CN115746486B - Preparation method of efficient and stable hydrogel-based gas hydrate accelerator - Google Patents
Preparation method of efficient and stable hydrogel-based gas hydrate accelerator Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 61
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 title claims abstract description 32
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of hydrate preparation, and particularly relates to a preparation method of a high-efficiency stable hydrogel-based gas hydrate accelerator, which is characterized in that hydrophilic macromolecular chains (sodium poly-p-styrenesulfonate-styrene, PSCS) wrapped and coated carbon nano tubes PSCS@CNTs are uniformly dispersed and crosslinked into a three-dimensional network structure of sodium poly-p-styrenesulfonate-acrylamide (PSCA) hydrogel in a physical-chemical double-crosslinking mode to prepare the gas hydrate accelerator PSCS@CNTs@PSCA with high acceleration efficiency and good recycling performance. The accelerator can obviously promote the generation rate of the hydrate, can be stably recycled for many times in the generation and decomposition processes of the hydrate, and simultaneously does not generate any environmental pollution caused by chemical reagents in the recycling process, so that the accelerator has great application potential and economic benefit in the aspect of industrial application of gas hydrate technology.
Description
Technical Field
The invention relates to a preparation method of a high-efficiency stable hydrogel-based gas hydrate accelerator, and belongs to the technical field of hydrate preparation.
Background
The hydrate is a cage structure formed by water molecules through hydrogen bonds, and guest molecules (methane, ethane, propane, CO) 2 And N 2 Isopolytics) are stored in the water molecular cages by van der waals forces, thereby forming a stable ice-like crystal structure. The hydrate technology is a safe and environment-friendly natural gas storage and transportation and CO 2 Trapping, gas separation and other methods, however, the problems of low production rate and long induction time still exist in the process of generating the hydrate, and the hydrate technology is severely restrictedIs used in industrial applications.
The hydrate generation is a gas-liquid interface reaction, and an effective promoting method is adopted to improve the heat transfer rate and the mass transfer rate of the gas-liquid interface, so that the rate of the hydrate generation and the gas storage quantity can be obviously improved. Conventional methods of promotion include both mechanical and non-mechanical methods. The mechanical method is used for continuously breaking the gas-liquid contact surface to promote the mass transfer rate of the gas-liquid interface by means of stirring, water spraying, bubbling and the like, however, the method has high energy consumption, and frictional heat generated in the operation process is unfavorable for the generation of hydrate. The non-mechanical method mainly adopts some chemical reagents as accelerators, including thermodynamic accelerators (such as tetra-n-butyl ammonium halide (TBAH), tetrahydrofuran (THF), cyclopentane (CP) and the like) and kinetic accelerators (surfactants, nanomaterials, porous media and the like). Although the accelerating agent has obvious accelerating effect on the generation process of the hydrate, the accelerating agent molecules occupy part of water molecule cages, so that the gas storage multiple is reduced, and part of the accelerating agent is inevitably lost in the generation and decomposition cycle process of the hydrate, so that the accelerating effect is weakened, and environmental pollution is caused.
In recent years, researchers have developed and employed some novel promotion methods to improve the efficiency of hydrate formation: the nano/micron-sized particle medium such as dry water and hydrogel which wraps or absorbs water is used for replacing the traditional liquid water system to carry out the hydrate generation reaction, and the particle water accelerator can greatly increase the gas-liquid contact area of gas and water and obviously improve the interface mass transfer rate, so that the efficient hydrate generation is realized. The copper powder dry water for improving the gas storage rate of the hydrate, as well as a preparation method and application thereof, disclosed in China patent 201010229978.7, comprises the steps of mixing hydrophobic fumed silica, copper powder and water, stirring for 30-120 s at 10000-30000 r/min to obtain copper powder dry water, wherein the hydrophobic fumed silica accounts for 5-15% wt of the copper powder dry water, the copper powder accounts for 5-20% wt, the balance is water, the particle size of the hydrophobic fumed silica is 7-40 nm, and the specific surface area is 100-300 m < 2 >/g; the use temperature of the copper powder dry water in hydrate gas storage is-80-30 ℃ and the pressure is 0-100 MPa; the invention can increase the gas-liquid contact area during the reaction of the hydrate, promote the mass transfer rate of the reaction system, further improve the generation rate and the gas storage capacity of the hydrate, and simultaneously, the high thermal conductivity of the copper powder can promote the heat transfer rate of the reaction system, and further accelerate the reaction of the hydrate; however, copper powder and water are associated with each other by weak physical force to form a dry water structure, so that water contained in dry water is easily separated out, particles adhere to each other, the structure collapses and breaks, the accelerating performance is greatly reduced, and the cycle performance is poor in repeated temperature and pressure rise and fall states accompanied by generation and decomposition cycles of hydrate. In the method for realizing reversible gas storage of gas hydrate by using hydrogel disclosed in China patent 201510212744.4, swelling polymethacrylate hydrogel is used as a gas storage medium, and hydrate is generated with methane gas under high pressure and low temperature; the decomposition process is to slowly and stably decompose the gas hydrate stored in the polymethacrylate hydrogel through heating, and ending the decomposition process after the temperature and the pressure are stabilized again; wherein the water content of the polymethacrylate hydrogel is 60-95 wt%, the pore size of the polymethacrylate hydrogel is 1-150 mu m, and the pressure and the temperature of the high-pressure reaction kettle are respectively regulated to 3-30 MPa and 0-20 ℃; the polymethacrylate hydrogel used in the invention has a stable three-dimensional network structure, and can fix water molecules in the pore canal and the three-dimensional network structure which are communicated with each other through hydrogen bonding and a physical separation method, so that the solid generation of gas hydrate is realized. In combination, the nano/micron-sized particle water accelerator taking dry water or hydrogel as a medium can effectively promote the generation of methane hydrate. However, the dry water particle structure and the hydrogel network structure have weak mechanical properties, and undergo repeated pressure rise and fall, temperature rise and fall and hydrate crystallization-melting processes in the process of hydrate generation and decomposition cycle, so that the particle structure is easily damaged, the promotion effect is reduced, and repeated use is difficult. Therefore, a particulate water accelerator having high mechanical properties, high and stable accelerating effect and a large number of cyclic utilization times has been developed and used.
Carbon nanotubes are one-dimensional carbon nanomaterials with excellent mechanical, electrical and heat transfer properties. In the functionalized double-network hydrogel and the application thereof disclosed in Chinese patent 202110527288.8, carboxylated carbon nanotubes are added into calcium alginate/polyacrylamide interpenetrating double-network hydrogel, and mechanical property quantitative analysis is carried out on the carboxylated carbon nanotubes, wherein the quantitative analysis comprises elongation at break, compressive strain rate, maximum tensile strength, maximum compressive strength and Young modulus, and the results show that the addition of the carbon nanotubes enables the hydrogel to have stronger tensile and compressive properties. Based on the above patent, the carbon nanotubes have a remarkable improvement effect on the mechanical properties of hydrogels. In the method for promoting the rapid generation of methane hydrate by using the carbon nano tube composite hydrogel disclosed in China patent 202011371680.X, the hydroxylated multi-wall carbon nano tube subjected to ultrasonic treatment is dispersed in polyacrylic acid-acrylamide to prepare the carbon nano tube composite hydrogel; the water-absorbing agent is applied to the promotion of methane hydrate to generate hydrogel particles with the particle diameter of 600-1000 mu m, the water content of 99.01 percent and the water absorption multiple of 100 times; hydrate is generated at the temperature of 1 ℃ and the pressure of 7 Mpa; in the synthesis process of methane hydrate, the contact area of methane gas molecules and water molecules can be increased, and the mass transfer rate is improved, but due to poor dispersibility of the hydroxylated multiwall carbon nanotubes in water, the carbon tubes in the prepared hydrogel are unevenly dispersed and are easy to agglomerate, and the hydrogel promotes the generation of the hydrate only through the mass transfer promotion effect of polyacrylic acid-acrylamide hydrogel particles and the heat transfer promotion effect of the carbon nanotubes, and lacks functional groups for obviously promoting the generation of the hydrate, so that the promotion force is relatively weak, and a good promotion effect cannot be achieved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a high-efficiency stable hydrogel-based gas hydrate accelerator, and the prepared accelerator has remarkable accelerating effect on the gas hydrate generation process, strong mechanical property and good recycling performance, and has huge industrialization application potential in the aspect of hydrate technology application.
The preparation method of the efficient and stable hydrogel-based gas hydrate accelerator disclosed by the invention is to crosslink a sodium poly (p-styrenesulfonate) -styrene-coated carbon nanotube into a three-dimensional network structure of the sodium poly (p-styrenesulfonate) -acrylamide hydrogel, and comprises the following steps of:
(1) Adding sodium p-styrenesulfonate and styrene into water for dissolution, adding an initiator, initiating a polymerization reaction, and obtaining a sodium p-styrenesulfonate-styrene (PSCS) solution after the reaction is finished;
(2) Adding Carbon Nanotubes (CNTs) into a sodium poly (p-styrenesulfonate) -styrene solution, mixing, performing ultrasonic treatment to obtain a dispersion liquid, performing suction filtration on the dispersion liquid to obtain filter residues, and washing and drying to obtain the sodium poly (p-styrenesulfonate) -styrene coated carbon nanotubes PSCS@CNTs;
(3) And (3) adding PSCS@CNTs into water for dissolution, adding acrylamide, sodium p-styrenesulfonate and N, N-methylene bisacrylamide for dissolution after ultrasonic treatment, adding an initiator, initiating a polymerization reaction, reacting to form a colloid solid, and washing and drying the colloid solid to obtain the accelerator PSCS@CNTs@PSCA.
The initiator is potassium persulfate or ammonium persulfate, the concentration of the initiator in the reaction system is 1-10 g/L, and the initiator is required to be added dropwise, so that the initiator is fully mixed in the polymerization reaction system, and the phenomenon that the reaction is violently coalesced due to excessive single addition is avoided.
The polymerization temperature is 70-95 ℃, and a constant-temperature water bath pot or an oil bath pot can be preferably used.
The stirring rotation speed in the polymerization reaction process is 200-500 rpm, and the stirring is carried out at a constant rotation speed from the adding of the reagent before the polymerization reaction to the end of the polymerization reaction in the step (1) and the step (3).
In the reaction system for preparing PSCS solution in the step (1), the concentration of sodium p-styrenesulfonate is 5-20 g/L, and the concentration of styrene is 5-20 g/L.
In the reaction system for preparing PSCS@CNTs in the step (2), the concentration of the carbon nano tube is 0.2-2wt%, a filter membrane used in vacuum suction filtration of the dispersion liquid is a polytetrafluoroethylene filter membrane with the pore diameter of 0.2 mu m, filter residues are repeatedly washed for 5-10 times, and PSCS macromolecular chains which are not coated on the surfaces of CNTs are removed.
In the reaction system for preparing PSCS@CNTs@PSCA in the step (3), the concentration of PSCS@CNTs is 5-20 g/L, the concentration of sodium p-styrenesulfonate is 50-250 g/L, the concentration of acrylamide is 50-250 g/L, and the concentration of N, N-methylenebisacrylamide is 1-10 g/L.
The addition of the above reagents should follow: all reagents are added one by one, and after any one reagent is added, the next reagent can be added by stirring until the reagent is fully dissolved, and if the reagents are added simultaneously, the dissolution rate may be reduced.
In the preparation method, two polymerization reactions respectively occur, and in the step (1), the reaction is continued until the reaction liquid presents yellow, and when the depth of the yellow is stable and unchanged, the reaction can be stopped, and the reaction time is 3-8 hours; in the step (3), after the polymerization reaction starts, a precipitate is formed continuously, and is stirred continuously along with the reaction, the precipitate is formed into a whole colloidal solid finally, a stirring device is stopped immediately, the colloidal solid is divided and taken out, and the catalyst PSCS@CNTs@PSCA is obtained after washing and drying, and is crushed, sieved and stored in a dry state, wherein the particle size of the catalyst PSCS@CNTs@PSCA is 600-1000 microns.
In actual operation, the ultrasonic time is controlled to be 3-12 h, the washing liquid can be distilled water or volatile ethanol solution, the drying temperature is controlled to be 70-80 ℃, and the drying time is 72h.
The using method of the promoter PSCS@CNTs@PSCA comprises the following steps: and (3) standing PSCS@CNTs@PSCA in water, after the PSCS@CNTs@PSCA fully absorbs water, putting the water into a high-pressure reaction kettle, sealing the high-pressure reaction kettle until the water content reaches 90.0% -99.9%, putting the high-pressure reaction kettle into a water bath with the rotating speed of a magnetic stirrer at the bottom of the reaction kettle of 100-400 rpm, cooling the high-pressure reaction kettle in a water bath with the temperature of-10 ℃, opening a methane gas bottle to inflate the high-pressure reaction kettle when the temperature in the reaction kettle is not changed any more, controlling the pressure to 3-20 MPa, closing an air valve, continuously monitoring the temperature and the pressure of the high-pressure reaction kettle, and indicating that the hydrate generation process is completely ended when the temperature and the pressure in the reaction kettle are not changed any more.
Compared with the prior art, the invention has the following beneficial effects:
the hydrogel-based gas hydrate accelerator PSCS@CNTs@PSCA disclosed by the invention has excellent accelerating performance and recycling performance, is a novel accelerator with high quality, economy and environmental friendliness, and has great application potential and economic value in the aspect of industrial application of a hydrate technology.
Firstly, the PSCS hydrophilic macromolecule chain is coated and wound on the carbon nanotube to prepare PSCS@CNTs, so that the problems of poor dispersibility and easy agglomeration of the carbon nanotube in water can be effectively solved; secondly, dispersing PSCS@CNTs into a soap-free emulsion polymerization reaction of sodium p-styrenesulfonate and acrylamide, and generating a large amount of immobilized functional groups-SO through physical-chemical double-crosslinking 3 - The hydrogel PSCS@CNTs@PSCA uniformly doped with the carbon nano tube is prepared by the method, and a large number of functional groups-SO are immobilized on a three-dimensional network structure of the hydrogel accelerator 3 - Such groups have a remarkable accelerating effect on the hydrate formation process; thirdly, the carbon nano tubes are uniformly dispersed in the hydrogel, so that on one hand, the mechanical strength of the hydrogel is enhanced, the deformation resistance, the compression resistance and the Wen Bianneng force resistance of the hydrogel in the hydrate generation and decomposition cycle process are improved, the recycling performance of the hydrogel accelerator is improved, and on the other hand, the carbon nano tubes have high heat conduction performance, the heat transfer rate of the hydrate reaction can be improved, and the hydrate generation efficiency is further improved; fourth, the hydrogel accelerator does not generate the problem of loss and the risk of environmental pollution of chemical solution accelerators in the recycling process.
Drawings
FIG. 1 is a schematic diagram of a PSCS@CNTs@PSCA three-dimensional network structure;
FIG. 2, a plot of gas storage fold versus time for PSCA promoting methane hydrate formation;
FIG. 3, PSCS@CNTs@PSCA promoting a time-dependent gas storage fold change curve during methane hydrate formation.
Detailed Description
The invention is further described below with reference to examples.
All the raw materials used in the examples were commercially available except for the specific descriptions.
Example 1
The preparation method of the efficient and stable hydrogel-based gas hydrate accelerator comprises the following steps:
(1) PSCS macromolecular solution preparation
1g of sodium p-styrenesulfonate is taken and dissolved in a three-neck flask containing 94ml of distilled water, and is placed in a water bath kettle (90 ℃) and stirred (300 rpm) until being dissolved; 1g of styrene is dropwise added into a sodium p-styrenesulfonate solution, stirred for 30min to be fully mixed, 0.3g of potassium persulfate is dissolved in 6ml of distilled water, and the solution is dropwise added into a flask to initiate polymerization; after the reaction solution had developed a stable yellow color, the reaction was stopped to give 100ml of PSCS solution.
(2) PSCS@CNTs preparation
Mixing 0.2g CNTs with 20ml PSCS solution for ultrasonic treatment for 3h, wherein the concentration of CNTs is 1 wt%, vacuum filtering the obtained CNTs dispersion liquid by using polytetrafluoroethylene filter membrane (PTFE) with pore diameter of 0.2 μm, and repeatedly washing the filter residue with ethanol and distilled water for 5 times; drying the filter residue at 70 ℃ to obtain hydrophilic macromolecular chain PSCS modified CNTs, and marking the CNTs as PSCS@CNTs;
(3) Preparation and treatment of PSCS@CNTs@PSCA
Dissolving 0.2g PSCS@CNTs in 5ml deionized water, carrying out ultrasonic treatment for 4 hours, rapidly pouring into a three-neck flask, putting into an oil bath pot (90 ℃) and continuously stirring (300 rpm); then, 2.676g of sodium p-styrenesulfonate, 3.324g of acrylamide and 0.02g of cross-linking agent N, N-methylene bisacrylamide are sequentially added into a three-neck flask, and stirring is continued until the mixture is dissolved; 0.14g of ammonium persulfate is taken and dissolved in 3ml of deionized water, and then is dropwise added into a three-neck flask, and stirring is continued; the volume of the whole reaction system is 20ml; stopping stirring when colloidal solids appear in the three-neck flask, taking out the colloidal solids, and flushing with distilled water for 5 times; drying for 72 hours in a drying oven at 80 ℃ to obtain solid PSCS@CNTs@PSCA hydrogel; crushing PSCS@CNTs@PSCA by using a high-speed crusher, screening PSCA hydrogel by using a sieve to obtain hydrogel particles with the particle size range of 600-1000 mu m, sealing, drying and storing.
Example 2
The preparation method of the efficient and stable hydrogel-based gas hydrate accelerator comprises the following steps:
(1) PSCS macromolecular solution preparation
Dissolving 0.5g of sodium p-styrenesulfonate in a three-neck flask containing 94ml of distilled water, placing in a water bath (95 ℃) and stirring (200 rpm) until the sodium p-styrenesulfonate is dissolved; adding 0.5g of styrene into a sodium p-styrenesulfonate solution dropwise, stirring for 30min to fully mix, dissolving 0.1g of potassium persulfate in 6ml of distilled water, and adding the solution dropwise into a flask to initiate polymerization; after the reaction solution had developed a stable yellow color, the reaction was stopped to give 100ml of PSCS solution.
(2) PSCS@CNTs preparation
Mixing 0.4g CNTs with 20ml PSCS solution for ultrasonic treatment for 3h, wherein the concentration of CNTs is 2wt%, vacuum filtering the obtained CNTs dispersion liquid by using polytetrafluoroethylene filter membrane (PTFE) with pore diameter of 0.2 μm, and repeatedly washing the filter residue with ethanol and distilled water for 5 times; drying the filter residue at 70 ℃ to obtain hydrophilic macromolecular chain PSCS modified CNTs, and marking the CNTs as PSCS@CNTs;
(3) Preparation and treatment of PSCS@CNTs@PSCA
Dissolving 0.1g PSCS@CNTs in 5ml deionized water, carrying out ultrasonic treatment for 4 hours, rapidly pouring into a three-neck flask, putting into an oil bath pot (95 ℃) and continuously stirring (200 rpm); then, 4.578g of sodium p-styrenesulfonate, 1.422g of acrylamide and 0.02g of cross-linking agent N, N-methylene bisacrylamide are sequentially added into a three-neck flask, and stirring is continued until the mixture is dissolved; 0.2g of ammonium persulfate is taken and dissolved in 3ml of deionized water, and then is dropwise added into a three-neck flask, and stirring is continued; the volume of the whole reaction system is 20ml; stopping stirring when colloidal solids appear in the three-neck flask, taking out the colloidal solids, and flushing with distilled water for 5 times; drying for 72 hours in a drying oven at 80 ℃ to obtain solid PSCS@CNTs@PSCA hydrogel; crushing PSCS@CNTs@PSCA by using a high-speed crusher, screening PSCA hydrogel by using a sieve to obtain hydrogel particles with the particle size range of 600-1000 mu m, sealing, drying and storing.
Example 3
The preparation method of the efficient and stable hydrogel-based gas hydrate accelerator comprises the following steps:
(1) PSCS macromolecular solution preparation
2g of sodium p-styrenesulfonate is taken and dissolved in a three-neck flask containing 94ml of distilled water, and is placed in a water bath kettle (70 ℃) and stirred (500 rpm) until being dissolved; 2g of styrene is dropwise added into a sodium p-styrenesulfonate solution, stirred for 30min to be fully mixed, 0.5g of potassium persulfate is dissolved in 6ml of distilled water, and the solution is dropwise added into a flask to initiate polymerization; after the reaction solution had developed a stable yellow color, the reaction was stopped to give 100ml of PSCS solution.
(2) PSCS@CNTs preparation
Mixing 0.04g CNTs with 20ml PSCS solution for ultrasonic treatment for 3 hours, wherein the concentration of CNTs is 0.2wt%, vacuum filtering the obtained CNTs dispersion liquid by using a polytetrafluoroethylene filter membrane (PTFE) with the pore diameter of 0.2 mu m, and repeatedly washing filter residues for 5 times by using ethanol and distilled water; drying the filter residue at 70 ℃ to obtain hydrophilic macromolecular chain PSCS modified CNTs, and marking the CNTs as PSCS@CNTs;
(3) Preparation and treatment of PSCS@CNTs@PSCA
Dissolving 0.4g PSCS@CNTs in 5ml deionized water, carrying out ultrasonic treatment for 4 hours, rapidly pouring into a three-neck flask, putting into an oil bath pot (70 ℃), and continuously stirring (500 rpm); then, 1.722g of sodium p-styrenesulfonate, 4.278g of acrylamide and 0.2g of cross-linking agent N, N-methylene bisacrylamide are sequentially added into a three-neck flask, and stirring is continued until the mixture is dissolved; 0.1g of ammonium persulfate is taken and dissolved in 3ml of deionized water, and then added into a three-neck flask dropwise, and stirring is continued; the volume of the whole reaction system is 20ml; stopping stirring when colloidal solids appear in the three-neck flask, taking out the colloidal solids, and flushing with distilled water for 5 times; drying for 72 hours in a drying oven at 80 ℃ to obtain solid PSCS@CNTs@PSCA hydrogel; crushing PSCS@CNTs@PSCA by using a high-speed crusher, screening PSCA hydrogel by using a sieve to obtain hydrogel particles with the particle size range of 600-1000 mu m, sealing, drying and storing.
Comparative example 1
Preparation of methane hydrate formation hydrogel promoter PSCA:
2.676g of sodium p-styrenesulfonate is taken and added into a three-neck flask containing a certain amount of distilled water, and the three-neck flask is placed into an oil bath (90 ℃) and continuously stirred (300 rpm) until the sodium p-styrenesulfonate is dissolved; then, 3.324g of acrylamide and 0.02g of cross-linking agent N, N-methylene bisacrylamide are sequentially added into a three-neck flask, and stirring is continued until the mixture is dissolved; dissolving 0.14g of ammonium persulfate in 3ml of deionized water, dropwise adding the solution into a three-neck flask as an initiator, and continuously stirring; the volume of the whole reaction system is 20ml; stopping stirring when colloidal solids appear in the three-neck flask, taking out the colloidal solids, and flushing with distilled water for 5 times; drying in a drying oven at 80 ℃ for more than 48 hours to obtain dried solid PSCA hydrogel; crushing PSCA with a high-speed crusher, sieving PSCA hydrogel with a sieve to obtain hydrogel particles with the particle size of 600-1000 mu m, sealing, drying and storing.
Experiment of methane hydrate formation and decomposition cycle with the accelerators obtained in example 1 and comparative example 1
Mixing 0.083g of hydrogel accelerator with 10g of deionized water, standing until the water content reaches 99.18% after the hydrogel is fully swelled, placing the mixture into a stainless steel high-pressure reaction kettle with the volume of 100ml, placing a magnetic stirrer (350 rpm) at the bottom, sealing the reaction kettle, and placing the reaction kettle into a water bath (1 ℃); after the temperature is stabilized at 1 ℃, opening an air valve to inject methane gas into the reaction kettle, enabling the pressure to reach and be stabilized at 7MPa, and closing the air valve; when the pressure continuously decreases and the temperature rises, the generation of methane hydrate is started, and after a period of time, when the pressure and the temperature are regressively stable again and are not changed, the generation reaction of methane hydrate is ended; rapidly releasing unreacted gas, taking the reaction kettle out of the water bath, and placing the reaction kettle at normal temperature to decompose the hydrate; when the temperature and pressure are no longer changed, the decomposition is completed; and continuing cooling, inflating, generating, releasing pressure, heating and decomposing, and repeating the generating and decomposing circulation processes for a plurality of times.
As shown in FIG. 2, PSCA has remarkable accelerating effect in the 1 st cycle, and the reaction rate is 0.0249 mmol ml -1 min -1 The final air storage multiple reaches 115.16v/v, which proves that the PSCA hydrogel is rich in-SO 3 - The increase of the gas-liquid contact area has remarkable promotion effect on the generation process of methane hydrate; however, in the 2 nd cycle, the accelerating effect was greatly reduced, and the reaction rate was0.0043 mmol ml -1 min -1 The gas storage multiple is 30.18 v/v, the promoting effect is further reduced in the 3 rd cycle, and the reaction rate is 0.005 mmol ml -1 min -1 The gas storage multiple is only 14.9 v/v, and in the 4 th cycle, PSCA has almost no obvious promoting effect, and hydrate almost stops being generated. The results show that the PSCA promotion performance is greatly reduced with the increase of the recycling times, and the recycling performance is poor.
As shown in FIG. 3, PSCS@CNTs@PSCA had hydrate formation rates of 0.0829, 0.0773, 0.0328, 0.0322, 0.0320, 0.0241, 0.0275, 0.0242, 0.0230, 0.0194 mmol ml in cycles 1 to 10 of methane hydrate formation, respectively -1 min -1 The air storage times reach 97.66, 93.52, 111.64, 102.04, 99.76, 94.30, 99.80, 96.75, 100.74 and 95.17 v/v. As the number of cycles increases, the reaction rate decreases, but the final gas storage capacity is not significantly affected. Compared with the PSCA hydrogel of the comparative example, the PSCS@CNTs@PSCA hydrogel can obviously promote the methane hydrate generation process for at least 10 times, which shows that after the PSCS@CNTs are added, the hydrogel not only can keep good promoting effect, but also can improve the mechanical property, so that the recycling property is obviously improved.
Claims (3)
1. A preparation method of a high-efficiency stable hydrogel-based gas hydrate accelerator is characterized by comprising the following steps of: crosslinking the sodium poly (p-styrenesulfonate) -styrene-coated carbon nano tube into a three-dimensional network structure of the sodium poly (p-styrenesulfonate) -acrylamide hydrogel, wherein the method comprises the following steps of:
(1) Adding sodium p-styrenesulfonate and styrene into water for dissolution, adding an initiator to initiate polymerization reaction, and obtaining a sodium poly-p-styrenesulfonate-styrene solution after the reaction is finished;
(2) Adding the carbon nano tube into a sodium poly (p-styrenesulfonate) -styrene solution, mixing, carrying out ultrasonic treatment to obtain a dispersion liquid, carrying out suction filtration on the dispersion liquid to obtain filter residues, and washing and drying to obtain the sodium poly (p-styrenesulfonate) -styrene coated carbon nano tube PSCS@CNTs;
(3) Dissolving PSCS@CNTs in water, adding acrylamide, sodium p-styrenesulfonate and N, N-methylene bisacrylamide after ultrasonic treatment, adding an initiator, initiating a polymerization reaction to form a colloid solid, and washing and drying the colloid solid to obtain the accelerator PSCS@CNTs@PSCA;
the concentration of the initiator in the reaction system is 1-10 g/L, and the initiator should be added dropwise, so that the initiator is fully mixed in the polymerization reaction system, and the severe reaction coalescence caused by excessive single addition is avoided;
the polymerization temperature is 70-95 ℃;
the stirring rotation speed in the polymerization reaction process is 200-500 rpm, and the stirring is carried out at a constant rotation speed from the time of adding the reagent before the polymerization reaction to the time of finishing the polymerization reaction in the step (1) and the step (3);
in the reaction system for preparing PSCS solution in the step (1), the concentration of sodium p-styrenesulfonate is 5-20 g/L, and the concentration of styrene is 5-20 g/L;
in the reaction system for preparing PSCS@CNTs in the step (2), the concentration of the carbon nano tube is 0.2-2wt%;
in the reaction system for preparing PSCS@CNTs@PSCA in the step (3), the concentration of PSCS@CNTs is 5-20 g/L, the concentration of sodium p-styrenesulfonate is 50-250 g/L, the concentration of acrylamide is 50-250 g/L, and the concentration of N, N-methylenebisacrylamide is 1-10 g/L;
the addition of the above reagents should follow: all reagents are added one by one, and after any one reagent is added, the next reagent can be added by stirring until the reagent is fully dissolved, and if the reagents are added simultaneously, the dissolution rate may be reduced.
2. The method for preparing the hydrogel-based gas hydrate promoter according to claim 1, wherein: the initiator is potassium persulfate or ammonium persulfate.
3. The method for preparing the hydrogel-based gas hydrate promoter according to claim 1, wherein: the suction filtration membrane is a polytetrafluoroethylene filtration membrane with the pore diameter of 0.2 mu m.
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