcite; 5-10 wt. %, preferably 6-9 wt. %, preferably 6-8 wt. %, preferably 6.4 wt. % dolomite; 1-5 wt. %, preferably 1-4 wt. %, preferably 1.4 wt. % scapolite; 0.1-1 wt. %, preferably 0.1-0.5 wt. %, preferably 0.2 wt % quartz; 0.1-1 wt. %, preferably 0.1-0.5 wt. %, preferably 0.1 wt. % aragonite, 0.1-1 wt. %, preferably 0.1-0.5 wt. % feldspar, and 0.1-1 wt. %, preferably 0.1-0.5 wt. %, preferably 0.3 wt. % siderite.
(98) In some embodiments, after injecting the brine solution, a barium chloride solution is injected into the subterranean anhydrite-rich formation. The barium chloride reacts with the subterranean anhydrite-rich formation to precipitate barium sulfate and barium carbonate. The addition of BaCl.sub.2 is to enforce the concurrent precipitation of barium sulfate and carbonate while maintaining a balanced reaction that involves the dissolution of rock and the precipitation of carbonate minerals. This addition of BaCl.sub.2 is a controlled step designed to influence the CO.sub.2 mineralization processes during the rock-CO.sub.2-brine interaction, thus enhancing the dissolution/precipitation and overall dynamics of the reactions.
(99) In some embodiments, the concentration of BaCl.sub.2 salt in the brine used for the initial CO.sub.2-brine interaction may range from 0.01-0.1 M, 0.05-0.1 M, 0.1-0.4 M, 0.08-0.2 M, 0.1-0.2 M, or 0.1-0.15 M. In a preferred embodiment, the concentration of BaCl.sub.2 salt in the brine for the initial CO.sub.2-brine interaction is 0.1 molar (M).
(100) It should be noted that the brine and CO.sub.2 are injected directly into the anhydrite formation or into a wellbore that terminates in or above an anhydrite formation. The brine solution and carbon dioxide are injected into the subterranean anhydrite-rich formation through tubing present in one or more boreholes that extend from the surface into the subterranean anhydrite-rich formation, and the brine and carbon dioxide are injected only into the subterranean anhydrite-rich formation. While the brine may include other components such as surfactants, in one or more embodiments, the injected brine, CO.sub.2, and the formation before injection are substantially free from hydrocarbons. Typically, this method will take advantage of anhydrite formations not involved with hydrocarbon production, using anhydrite formations substantially free from hydrocarbons to sequester CO.sub.2.
(101) In some embodiments, the primary mineral content of the subterranean anhydrite-rich formation treated with CO.sub.2-saturated brine and BaCl.sub.2 includes 80-90 wt. %, preferably 82-88 wt. %, preferably 84-86 wt. %, preferably 84.9 wt. % anhydrite; 1-5 wt. %, preferably 2-4.5 wt. %, preferably 4.5 wt. % calcite; 1-10 wt. %, preferably 2-9 wt. %, preferably 3-8 wt. %, preferably 4.5 wt. % dolomite; 1-5 wt. %, preferably 1-4 wt. %, preferably 1 wt. % scapolite; 0.1-1 wt. %, preferably 0.1-0.5 wt. %, preferably 0.2 wt % quartz; and 0.1-1 wt. %, preferably 0.1-0.4 wt. % feldspar.
(102) At step 54, the method 50 includes injecting carbon dioxide into the subterranean anhydrite-rich formation. The carbon dioxide is injected into the subterranean anhydrite-rich formation as a supercritical fluid. Carbon dioxide behaves as a supercritical fluid above its critical temperature (304.25 kelvin (K), 31.10 centigrade ( C.), 87.98 Fahrenheit ( F.)) and critical pressure (72.9 atmospheric pressure (atm), 7.39 Megapascal (MPa), 1,071 pounds per square inch (psi), 73.9 bar), expanding to fill its container like a gas but with a density like that of a liquid.
(103) In some embodiments, the temperature in the subterranean anhydrite-rich formation may range from 300 to 370 K, 315 to 355 K, 325 to 345 K, and 330 to 340 K. In a preferred embodiment, the temperature in the subterranean anhydrite-rich formation is 333 K.
(104) In some embodiments, the pressure in the subterranean anhydrite-rich formation may range from 90 to 120 bar, 95 to 115 bar, 100 to 110 bar, 100 to 115 bar, and 95 to 105 bar. In a preferred embodiment, the pressure in the subterranean anhydrite-rich formation is 104 bar.
(105) In some embodiments, supercritical fluid may include methane (CH.sub.4), nitrogen (N.sub.2), water (H.sub.2O), hydrogen (H.sub.2), sulfur hexafluoride (SF.sub.6), ethane (C.sub.2H.sub.6), ammonia (NH.sub.3), ethylene (C.sub.2H.sub.4), argon (Ar), hydrogen sulfide (H.sub.2S). In a preferred embodiment, high-purity carbon dioxide (CO.sub.2) at about 95%, preferably 97%, preferably 98%, preferably 99%, preferably 99.5, and preferably 99.9% was employed as the supercritical fluid for brine carbonation and interactions with anhydrite. The volume ratio of the brine solution to the supercritical carbon dioxide is in the range of 1:5 to 5:1, preferably 1:4 to 4:1, preferably 1:3 to 3:1, preferably 3:1.
(106) In some embodiments, the subterranean anhydrite-rich formation may have a gas porosity of 0.5 to 5%, 1 to 4%, 1 to 3%, or 1 to 2%. In a preferred embodiment, the subterranean anhydrite-rich formation has a gas porosity of 1.46%.
(107) In some embodiments, the subterranean anhydrite-rich formation may have a gas permeability of 0.015 to 0.1 mD, 0.025 to 0.09 mD, 0.035 to 0.08 mD, 0.045 to 0.08 mD, 0.055 to 0.075 mD. In a preferred embodiment, the subterranean anhydrite-rich formation may have a gas permeability of 0.068 mD.
(108) At step 56, the method 50 includes reacting the carbon dioxide with the subterranean anhydrite-rich formation to form one or more minerals thereby sequestering the carbon dioxide in the subterranean anhydrite-rich formation. Supercritical CO.sub.2 plays a role in carbon storage through brine carbonation, particularly in anhydrite-rich subterranean formations. When injected into deep formations under high-pressure and high-temperature conditions, CO.sub.2 reaches its supercritical state, combining the density of a liquid with the diffusivity of a gas. This enhances its ability to penetrate porous rock formations and dissolve into the brine present in the reservoir. In anhydrite-rich environments, supercritical CO.sub.2 dissolves in the brine, initiating reactions with calcium ions (Ca.sup.2+) released from the dissolution of anhydrite (CaSO.sub.4). This leads to the formation of calcium carbonate (CaCO.sub.3) through a process called carbonation. The precipitation of CaCO.sub.3 results in the permanent trapping of CO.sub.2 in a stable, solid mineral form, which enhances the long-term security of the storage. The interaction of CO.sub.2 with anhydrite-rich formations not only promotes carbonation but can also alter the geochemical dynamics of the reservoir. The dissolution of anhydrite in the presence of supercritical CO.sub.2 increases the availability of calcium, facilitating more extensive mineral trapping of CO.sub.2. This mineralization is a mechanism for reducing the mobility of CO.sub.2, preventing it from migrating out of the storage formation. However, the process may also alter the porosity and permeability of the rock, potentially affecting fluid flow and the integrity of the storage reservoir over time. In this context, supercritical CO.sub.2-driven brine carbonation in anhydrite-rich formations is a promising method for carbon capture and storage (CCS), offering a secure, long-term solution by converting CO.sub.2 into geochemically stable mineral forms.
(109) In some embodiments, the interaction duration of brine solution and carbon dioxide in the subterranean anhydrite-rich formation may be varied from 10-20 days, 10-30 days, 20-30 days, 25-30 days and 10-25 days. In preferred embodiments, the interaction duration of brine solution and carbon dioxide in the subterranean anhydrite-rich formation is 15 days. The interaction duration may be longer than this period, but a longer interaction duration may not be useful if carbonation is no longer occurring. The method includes sequestering the carbon dioxide in the subterranean anhydrite-rich formation in the form of one or more minerals. Carbon dioxide (CO.sub.2) is sequestered in a subterranean anhydrite-rich formation in the form of one or more stable minerals. The minerals include one or more of calcite, siderite, feldspar and barite. This process leverages the natural geochemical reactions between injected CO.sub.2 and the surrounding mineral-rich environment to convert the gas into solid forms, such as carbonates. When CO.sub.2 is injected into the deep formation, it often exists in its supercritical state, allowing it to dissolve in the formation brine. In anhydrite-rich formations, the dissolution of anhydrite (CaSO.sub.4) releases calcium ions (Ca.sup.2+) into the brine. These calcium ions react with the dissolved CO.sub.2, leading to the precipitation of calcium carbonate (CaCO.sub.3) or similar carbonate minerals. This mineral trapping is a main mechanism of the CO.sub.2 sequestration, as it locks the gas into a stable, solid form that cannot easily migrate or escape from the reservoir. This sequestration as stable, solid minerals is preferable to storing as other forms of CO.sub.2, which are prone to leakage or escape.
(110) In some embodiments, a final calcite concentration of the anhydrite-rich formation increases by at least 1 wt. %, 1.25 wt. %, 1.5 wt. %, 1.75 wt. %, 2 wt. %, 2.25 wt. %, compared to an initial calcite concentration of the anhydrite-rich formation before the reacting. In a preferred embodiment, the final calcite concentration of the anhydrite-rich formation increases from 2.2 wt. % to 4.4 wt. % compared to an initial calcite concentration of the anhydrite-rich formation before the reacting.
(111) In some embodiments, a final dolomite concentration of the anhydrite-rich formation decreases by at least 1 wt. %, 2 wt. %, 3 wt. %, 4 wt. %, 5 wt. % compared to an initial dolomite concentration of the anhydrite-rich formation before the reacting. In a preferred embodiment, the final dolomite concentration of the anhydrite-rich formation decreases from 7.8 wt. % to 6.4 wt. % compared to an initial dolomite concentration of the anhydrite-rich formation before the reacting.
(112) In some embodiments, a final feldspar concentration of the anhydrite-rich formation increases by at least 0.1 wt. %, 0.2 wt. %, 0.3 wt. %, 0.4 wt. %, 0.5 wt. % compared to an initial feldspar concentration of the anhydrite-rich formation before the reacting. In a preferred embodiment, a final feldspar concentration of the anhydrite-rich formation increases from 0.2 to 0.5 wt. % compared to an initial feldspar concentration of the anhydrite-rich formation before the reacting.
(113) In some embodiments, a final barite concentration of the anhydrite-rich formation increases by at least 0.1 wt. %, 0.3 wt. %, 0.5 wt. %, 0.7 wt. %, 0.9 wt. %, 1.1 wt. %, 1.3 wt. %, 1.5 wt. % compared to an initial barite concentration of the anhydrite-rich formation before the reacting. In a preferred embodiment, a final barite concentration of the anhydrite-rich formation increases by at least 0.9 wt. % compared to an initial barite concentration of the anhydrite-rich formation before the reacting.
(114) In some embodiments, after the reacting the subterranean anhydrite-rich formation has a greater than 150%, 160%, 170%, 240%, 250%, 260% increase in total carbon compared to an initial amount of total carbon in the subterranean anhydrite-rich formation before the reacting wherein the reaction time is 15 days. In a preferred embodiment, increase in total carbon (TC) content of up to 177% for the CO.sub.2-brine treatment and 266% for the CO.sub.2-brine+BaCl.sub.2 treatment wherein the reaction time is 15 days.
(115) In some embodiments, after the reacting, brine is recovered from the anhydrite rich formation as brine that is substantially free of dissolved CO.sub.2. Also, any recovered brine is substantially free of hydrocarbons.
EXAMPLES
(116) The following examples provide the method 50 of carbon dioxide (CO.sub.2) storage. The examples are provided solely for illustration and are not to be construed as limitations of the present disclosure, as many variations thereof are possible without departing from the spirit and scope of the present disclosure.
Example 1: FluidsBrine and CO.SUB.2
(117) The brine solution was prepared using five salts sodium chloride (NaCl), calcium chloride (CaCl.sub.2), magnesium chloride (MgCl.sub.2), sodium bicarbonate (NaHCO.sub.3), and sodium sulfate (Na.sub.2SO.sub.4). The listed salts were combined in specific proportions to create a synthetic brine solution that closely mimicked the ionic composition of seawater typically found in the Arabian Gulf. High-purity carbon dioxide (CO.sub.2) at 99.9% was employed as the gas phase for brine carbonation and interactions with anhydrite. The ionic composition of the seawater is detailed in Table 1.
(118) TABLE-US-00001 TABLE 1 Ionic composition of Arabian gulf seawater Ions Concentration (ppm) Ca.sup.2+ 650 Mg.sup.2+ 2,110 SO.sub.4.sup.2 4,290 Cl.sup. 32,200 HCO.sup.3 120 Total dissolved solids 57,670
Example 2: Experimental Procedure
(119) The described experimental procedure was carried out using anhydrite-rich rock and a series of experiments were performed to characterize rock. The initial gas porosity and permeability of the rock sample were measured at 1.46% and 0.068 mD, respectively. The rock was then cut into smaller samples with dimensions measuring 8 mm and 15 mm in diameter and each having a thickness of about 7 mm. The (78) mm samples were used for micro-computed tomography (micro-CT) and scanning electron microscopy electron dispersive X-ray spectroscopy (SEM-EDS) analysis while the (715) mm samples were used for other measurements pre-experiments and post-experiments. To assess the bulk mineral composition of the rock, X-ray diffraction (XRD) analysis was performed. The primary constituent of the sample was identified as calcium sulfate (CaSO.sub.4), with amounts of other minerals such as quartz, dolomite, calcite, and the scapolite group. The initial properties of the rock before undergoing CO.sub.2-brine treatments measured: Initial evaluations included measurements of the mineralogical and elemental compositions via XRD and X-ray fluorescence (XRF), Fourier transform infrared (FTIR) spectroscopy, micro-CT imaging, and total carbon (TC) content. The FTIR analysis provides information on the changes in functional groups and modifications that occurred during the CO.sub.2-brine treatments. Micro-CT scans were conducted to quantify the dissolution/precipitation and evaluate the changes in porosity following the interactions. Additionally, TC analysis was employed to determine the carbon content of the rock corresponding to CO.sub.2 mineralization. The subsequent step involved exposing smaller rock samples to a supercritical CO.sub.2-saturated brine treatment under high-pressure high-temperature (HPHT) conditions in the presence and absence of BaCl.sub.2, respectively. The addition of BaCl.sub.2 is to enforce the concurrent precipitation of barium sulfate and carbonate while maintaining a balanced reaction that involves the dissolution of rock and the precipitation of carbonate minerals. This addition of BaCl.sub.2 is a controlled step designed to influence the CO.sub.2 mineralization processes during the rock-CO.sub.2-brine interaction, thus enhancing the dissolution/precipitation and overall dynamics of the reactions. The treatments were conducted in a 300 ml static reactor, in which about 75 percent by volume (vol. %) was filled with brine while 25 vol. % was occupied by supercritical CO.sub.2. The interaction duration is fifteen days, with operating conditions set at a temperature of 333 K and a pressure of 104 bar while collecting effluent samples at predetermined intervals.
(120) The series of assessments were repeated post CO.sub.2-brine treatment. The assessments include the measurement of the mineralogical composition of the rock, micro-CT imaging, XRF, FTIR, SEM-EDS, and carbon content for both rock and effluent fluids. Moreover, the same set of procedures was replicated on the other smaller rock sample, adding 2.08 percent by weight (wt. %), equivalent to 0.1 molar (M) BaCl.sub.2 salt, to the brine used in the initial CO.sub.2-brine interaction. It may be noted that the solution was filtered before use in the experiments.
Example 3: Geochemical Analysis
(121) To monitor the geochemical changes, 2 ml samples of the effluent were collected approximately three times per week (making a total of 14 ml for seven samples) during the anhydrite-CO.sub.2-brine interactions. While the periodic collection of effluent samples may slightly alter the rock-CO.sub.2-brine ratio in the reactor and potentially influence the carbonation process, it should be noted that the total sampled volume, approximately 6% of the initial brine volume, has no impact on the reaction temperature. Moreover, the sampling procedure does not lead to a pressure decrease. The final pressure at the end of the experiment remains at 101 bar, indicating only a minor 3-bar drop. A required volume of the collected effluent samples was diluted by a factor of 100 using deionized water with a specific resistance of 18.2 mega ohms centimetres (M-cm) at a temperature of 25 C. This dilution was necessary to allow the samples to fall within the linear range of a Metrohm compact IC flex-compact ion chromatography (IC) system. After completing the IC, a series of peaks corresponding to each ion present in the effluent sample was generated. The area under each peak was considered to be directly proportional to the concentration of the respective ions in the fluid. This proportional relationship was established by comparing the peak areas to known standards with predetermined concentrations. The analysis of total inorganic carbon (TIC) for carbonate and bicarbonate ions was conducted using flow injection TOC analyser. The pH of both the initial brines and the effluent was determined using a pH/conductivity benchtop multi-parameter meter.
(122) Anhydrite, a mineral composed of calcium sulfate (CaSO.sub.4), may be favorable for mineral carbonation. Carbonation involves the capture and storage of carbon dioxide (CO.sub.2) by reacting it with minerals to form stable carbonate compounds, effectively removing CO.sub.2 from the atmosphere and storing it in a solid form within subsurface geological formations.
(123) Assessment of Modification of Minerals
(124) The XRD analysis of the rock samples exposed to various treatments revealed changes in their mineral composition. Anhydrite is chemically reactive and can readily dissolve in water. When CO.sub.2 is injected into an underground reservoir such as a depleted oil or gas reservoir or a saline aquifer, or mixed with water and brought into contact with anhydrite-rich rocks or minerals, it can react with the anhydrite to form carbonates including, but not limited to, CaCO.sub.3 and FeCO.sub.3, sulfates (SO.sup.2), and other rock minerals depending on the fluids composition and rock mineral impurities. The resulting carbonates are stable solid minerals that do not readily dissolve. These minerals can precipitate within the rock formations, effectively locking away the carbon dioxide in a geological reservoir. These reactions can be represented as follows:
CaSO.sub.4(s)Ca.sup.2+(aq)+SO.sub.4.sup.2(aq)[bull rock dissolution]
CaSO.sub.4(s)+CO.sub.2+H.sub.2OCaCO.sub.3+2H.sup.++SO.sub.4.sup.2(aq)[carbonation of anhydrite]
Ba.sup.2+(aq)+SO.sub.4.sup.2(aq)BaSO.sub.4[formation of barite]
Fe.sup.2++CO.sub.3.sup.2FeCO.sub.3(s)[formation of siderite]
CaMg(CO.sub.3).sub.2(s)Mg.sup.2++Ca.sup.2++2CO.sub.3.sup.2[dissolution of dolomite]
(125) As shown in
(126) Upon CO.sub.2-brine interaction, a pronounced shift in mineral composition became evident. The most notable transformation occurred in calcite, which increased from 2.2 wt. % to 4.1 wt. %, and dolomite, which decreased from 7.8 wt. % to 6.4 wt. %. Notably, the NaCl-scapolite (marialite) decreased from 2.6 wt. % to 0.2 wt. %, while CaCO.sub.3-scapolite (meionite) increases from 0.2 wt. % to 1.2 wt. %. Moreover, the scapolite group increased from 0.6 wt. % to 1.4 wt. %. This shows a shift in the composition of minerals after CO.sub.2-brine interaction. In addition, there were increases in the proportions of feldspar and siderite, shifting from 0.2 wt. % to 0.5 wt. % and 0.1 wt. % to 0.3 wt. %, respectively. This altered mineral composition in the CO.sub.2-brine treated sample strongly suggests the formation of carbonate minerals, with an increase in the presence of CO.sub.2. Further, it indicates a slight decrease in aragonite and a decline in the weight percentage of dolomite, which implies its dissolution from the rock under these conditions. In the case of the CO.sub.2-brine plus BaCl.sub.2 treated sample, the prominent alteration occurred in calcite as it increased from 2.2 wt. % to 4.5 wt. %. In contrast, the composition of dolomite showed a marked reduction from 7.8 wt. % to 4.5 wt. %. The transformation in the scapolite endmembers is not as prominent as in the case of CO.sub.2-brine treatment. The meionite increases from 0.2 wt. % to 0.4 wt. %, while the CaSO.sub.4 endmember slightly increased from 0.3 wt. % to 0.6 wt. %. Furthermore, there was a slight increase in feldspar from 0.2 wt. % to 0.4 wt. %, and the emergence of barite (0.9 wt. %). These observations suggest mineralization and the formation of calcite, barite, and transformation of scapolite endmembers in response to CO.sub.2-brine plus BaCl.sub.2 treatment. Meanwhile, the decrease in the weight percentage of dolomite implies its dissolution during exposure to this fluid and conditions. The formation of carbonates favors carbonation, while the dissolution of dolomite promotes de-carbonation. The net consumption of CO.sub.2 in the process is further discussed in the subsequent sections. These changes in mineral composition provide valuable insights into how different treatments affect the mineralogical makeup of the rock, which can have implications for various geological and engineering applications related to CO.sub.2 storage. This minerals transformation process helps to store the captured CO.sub.2 securely over geological timescales. Once CO.sub.2 is mineralized into carbonates, it is no longer in a gaseous form and is thus stable and immobile. This provides a long-term CO.sub.2 storage solution, as the carbonate minerals may persist for thousands or even millions of years without releasing the stored CO.sub.2 back into the atmosphere.
(127) XRF Analysis for Elemental Composition
(128) The principal elements including the analyzed rock are calcium and sulfur, with smaller quantities of silicon, aluminum, iron, and magnesium. The XRF analysis of the sample following exposure to supercritical CO.sub.2-saturated brine indicate that the elemental composition remained relatively consistent with the original composition, except for the observable higher intensity of silicon and chlorine, as shown in
(129) SEM Morphology
(130) The SEM images provide insights into the structural changes within the three different rock samples including the untreated rock, the rock exposed to supercritical CO.sub.2-saturated brine, and the rock interacted with supercritical CO.sub.2-saturated brine in the presence of BaCl.sub.2. The SEM images shown in
(131) SEM-EDS Analysis
(132) The EDX spectroscopy elemental mapping focuses on the elements present. The results of the EDX spectroscopy reveal that the untreated rock primarily consists of CaSO.sub.4 with scattered areas of carbonates, as shown in
(133) The analysis of the CO.sub.2-brine treated rock revealed notable alteration in minerals.
(134)
(135) FTIR Analysis
(136) The spectral domain within the range of 4000 cm.sup.1 to 500 cm.sup.1 was analyzed in order to identify one or more species formed after CO.sub.2-brine interactions. The analysis of FTIR spectra is shown in
(137) The FTIR results provide insights on the mineralogical transformations that occurred during the CO.sub.2-brine treatments and their subsequent impact on the composition of the samples. The presence of absorption bands within the range of 2800 cm.sup.1 to 3000 cm.sup.1 is useful for indicating the presence of the scapolite group. The absorption peaks at 2885 cm.sup.1 and 2962 cm.sup.1 are attributed to the frequency doubling peak of CO.sub.3.sup.2 antisymmetric stretching vibration which is related to the content of scapolite. Meanwhile, the band near 2850 cm.sup.1 is linked to calcite, presumably a CaCO.sub.3-scapolite end-member as shown in the XRD section. The absorption peak at 1001 cm.sup.1 is caused by an aluminosilicate, while the band near 1004 cm.sup.1 corresponds to silica vibration.
(138) Geochemical Analysis
(139) CO.sub.2 is an active gas that can initiate the dissolution and precipitation of minerals. In addition, CO.sub.2 may dissolve in water to generate carbonic acid (H.sub.2CO.sub.3), which may further dissociate to bicarbonate and carbonate ions according to the following equilibrium reactions:
CO.sub.2+H.sub.2OH.sub.2CO.sub.3[Brine carbonation]
H.sub.2CO.sub.3H.sup.++HCO.sub.3.sup.[Bicarbonate]
H.sup.++HCO.sub.3.sup.2H.sup.++CO.sub.3[Carbonate ion formation]
(140) The carbonates and bicarbonates are collectively categorized as total inorganic carbon (TIC) content in the interacting fluids.
(141) CO.sub.2-Brine Rock Interactions
(142) Rock-fluid interactions have an impact on the ion concentration of the effluent brine.
(143) decreasing concentration of Cl ion is also noticeable, confirming that both Na and Cl were adsorbed by the rock or precipitated on the rock. Further, a dissolution of calcium sulfate of the rock released calcium ions into the solution, this is evident from the observed increase in Ca and SO.sub.4 ions concentration of the effluent fluid, as shown in
CO.sub.2-Brine and BaCl.sub.2 Rock Interactions
(144) The ion concentrations of the effluent including Ca, Na, and Ba ions, along with their initial concentrations, are presented in
(145) precipitation of barium sulfate as seen in the XRD as discussed earlier.
(146) Unlike sulfate ions, TIC concentration shows a consistent increase over time. This behavior is due to the carbonation of CO.sub.2 in brine. When CO.sub.2 dissolves in water, it forms carbonic acid. As described above, carbonic acid, in turn, may dissociate into bicarbonate ions and carbonate ions. As CO.sub.2 continuously dissolves in the brine during the interactions, it leads to the gradual accumulation of the carbonate and bicarbonate species. This increase leads to a decrease in the pH level of the brine. The acidity is a result of the formation of hydrogen ions during CO2 carbonation. The pH measurement was conducted on the effluent samples immediately after collection, before degassing and cooling.
(147) Micro-CT (-CT) Analysis
(148) -CT scans of two similar anhydrite-rich mini-plugs were performed pre and post exposure to CO.sub.2-brine and CO.sub.2-brine plus BaCl.sub.2 using the Zeiss Versa 500 -CT equipment. The measured dimensions and mass for the two samples before and after CO.sub.2-brine interactions are listed in Table 2. Comparing the masses before and after interaction, the CO.sub.2-brine treatment showed a more substantial change with a decrease of up to 7.37%, whereas exposure to CO.sub.2-brine with added BaCl.sub.2 exhibited a smaller decrease of 2.45%. However, relying solely on mass changes for a precise conclusion is limited. This implies the potential for either higher dissolution in CO.sub.2-brine treatment than CO.sub.2-brine plus BaCl.sub.2 or lower precipitation in CO.sub.2-brine compared to CO.sub.2-brine plus BaCl.sub.2 treatment. This observation aligns with the findings in the SEM and geochemical analysis signifying higher dissolution in the CO.sub.2-brine treatment.
(149) TABLE-US-00002 TABLE 2 Dimensions and mass of the samples before and after CO.sub.2-brine interactions Initial Dry mass Average dry after Change Length diameters mass interaction in Treatment (mm) (mm) (g) (g) mass (g) CO.sub.2-brine 7.12 8.4 0.6815 0.6313 0.0502 CO.sub.2-brine + BaCl.sub.2 7.25 8.5 0.6762 0.6581 0.0166
(150) An explanation of these changes may be described through -CT analysis. In order to quantify the change that resulted from dissolution and precipitation, the -CT scans of the rocks pre and post CO.sub.2-brine exposure were analyzed. The voxel resolution was set to 4.5 micrometers (m) for all the scans while the entire sample is included in the field of view. An X-ray tube voltage of 140 kilovolts (kV) and target current of 64 microampere (A) was used, and 2401 projections were obtained with an exposure time of 3.4 sec. A filtered back projection (FBP) reconstruction algorithm was used to generate the 3D tomogram from the X-ray projections while also performing center shift, beam hardening and sample drift corrections. These images were computationally assessed using PerGeos software (FEI-ThermoFisher) to evaluate the changes in the mineral matrix before and after treatment.
(151) The image processing involved first aligning the orientations of the set of scans for each sample pre and post treatment. This was followed by registering the two images using normalized mutual information as the metric while keeping the image of the untreated sample as a reference. The transformed image was resampled using Lanczos interpolation. The registered images were compared to visually identify the dissolved and precipitated regions.
(152) TABLE-US-00003 TABLE 3 Volume fractions of the segmented labels with computed amount of grain precipitation and dissolution Dissolved region as Precipitated region percentage of as percentage total volume of total volume of untreated of untreated Treatment rock sample rock sample CO.sub.2-brine 9.85% 0.91% CO.sub.2-brine + BaCl.sub.2 2.35% 6.04%
Analysis of Total Carbon (TC) Content
(153) The TC content (combining both organic and inorganic) of the rock power was assessed using TOC equipment and the results obtained are shown in
(154) Upon treating the sample with supercritical CO.sub.2-brine with added BaCl.sub.2, a higher TC content of 1.275 wt. % (266.4% increase in TC) was recorded. The increase demonstrates enhanced CO.sub.2 mineralization in comparison to the sample treated solely with CO.sub.2-brine. While the addition of BaCl.sub.2 enhances CO.sub.2 mineralization, it may reduce the porosity in comparison to cases without BaCl.sub.2. The formation of barite, facilitated by the addition of BaCl.sub.2, may occupy some pore spaces that might otherwise be available for storing other minerals and may impact the available pore space for storing minerals formed during the treatment.
(155) The present disclosure describes the method 50 for CO.sub.2 storage. As described, carbon mineralization may be a geologically stable and environmentally-friendly method. By converting gaseous CO.sub.2 into solid minerals within subsurface rock formations, the present disclosure may offer an effective means of safely storing CO.sub.2. Further, method 50, as described herein, delves into the mechanisms and potential of anhydrite-CO.sub.2-brine interactions for carbon storage in anhydrite-bearing reservoirs. The results presented herein were obtained through experiments conducted over fifteen days, including mineral transformation within a static reactor under high-temperature and high-pressure conditions. The results revealed that anhydrite, when exposed to supercritical CO.sub.2-saturated brine, undergoes a mineral transformation, leading to the formation of stable minerals like calcite, siderite, feldspar, and in the presence of barium chlorite and barite. Analytical results showed that the untreated rock had about 0.348 wt. % total TC, and exposure to CO.sub.2-brine treatment resulted in a 176.7% increase in TC. Furthermore, treating the sample with supercritical CO.sub.2-saturated brine with added BaCl.sub.2 led to a higher TC content of 1.275 wt. %.
(156) Numerous modifications and variations of the present disclosure are possible in light of the above teachings. It is, therefore, to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.