CN109628183B - Method for storing natural gas hydrate - Google Patents
Method for storing natural gas hydrate Download PDFInfo
- Publication number
- CN109628183B CN109628183B CN201811552502.XA CN201811552502A CN109628183B CN 109628183 B CN109628183 B CN 109628183B CN 201811552502 A CN201811552502 A CN 201811552502A CN 109628183 B CN109628183 B CN 109628183B
- Authority
- CN
- China
- Prior art keywords
- natural gas
- hydrate
- water
- micro
- pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
Abstract
The invention relates to a method for storing natural gas hydrates. The method for storing natural gas hydrates comprises the following steps: (1) placing a porous medium and water with the same pore volume as the porous medium in the micro-nano scale restricted space, sealing and standing to ensure that the water is absorbed by the porous medium to obtain a water-containing porous medium; (2) putting the water-containing porous medium into a reaction container, injecting hydrate into the reaction container to generate required gas, and synthesizing the micro-nano scale confined space natural gas hydrate; (3) and (4) storing the natural gas hydrate in the micro-nano scale limited space under normal pressure, namely realizing the storage of the natural gas hydrate. The invention provides a brand-new high-quality energy-saving safe and efficient natural gas hydrate storage and transportation method by utilizing the unique physicochemical property of water in the micro-nano scale limited space and the unique forming and decomposition kinetic characteristics of the natural gas hydrate in the micro-nano scale limited space.
Description
Technical Field
The invention relates to the technical field of natural gas hydrates, in particular to a method for storing natural gas hydrates.
Background
The natural gas hydrate is a cage-type compound formed by natural gas and water at low temperature and high pressure, and the natural gas hydrate of 1 cubic meter can release 164 cubic meters of natural gas at normal temperature and normal pressure. The natural gas hydrate method is a natural gas hydrate method natural gas storage and transportation technology, and is characterized in that natural gas is synthesized into solid hydrate through a certain process, then the hydrate is transported to a gas storage station, and finally the hydrate is gasified and decomposed to form natural gas. The technology for storing and transporting natural gas hydrates is divided into 3 steps, namely the rapid synthesis, safe storage and transportation and efficient decomposition of the hydrates.
The key of the natural gas hydrate method natural gas storage and transportation technology is to rapidly prepare a high-quality natural gas hydrate sample. On a macroscopic scale, a sample prepared by a laboratory through a hydration method usually has the problems of sample looseness, large pores and need of compaction and compaction, the possibility of pollution or hydrate decomposition in the transmission and treatment process is brought when the sample is compacted and compacted, and the 'wall climbing effect' exists in the synthesis of the hydrate on the macroscopic scale, and the 'wall climbing effect' is generated due to the accumulation of the generated hydrate on a solid cold wall surface, namely the accumulation effect on the inner wall surface of a reaction kettle, or the accumulation of the hydrate above a gas-liquid interface. The existence of the wall climbing effect causes the growth of the hydrate to be uneven, and the surface of the generated hydrate block is quite uneven. It is common practice to use a piston device to compact it by in situ pressurization. However, the in-situ pressure densification cannot be performed on the hydrate with excessive hardness, such as carbon dioxide hydrate. In fact, many factors affect the formation and growth process of hydrate crystals, such as the surface condition of the inner wall of the reaction kettle, the chemical composition of the solute in the solution, the existence of electric field and magnetic field, and even the illumination can affect the nucleation and growth of the hydrate crystals. On a macroscopic scale, researches find that the reaction kettle material can influence the appearance position of hydrate nucleation and the mass transfer characteristic in the hydrate forming process.
Compared with compressed natural gas and liquefied natural gas, natural gas hydrate is adopted for storing and transporting natural gas, the natural gas hydrate has high gas storage capacity, mild preparation conditions are adopted, but the hydrate generation rate is slow, the compactness is poor, the water recovery needs to be considered, and the like.
Disclosure of Invention
The invention aims to provide a method for storing natural gas hydrate, and provides a brand-new high-quality, energy-saving, safe and efficient natural gas hydrate storage and transportation method by utilizing the unique physicochemical property of water in a micro-nano scale limited space and the unique forming and decomposition kinetic characteristics of the natural gas hydrate in the micro-nano scale limited space.
The invention aims to provide a method for storing natural gas hydrate, which comprises the following steps:
(1) placing a porous medium and water with the same pore volume as the porous medium in the micro-nano scale restricted space, sealing and standing to ensure that the water is absorbed by the porous medium to obtain a water-containing porous medium;
(2) putting the water-containing porous medium obtained in the step (1) into a reaction container, injecting hydrate into the reaction container to generate required gas, and synthesizing the micro-nano scale confined space natural gas hydrate;
(3) and (3) storing the micro-nano scale limited space natural gas hydrate obtained in the step (2) under normal pressure, namely storing the natural gas hydrate.
In the micro-nano scale limited space, the Raman frequency of water molecules is reduced, the attraction among the water molecules is enhanced, so that OH bonds are increased, and the effect of OH chemical bonds is weakened. The water in the micro-nano scale limited space still exists in a liquid state at a very low temperature due to the structural characteristics. At normal temperature, in the micro-nano scale restricted space, the gauss peak of two structures of water molecules DDAA (double-acceptor) and DA (single-double-single-acceptor) accounts for more than 90%, compared with the OH key gauss peak of free water molecules in a normal state, the gauss peak of the DDAA structure of water in the micro-nano scale restricted space is obviously enhanced, while the gauss peak of DA is obviously weakened, and compared with the free water in a macroscopic scale normal state, a part of the DA structure in the water in the micro-nano scale restricted space is converted into the DDAA structure, so that the proportion of the DDAA structure is higher than that of the DA structure. Therefore, water molecules in the micro-nano scale restricted space are trapped in a tetrahedral hydrogen bond network structure formed by the water molecules. The structure of the water in the micro-nano scale restricted space is very beneficial to the formation of natural gas hydrate. Under the condition of a certain supercooling degree, the synthesis reaction of the water and the natural gas in the micro-nano scale limited space is almost instantly finished, and the synthesized natural gas hydrate sample is very compact. The invention utilizes the characteristic that water in the micro-nano scale limited space is not easy to form ice and is easy to form natural gas hydrate, and the synthesized natural gas hydrate sample is very compact in structure, so that the natural gas hydrate sample is rapidly synthesized.
And decomposing the natural gas hydrate in the micro-nano scale restricted space at normal temperature to obtain natural gas and water in the micro-nano scale restricted space. The water in the micro-nano scale limited space can be used for synthesizing the natural gas hydrate in the micro-nano scale limited space again.
Preferably, the porous medium in the step (1) is column chromatography silica gel or three-dimensional porous graphene oxide.
Preferably, the gas in step (2) is methane.
Preferably, the step (2) comprises the following specific steps: and (2) putting the water-containing porous medium obtained in the step (1) into a reaction container, introducing high-pressure gas required for generating hydrate into the reaction container for a plurality of times for vacuumizing, injecting gas required for generating hydrate into the reaction container until the pressure in the reaction container is 12-16 MPa, closing the reaction container, and synthesizing the micro-nano scale confined space natural gas hydrate.
Preferably, the step (3) comprises the following specific steps: and (3) releasing part of the gas from the micro-nano scale limited space natural gas hydrate obtained in the step (2), and adjusting the pressure of the natural gas hydrate in the reaction container to a required pressure, so that the natural gas hydrate is in a metastable state area or a stable state area, after the temperature and the pressure in the reaction container are stable, cooling the temperature in the reaction container to 227-237K, and after the temperature is stable, releasing the pressure of the gas in the reaction container to be normal pressure, and storing the gas at the normal pressure, namely realizing the storage of the natural gas hydrate.
The natural gas hydrate in the micro-nano scale limited space is decomposed at 227K under 1atm, and undergoes the evolution process of hydrate-supercooled water-high-density amorphous ice, and the supercooled water forms very high-density amorphous ice immediately after decomposition occurs, and the very high-density amorphous ice exists for a long time. The very high density amorphous ice has no fixed shape and does not have a crystal structure, and is more like an extremely viscous liquid in a solid state, so that guest molecules cannot overflow in a short time. According to the invention, natural gas hydrate in a micro-nano scale limited space is decomposed to form very high-density amorphous ice to wrap the crystalline natural gas hydrate, so that heat absorption in the decomposition process is hindered, the natural gas hydrate can be stored at 227K under 1atm in a characteristic of stable existence for a long time, and the storage and transportation cost is effectively reduced.
Under normal temperature and normal pressure, natural gas hydrate in the micro-nano scale limited space is decomposed to form natural gas and water, the natural gas is slowly released, and safety is improved. The heat absorption of decomposition comes from air, and no additional heating is needed. The water formed by decomposition still stays in the micro-nano scale limited space, and can be repeatedly used for synthesis of a natural gas hydrate sample, so that the problem of water recovery is avoided.
Further preferably, the pressure of the natural gas hydrate in the reaction vessel in step (3) is adjusted to 2.75MPa so that the natural gas hydrate is in a metastable state region, or a steady state region.
The method of the invention overcomes the defects of the sample processing method in the prior art, and compared with the prior art, the method has the following excellent effects:
1. the invention provides a brand-new high-quality energy-saving safe and efficient natural gas hydrate storage and transportation method by utilizing the unique physicochemical property of water in the micro-nano scale limited space and the unique forming and decomposition kinetic characteristics of the natural gas hydrate in the micro-nano scale limited space.
2. The invention provides a natural gas hydrate storage and transportation method which adopts micro-nano scale confined space to hydrate a natural gas hydrate sample, stores the natural gas hydrate at 227K normal pressure, and decomposes the natural gas hydrate at normal temperature and normal pressure to obtain natural gas. The micro-nano scale confined space is hydrated into the natural gas hydrate very quickly, after 227K is decompressed, the surface layer of the natural gas hydrate forms very high-density amorphous ice which wraps the natural gas hydrate, so that the natural gas hydrate can be stored at 227K under normal pressure, and the natural gas hydrate is slowly decomposed at normal temperature and normal pressure to obtain the natural gas. The method has the technical advantages of high hydrate generation rate, high sample density, effective reduction of storage and transportation cost, slow decomposition, increased safety, no need of considering water recovery and the like.
Drawings
Fig. 1 is a schematic diagram of an experimental flow structure of a method for storing natural gas hydrates according to an embodiment of the present invention.
Detailed description of the invention
The invention is further described by the following specific examples, but is not limited thereto. The method for storing natural gas hydrates in the invention is applicable to most of the gases that natural gas can cover, and methane is taken as an example in the embodiment of the invention.
As shown in fig. 1, a method for storing natural gas hydrate specifically includes the following steps:
1. synthesizing micro-nano scale restricted space water, wherein a porous medium of the micro-nano scale restricted space is columnar chromatography silica gel or three-dimensional porous graphene oxide, and fully mixing water with the same pore volume as the columnar chromatography silica gel or the three-dimensional porous graphene oxide with the columnar chromatography silica gel or the three-dimensional porous graphene oxide. And sealing and standing for 5 days to ensure that water is absorbed by the porous medium. The water in the present invention is distilled water.
2. And (3) putting water-containing columnar chromatographic silica gel or water-containing three-dimensional porous graphene oxide into the reaction kettle. The reaction kettle is a stainless steel reaction kettle.
3. And introducing high-pressure gas such as methane gas required by hydrate generation into the reaction kettle for many times, blowing away air in the reaction kettle and the pipeline, or pumping away air in the reaction kettle and the pipeline in a vacuumizing mode.
4. And cooling the reaction kettle to be below the phase equilibrium point of the hydrate, and precooling the gas in the buffer tank at the same time.
5. Then injecting hydrate into the reaction kettle to generate required high-pressure gas, reaching a certain pressure, and closing the reaction kettle.
6. Injecting hydrate into the reaction kettle to generate required high-pressure gas to a certain pressure, and synthesizing the natural gas hydrate in the micro-nano scale limited space within hours.
7. After the natural gas hydrate sample is synthesized, partial gas is released, the pressure of the natural gas hydrate in the kettle is adjusted to a required pressure value, and finally the natural gas hydrate sample is in a metastable state area or a stable state area.
8. After 5h, after the temperature and the pressure are stabilized, cooling to 227K, after the temperature is stabilized, releasing the gas in the reaction kettle to normal pressure, closing a valve, and forming very high-density amorphous ice on the surface layer of the natural gas hydrate.
8. The natural gas hydrate is stored and transported under 227K normal pressure.
9. And closing the air bath, slowly heating the reaction kettle to normal temperature, decomposing the natural gas hydrate to form natural gas and water, overflowing the natural gas from the micro-nano scale limited space, and keeping the water in the micro-nano scale limited space, so that the natural gas hydrate in the micro-nano scale limited space can be repeatedly synthesized.
Example 1
The method comprises the steps of taking column chromatography silica gel with the pore diameter of about 20nm and the particle diameter of about 0.1-0.3 mm, distilled water and methane gas as experimental materials, and carrying out natural gas hydrate storage and transportation test experiments on methane hydrate samples through synthesis, storage and decomposition.
Synthesizing water-containing column chromatography silica gel, mixing water with the same volume as the pore volume of the column chromatography silica gel with the column chromatography silica gel, and stirring. Sealing and standing for 5 days to ensure that the distilled water is absorbed by the pores of the column chromatography silica gel. Putting water-containing column chromatography silica gel into the reaction kettle. Air in the reaction kettle and the pipeline is pumped away in a vacuumizing mode. And cooling the reaction kettle to be below the phase equilibrium point of the hydrate and have the supercooling degree of more than 5K, and precooling the gas in the buffer tank to make the methane gas and the water-containing column chromatography silica gel be at about 273K. And then injecting precooled methane gas into the reaction kettle, and closing the reaction kettle when the pressure reaches 12 MPa. The synthesis of methane hydrate in the pores of the column chromatography silica gel is completed within hours.
And adjusting the temperature of the air bath to enable the temperature of the hydrate sample to be close to the four-phase equilibrium point temperature of 269.18K, releasing part of gas after the temperature and the pressure are stable, and reducing the pressure to 2.75MPa to enable the hydrate sample to be in a metastable state region. And (4) adjusting the temperature of the air bath to enable the temperature in the kettle to be about 227K, and releasing the pressure to normal pressure after the temperature is stable. The reaction kettle is closed. And storing and transporting the methane hydrate in the pores of the column chromatography silica gel at 227K under normal pressure.
And closing the air bath, slowly heating the reaction kettle to normal temperature, decomposing methane hydrate in the columnar chromatography silica gel pores to form methane gas and water, overflowing the methane gas from the columnar chromatography silica gel pores, and keeping the water in the columnar chromatography silica gel pores, wherein the methane gas and the water can be repeatedly used for synthesizing the natural gas hydrate in the micro-nano scale restricted space.
Repeated experiments show that when methane gas is injected into the reaction kettle until the pressure in the reaction kettle is 12-16 MPa, the reaction kettle is closed, and the micro-nano scale limited space natural gas hydrate is synthesized. After the temperature and the pressure in the reaction kettle are stable, the temperature in the reaction kettle is reduced to 227-237K, and the natural gas hydrate can be stored and transported under normal pressure.
Example 2
The thickness is 0.55 to 1.2nm, the diameter is 0.5 to 3 μm, and the specific surface area is 200 to 480m2.g–1Pore volume 1.3cm3.g–1The three-dimensional porous graphene oxide, distilled water and methane gas are used as experimental materials, and natural gas hydrate storage and transportation test experiments for synthesizing, storing and decomposing methane gas from a methane hydrate sample are carried out by utilizing the steps of the method.
The three-dimensional porous graphene oxide structure contains a large number of oxygen-containing functional groups such as hydroxyl, carboxyl and epoxy groups, so that the graphene oxide is very easy to absorb water, the dried three-dimensional porous graphene oxide is loose and porous in powder and spongy, and can be quickly and completely dissolved after water is added, and the original sol property can be almost immediately recovered.
Synthesizing the water-containing three-dimensional porous graphene oxide. And fully mixing the water with the same volume as the pore volume of the three-dimensional porous graphene oxide with the three-dimensional porous graphene oxide, and stirring. And sealing and standing for 5 days to ensure that the distilled water is absorbed by the pores of the three-dimensional porous graphene oxide. And (3) putting the water-containing three-dimensional porous graphene oxide into the reaction kettle, and pumping away air in the reaction kettle and the pipeline in a vacuumizing mode. And cooling the reaction kettle to be below the phase equilibrium point of the hydrate and have the supercooling degree of more than 5K, and precooling the gas in the buffer tank to ensure that the methane gas and the water-containing graphene oxide are at about 273K. And then injecting precooled methane gas into the reaction kettle, and closing the reaction kettle when the pressure reaches 12 MPa. The synthesis of the methane hydrate in the pores of the three-dimensional porous graphene oxide is completed within hours.
And adjusting the temperature of the air bath to enable the temperature of the hydrate sample to be close to the four-phase equilibrium point temperature of 269.18K, releasing part of gas after the temperature and the pressure are stable, and reducing the pressure to 2.75MPa to enable the hydrate sample to be in a metastable state region. And (4) adjusting the temperature of the air bath to enable the temperature in the kettle to be about 227K, and releasing the pressure to normal pressure after the temperature is stable. The reaction kettle is closed. And (3) storing and transporting the methane hydrate in the pores of the three-dimensional porous graphene oxide at 227K under normal pressure.
And closing the air bath, slowly heating the reaction kettle to normal temperature, decomposing methane hydrate in the three-dimensional porous graphene oxide pores to form methane gas and water, overflowing the methane gas from the three-dimensional porous graphene oxide pores, and stopping the water in the three-dimensional porous graphene oxide pores, wherein the methane gas and the water can be repeatedly used for synthesizing natural gas hydrate in the micro-nano scale limited space.
The detailed description is specific to possible embodiments of the invention, which are not intended to limit the scope of the invention, but rather are intended to include equivalent implementations or modifications within the scope of the invention.
Claims (2)
1. A method of storing natural gas hydrates, comprising the steps of:
(1) placing a porous medium and water with the same pore volume as the porous medium in a micro-nano scale restricted space, sealing and standing to ensure that the water is absorbed by the porous medium to obtain a water-containing porous medium, wherein the porous medium is columnar chromatography silica gel or three-dimensional porous graphene oxide;
(2) putting the water-containing porous medium obtained in the step (1) into a reaction container, introducing high-pressure gas required for generating hydrate into the reaction container for several times for vacuumizing, injecting gas required for generating hydrate into the reaction container until the pressure in the reaction container is 12-16 MPa, closing the reaction container, and synthesizing the micro-nano scale confined space natural gas hydrate, wherein the gas is methane;
(3) and (3) releasing partial natural gas from the micro-nano scale limited space natural gas hydrate obtained in the step (2), and adjusting the pressure of the natural gas hydrate in the reaction container to a required pressure, so that the natural gas hydrate is in a metastable state area or a stable state area, after the temperature and the pressure in the reaction container are stable, cooling the temperature in the reaction container to 227-237K, and after the temperature is stable, releasing the pressure of the natural gas in the reaction container to be normal pressure, and storing the natural gas hydrate at the normal pressure, namely realizing the storage of the natural gas hydrate.
2. The method for storing natural gas hydrates according to claim 1, wherein the pressure of the natural gas hydrates in the reaction vessel is adjusted to 2.75MPa in step (3) so that the natural gas hydrates are in a metastable state region, or a steady state region.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811552502.XA CN109628183B (en) | 2018-12-18 | 2018-12-18 | Method for storing natural gas hydrate |
| PCT/CN2018/124246 WO2020124660A1 (en) | 2018-12-18 | 2018-12-27 | Method for storing natural gas hydrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811552502.XA CN109628183B (en) | 2018-12-18 | 2018-12-18 | Method for storing natural gas hydrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109628183A CN109628183A (en) | 2019-04-16 |
| CN109628183B true CN109628183B (en) | 2020-10-30 |
Family
ID=66075294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811552502.XA Active CN109628183B (en) | 2018-12-18 | 2018-12-18 | Method for storing natural gas hydrate |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN109628183B (en) |
| WO (1) | WO2020124660A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111120869A (en) * | 2020-01-10 | 2020-05-08 | 兰州理工大学 | Biological natural gas storage and use system and storage and use method |
| CN114718518B (en) * | 2020-12-22 | 2023-07-25 | 中国科学院广州能源研究所 | Quantitative method for distinguishing distribution and morphology of micro-pore natural gas hydrate |
| CN114015487B (en) * | 2021-11-10 | 2022-07-05 | 燕山大学 | Preparation method of nano ice hydrate |
| CN117343766A (en) * | 2023-10-13 | 2024-01-05 | 中国科学院广州能源研究所 | Method for improving natural gas hydrate gas storage capacity based on crystal regulation and control principle |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006002000A (en) * | 2004-06-16 | 2006-01-05 | Oshima Shipbuilding Co Ltd | Methane hydrate generation device and methane gas supply system |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101358685A (en) * | 2007-07-31 | 2009-02-04 | 中国石油天然气管道局 | Method and device for generating gas hydrate |
| US8486340B2 (en) * | 2009-09-15 | 2013-07-16 | Korea Institute Of Industrial Technology | Apparatus and method for continuously producing and pelletizing gas hydrates using dual cylinder |
| KR101274310B1 (en) * | 2011-03-29 | 2013-06-13 | 에스티엑스조선해양 주식회사 | gas hydrate continually manufacturing method |
| CN102338278A (en) * | 2011-09-02 | 2012-02-01 | 中国石油大学(北京) | Method for increasing natural gas adsorption storage capability |
| CN105334546B (en) * | 2015-09-23 | 2017-02-08 | 中国石油大学(华东) | Simulated experiment testing method of gas hydrate in porous medium |
| CN108295777A (en) * | 2018-03-30 | 2018-07-20 | 清华大学深圳研究生院 | A kind of gas hydrate reinforcing generation method |
| CN108587712A (en) * | 2018-04-27 | 2018-09-28 | 中国石油大学(华东) | A kind of synthetic method of high saturation hydrate |
-
2018
- 2018-12-18 CN CN201811552502.XA patent/CN109628183B/en active Active
- 2018-12-27 WO PCT/CN2018/124246 patent/WO2020124660A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006002000A (en) * | 2004-06-16 | 2006-01-05 | Oshima Shipbuilding Co Ltd | Methane hydrate generation device and methane gas supply system |
Non-Patent Citations (2)
| Title |
|---|
| Methane hydrate formation in mixed-size porous media with gas circulation:Effects of sediment properties on gas consumption, hydrate saturation and rate constant;Baoyong Zhang;《Fue》;20180615;第233卷;94-102 * |
| Structural stability of methane hydrates in porous medium: Raman spectroscopic study;Vangala Dhanunjana Chari;《Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy》;20131030;636-641 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2020124660A1 (en) | 2020-06-25 |
| CN109628183A (en) | 2019-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109628183B (en) | Method for storing natural gas hydrate | |
| Zhao et al. | N2O hydrate formation in porous media: A potential method to mitigate N2O emissions | |
| US8709971B2 (en) | Activated carbon cryogels and related methods | |
| Zhao et al. | Semi-clathrate hydrate process of methane in porous media-mesoporous materials of SBA-15 | |
| JP4679057B2 (en) | Compositions and methods for hydrogen storage | |
| Casco et al. | Influence of surface wettability on methane hydrate formation in hydrophilic and hydrophobic mesoporous silicas | |
| Xiao et al. | Improving methane hydrate formation in highly water-saturated fixed bed with diesel oil as gas channel | |
| Kang et al. | Confined tetrahydrofuran in a superabsorbent polymer for sustainable methane storage in clathrate hydrates | |
| Mahboub et al. | Improving methane storage on wet activated carbons at various amounts of water | |
| Cheng et al. | Kinetic analysis of nano-SiO2 promoting methane hydrate formation in porous medium | |
| Chen et al. | A covering liquid method to intensify self-preservation effect for safety of methane hydrate storage and transportation | |
| CN113201373A (en) | Low-pressure preservation method of natural gas hydrate | |
| US20100055031A1 (en) | Ice nanorods for hydrogen storage | |
| WO2022152669A1 (en) | Hydrogen storage | |
| Chen et al. | Adsorption-hydration sequence method for methane storage in porous material slurry | |
| KR101147842B1 (en) | Method for producing hydrogen hydrate and method for stroing hydrogen using gas accelerator | |
| Kummamuru et al. | Accelerated methane storage in clathrate hydrates using mesoporous (Organo-) silica materials | |
| JP2002255865A (en) | Storage and transportation of hydrocarbon gas | |
| JP4638706B2 (en) | Gas hydrate manufacturing method | |
| Tulk et al. | Storage and handling of natural gas hydrate | |
| Spalaris | The micropore structure of artificial graphite | |
| US20010037647A1 (en) | Method of storing a gas | |
| CN114955986A (en) | Method for improving stability of hydrogen hydrate | |
| JP2015218122A (en) | Production method of high-gas-density hydrate | |
| Zhang et al. | Decomposition behaviors of methane hydrate in porous media below the ice melting point by depressurization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |