A snowflake-shaped porous hydrate material capable of absorbing CO2 and its application system

Abstract

The present invention discloses a snowflake-shaped porous hydrate material capable of absorbing CO2 and an application system, including a snowflake-shaped porous hydrate material, characterized in that: the snowflake-shaped porous hydrate material is prepared from tetraethyl orthosilicate, a cationic surfactant, a small molecule organic amine and deionized water by a soft template method; the average pore size and pore volume of the sample are calculated by a BJH model. The present invention relates to the field of coal mine fire prevention and extinguishing, and specifically, to a snowflake-shaped porous hydrate material capable of absorbing CO2 and an application system. The technical problem to be solved by the present invention is to provide a snowflake-shaped porous hydrate material capable of absorbing CO2 and an application system. The snowflake-shaped porous hydrate has a good ability to absorb CO2. When transported to the mine, the working surface temperature can be reduced, so that the coal is not easy to reach its spontaneous combustion point, which is beneficial to the prevention and control of coal spontaneous combustion.

Description

Technical Field

[0001] The invention relates to the field of coal mine fire prevention and extinguishing, and in particular to a snowflake-shaped porous hydrate material capable of absorbing CO2 and an application system thereof. Background Art

[0002] Spontaneous combustion of coal is one of the five major disasters faced by coal mines. In the process of underground coal mining, it is inevitable that residual coal will be produced in the goaf. This part of the residual coal will undergo an exothermic oxidation reaction under the action of air leakage, and then there will be a risk of spontaneous combustion. Spontaneous combustion of coal will not only burn a large amount of equipment, instruments and coal, causing great waste of resources and posing a major threat to the safety of workers, but also emit a large amount of CO2 and damage the ecological environment. One of the main reasons for the spontaneous combustion of coal is that the coal body has good oxygen supply conditions. Therefore, blocking the oxygen supply or reducing the oxygen concentration is the key to preventing and controlling the spontaneous combustion of coal. In addition, nowadays, there are many production systems that produce CO2, and the CO2 gas produced by these production systems is often directly discharged into the atmosphere. Not only can it not be utilized, but it will also cause a greenhouse effect and increase global temperatures.

[0003] In response to the above problems, a snowflake-shaped porous hydrate material capable of absorbing CO2 and its application system are proposed. When a fire occurs in a mine, the system can prepare a snowflake-shaped porous hydrate material to absorb CO2 in industrial waste gas, and transport it to the mine to extinguish the fire and cool it down; when the coal mine is working normally, the system can transport a small amount of material to the working face to cool it down. The system can prevent and control underground fires, and at the same time absorb CO2 in factory waste gas, meeting the requirements of carbon emission reduction. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a snowflake-shaped porous hydrate material and application system that can adsorb CO2. The snowflake-shaped porous hydrate has a good ability to adsorb CO2. Transporting it to the mine can reduce the temperature of the working surface, making it difficult for coal to reach its auto-ignition point, which is beneficial to preventing and controlling coal spontaneous combustion.

[0005] The present invention adopts the following technical solutions to achieve the invention objectives:

[0006] A snowflake-shaped porous hydrate material capable of adsorbing CO2 and an application system, comprising a snowflake-shaped porous hydrate material, characterized in that: the snowflake-shaped porous hydrate material is prepared from tetraethyl orthosilicate, a cationic surfactant, a small molecule organic amine and deionized water by a soft template method; the average pore size and pore volume of the sample are calculated by a BJH model; the particle size of the mix-3 particles used to synthesize the snowflake-shaped porous hydrate is less than 170 nm, and the snowflake-shaped porous hydrate has mostly mesopores with a pore size of 2 to 50 nm.

[0007] As a further limitation of the present technical solution, the mass fraction ratio of the tetraethyl orthosilicate, the cationic surfactant, the small molecule organic amine and the deionized water is: 8.4:1.6:0.2:90.5~220.6.

[0008] As a further limitation of the present technical solution, the cationic surfactant is hexadecyltrimethylammonium toluenesulfonate, and the small molecule organic amine is triethanolamine.

[0009] As a further limitation of the present technical solution, the soft template method comprises the following steps:

[0010] Step 1: Weigh a certain mass of the cationic surfactant and add it into a beaker, weigh a certain mass of the small molecule organic amine and the deionized water and add them into the beaker containing the cationic surfactant in sequence, add a magnet into the beaker, place the beaker on a magnetic stirrer for the first stirring to mix them evenly, and obtain a mixture mix-1;

[0011] Step 2: After the cationic surfactant is completely dissolved in the small molecule organic amine, the tetraethyl orthosilicate is quickly added to the mixture mix-1 to obtain a new mixture mix-2;

[0012] Step 3: placing the mixture mix-2 on a magnetic stirrer for a second stirring, filtering the product after the stirring with a Buchner funnel, washing, and drying in an oven to obtain mix-3 particles;

[0013] Step 4: Mix the mix-3 particles and the deionized water, and then place them in a high-speed stirrer, and stir for a certain period of time to obtain the snowflake-shaped porous hydrate material.

[0014] A snowflake-shaped porous hydrate material application system capable of absorbing CO2, characterized in that it comprises: a snowflake-shaped porous hydrate preparation and application module, an intelligent control module and a carbon dioxide hydrate grouting module;

[0015] The snowflake-shaped porous hydrate preparation and application module includes: a liquid CO2 source, a gaseous CO2 source, a CO2 vaporization device, a reactor, a mix-3 particle preparation system, a water pump, a high-speed stirrer, a magnetic stirrer, an oven, a filter, a material storage tank and several valves;

[0016] The material storage tanks include a deionized water storage tank, a ethyl orthosilicate storage tank, a small molecule organic amine storage tank, a cationic surfactant storage tank, a second deionized water storage tank and a liquid CO2 storage tank;

[0017] The liquid CO2 source is connected to the liquid CO2 storage tank and the CO2 vaporizer through pipelines respectively, the CO2 vaporizer is connected to the reactor through a pipeline, and a first valve is installed on the pipeline connecting the CO2 vaporizer and the reactor; the gaseous CO2 source is connected to the reactor through a pipeline and a second valve is installed on the pipeline;

[0018] A sixth valve is installed on the pipeline connecting the reactor and the high-speed stirrer;

[0019] The upper end of the pipeline 1 is connected to the ground, a tenth valve is installed in the middle of the pipeline 1, and the lower end of the pipeline 1 is connected to the water pump. When the tenth valve is opened, deionized water can be transported to the water pump through the pipeline 1;

[0020] The mix-3 particle preparation system is connected to the high-speed agitator through a pipeline and a third valve is installed on the pipeline, the water pump is connected to the high-speed agitator through a pipeline and a fourth valve is installed on the pipeline, and the mix-3 particle preparation system is connected to the water pump through a pipeline and a fifth valve is installed on the pipeline;

[0021] The carbon dioxide hydrate grouting module includes a grouting pump, a seventh valve and a flow sensor. The grouting pump is connected to the reactor through a pipeline. The grouting pump is connected to pipeline 2, the flow sensor is installed on pipeline 2, and the seventh valve is installed between the flow sensor and the grouting pump. The flow sensor can monitor the flow of snowflake-shaped porous hydrate in real time during the grouting process.

[0022] As a further limitation of the present technical solution, the intelligent control module includes a display control device and a control wire, the display control device is installed on the well, and the control wire is used to electrically connect the reactor, the high-speed stirrer, the magnetic stirrer, the filter, the oven, the ion water storage tank, the ethyl orthosilicate storage tank, the small molecule organic amine storage tank, the cationic surfactant storage tank, the deionized water storage tank 2, the grouting pump and the flow sensor to the display control device, so that the intelligent control module controls the preparation of snowflake-shaped porous hydrates, adsorption of CO2 and grouting operations in the well. The intelligent control module can monitor the reactor, water pump, high-speed stirrer, magnetic stirrer and carbon dioxide hydrate grouting module of the snowflake-shaped porous hydrate preparation and application module, realize automatic grouting in the well, prevent and control coal mine fires, provide convenience for operators on the well, and reduce the probability of human errors and improve the safety of the staff.

[0023] As a further limitation of the technical solution, the process of preparing the snowflake-shaped porous hydrate underground is:

[0024] The material storage tank is controlled by the intelligent control module, 1.6 parts of the cationic surfactant is first added to the magnetic stirrer, and then 0.2 parts of a small molecule organic amine and 58 parts of deionized water are added in sequence. After the addition is completed, the magnetic stirrer is turned on, the stirring speed is 1200 rpm, the stirring temperature is 80° C., and the stirring is performed for 1 hour;

[0025] After the stirring is completed, 8.4 parts of the tetraethyl orthosilicate are added, the magnetic stirrer is turned on, the stirring speed is 1200 rpm, the stirring temperature is 80°C, and the stirring time is 1h. The obtained product is filtered and washed through the filtering device, and then transported to the oven for drying to obtain the mix-3 particles, wherein the filtration is carried out at room temperature, the drying temperature of the oven is set to 100°C, and the drying time is set to 20h;

[0026] Add the mix-3 particles and the deionized water into the high-speed agitator in a mass ratio of 1:9-19, wherein the deionized water comes from the deionized water storage tank 2, turn on the high-speed agitator at a speed of 19000 rpm, and stir for 60 seconds to obtain a snowflake-shaped porous hydrate.

[0027] As a further limitation of the technical solution, the application method of the snowflake-shaped porous hydrate is:

[0028] Open the sixth valve, transport the snowflake-shaped porous hydrate to the reactor through a pipeline, and use the vacuum pump provided by the reactor to extract the gas in the reactor and the pipeline;

[0029] When the vacuum pressure in the reactor reaches 2 atm, close the vacuum pump suction valve, open the vacuum pump inlet valve, and start to introduce CO2.

[0030] When introducing CO2, if the liquid CO2 source is selected, the liquid CO2 storage tank on the well is transported to the well as a material storage tank, the liquid CO2 storage tank is hoisted and transported from the vertical shaft to the well by transportation equipment, introduced to the liquid CO2 source, vaporized by the CO2 vaporizer, and the first valve is opened to introduce CO2 into the reactor;

[0031] If the gaseous CO2 source is selected, the second valve is opened to introduce CO2 into the reactor;

[0032] If the adsorbed CO2 is to be gaseous, the final pressure in the reactor is less than 6atm after the CO2 gas is filled in. If the adsorbed CO2 is to be liquid, the final pressure in the reactor is greater than 6atm after the CO2 gas is filled in.

[0033] When the pressure in the reactor reaches a specified value, the high-speed agitator is turned on to start the combination reaction of CO2 and the snowflake-shaped porous hydrate. After the reaction is carried out for 4 hours, the device is closed to obtain carbon dioxide hydrate.

[0034] As a further limitation of the present technical solution, when the carbon dioxide hydrate is input into pipeline 2 through the grouting pump and flows through the flow sensor, the flow sensor feeds back the obtained monitoring data to the intelligent control module. The intelligent control module adjusts the rate of synthesizing snowflake-shaped porous hydrate and the rate of adsorption of CO2 by the snowflake-shaped porous hydrate according to the feedback data, thereby adjusting the flow of the substance in the pipeline.

[0035] As a further limitation of the technical solution, the pipeline 2 is connected to the pipeline 3 and the pipeline 4, the pipeline 3 is installed with an eighth valve leading to the working face, and the pipeline 4 is installed with a ninth valve (9) leading to the goaf.

[0036] As a further limitation of the present technical solution, the snowflake-shaped porous hydrate material can be used to prevent and control coal spontaneous combustion, and its application principle is as follows: the snowflake-shaped porous hydrate adsorbs CO2 to generate a carbon dioxide hydrate, which is injected into the surface of the coal gap through a grouting pump to seal the cracks. When the temperature rises, the CO2 in the carbon dioxide hydrate will be released, reducing the oxygen concentration on the surface of the coal body in situ, thereby delaying or inhibiting the occurrence of coal spontaneous combustion.

[0037] Compared with the prior art, the advantages and positive effects of the present invention are:

[0038] 1. This material has a good ability to absorb CO2. By absorbing CO2 in factory exhaust gas, it can not only use CO2 in factory exhaust gas to extinguish fires and cool down coal mines, but also reduce CO2 emissions and make rational use of CO2 in industrial exhaust gas.

[0039] 2. The device prepares snowflake-shaped porous hydrates through computer control. The addition of materials and the reaction can be strictly and accurately monitored and operated, realizing underground automated grouting, providing convenience for workers, reducing human errors and improving safety.

[0040] 3. After the snowflake-shaped porous hydrate adsorbs CO2, it can not only reduce the oxygen concentration and inhibit the coal-oxygen reaction, but also reduce the temperature at the fire source and reduce the probability of re-ignition. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 Diagram of the preparation of snowflake-shaped porous hydrate and its application in goaf and working face.

[0042] Figure 2 This is the intelligent control module diagram.

[0043] Figure 3 TEM image of snowflake-like porous hydrate.

[0044] Figure 4 N2 adsorption / desorption isotherms and pore size distribution curves of the samples.

[0045] In the figure: 1. first valve; 2. second valve; 3. third valve; 4. fourth valve; 5. fifth valve; 6. sixth valve; 7. seventh valve; 8. eighth valve; 9. ninth valve; 10. tenth valve; 11. liquid CO2 source; 12. gaseous CO2 source; 13. CO2 vaporizer; 14. reactor; 15. mix-3 particle preparation device; 16. water pump; 17. high-speed agitator; 18. grouting pump; 19. flow sensor; 20. intelligent control module; 21. liquid CO2 storage tank; 22. deionized water storage tank; 23. tetraethyl orthosilicate storage tank; 24. small molecule organic amine storage tank; 25. cationic surfactant storage tank; 26. magnetic agitator; 27. filtering device; 28. oven; 29. ​​deionized water storage tank; 30. pipeline one; 31. pipeline two; 32. pipeline three; 33. pipeline four. DETAILED DESCRIPTION

[0046] A specific implementation of the present invention is described in detail below in conjunction with the accompanying drawings, but it should be understood that the protection scope of the present invention is not limited by the specific implementation.

[0047] The present invention includes a snowflake-shaped porous hydrate material, which is prepared from tetraethyl orthosilicate, a cationic surfactant, a small molecule organic amine and deionized water by a soft template method. The average pore size and pore volume of the sample are calculated by a BJH model. The particle size of the mix-3 particles used to synthesize the snowflake-shaped porous hydrate is less than 170 nm. Most of the snowflake-shaped porous hydrate has mesopores with a pore size of 2 to 50 nm.

[0048] According to experiments, the mesopores of this material with a pore size between 15-16nm have excellent CO2 adsorption capacity.

[0049] Depend on Figure 4 It can be seen that there is a hysteresis loop in the adsorption / desorption isotherm, indicating that the sample has a mesoporous structure, which is conducive to its adsorption of CO2, which is consistent with the TEM results. The pore size distribution curve is unimodal, and the peak is mainly around 15-16nm, indicating that the adsorption effect is best within this range.

[0050] The mass fraction ratio of the tetraethyl orthosilicate, the cationic surfactant, the small molecule organic amine and the deionized water is: 8.4:1.6:0.2:90.5~220.6.

[0051] The cationic surfactant is hexadecyltrimethylammonium p-toluenesulfonate, and the small molecule organic amine is triethanolamine.

[0052] The soft template method comprises the following steps:

[0053] Step 1: Weigh a certain mass of the cationic surfactant and add it into a beaker, weigh a certain mass of the small molecule organic amine and the deionized water and add them into the beaker containing the cationic surfactant in sequence, add a magnet into the beaker, place the beaker on a magnetic stirrer for the first stirring to mix them evenly, and obtain a mixture mix-1;

[0054] Step 2: After the cationic surfactant is completely dissolved in the small molecule organic amine, the tetraethyl orthosilicate is quickly added to the mixture mix-1 to obtain a new mixture mix-2;

[0055] Step 3: placing the mixture mix-2 on a magnetic stirrer for a second stirring, filtering the product after the stirring with a Buchner funnel, washing, and drying in an oven to obtain mix-3 particles;

[0056] Step 4: Mix the mix-3 particles and the deionized water, and then place them in a high-speed stirrer, and stir for a certain period of time to obtain the snowflake-shaped porous hydrate material.

[0057] In the step 1, the mass ratio of the cationic surfactant, the small molecule organic amine and the deionized water is 1.6:0.2:58, and the mass ratio of the tetraethyl orthosilicate and the mixture mix-1 is 8.4:59.8;

[0058] In the step 1, the first stirring setting parameters of the magnetic stirrer are as follows: stirring time is 1h, stirring speed is 1200 rpm, stirring temperature is 80°C, and the second stirring parameters of the magnetic stirrer are as follows: stirring time is 1h, stirring speed is 1200 rpm, stirring temperature is 80°C;

[0059] In the step 1, the filtration is carried out at room temperature, the temperature of the oven is set to 100° C. during drying, and the drying time is set to 20 h;

[0060] In the step 1, the particle size of the obtained mix-3 particles is between 115 and 170 nm, wherein the particle size of most particles is between 135 and 145 nm;

[0061] In the step 2, the mass ratio of mix-3 particles to deionized water is 1:9~19.

[0062] In the step 2, the setting parameters of the high-speed stirrer are as follows: stirring time is 60s, and stirring speed is 19000 rpm.

[0063] A snowflake-shaped porous hydrate material application system capable of absorbing CO2, characterized in that it comprises: a snowflake-shaped porous hydrate preparation and application module, an intelligent control module 20 and a carbon dioxide hydrate grouting module;

[0064] The snowflake-shaped porous hydrate preparation and application module includes: a liquid CO2 source 11, a gaseous CO2 source 12, a CO2 vaporization device 13, a reactor 14, a mix-3 particle preparation system 15, a water pump 16, a high-speed stirrer 17, a magnetic stirrer 26, an oven 28, a filter device 27, a material storage tank and several valves;

[0065] The material storage tanks include a deionized water storage tank 22, a tetraethyl orthosilicate storage tank 23, a small molecule organic amine storage tank 24, a cationic surfactant storage tank 25, a deionized water storage tank 29 and a liquid CO2 storage tank 21;

[0066] The liquid CO2 source 11 is connected to the liquid CO2 storage tank 21 and the CO2 vaporizer 13 through pipelines, respectively. The CO2 vaporizer 13 is connected to the reactor 14 through pipelines. A first valve 1 is installed on the pipeline connecting the CO2 vaporizer 13 and the reactor 14. The gaseous CO2 source 12 is connected to the reactor 14 through pipelines and a second valve 2 is installed on the pipeline.

[0067] A sixth valve 6 is installed on the pipeline connecting the reactor 14 and the high-speed stirrer 17;

[0068] The upper end of the pipeline 1 30 is connected to the ground, the middle of the pipeline 1 30 is provided with a tenth valve 10, and the lower end of the pipeline 1 30 is connected to the water pump 16. When the tenth valve 10 is opened, deionized water can be transported to the water pump 16 through the pipeline 1 30;

[0069] The mix-3 particle preparation system 15 is connected to the high-speed agitator 17 through a pipeline and a third valve 3 is installed on the pipeline, the water pump 16 is connected to the high-speed agitator 17 through a pipeline and a fourth valve 4 is installed on the pipeline, and the mix-3 particle preparation system 15 is connected to the water pump 16 through a pipeline and a fifth valve 5 is installed on the pipeline;

[0070] The carbon dioxide hydrate grouting module includes a grouting pump 18, a seventh valve 7 and a flow sensor 19. The grouting pump 18 is connected to the reactor 14 through a pipeline. The grouting pump 18 is connected to the pipeline 2 31. The flow sensor 19 is installed on the pipeline 2 31. The seventh valve 7 is installed between the flow sensor 19 and the grouting pump 18.

[0071] The flow sensor 19 can monitor the flow of snowflake-shaped porous hydrate in real time during the grouting process.

[0072] The intelligent control module 20 includes a display control device and a control wire, the display control device is installed on the well, and the control wire is used to electrically connect the reactor 14, the high-speed stirrer 17, the magnetic stirrer 26, the filter 27, the oven 28, the ion water storage tank 22, the ethyl orthosilicate storage tank 23, the small molecule organic amine storage tank 24, the cationic surfactant storage tank 25, the deionized water storage tank 29, the grouting pump 18 and the flow sensor 19 to the display control device, so that the intelligent control module controls the preparation, adsorption of CO2 and grouting operations of snowflake-shaped porous hydrates in the well. The intelligent control module 20 can monitor the reactor 14, water pump 16, high-speed stirrer 17, magnetic stirrer 26 and carbon dioxide hydrate grouting module of the snowflake-shaped porous hydrate preparation and application module, realize automatic grouting in the well, prevent and control coal mine fires, provide convenience for operators on the well, and reduce the probability of human errors and improve the safety of workers.

[0073] The process of preparing the snowflake-shaped porous hydrate underground is:

[0074] The material storage tank is controlled by the intelligent control module 20, and 1.6 parts of the cationic surfactant are first added to the magnetic stirrer 26, and then 0.2 parts of small molecule organic amine and 58 parts of deionized water are added in sequence. After the addition is completed, the magnetic stirrer 26 is turned on, the stirring speed is 1200 rpm, the stirring temperature is 80° C., and the stirring is performed for 1 hour;

[0075] After the stirring is completed, 8.4 parts of the tetraethyl orthosilicate are added, the magnetic stirrer 26 is turned on, the stirring speed is 1200 rpm, the stirring temperature is 80° C., and the stirring time is 1 h. The obtained product is filtered and washed by the filtering device 27, and then transported to the oven 28 for drying to obtain the mix-3 particles, wherein the filtration is carried out at room temperature, the drying temperature of the oven 28 is set to 100° C., and the drying time is set to 20 h;

[0076] Add the mix-3 particles and the deionized water into the high-speed agitator 17 in a mass ratio of 1:9-19, wherein the deionized water comes from the deionized water storage tank 29, turn on the high-speed agitator 17 at a speed of 19000 rpm, and stir for 60 seconds to obtain a snowflake-shaped porous hydrate.

[0077] The application method of the snowflake-shaped porous hydrate is as follows:

[0078] Open the sixth valve 6, transport the snowflake-shaped porous hydrate to the reactor 14 through the pipeline, and use the vacuum pump of the reactor 14 to extract the gas in the reactor 14 and the pipeline;

[0079] When the vacuum pressure in the reactor 14 reaches 2 atm, close the vacuum pump suction valve, open the vacuum pump inlet valve, and start to introduce CO2.

[0080] When CO2 is introduced, if the liquid CO2 source 11 is selected, the liquid CO2 storage tank 21 on the well is transported to the well as a material storage tank, and the liquid CO2 storage tank 21 is hoisted and transported from the vertical shaft to the well by transportation equipment, introduced to the liquid CO2 source 11, vaporized by the CO2 vaporizer 13, and the first valve 1 is opened to introduce CO2 into the reactor 14;

[0081] If the gaseous CO2 source 12 is selected, the second valve 2 is opened to introduce CO2 into the reactor 14;

[0082] If the adsorbed CO2 is to be gaseous, the final pressure in the reactor 14 is less than 6 atm after the CO2 gas is filled in. If the adsorbed CO2 is to be liquid, the final pressure in the reactor 14 is greater than 6 atm after the CO2 gas is filled in.

[0083] When the pressure in the reactor 14 reaches a specified value, the high-speed agitator 17 is turned on to start the combination reaction of CO2 and the snowflake-shaped porous hydrate. After the reaction is carried out for 4 hours, the device is closed to obtain carbon dioxide hydrate.

[0084] The carbon dioxide hydrate is input into pipeline 2 31 through the grouting pump 18. When it flows through the flow sensor 19, the flow sensor 19 feeds back the obtained monitoring data to the intelligent control module 20. The intelligent control module 20 adjusts the rate of synthesizing snowflake-shaped porous hydrate and the rate of adsorption of CO2 by snowflake-shaped porous hydrate according to the feedback data, thereby adjusting the flow of the material in the pipeline.

[0085] The pipeline 2 31 is connected to the pipeline 3 32 and the pipeline 4 33. The pipeline 3 32 is installed with an eighth valve 8 leading to the working face. The pipeline 4 33 is installed with a ninth valve 9 leading to the goaf.

[0086] The snowflake-shaped porous hydrate material can be used to prevent and control coal spontaneous combustion, and its application principle is: the snowflake-shaped porous hydrate adsorbs CO2 to generate a carbon dioxide hydrate, which is injected into the surface of the coal gap through a grouting pump to seal the cracks. When the temperature rises, the CO2 in the carbon dioxide hydrate will be released, reducing the oxygen concentration on the surface of the coal body in situ, thereby delaying or inhibiting the occurrence of coal spontaneous combustion.

[0087] The above disclosure is only a specific embodiment of the present invention, but the present invention is not limited thereto, and any changes that can be conceived by those skilled in the art should fall within the protection scope of the present invention.

Claims

1. A snowflake-shaped porous hydrate material capable of adsorbing CO2, comprising a snowflake-shaped porous hydrate material, characterized in that: The snowflake-shaped porous hydrate material is prepared from tetraethyl orthosilicate, a cationic surfactant, a small molecule organic amine and deionized water by a soft template method, wherein the cationic surfactant is hexadecyltrimethylammonium p-toluenesulfonate, the small molecule organic amine is triethanolamine, and the mass fraction ratio of the tetraethyl orthosilicate, the cationic surfactant, the small molecule organic amine and the deionized water is: 8.4:1.6:0.2:90.5~220.6, the specific steps are as follows: Step 1: Weigh a certain mass of the cationic surfactant and add it into a beaker, weigh a certain mass of the small molecule organic amine and the deionized water and add them into the beaker containing the cationic surfactant in sequence, add a magnet into the beaker, place the beaker on a magnetic stirrer for the first stirring to mix them evenly, and obtain a mixture mix-1; Step 2: After the cationic surfactant is completely dissolved in the small molecule organic amine, the tetraethyl orthosilicate is quickly added to the mixture mix-1 to obtain a new mixture mix-2; Step 3: placing the mixture mix-2 on a magnetic stirrer for a second stirring, filtering the product after the stirring with a Buchner funnel, washing, and drying in an oven to obtain mix-3 particles; Step 4: Mix the mix-3 particles and the deionized water, and then place them in a high-speed stirrer, and stir for a certain period of time to obtain the snowflake-shaped porous hydrate material; the particle size of the mix-3 particles is less than 170 nm, and the average pore size and pore volume of the sample are calculated using the BJH model. The snowflake-shaped porous hydrate has mesopores with a pore size of 2~50nm.

2. An application system using the method for preparing the snowflake-shaped porous hydrate material capable of adsorbing CO2 according to claim 1, characterized in that: include: A snowflake-shaped porous hydrate preparation and application module, an intelligent control module (20) and a carbon dioxide hydrate grouting module; The snowflake-shaped porous hydrate preparation and application module comprises: a liquid CO2 source (11), a gaseous CO2 source (12), a CO2 vaporization device (13), a reaction kettle (14), a mix-3 particle preparation system (15), a water pump (16), a high-speed stirrer (17), a magnetic stirrer (26), an oven (28), a filtering device (27), a material storage tank and a plurality of valves; The material storage tanks include a deionized water storage tank (22), a tetraethyl orthosilicate storage tank (23), a small molecule organic amine storage tank (24), a cationic surfactant storage tank (25), a second deionized water storage tank (29) and a liquid CO2 storage tank (21); The liquid CO2 source (11) is connected to the liquid CO2 storage tank (21) and the CO2 vaporizer (13) through pipelines, respectively; the CO2 vaporizer (13) is connected to the reactor (14) through a pipeline; a first valve (1) is installed on the pipeline connecting the CO2 vaporizer (13) and the reactor (14); the gaseous CO2 source (12) is connected to the reactor (14) through a pipeline and a second valve (2) is installed on the pipeline; A sixth valve (6) is installed on the pipeline connecting the reaction kettle (14) and the high-speed stirrer (17); The upper end of the pipeline one (30) is connected to the ground, a tenth valve (10) is installed in the middle of the pipeline one (30), and the lower end of the pipeline one (30) is connected to the water pump (16). When the tenth valve (10) is opened, deionized water can be transported to the water pump (16) through the pipeline one (30); The mix-3 particle preparation system (15) is connected to the high-speed agitator (17) via a pipeline and a third valve (3) is installed on the pipeline, the water pump (16) is connected to the high-speed agitator (17) via a pipeline and a fourth valve (4) is installed on the pipeline, and the mix-3 particle preparation system (15) is connected to the water pump (16) via a pipeline and a fifth valve (5) is installed on the pipeline; The carbon dioxide hydrate grouting module comprises a grouting pump (18), a seventh valve (7) and a flow sensor (19); the grouting pump (18) is connected to the reactor (14) via a pipeline; the grouting pump (18) is connected to a second pipeline (31); the flow sensor (19) is installed on the second pipeline (31); and the seventh valve (7) is installed between the flow sensor (19) and the grouting pump (18); The intelligent control module (20) comprises a display control device and control wires. The display control device is installed on the well. The control wires are used to electrically connect the reaction kettle (14), the high-speed stirrer (17), the magnetic stirrer (26), the filtering device (27), the oven (28), the ion water storage tank (22), the tetraethyl orthosilicate storage tank (23), the small molecule organic amine storage tank (24), the cationic surfactant storage tank (25), the second deionized water storage tank (29), the grouting pump (18) and the flow sensor (19) to the display control device.

3. The application system of the snowflake-shaped porous hydrate material capable of adsorbing CO2 according to claim 2 is characterized in that: The process of preparing the snowflake-shaped porous hydrate underground is: The material storage tank is controlled by the intelligent control module (20), and 1.6 parts of the cationic surfactant is first added to the magnetic stirrer (26), and then 0.2 parts of a small molecule organic amine and 58 parts of deionized water are added in sequence. After the addition is completed, the magnetic stirrer (26) is turned on, the stirring speed is 1200 rpm, the stirring temperature is 80°C, and the stirring is continued for 1 hour; After the stirring is completed, 8.4 parts of the tetraethyl orthosilicate are added, the magnetic stirrer (26) is turned on, the stirring speed is 1200 rpm, the stirring temperature is 80° C., and the stirring time is 1 h. The obtained product is filtered and washed through the filtering device (27), and then transported to the oven (28) for drying to obtain the mix-3 particles, wherein the filtration is carried out at room temperature, the drying temperature of the oven (28) is set to 100° C., and the drying time is set to 20 h; Add the mix-3 particles and the deionized water into the high-speed agitator (17) in a mass ratio of 1:9 to 19, wherein the deionized water comes from the deionized water storage tank 2 (29), turn on the high-speed agitator (17) at a speed of 19,000 rpm, and stir for 60 seconds to obtain a snowflake-shaped porous hydrate.

4. The application system of the snowflake-shaped porous hydrate material capable of adsorbing CO2 according to claim 2 is characterized in that: The application method of the snowflake-shaped porous hydrate is as follows: Open the valve (6), transport the snowflake-shaped porous hydrate to the reactor (14) through the pipeline, and use the vacuum pump provided in the reactor (14) to extract the gas in the reactor (14) and the pipeline; When the vacuum pressure in the reactor (14) reaches 2 atm, close the vacuum pump suction valve, open the vacuum pump air inlet valve, and start to introduce CO2; When adsorbing CO2, if the liquid CO2 source (11) is selected, the liquid CO2 storage tank (21) on the well is transported to the well as a material storage tank, the liquid CO2 storage tank (21) is hoisted from the vertical shaft to the well by transportation equipment, introduced into the liquid CO2 source (11), vaporized by the CO2 vaporizer (13), and the first valve (1) is opened to introduce CO2 into the reactor (14); If the gaseous CO2 source (12) is selected, the second valve (2) is opened to introduce CO2 into the reaction kettle (14); If the adsorbed CO2 is to be in a gaseous state, the final pressure in the reactor (14) is less than 6 atm after the CO2 gas is filled in; if the adsorbed CO2 is to be in a liquid state, the final pressure in the reactor (14) is greater than 6 atm after the CO2 gas is filled in; When the pressure in the reactor (14) reaches a specified value, the high-speed agitator (17) is turned on to start the combination reaction of CO2 and the snowflake-shaped porous hydrate. After the reaction is carried out for 4 hours, the device is closed to obtain carbon dioxide hydrate.

5. The application system of the snowflake-shaped porous hydrate material capable of absorbing CO2 according to claim 4 is characterized in that: The carbon dioxide hydrate is input into pipeline 2 (31) through the grouting pump (18). When it flows through the flow sensor (19), the flow sensor (19) feeds back the obtained monitoring data to the intelligent control module (20). The intelligent control module (20) adjusts the rate of synthesizing snowflake-shaped porous hydrate and the rate of adsorption of CO2 by the snowflake-shaped porous hydrate according to the feedback data, thereby adjusting the flow rate of the material in the pipeline.

6. The application system of the snowflake-shaped porous hydrate material capable of absorbing CO2 according to claim 4 is characterized in that: The pipeline 2 (31) is connected to the pipeline 3 (32) and the pipeline 4 (33); the pipeline 3 (32) is provided with an eighth valve (8) leading to the working face; the pipeline 4 (33) is provided with a ninth valve (9) leading to the goaf.

7. The application system of the snowflake-shaped porous hydrate material capable of absorbing CO2 according to claim 3 is characterized in that: The snowflake-shaped porous hydrate material can be used to prevent and control coal spontaneous combustion, and its application principle is: the snowflake-shaped porous hydrate adsorbs CO2 to generate a carbon dioxide hydrate, which is injected into the surface of the coal gap through a grouting pump to seal the cracks. When the temperature rises, the CO2 in the carbon dioxide hydrate will be released, reducing the oxygen concentration on the surface of the coal body in situ, thereby delaying or inhibiting the occurrence of coal spontaneous combustion.

Images