WO2007116456A1 - ガスハイドレートペレットの製造方法 - Google Patents
ガスハイドレートペレットの製造方法 Download PDFInfo
- Publication number
- WO2007116456A1 WO2007116456A1 PCT/JP2006/306746 JP2006306746W WO2007116456A1 WO 2007116456 A1 WO2007116456 A1 WO 2007116456A1 JP 2006306746 W JP2006306746 W JP 2006306746W WO 2007116456 A1 WO2007116456 A1 WO 2007116456A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gas hydrate
- pellets
- gas
- granulator
- concentration
- Prior art date
Links
- 0 CC1C*CC1 Chemical compound CC1C*CC1 0.000 description 1
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
-
- 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
- C10L5/00—Solid fuels
-
- 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
- C10L5/00—Solid fuels
- C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
- C10L5/34—Other details of the shaped fuels, e.g. briquettes
- C10L5/36—Shape
- C10L5/363—Pellets or granulates
Definitions
- the present invention reacts a raw material gas with raw material water at a predetermined temperature and pressure to produce gas and an idle, and then forms the gas hydrate into a pellet by a granulator.
- the present invention relates to a method for producing hydrate pellets.
- the powdered gas hydrate is cooled to below freezing point (for example, -20 ° C) by the cooler 4 to be smooth.
- the atmosphere in which the cooler 4 is present (5.4 MPa) is depressurized to atmospheric pressure (0. IMPa), and then the powdery gas hydrate a is molded into pellets p by the granulator 6.
- the gas hydrate concentration decreased by 15 to 30% by weight.
- Gas hydrate a is a generation zone X, that is, a force under the condition of sign A in Fig. 7 (5.4 MPa, 20 ° C (257K)).
- Y that is, rush into the condition of sign ⁇ ⁇ ⁇ ⁇ in Fig. 7 (0. lMPa, one 20 ° C (257K)).
- a powder-like gas hydrate with a small particle size has a large specific surface area, so that the amount of decomposition is remarkably increased.
- the present invention has been made to solve such a problem, and its object is to suppress the decomposition of the gas hydrate at the time of depressurization or pellet molding, and thereby the gas hydrate concentration
- An object of the present invention is to provide a method for producing gas hydrate pellets, which produces gas hydrate pellets having a high gas content and a small amount of gas decomposition during storage.
- Another object of the present invention is to provide a method for producing gas hydrate pellets in which blockage of the decompression device and the pipes before and after the depressurization device hardly occurs.
- the present invention is configured as follows to solve the above-mentioned problems! Speak.
- the method for producing a gas hydrate pellet according to the invention of claim 1 generates a gas hydrate by reacting a raw material gas and raw material water under a predetermined temperature and pressure condition, and this gas hydrate.
- the rate is formed into pellets by a granulator, the gas hydrate is still in the wet state after generation or during dehydration, and the granulation is performed under the conditions of the gas hydrate generation temperature and generation pressure. It is characterized in that it is formed into pellets by a machine, and then the pellets after molding are cooled below the freezing point by a cooler.
- the method for producing a gas hydrate pellet according to the invention of claim 2 is described in claim 1.
- the method of manufacturing a gas hydrate pellets, after gas hydrate formation, the concentration of Gasuhai Doreto is to feature that molding the gas hydrate 70-95 weight 0/0 into pellets.
- the method for producing gas hydrate pellets according to the invention of claim 3 is the method for producing gas hydrate pellets of claim 1, wherein the concentration of the gas hydrate is 30 to 70% during dehydration. 0/0 gas hydrate characterized by molding into pellets.
- the method for producing a gas hydrate pellet according to the invention of claim 4 generates a gas hydrate by reacting a raw material gas and raw material water under predetermined temperature and pressure conditions, and this gas hydrate.
- the gas hydrate is formed into pellets by a granulator, after the gas hydrate is formed, the gas hydrate is cooled to below freezing point, and thereafter, the pellet is formed into pellets by the granulator under the condition of the gas hydrate formation pressure. It is characterized by that.
- the gas hydrate in a state in which moisture still remains after generation or during dehydration is obtained under the conditions of the gas hydrate generation temperature and the generation pressure. Since it is formed into pellets by a granulator, it becomes a solid gas hydrate pellet that is tightly clamped, and a semitransparent beret that contains water in the slight gaps between the gas hydrate particles.
- the pellet is substantially solid, and the specific surface area involved in the decomposition is smaller than that of the conventional pellet having a gap between hydrate particles. For this reason, even if the depressurization device depressurizes from a stable production area (eg, 5.4 MPa) to an unstable atmospheric pressure (0. IMPa), almost no decomposition occurs. In addition, since only the outer surface of the pellets is exposed to the atmosphere, the gas hydrate concentration during storage is small compared to conventional porous gas hydrate pellets, and the gas hydrate concentration at the time of gas hydrate formation is almost the same. It is maintained as it is.
- the pellets are cooled below freezing point (for example, 20 ° C) by a cooler, the water existing between the particles of gas and idrate freezes to become strong pellets, so that further decomposition occurs. It becomes difficult to do.
- this pellet is much larger in size than powder V, and it is tightly clamped, so it does not stick to the depressurization device!
- the gas hydrate having a gas hydrate concentration of 30 to 70% by weight is formed into a pellet during dehydration, so that it becomes a solid gas hydrate pellet that is tightly tightened. It becomes a translucent bullet with water in the gaps between the gas hydrate particles.
- this pellet has a smaller specific surface area related to decomposition than conventional pellets with gaps between the particles because the particles of gas hydrate are blocked by water. For this reason, there is almost no decomposition even when the pressure is released from the stable production zone (eg, 5.4 MPa) to the unstable atmospheric pressure (0. IMPa) by the decompressor! /.
- the gas hydrate is cooled to below freezing point, and then molded into pellets by a granulator under gas hydrate production pressure conditions. Therefore, it is possible to suppress a decrease in the gas storage rate of the pellets.
- FIG. 1 is a first production process diagram for carrying out a method for producing gas hydrate pellets according to the present invention.
- FIG. 2 is a schematic configuration diagram of a granulator.
- FIG. 3 is a side view of pellets produced by the method of the present invention.
- FIG. 4 is a second production process diagram for carrying out the gas hydrate pellet production method according to the present invention.
- FIG. 5 is a third production process diagram for carrying out the method for producing gas hydrate pellets according to the present invention.
- FIG. 6 is a diagram showing the relationship between “gas hydrate concentration (%)” and “gas hydrate concentration transition in each process (time (h))”.
- FIG. 7 is a methane hydrate equilibrium curve.
- FIG. 8 is a schematic configuration diagram of a conventional gas hydrate manufacturing process.
- FIG. 9 is a side view of a pellet produced by a conventional method.
- 1 is a first generator
- 2 is a dehydrator
- 3 is a second generator
- 4 is a cooler
- 5 is a depressurizer
- 6 is a granulator (a pelletizer)
- a high pressure for example, a pelletizer
- 4MPa raw gas (natural gas) g and raw water w at a specified temperature (for example, 4 ° C) are introduced into the first generator 1, and any method such as a stirring method or publishing method is introduced.
- the raw material gas g and the raw material water w and the reacted slurry one form (e.g., gas hydrate concentration: 20 to 30 weight 0/0) to produce the gas hydrate.
- the reaction heat is removed by a refrigerator (not shown).
- the generation pressure condition is usually 3.5MPa (273K) to 8MPa (284K or lower). If the temperature conditions for producing pellets under high pressure, for example, the range of 20 ° C to 0 ° C are included, the generation pressure conditions are 253K (2MPa) to 284K (8MPa).
- the slurry-like gas and idrate generated in the first generator 1 is physically dehydrated by the dehydrator 2.
- the gas hydrate having a gas hydrate concentration of 40 to 50% by weight physically dehydrated by the dehydrator 2 is introduced into the second generator 3.
- the raw material gas g is introduced from the first generator 1 to cause a hydration reaction with the unreacted raw material water w, thereby increasing the gas hydrate concentration to about 90 wt%.
- the reaction heat is removed by a refrigerator not shown in the same manner as the first generator 1.
- the gas hydrate hydrated and dehydrated in the second generator 3 is formed into an arbitrary shape (for example, spherical shape, lens shape, charcoal shape, etc.) and size (for example, about 5 to 30 mm) by the granulator 6. Molded into a pellet. Since the gas hydrate dehydrated in the second generator 3 is somewhat moist, when it is formed into pellets by the granulator 6, as shown in FIG. In the case of the figure, it becomes a pellet p of a spherical shape, a lens shape, a charcoal shape, etc., and a semi-transparent pellet containing water w in a slight gap between adjacent gas hydrate particles a. .
- the concentration of gas hydrate during pelleting are preferred in the range of 70 to 95 weight 0/0 That's right.
- concentration of gas hydrate after generation is more than 95 weight 0/0, since the air-fuel Ri humidity of the gas hydrate is low, hardly can no clearance pellets.
- concentration of the gas hydrate after generation is less than 70% by weight, the amount of gas held will decrease due to the high moisture content.
- the depressurization device 5 depressurizes the gas hydrate generation pressure (5.4 MPa) force to atmospheric pressure (0. IMPa) and stores it in a storage tank (not shown).
- any granulator can be applied as the granulator 6, since it is used under an atmosphere of high pressure generation conditions (for example, 5.4 MPa), as shown in FIG.
- a so-called precettling roll type granulator that makes gas hydrate a bite into a pellet molding mold (pocket) provided on the surface of a pair of rotating rolls 61 and compresses this into pellets p is desirable.
- reference numeral 62 indicates a box
- 63 indicates a hopper
- 64 indicates a motor that rotates a screw 65 in the hopper 63
- 66 indicates a shutter.
- 1 is a first generator
- 2 is a dehydrator
- 3 is a second generator
- 4 is a cooler
- 5 is a depressurizer
- 6 is a granulator (a pelletizer)
- a high pressure for example, a pelletizer
- the gas g and the raw water w are reacted to form a slurry gas hydrate. At that time, the heat of reaction is removed by a refrigerator (not shown).
- the slurry-like gas and idrate produced in the first generator 1 is physically dehydrated by the dehydrator 2.
- the concentration of the gas hydrate is almost 40 to 50% by weight, but it is molded and processed by the granulator 6 with a dehydrating function while squeezing excess water w. concentration is 70 to 80 weight 0/0 degree of pellet.
- the dehydrated water is returned to the raw water w.
- the pellets granulated by the granulator 6 are introduced into the second generator 3.
- the second re reaction from generator in 3 first generator 1 and the raw material water w of the introduced unreacted raw material gas g (hydration), gas hydrate concentration of the pellets, 90 weight 0/0 It will be about.
- the heat of reaction is removed by a refrigerator (not shown).
- the gas hydrate pellets hydrated and dehydrated in the second generator 3 are introduced into the cooler 4 and cooled below the freezing point (for example, 20 ° C). Then, the water w in the gaps between the gas hydrate particles a freezes and becomes a stronger pellet. Thereafter, the pressure is released from the gas hydrate generation pressure (5.4 MPa) to the atmospheric pressure (0. IMPa) by the depressurization device 5 and stored in a storage tank (not shown).
- the gas hydrate concentration during the dehydration that is, the gas hydrate dehydrated by the dehydrator 2 is preferably in the range of 30 to 70% by weight.
- 1 is a first generator
- 2 is a dehydrator
- 3 is a second generator
- 4 is a cooler
- 5 is a depressurizer
- 6 is a granulator (one pelletizer).
- Feed gas (natural gas) g of high pressure (for example, 5.4 MPa) g and raw water w of a predetermined temperature (for example, 4 ° C) are introduced into the first generator 1 and can be optionally mixed with a stirring method or a publishing method. In this manner, the raw material gas g and the raw material water w are reacted to produce a slurry gas hydrate. At that time, the heat of reaction is removed by a refrigerator (not shown).
- the slurry-like gas and idrate generated in the first generator 1 is physically dehydrated by the dehydrator 2. At this stage, the concentration of the gas hydrate is almost 40% to 50% by weight.
- This gas hydrate is introduced into the second generator 3.
- the raw material gas g is introduced from the first generator 1, and hydrated with the unreacted raw water W, so that the concentration of gas hydrate is about 90% by weight.
- the reaction heat is removed by a refrigerator (not shown).
- the gas hydrate hydrated and dehydrated in the second raw vessel 3 is cooled below the freezing point (eg, -20 ° C) by the cooler 4.
- the gas hydrate cooled below freezing point (for example, -20 ° C) by the chiller 4 can have any shape (for example, spherical shape, lens shape, charcoal shape, etc.) and size (for example, 5 to 5 ° C) by the granulator 6. 30mm) pellets.
- the pressure is released to IMPa) and the gas hydrate beret is stored in a storage tank (not shown).
- the gas hydrate is cooled below freezing point, and after that, By pelletizing with the granulator 6, it is possible to obtain a stronger pellet, so that it is possible to suppress a decrease in the gas occluding rate of the gas hydrate pellet.
- any granulator can be applied as the granulator 6, but it is used in an atmosphere of high pressure generation conditions (for example, 5.4MPa).
- a so-called pre-ketting roll method in which a gas hydrate a is eaten into a mold (pocket) for molding a pellet provided on the surface of a pair of rotating rolls 61 and compressed into pellets p.
- a granulator is desirable.
- FIG. 6 is a graph showing the relationship between “gas hydrate concentration (%)” and “gas hydrate concentration transition (time (h))” in each process.
- the gas hydrate concentration after generation (point E) is 93% by weight.
- Gasuno the depressurized (F point), Hydrate concentration 89 weight 0/0, the gas hydrate concentration after storage completion (G point) is 87 wt%.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNA2006800541133A CN101415801A (zh) | 2006-03-30 | 2006-03-30 | 气体水合物颗粒的制造方法 |
EP06730694A EP2006362A4 (en) | 2006-03-30 | 2006-03-30 | PROCESS FOR THE PRODUCTION OF GASHYDRATE PELLET |
PCT/JP2006/306746 WO2007116456A1 (ja) | 2006-03-30 | 2006-03-30 | ガスハイドレートペレットの製造方法 |
US12/225,808 US7999141B2 (en) | 2006-03-30 | 2008-03-30 | Process for producing gas hydrate pellet |
NO20084589A NO20084589L (no) | 2006-03-30 | 2008-10-29 | Fremgangsmate for fremstilling av gasshydratpellets |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2006/306746 WO2007116456A1 (ja) | 2006-03-30 | 2006-03-30 | ガスハイドレートペレットの製造方法 |
Publications (1)
Publication Number | Publication Date |
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WO2007116456A1 true WO2007116456A1 (ja) | 2007-10-18 |
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ID=38580765
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2006/306746 WO2007116456A1 (ja) | 2006-03-30 | 2006-03-30 | ガスハイドレートペレットの製造方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US7999141B2 (ja) |
EP (1) | EP2006362A4 (ja) |
CN (1) | CN101415801A (ja) |
NO (1) | NO20084589L (ja) |
WO (1) | WO2007116456A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2009242682A (ja) * | 2008-03-31 | 2009-10-22 | Mitsui Eng & Shipbuild Co Ltd | ガスハイドレート製造方法及び製造設備 |
JP2010227810A (ja) * | 2009-03-26 | 2010-10-14 | Mitsui Eng & Shipbuild Co Ltd | ガスハイドレートの脱圧装置 |
RU2488625C2 (ru) * | 2011-11-03 | 2013-07-27 | федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Тюменский государственный университет" | Способ утилизации попутного нефтяного газа |
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JP2008248190A (ja) * | 2007-03-30 | 2008-10-16 | Mitsui Eng & Shipbuild Co Ltd | 混合ガスハイドレート製造方法 |
WO2009044468A1 (ja) * | 2007-10-03 | 2009-04-09 | Mitsui Engineering & Shipbuilding Co., Ltd. | ガスハイドレートペレットの製造方法及び製造装置 |
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 |
CA2834763C (en) * | 2011-03-30 | 2019-09-24 | Mitsui Engineering And Shipbuilding Co., Ltd. | Method of molding gas hydrate pellet |
BR112018009410B1 (pt) * | 2015-11-30 | 2022-09-20 | Unilever Ip Holdings B.V. | Processo para a fabricação dos hidratos de gás congelados para uso em um produto de confeitaria congelado |
CN110055119B (zh) * | 2019-04-03 | 2021-01-29 | 常州大学 | 一种水合物球连续加工装置 |
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Also Published As
Publication number | Publication date |
---|---|
EP2006362A1 (en) | 2008-12-24 |
EP2006362A4 (en) | 2010-11-10 |
NO20084589L (no) | 2008-10-29 |
CN101415801A (zh) | 2009-04-22 |
US7999141B2 (en) | 2011-08-16 |
US20090247797A1 (en) | 2009-10-01 |
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