Device for simulating carbon dioxide mineralization reaction under basalt stratum condition

Abstract

The invention provides a carbon dioxide mineralization reaction device under simulated formation conditions, and belongs to the technical field of carbon dioxide geological storage. A reaction solution involved in the reaction device is a carbonic anhydrase solution. The reaction device comprises a carbon dioxide injection system, a reaction system, a carbonic anhydrase solution input system, an exhaust and liquid discharge analysis system and a data acquisition early warning system, and the reaction system consists of a constant-temperature heating box and a reaction kettle 302 placed in the constant-temperature heating box. According to the device, through cooperative work of the systems, the state of the carbon dioxide mineralization reaction under the basalt stratum condition in the real environment can be more accurately simulated, and automatic real-time monitoring of a plurality of index change rules is realized, so that the microscopic state of a rock sample under the carbon dioxide reaction is further mastered. The method is also suitable for rock samples with different lithology, and the whole experiment system is free of special materials and instruments, economical, suitable and convenient to popularize and use.

Description

Technical Field

[0001] The invention belongs to the technical field of geological storage of carbon dioxide, and relates to a carbon dioxide mineralization reaction device under simulated basalt formation conditions. The reaction liquid involved in the reaction device is a carbonic anhydrase solution. Background Art

[0002] Carbon dioxide geological storage is an important technical option for achieving emission reduction and carbon sink increase. It can store carbon dioxide in underground rock formations for a long time and safely. Basalt is a new type of carbon dioxide storage geological body that has gradually attracted attention in recent years, further enriching and expanding the technical means and carbon sink potential of carbon dioxide geological storage. The mechanism of carbon dioxide storage in basalt is that carbonic acid formed after carbon dioxide dissolves in water can react with +2-valent metal ions (Mg 2+ , Ca 2+ , Fe 2+ ) to produce carbonate mineral precipitation, thereby achieving permanent mineralization and storage of carbon dioxide. The CarbFix storage project in Iceland has verified the feasibility of basalt mineralization and storage of carbon dioxide.

[0003] Studies have shown that mineralization of carbon dioxide storage is the safest and most reliable, but due to the slow hydration reaction of carbon dioxide, the storage time is relatively long, and a method of rapid mineralization of carbon dioxide storage is needed. In the natural state, the hydration reaction of carbon dioxide, that is, the reaction to produce carbonic acid, is very slow, with a hydration rate of only 6.2×10 -3 s -1 However, with the addition of carbonic anhydrase, the carbon dioxide hydration reaction mechanism changed, so that the carbon dioxide hydration rate can be increased to 10 3 -10 7 s -1 The rate of hydration reaction has been significantly improved, greatly reducing the carbon dioxide storage time.

[0004] To study the mineralization reaction of carbon dioxide, high temperature and high pressure static reaction experiments are an effective research method. Most existing water-rock reaction devices do not consider the possibility of adding carbonic anhydrase during the reaction process, and cannot continuously inject carbon dioxide during the reaction. In the current methods for studying water-rock reactions, the changes in the physical and chemical properties such as the porosity of rock samples after the addition of carbonic anhydrase and the dissolution and diffusion rate of carbon dioxide into water are often ignored. Therefore, there is an urgent need for an experimental device and method for the mineralization reaction of carbonic anhydrase under simulated basalt formation conditions, considering the effect of the addition of carbonic anhydrase on the mineralization and storage of carbon dioxide in basalt, and providing research means for the geological storage of carbon dioxide and the resource utilization of carbon dioxide. Summary of the invention

[0005] The technical problem to be solved by the present invention is that the existing experimental device cannot add carbonic anhydrase and continuously inject carbon dioxide during the reaction process. The above problem is solved by providing a carbonic anhydrase-participated carbon dioxide mineralization reaction experimental device under simulated basalt formation conditions.

[0006] The technical solution of the present invention is as follows:

[0007] A carbon dioxide mineralization reaction device simulating basalt formation conditions, wherein the reaction liquid involved in the reaction device is a carbonic anhydrase solution, comprising a carbon dioxide injection system, a reaction system, a carbonic anhydrase solution input system, an exhaust and liquid analysis system, and a data acquisition and early warning system;

[0008] The carbon dioxide injection system comprises a first water storage tank, a carbon dioxide gas cylinder, a constant speed and constant pressure pump, and a carbon dioxide resistant piston container; the carbon dioxide resistant piston container comprises a piston, and the interior of the container is divided into an upper cavity and a lower cavity by the piston; the carbon dioxide gas cylinder is connected to the upper cavity of the carbon dioxide resistant piston container through a pressure reducing valve and a first high temperature and high pressure resistant pipeline with a first injection valve in sequence; the first water storage tank is connected to the constant speed and constant pressure pump through a water pipeline, and the constant speed and constant pressure pump is connected to the lower cavity of the carbon dioxide resistant piston container through a second high temperature and high pressure resistant pipeline with a second injection valve; a drain pipe connected to the lower cavity of the carbon dioxide resistant piston container is installed at the bottom of the carbon dioxide resistant piston container, and a drain valve is installed on the drain pipe; an exhaust pipe connected to the upper cavity of the carbon dioxide resistant piston container is installed at the top of the carbon dioxide resistant piston container, and a first exhaust valve is installed on the exhaust pipe;

[0009] The reaction system is composed of a constant temperature heating box and a reactor placed in the constant temperature heating box; the reactor is connected to the upper cavity of the carbon dioxide resistant piston container through a third high temperature and high pressure resistant pipeline with a third injection valve passing through the constant temperature heating box; an exhaust pipe connected to the inner cavity of the reactor is installed on the top of the reactor, the exhaust pipe passes through the constant temperature heating box, and a second exhaust valve is installed on the exhaust pipe passing through the exhaust pipe;

[0010] The carbonic anhydrase solution input system comprises a carbonic anhydrase solution storage tank, a first constant speed and constant pressure infusion pump, a second water storage tank and a second constant speed and constant pressure infusion pump; the carbonic anhydrase solution storage tank is communicated with the first constant speed and constant pressure infusion pump through a corrosion-resistant water pipeline, and the first constant speed and constant pressure infusion pump is communicated with the reactor through a fourth high temperature and high pressure pipeline with a fourth injection valve passing through the top of the reactor; the second water storage tank is communicated with the second constant speed and constant pressure infusion pump through the water pipeline, and the second constant speed and constant pressure infusion pump is communicated with the reactor through a fifth high temperature and high pressure pipeline with a fifth injection valve passing through the top of the reactor;

[0011] The exhaust and liquid analysis system includes a gas chromatograph, a liquid sampler and an ion chromatograph; the gas chromatograph has its own pipeline passing through a constant temperature heating box through a seventh high temperature and high pressure pipeline with a back pressure valve, and is connected to the reactor from the top of the reactor to sample the gas; the liquid sampler passes through a sixth high temperature and high pressure pipeline with a sixth injection valve through the constant temperature heating box, and is connected to the reactor from the bottom of the reactor to sample the liquid, and then analyzes it through the ion chromatograph;

[0012] The data acquisition and early warning system includes a computer, a first pressure transmitter, a second pressure transmitter and a high-temperature and high-pressure PH probe; the high-temperature and high-pressure PH probe passes through a constant temperature heating box and is inserted into the reactor; the second pressure transmitter passes through the constant temperature heating box and is installed on the top of the reactor, and the first pressure transmitter is installed on the top of the carbon dioxide piston container.

[0013] Preferably, the first pressure transmitter, the second pressure transmitter, the high temperature and high pressure resistant pH probe, the gas chromatograph and the ion chromatograph are all connected to a computer to transmit the collected and analyzed data to the computer.

[0014] Preferably, the reactor consists of a reactor cover and a reactor body, and the reactor cover and the reactor body are rotationally fastened by means of a spiral pattern.

[0015] Preferably, the carbonic anhydrase solution storage tank is filled with a carbonic anhydrase solution having a concentration greater than 0 mg / L and is prepared by dissolving carbonic anhydrase freeze-dried powder in water; the carbonic anhydrase solution storage tank is in a sealed state during operation.

[0016] Preferably, when conducting the experiment, a rock sample is placed in the reactor.

[0017] Preferably, all pipelines communicating with the inner cavity of the reactor and the exhaust pipe equipped with the second exhaust valve are provided with sealing rings at the places where they pass through the reactor, that is, the reactor is in a sealed state during the experiment.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] 1. Through the carbonic anhydrase solution input system in this device, water or carbonic anhydrase solution can be quantitatively injected into the reactor, which is convenient for setting up comparative experiments; at the same time, the carbonic anhydrase solution can reduce contact with air during injection into the reaction system, reducing experimental errors. Because carbonic anhydrase, as a catalyst for the carbon dioxide-water dissolution reaction, can greatly accelerate the speed of the carbon dioxide-water dissolution reaction, and can continuously inject carbon dioxide into the reaction process in a pressure-maintaining manner while keeping the temperature, so that the experimental environment simulates the natural environment to the greatest extent.

[0020] 2. The carbon dioxide injection system in this device is used for pressure-maintaining operation, so that new carbon dioxide can be injected from the carbon dioxide-resistant piston container while carbon dioxide is consumed in the reactor, simulating the real environment to the greatest extent.

[0021] 3. Adding pressure transmitters and computers can monitor the pressure changes in the CO2-resistant piston container and reactor during the pressure maintenance process in real time, and then check the air tightness of the CO2-resistant piston container and reactor. Once the pressure is abnormal, the computer can provide early warning in time to avoid danger.

[0022] 4. Adding a gas chromatograph can detect the gas composition before the experiment begins and observe whether all the air in the reactor is exhausted. Adding a gas chromatograph and an ion chromatograph can analyze the liquid in the reactor in real time.

[0023] 5. Adding a high temperature and high pressure resistant pH probe can monitor the pH value changes of the solution in the reactor in real time. The pH value is an important indicator for evaluating the process of carbon dioxide dissolving in water and can provide data support for the experiment.

[0024] 6. Adding a constant temperature heating box can set different temperature gradients. Temperature has a great influence on the activity of carbonic anhydrase. The constant temperature heating box can keep the temperature in the reactor at a constant temperature, which is convenient for setting up comparative experiments.

[0025] In summary, through the coordinated work of the carbon dioxide injection system, reaction system, carbonic anhydrase solution input system, exhaust and liquid analysis system, and data acquisition and early warning system, this device can more accurately simulate the state of carbon dioxide mineralization reaction under the conditions of realistic basalt formations, and realize automatic real-time monitoring of the changing laws of multiple indicators. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is a schematic diagram of the structure of the testing device of the present invention.

[0027] In the figure: 001 basalt sample; 101 first injection valve; 01 first high temperature and high pressure pipeline; 102 second injection valve; 02 second high temperature and high pressure pipeline; 103 third injection valve; 03 third high temperature and high pressure pipeline; 104 with fourth injection valve; 04 fourth high temperature and high pressure pipeline; 105 fifth injection valve; 05 fifth high temperature and high pressure pipeline; 106 sixth injection valve; 06 sixth high temperature and high pressure pipeline; 107 back pressure valve; 07 seventh high temperature and high pressure pipeline; 10 corrosion resistant water pipeline; 201 first water storage tank; 202 carbon dioxide cylinder ; 203 constant speed and constant pressure pump; 204 carbon dioxide resistant piston container; 205 pressure reducing valve; 206 drain valve; 207 first exhaust valve; 301 constant temperature heating box; 302 reactor; 303 second exhaust valve; 401 gas chromatograph; 402 ion chromatograph; 403 liquid sampler; 501 carbonic anhydrase solution storage tank; 502 first constant speed and constant pressure infusion pump; 503 second water storage tank; 504 second constant speed and constant pressure infusion pump; 601 computer; 602 first pressure transmitter; 603 second pressure transmitter; 604 high temperature and high pressure resistant pH probe. DETAILED DESCRIPTION

[0028] The present invention is further described in detail below in combination with the technical scheme and the accompanying drawings:

[0029] Figure 1 It is a schematic diagram of the structure of the test device of the present invention, Figure 1 It can be seen that the present invention is a carbon dioxide mineralization reaction device under the conditions of simulating basalt formations, and the reaction liquid involved in the reaction device is a carbonic anhydrase solution. The experimental device includes a carbon dioxide injection system, a reaction system, a carbonic anhydrase solution input system, an exhaust and liquid analysis system, and a data acquisition and early warning system.

[0030] The carbon dioxide injection system comprises a first water storage tank 201, a carbon dioxide gas cylinder 202, a constant speed and pressure pump 203, and a carbon dioxide resistant piston container 204; the carbon dioxide resistant piston container 204 comprises a piston, and the interior of the carbon dioxide resistant piston container 204 is divided into an upper cavity and a lower cavity by the piston; the carbon dioxide gas cylinder 202 is connected to the upper cavity of the carbon dioxide resistant piston container 204 through a pressure reducing valve 205 and a first high temperature and high pressure resistant pipeline 01 with a first injection valve 101 in sequence; the first water storage tank 201 is connected to the constant speed and pressure pump 203 through a water pipeline The constant speed and constant pressure pump 203 is connected to the lower cavity of the carbon dioxide resistant piston container 204 through a second high temperature and high pressure resistant pipeline 02 with a second injection valve 102; a drain pipe connected to the lower cavity of the carbon dioxide resistant piston container 204 is installed at the bottom of the carbon dioxide resistant piston container 204, and a drain valve 206 is installed on the drain pipe; an exhaust pipe connected to the upper cavity of the carbon dioxide resistant piston container 204 is installed at the top of the carbon dioxide resistant piston container 204, and a first exhaust valve 207 is installed on the exhaust pipe.

[0031] The reaction system consists of a constant temperature heating box 301 and a reactor 302 placed in the constant temperature heating box 301; the reactor 302 is connected to the upper cavity of the carbon dioxide resistant piston container 204 through a third high temperature and high pressure resistant pipeline 03 with a third injection valve 103 passing through the constant temperature heating box 301; an exhaust pipe connected to its inner cavity is installed on the top of the reactor 302, the exhaust pipe passes through the constant temperature heating box 301, and a second exhaust valve 303 is installed on the outlet part of the exhaust pipe.

[0032] The reaction kettle 302 contains a rock sample 001. In this embodiment, the rock sample 001 is a basalt rock sample.

[0033] In this embodiment, the reactor 302 is composed of a reactor cover and a reactor body. When conducting experiments, the reactor cover and the reactor body are fastened by rotating with spiral patterns.

[0034] In this embodiment, the constant temperature heating box 301 is divided into a box body and a box door. When conducting an experiment, the box door is closed and the constant temperature heating box 301 is in a closed state.

[0035] The carbonic anhydrase solution input system includes a carbonic anhydrase solution storage tank 501, a first constant speed and constant pressure infusion pump 502, a second water storage tank 503 and a second constant speed and constant pressure infusion pump 504; the carbonic anhydrase solution storage tank 501 is communicated with the first constant speed and constant pressure infusion pump 502 through a corrosion-resistant water pipeline 10, and the first constant speed and constant pressure infusion pump 502 is communicated with the reactor 302 through a fourth high temperature and high pressure pipeline 04 with a fourth injection valve 104 passing through the top of the reactor 302; the second water storage tank 503 is communicated with the second constant speed and constant pressure infusion pump 504 through a water pipeline, and the second constant speed and constant pressure infusion pump 504 is communicated with the reactor 302 through a fifth high temperature and high pressure pipeline 05 with a fifth injection valve 105 passing through the top of the reactor 302.

[0036] In this embodiment, the carbonic anhydrase solution storage tank 501 is filled with a carbonic anhydrase solution having a concentration greater than 0 mg / L and is prepared by dissolving carbonic anhydrase freeze-dried powder in water; the carbonic anhydrase solution storage tank 501 is in a sealed state during operation.

[0037] The exhaust and liquid analysis system includes a gas chromatograph 401, a liquid sampler 403 and an ion chromatograph 402; the gas chromatograph 401 has its own pipeline that passes through the constant temperature heating box 301 through the seventh high temperature and high pressure pipeline 07 with a back pressure valve 107, and is connected to the reactor 302 from the top of the reactor 302 to sample the gas; the liquid sampler 403 passes through the constant temperature heating box 301 through the sixth high temperature and high pressure pipeline 06 with a sixth injection valve 106, and is connected to the reactor 302 from the bottom of the reactor 302 to sample the liquid, and then analyzes it through the ion chromatograph 402.

[0038] The data acquisition and early warning system includes a computer 601, a first pressure transmitter 602, a second pressure transmitter 603 and a high temperature and high pressure resistant PH probe 604; the high temperature and high pressure resistant PH probe 604 passes through the constant temperature heating box 301 and is inserted into the reactor 302; the second pressure transmitter 602 passes through the constant temperature heating box 301 and is installed on the top of the reactor, and the first pressure transmitter 603 is installed on the top of the carbon dioxide piston container 204.

[0039] In this embodiment, the first pressure transmitter 602, the second pressure transmitter 603, the high temperature and high pressure resistant pH probe 604, the gas chromatograph 401 and the ion chromatograph 402 are all connected to the computer 601 to transmit the collected and analyzed data to the computer 601.

[0040] In this embodiment, all pipelines communicating with the inner cavity of the reactor 302 and the exhaust pipe equipped with the second exhaust valve 303 are provided with sealing rings at the places where they pass through the reactor 302, that is, during the experiment, the reactor 302 is in a sealed state.

[0041] Through the collaborative work of the above systems, the state of carbon dioxide mineralization reaction under the conditions of real basalt formations can be simulated more accurately, and automatic real-time monitoring of the changing laws of multiple indicators can be achieved.

[0042] In addition, during the experiment, through various tests on the rock samples before and after the experiment, we can further understand the microscopic state of the rock samples under the carbon dioxide reaction, understand the effect of the addition of carbonic anhydrase on the carbon dioxide storage reaction of basalt mineralization, and provide research methods for carbon dioxide geological storage and carbon dioxide resource utilization. The various tests of the rock samples before the experiment include ultrasonic testing, nuclear magnetic resonance testing, porosity testing, permeability testing, and acoustic emission-stress strain testing; the various tests of the rock samples before the experiment include ultrasonic testing, nuclear magnetic resonance testing, porosity testing, permeability testing, acoustic emission-stress strain testing, XRD testing, and SEM testing. Based on the real-time monitoring of the pH value data during the reaction process, the pH changes of the reaction liquid during the reaction process can be intuitively understood. Based on the ultrasonic test, nuclear magnetic resonance test, and porosity test data, the porosity size changes and pore distribution changes of the basalt samples before and after the reaction are obtained. Based on the permeability test data, the permeability changes of the basalt samples before and after the reaction are obtained. Based on the acoustic emission-stress-strain test data, 0rigin software is used to draw graphs, and the elastic modulus, Poisson's ratio and uniaxial compressive strength of the basalt samples after the reaction are calculated. Based on the XRD test data, Jade software is used to make XRD spectrum curves, and the microscopic morphology of the generated calcium carbonate and other major minerals is observed based on SEM tests.

Claims

1. A carbon dioxide mineralization reaction device simulating basalt formation conditions, wherein the reaction liquid involved in the reaction device is a carbonic anhydrase solution, characterized in that: It includes a carbon dioxide injection system, a reaction system, a carbonic anhydrase solution input system, an exhaust and liquid analysis system, and a data acquisition and early warning system; The carbon dioxide injection system comprises a first water storage tank (201), a carbon dioxide gas cylinder (202), a constant speed and pressure pump (203), and a carbon dioxide resistant piston container (204); the carbon dioxide resistant piston container (204) comprises a piston, and the interior of the carbon dioxide resistant piston container (204) is divided into an upper cavity and a lower cavity by the piston; the carbon dioxide gas cylinder (202) is connected to the upper cavity of the carbon dioxide resistant piston container (204) via a pressure reducing valve (205) and a first high temperature and high pressure resistant pipeline (01) with a first injection valve (101) in sequence; the first water storage tank (201) is connected to the constant speed and pressure pump (203) via a water delivery pipeline The constant speed and constant pressure pump (203) is connected to the lower cavity of the carbon dioxide resistant piston container (204) through a second high temperature and high pressure resistant pipeline (02) with a second injection valve (102); a drainage pipe connected to the lower cavity of the carbon dioxide resistant piston container (204) is installed at the bottom of the carbon dioxide resistant piston container (204), and a drainage valve (206) is installed on the drainage pipe; an exhaust pipe connected to the upper cavity of the carbon dioxide resistant piston container (204) is installed at the top of the carbon dioxide resistant piston container (204), and a first exhaust valve (207) is installed on the exhaust pipe; The reaction system is composed of a constant temperature heating box (301) and a reaction kettle (302) placed in the constant temperature heating box (301); the reaction kettle (302) is connected to the upper cavity of the carbon dioxide resistant piston container (204) through a third high temperature and high pressure resistant pipeline (03) with a third injection valve (103) passing through the constant temperature heating box (301); an exhaust pipe connected to the inner cavity of the reaction kettle (302) is installed on the top of the reaction kettle (302), the exhaust pipe passes through the constant temperature heating box (301), and a second exhaust valve (303) is installed on the exhaust pipe outlet portion; The carbonic anhydrase solution input system comprises a carbonic anhydrase solution storage tank (501), a first constant speed constant pressure infusion pump (502), a second water storage tank (503) and a second constant speed constant pressure infusion pump (504); the carbonic anhydrase solution storage tank (501) is communicated with the first constant speed constant pressure infusion pump (502) through a corrosion-resistant water pipeline (10); the first constant speed constant pressure infusion pump (502) is communicated with the reactor (302) through a fourth high temperature and high pressure resistant pipeline (04) with a fourth injection valve (104) passing through the top of the reactor (302); the second water storage tank (503) is communicated with the second constant speed constant pressure infusion pump (504) through the water pipeline; the second constant speed constant pressure infusion pump (504) is communicated with the reactor (302) through a fifth high temperature and high pressure resistant pipeline (05) with a fifth injection valve (105) passing through the top of the reactor (302); The exhaust and liquid analysis system comprises a gas chromatograph (401), a liquid sampler (403) and an ion chromatograph (402); the gas chromatograph (401) has its own pipeline which passes through a seventh high-temperature and high-pressure pipeline (07) with a back-pressure valve (107) through a constant temperature heating box (301) and communicates with the reactor (302) from the top of the reactor (302) to sample the gas; the liquid sampler (403) passes through a sixth high-temperature and high-pressure pipeline (06) with a sixth injection valve (106) through a constant temperature heating box (301) and communicates with the reactor (302) from the bottom of the reactor (302) to sample the liquid, which is then analyzed by the ion chromatograph (402); The data acquisition and early warning system comprises a computer (601), a first pressure transmitter (602), a second pressure transmitter (603) and a high temperature and high pressure resistant pH probe (604); the high temperature and high pressure resistant pH probe (604) passes through a constant temperature heating box (301) and is inserted into a reaction kettle (302); the second pressure transmitter (603) passes through the constant temperature heating box (301) and is installed on the top of the reaction kettle (302), and the first pressure transmitter (602) is installed on the top of a carbon dioxide piston container (204).

2. The carbon dioxide mineralization reaction device under simulated basalt formation conditions according to claim 1, characterized in that: The first pressure transmitter (602), the second pressure transmitter (603), the high temperature and high pressure resistant pH probe (604), the gas chromatograph (401) and the ion chromatograph (402) are all connected to the computer (601) to transmit the collected and analyzed data to the computer (601).

3. The carbon dioxide mineralization reaction device under simulated basalt formation conditions according to claim 1, characterized in that: The reactor (302) is composed of a reactor cover and a reactor body, and the reactor cover and the reactor body are rotationally fastened by means of a spiral pattern.

4. The carbon dioxide mineralization reaction device under simulated basalt formation conditions according to claim 1, characterized in that: The carbonic anhydrase solution storage tank (501) is filled with a carbonic anhydrase solution, the concentration of which is greater than 0 mg / L and is prepared by dissolving carbonic anhydrase freeze-dried powder in water; the carbonic anhydrase solution storage tank (501) is in a sealed state during operation.

5. The carbon dioxide mineralization reaction device under simulated basalt formation conditions according to claim 1, characterized in that: When conducting the experiment, a rock sample (001) is placed in the reaction kettle (302).

6. The carbon dioxide mineralization reaction device under simulated basalt formation conditions according to claim 1, characterized in that: All pipelines communicating with the inner cavity of the reactor (302) and the exhaust pipe equipped with the second exhaust valve (303) are provided with sealing rings at the places where they pass through the reactor (302), that is, when conducting the experiment, the reactor (302) is in a sealed state.

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