CN116393099A - Adsorbable CO 2 Snowflake-shaped porous hydrate material and application system thereof - Google Patents
Adsorbable CO 2 Snowflake-shaped porous hydrate material and application system thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 67
- 241000533950 Leucojum Species 0.000 claims abstract description 47
- 239000008367 deionised water Substances 0.000 claims abstract description 45
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 45
- 239000003245 coal Substances 0.000 claims abstract description 35
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 33
- 150000001412 amines Chemical class 0.000 claims abstract description 30
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 238000001179 sorption measurement Methods 0.000 claims abstract description 12
- 238000003860 storage Methods 0.000 claims description 62
- 238000006243 chemical reaction Methods 0.000 claims description 60
- 238000003756 stirring Methods 0.000 claims description 43
- 239000002245 particle Substances 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 29
- VTVVPPOHYJJIJR-UHFFFAOYSA-N carbon dioxide;hydrate Chemical compound O.O=C=O VTVVPPOHYJJIJR-UHFFFAOYSA-N 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 13
- 239000006200 vaporizer Substances 0.000 claims description 13
- 238000002485 combustion reaction Methods 0.000 claims description 11
- 230000002269 spontaneous effect Effects 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 101100184147 Caenorhabditis elegans mix-1 gene Proteins 0.000 claims description 7
- 230000001276 controlling effect Effects 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 230000008016 vaporization Effects 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 230000003111 delayed effect Effects 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000009834 vaporization Methods 0.000 claims description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims 1
- 230000002265 prevention Effects 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Natural products O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000007569 slipcasting Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21F—SAFETY DEVICES, TRANSPORT, FILLING-UP, RESCUE, VENTILATION, OR DRAINING IN OR OF MINES OR TUNNELS
- E21F5/00—Means or methods for preventing, binding, depositing, or removing dust; Preventing explosions or fires
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/006—Processes utilising sub-atmospheric pressure; Apparatus therefor
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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Abstract
The invention discloses a method for adsorbing CO 2 Snowflake-shaped porous hydrate material and application system thereof, comprising snowflake-shaped porous hydrate material, characterized in that: the snowflake porous hydrate material is prepared from tetraethoxysilane, a cationic surfactant, small molecular organic amine and deionized water by adopting a soft template method; the average pore size and pore volume of the samples were calculated using the BJH model. The invention relates to the field of coal mine fire prevention and extinguishment, in particular to a device capable of adsorbing CO 2 Snowflake-shaped porous hydrate material and application system thereof. The invention aims to solveThe technical problem is to provide a device capable of adsorbing CO 2 Snowflake-shaped porous hydrate material and application system thereof, and snowflake-shaped porous hydrate has good CO adsorption 2 The coal is transported to the place under the mine, so that the temperature of the working face can be reduced, the coal is not easy to reach the self-ignition point, and further the self-ignition of the coal is prevented.
Description
Technical Field
The invention relates to the field of coal mine fire prevention and extinguishment, in particular to a device capable of adsorbing CO 2 Snowflake-shaped porous hydrate material and application system thereof.
Background
Coal spontaneous combustion fire is one of five disasters faced downhole in coal mines. In the underground coal mining process, coal is inevitably left in the goaf, and oxidation exothermic reaction can be generated on the coal left under the action of air leakage, so that spontaneous combustion and ignition danger can be generated. The spontaneous combustion of coal not only can burn a large amount of equipment, equipment and coal, greatly wastes resources and brings great threat to the safety of staff, but also can discharge a large amount of CO 2 The ecological environment is destroyed. One of the main reasons for spontaneous combustion of coal is that coal has good oxygen supply conditions, so that blocking oxygen supply or reducing oxygen concentration is a key for preventing and controlling spontaneous combustion of coal. In addition, there are many CO generation at present 2 And the CO produced by these production systems 2 The gas is often directly discharged into the atmosphere, which not only can not be utilized, but also can cause a greenhouse effect and raise the global temperature.
In order to solve the problems, a method for adsorbing CO is provided 2 Snowflake-shaped porous hydrate material and application system thereof. In case of fire in mine, the system can adsorb CO from industrial waste gas by preparing snowflake porous hydrate material 2 Transporting the fire source to the underground mine to extinguish the fire and reduce the temperature; when the coal mine works normally, the system canTo cool the work surface by transporting a small amount of material to the work surface. The system can prevent and treat underground fire and absorb CO in waste gas of factories 2 Meets the requirements of carbon emission reduction.
Disclosure of Invention
The invention aims to provide a device capable of adsorbing CO 2 Snowflake-shaped porous hydrate material and application system thereof, and snowflake-shaped porous hydrate has good CO adsorption 2 The coal is transported to the place under the mine, so that the temperature of the working face can be reduced, the coal is not easy to reach the self-ignition point, and further the self-ignition of the coal is prevented.
The invention adopts the following technical scheme to realize the aim of the invention:
adsorbable CO 2 Snowflake-shaped porous hydrate material and application system thereof, comprising snowflake-shaped porous hydrate material, characterized in that: the snowflake porous hydrate material is prepared from tetraethoxysilane, a cationic surfactant, small molecular organic amine and deionized water by adopting a soft template method; the average pore diameter and pore volume of the sample are calculated by adopting a BJH model; the size of mix-3 particles used for synthesizing snowflake porous hydrate is smaller than 170 and nm, and most of snowflake porous hydrate has mesopores with the pore diameter of 2-50 nm.
As a further limitation of the technical scheme, the mass fraction ratio of the tetraethoxysilane, the cationic surfactant, the small molecular organic amine and the deionized water is as follows: 8.4:1.6:0.2: 90.5-220.6.
As a further limitation of the present technical solution, the cationic surfactant is cetyltrimethyl-p-toluenesulfonammonium and the small molecule organic amine is triethanolamine.
As a further limitation of the present technical solution, the soft template method includes the following steps:
step 1: weighing a certain mass of cationic surfactant, adding the cationic surfactant into a beaker, weighing a certain mass of small molecular organic amine and deionized water, sequentially adding the small molecular organic amine and the deionized water into the beaker containing the cationic surfactant, adding a magnet into the beaker, placing the beaker on a magnetic stirrer, and stirring for the first time to uniformly mix the two materials to obtain a mixture mix-1;
step 2: after the cationic surfactant is completely dissolved in the small molecular organic amine, quickly adding the ethyl orthosilicate into the mixture mix-1 to obtain a new mixture mix-2;
step 3: placing the mixture mix-2 on a magnetic stirrer for secondary stirring, filtering the stirred product by using a Buchner funnel, washing, and drying by using an oven to obtain mix-3 particles;
step 4: mixing the mix-3 particles with the deionized water, then placing the mixture in a high-speed stirrer, and stirring for a certain time to obtain the snowflake-shaped porous hydrate material.
Adsorbable CO 2 A snowflake-shaped porous hydrate material application system, comprising: the device comprises a snowflake porous hydrate preparation and application module, an intelligent control module and a carbon dioxide hydrate grouting module;
the snowflake porous hydrate preparation and application module comprises: liquid CO 2 Source, gaseous CO 2 Source, CO 2 The device comprises a vaporization device, a reaction kettle, a mix-3 particle preparation system, a water pump, a high-speed stirrer, a magnetic stirrer, an oven, a filtering device, a material storage tank and a plurality of valves;
the material storage tank comprises a deionized water storage tank, an ethyl orthosilicate storage tank, a micromolecular organic amine storage tank, a cationic surfactant storage tank, a deionized water storage tank II and liquid CO 2 A storage tank;
said liquid CO 2 The source is respectively connected with the liquid CO through pipelines 2 Storage tank and CO 2 The vaporizer is communicated with CO 2 The vaporizer is communicated with the reaction kettle through a pipeline, and the CO 2 A first valve is arranged on a connecting pipeline of the vaporizer and the reaction kettle; said gaseous CO 2 The source is connected with the reaction kettle through a pipeline, and a second valve is arranged on the pipeline;
a sixth valve is arranged on the communication pipeline between the reaction kettle and the high-speed stirrer;
the upper end of the first pipeline is connected to the ground, a tenth valve is arranged in the middle of the first pipeline, the lower end of the first pipeline is connected with the water pump, the tenth valve is opened, and deionized water can be conveyed into the water pump through the first pipeline;
the mix-3 particle preparation system is communicated with the high-speed stirrer through a pipeline, a third valve is arranged on the pipeline, the water pump is communicated with the high-speed stirrer through a pipeline, a fourth valve is arranged on the pipeline, and the mix-3 particle preparation system is communicated with the water pump through a pipeline, and a fifth valve is arranged on the pipeline;
the carbon dioxide hydrate grouting module comprises a grouting pump, a seventh valve and a flow sensor, wherein the grouting pump is communicated with the reaction kettle through a pipeline, the grouting pump is communicated with a pipeline II, the flow sensor is arranged on the pipeline II, and the seventh valve is arranged between the flow sensor and the grouting pump. The flow sensor can monitor snowflake porous hydrate flow in real time in the grouting process.
As a further limitation of the technical scheme, the intelligent control module comprises a display control device and a control wire, wherein the display control device is installed on a well, and the control wire is used for electrically connecting the reaction kettle, the high-speed stirrer, the magnetic stirrer, the filtering device, the oven, the ionized water storage tank, the tetraethyl orthosilicate storage tank, the small molecular organic amine storage tank, the cationic surfactant storage tank, the deionized water storage tank II, the grouting pump and the flow sensor to the display control device, so that the intelligent control module controls preparation of underground snowflake porous hydrate, CO2 adsorption and grouting operation. The intelligent control module can monitor the reaction kettle, the water pump, the high-speed stirrer, the magnetic stirrer and the carbon dioxide hydrate grouting module of the snowflake porous hydrate preparation and application module, realize underground automatic grouting, prevent and treat coal mine fires, provide convenience for operators on the well, reduce the probability of human errors and improve the safety of the operators.
As a further limitation of the technical scheme, the flow of the snowflake porous hydrate prepared under the well is as follows:
the intelligent control module is used for controlling the material storage tank, 1.6 parts of the cationic surfactant is firstly added into the magnetic stirrer, then 0.2 part of the micromolecular organic amine and 58 parts of deionized water are sequentially added, after the addition is finished, the magnetic stirrer is started, the stirring speed is 1200 revolutions per minute, the stirring temperature is 80 ℃, and the stirring is carried out for 1 hour;
after stirring, adding 8.4 parts of ethyl orthosilicate, starting the magnetic stirrer, wherein the stirring speed is 1200 r/min, the stirring temperature is 80 ℃, the stirring time is 1h, filtering and washing the obtained product by the filtering device, and then conveying the product to the oven for drying to obtain mix-3 particles, wherein the filtering is performed at normal temperature, the drying temperature of the oven is set to 100 ℃, and the drying time is set to 20h;
and adding mix-3 particles and deionized water into the high-speed stirrer, wherein the mass ratio of the mix-3 particles to the deionized water is 1: 9-19, wherein the deionized water is sourced from the second deionized water storage tank, the high-speed stirrer is started, the rotating speed is 19000 r/min, and the snowflake porous hydrate is obtained after stirring for 60 s.
As a further limitation of the technical scheme, the snowflake porous hydrate is applied by the following method:
opening the sixth valve, transporting the snowflake porous hydrate into the reaction kettle through a pipeline, and pumping out the gases in the reaction kettle and the pipeline by utilizing a vacuum pump of the reaction kettle;
when the vacuum pressure in the reaction kettle reaches 2atm, closing a vacuum pump suction valve, opening a vacuum pump air inlet valve, and starting to introduce CO 2 ，
CO is introduced into 2 If the liquid CO is selected 2 A source for feeding said liquid CO into the well 2 The storage tank is transported underground as a material storage tank, and the liquid CO 2 The storage tank is hoisted and transported from the vertical shaft to the underground through the transportation equipment and is introduced into the liquid CO 2 A source through the CO 2 The vaporizer is used for vaporization, the first valve is opened to introduce CO into the reaction kettle 2 ；
If the gaseous CO is selected 2 The source is used for opening the second valve to introduce CO into the reaction kettle 2 ；
To make the absorbed CO 2 In the gaseous state, is filled with CO 2 After the gas is discharged, the final pressure in the reaction kettle is less than 6atm, if the adsorbed CO is required 2 Is in liquid state and is filled with CO 2 After the gas is discharged, the final pressure in the reaction kettle is higher than 6atm;
when the pressure in the reaction kettle reaches a specified value, starting the high-speed stirrer to start CO 2 And (3) carrying out a combination reaction with the snowflake porous hydrate, and closing the device after the reaction is carried out for 4 hours to obtain the carbon dioxide hydrate.
As a further limitation of the technical scheme, when the carbon dioxide hydrate flows through the flow sensor through the second grouting pump input pipeline, the flow sensor feeds back obtained monitoring data to the intelligent control module, and the intelligent control module adjusts the rate of synthesizing snowflake porous hydrate and the adsorption of CO by the snowflake porous hydrate according to the feedback data 2 Thereby regulating the flow of material in the conduit.
As a further limitation of the technical scheme, the pipeline II is communicated with the pipeline III and the pipeline IV, an eighth valve is arranged on the pipeline III and leads to the working face, and a ninth valve (9) is arranged on the pipeline IV and leads to the goaf.
As a further limitation of the technical scheme, the snowflake porous hydrate material can be used for preventing and controlling spontaneous combustion of coal, and the application principle is as follows: snowflake porous hydrate adsorption of CO 2 Then generating a carbon dioxide hydrate, injecting the carbon dioxide hydrate into the coal gap surface by a grouting pump, plugging the cracks, and when the temperature rises, CO in the carbon dioxide hydrate 2 The oxygen concentration on the surface of the coal body is reduced in situ, so that the spontaneous combustion of the coal is delayed or inhibited.
Compared with the prior art, the invention has the advantages and positive effects that:
1. the material has good CO adsorption 2 By absorbing CO in the plant exhaust gas 2 Not only can utilize CO in factory waste gas 2 Fire extinguishing and cooling are carried out on the coal mine, and meanwhile CO is reduced 2 For CO in industrial waste gas 2 And the reasonable utilization is performed.
2. The device prepares snowflake porous hydrate through computer control, can carry out strict accurate control and operation to the interpolation of material and the reaction, realizes automatic slip casting in the pit, provides convenience for the staff, reduces human error, improves the security.
3. The snowflake porous hydrate adsorbs CO 2 After that, not only can the oxygen concentration be reduced, the coal oxygen reaction is stopped, but also the temperature at the fire source can be reduced, and the probability of reburning is reduced.
Drawings
FIG. 1 is a diagram of snowflake-like porous hydrate preparation and application in goaf and working face.
Fig. 2 is a block diagram of the intelligent control module.
Fig. 3 is a TEM image of snowflake-like porous hydrate.
Fig. 4 is an N2 adsorption/desorption isotherm and pore size distribution curve of the sample.
In the figure: 1. a first valve; 2. a second valve; 3. a third valve; 4. a fourth valve; 5. a fifth valve; 6. a sixth valve; 7. a seventh valve; 8. an eighth valve; 9. a ninth valve; 10. a tenth valve; 11. liquid CO 2 A source; 12. gaseous CO 2 A source; 13. CO 2 A vaporizer; 14. a reaction kettle; 15. mix-3 particle preparation device; 16. a water pump; 17. a high-speed stirrer; 18. a grouting pump; 19. a flow sensor; 20. an intelligent control module; 21. liquid CO 2 A storage tank; 22. a deionized water storage tank; 23. an ethyl orthosilicate storage tank; 24. a small molecule organic amine storage tank; 25. a cationic surfactant reservoir; 26. a magnetic stirrer; 27. a filtering device; 28. an oven; 29. a deionized water storage tank; 30. a first pipeline; 31. a second pipeline; 32. a third pipeline; 33. and a pipeline IV.
Detailed Description
One embodiment of the present invention will be described in detail below with reference to the attached drawings, but it should be understood that the scope of the present invention is not limited by the embodiment.
The snowflake porous hydrate material is prepared from tetraethoxysilane, a cationic surfactant, small molecular organic amine and deionized water by adopting a soft template method, the average pore diameter and the pore volume of a sample are calculated by adopting a BJH model, the particle size of mix-3 particles for synthesizing the snowflake porous hydrate is smaller than 170 and nm, and most of the snowflake porous hydrate has mesopores with the pore diameter of 2-50 nm.
According to experiments, the mesoporous material with the aperture of 15-16nm has excellent CO 2 Adsorption capacity.
From FIG. 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 beneficial to CO 2 This is consistent with TEM results. The pore size distribution curve is unimodal, and the peak value is mainly about 15-16nm, which shows that the adsorption effect is optimal in the range.
The mass fraction ratio of the tetraethoxysilane to the cationic surfactant to the small molecular organic amine to the deionized water is as follows: 8.4:1.6:0.2: 90.5-220.6.
The cationic surfactant is cetyl trimethyl para-toluenesulfonammonium, and the small molecular organic amine is triethanolamine.
The soft template method comprises the following steps:
step 1: weighing a certain mass of cationic surfactant, adding the cationic surfactant into a beaker, weighing a certain mass of small molecular organic amine and deionized water, sequentially adding the small molecular organic amine and the deionized water into the beaker containing the cationic surfactant, adding a magnet into the beaker, placing the beaker on a magnetic stirrer, and stirring for the first time to uniformly mix the two materials to obtain a mixture mix-1;
step 2: after the cationic surfactant is completely dissolved in the small molecular organic amine, quickly adding the ethyl orthosilicate into the mixture mix-1 to obtain a new mixture mix-2;
step 3: placing the mixture mix-2 on a magnetic stirrer for secondary stirring, filtering the stirred product by using a Buchner funnel, washing, and drying by using an oven to obtain mix-3 particles;
step 4: mixing the mix-3 particles with the deionized water, then placing the mixture in a high-speed stirrer, and stirring for a certain time to obtain the snowflake-shaped porous hydrate material.
In the step 1, the mass ratio of the cationic surfactant, the small molecular organic amine and the deionized water is 1.6:0.2:58, the mass ratio of the tetraethoxysilane to the mixture mix-1 is 8.4:59.8;
in the step 1, the first stirring setting parameters of the magnetic stirrer are as follows: the stirring time is 1h, the stirring rotating speed is 1200 rpm, the stirring temperature is 80 ℃, and the setting of the magnetic stirrer and the setting of the second stirring parameters are as follows: stirring time is 1h, stirring speed is 1200 rpm, and stirring temperature is 80 ℃;
in the step 1, the filtration is carried out at normal temperature, the temperature of an oven is set to be 100 ℃ during the drying, and the drying time is set to be 20 hours;
in the step 1, the particle size of the obtained mix-3 particles is 115-170 nm, wherein the particle size of most particles is 135-145 nm;
in the step 2, the mass ratio of the mix-3 particles to the deionized water is 1: 9-19.
In the step 2, the setting parameters of the high-speed stirrer are as follows: the stirring time is 60s, and the stirring rotating speed is 19000 r/min.
Adsorbable CO 2 A snowflake-shaped porous hydrate material application system, comprising: the device comprises a snowflake porous hydrate preparation and application module, an intelligent control module 20 and a carbon dioxide hydrate grouting module;
the snowflake porous hydrate preparation and application module comprises: liquid CO 2 Source 11, gaseous CO 2 Source 12, CO 2 The gasification device 13, the reaction kettle 14, the mix-3 particle preparation system 15, the water pump 16, the high-speed stirrer 17, the magnetic stirrer 26, the oven 28, the filtering device 27, the material storage tank and a plurality of valves;
the material storage tank comprises a deionized water storage tank 22, an ethyl orthosilicate storage tank 23, a micromolecular organic amine storage tank 24, a cationic surfactant storage tank 25, a deionized water storage tank II 29 and liquid CO 2 A storage tank 21;
said liquid CO 2 The source 11 is respectively connected with the liquid CO through pipelines 2 Storage tank 21 and CO 2 The vaporizer 13 is communicated with CO 2 The vaporizer 13 is communicated with the reaction kettle 14 through a pipeline, and the CO 2 A first valve 1 is arranged on a connecting pipeline of the vaporizer 13 and the reaction kettle 14; said gaseous CO 2 The source 12 is connected with the reaction kettle 14 through a pipeline, and a second valve 2 is arranged on the pipeline;
a sixth valve 6 is arranged on a pipeline communicated with the reaction kettle 14 and the high-speed stirrer 17;
the upper end of the first pipeline 30 is connected to the ground, a tenth valve 10 is arranged in the middle of the first pipeline 30, the lower end of the first pipeline 30 is connected with the water pump 16, the tenth valve 10 is opened, and deionized water can be conveyed into the water pump 16 through the first pipeline 30;
the mix-3 particle preparation system 15 is communicated with the high-speed stirrer 17 through a pipeline, a third valve 3 is arranged on the pipeline, the water pump 16 is communicated with the high-speed stirrer 17 through a pipeline, a fourth valve 4 is arranged on the pipeline, and the mix-3 particle preparation system 15 is communicated with the water pump 16 through a pipeline, and a fifth valve 5 is arranged on the pipeline;
the carbon dioxide hydrate grouting module comprises a grouting pump 18, a seventh valve 7 and a flow sensor 19, wherein the grouting pump 18 is communicated with the reaction kettle 14 through a pipeline, the grouting pump 18 is communicated with a pipeline II 31, the flow sensor 19 is arranged on the pipeline II 31, and the seventh valve 7 is arranged between the flow sensor 19 and the grouting pump 18.
The flow sensor 19 can monitor snowflake-shaped porous hydrate flow in real time in the grouting process.
The intelligent control module 20 comprises a display control device and control wires, wherein the display control device is installed on a well, and the control wires are used for electrically connecting the reaction kettle 14, the high-speed stirrer 17, the magnetic stirrer 26, the filtering device 27, the oven 28, the ionized water storage tank 22, the ethyl orthosilicate storage tank 23, the small molecular organic amine storage tank 24, the cationic surfactant storage tank 25, the deionized water storage tank II 29, the grouting pump 18 and the flow sensor 19 with the display control device, so that the intelligent control module controls preparation of underground snowflake porous hydrate, CO2 absorption and grouting operation. The intelligent control module 20 can monitor the reaction kettle 14, the water pump 16, the high-speed stirrer 17, the magnetic stirrer 26 and the carbon dioxide hydrate grouting module of the snowflake porous hydrate preparation and application module, realize underground automatic grouting, prevent and treat coal mine fires, provide convenience for operators on the well, reduce the probability of human errors and improve the safety of the operators.
The snowflake porous hydrate is prepared underground by the following steps:
controlling the material storage tank through the intelligent control module 20, firstly adding 1.6 parts of the cationic surfactant into the magnetic stirrer 26, then sequentially adding 0.2 part of small molecular organic amine and 58 parts of deionized water, starting the magnetic stirrer 26 after the addition, wherein the stirring speed is 1200 revolutions per minute, the stirring temperature is 80 ℃, and stirring for 1h;
after the stirring is completed, 8.4 parts of tetraethoxysilane is added, the magnetic stirrer 26 is started, the stirring speed is 1200 r/min, the stirring temperature is 80 ℃, the stirring time is 1h, the obtained product is filtered and washed by the filter device 27, and then the obtained product is conveyed to the oven 28 for drying, so that the mix-3 particles are obtained, wherein the filtering is performed at normal temperature, the drying temperature of the oven 28 is set to 100 ℃, and the drying time is set to 20h;
mix-3 particles and deionized water were added to the high-speed stirrer 17 in a mass ratio of 1: 9-19, wherein the deionized water is sourced from the second deionized water storage tank 29, the high-speed stirrer 17 is started, the rotating speed is 19000 r/min, and the snowflake porous hydrate is obtained after stirring for 60 s.
The application method of the snowflake porous hydrate comprises the following steps:
opening the sixth valve 6, transporting the snowflake-shaped porous hydrate into the reaction kettle 14 through a pipeline, and pumping the gases in the reaction kettle 14 and the pipeline by utilizing a vacuum pump of the reaction kettle 14;
when the vacuum pressure in the reaction kettle 14 reaches 2atm, the vacuum pump suction valve is closed, the vacuum pump air inlet valve is opened, and CO is started to be introduced 2 ，
CO is introduced into 2 If the liquid CO is selected 2 Source 11 will then be the liquid CO on the well 2 The storage tank 21 is transported downhole as a material storage tank, the liquid CO 2 The storage tank 21 is hoisted and transported from the vertical shaft to the underground through a transportation device and is introduced into the liquid CO 2 A source 11 through the CO 2 The vaporizer 13 is vaporized, the first valve 1 is opened to introduce CO into the reaction kettle 14 2 ；
If the gaseous CO is selected 2 A source 12, which opens the second valve 2 to feed CO into the reaction kettle 14 2 ；
To make the absorbed CO 2 In the gaseous state, is filled with CO 2 After the gas, the final pressure in the reaction kettle 14 is less than 6atm, if the adsorbed CO is to be obtained 2 Is in liquid state and is filled with CO 2 After the gas, the final pressure in the reaction kettle 14 is greater than 6atm;
when the pressure in the reaction kettle 14 reaches a specified value, the high-speed stirrer 17 is started to start CO 2 And (3) carrying out a combination reaction with the snowflake porous hydrate, and closing the device after the reaction is carried out for 4 hours to obtain the carbon dioxide hydrate.
When the carbon dioxide hydrate flows through the flow sensor 19 through the second input pipeline 31 of the grouting pump 18, the flow sensor 19 feeds back obtained monitoring data to the intelligent control module 20, and the intelligent control module 20 adjusts the rate of synthesizing snowflake porous hydrate and the adsorption of CO by the snowflake porous hydrate according to the feedback data 2 Thereby regulating the flow of material in the conduit.
The second pipeline 31 is communicated with the third pipeline 32 and the fourth pipeline 33, the eighth valve 8 is arranged on the third pipeline 32 and leads to the working surface, the ninth valve 9 is arranged on the fourth pipeline 33 and leads to the goaf.
The snowflake porous hydrate material can be used for preventing and controlling spontaneous combustion of coal, and the application principle is as follows: snowflake porous hydrate adsorption of CO 2 Then generating a carbon dioxide hydrate, injecting the carbon dioxide hydrate into the coal gap surface by a grouting pump, plugging the cracks, and when the temperature rises, CO in the carbon dioxide hydrate 2 The oxygen concentration on the surface of the coal body is reduced in situ, so that the spontaneous combustion of the coal is delayed or inhibited.
The above disclosure is merely illustrative of specific embodiments of the present invention, but the present invention is not limited thereto, and any variations that can be considered by those skilled in the art should fall within the scope of the present invention.
Claims (10)
1. Adsorbable CO 2 A snowflake-shaped porous hydrate material comprising a snowflake-shaped porous hydrate material characterized in that:
the snowflake porous hydrate material is prepared from tetraethoxysilane, a cationic surfactant, small molecular organic amine and deionized water by adopting a soft template method;
the average pore diameter and pore volume of the sample are calculated by adopting a BJH model;
the size of mix-3 particles used for synthesizing snowflake porous hydrate is smaller than 170 and nm, and most of snowflake porous hydrate has mesopores with the pore diameter of 2-50 nm.
2. The adsorbable CO of claim 1 2 A snowflake-like porous hydrate material characterized by: the mass fraction ratio of the tetraethoxysilane to the cationic surfactant to the small molecular organic amine to the deionized water is as follows: 8.4:1.6:0.2: 90.5-220.6.
3. Adsorbable CO according to claim 2 2 A snowflake-like porous hydrate material characterized by: the cationic surfactant is cetyl trimethyl para-toluenesulfonammonium, and the small molecular organic amine is triethanolamine.
4. The adsorbable CO of claim 2 2 A snowflake-like porous hydrate material characterized by: the soft template method comprises the following steps:
step 1: weighing a certain mass of cationic surfactant, adding the cationic surfactant into a beaker, weighing a certain mass of small molecular organic amine and deionized water, sequentially adding the small molecular organic amine and the deionized water into the beaker containing the cationic surfactant, adding a magnet into the beaker, placing the beaker on a magnetic stirrer, and stirring for the first time to uniformly mix the two materials to obtain a mixture mix-1;
step 2: after the cationic surfactant is completely dissolved in the small molecular organic amine, quickly adding the ethyl orthosilicate into the mixture mix-1 to obtain a new mixture mix-2;
step 3: placing the mixture mix-2 on a magnetic stirrer for secondary stirring, filtering the stirred product by using a Buchner funnel, washing, and drying by using an oven to obtain mix-3 particles;
step 4: mixing the mix-3 particles with the deionized water, then placing the mixture in a high-speed stirrer, and stirring for a certain time to obtain the snowflake-shaped porous hydrate material.
5. The adsorbable CO of claim 4 2 An application system of a snowflake-shaped porous hydrate material preparation method, which is characterized by comprising the following steps: the device comprises a snowflake porous hydrate preparation and application module, an intelligent control module (20) and a carbon dioxide hydrate grouting module;
the snowflake porous hydrate preparation and application module comprises: liquid CO 2 Source (11) and gaseous CO 2 Source (12), CO 2 The device comprises a 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 tank comprises a deionization deviceA sub-water storage tank (22), an ethyl orthosilicate storage tank (23), a micromolecular organic amine storage tank (24), a cationic surfactant storage tank (25), a deionized water storage tank II (29) and liquid CO 2 A storage tank (21);
said liquid CO 2 The source (11) is respectively connected with the liquid CO through pipelines 2 Storage tank (21) and CO 2 The vaporizer (13) is communicated with CO 2 The vaporizer (13) is communicated with the reaction kettle (14) through a pipeline, and the CO 2 A first valve (1) is arranged on a connecting pipeline of the vaporizer (13) and the reaction kettle (14); said gaseous CO 2 The source (12) is connected with the reaction kettle (14) through a pipeline, and a second valve (2) is arranged on the pipeline;
a sixth valve (6) is arranged on a pipeline communicated with the high-speed stirrer (17) through the reaction kettle (14);
the upper end of the first pipeline (30) is connected to the ground, a tenth valve (10) is arranged in the middle of the first pipeline (30), the lower end of the first pipeline is connected with the water pump (16), the tenth valve (10) is opened, and deionized water can be conveyed into the water pump (16) through the first pipeline (30);
the mix-3 particle preparation system (15) is communicated with the high-speed stirrer (17) through a pipeline, a third valve (3) is arranged on the pipeline, the water pump (16) is communicated with the high-speed stirrer (17) through a pipeline, a fourth valve (4) is arranged on the pipeline, and the mix-3 particle preparation system (15) is communicated with the water pump (16) through a pipeline, and a fifth valve (5) is arranged on the pipeline;
the carbon dioxide hydrate grouting module comprises a grouting pump (18), a seventh valve (7) and a flow sensor (19), wherein the grouting pump (18) is communicated with the reaction kettle (14) through a pipeline, the grouting pump (18) is communicated with a pipeline II (31), the flow sensor (19) is arranged on the pipeline II (31), and the seventh valve (7) is arranged between the flow sensor (19) and the grouting pump (18);
the intelligent control module (20) comprises a display control device and a control wire, wherein the display control device is installed on a well, the control wire is used for enabling the reaction kettle (14), the high-speed stirrer (17), the magnetic stirrer (26), the filtering device (27), the oven (28), the ionized water storage tank (22), the ethyl orthosilicate storage tank (23), the micromolecular organic amine storage tank (24), the cationic surfactant storage tank (25), the deionized water storage tank II (29), the grouting pump (18) and the flow sensor (19) are electrically connected with the display control device.
6. The adsorbable CO of claim 5 2 A snowflake-shaped porous hydrate material application system characterized by: the snowflake porous hydrate is prepared underground by the following steps:
the intelligent control module (20) is used for controlling the material storage tank, 1.6 parts of the cationic surfactant is firstly added into the magnetic stirrer (26), then 0.2 part of the micromolecular organic amine and 58 parts of deionized water are sequentially added, after the addition is finished, the magnetic stirrer (26) is started, the stirring speed is 1200 revolutions per minute, the stirring temperature is 80 ℃, and the stirring time is 1h;
after stirring, adding 8.4 parts of ethyl orthosilicate, starting a magnetic stirrer (26), wherein the stirring speed is 1200 r/min, the stirring temperature is 80 ℃, the stirring time is 1h, filtering and washing the obtained product through a filtering device (27), and then conveying the product to a drying oven (28) for drying to obtain mix-3 particles, wherein the filtering is performed at normal temperature, and the drying temperature of the drying oven (28) is set to be 100 ℃ and the drying time is set to be 20h;
and adding mix-3 particles and deionized water into the high-speed stirrer (17), wherein the mass ratio of the mix-3 particles to the deionized water is 1: 9-19, wherein the deionized water is sourced from the second deionized water storage tank (29), the high-speed stirrer (17) is started, the rotating speed is 19000 r/min, and the snowflake porous hydrate is obtained after stirring for 60 s.
7. The inhalable according to claim 5CO attached 2 A snowflake-shaped porous hydrate material application system characterized by: the application method of the snowflake porous hydrate comprises the following steps:
opening the sixth valve (6), conveying the snowflake-shaped porous hydrate into the reaction kettle (14) through a pipeline, and pumping the gases in the reaction kettle (14) and the pipeline by using a vacuum pump of the reaction kettle (14);
when the vacuum pressure in the reaction kettle (14) reaches 2atm, closing a vacuum pump suction valve, opening a vacuum pump air inlet valve, and starting to introduce CO 2 ；
CO is introduced into 2 If the liquid CO is selected 2 A source (11) for feeding said liquid CO into the well 2 The storage tank (21) is transported downhole as a material storage tank, the liquid CO 2 The storage tank (21) is hoisted and transported from a vertical shaft to the underground through a transportation device and is introduced into the liquid CO 2 A source (11) through the CO 2 The vaporizer (13) is used for vaporizing, the first valve (1) is opened to introduce CO into the reaction kettle (14) 2 ；
If the gaseous CO is selected 2 A source (12) for opening the second valve (2) to introduce CO into the reaction kettle (14) 2 ；
To make the absorbed CO 2 In the gaseous state, is filled with CO 2 After the gas is discharged, the final pressure in the reaction kettle (14) is less than 6atm, if the adsorbed CO is to be absorbed 2 Is in liquid state and is filled with CO 2 After the gas, the final pressure in the reaction kettle (14) is higher than 6atm;
when the pressure in the reaction kettle (14) reaches a specified value, the high-speed stirrer (17) is started to start CO 2 And (3) carrying out a combination reaction with the snowflake porous hydrate, and closing the device after the reaction is carried out for 4 hours to obtain the carbon dioxide hydrate.
8. The adsorbable CO of claim 7 2 A snowflake-shaped porous hydrate material application system characterized by: the carbon dioxide hydrate is input into a pipeline II through the grouting pump (18)(31) When flowing through the flow sensor (19), the flow sensor (19) feeds back obtained monitoring data to the intelligent control module (20), and the intelligent control module (20) adjusts the rate of synthesizing snowflake-shaped porous hydrate and the adsorption rate of CO of the snowflake-shaped porous hydrate according to the feedback data 2 Thereby regulating the flow of material in the conduit.
9. The adsorbable CO of claim 7 2 A snowflake-shaped porous hydrate material application system characterized by: the pipeline II (31) is communicated with the pipeline III (32) and the pipeline IV (33), an eighth valve (8) is arranged on the pipeline III (32) and leads to a working surface, and a ninth valve (9) is arranged on the pipeline IV (33) and leads to a goaf.
10. The adsorbable CO of claim 6 2 A snowflake-shaped porous hydrate material application system characterized by: the snowflake porous hydrate material can be used for preventing and controlling spontaneous combustion of coal, and the application principle is as follows: snowflake porous hydrate adsorption of CO 2 Then generating a carbon dioxide hydrate, injecting the carbon dioxide hydrate into the coal gap surface by a grouting pump, plugging the cracks, and when the temperature rises, CO in the carbon dioxide hydrate 2 The oxygen concentration on the surface of the coal body is reduced in situ, so that the spontaneous combustion of the coal is delayed or inhibited.
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