WO2010010372A1 - Clathrates for gas storage - Google Patents
Clathrates for gas storage Download PDFInfo
- Publication number
- WO2010010372A1 WO2010010372A1 PCT/GB2009/050797 GB2009050797W WO2010010372A1 WO 2010010372 A1 WO2010010372 A1 WO 2010010372A1 GB 2009050797 W GB2009050797 W GB 2009050797W WO 2010010372 A1 WO2010010372 A1 WO 2010010372A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gas
- water
- exogenous
- hydrate
- emulsion
- Prior art date
Links
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
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C11/00—Use of gas-solvents or gas-sorbents in vessels
- F17C11/007—Use of gas-solvents or gas-sorbents in vessels for hydrocarbon gases, such as methane or natural gas, propane, butane or mixtures thereof [LPG]
-
- 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
Definitions
- the present invention relates to a gas hydrate (often referred to as a clathrate) comprising a water-in-gas emulsion (eg dry water (DW)) and an enclathrated exogenous gas such as for example methane, natural gas, hydrogen or carbon dioxide.
- a gas hydrate often referred to as a clathrate
- DW dry water
- exogenous gas such as for example methane, natural gas, hydrogen or carbon dioxide.
- Natural gas, methane and other gases are important sources of energy for (for example) vehicular systems. Cost-effective applications and uses of such gases rely to a large extent on effective, economical and user-friendly means of storage, transportation and release. The efficient capture of certain gases from waste streams (for example carbon dioxide) is also important.
- Gas hydrates comprise "host” assemblies of H 2 O cages in which are entrapped "guest” gases.
- Gas hydrates have the potential to provide a safe and environmentally friendly means for hydrogen storage (see for example Struzhkin, V. V.; Militzer, B.; Mao, W. L.; Mao, H. K.; Hemley, R. J. Chem. Rev. 2007, 707, 4133).
- the incorporation of hydrogen into a gas hydrate is a lengthy process, often taking days or weeks (see for example Strobel, T. A.; Taylor, C. J.; Hester, K. C; Dec, S. F.; Koh, C. A.; Miller, K. T.; Sloan, E. D. J. Phys.
- MGHs methane gas hydrates
- Natural gas hydrate is an important source of natural energy which also has potential for gas storage and transportation.
- MGH methane gas hydrate
- Liquefied natural gas has a much higher energy density but must be stored at very low temperatures (113 K). It has been suggested that it is economically feasible to transport natural gas in hydrated form (Sloan, E. D. Nature, 2003, 426, 353-359).
- NGH is typically synthesized by cooling a mixture of natural gas and water under pressure or by the reaction of natural gas with preformed ice.
- clathrates In principle a wide range of gases may be stored within clathrates.
- the host and guest must be sufficiently compatible (for example in terms of the guest size) to form a stable clathrate structure, optionally in the presence of additional stabilizing agents.
- Known clathrates include those comprising (as guest) inter alia H 2 , O 2 , N 2 , CH 4 , CO 2 , H 2 S, Ar, Kr, Xe, He and Ne (see for example WO-A-2006/131738 and Lokshin, K. A. et al, Phys. Rev. Lett. 2004, 93, 125503) or a gas mixture (for example natural gas and air).
- the present invention is based on the recognition that preformed dry water powder exhibits desirable rates and levels of uptake of an exogenous gas by forming a gas hydrate.
- the present invention provides a gas hydrate comprising: a water-in-gas emulsion of water droplets or particles stabilised by a network of hydrophobic particles; and an exogenous gas enclathrated in the water-in-gas emulsion.
- the gas hydrate of the invention exhibits advantageous exogenous gas enclathration kinetics and recyclability.
- the exogenous gas is advantageously released rapidly from the gas which facilitates its ease of use at the point where it is required (for example in fuel cells).
- the stabilization of the water-in- gas emulsion by the network of hydrophobic particles results in the formation of small domains. This compartmentalizes the water and the path length for diffusion of the enclathrated gas into (or out of) the water during clathrate formation (or dissociation) is reduced.
- the hydrophobic particles coat the water and divide up the host during clathrate formation but do not cover the water-gas interface sufficiently to prevent the ingress of gas.
- a water-in-gas emulsion of water droplets is frequently referred to as dry water. It generally takes the form of a free-flowing powder.
- the network of hydrophobic particles prevents coalescence by effectively coating the water droplets thereby reducing the energy required to keep the water in droplet form in a gaseous medium relative to the energy required to form bulk water.
- the preparation of dry water is described (for example) in Binks, B. P.; Murakami, R. Nat. Materials 2006, 5, 865-869 and may be carried out straightforwardly in known apparatus.
- hydrophobic particles and water may be aerated by stirring at high speed (eg in a domestic food blender).
- a rotastater, a blender, a folder or a sonicator may be used.
- the exogenous gas predominantly occupies cavities in the caged framework structure of the water-in-gas emulsion.
- the gas hydrate may be a clathrate.
- a proportion of the exogenous gas may form part of the caged framework structure.
- the gas hydrate may be a semi-clathrate.
- the water-in-gas emulsion is a water-in-air emulsion.
- the gas of the water-in-gas emulsion is the same as the exogenous gas. This conveniently promotes optimum enclathration or release of the exogenous gas and avoids its contamination.
- the water-in-gas emulsion is a water-in-methane emulsion.
- the exogenous gas may be methane.
- CH 4 molecules are stored within H 2 O cages formed within the matrix of the water-in-gas emulsion.
- the water-in-gas emulsion comprises 95wt% or more of water.
- the water-in-gas emulsion comprises 5wt% or less of hydrophobic particles.
- the water-in-gas emulsion is non-agglomerative.
- the water-in-gas emulsion is non-coalescent.
- the hydrophobic particles may be selected from the group consisting of modified silica particles, polymer particles, hydrophobically modified inorganic particles and polymer latex particles.
- the hydrophobic particles may be particles of a fluoropolymer such as Zonyl® MP 1400 (Dupont).
- the hydrophobic particles may be hydrophobic silica particles (preferably hydrophobic fumed silica particles).
- the hydrophobic silica particles may be surface modified (eg surface modified by siloxy groups such as dimethylsiloxy, polydimethylsiloxy or trimethylsiloxy groups).
- the hydrophobic silica particles may be alkylated or fluorinated silica.
- Hydrophobic silica particles are available commercially from Wacker Chemie AG.
- the hydrophobic silica particles may be one or more of the group consisting of HDKl 8, HDK13L, HDK15, HDK20, HDK30, HDK17, HDK2000, HDK20RM and HDK30RM from Wacker Chemie AG. Preferred is HDKl 8.
- the hydrophobic silica particles have a residual silanol content of 66wt% or less, particularly preferably 50wt% or less, more preferably 25wt% or less.
- Enclathration of an exogenous gas may be carried out for example by adding the exogenous gas to a conventional containment vessel such as a pressure reactor in the absence of mechanical agitation and proceeding at high pressure and low temperature. Enclathration may be monitored for example by observing the pressure drop in the vessel as a function of time using conventional apparatus.
- a conventional containment vessel such as a pressure reactor in the absence of mechanical agitation and proceeding at high pressure and low temperature.
- Enclathration may be monitored for example by observing the pressure drop in the vessel as a function of time using conventional apparatus.
- the exogenous gas enclathrated in the water-in-air emulsion is typically released by heating.
- the exogenous gas is a non-ambient gas (ie a gas other than air).
- the exogenous gas is hydrogen, carbon dioxide or a saturated or unsaturated hydrocarbon (eg a Ci -4 hydrocarbon).
- the exogenous gas may be for example methane, ethane, ethene, propane, propene or butane.
- the exogenous gas may be CH 4 , CO 2 , O 2 , H 2 , N 2 , H 2 S, Ar, Kr, Xe, He, Ne or a mixture thereof.
- the exogenous gas may be mixed with air.
- the exogenous gas is hydrogen
- the exogenous gas is carbon dioxide.
- the exogenous gas is methane.
- the exogenous gas is krypton.
- the gas hydrate may further comprise a stabilizer or promoter.
- the stabiliser or promoter may serve to lower the gas clathration pressure.
- the stabilizer or promoter may be enclathrated or may form part of the caged framework structure.
- the average size of the primary droplets is less than about lmm.
- the upper limit may be one of lOO ⁇ m, lO ⁇ m, or l ⁇ m.
- the droplets may form agglomerates which are larger than the primary droplet.
- the diameter of the agglomerates may be (for example) up to lmm.
- the average diameter of the primary droplets is less than about lOO ⁇ m, particularly preferably less than about 20 ⁇ m.
- the amount of hydrophobic particles relative to the amount of water and any stabiliser is no more than 20wt%, more preferably no more than 15wt%, more preferably no more than 10wt%, even more preferably no more than 5wt%, most preferably no more than lwt%.
- the hydrophobic particles have an upper size limit of 500 nm, 100 nm or 50 nm.
- the size of the hydrophobic particles may be approximately 10 nm to 20 nm.
- the size of the hydrophobic particles is less than 500 nm.
- the present invention provides use of a water-in-gas emulsion (eg dry water) in the enclathration of an exogenous gas.
- a water-in-gas emulsion eg dry water
- a water-in-gas emulsion according to the present invention may be deployed in gas storage, gas transportation/distribution, fuel use, gas sequestration, waste gas trapping and the separation of one or more gases from a mixture (for example by preferential enclathration of methane over hydrogen, ethane or propane, carbon dioxide over methane or nitrogen or hydrofluorocarbons from gas mixtures).
- Dry water exhibits a rate of gas hydrate formation which allows an exogenous gas to be incorporated into clathrate cages more quickly than has previously been possible. This permits more straightforward and less expensive gas charging in a specialized gas charging plant or in situ. The use of dry water allows gas uptake to occur rapidly and reproducibly without agitation or mechanical mixing.
- the present invention provides a process for preparing a gas hydrate as hereinbefore defined comprising: exposing a water-in-gas emulsion to an exogenous gas in a contained environment at a temperature less than ambient temperature and an elevated pressure.
- the pressure may be in the range 1 to 12MPa, preferably 6 to 10MPa.
- the temperature may be 293K or less, preferably 273K or less.
- the process may be carried out without forced agitation.
- the present invention provides a method comprising the enclathration of a gas, and/or the dissociation of a gas from a gas hydrate, in the form of dry water.
- the present invention provides use of dry water in enhancing the enclathration of a gas, and/or the dissociation of a gas from a clathrate hydrate.
- the present invention provides a composition in a form suitable for forming a gas hydrate comprising dry water and an isolated gas.
- the present invention provides an apparatus comprising dry water and optionally a gas, wherein said apparatus is selected from one of the following devices or a component thereof: a fuel cell, an energy storage device, a gas storage device for example a modified gas tank, a gas separation device for example an in-line gas separation cartridge, a gas sequestration device for example an in-line gas sequestration cartridge, a gas transportation device for example a modified gas tank, and a vehicle for example an automobile.
- a fuel cell for example a modified gas tank
- a gas separation device for example an in-line gas separation cartridge
- a gas sequestration device for example an in-line gas sequestration cartridge
- a gas transportation device for example a modified gas tank
- a vehicle for example an automobile.
- FIG 1 is a schematic illustration of methane gas hydrate (MGH) forming within dry water (ie the enclathration of methane within a H 2 O clathrate host where H 2 O is in the form of dry water droplets);
- MGH methane gas hydrate
- Figure 2 shows a standard food blender which can be used to make dry water and free- flowing dry water powder photographed flowing through a funnel;
- Figure 3 shows optical micrographs of three batches of dry water
- Figure 4 is a schematic diagram of an experimental apparatus used to prepare and test the gas hydrate
- Figure 5 shows pressure versus temperature plots for control experiments which involved cooling and heating under CH 4 pressure
- Figure 6 shows pressure versus temperature plots for a control experiment in comparison with an experiment in accordance with the present invention
- Figure 7 shows kinetic plots (capacity versus time) for CH 4 enclathration in dry water in comparison to bulk water;
- Figure 8 shows kinetic plots in a different format (pressure versus time) for the same experiments shown in Figure 7;
- Figures 9 and 10 show plots relating to multiple re-use of the dry water system.
- Figure 11 shows pressure versus time plots for an experiment where the dry water was re- blended prior to being re-used.
- FIG. 1 shows a schematic representation of dry water droplets coated with small hydrophobic particles to enable the enclathration of (for example) methane to form methane gas hydrate (MGH).
- Example 2 Apparatus for gas hydrate formation
- the gas pressure was monitored using a High- Accuracy Gauge Pressure Transmitter (Cole-Parmer, 0-3000 psia). Both thermocouple and transmitter were connected to a Digital Universal Input Panel Meter (Cole-Parmer), which communicates with a computer. Prior to experiments, the cell was slowly purged with methane (UHP 99.999%, BOC Gases, Manchester, UK) three times at atmospheric pressure to remove any air, and then pressurized to the desired pressure at the designated temperature. The temperature (T, K) and pressure (P, psia) and time (t, min) were automatically interval-logged using MeterView 3.0 software (Cole-Parmer).
- methane UHP 99.999%, BOC Gases, Manchester, UK
- Figure 5 shows Control Experiments: P-T plots for cooling and heating under CH 4 pressure (temperature ramp: 2.0 K/h): (a) and (b) 19.5 cm 3 glass beads; (c) and (d) unblended mixture of water (19 g) and hydrophobic silica nanoparticles Hl 8 (Ig).
- the system approximated to ideal gas behavior for the glass bead control experiment and no leaks were detected.
- the behavior was similar for the unmixed water/silica control although a small pressure inflection ( ⁇ 0.1 MPa) was observed. This was most likely due to a very small degree of MGH formation at the gas-liquid interface.
- Figure 2 shows a typical sample of dry water formed by rapid mixing of hydrophobic silica (Hl 8), water and air in a conventional blender.
- the free-flowing dry water powder was prepared by aerating 5g of hydrophobic silica nanoparticles H18 and 95g of water at 19,000 rpm for 90 seconds. The powder is photographed flowing through a funnel.
- the particle size can be altered by varying the speed at which mixing is carried out.
- Figure 3 shows optical micrographs showing three different batches of dry water prepared at different speeds (left to right [bottom to top]: 16450, 17500 and 19000 rpm).
- the scale bar in Figure 3 represents 50 ⁇ m in all cases.
- Figure 6 shows the cooling/heating curves for the CH 4 -dry water system with and without mixing.
- P-T plots for CH 4 and dry water during cooling and heating (temperature ramp: 2 K/h): (A) unblended mixture of water (19 g) and hydrophobic silica nanoparticles Hl 8 (1 g); (B) 20 g dry water powder (portion of a sample produced from 95 g of water + 5 g of hydrophobic silica nanoparticles Hl 8) formed by mixing at 19,000 rpm for 90 seconds.
- Figure 8 shows P-t kinetic plots for dry water-MGH formation at 273.2 K: (a) Control experiment, 19.5 cm glass beads; no pressure change is observed after initial thermal equilibration upon adding CH 4 gas which occurred in ⁇ 3 min; (b) Control experiment, 19.0 g water and 1 g silica (Hl 8), no mixing; very little pressure change is observed; (c) 19.0 g water and 1 g silica (Hl 8), dry water powder formed by blending at 16,450 rpm for 90s; (d) 19.0 g water and 1 g silica (H18), dry water powder formed by blending at 17,500 rpm for 90s; (e) 19.0 g water and 1 g silica (Hl 8), dry water powder formed by blending at 19,000 rpm for 90s.
- the methane uptakes calculated from pressure changes were consistent with values obtained by decomposing the dry water-MGH and measuring the volume of methane that was released.
- the following table shows the amount of CH 4 enclathrated in dry water-MGH, as measured by volumetric release experiments (Circone, S., Kirby S.H., and Stern L.A. J. Phys. Chem. B 2005, 109, 9468-9475; Stern L.A., Circone, S., and Kirby S.H. J. Phys. Chem. B 2001, 105, 1756-1762).
- the free space volume of the vessel was obtained by subtracting the sum volume of methane gas hydrate, unreacted water and Hl 8. Taking into account non-ideality factors, GASPAK v3.41 software (Horizon Technologies, USA) was employed to calculate the methane enclathration capacity, according to the pressure and the temperature.
- liquid and gas phases inside the vessel were formed exclusively out of the water and the guest gas respectively (neglecting any dissolution of the guest gas into the liquid phase and any mixing of the water vapor in the gas phase).
- the temperature inside the vessel was assumed to be uniform throughout the operation.
- the density of the Hl 8 was 2.2 g/ cm 3 .
- the density of water DH 2O was 1.0 g/ cm 3 .
- the density of methane in GAS PHASE D g and the density of methane at STP Dem, S TP were from GASPAK v3.41 software according to P g & T g .
- M C H 4 & M H2 o were molecular weight of methane and water respectively.
- the mass of sample m s ° was 20.0 g, the initial volume of sample V 5 0 was 19.5 cm 3 .
- the initial volume of methane in GAS PHASE V g ° was 48.5 cm 3 .
- the present invention can be contrasted with prior art methods which attempt to increase MGH formation rates by stirring the mixture vigorously (Sloan, E. D.; Koh, C. A. Clathrate Hydrates of Natural Gases, 3 rd Edition; CRC Press: Boca Raton, 2007; Koh, C. A. Chem. Soc. Rev. 2002, 31, 157-167; Sloan, E. D. Nature, 2003, 426, 353-359, and references therein; Susilo, R. Methane Storage and Transport via Structure H Clathrate Hydrate, Ph.D. thesis, 2008, The University of British Columbia).
- the energy required to stir the thickening slurry is significant.
- the gas-water interfacial surface area is increased by forming a dispersed water phase at ambient temperature prior to enclathration.
- the weight "penalty” is low because only 5 wt % silica is added with respect to water.
- FIG. 9 shows a P- T plot illustrating partial recyclability of dry water-MGH system (19.O g water and 1 g Hl 8, formed at 19,000 rpm for 90s) over three cooling / heating cycles under CH 4 pressure (temperature ramp: 2.0 K/h).
- Figure 10 shows a P-t kinetic plot illustrating partial recyclability of dry water-MGH system (19.0 g water and 1 g H18, formed at 19,000 rpm for 90s) over three cooling / heating cycles under CH 4 pressure.
- Fig. 11 shows a P-t kinetic plot illustrating recovery of fast CH 4 uptake kinetics after reblending the destabilized dry water sample for 90 s.
- MGHs are in principle stable for significant periods at atmospheric pressure with moderate cooling (Stern L.A., Circone, S., Kirby S.H. J. Phys. Chem. B 2001, 105, 1756-1762). This is very difficult to achieve with physisorptive materials.
- Example 7 Storage of carbon dioxide in dry water
- the procedure for preparing a CO 2 -dry water system is the same as that described for the CH 4 -dry water system in Example 5 but with a starting pressure of 3.3MPa.
- the starting pressure is lower than for methane in order to keep the carbon dioxide in gaseous form.
- the time required to reach 90% capacity was (tgo) was 200 min. An uptake of 150v/v was achieved.
- Example 8 Storage of Krypton in dry water
- enclathration of krypton in dry water is possible.
- Dry water gas hydrates represent a viable platform for recyclable gas storage on a practicable timescale in a static, unmixed system.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Filling Or Discharging Of Gas Storage Vessels (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Gas Separation By Absorption (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2009801300532A CN102119207A (en) | 2008-07-25 | 2009-07-07 | Clathrates for gas storage |
CA2731389A CA2731389A1 (en) | 2008-07-25 | 2009-07-07 | Clathrates for gas storage |
JP2011519240A JP2011529036A (en) | 2008-07-25 | 2009-07-07 | Inclusion compounds for gas storage |
US13/055,915 US20110185623A1 (en) | 2008-07-25 | 2009-07-07 | Clathrates for Gas Storage |
EP09785277A EP2318486A1 (en) | 2008-07-25 | 2009-07-07 | Clathrates for gas storage |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0813650.9 | 2008-07-25 | ||
GBGB0813650.9A GB0813650D0 (en) | 2008-07-25 | 2008-07-25 | Clathrates for gas storage |
Publications (1)
Publication Number | Publication Date |
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WO2010010372A1 true WO2010010372A1 (en) | 2010-01-28 |
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ID=39746937
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/GB2009/050797 WO2010010372A1 (en) | 2008-07-25 | 2009-07-07 | Clathrates for gas storage |
Country Status (7)
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US (1) | US20110185623A1 (en) |
EP (1) | EP2318486A1 (en) |
JP (1) | JP2011529036A (en) |
CN (1) | CN102119207A (en) |
CA (1) | CA2731389A1 (en) |
GB (1) | GB0813650D0 (en) |
WO (1) | WO2010010372A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101863483A (en) * | 2010-06-18 | 2010-10-20 | 华南理工大学 | Dry water for synthesizing gas hydrate and preparation method and application thereof |
RU2704971C1 (en) * | 2019-07-12 | 2019-11-01 | федеральное государственное автономное образовательное учреждение высшего образования "Российский государственный университет нефти и газа (национальный исследовательский университет) имени И.М. Губкина" | Method of producing clathrate hydrates for storage and transportation of gases |
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US9303819B2 (en) | 2012-06-04 | 2016-04-05 | Elwha Llc | Fluid recovery in chilled clathrate transportation systems |
US9822932B2 (en) | 2012-06-04 | 2017-11-21 | Elwha Llc | Chilled clathrate transportation system |
US9708947B2 (en) | 2013-08-01 | 2017-07-18 | Elwha Llc | Systems, methods, and apparatuses related to vehicles with reduced emissions |
US9494064B2 (en) * | 2013-08-01 | 2016-11-15 | Elwha Llc | Systems, methods, and apparatuses related to vehicles with reduced emissions |
US9574476B2 (en) | 2013-08-01 | 2017-02-21 | Elwha Llc | Systems, methods, and apparatuses related to vehicles with reduced emissions |
JP6480827B2 (en) * | 2015-08-03 | 2019-03-13 | 信越石英株式会社 | Method for storing hydrogen-doped silica powder and method for producing quartz glass crucible for pulling silicon single crystal |
CN108117076A (en) * | 2017-12-15 | 2018-06-05 | 浙江海洋大学 | A kind of carbon dioxide hydrate reaction unit and the method for improving its generation effect |
US10344234B1 (en) * | 2018-02-19 | 2019-07-09 | Hemotek, Llc | Fuel including poly-oxygenated metal hydroxide |
US11439858B1 (en) * | 2019-08-14 | 2022-09-13 | Dieter R. Berndt | Fire extinguisher and method |
CN112251265B (en) * | 2020-10-21 | 2021-07-23 | 中国科学院西北生态环境资源研究院 | Method for forming hydrate by clay medium |
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JP2000063296A (en) | 1998-08-14 | 2000-02-29 | Chiyoda Corp | Production of hydrated gas and agent for promoting production of hydrated gas |
WO2001000755A1 (en) | 1999-06-24 | 2001-01-04 | Metasource Pty Ltd | Natural gas hydrate and method for producing same |
WO2006040541A1 (en) | 2004-10-11 | 2006-04-20 | Heriot-Watt University | Novel methods for the manufacture and use of gas hydrates |
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US4008170A (en) * | 1975-11-28 | 1977-02-15 | The United States Of America As Represented By The Secretary Of The Army | Dry water |
US5106520A (en) * | 1985-11-22 | 1992-04-21 | The University Of Dayton | Dry powder mixes comprising phase change materials |
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US5370814A (en) * | 1990-01-09 | 1994-12-06 | The University Of Dayton | Dry powder mixes comprising phase change materials |
US5423996A (en) * | 1994-04-15 | 1995-06-13 | Phase Change Laboratories, Inc. | Compositions for thermal energy storage or thermal energy generation |
US5755216A (en) * | 1995-06-06 | 1998-05-26 | The University Of Dayton | Building products incorporating phase change materials and method of making same |
US7030071B2 (en) * | 2002-02-26 | 2006-04-18 | The Regents Of The University Of California | Solid-water detoxifying reagents for chemical and biological agents |
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US7196268B2 (en) * | 2004-08-17 | 2007-03-27 | Ilsco Corporation | Self sealing electrical connector |
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2008
- 2008-07-25 GB GBGB0813650.9A patent/GB0813650D0/en not_active Ceased
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2009
- 2009-07-07 CA CA2731389A patent/CA2731389A1/en not_active Abandoned
- 2009-07-07 JP JP2011519240A patent/JP2011529036A/en active Pending
- 2009-07-07 CN CN2009801300532A patent/CN102119207A/en active Pending
- 2009-07-07 EP EP09785277A patent/EP2318486A1/en not_active Withdrawn
- 2009-07-07 WO PCT/GB2009/050797 patent/WO2010010372A1/en active Application Filing
- 2009-07-07 US US13/055,915 patent/US20110185623A1/en not_active Abandoned
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101863483A (en) * | 2010-06-18 | 2010-10-20 | 华南理工大学 | Dry water for synthesizing gas hydrate and preparation method and application thereof |
RU2704971C1 (en) * | 2019-07-12 | 2019-11-01 | федеральное государственное автономное образовательное учреждение высшего образования "Российский государственный университет нефти и газа (национальный исследовательский университет) имени И.М. Губкина" | Method of producing clathrate hydrates for storage and transportation of gases |
Also Published As
Publication number | Publication date |
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CA2731389A1 (en) | 2010-01-28 |
CN102119207A (en) | 2011-07-06 |
EP2318486A1 (en) | 2011-05-11 |
US20110185623A1 (en) | 2011-08-04 |
GB0813650D0 (en) | 2008-09-03 |
JP2011529036A (en) | 2011-12-01 |
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