CN115490203B - Method for promoting hydrate hydrogen storage by using solid nano particles - Google Patents
Method for promoting hydrate hydrogen storage by using solid nano particles Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 84
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 84
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 43
- 239000007787 solid Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000001737 promoting effect Effects 0.000 title claims abstract description 9
- 238000003860 storage Methods 0.000 title claims description 53
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 38
- VBYZSBGMSZOOAP-UHFFFAOYSA-N molecular hydrogen hydrate Chemical compound O.[H][H] VBYZSBGMSZOOAP-UHFFFAOYSA-N 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000008014 freezing Effects 0.000 claims abstract description 16
- 238000007710 freezing Methods 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000002474 experimental method Methods 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000011049 filling Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 230000003446 memory effect Effects 0.000 claims description 7
- 150000004677 hydrates Chemical class 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 4
- 230000006911 nucleation Effects 0.000 abstract description 3
- 238000010899 nucleation Methods 0.000 abstract description 3
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 99
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 45
- 239000007789 gas Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000011232 storage material Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention discloses a method for promoting hydrate to store hydrogen by using solid nano particles. The method comprises the following steps: (1) After THF, hydrophobic silica nano particles are mixed with deionized water, the mixture is put into a sealed container for freezing, and THF hydrate is added into liquid nitrogen for grinding to obtain THF hydrate particles; (2) Filling THF hydrate particles into a pre-cooled reaction container, vacuumizing, filling pre-cooled hydrogen, keeping the pressure constant, and reacting to obtain hydrogen hydrate; (3) And (3) heating the reaction vessel to decompose the hydrogen hydrate, releasing hydrogen and a silicon dioxide nano particle-THF aqueous solution, cooling to a temperature below the freezing point again, and carrying out a hydrogen hydrate generation experiment again until the pressure is reduced to a certain extent and then the reaction vessel tends to be stable, thus obtaining the THF-H 2 hydrate. After the hydrate template is prepared by using a conventional ice powder method, the nucleation and growth of the THF solution-H 2 hydrate are doubly enhanced by combining the good heat and mass transfer performance of the nano particles.
Description
Technical field:
the invention relates to the technical field of hydrate hydrogen storage, in particular to a method for promoting hydrate hydrogen storage by using solid nano particles.
The background technology is as follows:
The utilization of hydrogen energy involves four links of preparation, storage, transportation and application, but storage and transportation are key, and account for 30% -40% of the total cost. Hydrogen exists in a gaseous form under normal conditions, is inflammable, explosive and diffusive, so how to store hydrogen efficiently and safely is one of technical challenges for the development of hydrogen energy.
Traditional gaseous and liquefied hydrogen storage methods require high pressure and low temperature conditions, and the safety, energy consumption and economy are difficult to meet the hydrogen energy industry requirements. For this reason, it has been proposed to use solid physical adsorption or chemical reaction of hydrogen gas to store, and to develop hydrogen storage materials such as carbonaceous materials, metal alloys, metal Organic Frameworks (MOFs), and zeolites. Unlike the solid hydrogen storage materials described above, hydrates store hydrogen in a solid state, and "capture" hydrogen molecules through the three-dimensional cage structure formed by hydrogen bonding between water molecules. Therefore, the solid hydrogen storage raw material of the hydrate is water, the inflation and deflation processes are reversible, and the method is environment-friendly and low in cost. Second, mao et al (2004) indicated that pure hydrogen (H 2) hydrate can store up to 5.3wt% of the gas under 200-300MPa and 240-249K conditions, which can meet the hydrogen storage objectives set forth in us department of energy 2015, but the required hydrogen storage temperature and pressure conditions are severe. Later researchers found that by adding promoters (such as cyclopentane CP, tetrahydrofuran THF, tetrabutylammonium bromide TBAB, propane, etc.), thermodynamic conditions for hydrogen hydrate formation could be moderated, greatly improving safety, but the promoters would occupy the hydrate cage and would be detrimental to hydrogen storage (ZL 201310574070.3). For example Veluswamy and Linga (2013) found that the hydrogen storage of 5mol% aqueous THF was 0.12wt% in THF-H 2 binary hydrate formed at 8.8MPa and 278K.
At present, the hydrate has the defects of low gas storage rate, low gas storage density and the like, and greatly restricts the application of the technology in the aspect of hydrogen storage. Researchers have found that compounding thermodynamic promoters with kinetic promoters (e.g., surfactants SDS, DBSA, etc.) can improve both hydrogen storage conditions and hydrogen storage rates. By prefabricating a normal-pressure or low-pressure hydrate powder 'template', the mass transfer rate between solid and gas phases is improved by utilizing the large specific surface area of micro-scale particles, the generation of hydrogen hydrate is promoted, and the gas storage process is accelerated (CN 101774541A, CN 108373137A). Recently, researchers have sequentially proposed a method of combining solid-state hydrogen storage of hydrates with a physical or chemical hydrogen storage multi-form hydrogen storage mode (ZL 202110088257.7, CN111204706 a). However, these technologies have not been able to meet the practical requirements for a short time, and there is still a need to develop a new, efficient and simple method for storing hydrogen in hydrates.
The invention comprises the following steps:
the invention solves the problems of low hydrogen storage rate, low hydrogen storage density and the like in the prior art, and provides a method for promoting hydrate hydrogen storage by using solid nano particles, wherein after a hydrate template is prepared by using a conventional ice powder method, the nucleation and growth of THF solution-H 2 hydrate are doubly enhanced by combining the good heat and mass transfer performance of the nano particles.
The invention aims to provide a method for promoting hydrate to store hydrogen by using solid nano particles, which comprises the following steps:
(1) Mixing liquid accelerator THF (tetrahydrofuran) and hydrophobic silica nano particles with deionized water, placing the mixture into a sealed container, placing the container into a freezing container, freezing for 0.5-2 hours to obtain normal-pressure solid THF hydrate, adding liquid nitrogen into the THF hydrate, grinding and crushing the THF hydrate, and sieving the THF hydrate to obtain THF hydrate particles;
(2) Filling THF hydrate particles into a pre-cooled reaction container, wherein the temperature in the reaction container is between minus 20 ℃ and minus 5 ℃, vacuumizing the reaction container, filling pre-cooled hydrogen to 1-20MPa, keeping the pressure in the reaction container constant, and reacting for 9-11h to obtain hydrogen hydrate;
(3) And (3) heating the reaction vessel to the outside of a phase equilibrium curve to decompose the hydrogen hydrate, releasing hydrogen and a silicon dioxide nano particle-THF aqueous solution, re-cooling to the temperature below the freezing point by utilizing the memory effect of the hydrogen hydrate aqueous solution in the step (2), and performing a hydrogen hydrate generation experiment again until the pressure is reduced to a certain extent and then the hydrogen hydrate tends to be stable, thus obtaining the THF-H 2 hydrate.
The procedure for calculating the hydrogen storage amount of the hydrate THF-H 2 is as follows:
The hydrogen storage amount epsilon (the mass fraction of hydrogen in the hydrate) of the THF-H 2 hydrate is obtained by calculating the amount of hydrogen consumed in the system. The formula is as follows:
Wherein M g represents the total gas storage capacity, p 1、V1、T1 represents the gas phase pressure, the gas phase volume and the gas phase temperature after the decomposition of the hydrogen hydrate (hydrogen-THF hydrate) particle system hydrate under the constant pressure in the step (2), p 2、V2、T2 represents the gas phase pressure, the gas phase volume and the gas phase temperature after the generation experiment of the hydrogen-THF solution system hydrate in the step (3), R represents the general gas constant, z represents the compression factor, M H2 represents the molar mass of H 2, and M h represents the hydrate mass.
Preferably, the molar concentration of THF in step (1) in the aqueous solution is 0.0556-5.56 mol%.
Preferably, in the step (1), the mass concentration of the hydrophobic silica nanoparticles is 1.0 to 5.0wt% based on the mass of deionized water.
Preferably, the hydrophobic silica nanoparticle of step (1) is prepared by the following steps: (1) By means ofSynthesizing silicon dioxide nano particles by a hydrolysis condensation method; (2) Dissolving octadecyltrimethoxy silane and silica nanoparticles in n-hexane, mixing, performing ultrasonic treatment, pouring into a reaction container, placing into a water bath at 40 ℃ for constant temperature reaction, centrifuging the reacted reaction liquid, pouring out supernatant, and cleaning and drying to obtain the hydrophobic silica nanoparticles.
Preferably, the particle size of the hydrophobic silica nanoparticles in the step (1) is 7-100 nm.
Preferably, the solid THF hydrate under normal pressure is obtained after the step (1) is frozen in a freezing container for 1 h.
Preferably, the temperature in the reaction vessel in the step (2) is-5 ℃, after the reaction vessel is vacuumized, the precooled hydrogen is filled to 9-10MPa, the pressure in the reaction vessel is kept constant, and the reaction is carried out for 10 hours to obtain the hydrogen hydrate.
Preferably, the specific steps of step (3) are: and (3) heating the reaction vessel to 10 ℃ to decompose the hydrogen hydrate, releasing hydrogen and a silicon dioxide nano particle-THF aqueous solution, cooling to-5 ℃ again by utilizing the memory effect of the hydrogen hydrate aqueous solution in the step (2), performing a hydrogen hydrate generation experiment again until the pressure is stable after being reduced to a certain extent, and repeating the steps at least 3 times to obtain the THF-H 2 hydrate.
Compared with the prior art, the invention has the following advantages:
(1) The hydrogen hydrate containing the liquid accelerator THF provided by the invention has milder generation conditions, the generation temperature is between-20 ℃ and-5 ℃, and the generation pressure is between 1 MPa and 20MPa; (2) After the hydrate template is prepared by using a conventional ice powder method, the nucleation and growth of the THF solution-H 2 hydrate are doubly enhanced by combining the good heat and mass transfer performance of the nano particles; (3) Hydrophobic silica nanoparticles can adsorb hydrophobic nonpolar hydrogen molecules, so that the stability of hydrogen storage of a single hydrate cage is enhanced; (4) The hydrogen storage materials can be reused, and based on the memory effect, the more the circulation times are, the faster the gas storage rate is.
Description of the drawings:
FIG. 1 is a hydrogen storage-gassing cycle containing 5.0wt% hydrophobic silica nanoparticles having a particle size of 7nm and 5.56mol% THF-H 2 hydrate.
The specific embodiment is as follows:
The following examples are further illustrative of the invention and are not intended to be limiting thereof.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention. Unless otherwise indicated, the experimental materials and reagents herein are all commercially available products conventional in the art.
The hydrate generating device comprises a high-pressure reaction kettle, a temperature control system, an air supply system and a data acquisition system. The highest working pressure of the high-pressure reaction kettle can resist 30MPa, and the high-pressure reaction kettle is immersed in a low-temperature constant-temperature tank; the air supply system consists of a high-pressure hydrogen tank, a booster pump, a control valve and corresponding pipelines; the temperature control system consists of an externally connected circulating low-temperature constant-temperature tank, and can provide refrigerant circulating liquid at the temperature of-50 ℃ to 100 ℃ for the high-pressure reaction kettle; the data acquisition system consists of pressure and temperature sensors and a control computer, and experimental data are recorded in real time.
Based on the experimental device, the method for promoting the hydrogen storage of the hydrate by using the solid nano particles comprises the following steps:
(1) And mixing a certain amount of liquid accelerator THF, silica nanoparticles and deionized water, putting the mixture into a sealed container, putting the container into a freezer, freezing for 0.5-2 hours to obtain normal-pressure solid THF hydrate, taking out the normal-pressure solid THF hydrate, putting the solid THF hydrate into a mortar, adding liquid nitrogen, and grinding to obtain THF hydrate particles.
(2) Before air intake, calibration of the temperature and pressure sensors of the whole system and air tightness check are completed. In order to avoid melting the experimental sample in the step (1), a constant-temperature water bath is started in advance to pre-cool the reaction kettle, and then THF hydrate particles are filled. After vacuumizing, filling precooled hydrogen to experimental pressure, keeping the pressure in the kettle constant by means of a gas booster pump, and finishing the reaction for about 10 hours to generate hydrogen hydrate.
(3) The temperature is raised to be out of the phase equilibrium curve to decompose the hydrate and release hydrogen and the silicon dioxide nano particle-THF aqueous solution. And (3) re-cooling to the temperature below the freezing point by utilizing the memory effect of the aqueous solution in the step (2), carrying out a hydrogen hydrate generation experiment again until the pressure is reduced to a certain extent and the hydrogen hydrate is stable, indicating that THF-H 2 hydrate is generated, and leading out data after the experiment is ended. As shown in fig. 1, step (3) is repeated three times in this way to obtain the cycle performance of the hydrogen storage material.
(4) The procedure for calculating the hydrogen storage amount of the hydrate THF-H 2 is as follows:
The hydrogen storage amount epsilon (the mass fraction of hydrogen in the hydrate) of the THF-H 2 hydrate is obtained by calculating the amount of hydrogen consumed in the system. The formula is as follows:
Wherein M g represents the total gas storage capacity, p 1、V1、T1 represents the gas phase pressure, the gas phase volume and the gas phase temperature after the decomposition of the hydrogen hydrate (hydrogen-THF hydrate) particle system hydrate under the constant pressure in the step (2), p 2、V2、T2 represents the gas phase pressure, the gas phase volume and the gas phase temperature after the generation experiment of the hydrogen-THF solution system hydrate in the step (3), R represents the general gas constant, z represents the compression factor, M H2 represents the molar mass of H 2, and M h represents the hydrate mass.
In the examples described below, the molar concentration of THF is 0.0556 to 5.56mol%, based on the mass of deionized water, and the mass concentration of hydrophobic silica nanoparticles is 1.0 to 5.0wt%.
In the following examples, hydrophobic silica nanoparticles were prepared by the following steps: (1) Mixing tetraethyl orthosilicate with absolute ethanol serving as a solvent according to a certain volume ratio (1:10-1:100), adding deionized water and ammonia water serving as a catalyst, stirring and mixing uniformly by magnetic force, reacting at 25 ℃ for 5-13 h, and performing repeated cyclic centrifugation, alcohol washing and drying on the obtained sample. Preparing and synthesizing silica nano particles with certain particle size; (2) Dissolving octadecyltrimethoxy silane and silicon dioxide nano particles in 20mL of n-hexane according to the molar ratio of 2:3, mixing and carrying out ultrasonic treatment for 2 hours, pouring the mixture into a round bottom flask, placing the round bottom flask into a water bath with the temperature of 40 ℃ for constant temperature for 8 hours, centrifuging the reaction liquid after reaction, pouring out supernatant, repeatedly using n-hexane and ethanol to clean solid powder, and finally carrying out vacuum drying at the temperature of 100 ℃ for 30 minutes to obtain the hydrophobic silicon dioxide nano particles. The volume ratio of the tetraethyl orthosilicate to the absolute ethanol solvent is preferably 1:50.
Example 1
A method for promoting hydrogen storage of hydrates using solid nanoparticles, comprising the steps of:
(1) 30g of water, 7.076g of tetrahydrofuran and 0.3g of 7nm hydrophobic silica nanoparticles are mixed and placed in a sealed container, the sealed container is placed in a freezer and frozen for 1h to obtain normal pressure solid THF hydrate, then the normal pressure solid THF hydrate is taken out, placed in a mortar, added with liquid nitrogen for grinding, and sieved by a 100-mesh sieve to obtain THF hydrate particles.
(2) Before air intake, calibration of the temperature and pressure sensors of the whole system and air tightness check are completed. In order to avoid melting the experimental sample in the step (1), a constant-temperature water bath is started in advance to pre-cool the reaction kettle (-5 ℃), and then THF hydrate particles are filled. After vacuumizing, filling precooled hydrogen to the experimental pressure of 9.15MPa, keeping the pressure in the kettle constant by means of a gas booster pump, and finishing the reaction for about 10 hours to generate hydrogen hydrate.
(3) The temperature is raised beyond the phase equilibrium curve (10 ℃) to decompose the hydrate and release hydrogen and the aqueous silica nanoparticle-THF solution. And (3) re-cooling to the temperature (-5 ℃) below the freezing point by utilizing the memory effect of the aqueous solution in the step (2), carrying out a hydrogen hydrate generation experiment again until the pressure is reduced to a certain extent and the hydrogen hydrate is stable, indicating that THF-H 2 hydrate is generated, and leading out data after the experiment is ended. Repeating the step (3) for three times, and testing the cycle performance of the hydrogen storage material.
The hydrogen storage amount was calculated according to the formula (2), and the hydrogen storage amount in this example was 0.202wt%. The hydrogen storage-release circulation process of the THF-H 2 hydrate is shown in figure 1, the THF hydrate powder system is obtained from figure 1 after constant pressure reaction for 10 hours, the temperature is raised to 10 ℃, the hydrate is decomposed to release gas, the pressure is raised to 10.44MPa, then the temperature is lowered to-5 ℃, and the circulation is repeated for three times.
Example 2
The same as in example 1, except that: (1) 30g of water, 7.076g of tetrahydrofuran and 1.5g of 7nm hydrophobic silica nanoparticles are mixed and placed in a sealed container, the sealed container is placed in a freezer and frozen for 1h to obtain normal pressure solid THF hydrate, then the normal pressure solid THF hydrate is taken out, placed in a mortar, added with liquid nitrogen for grinding, and sieved by a 100-mesh sieve to obtain THF hydrate particles.
The hydrogen storage amount was calculated according to the formula (2), and the hydrogen storage amount in this example was 0.284wt%.
Example 3
The same as in example 1, except that: (1) 30g of water, 7.076g of tetrahydrofuran and 1.5g of 100nm hydrophobic silica nanoparticles are mixed and placed in a sealed container, the sealed container is placed in a freezer and frozen for 1h to obtain normal-pressure solid THF hydrate, then the normal-pressure solid THF hydrate is taken out, placed in a mortar, added with liquid nitrogen for grinding, and sieved by a 100-mesh sieve to obtain THF hydrate particles.
The hydrogen storage amount was calculated according to the formula (2), and the hydrogen storage amount in this example was 0.35wt%.
Comparative example 1
The same as in example 2, except that: (1) Mixing 30g of water and 7.076g of tetrahydrofuran, putting into a sealed container, putting into a freezer, freezing for 1h to obtain normal pressure solid THF hydrate, taking out the normal pressure solid THF hydrate, putting into a mortar, adding liquid nitrogen for grinding, and sieving with a 100-mesh sieve to obtain THF hydrate particles.
The hydrogen storage amount was calculated according to the formula (2), and the hydrogen storage amount in comparative example 1 was 0.223wt%.
Comparative example 2
Unlike the hydrogen storage methods of all of the above examples and comparative example 1, in this comparative example, a THF solution-hydrogen system experiment was directly employed. Firstly, the calibration and the air tightness check of the temperature and the pressure sensors of the whole system are completed. Then 30g of water, 7.076 g tetrahydrofuran and 1.5g of 7nm hydrophobic silica nanoparticles were mixed and placed in a reaction kettle. And starting a constant-temperature water bath to reduce the temperature in the kettle to be beyond the phase equilibrium curve (10 ℃), vacuumizing to remove residual air, and then introducing hydrogen to the experimental pressure of 10.45MPa. After the pressure-temperature is stable, the temperature is reduced to-5 ℃. After the reaction is finished, the temperature is raised to 10 ℃ again, then the temperature is lowered to-5 ℃, and the cycle is carried out for 3 times. The hydrogen storage amount was calculated according to formula (2) to be 0.26wt%.
As is clear from examples 1 to 3 and comparative example 1, under the same conditions, the addition of hydrophobic silica nanoparticles having a certain concentration and particle diameter can effectively accelerate the gas storage rate and increase the hydrogen storage amount, and example 2, compared with comparative example 1 and comparative example 2, the tetrahydrofuran and the hydrophobic silica nanoparticles cooperate to not only accelerate the gas storage rate but also increase the hydrogen storage amount. Compared with comparative example 2, the prefabricated hydrate particle template has a faster reaction rate and slightly higher gas storage capacity than the solution system.
Example 4
The same as in example 2, except that:
(1) The molar percentage of THF is 0.0556mol% (0.67 g), the mass concentration of the 7nm hydrophobic silica nano particles is 1.0wt% based on the mass of deionized water (30 g), and the THF is placed in a freezing container to be frozen for 0.5h, so that normal-pressure solid THF hydrate is obtained;
(2) The temperature in the reaction kettle is-20 ℃, after the reaction vessel is vacuumized, pre-cooled hydrogen is filled to 1MPa, the pressure in the reaction vessel is kept constant, and the reaction is carried out for 9 hours to obtain hydrogen hydrate.
The hydrogen storage amount was calculated according to formula (2) to be 0.02wt%.
Example 5
The same as in example 2, except that:
(1) The molar percentage of THF is 5.56mol% (7.076 g), the mass concentration of the 7nm hydrophobic silica nano particles is 5.0wt% based on the mass (30 g) of deionized water, and the THF is frozen in a freezing container for 2 hours to obtain normal pressure solid THF hydrate;
(2) The temperature in the reaction kettle is-5 ℃, after the reaction vessel is vacuumized, pre-cooled hydrogen is filled to 20MPa, the pressure in the reaction vessel is kept constant, and the reaction is carried out for 11 hours to obtain hydrogen hydrate.
The hydrogen storage amount was calculated according to formula (2) to be 0.6wt%.
The above embodiments are only described to assist in understanding the technical solution of the present invention and its core idea, and it should be noted that it will be obvious to those skilled in the art that several improvements and modifications can be made to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.
Claims (6)
1. A method for promoting hydrogen storage of hydrates by using solid nano particles, which is characterized by comprising the following steps:
(1) Mixing liquid accelerator THF and hydrophobic silica nano particles with deionized water, wherein the molar concentration of THF in an aqueous solution is 0.0556-5.56 mol%, the mass concentration of the hydrophobic silica nano particles is 1.0-5.0 wt% based on the mass of the deionized water, placing the mixture into a sealed container, placing the sealed container into a freezing container for freezing for 0.5-2h to obtain normal-pressure solid THF hydrate, adding the THF hydrate into liquid nitrogen, grinding and crushing the THF hydrate, and sieving the THF hydrate to obtain THF hydrate particles;
(2) Filling THF hydrate particles into a pre-cooled reaction container, wherein the temperature in the reaction container is between minus 20 ℃ and minus 5 ℃, vacuumizing the reaction container, filling pre-cooled hydrogen to 1-20MPa, keeping the pressure in the reaction container constant, and reacting for 9-11h to obtain hydrogen hydrate;
(3) And (3) heating the reaction vessel to the outside of a phase equilibrium curve to decompose the hydrogen hydrate, releasing hydrogen and a silicon dioxide nano particle-THF aqueous solution, re-cooling to the temperature below the freezing point by utilizing the memory effect of the hydrogen hydrate aqueous solution in the step (2), and performing a hydrogen hydrate generation experiment again until the pressure is reduced to a certain extent and then the hydrogen hydrate tends to be stable, thus obtaining the THF-H 2 hydrate.
2. The method of claim 1, wherein the hydrophobic silica nanoparticles of step (1) are prepared by: (1) By means ofSynthesizing silicon dioxide nano particles by a hydrolysis condensation method; (2) Dissolving octadecyltrimethoxy silane and silica nanoparticles in n-hexane, mixing, performing ultrasonic treatment, pouring into a reaction container, placing into a water bath at 40 ℃ for constant temperature reaction, centrifuging the reacted reaction liquid, pouring out supernatant, and cleaning and drying to obtain the hydrophobic silica nanoparticles.
3. The method according to claim 1, wherein the hydrophobic silica nanoparticles of step (1) have a particle diameter of 7 to 100nm.
4. The method according to claim 1, wherein the normal pressure solid THF hydrate is obtained after the step (1) is frozen in a freezing vessel for 1 hour.
5. The method of claim 1, wherein the temperature in the reaction vessel in the step (2) is-5 ℃, the reaction vessel is vacuumized, pre-cooled hydrogen is filled to 9-10MPa, the pressure in the reaction vessel is kept constant, and the reaction is carried out for 10 hours to obtain the hydrogen hydrate.
6. The method according to claim 1, wherein the specific steps of step (3) are: and (3) heating the reaction vessel to 10 ℃ to decompose the hydrogen hydrate, releasing hydrogen and a silicon dioxide nano particle-THF aqueous solution, cooling to-5 ℃ again by utilizing the memory effect of the hydrogen hydrate aqueous solution in the step (2), performing a hydrogen hydrate generation experiment again until the pressure is stable after being reduced to a certain extent, and repeating the steps at least 3 times to obtain the THF-H 2 hydrate.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774541A (en) * | 2009-12-23 | 2010-07-14 | 中国科学院广州能源研究所 | Rapid generation method for hydrogen hydrate |
| CN102784604A (en) * | 2012-07-24 | 2012-11-21 | 华南理工大学 | Promoter for generation of gas hydrate, and preparation method and application thereof |
| CN103613065A (en) * | 2013-11-13 | 2014-03-05 | 大连理工大学 | Memory-effect-based hydrate hydrogen storage device and method |
| CN112980401A (en) * | 2019-12-02 | 2021-06-18 | 中国石油化工股份有限公司 | Hydrophobic nano silicon dioxide and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100055031A1 (en) * | 2008-08-28 | 2010-03-04 | Dong June Ahn | Ice nanorods for hydrogen storage |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774541A (en) * | 2009-12-23 | 2010-07-14 | 中国科学院广州能源研究所 | Rapid generation method for hydrogen hydrate |
| CN102784604A (en) * | 2012-07-24 | 2012-11-21 | 华南理工大学 | Promoter for generation of gas hydrate, and preparation method and application thereof |
| CN103613065A (en) * | 2013-11-13 | 2014-03-05 | 大连理工大学 | Memory-effect-based hydrate hydrogen storage device and method |
| CN112980401A (en) * | 2019-12-02 | 2021-06-18 | 中国石油化工股份有限公司 | Hydrophobic nano silicon dioxide and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| Effect of Hydrate Shell Formation on the Stability of Dry Water;Juwoon Park et al.;J. Phys. Chem. C;20150105;第119卷;第1690-1699页 * |
| Intensification of methane and hydrogen storage in clathrate hydrate and future prospect;Xuemei Lang et al.;Journal of Natural Chemistry;第19卷;第205页左栏第2段-第206页左栏第1段 * |
| 水合物形成促进剂研究进展;周麟晨等;化工进展;20191231;第38卷(第9期);第4131-4141页 * |
| 纳米颗粒及其表面润湿性对水合物相平衡与形成动力学的影响研究;廖祥瑞;中国优秀硕士学位论文全文数据库 工程科技I辑;第9页-第11页"1.4 纳米材料在水合物领域的研究" * |
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