Device and Method for Measuring Dynamic Carbon Dioxide-Water-Rock Reaction

Abstract

The present invention relates to the technical field of oil and gas reservoirs, and discloses a device and a method for measuring the dynamic water-rock reaction of carbon dioxide. The method uses five groups of rock samples from the same well and at the same well depth for parallel control experiments. The five groups of rock samples respectively correspond to five reaction times set in the experiment. After each reaction, the porosity, permeability, mineral composition and clay mineral composition of the corresponding rock samples are measured, and the fluid ion concentration after the reaction is measured and analyzed, and the carbon dioxide storage amount is calculated, without interfering with the experiments of other groups, and can ensure the continuity of the reaction and the sealing of the reaction system, and more truly simulate the formation reaction environment.

Description

Technical Field

[0001] The present invention relates to the technical field of oil and gas reservoirs, and particularly relates to a device and method for measuring the dynamic water-rock reaction of carbon dioxide. Background Art

[0002] Carrying out carbon dioxide storage and utilization in oil and gas reservoirs can, on the one hand, effectively improve the recovery rate of oil and gas reservoirs, and on the other hand, effectively store carbon dioxide in underground reservoirs, which is a dual measure with both economic benefits and social and environmental effects. After being injected into the oil and gas reservoir, carbon dioxide will interact with formation water and reservoir rocks, causing mineral dissolution and precipitation. The dissolution of mineral components and ion reaction precipitation will cause changes in the pore structure of the reservoir. Accurately characterizing the influence of the water-rock reaction on the porosity and permeability of the reservoir is of great significance for evaluating the change in reservoir seepage capacity and storage effect. Measuring the influence of the water-rock reaction on the reservoir through experiments is a commonly used research method at present.

[0003] The prior art CN 110320339A provides a water-rock reaction device and operation method for simulating a formation closed environment. This device uses two reaction vessels. The first reaction vessel replenishes the reaction fluid, and the second reaction vessel collects the fluid after the reaction, attempting to close the reaction environment to simulate the real formation reaction environment. However, when the fluid in the first reaction vessel is replenished to the second reaction vessel for continuous water-rock reaction, the fluid composition in the second reaction vessel changes, and the real water-rock reaction formation water environment cannot be restored. The technology CN 109459362A discloses an integrated test device and method for high-temperature and high-pressure water-rock reaction and gas permeability, which can simulate the real high-temperature and high-pressure environment of the formation, and can directly measure the gas permeability of the core after the water-rock reaction. This device can more conveniently and safely measure the physical property changes of the rock in the water-rock reaction. Since the high-temperature and high-pressure water-rock reaction is a long-term dynamic change, this technology can only measure the physical property changes of the core after a single reaction stage and cannot study the influence of the water-rock reaction on the rock over time. The technology CN 117269221A proposes a nuclear magnetic resonance high-temperature and high-pressure water-rock reaction device and test method based on this. This technology can monitor the change in the pore throat distribution of the rock during the water-rock reaction in real time through nuclear magnetic resonance scanning, but the dynamic changes in permeability, the changes in reservoir minerals and ion components in the formation during the water-rock reaction cannot be dynamically characterized.

[0004] Therefore, how to accurately characterize the dynamic change law of reservoir physical properties after carbon dioxide is injected into the formation to accurately evaluate the reservoir stability during the carbon dioxide storage process is a technical problem that urgently needs to be solved at present. Summary of the Invention

[0005] The object of the present invention is to provide a device and a measurement method for dynamic carbon dioxide-water-rock reaction, aiming to accurately restore the formation water ion components, core permeability, porosity, mineral composition and clay mineral content changes during different water-rock reaction stages under the condition of the reservoir fluid configuration relationship after carbon dioxide injection into the formation, and at the same time be able to accurately evaluate the carbon dioxide mineralization burial amount.

[0006] To achieve the above object, the following technical solutions are adopted:

[0007] In the first aspect, the present invention provides a device for dynamic carbon dioxide-water-rock reaction measurement, including an injection pump, a constant pressure pump, a formation water container, and a formation water intermediate container. The injection pump is connected to a carbon dioxide intermediate container, a first helium intermediate container, and a second nitrogen intermediate container through pipelines; a heating device is arranged outside the second nitrogen intermediate container. The carbon dioxide intermediate container is connected to a solution configurator through a pipeline. A heating module and a rotation control button are arranged on the solution configurator. The rotation control button is connected to the heating module to control the power of the heating module. The solution configurator is connected to a first liquid collection device and a first six-way valve through pipelines. The first helium intermediate container and the second nitrogen intermediate container are connected to the first six-way valve through pipelines. The constant pressure pump is connected to the formation water intermediate container through a pipeline. The formation water intermediate container is connected to the solution configurator through a pipeline. The formation water container is connected to the pipeline connecting the carbon dioxide intermediate container and the solution configurator through a pipeline. A first pressure gauge is arranged on the pipeline connecting the carbon dioxide intermediate container and the solution configurator. The solution configurator is connected to the first six-way valve and the first liquid collection device through pipelines. The first liquid collection device is connected to a first drainage gas collection device through a pipeline. The first six-way valve is connected to a first temperature sensor, a second six-way valve, and a spherical valve through pipelines. A second pressure gauge is arranged on the pipeline connecting the first six-way valve and the first temperature sensor. The spherical valve is connected to a reference chamber and a constant temperature box through a pipeline. A second temperature sensor and a third pressure gauge are arranged outside the constant temperature box. A first core holder, a second core holder, a third core holder, a fourth core holder, and a fifth core holder are arranged inside the constant temperature box. The reference chamber is connected to the first core holder, the second core holder, the third core holder, the fourth core holder, and the fifth core holder in sequence through pipelines. Each of the first core holder, the second core holder, the third core holder, the fourth core holder, and the fifth core holder is connected to a confining pressure pump. The outside of the constant temperature box is connected to a back pressure valve and a back pressure pump through pipelines. The back pressure valve is connected to a second liquid collection device, a vacuum pump, anhydrous calcium chloride, and an electronic flowmeter through pipelines. The anhydrous calcium chloride is arranged on the upper end of an electronic balance. The second liquid collection device is connected to a second drainage gas collection device through a pipeline.

[0008] Further, it further includes a valve assembly, and the valve assembly includes eighteen valves, namely a first valve, a second valve, a third valve, a fourth valve, a fifth valve, a sixth valve, a seventh valve, an eighth valve, a ninth valve, a tenth valve, an eleventh valve, a twelfth valve, a thirteenth valve, a fourteenth valve, a fifteenth valve, a sixteenth valve, a seventeenth valve, and an eighteenth valve; among which:

[0009] A first valve and a second valve are provided on the connecting pipeline between the carbon dioxide intermediate container and the solution configurator and the connecting pipeline of the formation water container;

[0010] A third valve and a fourth valve are respectively provided on the connecting pipelines of the first helium intermediate container and the second nitrogen intermediate container with the first six-way valve;

[0011] A fifth valve is provided on the connecting pipeline between the formation water intermediate container and the solution configurator;

[0012] A sixth valve is provided on the connecting pipeline between the solution configurator and the first liquid collection device;

[0013] A seventh valve is provided on the connecting pipeline between the first liquid collection device and the first drainage gas production device;

[0014] An eighth valve is provided on the connecting pipeline between the first six-way valve and the first temperature sensor;

[0015] The first core holder, the second core holder, the third core holder, the fourth core holder, and the fifth core holder are connected through a circulation pipeline, and on the circulation pipeline, a ninth valve, a tenth valve, an eleventh valve, a twelfth valve, and a thirteenth valve are respectively provided corresponding to the first core holder, the second core holder, the third core holder, the fourth core holder, and the fifth core holder;

[0016] A fourteenth valve is provided on one side of the back pressure valve, a fifteenth valve is provided on the connecting pipeline between the back pressure valve and the second liquid collection device, a sixteenth valve is provided on the connecting pipeline between the second liquid collection device and the second drainage gas production device, a seventeenth valve is provided on the connecting pipeline between the back pressure valve and the anhydrous calcium chloride, and an eighteenth valve is provided on the connecting pipeline between the back pressure valve and the vacuum pump.

[0017] In a second aspect, the present invention provides a measurement method based on the carbon dioxide dynamic water-rock reaction measurement device as described above, and the measurement method includes:

[0018] Step 1, preparing rock samples to obtain a first rock sample, a second rock sample, a third rock sample, a fourth rock sample, and a fifth rock sample;

[0019] Step 2: Load the first rock sample, the second rock sample, the third rock sample, the fourth rock sample, and the fifth rock sample into the first core holder, the second core holder, the third core holder, the fourth core holder, and the fifth core holder respectively. Start the confining pressure pump and open the valves of the corresponding pipelines to load the confining pressure to the experimental value on the core holders. Then, open the vacuum pump to evacuate the cores.

[0020] Step 3: Prepare saturated carbon dioxide formation water.

[0021] Step 4: Collect the pre-reaction fluid.

[0022] Step 5: Conduct the carbon dioxide-water-rock reaction.

[0023] Step 6: Collect the post-reaction fluid.

[0024] Step 7: Measure the gas permeability of the rock sample: Open the valves of the corresponding pipelines of the second nitrogen intermediate container and the first core holder 31. Turn on the heating device to heat the nitrogen to 120 °C fully. Then, open the third valve and displace the first core holder with the high-temperature nitrogen. When the reading of the electronic balance no longer changes, it means that the outlet gas no longer contains water vapor, indicating that the core has been dried. Adjust the inlet of the first core holder to be driven by constant-pressure nitrogen. Open the back-pressure pump and the back-pressure valve, and set a specified back-pressure at the outlet end to form a stable pressure difference at both ends of the first core holder. Read the gas flow rate through the core per unit time through the electronic flowmeter, and calculate the gas permeability of the core using the following formula:

[0025]

[0026] In the formula:

[0027] K - Gas permeability measured, unit: μm 2 ;

[0028] p0 - Atmospheric pressure, unit: MPa;

[0029] p1 - Inlet end pressure, unit: MPa;

[0030] p2 - Outlet end pressure, unit: MPa;

[0031] μ - Gas viscosity, unit: mPa·s;

[0032] L - Core length, unit: cm;

[0033] d - Core diameter, unit: cm;

[0034] Q0 - Gas volume flow rate, unit: mL / s;

[0035] Step 8, in the case where the core gas permeability is greater than the liquid permeability, calculate the Klinkenberg permeability of the rock sample based on the gas permeability model;

[0036] Step 9, measure the porosity of the rock sample;

[0037] Step 10, measure the mineral components of the rock sample before and after the reaction by X-ray diffraction. After measuring the porosity, take out the first rock sample, cut the rock sample with a set length, grind the two rock samples with the set length before and after the reaction into powder respectively, perform X-ray diffraction to measure their mineral components and clay mineral components, and conduct comparative analysis of the mineral changes;

[0038] Step 11, after the experiment of the first group of rock samples is completed, repeat Steps 1 to 10 according to the different reaction stages set in the experiment until the measurement of the four groups of experiments is completed. By comparing the porosity, permeability, ion concentration changes, mineral composition changes and burial amounts at different reaction times, comprehensively evaluate the influence of the water-rock reaction on the reservoir and the mineralized burial amount.

[0039] Further, the preparation of the rock sample includes: taking samples from the same well and the same well section, with the porosity and permeability deviation of the samples not exceeding 5%, the sample length being 12 cm, the diameter being 2.54 cm, and the number of samples being 5. Cut each sample into two sections of 2 cm and 10 cm.

[0040] Further, the preparation of the saturated carbon dioxide formation water includes:

[0041] Constantly inject formation water into the solution configurator through an intermediate container at a constant speed, start the heating module of the solution configurator, heat the temperature of the solution configurator to the formation temperature, and set the constant temperature condition. Then, under the control of an injection pump, inject carbon dioxide into the solution configurator at a constant pressure through a carbon dioxide intermediate container. When the temperature of the solution configurator is stable at the formation temperature and the first pressure gauge reaches the formation pressure, close the fifth valve, start the heating module and the rotation control button of the solution configuration container, stir under the formation temperature and pressure conditions until the formation fluid state is reached. After the solution configuration is completed, place the solution configurator vertically.

[0042] Further, the collection of the fluid before the reaction includes:

[0043] Open the liquid collection device and the corresponding valves, collect the prepared saturated carbon dioxide formation water, measure the ion components of the saturated carbon dioxide formation water, measure the carbon dioxide volume through a drainage gas production device, and calculate the carbon dioxide solubility.

[0044] Further, the carrying out of the carbon dioxide water-rock reaction includes:

[0045] Open the first six-way valve, inject the prepared saturated carbon dioxide formation water into the first core holder, the second core holder, the third core holder, the fourth core holder and the fifth core holder, raise the pressure to the formation pressure, then close the first six-way valve, open the thermostat 30, adjust the temperature to the experimental set value, and start the carbon dioxide-water-rock reaction.

[0046] Further, the collection of the post-reaction fluid includes: when the reaction proceeds to the set first time cut-off point, open the second liquid collection device and the corresponding pipeline valves, collect the post-reaction fluid and measure the ionic composition and concentration, and measure the carbon dioxide volume using the second drainage and gas collection device to determine the current carbon dioxide solubility, and analyze the changes in the ionic composition and ionic concentration of the fluid before and after the reaction in combination with step 4, and calculate the carbon dioxide storage capacity.

[0047] Further, in the case where the core gas permeability is greater than the liquid permeability, calculating the absolute permeability of the rock sample based on the gas permeability model includes:

[0048] Conduct experiments at multiple different average pressures, and calculate the gas-measured permeability according to the following formula:

[0049]

[0050] Determine the relationship between Kg and as follows:

[0051]

[0052] In the formula:

[0053] K ∞ represents the absolute permeability, with the unit of μm 2 ;

[0054] Kg represents the gas-measured permeability, with the unit of μm 2 ;

[0055] represents the average pressure at the inlet and outlet of the core, with the unit of MPa;

[0056] b represents a constant depending on the gas properties and the rock pore structure;

[0057] Plot the relationship curve between Kg and where there is a linear relationship between Kg and The intercept of the linear relationship on the Kg axis is K ∞ , that is, the absolute permeability of the rock.

[0058] Further, the measurement of the porosity of the rock sample includes:

[0059] Close the valve of the first nitrogen intermediate container, turn on the vacuum to evacuate the first core holder to vacuum, then turn off the vacuum pump. Open the valves of the first helium intermediate container and the pipeline corresponding to the first rock sample, inject helium into the reference chamber, read the data T1 of the first temperature sensor and the data P1 of the second pressure gauge and record the data. Then open the second six-way valve to diffuse the gas in the reference chamber into the first core holder, read the data T2 of the second temperature sensor and the data P2 of the third pressure gauge 42 and record the data. Calculate the porosity through the following formula:

[0060]

[0061] In the formula:

[0062] P1 represents the initial absolute pressure in the reference chamber;

[0063] P2 represents the absolute pressure after expansion;

[0064] P a represents the initial absolute atmospheric pressure in the rock sample;

[0065] z1 represents the gas deviation factor at P1 and T1;

[0066] z2 represents the gas deviation factor at P2 and T2;

[0067] T 1r represents the absolute temperature of the reference chamber at P1;

[0068] T1 represents P a the absolute temperature of the pore space in the rock sample at this time;

[0069] T2 represents the absolute temperature of the rock sample and the reference chamber after P2 reaches equilibrium;

[0070] V r represents the volume of the reference chamber;

[0071] V p represents the pore volume of the rock sample;

[0072] V v represents the valve displacement volume;

[0073] V d represents the system dead volume.

[0074] The beneficial effects of the present invention are:

[0075] The present invention uses five groups of rock samples from the same well and at the same well depth for parallel control experiments. The five groups of rock samples respectively correspond to five reaction times set in the experiment. After each reaction, the porosity, permeability, mineral composition, and clay mineral composition of the corresponding rock samples are measured, and the fluid ion concentration after the reaction is measured and analyzed, and the carbon dioxide storage amount is calculated, without interfering with the experiments of other groups, ensuring the continuity of the reaction and the sealing of the reaction system, and more truly simulating the formation reaction environment. BRIEF DESCRIPTION OF THE DRAWINGS

[0076] Figure 1 FIG. shows a structural diagram of a carbon dioxide dynamic water-rock reaction measurement device according to an embodiment of the present invention.

[0077] Figure 2 FIG. shows a flowchart of a measurement method according to an embodiment of the present invention.

[0078] REFERENCE SIGNS:

[0079] 1 - injection pump; 2 - carbon dioxide intermediate container; 3 - first helium intermediate container; 4 - second nitrogen intermediate container; 5 - heating device; 6 - constant pressure pump; 7 - formation water container; 8 - first valve; 9 - formation water intermediate container; 10 - second valve; 11 - third valve; 12 - fourth valve; 13 - fifth valve; 14 - first pressure gauge; 15 - solution configurator; 16 - heating module; 17 - rotation control button; 18 - sixth valve; 19 - first liquid collection device; 20 - seventh valve; 21 - first drainage and gas collection device; 22 - first six-way valve; 23 - second pressure gauge; 24 - eighth valve; 25 - first temperature sensor; 26 - reference chamber; 27 - second six-way valve; 28 - spherical valve; 29 - second temperature sensor; 30 - constant temperature box; 31 - first core holder; 32 - second core holder; 33 - third core holder; 34 - fourth core holder; 35 - fifth core holder; 36 - ninth valve; 37 - tenth valve; 38 - eleventh valve; 39 - twelfth valve; 40 - thirteenth valve; 41 - confining pressure pump; 42 - third pressure gauge; 43 - back pressure pump; 44 - back pressure valve; 45 - fourteenth valve; 46 - fifteenth valve; 47 - second liquid collection device; 48 - sixteenth valve; 49 - second drainage and gas collection device; 50 - electronic balance; 51 - anhydrous calcium chloride; 52 - seventeenth valve; 53 - electronic flowmeter; 54 - eighteenth valve; 55 - vacuum pump. DETAILED DESCRIPTION OF THE INVENTION

[0080] The following specific examples illustrate the implementation manners of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific implementation manners. Various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention. It should be noted that, without conflict, the following embodiments and the features in the embodiments can be combined with each other.

[0081] The following further describes in detail the specific implementation manners of the present invention in conjunction with the accompanying drawings and embodiments.

[0082] Figure 1 The structural diagram of a carbon dioxide dynamic water-rock reaction measurement device according to an embodiment of the present invention is shown. An embodiment of the present invention provides a carbon dioxide dynamic water-rock reaction measurement device. Please refer to Figure 1, the carbon dioxide dynamic water-rock reaction measurement device includes an injection pump 1, a constant pressure pump 6, a formation water container 7, and a formation water intermediate container 9. The injection pump is connected to a carbon dioxide intermediate container 2, a first helium intermediate container 3, and a second nitrogen intermediate container 4 through pipelines; a heating device 5 is arranged outside the second nitrogen intermediate container 4. The carbon dioxide intermediate container 2 is connected to a solution configurator 15 through a pipeline. A heating module 16 and a rotation control button 17 are arranged on the solution configurator 15. The rotation control button 17 is connected to the heating module 16 to control the power of the heating module 16. The solution configurator 15 is connected to a first liquid collection device 19 and a first six-way valve 22 through pipelines. The first helium intermediate container 3 and the second nitrogen intermediate container 4 are connected to the first six-way valve 22 through pipelines. The constant pressure pump 6 is connected to the formation water intermediate container 9 through a pipeline. The formation water intermediate container 9 is connected to the solution configurator 15 through a pipeline. The formation water container 7 is connected to the pipeline connecting the carbon dioxide intermediate container 2 and the solution configurator 15 through a pipeline. A first pressure gauge 14 is arranged on the pipeline connecting the carbon dioxide intermediate container 2 and the solution configurator 15. The solution configurator 15 is connected to the first six-way valve 22 and the first liquid collection device 19 through pipelines. The first liquid collection device 19 is connected to a first drainage and gas collection device 21 through a pipeline. The first six-way valve 22 is connected to a first temperature sensor 25, a second six-way valve 27, and a spherical valve 28 through pipelines. A second pressure gauge 23 is arranged on the pipeline connecting the first six-way valve 22 and the first temperature sensor 25. The spherical valve 28 is connected to a reference chamber 26 and a constant temperature chamber 30 through pipelines. A second temperature sensor 29 and a third pressure gauge 42 are arranged outside the constant temperature chamber 30. A first core holder 31, a second core holder 32, a third core holder 33, a fourth core holder 34, and a fifth core holder 35 are arranged inside the constant temperature chamber 30. The reference chamber 26 is connected to the first core holder 31, the second core holder 32, the third core holder 33, the fourth core holder 34, and the fifth core holder 35 in sequence through pipelines. The first core holder 31, the second core holder 32, the third core holder 33, the fourth core holder 34, and the fifth core holder 35 are all connected to an confining pressure pump 41. The outside of the constant temperature chamber 30 is connected to a back pressure valve 44 and a back pressure pump 43 through pipelines. The back pressure valve 44 is connected to a second liquid collection device 47, a vacuum pump 55, anhydrous calcium chloride 51, and an electronic flowmeter 53 through pipelines. The anhydrous calcium chloride 51 is arranged at the upper end of an electronic balance 50. The second liquid collection device 47 is connected to a second drainage and gas collection device 49 through a pipeline.

[0083] In some embodiments, the carbon dioxide dynamic water-rock reaction measurement device further includes a valve assembly. The valve assembly includes eighteen valves, namely the first valve 8, the second valve 10, the third valve 11, the fourth valve 12, the fifth valve 13, the sixth valve 18, the seventh valve 20, the eighth valve 24, the ninth valve 36, the tenth valve 37, the eleventh valve 38, the twelfth valve 39, the thirteenth valve 40, the fourteenth valve 45, the fifteenth valve 46, the sixteenth valve 48, the seventeenth valve 52, and the eighteenth valve 54. Among them: the first valve 8 and the second valve 10 are provided on the connecting pipeline between the connecting pipeline of the carbon dioxide intermediate container 2 and the solution configurator 15 and the connecting pipeline of the formation water container 7; the third valve 11 and the fourth valve 12 are respectively provided on the connecting pipelines of the first helium intermediate container 3 and the second nitrogen intermediate container 4 with the first six-way valve 22; the fifth valve 13 is provided on the connecting pipeline between the formation water intermediate container 9 and the solution configurator 15; the sixth valve 18 is provided on the connecting pipeline between the solution configurator 15 and the first liquid collection device 19; the seventh valve 20 is provided on the connecting pipeline between the first liquid collection device 19 and the first drainage gas production device 21; the eighth valve 24 is provided on the connecting pipeline between the first six-way valve 22 and the first temperature sensor 25; the first core holder 31, the second core holder 32, the third core holder 33, the fourth core holder 34, and the fifth core holder 35 are connected through a circulation pipeline. On the circulation pipeline, the ninth valve 36, the tenth valve 37, the eleventh valve 38, the twelfth valve 39, and the thirteenth valve 40 are respectively provided corresponding to the first core holder 31, the second core holder 32, the third core holder 33, the fourth core holder 34, and the fifth core holder 35; the fourteenth valve 45 is provided on one side of the back pressure valve 44, the fifteenth valve 46 is provided on the connecting pipeline between the back pressure valve 44 and the second liquid collection device 47, the sixteenth valve 48 is provided on the connecting pipeline between the second liquid collection device 47 and the second drainage gas production device 49, the seventeenth valve 52 is provided on the connecting pipeline between the back pressure valve 44 and the anhydrous calcium chloride 51, and the eighteenth valve 54 is provided on the connecting pipeline between the back pressure valve 44 and the vacuum pump 55.

[0084] In some embodiments, the embodiments of the present invention further provide a measurement method. As Figure 2 shown, it is a flowchart of the measurement method. The measurement method is based on the carbon dioxide dynamic water-rock reaction measurement device described above and includes the following steps:

[0085] Step 1, preparation of rock samples. Requirements for rock sample sampling: taken from the same well and the same well section, with the porosity and permeability deviation not exceeding 5%, which can reduce the error caused by reservoir heterogeneity. The sample length is 12 cm, the diameter is 2.54 cm, and the number of samples is 5. Each sample is cut into two sections of 2 cm and 10 cm.

[0086] Step 2, rock sample equipment. Five groups of rock samples are loaded into five core holders 31-35 respectively, and then the confining pressure pump 41 is started and the valves of the corresponding pipelines are opened to load the confining pressure to the core holders to the experimental value, and then the vacuum pump is turned on to evacuate the cores.

[0087] Step 3, prepare saturated carbon dioxide formation water. First, inject 200mL of formation water into the solution preparer 15 at a constant rate through the intermediate container 9. Start the solution preparer heating module 16, heat the solution preparer temperature to the formation temperature, and set the constant temperature condition. Then, under the control of the injection pump 1, inject carbon dioxide into 15 at a constant pressure through the carbon dioxide intermediate container 2. When the solution preparer temperature stabilizes at the formation temperature and the pressure gauge 14 reaches the formation pressure, close the valve 13. Start the heating module and the rotary button 17 of the solution preparation container 15, and stir for 2 hours under the formation temperature and pressure conditions until the formation fluid state is reached. After the solution preparation is completed, the liquid preparer is placed vertically.

[0088] Step 4, collecting the fluid before the reaction. Open the liquid collection device 19 and the corresponding valves, collect the prepared saturated carbon dioxide formation water, determine its ion components, measure the carbon dioxide volume through the drainage gas collection device 21, and calculate the carbon dioxide solubility.

[0089] Step 5, conduct the carbon dioxide water-rock reaction. Open the first six-way valve 22, inject the prepared saturated carbon dioxide formation water into the five core holders, and raise the pressure to the formation pressure, then close the first six-way valve. Open the thermostat 30, adjust the temperature to the experimental setting value, and start the carbon dioxide water-rock reaction.

[0090] Step 6, collect the fluid after the reaction. When the reaction reaches the set first time cutoff point, open the liquid collection device 47 and the corresponding pipeline valve, collect the fluid after the reaction and determine the ion composition and concentration, and use the drainage gas collection device 49 to measure the volume of carbon dioxide. Determine the current solubility of carbon dioxide. Combined with step 4, analyze the changes in the ion composition and ion concentration of the fluid before and after the reaction, and calculate the carbon dioxide storage capacity.

[0091] Step 7, measure the gas permeability of the rock sample. Open the nitrogen intermediate container 4, the corresponding pipeline valve of the first core clamp 31, open the nitrogen bottle heating device 5, fully heat the nitrogen to 120°C, and then open the valve 11 to use the high-temperature nitrogen to displace the first core clamp. When the reading of the electronic balance 50 no longer changes, it means that the outlet gas no longer contains water vapor, which means that the core has been dried. Adjust the inlet of the core clamp 31 to constant pressure nitrogen drive, open the back pressure pump 43 back pressure valve 44, set the specified back pressure at the outlet, form a stable pressure difference at both ends of the clamp 31, read the gas flow rate passing through the core per unit time through the electronic flowmeter 53, and calculate the core gas permeability using the following formula:

[0092]

[0093] Wherein:

[0094] K - gas permeability, unit: μm 2 ;

[0095] p0 - atmospheric pressure, unit: MPa;

[0096] p1 - inlet end pressure, unit: MPa;

[0097] p2 - outlet end pressure, unit: MPa;

[0098] μ - gas viscosity, unit: mPa·s;

[0099] L - core length, unit: cm;

[0100] d - core diameter, unit: cm;

[0101] Q0 - gas volume flow rate, unit: mL / s.

[0102] Step 8, Klinkenberg correction of gas permeability. Due to the gas slip effect, the measured gas permeability is greater than the liquid permeability. The absolute permeability of the rock sample can be calculated by the gas permeability model considering the gas slip effect given by Klinkenberg. Conduct experiments at 5 different average pressures, calculate Kg according to the following formula, and plot the relationship curve between Kg and There is a linear relationship between Kg and The intercept of this straight line on the Kg axis is K ∞ , that is, the absolute permeability of the rock.

[0103]

[0104] Wherein:

[0105] K ∞ represents the absolute permeability, unit: μm 2 ;

[0106] Kg represents the gas permeability measured by gas, unit: μm 2 ;

[0107] represents the average pressure at the inlet and outlet of the core, unit: MPa;

[0108] b represents a constant depending on the gas properties and the pore structure of the rock.

[0109] Step 9: Measure the porosity of the rock sample. Close the valve of the nitrogen intermediate container, turn on the vacuum pump 55 to evacuate the first core 31 to vacuum, then turn off the vacuum pump. Open the valves of the helium intermediate container 3 and the pipeline corresponding to the first rock sample, inject helium into the reference chamber 26, read the data T1 of the first temperature sensor 25 and the data P1 of the second pressure gauge 23 and record the data. Then open the valve corresponding to the first core of the second six-way valve 27, diffuse the gas in the reference chamber to the first core holder, read the data T2 of the second temperature sensor 29 and the data P2 of the third pressure gauge 42 and record the data. Calculate the porosity through the following formula:

[0110]

[0111] In the formula:

[0112] P1 represents the initial absolute pressure of the reference chamber;

[0113] P2 represents the absolute pressure after expansion;

[0114] P a represents the initial absolute atmospheric pressure in the rock sample;

[0115] z1 represents the gas deviation factor at P1 and T1;

[0116] z2 represents the gas deviation factor at P2 and T2;

[0117] T 1r represents the absolute temperature of the reference chamber at P1;

[0118] T1 represents P a when it is the absolute temperature of the pore space of the rock sample;

[0119] T2 represents the absolute temperature of the rock sample and the reference chamber after P2 is balanced;

[0120] V r represents the volume of the reference chamber;

[0121] V p represents the pore volume of the rock sample;

[0122] V v represents the valve displacement volume;

[0123] V d represents the system dead volume.

[0124] Step 10: Measure the mineral components of the rock sample before and after the reaction by X-ray diffraction. After measuring the porosity, take out the first rock sample, cut a 2-cm rock sample, grind the two 2-cm rock samples before and after the reaction into powder respectively, conduct X-ray diffraction to measure their mineral components and clay mineral components, and conduct comparative analysis of the mineral changes.

[0125] Step 11, complete the remaining four groups of parallel experiments. After the first group of rock sample experiments, according to the different reaction stages set in the experiment, repeat Steps 1 to 10 until the measurement of the four groups of experiments is completed. By comparing the porosity, permeability, changes in ion concentration, changes in mineral composition, and buried storage amounts at different reaction times, comprehensively evaluate the impact of water-rock reactions on the reservoir and the buried storage amount of minerals.

[0126] The above embodiments are only used to illustrate the present invention and are not intended to limit the present invention. Those of ordinary skill in the relevant technical fields can also make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the patent protection scope of the present invention shall be defined by the claims.

Claims

1. A device for measuring the dynamic water-rock reaction of carbon dioxide, characterized in that, It includes an injection pump, a constant-pressure pump, a formation water container, and a formation water intermediate container. The injection pump is connected to a carbon dioxide intermediate container, a first helium intermediate container, and a second nitrogen intermediate container through pipelines; a heating device is arranged outside the second nitrogen intermediate container. The carbon dioxide intermediate container is connected to a solution configurator through a pipeline. A heating module and a rotation control button are arranged on the solution configurator. The rotation control button is connected to the heating module to control the power of the heating module. The solution configurator is connected to a first liquid collection device and a first six-way valve through pipelines. The first helium intermediate container and the second nitrogen intermediate container are connected to the first six-way valve through pipelines. The constant-pressure pump is connected to the formation water intermediate container through a pipeline. The formation water intermediate container is connected to the solution configurator through a pipeline. The formation water container is connected to the pipeline connecting the carbon dioxide intermediate container and the solution configurator through a pipeline. A first pressure gauge is arranged on the pipeline connecting the carbon dioxide intermediate container and the solution configurator. The solution configurator is connected to the first six-way valve and the first liquid collection device through pipelines. The first liquid collection device is connected to a first drainage and gas production device through a pipeline. The first six-way valve is connected to a first temperature sensor, a second six-way valve, and a spherical valve through pipelines. A second pressure gauge is arranged on the pipeline connecting the first six-way valve and the first temperature sensor. The spherical valve is connected to a reference chamber and a constant-temperature box through a pipeline. A second temperature sensor and a third pressure gauge are arranged outside the constant-temperature box. A first core holder, a second core holder, a third core holder, a fourth core holder, and a fifth core holder are arranged inside the constant-temperature box. The reference chamber is connected to the first core holder, the second core holder, the third core holder, the fourth core holder, and the fifth core holder in sequence through pipelines. Each of the first core holder, the second core holder, the third core holder, the fourth core holder, and the fifth core holder is connected to a confining pressure pump. The outside of the constant-temperature box is connected to a backpressure valve and a backpressure pump through pipelines. The backpressure valve is connected to a second liquid collection device, a vacuum pump, anhydrous calcium chloride, and an electronic flowmeter through pipelines. The anhydrous calcium chloride is arranged above an electronic balance. The second liquid collection device is connected to a second drainage and gas production device through a pipeline.

2. The carbon dioxide dynamic water-rock reaction measurement device according to claim 1, wherein It further includes a valve assembly. The valve assembly includes eighteen valves, namely a first valve, a second valve, a third valve, a fourth valve, a fifth valve, a sixth valve, a seventh valve, an eighth valve, a ninth valve, a tenth valve, an eleventh valve, a twelfth valve, a thirteenth valve, a fourteenth valve, a fifteenth valve, a sixteenth valve, a seventeenth valve, and an eighteenth valve; where: A first valve and a second valve are arranged on the pipeline connecting the pipeline connecting the carbon dioxide intermediate container and the solution configurator and the formation water container; A third valve and a fourth valve are respectively arranged on the pipelines connecting the first helium intermediate container and the second nitrogen intermediate container and the first six-way valve; A fifth valve is arranged on the pipeline connecting the formation water intermediate container and the solution configurator; A sixth valve is provided on the connecting pipeline between the solution configurator and the first liquid collection device; A seventh valve is provided on the connecting pipeline between the first liquid collection device and the first drainage gas production device; An eighth valve is provided on the connecting pipeline between the first six-way valve and the first temperature sensor; The first core holder, the second core holder, the third core holder, the fourth core holder, and the fifth core holder are connected through a circulation pipeline. On the circulation pipeline, ninth valves, tenth valves, eleventh valves, twelfth valves, and thirteenth valves are respectively provided corresponding to the first core holder, the second core holder, the third core holder, the fourth core holder, and the fifth core holder; A fourteenth valve is provided on one side of the back pressure valve. A fifteenth valve is provided on the connecting pipeline between the back pressure valve and the second liquid collection device. A sixteenth valve is provided on the connecting pipeline between the second liquid collection device and the second drainage gas production device. A seventeenth valve is provided on the connecting pipeline between the back pressure valve and the anhydrous calcium chloride. An eighteenth valve is provided on the connecting pipeline between the back pressure valve and the vacuum pump.

3. A measurement method of the carbon dioxide dynamic water-rock reaction measurement device according to claim 2, characterized in that The measurement method includes: Step 1: Prepare rock samples to obtain the first rock sample, the second rock sample, the third rock sample, the fourth rock sample, and the fifth rock sample; Step 2: Respectively load the first rock sample, the second rock sample, the third rock sample, the fourth rock sample, and the fifth rock sample into the first core holder, the second core holder, the third core holder, the fourth core holder, and the fifth core holder. Start the confining pressure pump and open the valves of the corresponding pipelines to load the confining pressure to the experimental value on the core holders, and then open the vacuum pump to evacuate the cores; Step 3: Configure saturated carbon dioxide formation water; Step 4: Collect the pre-reaction fluid; Step 5: Carry out the carbon dioxide-water-rock reaction; Step 6: Collect the post-reaction fluid; Step 7: Measure the gas permeability of the rock sample: Open the valves of the corresponding pipelines of the second nitrogen intermediate container and the first core holder, turn on the heating device, heat the nitrogen to 120 °C fully, then open the third valve, displace the first core holder with high-temperature nitrogen. When the reading of the electronic balance no longer changes, it means that the outlet gas no longer contains water vapor, which means the core has been dried. Adjust the inlet of the first core holder to be driven by constant-pressure nitrogen, turn on the back pressure pump and the back pressure valve, set a specified back pressure at the outlet end, form a stable pressure difference at both ends of the first core holder, read the gas flow rate passing through the core per unit time through the electronic flowmeter, and calculate the gas permeability of the rock sample using the following formula: In the formula: K - air permeability, unit: μm 2 ; p0 - Atmospheric pressure, unit: MPa; p1 - Inlet end pressure, unit: MPa; p2 - Outlet end pressure, unit: MPa; μ - Gas viscosity, unit: mPa·s; L - Core length, unit: cm; d - Core diameter, unit: cm; Q0 - Gas volume flow rate, unit: mL / s; Step 8: When the gas permeability of the rock sample is greater than the liquid permeability, calculate the Klinkenberg permeability of the rock sample based on the gas permeability model; Step 9: Measure the porosity of the rock sample; Step 10: Measure the mineral components of the rock samples before and after the reaction by X-ray diffraction. After measuring the porosity, take out the first rock sample, cut a rock sample of a set length, grind the two rock samples of the set length before and after the reaction into powder respectively, and conduct X-ray diffraction to measure their mineral components and clay mineral components for comparative analysis of mineral changes. Step 11: After the experiment on the first group of rock samples is completed, repeat Step 1 to Step 10 according to different reaction stages set in the experiment until the measurement of the four groups of experiments is completed. By comparing the porosity, permeability, ion concentration changes, mineral composition changes and burial amounts at different reaction times, comprehensively evaluate the influence of the water-rock reaction on the reservoir and the mineralization burial amount.

4. The measurement method according to claim 3, wherein, The preparation of the rock samples includes: taking samples from the same well and the same well section, with the porosity and permeability deviation of the samples not exceeding 5%, the sample length being 12 cm, the diameter being 2.54 cm, and the number of samples being 5. Cut each sample into two sections of 2 cm and 10 cm.

5. The measuring method according to claim 3, characterized in that The configuration of the saturated carbon dioxide formation water includes: Constantly inject formation water into the solution configurator through an intermediate container at a constant speed, start the heating module of the solution configurator, heat the temperature of the solution configurator to the formation temperature, and set the constant temperature condition. Then, under the control of the injection pump, inject carbon dioxide into the solution configurator at a constant pressure through the carbon dioxide intermediate container. When the temperature of the solution configurator is stable at the formation temperature and the first pressure gauge reaches the formation pressure, close the fifth valve, start the heating module and the rotation control button of the solution configuration container, and stir under the formation temperature and pressure conditions until the formation fluid state is reached. After the solution configuration is completed, place the solution configurator vertically.

6. The measurement method according to claim 3, characterized in that The collection of the fluid before the reaction includes: Open the liquid collection device and the corresponding valves, collect the configured saturated carbon dioxide formation water, measure the ion components of the saturated carbon dioxide formation water, measure the carbon dioxide volume through the drainage gas collection device, and calculate the carbon dioxide solubility.

7. The measuring method according to claim 3, characterized in that The carrying out of the carbon dioxide water-rock reaction includes: Open the first six-way valve, inject the configured saturated carbon dioxide formation water into the first core holder, the second core holder, the third core holder, the fourth core holder and the fifth core holder, and raise the pressure to the formation pressure. Then close the first six-way valve, open the constant temperature box, adjust the temperature to the experimental set value, and start the carbon dioxide water-rock reaction.

8. The measuring method according to claim 3, characterized in that The collection of the fluid after the reaction includes: when the reaction proceeds to the set first time cut-off point, open the second liquid collection device and the corresponding pipeline valves, collect the fluid after the reaction and measure the ion composition and concentration, and use the second drainage gas collection device to measure the carbon dioxide volume to determine the current carbon dioxide solubility. Combine with Step 4 to analyze the changes in the ion composition and ion concentration of the fluid before and after the reaction, and calculate the carbon dioxide burial amount.

9. The measurement method according to claim 3, characterized in that, In the case where the core gas permeability is greater than the liquid permeability, calculate the absolute permeability of the rock sample based on the gas permeability model, including: Conduct experiments at multiple different average pressures, and calculate the gas-measured permeability according to the following formula: Determine K according to the following formula ∞ and The relationship is: In the formula: K ∞ represents the absolute permeability, with the unit of μm 2 ; Kg represents the gas permeability, with the unit of μm 2 ; Denote the average pressure at the inlet and outlet of the core, with the unit of MPa; b represents a constant depending on the gas properties and the rock pore structure; Plot the curve of Kg versus wherein there is a linear relationship between Kg and , and the intercept of the linear relationship on the Kg axis is K ∞ , which is the absolute permeability of the rock.

10. The measuring method according to claim 3, characterized in that, The measurement of the rock sample porosity includes: Close the valve of the first nitrogen intermediate container, turn on the vacuum pump to evacuate the first core holder to vacuum, then turn off the vacuum pump. Open the valves of the first helium intermediate container and the pipeline corresponding to the first rock sample, inject helium into the reference chamber, read the data T1 of the first temperature sensor and the data P1 of the second pressure gauge and record the data. Then open the second six-way valve to diffuse the gas in the reference chamber into the first core holder, read the data T2 of the second temperature sensor and the data P2 of the third pressure gauge 42 and record the data. Calculate the porosity through the following formula: Where: P1 represents the initial absolute pressure of the reference chamber; P2 represents the absolute pressure after expansion; P a represents the initial absolute atmospheric pressure in the rock sample; z1 represents the gas deviation factor at P1 and T1; z2 represents the gas deviation factor at P2 and T2; T 1r represents the absolute temperature of the reference chamber at the time of P1; T1 represents P a the absolute temperature of the pore space of the rock sample at T2 represents the absolute temperature of the rock sample and the reference chamber after P2 is balanced; V r represents the volume of the reference chamber; V p represents the pore volume of the rock sample; V v represents the valve displacement volume; V d represents the system dead volume.

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