CN112480983A - Method for promoting efficient generation of methane hydrate by sulfonic acid-based hydrogel - Google Patents
Method for promoting efficient generation of methane hydrate by sulfonic acid-based hydrogel Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 76
- 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 74
- 238000000034 method Methods 0.000 title claims abstract description 46
- 230000001737 promoting effect Effects 0.000 title claims abstract description 21
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 77
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 62
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 45
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000012153 distilled water Substances 0.000 claims abstract description 22
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 18
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 57
- 230000008569 process Effects 0.000 claims description 21
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- -1 poly (acrylamide-sodium p-styrenesulfonate Chemical compound 0.000 claims description 5
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- 238000000354 decomposition reaction Methods 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 abstract description 7
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- 229910021641 deionized water Inorganic materials 0.000 abstract 1
- 238000005187 foaming Methods 0.000 abstract 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 27
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
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- WFRUBUQWJYMMRQ-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F WFRUBUQWJYMMRQ-UHFFFAOYSA-M 0.000 description 4
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- 238000010521 absorption reaction Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- QZHDEAJFRJCDMF-UHFFFAOYSA-N perfluorohexanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QZHDEAJFRJCDMF-UHFFFAOYSA-N 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
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- 238000004364 calculation method Methods 0.000 description 2
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- 229910052700 potassium Inorganic materials 0.000 description 2
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- LVTHXRLARFLXNR-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LVTHXRLARFLXNR-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical group CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- UAWBWGUIUMQJIT-UHFFFAOYSA-N azanium;1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound N.OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F UAWBWGUIUMQJIT-UHFFFAOYSA-N 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical class C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
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- 238000005507 spraying Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
-
- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
- B01J13/0065—Preparation of gels containing an organic phase
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- C08J3/075—Macromolecular gels
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/18—Homopolymers or copolymers of nitriles
- C08J2333/20—Homopolymers or copolymers of acrylonitrile
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Abstract
The invention belongs to the technical field of hydrate preparation, and relates to a method for promoting high-efficiency generation of methane hydrate by sulfonic acid group hydrogel, which comprises the steps of dissolving sodium p-styrenesulfonate in deionized water, stirring while carrying out oil bath, sequentially adding acrylamide and N, N-methylene bisacrylamide to form a cross-linked structure, adding an ammonium persulfate aqueous solution to initiate solution polymerization to obtain sulfonic acid group hydrogel, drying and processing the sulfonic acid group hydrogel into particles, absorbing distilled water, constructing a hydrogel solid water system, and reacting with methane to generate the methane hydrate; the sulfonic acid radical is anchored in the hydrogel, so that the generation rate of methane hydrate can be effectively increased, and the foaming problem during adherent growth and decomposition can not be caused.
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 sulfonic acid group hydrogel.
Background art:
the methane hydrate is also called as combustible ice, and is a crystal form compound which is formed by water and methane molecules under high pressure and low temperature and stores a large amount of gas among water molecules, wherein the water molecules are main molecules and are connected with each other by strong hydrogen bonds to form a cage-shaped main structure; methane is taken as a guest molecule, interacts with a host molecule with weak van der Waals force, and is filled in a cavity formed by water molecules. Under the standard condition, the hydrate can theoretically store 180 times of the volume of natural gas, meanwhile, the generated hydrate can be stored under the mild condition, the stability of the storage, transportation and decomposition process is high, the high gas storage density and high safety performance scheduling and storage of methane can be realized, and the methane storage and transportation system has high application potential in the aspect of methane storage and transportation. However, the methane hydrate technology still faces some problems, for example, the methane has the characteristic of being difficult to dissolve in water, so that the mass transfer rate of the methane entering the liquid phase from the gas phase for reaction is limited, the problems of slow reaction, long induction period, harsh reaction conditions, low water conversion rate and the like are caused, and the large-scale industrial application of the technology is severely limited.
Some facilitating methods, including mechanical and non-mechanical methods, are introduced into the hydrate reaction to increase the efficiency of the methane hydrate reaction. For example: chinese patent 201910180760.8 discloses a nailA process for the preparation of an alkane hydrate comprising the steps of: dissolving a fluorine surfactant in distilled water until the mass percent concentration of the fluorine surfactant is 0.05-1.5 wt%, pouring a certain amount of the solution into a high-pressure reaction kettle, cooling to 1-10 ℃, filling 1-10MPa of methane gas into the kettle, reacting for 15-30min to generate methane hydrate, wherein the mass percent concentration of the fluorine surfactant is 0.2-0.8 wt%, pouring a certain amount of the solution into the high-pressure reaction kettle, cooling to 2-6 ℃, filling 4-8MPa of methane gas into the kettle, and the fluorine surfactant is selected from perfluoroalkyl phosphate (YF-807, C-perfluoroalkyl phosphate)27H25F34N2O8PS2) Perfluoroalkyl betaine (YF-006, C)8F17SO2NHCH2CH2CH2N+(CH3)2CH2COO-) Potassium perfluorobutylsulfonate (FC-98), potassium perfluorohexylsulfonate (YF-608), potassium perfluorooctylsulfonate (FC-95), ammonium perfluorooctylsulfonate (FC-120), perfluorooctylquaternary ammonium iodide (FC-134, CF)3(CF2)7SO2NHCH2CH2N+(CH3)3I-) Perfluorooctylsulfonic acid tetraethylene amine (FC-248 and CF)3(CF2)7SO3 -(C2H5)4N+) The fluorine surfactant is potassium perfluorobutyl sulfonate (FC-98), potassium perfluorohexyl sulfonate (YF-608) or potassium perfluorooctyl sulfonate (FC-95). The mechanical method comprises stirring, bubbling, spraying and the like, and the methane mass transfer rate is improved by increasing the gas-liquid contact area, so that the generation of the hydrate is promoted, however, the mechanical method consumes a large amount of capital and energy, and the heat generated in the operation process is not beneficial to the hydrate reaction. The non-mechanical method is characterized in that hydrate generation is promoted by adding a promoter, and the promoter is divided into a thermodynamic promoter and a kinetic promoter, wherein the thermodynamic promoter (such as tetrahydrofuran) promotes hydrate generation by reducing the phase equilibrium condition of methane hydrate reaction; the kinetic accelerator (such as sodium dodecyl benzene sulfonate (SDS), carbon nano structure and porous material) contains sulfonic acid groupThe SDS has the best promotion effect, however, the hydrate generated under the SDS promotion effect grows along the wall, the appearance is loose, the density is low, and foam is easily generated in the decomposition process, so that the SDS is not beneficial to practical industrial application. In addition, the introduction of the accelerant occupies a part of the cage-shaped cavities, so that the gas storage multiple is reduced. Therefore, there is an urgent need for a more efficient acceleration method to improve the reaction efficiency of methane hydrate.
In recent years, scholars adopt hydrophobic silica particles and water to form 'dry water' through high-speed centrifugal mixing to replace the traditional hydrate reaction between liquid water and methane gas, and water droplets are wrapped by hydrophobic silica to form a very fine droplet structure and have a large specific surface area, so that the mass transfer rate of methane is improved, and further, the reaction rate of the hydrate is improved. However, the structure of the 'dry water' is extremely unstable, and after the generation and decomposition process of the hydrate, the structure is extremely easy to damage, the recycling performance is poor, and the efficient recycling application of the 'dry water' in the hydrate reaction is greatly limited. The hydrogel is a three-dimensional network structure formed by slightly crosslinked polymer, can absorb hundreds of times of water or aqueous solution, can still keep a solid state after absorbing water, and has wide application in the aspects of medicine, health care, agriculture, building, petrochemical industry and the like. Inspired by the research, the solid hydrogel capable of absorbing water is introduced into a methane hydrate reaction system, and is assisted by a functional group sulfonic group to promote the methane hydrate reaction efficiency, so that the method has positive significance for the storage and transportation of methane gas.
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 sulfonic acid group-containing hydrogel, wherein a solid water system is constructed by the sulfonic acid group-containing hydrogel, and the solid water system participates in the reaction of the methane hydrate, so that the efficient reaction of the methane hydrate is realized.
In order to achieve the purpose, the technical process of the method for promoting the efficient generation of the methane hydrate by the sulfonic acid group hydrogel comprises two steps of preparation of the sulfonic acid group hydrogel and generation of the methane hydrate:
(1) preparation of sulfonic acid-based hydrogel:
preparing sulfonic acid group hydrogel by adopting a soap-free emulsion polymerization method, placing sodium p-styrenesulfonate powder into a three-neck flask, pouring distilled water for dissolving, placing the three-neck flask into an oil bath pot, setting the oil bath temperature, using circulating condensed water for cooling and keeping, placing a magnetic stirrer at the upper end, keeping constant rotating speed for stirring, and completely dissolving the sodium p-styrenesulfonate powder into the distilled water to obtain a sodium p-styrenesulfonate aqueous solution;
in the stirring process, sequentially pouring acrylamide and N, N-Methylene Bisacrylamide (MBA) as a cross-linking agent into a sodium p-styrenesulfonate aqueous solution, and continuously stirring;
dissolving Ammonium Persulfate (APS) in distilled water, dropwise adding the dissolved Ammonium Persulfate (APS) serving as an initiator into a three-neck flask, reacting to generate a solid, taking out, washing with distilled water, drying and crushing to obtain granular sulfonic hydrogel;
(2) formation of methane hydrate:
mixing the granular sulfonic acid group hydrogel with water, standing, putting the mixture into a high-pressure reaction kettle after the sulfonic acid group hydrogel fully absorbs water, sealing the high-pressure reaction kettle, and putting the high-pressure reaction 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, and closing the methane gas cylinder after the high-pressure reaction kettle is inflated to the set pressure to generate the methane hydrate.
The sodium p-styrene sulfonate, acrylamide, N-methylene bisacrylamide, ammonium persulfate and distilled water related to the step (1) of the invention form a polymerization reaction system for preparing sulfonic acid group hydrogel, wherein the concentration of the sodium p-styrene sulfonate is 120g L-1(ii) a The concentration of acrylamide was 166g L-1(ii) a The concentration of N, N-methylene-bisacrylamide is 1g L-1(ii) a The concentration of ammonium persulfate is 7g L-1(ii) a The oil bath temperature was 90 ℃ and the rotational speed of the magnetic stirrer was 300 rpm.
The particle size of the granular sulfonic acid group hydrogel related to the step (2) is 1000um, and the mass ratio of the granular sulfonic acid group hydrogel to water is 1: 120; the set pressure of the high-pressure reaction kettle is 7 MPa.
After the granular sulfonic acid group hydrogel absorbs water, a solid water system carrying functional groups is formed, the specific surface area of the system is large, the gas-liquid contact area is increased, and the mass transfer rate of methane from a gas phase to a liquid phase is increased; meanwhile, a functional group sulfonic group is introduced into the solid water system and is firmly fixed on the hydrogel, so that the methane hydrate reaction can be promoted; in addition, the sulfonic acid-group hydrogel still maintains a solid state after absorbing water, has good mechanical strength, can not melt or flow, can stably fix water in a certain space, avoids the adherent growth of methane hydrate, and can generate the methane hydrate which is more compact and convenient to store and transport; in addition, the three-dimensional network structure formed by crosslinking macromolecules in the sulfonic acid group hydrogel is very stable, the structure of the sulfonic acid group hydrogel cannot be damaged along with the generation and decomposition of methane hydrate, the sulfonic acid group hydrogel can be continuously recycled, and the method is a promotion method with good recycling property.
Compared with the prior art, the invention takes acrylamide as a hydrophobic monomer, sodium p-styrenesulfonate as a hydrophobic monomer, carries out soap-free emulsion polymerization reaction under the conditions that MBA is a cross-linking agent and APS is an initiator to prepare polyacrylamide-sodium p-styrenesulfonate hydrogel, processes the prepared hydrogel into micron-level particles, absorbs a set amount of distilled water to construct a hydrogel solid water system, uses the solid water system to replace the traditional liquid water system, carries out hydrate reaction with methane gas at high pressure and low temperature, can reach higher gas-liquid mass transfer rate in the process of using the solid water system to generate the methane hydrate without stirring, and generates the methane hydrate which does not grow along the wall and has compact structure, and simultaneously has the advantages of no foam decomposition and excellent recycling performance, thereby finally realizing the great improvement of the generation efficiency of the methane hydrate, the methane hydrate is convenient for storage, transportation and peak regulation, and has a promoting effect on the large-scale practical application of the methane hydrate technology.
Description of the drawings:
FIG. 1 is a graph showing the change of the gas storage factor of methane hydrate with time according to example 2 of the present invention.
FIG. 2 is a schematic diagram of foam generation in the methane hydrate decomposition process according to example 3 of the present invention.
FIG. 3 is a schematic view of the appearance of methane hydrate according to example 4 of the present invention.
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 process of the method for promoting efficient generation of methane hydrate by using the sulfonic acid group hydrogel comprises three steps of preparation of the sulfonic acid group hydrogel and treatment of generation of the sulfonic acid group hydrogel and methane hydrate:
(1) preparation of sulfonic acid-based hydrogel:
adding 13.38g of sodium p-styrenesulfonate and 95ml of distilled water into a three-neck flask in sequence, placing the three-neck flask in an oil bath pot, setting the oil bath temperature to be 90 ℃, adopting circulating water to cool and maintain, placing a magnetic stirrer at the upper end, and stirring for 10min under the condition that the rotating speed is 300rmp to completely dissolve the sodium p-styrenesulfonate in the distilled water to obtain a sodium p-styrenesulfonate aqueous solution;
adding 16.62g of acrylamide into a three-neck flask under the condition of continuous stirring until the acrylamide is completely dissolved;
under the state of continuous stirring, 0.1g of crosslinking agent MBA is added into a three-neck flask to completely dissolve the MBA;
adding 0.7g of APS into 5ml of distilled water, after complete dissolution, dropwise adding the APS into a three-neck flask as an initiator under the state of continuous stirring, and stopping stirring when solids appear in the three-neck flask to obtain a sulfonic acid group hydrogel;
(2) treating the sulfonic acid-based hydrogel: placing the sulfonic acid group hydrogel obtained in the step (1) in a drying box, drying for 24-48h at the temperature of 80 ℃ until no moisture exists in the sulfonic acid group hydrogel, taking out, crushing by a crusher or grinding by a mortar, taking particles with the particle size range of 1-1000 mu m, classifying according to different particle sizes, sealing, drying and storing;
(3) and (3) generation of methane hydrate: 0.083g of sulfonic acid group hydrogel particles with the particle size of 1000 microns are placed in 10g of distilled water, after the sulfonic acid group hydrogel fully absorbs water and swells, the water content is 99.18 percent (at the moment, the water absorption multiple is 120 times), the particles are placed in a stainless steel high-pressure reaction kettle with the volume of 80ml, the stainless steel high-pressure reaction kettle is placed in a water bath with the temperature of 1 ℃, the real-time temperature and the pressure of the reaction kettle are respectively recorded by a temperature sensor and a pressure sensor, after the temperature reading is constant to be 1 ℃, a methane gas cylinder is opened, methane is injected into the reaction kettle until the pressure of the reaction kettle reaches 7MPa, the methane gas cylinder is closed, when the pressure is continuously reduced and the temperature is continuously increased, the generation of methane hydrate is indicated, after a period of time, when the pressure and the temperature return to be stable again and do not change any more, the generation reaction of the methane hydrate is indicated to be finished, the stainless, obtaining methane hydrate; in addition, a group of control groups without hydrogel is set, namely 10g of distilled water is put into a stainless steel high-pressure reaction kettle, the generation of methane hydrate is carried out under the same conditions and operation process, and the temperature and pressure change curve of the generation process of the methane hydrate is recorded.
Example 2:
the gas storage multiple C of the methane hydrate prepared by the method for promoting efficient generation of the methane hydrate by using the sulfonic acid group hydrogelsAccording to the temperature and the pressure, the formula is adopted:
and
calculated, where n is the methane consumption, P0And PtThe pressure of the stainless steel high-pressure reaction kettle at the time 0 and the time t, V0And VtThe volume of gas phase in the stainless steel high-pressure reaction kettle at 0 moment and T moment respectively0And TtThe temperature of the stainless steel high-pressure reaction kettle at 0 moment and t moment respectively, R is a universal gas constant, z0And ztRespectively, time 0 andgas compression factor at time T, m being the theoretical value of the number of methane hydrates 5.75, TcAnd PcThe critical temperature and the critical pressure of the methane are respectively 190.6K and 4.599MPa, omega is the eccentric factor of the methane is 0.012, VmgAnd VmwMolar volumes of gas and water, V, respectivelyiAnd VuRespectively the volume of the initial reaction liquid and the volume of the reaction liquid which does not participate in the reaction after the reaction is finished, wherein delta V is the molar volume difference between the methane hydrate and the water, and the theoretical value is 4.6cm3. The curve of the gas storage times with time obtained by calculation is shown in figure 1. The result shows that the distilled water system without the hydrogel has no obvious generation of hydrate, and the gas storage multiple is 0, compared with the solid water system with the sulfonic acid group hydrogel, the solid water system has obvious hydrate reaction, and the gas storage multiple reaches 110 times (V/V). This shows that, compared with the traditional liquid water, the solid water system constructed by sulfonic acid group hydrogel water absorption can greatly promote the generation of methane hydrate, remarkably improve the reaction rate, shorten the induction time and improve the gas storage multiple.
Example 3:
the sulfonic acid-based hydrogel prepared by the method for promoting efficient generation of methane hydrate according to the embodiment is used for decomposing methane hydrate, the methane hydrate is placed in a 100ml measuring cylinder, 10ml of distilled water is added, the decomposition process of the methane hydrate is observed, and the foam generation condition is photographed and recorded by a high-definition digital camera, so that the foam generation condition in the methane hydrate decomposition process shown in fig. 2 is obtained. As can be seen from the figure, the methane hydrate generated by adding the sulfonic acid group hydrogel does not generate a large amount of foam when the methane hydrate generated by SDS promotion is decomposed, so that the problem of environmental pollution caused by loss of the surfactant is avoided, and the recycling performance is better.
Example 4:
the method for promoting efficient generation of methane hydrate by using sulfonic acid group hydrogel in the embodiment comprises the following specific processes: 0.0166g of sulfonic acid group hydrogel particles with the particle size of 1000 microns are dissolved in 2g of distilled water, the water content of the sulfonic acid group hydrogel particles is 99.18% (at the moment, the water absorption multiple is 120 times), the sulfonic acid group hydrogel particles are placed into a visual high borosilicate high-pressure reaction kettle with the volume of 15ml after the swelling balance is achieved, the visual high borosilicate high-pressure reaction kettle is placed in a water bath at the temperature of 0 ℃, the real-time temperature and the real-time pressure of the visual high borosilicate high-pressure reaction kettle are respectively recorded by a temperature sensor and a pressure sensor, a methane gas cylinder is opened after the temperature index in the reaction kettle is 0 ℃ and is not changed any more, methane is injected into the reaction kettle, and the methane gas cylinder is closed when the pressure of the reaction kettle reaches. If the pressure is continuously reduced and the temperature is continuously increased, the methane hydrate is generated, and after a period of time, the pressure and the temperature are stable again and do not change any more, the methane hydrate generation reaction is finished; according to the data recorded by the temperature sensor and the pressure sensor, the gas storage multiple of methane hydrate generated by the sulfonic acid group hydrogel in the visible high borosilicate high-pressure reaction kettle reaches 96(V/V) through calculation; the appearance of the generated methane hydrate is shot and recorded by a high-definition digital camera, as shown in fig. 3, it can be seen that the sulfonic acid group hydrogel promotes the generated methane hydrate to have a compact structure and does not grow along the wall, which shows that the sulfonic acid group hydrogel can prevent the hydrate from growing along the wall while generating the methane hydrate with high efficiency and high gas storage multiple, so that the generated hydrate has a compact structure, small occupied volume and easy storage and transportation, and the sulfonic acid group hydrogel has high economic benefit and practical value in the storage and transportation process of the methane hydrate and has positive significance for large-scale industrial application of the methane hydrate technology.
Claims (10)
1. The method for promoting efficient generation of methane hydrate by using sulfonic acid group hydrogel is characterized in that the technical process comprises two steps of preparing sulfonic acid group hydrogel and generating methane hydrate:
step (I): carrying out soap-free emulsion polymerization reaction by taking acrylamide as a hydrophobic monomer and sodium p-styrenesulfonate as a hydrophobic monomer under the conditions that N' -methylene bisacrylamide is taken as a cross-linking agent and ammonium persulfate is taken as an initiator to prepare a poly (acrylamide-sodium p-styrenesulfonate) hydrogel;
step (II): processing the prepared poly (acrylamide-sodium p-styrenesulfonate) hydrogel into micron-scale particles, absorbing distilled water to construct a solid water system, and then carrying out hydrate reaction with methane gas at high pressure and low temperature to obtain the methane hydrate.
2. The method for promoting efficient generation of methane hydrate by using the sulfonic acid-based hydrogel according to claim 1, wherein the specific process in the step (I) is as follows:
preparing sulfonic acid group hydrogel by adopting a soap-free emulsion polymerization method, placing sodium p-styrenesulfonate powder into a three-neck flask, pouring distilled water for dissolving, placing the three-neck flask into an oil bath pot, setting the oil bath temperature, using circulating condensed water for cooling and keeping, placing a magnetic stirrer at the upper end, keeping constant rotating speed for stirring, and completely dissolving the sodium p-styrenesulfonate powder into the distilled water to obtain a sodium p-styrenesulfonate aqueous solution;
in the stirring process, sequentially pouring acrylamide and N, N-Methylene Bisacrylamide (MBA) as a cross-linking agent into a sodium p-styrenesulfonate aqueous solution, and continuously stirring;
dissolving Ammonium Persulfate (APS) in distilled water, dropwise adding the dissolved Ammonium Persulfate (APS) serving as an initiator into a three-neck flask, reacting to generate a solid, taking out, washing with distilled water, drying and crushing to obtain the granular sulfonic acid group hydrogel.
3. The method for promoting efficient generation of methane hydrate by using the sulfonic acid-based hydrogel according to claim 2, wherein the specific process in the step (II) comprises the following steps:
mixing the granular sulfonic acid group hydrogel with water, standing, putting the mixture into a high-pressure reaction kettle after the sulfonic acid group hydrogel fully absorbs water, sealing the high-pressure reaction kettle, and putting the high-pressure reaction 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, and closing the methane gas cylinder after the high-pressure reaction kettle is inflated to the set pressure to generate the methane hydrate.
4. The method for promoting efficient generation of methane hydrate by using the sulfonic acid-based hydrogel according to claim 2 or 3, wherein the polymerization reaction system for preparing the sulfonic acid-based hydrogel is composed of sodium p-styrenesulfonate, acrylamide, N-methylene bisacrylamide, ammonium persulfate and distilled water, which are involved in the step (1); the oil bath temperature was 90 ℃ and the rotational speed of the magnetic stirrer was 300 rpm.
5. The method for promoting efficient generation of methane hydrate by using the sulfonic acid-based hydrogel as claimed in claim 4, wherein the concentration of sodium p-styrenesulfonate in the polymerization reaction system is 120g L-1。
6. The method for promoting efficient generation of methane hydrate by using the sulfonic acid-based hydrogel as claimed in claim 4, wherein the concentration of acrylamide in the polymerization reaction system is 166g L-1。
7. The method for promoting efficient generation of methane hydrate by using the sulfonic acid-based hydrogel as claimed in claim 4, wherein the concentration of N, N-methylenebisacrylamide in the polymerization reaction system is 1g L-1。
8. The method for promoting efficient generation of methane hydrate by using sulfonic acid-based hydrogel as claimed in claim 4, wherein the concentration of ammonium persulfate in the polymerization reaction system is 7g L-1。
9. The method for promoting efficient generation of methane hydrate by using the sulfonic acid-based hydrogel according to claim 3, wherein the particle size of the particulate sulfonic acid-based hydrogel is 1000um, and the mass ratio of the particulate sulfonic acid-based hydrogel to water is 1: 120.
10. The method for promoting efficient generation of methane hydrate by using the sulfonic acid-based hydrogel according to claim 3, wherein the set pressure of the high-pressure reaction kettle is 7 MPa.
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