Carbon dioxide mineralization storage method based on reaction interface reconstruction

Abstract

The invention relates to the technical field of carbon dioxide sequestration, and provides a carbon dioxide mineralization sequestration method based on reaction interface reconstruction, which comprises the following steps: S1, injecting a hydroxyethyl cellulose solution into target deep volcanic rock formation water, and then injecting an activating fluid at a stepped flow rate to perform formation pretreatment, the deep volcanic rock pretreatment formation water is obtained; the activating fluid comprises ammonium fluoride, fluoboric acid, mixed acid, transition metal salt, an antioxidant and a solvent; and S2, carbon dioxide is injected into the deep volcanic rock pretreatment formation water, so that carbon dioxide mineralization and storage are carried out. According to the method, through interface reconstruction and catalytic acceleration, compared with a traditional method, the CO2 mineralization rate and the carbonate precipitation amount can be greatly increased, the generated carbonate rock is stable in property, and long-term geological sequestration of carbon is achieved.

Description

Technical Field

[0001] The present invention belongs to the technical field of carbon dioxide sequestration, and in particular relates to a method for mineralizing and sequestering carbon dioxide based on reaction interface reconstruction. Background Art

[0002] Carbon dioxide geological storage (CCS) is considered a key technology for achieving carbon neutrality. It primarily achieves long-term storage by injecting supercritical CO2 into geological structures such as oil and gas fields, saline aquifers, or unmineable coal seams. 13 Among these, deep volcanic rock (basalt / peridotite) mineralization storage holds the greatest potential due to its ability to permanently fix CO2 into carbonate minerals. By injecting a CO2-water mixture into basalt layers, over 95% of the CO2 can be converted into carbonate minerals within two years, making storage significantly safer than traditional structural storage.

[0003] However, deep volcanic rock (basalt / peridotite) mineralization storage has the following problems: (1) Storing 1 ton of CO2 requires 25 tons of water, which is difficult to promote in arid areas; (2) The mineralization rate is limited: the dissolution rate of silicate minerals under natural conditions is only 10 -12 ~10 -10 mol / m 2 / s, resulting in an overall storage period of several decades; (3) Risk of pore blockage: The carbonate precipitation rate is much higher than the silicate dissolution rate, which can easily block the fracture channel and reduce the long-term sealing efficiency.

[0004] For example, the Chinese patent with publication number CN116553060A discloses a method for the combined storage of CO2 in deep and shallow strata. First, a stratum is selected according to certain conditions, and then a well is laid in a certain manner in combination with the selected stratum, and then the CO2 is stored. The method of the present invention makes full use of deep and shallow geological bodies to improve the storage efficiency; and the deep saline water layer is combined with the shallow basalt, and the shallow basalt forms a precipitate after carbon fixation, which can also effectively prevent the CO2 sealed in the deep saline water layer from leaking to the shallow surface; in addition, the deep saline water is utilized in situ, which solves the environmental problems caused by the extraction of saline water and saves the high cost of water treatment. However, the geological combination of "deep saline water layer + shallow basalt" must be met at the same time. At the same time, the saline water and CO2 naturally diffuse and mix in the cracks, and the mineralization rate is low.

[0005] Therefore, based on the above description, it is urgent to improve the CO2 mineralization rate and CO2 storage rate in the process of carbon dioxide mineralization and storage. Summary of the Invention

[0006] In view of the above-mentioned deficiencies in the prior art, the present invention aims to provide a method for carbon dioxide mineralization storage based on reaction interface reconstruction. Through interface reconstruction and catalytic acceleration, the CO2 mineralization rate and carbonate precipitation amount can be greatly improved compared with traditional methods, and the generated carbonate rock has stable properties, thus achieving long-term geological storage of carbon. At the same time, the mineralization reaction reduces the Ca in the formation water. 2+ / Mg 2+ concentration, improve deep water quality, and have the dual value of carbon emission reduction and geological environment optimization, which is in line with the "dual carbon" goals and sustainable development needs.

[0007] The present invention is achieved through the following technical solutions:

[0008] A method for mineralization storage of carbon dioxide based on reaction interface reconstruction comprises the following steps:

[0009] S1. Injecting a hydroxyethyl cellulose solution into target deep volcanic formation water, and then injecting an activated fluid at a stepped flow rate to pretreat the formation, thereby obtaining deep volcanic pretreated formation water; the activated fluid comprises: ammonium fluoride, fluoroboric acid, a mixed acid, a transition metal salt, an antioxidant, and a solvent;

[0010] S2. Injecting carbon dioxide into the deep volcanic rock pre-treated formation water to mineralize and store carbon dioxide.

[0011] Step S1 is the formation activation pretreatment. Hydroxyethyl cellulose solution is injected. Hydroxyethyl cellulose acts as a thickener to increase fluid viscosity, slow down the flow rate of the activated fluid, and ensure full contact with the volcanic rock. At the same time, gelation temporarily blocks the high permeability area, forcing the activated fluid into the low permeability area and expanding the reaction interface. The activated fluid is injected as a key medium for the reconstruction of the micro-nano structure of the formation. Through the synergistic effect of multiple components, the rock pore topology is transformed, the catalytic interface is constructed in situ, and the reaction environment is maintained for a long time. The specific functions of each component of the activated fluid are as follows:

[0012] Ammonium fluoride and fluoboric acid synergistically modify mineral surfaces: the fluoride ions released by ammonium fluoride (0.20-0.30 mol / L) and fluoboric acid (0.03-0.08 mol / L) react with formation minerals, changing their surface hydrophilicity and chemical activity. At the same time, the borate ions in fluoboric acid destroy the mineral lattice through complexation reaction, creating conditions for subsequent acid dissolution reaction and improving formation permeability.

[0013] Mixed acid (phosphoric acid + phytic acid) efficiently dissolves minerals and regulates pore structure: A mixed acid (0.08-0.18 mol / L) composed of phosphoric acid and phytic acid in a molar ratio of (1-3):1 can not only dissolve insoluble minerals (such as Ca / Mg silicates in peridotite and basalt) through the strong acidity of phosphoric acid, but also utilize the polyhydroxy complexing ability of phytic acid to stabilize the dissolved products and avoid secondary precipitation. At the same time, it forms porous microcracks on the mineral surface, increasing reaction sites.

[0014] Transition metal salt (ferrous chloride + cerium chloride) catalyzes the mineralization reaction: ferrous chloride and cerium chloride are mixed in a molar ratio of (2-5):1 (0.02-0.08 mol / L), Fe 2+ With Ce 3+ Can be used as a catalyst to accelerate the reaction of CO2 and Ca 2+ / Mg 2+ The carbonation reaction rate of Ce 3+ It forms a stable catalytic interface by complexing with the hydroxyl groups on the mineral surface, maintaining the reaction activity for a long time.

[0015] Antioxidants (ascorbic acid + sodium dithionite) protect the formation structure: Ascorbic acid and sodium dithionite are combined in a molar ratio of (5-15):1 (0.001-0.003 mol / L), which can effectively inhibit oxidation reactions caused by oxygen or high-valent metal ions in the formation, prevent mineral structure damage and by-product generation, and maintain the stability of the activated fluid and the integrity of the formation.

[0016] By adding antioxidants, the formation can be protected from damage by oxidation reactions while maintaining the stability of the activated fluid. Step S2 is the stage of carbon dioxide mineralization and storage, which is mainly achieved by injecting carbon dioxide into pretreated formation water. Step S1 changes the surface properties and chemical environment of the formation rock through the injection of activated fluid, providing a favorable reaction interface for the carbon dioxide mineralization reaction in step S2. The microcracks that can be formed during the pretreatment process increase the permeability and reaction area of ​​the rock, which is conducive to the deep penetration and reaction of carbon dioxide. At the same time, by adjusting the composition and injection method of the activated fluid in step S1, favorable reaction conditions are created for the carbon dioxide storage in step S2. For example, by dissolving the mineral components in the rock to release reaction sites, using transition metal salts as catalysts to accelerate the reaction, etc.

[0017] By injecting carbon dioxide into deep volcanic rocks (especially ultramafic rocks and mafic rocks), carbon dioxide dissolves in groundwater and can react with excess Ca in the formation water of deep volcanic rocks composed of peridotite and basalt. 2+ and Mg 2+ Ion reaction, forming carbonate precipitates, effectively reducing the Ca content in deep volcanic rock formation water 2+ and Mg 2+At the same time, the injected carbon dioxide has been stored in deep volcanic rocks through the formation of carbonate rocks, achieving carbon sequestration.

[0018] Furthermore, in the activation fluid, the molar concentration of ammonium fluoride is 0.20-0.30 mol / L, the molar concentration of fluoroboric acid is 0.03-0.08 mol / L, the molar concentration of the mixed acid is 0.08-0.18 mol / L, the molar concentration of the transition metal salt is 0.02-0.08 mol / L, and the molar concentration of the antioxidant is 0.001-0.003 mol / L.

[0019] Furthermore, the mixed acid consists of phosphoric acid and phytic acid, and the molar ratio of the phosphoric acid to the phytic acid is (1-3):1.

[0020] Furthermore, the phytic acid is phytic acid, and its chemical formula is C6H 18 O 24 P6, exists in the form of free acid, with a purity of ≥85%.

[0021] Furthermore, the transition metal salt consists of ferrous chloride and cerium chloride, and the molar ratio of the ferrous chloride to the cerium chloride is (2-5):1.

[0022] Furthermore, the antioxidant consists of ascorbic acid and sodium dithionite, and the molar ratio of the ascorbic acid to the sodium dithionite is (5-15):1.

[0023] Furthermore, the mass concentration of the hydroxyethyl cellulose solution is 0.8-1.2%, and the injection volume is 0.4-0.6PV.

[0024] Furthermore, in step S1, injecting the activation fluid at a stepped flow rate includes:

[0025] The first 30% pore volume injection stage: the flow rate of the activation fluid is 0.05-0.15m 3 / h;

[0026] The remaining 70% pore volume injection stage: the flow rate of the activation fluid is 0.20~0.30m 3 / h.

[0027] In the first 30% pore volume injection stage of the activated fluid injection at a stepped flow rate, the flow rate is controlled at 0.05-0.15 m 3 / h, inject at a lower flow rate to ensure that the activated fluid is fully mixed and reacted with the deep volcanic formation water. This helps the activated fluid to penetrate evenly into the formation and avoid fluid short-circuiting and uneven reaction caused by too fast injection. During the injection stage of the remaining 70% pore volume, the flow rate is increased to 0.20-0.30m 3 / h. Based on the initial reaction, the flow rate is increased to flush and carry more dissolved products and activated fluid into the deep formation. This helps to further expand the reaction interface, improve the dissolution efficiency of minerals and the utilization rate of activated fluids.

[0028] Furthermore, after the activation fluid is injected in step S1, the well is shut in for 36 to 48 hours, and the pressure change is monitored during the shut-in period. When the pressure drops by more than 8%, it is determined that microcracks are generated.

[0029] The well is shut in for 36 to 48 hours, allowing the activated fluid to fully react with the formation, further dissolving the minerals and forming a network of microcracks. Simultaneously, monitoring pressure changes can be used to assess the formation of microcracks. A pressure drop of more than 8% typically indicates sufficient microcracks have formed in the formation, providing pathways for subsequent CO2 injection.

[0030] Furthermore, in step S2, the carbon dioxide injection is performed in a pulsed manner, and a single pulse cycle includes:

[0031] High-pressure period: inject carbon dioxide at a pressure of 12-18 MPa for 3-5 hours;

[0032] Pressure relief period: reduce the pressure to 4-6 MPa at a rate of 1.5-2.5 MPa / min;

[0033] Low-pressure period: injection of sodium bicarbonate solution pre-saturated with carbon dioxide;

[0034] Equilibrium period: shut down the well for 0.8 to 1.2 hours.

[0035] During the high-pressure phase of pulsed CO2 injection, the pressure ranges from 12 to 18 MPa. Injecting CO2 at high pressure allows it to exist in a supercritical state, resulting in higher solubility and diffusivity. This helps the CO2 penetrate deeper into the formation and react with mineral ions therein. The duration of the injection is 3 to 5 hours, ensuring sufficient time for the CO2 to fully react with mineral ions in the formation and form carbonate precipitation.

[0036] During the depressurization phase, the rate of depressurization is 1.5-2.5 MPa / min. This rapid depressurization can induce pressure oscillations in the formation, further expanding the microfracture network. This helps increase the contact area between CO2 and minerals in the formation, improving mineralization efficiency. The depressurization range is 4-6 MPa. The pressure range after depressurization should be low enough to avoid excessive pressure damage to the formation while maintaining the mobility of CO2 in the formation.

[0037] During the low pressure period, a sodium bicarbonate solution pre-saturated with CO2 is injected, which can provide HCO3 - ions, and Ca2+ Mg 2+ The plasma reaction generates carbonate precipitation. At the same time, the pre-saturated CO2 solution ensures that no additional gas pressure is introduced during the injection process, which helps promote the rapid precipitation of carbonates and improve mineralization efficiency.

[0038] During the equilibrium period, the well is shut in for 0.8 to 1.2 hours, which allows the formation enough time to stabilize the pressure, temperature, and chemical environment, ensuring the complete formation of carbonate precipitation, helping to consolidate the mineralization effect, and improving sealing efficiency and stability.

[0039] The beneficial effects of the present invention are:

[0040] (1) Through the combined technology of "thickening temporary plugging-gradient transformation-fracture induction" in the formation pretreatment stage, the bottlenecks of uneven fluid distribution and limited reaction interface in traditional methods are broken through: the viscosity control and temporary plugging effect of hydroxyethyl cellulose solution are used to force the activated fluid to penetrate evenly into the entire formation, and the reaction interface is expanded from the high permeability zone to the low permeability area; the multiple components of the activated fluid synergistically dissolve minerals, construct catalytic interfaces and form a micro-fracture network, which significantly increases the reaction area and active site density of the formation, provides sufficient contact space and efficient reaction conditions for CO2 mineralization, and fundamentally optimizes mass transfer and reaction kinetics.

[0041] (2) Through interface reconstruction and catalytic acceleration, the CO2 mineralization rate and carbonate precipitation amount can be greatly improved compared with traditional methods, and the generated carbonate rock has stable properties, realizing long-term geological storage of carbon.

[0042] (3) Targeting Ca-rich 2+ / Mg 2+ The deep volcanic rock (such as ultramafic rock and mafic rock) design of ions uses natural minerals in the formation as reaction media, without the need to add a large amount of additional chemical reagents, which is low cost and environmentally friendly.

[0043] (4) While storing CO2, reducing Ca in formation water through mineralization reaction 2+ / Mg 2+ concentration, improve deep water quality, and have the dual value of carbon emission reduction and geological environment optimization, which is in line with the "dual carbon" goals and sustainable development needs. DETAILED DESCRIPTION

[0044] To make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer are used. Where the manufacturer of the reagents or instruments is not specified, all are conventional products that can be purchased commercially.

[0045] Example 1

[0046] This embodiment provides a method for mineralization and storage of carbon dioxide based on reaction interface reconstruction, comprising the following steps:

[0047] S11. Injecting a hydroxyethyl cellulose solution into target deep volcanic formation water, and then injecting an activated fluid at a stepped flow rate to pretreat the formation, thereby obtaining deep volcanic pretreated formation water; the activated fluid comprises: ammonium fluoride, fluoroboric acid, a mixed acid, a transition metal salt, an antioxidant, and a solvent;

[0048] Wherein, in the activation fluid, the molar concentration of ammonium fluoride is 0.25 mol / L, the molar concentration of fluoroboric acid is 0.05 mol / L, the molar concentration of the mixed acid is 0.01 mol / L, the molar concentration of the transition metal salt is 0.06 mol / L, and the molar concentration of the antioxidant is 0.002 mol / L.

[0049] The mixed acid consists of phosphoric acid and phytic acid, and the molar ratio of the phosphoric acid to the phytic acid is 2:1.

[0050] The phytic acid is phytic acid, and its chemical formula is C6H 18 O 24 P6, exists in the form of free acid, with a purity of ≥85%.

[0051] The transition metal salt consists of ferrous chloride and cerium chloride, and the molar ratio of the ferrous chloride to the cerium chloride is 4:1.

[0052] The antioxidant consists of ascorbic acid and sodium dithionite, and the molar ratio of the ascorbic acid to the sodium dithionite is 10:1.

[0053] The mass concentration of the hydroxyethyl cellulose solution is 1%, and the injection volume is 0.5PV.

[0054] The step-by-step flow rate injection of activation fluid includes: the first 30% pore volume injection stage: the flow rate of activation fluid is 0.10m 3 / h; During the injection phase of the remaining 70% pore volume: the flow rate of the activated fluid is 0.25m 3 / h.

[0055] After the activation fluid was injected, the well was shut in for 40 hours, and the pressure changes were monitored during the shut-in period. When the pressure dropped by more than 8%, it was determined that microcracks had been generated.

[0056] S21. Injecting carbon dioxide into the deep volcanic rock pre-treated formation water to mineralize and store carbon dioxide.

[0057] Among them, carbon dioxide injection adopts pulse operation, and a single pulse cycle includes: high-pressure period: carbon dioxide is injected at a pressure of 16MPa and lasts for 4 hours; pressure relief period: the pressure is reduced to 5MPa at a rate of 2MPa / min; low-pressure period: sodium bicarbonate solution pre-saturated with carbon dioxide is injected; equilibrium period: the well is shut down for 1 hour.

[0058] Example 2

[0059] This embodiment provides a method for mineralization and storage of carbon dioxide based on reaction interface reconstruction, comprising the following steps:

[0060] S11. Injecting a hydroxyethyl cellulose solution into target deep volcanic formation water, and then injecting an activated fluid at a stepped flow rate to pretreat the formation, thereby obtaining deep volcanic pretreated formation water; the activated fluid comprises: ammonium fluoride, fluoroboric acid, a mixed acid, a transition metal salt, an antioxidant, and a solvent;

[0061] Wherein, in the activation fluid, the molar concentration of ammonium fluoride is 0.20 mol / L, the molar concentration of fluoroboric acid is 0.03 mol / L, the molar concentration of the mixed acid is 0.08 mol / L, the molar concentration of the transition metal salt is 0.02 mol / L, and the molar concentration of the antioxidant is 0.001 mol / L.

[0062] The mixed acid consists of phosphoric acid and phytic acid, and the molar ratio of the phosphoric acid to the phytic acid is 1:1.

[0063] The phytic acid is phytic acid, and its chemical formula is C6H 18 O 24 P6, exists in the form of free acid, with a purity of ≥85%.

[0064] The transition metal salt consists of ferrous chloride and cerium chloride, and the molar ratio of the ferrous chloride to the cerium chloride is 2:1.

[0065] The antioxidant consists of ascorbic acid and sodium dithionite, and the molar ratio of the ascorbic acid to the sodium dithionite is 5:1.

[0066] The mass concentration of the hydroxyethyl cellulose solution is 0.8%, and the injection volume is 0.4PV.

[0067] The step-by-step flow rate injection of activation fluid includes: the first 30% pore volume injection stage: the flow rate of the activation fluid is 0.05m 3 / h; during the injection phase of the remaining 70% pore volume: the flow rate of the activated fluid is 0.20m 3 / h.

[0068] After the activation fluid was injected, the well was shut in for 36 h, and the pressure changes were monitored during the shut-in period. Microcracks were determined to have formed when the pressure dropped by more than 8%.

[0069] S21. Injecting carbon dioxide into the deep volcanic rock pre-treated formation water to mineralize and store carbon dioxide.

[0070] Among them, carbon dioxide injection adopts pulse operation, and a single pulse cycle includes: high-pressure period: carbon dioxide is injected at a pressure of 12MPa and lasts for 5h; pressure relief period: the pressure is reduced to 6MPa at a rate of 1.5MPa / min; low-pressure period: sodium bicarbonate solution pre-saturated with carbon dioxide is injected; equilibrium period: the well is shut down for 0.8.

[0071] Example 3

[0072] This embodiment provides a method for mineralization and storage of carbon dioxide based on reaction interface reconstruction, comprising the following steps:

[0073] S11. Injecting a hydroxyethyl cellulose solution into target deep volcanic formation water, and then injecting an activated fluid at a stepped flow rate to pretreat the formation, thereby obtaining deep volcanic pretreated formation water; the activated fluid comprises: ammonium fluoride, fluoroboric acid, a mixed acid, a transition metal salt, an antioxidant, and a solvent;

[0074] Wherein, in the activation fluid, the molar concentration of ammonium fluoride is 0.30 mol / L, the molar concentration of fluoroboric acid is 0.08 mol / L, the molar concentration of the mixed acid is 0.18 mol / L, the molar concentration of the transition metal salt is 0.08 mol / L, and the molar concentration of the antioxidant is 0.003 mol / L.

[0075] The mixed acid consists of phosphoric acid and phytic acid, and the molar ratio of the phosphoric acid to the phytic acid is 3:1.

[0076] The phytic acid is phytic acid, and its chemical formula is C6H 18 O 24 P6, exists in the form of free acid, with a purity of ≥85%.

[0077] The transition metal salt consists of ferrous chloride and cerium chloride, and the molar ratio of the ferrous chloride to the cerium chloride is 5:1.

[0078] The antioxidant consists of ascorbic acid and sodium dithionite, and the molar ratio of the ascorbic acid to the sodium dithionite is 15:1.

[0079] The mass concentration of the hydroxyethyl cellulose solution is 1.2%, and the injection volume is 0.6 PV.

[0080] The step-by-step flow rate injection of activation fluid includes: the first 30% pore volume injection stage: the flow rate of the activation fluid is 0.15m 3 / h; during the injection phase of the remaining 70% pore volume: the flow rate of the activated fluid is 0.30m 3 / h.

[0081] After the activation fluid was injected, the well was shut in for 48 hours, and the pressure changes were monitored during the shut-in period. When the pressure dropped by more than 8%, it was determined that microcracks had been generated.

[0082] S21. Injecting carbon dioxide into the deep volcanic rock pre-treated formation water to mineralize and store carbon dioxide.

[0083] Among them, carbon dioxide injection adopts pulse operation, and a single pulse cycle includes: high-pressure period: carbon dioxide is injected at a pressure of 18MPa and lasts for 3 hours; pressure relief period: the pressure is reduced to 4MPa at a rate of 2.5MPa / min; low-pressure period: sodium bicarbonate solution pre-saturated with carbon dioxide is injected; equilibrium period: the well is shut down for 1.2 hours.

[0084] Comparative Example 1

[0085] This comparative example is modified as follows based on Example 1:

[0086] The activation fluid does not contain ammonium fluoride.

[0087] Comparative Example 2

[0088] This comparative example is modified as follows based on Example 1:

[0089] The activation fluid does not contain fluoboric acid.

[0090] Comparative Example 3

[0091] This comparative example is modified as follows based on Example 1:

[0092] The activation fluid does not contain mixed acids.

[0093] Comparative Example 4

[0094] This comparative example is modified as follows based on Example 1:

[0095] The activation fluid does not contain ferrous chloride.

[0096] Comparative Example 5

[0097] This comparative example is modified as follows based on Example 1:

[0098] The activation fluid does not contain cerium chloride.

[0099] Determination of CO2 storage rate, mineralization rate and Ca2+ storage rate after carbon dioxide mineralization and storage in Examples 1 to 3 and Comparative Examples 1 to 5 2+ / Mg 2+ Removal rate, the measurement results are shown in Table 1, the specific measurement method is as follows:

[0100] CO2 storage efficiency: The carbonate increment was measured by acid dissolution after core flooding experiments and calculated as: (mass of carbon in precipitated carbonate / mass of injected carbon) × 100%. The measurement standard is GB / T 29171-2012.

[0101] Mineralization rate: Real-time monitoring of HCO3 in effluent water - The concentration changes and the reaction rate per unit area are calculated using an online ion chromatograph.

[0102] Ca 2+ / Mg 2+ Removal rate: The difference in ion concentration before and after treatment was determined by atomic absorption spectrometry.

[0103] Table 1 CO2 storage rate, mineralization rate and Ca in the examples and comparative examples 2+ / Mg 2+ Removal rate

[0104]

[0105] As shown in Table 1, the CO2 storage rate in Examples 1 to 3 is 93-96%, and the mineralization rate is ≥1.8×10 -7 mol / m 2 / s, Ca 2+ / Mg 2+ The removal rate is 96-98%.

[0106] In Comparative Example 1, ammonium fluoride is missing. Ammonium fluoride is the main etching agent. After its absence, the amount of micropores generated is reduced, CO2 cannot effectively contact the mineral surface, and the mineralization rate decreases.

[0107] In Comparative Example 2, fluoroboric acid is missing, micropores are unevenly distributed, and there is no slow-release fluorine source, which leads to local over-etching. As a result, the mineralization rate is 58% lower than that of the embodiment, and the sealing rate is reduced by 26%.

[0108] In Comparative Example 3, there is no mixed acid, no crack network, the CO2 diffusion distance is limited, and the storage rate is only 35%.

[0109] In comparative example 4, ferrous chloride is missing, the catalytic function is lost, and there is no Fe 2+ Participates in the formation of pyrite, carbonate minerals are exposed and easily dissolved, and the mineralization rate decreases.

[0110] In Comparative Example 5, cerium chloride is missing, the catalyst layer is deactivated, and Ce 3+The lack of Fe(OH) leads to the oxidation of Fe(OH) to FeOOH, and the mineralization rate decreases.

[0111] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A method for mineralization and storage of carbon dioxide based on reaction interface reconstruction, characterized in that: The following steps are involved: S1. Injecting a hydroxyethyl cellulose solution into target deep volcanic formation water, and then injecting an activated fluid at a stepped flow rate to pretreat the formation, thereby obtaining deep volcanic pretreated formation water; the activated fluid comprises: ammonium fluoride, fluoroboric acid, a mixed acid, a transition metal salt, an antioxidant, and a solvent; S2. Injecting carbon dioxide into the deep volcanic rock pre-treated formation water to mineralize and store carbon dioxide.

2. The method for mineralization and storage of carbon dioxide based on reaction interface reconstruction according to claim 1, characterized in that: In the activation fluid, the molar concentration of ammonium fluoride is 0.20-0.30 mol / L, the molar concentration of fluoroboric acid is 0.03-0.08 mol / L, the molar concentration of the mixed acid is 0.08-0.18 mol / L, the molar concentration of the transition metal salt is 0.02-0.08 mol / L, and the molar concentration of the antioxidant is 0.001-0.003 mol / L.

3. The method for mineralization and storage of carbon dioxide based on reaction interface reconstruction according to claim 2, characterized in that: The mixed acid consists of phosphoric acid and phytic acid, and the molar ratio of the phosphoric acid to the phytic acid is (1-3):

1.

4. The method for mineralization and storage of carbon dioxide based on reaction interface reconstruction according to claim 3, characterized in that: The phytic acid is phytic acid, and its chemical formula is C6H 18 O 24 P6, exists in the form of free acid, with a purity of ≥85%.

5. The method for mineralization and storage of carbon dioxide based on reaction interface reconstruction according to claim 1, characterized in that: The transition metal salt consists of ferrous chloride and cerium chloride, and the molar ratio of the ferrous chloride to the cerium chloride is (2-5):

1.

6. The method for mineralization and storage of carbon dioxide based on reaction interface reconstruction according to claim 1, characterized in that: The antioxidant consists of ascorbic acid and sodium dithionite, and the molar ratio of the ascorbic acid to the sodium dithionite is (5-15):

1.

7. The method for mineralization and storage of carbon dioxide based on reaction interface reconstruction according to claim 1, characterized in that: The mass concentration of the hydroxyethyl cellulose solution is 0.8-1.2%, and the injection volume is 0.4-0.6PV.

8. The method for mineralization and storage of carbon dioxide based on reaction interface reconstruction according to claim 1, characterized in that: In step S1, the stepwise flow rate injection of the activation fluid includes: The first 30% pore volume injection stage: the flow rate of the activation fluid is 0.05-0.15m 3 / h; The remaining 70% pore volume injection stage: the flow rate of the activation fluid is 0.20~0.30m 3 / h.

9. The method for mineralization and storage of carbon dioxide based on reaction interface reconstruction according to claim 1, characterized in that: After the activation fluid is injected in step S1, the well is shut in for 36 to 48 hours, and the pressure changes are monitored during the shut-in period. When the pressure drops by more than 8%, it is determined that microcracks have been generated.

10. The method for mineralization and storage of carbon dioxide based on reaction interface reconstruction according to claim 1, characterized in that: In step S2, carbon dioxide injection is performed in a pulsed manner. A single pulse cycle includes: High-pressure period: inject carbon dioxide at a pressure of 12-18 MPa for 3-5 hours; Pressure relief period: reduce the pressure to 4-6 MPa at a rate of 1.5-2.5 MPa / min; Low-pressure period: injection of sodium bicarbonate solution pre-saturated with carbon dioxide; Equilibrium period: shut down the well for 0.8 to 1.2 hours.

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