CN112646624A - Method for promoting efficient generation of methane hydrate by graphene composite hydrogel - Google Patents
Method for promoting efficient generation of methane hydrate by graphene composite hydrogel Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 105
- 239000000017 hydrogel Substances 0.000 title claims abstract description 81
- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 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 64
- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000001737 promoting effect Effects 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000012546 transfer Methods 0.000 claims abstract description 23
- 238000010521 absorption reaction Methods 0.000 claims abstract description 13
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 25
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims 2
- 239000002245 particle Substances 0.000 abstract description 26
- 239000007788 liquid Substances 0.000 abstract description 6
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- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- VBYZSBGMSZOOAP-UHFFFAOYSA-N molecular hydrogen hydrate Chemical compound O.[H][H] VBYZSBGMSZOOAP-UHFFFAOYSA-N 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000000053 physical method Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
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- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000003655 absorption accelerator Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/108—Production of gas hydrates
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the technical field of hydrate preparation, and particularly relates to a method for promoting efficient generation of methane hydrate by using graphene composite hydrogel, which comprises three steps of preparing graphene oxide, preparing the graphene composite hydrogel and generating the methane hydrate, wherein the graphene composite hydrogel enables graphene monomers to be fixed in a macromolecular three-dimensional network structure of the hydrogel in a dispersed state, so that the problems of easy caking and poor dispersibility in a liquid phase environment are solved, the excellent thermal conductivity of the graphene monomers is fully exerted, and the heat transfer rate of the methane hydrate is improved; the graphene composite hydrogel particles after water absorption are small in particle size and large in specific surface area, so that the contact area of methane molecules and water molecules is greatly increased, and compared with the traditional liquid medium, the gas mass transfer rate is effectively increased; the principle is scientific and reliable, and the graphene composite hydrogel has the capability of improving the heat transfer and mass transfer efficiency of the methane hydrate reaction.
Description
The technical field is as follows:
the invention belongs to the technical field of hydrate preparation, and particularly relates to a method for promoting efficient generation of methane hydrate by graphene composite hydrogel.
Background art:
the methane hydrate is also called combustible ice, and is a cage-shaped structure formed by water molecules and methane molecules under the conditions of high pressure and low temperature. Wherein, water molecules are main molecules and are connected with each other by hydrogen bonds to form a clathrate hydrate; methane is taken as a guest molecule and is filled in a cage structure formed by water molecules under the action of van der Waals force. The cage-shaped structure can store a large amount of methane, and under the standard condition, a volume of methane hydrate can theoretically store 172 times of volume of methane gas; in addition, the storage and decomposition conditions of the methane hydrate are mild, and the methane hydrate has huge application potential in the aspects of scheduling and solid storage and transportation. However, the randomness of the induction time and the slow generation rate are two main problems to be solved in the formation process of the methane hydrate, and are also problems to be solved in the scale and industrial application of the generation of the methane hydrate.
Based on the above disadvantages of methane storage by hydrate method, finding a method for promoting rapid generation of methane hydrate is the key to realizing the modeling application of hydrate law. The current methods for promoting the rapid generation of methane hydrate mainly comprise physical methods and chemical methods. For example: the preparation method of the methane hydrate ball with high gas content disclosed in the Chinese patent 201911192123.9 comprises the following steps: preparing ice powder according to the required sample amount; selecting a mould, and filling ice powder into the mould; placing the filled ice sample and a mould thereof in a low-temperature sealing device, introducing high-purity methane gas, controlling the temperature, and completing a hydration reaction to obtain the ice powder, wherein ice particles with the particle size of not more than 0.5mm are used as raw materials; the filling of the ice powder is carried out in a low-temperature environment of not higher than-5 ℃, and the filling density of the ice powder is not more than 0.40g/cm3The mold is a spherical silica gel mold, the inner diameter of the spherical silica gel mold is 1-3 cm, an opening is formed in a shell of the spherical silica gel mold, a closed low-temperature device is pre-cooled, when the temperature in a kettle is stabilized at-13 ℃, a filled ice sample and the mold are placed in the closed low-temperature device together, then the kettle is vacuumized, and the specific conditions for introducing high-purity methane gas are as follows: slowly pressurizing to 7MPa to stop air intake and regulating the temperature in the kettleThe temperature is increased from-13 ℃ to 8 ℃, and the temperature increasing rate is 6 ℃/h; and (3) paying attention to the temperature rise condition in the pressurization process to avoid melting of ice powder, placing the sample in a closed low-temperature device after temperature rise for stable standing for 8-12 hours, cooling the closed low-temperature device to below-10 ℃, reducing the pressure to normal pressure, and taking out a hydrate sample, wherein the closed low-temperature device is a high-pressure reaction kettle. The physical method comprises stirring, bubbling, spraying and the like, and mainly improves the mass transfer rate of methane gas molecules and promotes the generation of methane hydrate by continuously updating a gas-liquid contact surface; however, the physical method has problems of increased equipment cost and energy consumption while improving the generation of the hydrate, and heat generated in the methane hydrate reaction system is not beneficial to the generation of the methane hydrate. The chemical method mainly uses additives to promote the generation of methane hydrate, wherein thermodynamic promoters such as tetrahydrofuran, tetrabutylammonium chloride and the like promote the generation of methane hydrate by reducing the phase equilibrium condition of hydrate reaction, however, promoter molecules occupy a part of cavities to influence the gas storage multiple of the final methane hydrate; the kinetic accelerator has various types, comprises a surfactant, a porous medium, a carbon nano material and the like, and promotes the generation of methane hydrate by improving the mass transfer or heat transfer rate of a reaction system. Among the accelerators, the surfactant Sodium Dodecyl Sulfate (SDS) has the most remarkable accelerating effect, but has the problems of wall growth, loose appearance and generation of a large amount of foam due to decomposition, and is not favorable for practical application.
Graphene is a novel two-dimensional carbon nanomaterial, has excellent properties such as good mechanical strength, high heat conductivity, large specific surface area and the like, has great potential in promoting methane hydrate, and is a novel accelerant which is concerned with. The high heat conductivity of the graphene can effectively improve the heat transfer rate of a methane hydrate reaction system, and the nanostructure of the graphene can provide sufficient nucleation sites for the methane hydrate reaction, so that the graphene has a certain promotion effect in the methane hydrate reaction process. However, graphene has extremely strong surface hydrophobicity and poor dispersibility in a liquid phase, and the promotion effect of the graphene on the generation of methane hydrate is greatly weakened. Therefore, an effective method is urgently needed to solve the problem of poor dispersibility of graphene in a methane hydrate reaction system.
The inventor adopts hydrogel particle absorption accelerator solution to replace the traditional liquid medium to react with hydrogen to accelerate the reaction of hydrogen hydrate. Hydrogen is similar to methane and is insoluble in water, so that the hydrogen hydrate reaction has the problem of low mass transfer rate, and the rapid proceeding of the hydrogen hydrate reaction is also limited. The hydrogel is a micro-crosslinked polymeric macromolecular compound, has super-water absorption capacity, and can absorb hundreds of even thousands of times of water or solution of the self weight. The particle size of the hydrogel after water absorption is still micron level, and the hydrogel has a large specific surface area, so that the gas-liquid contact area is greatly increased, the mass transfer rate of hydrogen is effectively improved, and finally, the hydrogen hydrate is quickly generated. Inspired by the method, the graphene is introduced into the synthesis process of the hydrogel, and the graphene composite hydrogel particles are used for absorbing water to replace the traditional liquid medium, so that the generation of methane hydrate is promoted. In the process, the graphene can be uniformly dispersed in the hydrogel and is not limited by poor dispersibility in a liquid phase, and the capacity of improving the heat transfer rate of a system is exerted; meanwhile, the hydrogel particles have huge specific surface area, increase the mass transfer rate of methane gas, promote the rapid generation of methane hydrate, and have very high positive significance and economic benefit in the large-scale application of hydrate technology.
The invention content is as follows:
the invention aims to overcome the defects in the prior art, and seeks to design a method for promoting efficient generation of methane hydrate by using graphene composite hydrogel, so that the high heat-conducting property of graphene and the high mass transfer rate of hydrogel particles are combined to effectively promote the reaction of methane hydrate.
In order to achieve the purpose, the technical process of the method for promoting the efficient generation of the methane hydrate by using the graphene composite hydrogel comprises three steps of preparing graphene oxide, preparing the graphene composite hydrogel and generating the methane hydrate:
(1) preparing graphene oxide:
adding concentrated sulfuric acid with the mass percentage concentration of 98% into a three-neck flask, putting the three-neck flask into an oil bath pot, cooling to 0-4 ℃, placing a magnetic stirrer at the upper end, stirring at a constant rotating speed, and sequentially adding graphite and sodium nitrate to be fully dissolved;
adding potassium permanganate into a three-neck flask for 6 times, fully dissolving, stirring at 10-15 deg.C for 2.5 hr, heating to 35 deg.C, maintaining for 30min, heating to 80-100 deg.C, and maintaining for 30 min;
adding hydrogen peroxide with the mass percent concentration of 5%, filtering, collecting filter residues, washing the filter residues with hydrochloric acid aqueous solution with the mass percent concentration of 5%, and drying to obtain graphene oxide;
(2) preparing graphene composite hydrogel:
placing an acrylic acid aqueous solution into a three-neck flask, adding a sodium hydroxide aqueous solution for neutralization, placing the three-neck flask into an oil bath pot, heating to a set temperature and keeping the temperature, placing a magnetic stirrer at the upper end, keeping a constant rotating speed, and stirring;
sequentially adding acrylamide and N, N-Methylene Bisacrylamide (MBA) into a three-neck flask, and continuously stirring until the acrylamide and the N, N-methylene bisacrylamide are fully dissolved;
pouring the graphene oxide aqueous solution subjected to ultrasonic treatment into a three-neck flask, and continuously stirring;
dropwise adding an Ammonium Persulfate (APS) aqueous solution serving as an initiator into a three-neck flask, continuously stirring, stopping stirring when a solid appears in the three-neck flask, taking out the solid, washing with deionized water, drying, and crushing to obtain the granular graphene composite hydrogel;
acrylic acid, sodium hydroxide, acrylamide, N-methylene bisacrylamide, graphene oxide, ammonium persulfate and distilled water form a polymerization reaction system for preparing the graphene composite hydrogel, wherein the molar concentration of the acrylic acid is 12mol L-1The neutralization degree of sodium hydroxide and acrylic acid is 80 percent, and the molar concentration of acrylamide is 12mol L-1Concentration of MBA 2g L-1The concentration of graphene oxide is 1g L-1APS concentration of 6g L-1;
(3) Generation of methane hydrate:
mixing the granular graphene composite hydrogel with water, standing until the graphene composite hydrogel fully absorbs water to ensure that the water content reaches 97.56% and the water absorption multiple is 40 times, putting the mixture into a high-pressure reaction kettle, sealing, and putting the kettle into a water bath at the temperature of 1 ℃ for cooling;
and when the temperature of the high-pressure reaction kettle is reduced to the set temperature and does not change any more, opening the methane gas cylinder to inflate the high-pressure reaction kettle, closing the methane gas cylinder after the high-pressure reaction kettle is inflated to the set pressure, starting the methane hydrate reaction, and continuously monitoring the temperature and the pressure of the high-pressure reaction kettle in the period.
The principle of the method for promoting the rapid generation of the methane hydrate by using the graphene composite hydrogel provided by the invention is as follows: the graphene is fully and uniformly dispersed in the hydrogel during the synthesis of the hydrogel, so that the high heat transfer performance of the graphene monomer is effectively exerted in the synthesis process of the methane hydrate, and the heat transfer rate is improved; the graphene composite hydrogel still keeps a solid state after absorbing water, has a very high specific surface area, increases the contact area of methane gas molecules and water molecules, is beneficial to improving the mass transfer rate, and enables methane hydrate to be generated quickly.
Compared with the prior art, the graphene composite hydrogel enables the graphene monomer to be fixed in a macromolecular three-dimensional network structure of the hydrogel in a dispersed state, so that the problems of easy caking and poor dispersibility in a liquid phase environment are solved, the excellent thermal conductivity of the graphene monomer can be fully exerted, and the heat transfer rate of the methane hydrate is improved; the graphene composite hydrogel particles after water absorption are small in particle size and large in specific surface area, so that the contact area of methane molecules and water molecules is greatly increased, and compared with the traditional liquid medium, the gas mass transfer rate is effectively increased; the principle is scientific and reliable, the graphene composite hydrogel has the capability of improving the reaction heat transfer and mass transfer efficiency of the methane hydrate, still keeps the solid state form after water absorption, has better mechanical strength, is not easy to damage the structure in the generation and decomposition cycle process of the methane hydrate, is easy to recycle, and has good economic performance.
Description of the drawings:
fig. 1 is a schematic view of a state of a graphene composite hydrogel according to the present invention after water absorption.
FIG. 2 is an electron microscope scanning schematic view of a three-dimensional network structure of graphene composite hydrogel according to the present invention.
Fig. 3 is a schematic diagram of a three-dimensional network structure of a graphene composite hydrogel according to the present invention.
Fig. 4 is a schematic diagram of a mechanism for promoting a reaction of the graphene composite hydrogel on methane hydrate.
The specific implementation mode is as follows:
the invention is further described below by way of an embodiment example in conjunction with the accompanying drawings.
Example 1:
the technical process of the method for promoting efficient generation of methane hydrate by using graphene composite hydrogel comprises four steps of preparing graphene oxide, preparing graphene oxide composite hydrogel, treating carbon nanotube composite hydrogel and generating methane hydrate:
(1) preparing graphene oxide:
adding 230ml of 98% concentrated sulfuric acid by mass into a three-neck flask, putting the three-neck flask into an oil bath pan, cooling to 0-4 ℃, placing a magnetic stirrer at the upper end, stirring at the rotation speed of 300rmp, and sequentially adding 10g of graphite and 5g of sodium nitrite; after the graphite and the sodium nitrite are completely dissolved, adding 30g of potassium permanganate for 6 times at the same time interval, adding 5g of potassium permanganate each time, keeping the rotating speed at 300rmp, and stirring for 2.5 hours at the oil bath pot temperature of 10-15 ℃; heating to 35 deg.C, and maintaining for 30 min; heating to 80-100 deg.C, maintaining for 30min, adding 5-10ml hydrogen peroxide with mass percent concentration of 5%, filtering, collecting filter residue, washing with 5% hydrochloric acid water solution until no SO is detected4 2-Washing filter residues with deionized water, and drying at 40 ℃ to prepare graphene oxide;
(2) preparing graphene composite hydrogel:
dissolving 8.77g of acrylic acid in 20ml of deionized water, stirring until the acrylic acid is dissolved, and preparing an acrylic acid aqueous solution; dissolving 3.9g of sodium hydroxide into 20ml of deionized water, and stirring to prepare a sodium hydroxide aqueous solution; mixing an acrylic acid aqueous solution and a sodium hydroxide aqueous solution to obtain a mixed solution with a neutralization degree of 80%; slowly pouring the mixed solution into a three-neck flask, placing the three-neck flask in an oil bath pot, heating to 90 ℃ and keeping, placing a magnetic stirrer at the upper end, keeping the rotating speed at 300rmp, and stirring for 5-10 min;
adding 8.77g of acrylamide into a three-neck flask, and continuously stirring for 10min until the acrylamide is completely dissolved; adding 0.2g of cross-linking agent N, N-Methylene Bisacrylamide (MBA) into a three-neck flask, and continuously stirring for 10min until the cross-linking agent N, N-Methylene Bisacrylamide (MBA) is completely dissolved;
adding 0.1g of graphene oxide into 55ml of deionized water to prepare a graphene oxide aqueous solution, placing the graphene oxide aqueous solution in an ultrasonic machine for ultrasonic treatment for 10-12h, pouring the uniformly dispersed graphene oxide solution into a three-neck flask, and continuously stirring for 5-10 min;
adding 0.6g of Ammonium Persulfate (APS) into 5ml of deionized water, sufficiently dissolving the Ammonium Persulfate (APS) to serve as an initiator, dropwise adding the initiator into a three-neck flask, continuously stirring until a solid appears in the three-neck flask, and stopping stirring to prepare the graphene composite hydrogel;
the total volume of a polymerization reaction system for preparing the graphene composite hydrogel, which is formed by acrylic acid, sodium hydroxide, acrylamide, N-methylene bisacrylamide, graphene oxide, ammonium persulfate and distilled water, is 100 ml;
(3) treating the graphene composite hydrogel:
placing the graphene composite hydrogel obtained in the step (2) in a drying box, drying for 24-48h at the temperature of 80 ℃ until the graphene oxide composite hydrogel is completely dried, taking out, grinding by using a grinder or a mortar, screening by using a sieve to obtain graphene composite hydrogel particles with the particle size of 600-1000 mu m, sealing, drying and storing;
(4) generation of methane hydrate:
placing 0.25g of the graphene composite hydrogel particles prepared in the step (2) into 10g of distilled water, so that the graphene composite hydrogel particles fully absorb water until free flowing water cannot be observed, at the moment, the water content of the graphene composite hydrogel particles is 97.56%, placing the graphene composite hydrogel particles after water absorption into a stainless steel high-pressure reaction kettle with the volume of 80ml, placing the stainless steel high-pressure reaction kettle into a water bath with the temperature of 1 ℃, respectively recording the real-time temperature and pressure of the stainless steel high-pressure reaction kettle by using a temperature sensor and a pressure sensor, opening a high-purity methane gas cylinder after the temperature indication is constant at 1 ℃, injecting methane gas into the stainless steel high-pressure reaction kettle, closing the gas cylinder after the pressure of the stainless steel high-pressure reaction kettle reaches 7MPa, and indicating that when the pressure continuously drops and the temperature continuously rises: methane hydrate is in the process of formation and when the pressure and temperature again return to stability and no longer change, it indicates that: and (5) after the generation process of the methane hydrate is finished, taking out and opening the stainless steel high-pressure reaction kettle to obtain the methane hydrate.
Example 2:
in this example, the graphene composite hydrogel prepared in step (1) of example 1 is subjected to a water absorption swelling test, and the appearance of the graphene composite hydrogel after water absorption is shown in fig. 1, and the water absorption swelling ratio is 97 times.
Example 3:
in this example, the graphene composite hydrogel particles prepared in step (3) of example 1 are observed by a scanning electron microscope: placing 0.25g of graphene composite hydrogel particles in 10g of distilled water, fully absorbing water of the graphene composite hydrogel particles until free flowing water cannot be observed, placing the graphene composite hydrogel particles with the water content of 97.56% in a refrigerator at-6 ℃ for freezing for 12 hours, taking out the frozen graphene composite hydrogel particles, placing the frozen graphene composite hydrogel particles in a freeze dryer, and carrying out vacuum freeze drying for 24-48 hours at the cold trap temperature of-56 ℃; the gold spraying treatment is carried out on the freeze-dried graphene composite hydrogel particles, then the observation is carried out by a scanning electron microscope, the photographed picture is shown in figure 2, the water-absorbing freeze-dried graphene composite hydrogel particles have a large number of three-dimensional network structures, water molecules can be retained, and the graphene composite hydrogel particles are endowed with high water absorption capacity.
Claims (9)
1. The method for promoting efficient generation of methane hydrate by using graphene composite hydrogel is characterized in that the process comprises three steps of preparing graphene oxide, preparing graphene composite hydrogel and generating methane hydrate:
(1) preparing graphene oxide:
adding concentrated sulfuric acid with the mass percentage concentration of 98% into a three-neck flask, putting the three-neck flask into an oil bath pot, cooling to 0-4 ℃, placing a magnetic stirrer at the upper end, stirring at a constant rotating speed, and sequentially adding graphite and sodium nitrate to be fully dissolved;
adding potassium permanganate into a three-neck flask for 6 times, fully dissolving, stirring at 10-15 deg.C for 2.5 hr, heating to 35 deg.C, maintaining for 30min, heating to 80-100 deg.C, and maintaining for 30 min;
adding hydrogen peroxide with the mass percent concentration of 5%, filtering, collecting filter residues, washing the filter residues with hydrochloric acid aqueous solution with the mass percent concentration of 5%, and drying to obtain graphene oxide;
(2) preparing graphene composite hydrogel:
placing an acrylic acid aqueous solution into a three-neck flask, adding a sodium hydroxide aqueous solution for neutralization, placing the three-neck flask into an oil bath pot, heating to a set temperature and keeping the temperature, placing a magnetic stirrer at the upper end, keeping a constant rotating speed, and stirring;
sequentially adding acrylamide and N, N-methylene bisacrylamide into a three-neck flask, and continuously stirring until the acrylamide and the N, N-methylene bisacrylamide are fully dissolved;
pouring the graphene oxide aqueous solution subjected to ultrasonic treatment into a three-neck flask, and continuously stirring;
dropwise adding an ammonium persulfate aqueous solution serving as an initiator into a three-neck flask, continuously stirring, stopping stirring when a solid appears in the three-neck flask, taking out the solid, washing with deionized water, drying, and crushing to obtain granular graphene composite hydrogel;
(3) generation of methane hydrate:
mixing the granular graphene composite hydrogel with water, standing until the graphene composite hydrogel fully absorbs water to ensure that the water content reaches 97.56% and the water absorption multiple is 40 times, putting the mixture into a high-pressure reaction kettle, sealing, and putting the kettle into a water bath at the temperature of 1 ℃ for cooling;
and when the temperature of the high-pressure reaction kettle is reduced to the set temperature and does not change any more, opening the methane gas cylinder to inflate the high-pressure reaction kettle, closing the methane gas cylinder after the high-pressure reaction kettle is inflated to the set pressure, starting the methane hydrate reaction, and continuously monitoring the temperature and the pressure of the high-pressure reaction kettle in the period.
2. The method for promoting efficient generation of methane hydrate by using the graphene composite hydrogel according to claim 1, wherein the polymerization reaction system for preparing the graphene composite hydrogel is composed of acrylic acid, sodium hydroxide, acrylamide, N-methylene bisacrylamide, graphene oxide, ammonium persulfate and distilled water involved in the step (2).
3. The method for promoting efficient generation of methane hydrate by using graphene composite hydrogel according to claim 2, wherein the molar concentration of acrylic acid in a polymerization reaction system is 12mol L-1。
4. The method for promoting efficient generation of methane hydrate by using the graphene composite hydrogel according to claim 2, wherein the neutralization degree of sodium hydroxide and acrylic acid in a polymerization reaction system is 80%.
5. The method for promoting efficient generation of methane hydrate by using graphene composite hydrogel according to claim 2, wherein the molar concentration of acrylamide in a polymerization reaction system is 12mol L-1。
6. The method for promoting efficient generation of methane hydrate by using graphene composite hydrogel according to claim 2, wherein the concentration of MBA in a polymerization reaction system is 2g L-1。
7. The method for promoting efficient generation of methane hydrate by using graphene composite hydrogel according to claim 2, wherein the concentration of graphene oxide in a polymerization reaction system is 1g L-1。
8. The method for promoting efficient generation of methane hydrate by using graphene composite hydrogel according to claim 2, wherein the method is characterized in thatThe concentration of APS in the polymerization system was 6g L-1。
9. The method for promoting efficient generation of methane hydrate by using graphene composite hydrogel according to claim 1, characterized in that the principle is as follows: the graphene is fully and uniformly dispersed in the hydrogel during the synthesis of the hydrogel, and the high heat transfer performance of the graphene monomer is exerted in the synthesis process of the methane hydrate, so that the heat transfer rate is improved; the graphene composite hydrogel still keeps a solid state after absorbing water, has a specific surface area, can increase the contact area of methane gas molecules and water molecules, improves the mass transfer rate, and enables methane hydrate to be generated quickly.
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