CN1962043A - A gas hydrate high-speed preparation method and device - Google Patents

A gas hydrate high-speed preparation method and device Download PDF

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Publication number
CN1962043A
CN1962043A CN 200610123056 CN200610123056A CN1962043A CN 1962043 A CN1962043 A CN 1962043A CN 200610123056 CN200610123056 CN 200610123056 CN 200610123056 A CN200610123056 A CN 200610123056A CN 1962043 A CN1962043 A CN 1962043A
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gas
hydrate
water
bubble generator
tubular reactor
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CN 200610123056
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CN100534604C (en
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冯自平
何世辉
黄冲
肖睿
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Guangzhou Institute of Energy Conversion of CAS
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Guangzhou Institute of Energy Conversion of CAS
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Abstract

The invention relates to a method for preparing gas hydrate, wherein it cools the needed water and gas and enters them into foam generator; the gas is absorbed by the passive pressure generated by flowing water through the foam generator; the mixture of water and gas enters into tubular reactor to obtain the hydrate. And the device comprises gas source, heat exchanger, foam generator, tubular reactor, cooling heat exchanger, separator, and connecting tube, valve, and water pump; the foam generator is formed by inner and outer tubes; the inner tube via one reduction part is connected to the outlet of generator; the sheath is connected to the outlet of generator outside the inner tube; the reactor has screw blades; the separator is connected to the gas or liquid inlet of foam generator for form circulate loop. The invention avoids using gas compressor.

Description

A kind of high-speed preparation method of gas hydrate and device
Technical field
The present invention relates to a kind of high-speed preparation method and device of gas hydrate.
Technical background
Gas hydrate is the ice attitude supermolecule cage shape thing that is formed by water and micro-molecular gas under a kind of high pressure low temperature condition, different types of gas forms different types of gas hydrate, 1 volumes of gas hydrate can discharge the gas of 100 ~ 200 volumes, and that is to say can be 100 ~ 200 times of its body compressions.On source of the gas ground gas and water in conjunction with process gas hydrate (as ice solid-state), transport solid-state gas hydrate to use the gas destination, discharge gas for life production use, the realization highly effective and safe transports purpose.This The Application of Technology needs a kind of gas hydrate efficiently to generate method and apparatus.
Such as, gas hydrates (NGH) are a kind of cage compounds that water and natural gas form under the cryogenic high pressure condition.Under-20 ℃, the condition of normal pressure, 1m 3Comprise about 170m in the hydrate 3Natural gas.Compare with compressed natural gas (CNG) storaging and transport technology with existing liquefied natural gas (LNG), NGH neither needs the high pressure of CNG to store, also do not need the ultralow temperature of LNG needs, therefore, NGH will play an important role in the natural gas storaging and transport technology in future, especially have powerful competitive advantage for medium and small gas field.Since the latter stage nineties, the gas production merchant in developed country such as Japan, European Union, the U.S. and area has begun to utilize gas hydrates to carry out the technological development of accumulating comprehensively, be used to replace most existing LNG storaging and transport technology, fully reduce the natural gas carrying cost.Undoubtedly, NGH will become one of major technique of following natural gas accumulating, and especially, this technology will replace existing LNG technology in the accumulating scope of 5000km, and have half share with LNG, CNG and pipeline conveying.
Chinese invention patent application 01118175.3 " solid-phase gas hydrate and preparation method thereof " has disclosed a kind of method that adopts porous media to quicken gas hydrate, and gas is led in the porous media, increases the contact area of gas and water.Chinese invention patent application 97190182.1 " production method of gas hydrate " has disclosed the method for a kind of bubble method of perturbation and mechanical mixing method combination, gas impacts water from container bottom through the nozzle ejection and forms the bubble disturbance, be installed in agitator in the container by driven by motor, increase the contact area of gas and water, quicken the generation of gas hydrate.The shortcoming of above-mentioned technology is, can't be continuously, process gas hydrate fast and efficiently.
Japanese patent laid-open 2004-075771 " a kind of hydrate manufacturing installation " discloses a kind of gas hydrate generation technique that adopts the minute yardstick bubble.This patent utilization tubular reactor generates gas hydrates.The flow process of system is as follows: liquids and gases enter static tubular reactor by pipeline respectively and are pre-mixed, and enter tubular reactor then.Flow in the pipe of air-water mixture one side in tubular reactor and react on one side, generating the heat that hydrate discharged is had the cooling collar of cold-producing medium to take away by stream in time.Hydrate, water, admixture of gas flow into separator subsequently.Separator passes through Gravity Separation.Isolated water and gas enter tubular reactor once more.Hydrate is sent to storage tank by conveying worm.The shortcoming of this invention is: must adopt compressor with gas injection tube shape reactor, produce energy consumption of compressor thus.
Summary of the invention
The object of the present invention is to provide a kind of can be continuously, the high-speed preparation method and the device of process gas hydrate fast and efficiently.
For achieving the above object, the present invention has taked following technical scheme:
The high-speed preparation method of gas hydrate of the present invention, may further comprise the steps: the first level that the water and the gas of hydration reaction needs are cooled to hydrate-formation temperature under the corresponding pressure, by bubble generator, the negative pressure that gas produces when flowing through bubble generator by water directly sucks generator then.The mixture of water and gas enters tubular reactor after mixing in bubble generator, obtain the hydrate that generates continuously in the exit of tubular reactor.
Described bubble generator is out-of-date at current, produces negative pressure in bubble generator, thus gas is sucked in the bubble generator naturally, and produces micro-bubble.
For the bubble generator structure that reaches above purpose use is: form by inner and outer pipes.Wherein, generate the required water of hydrate and enter generator, behind a contraction flow region, penetrate at a high speed, form high-speed jet thus from anterior interior pipe.Because flow velocity improves, and partly forms lower pressure at jet, in the natural gas suction jet with the outside sleeve pipe.Gas fully mixes with water, forms the water that has a large amount of micro-bubbles thus in the bubble generator exit.
Described tubular reactor is a tubular structure, and there is spiral blade inside, and the gas that comes from bubble generator and the mixture of water carry out helical form and flow tubular reactor, and gas and water obtain fully to mix the hydrate that generates with continuous acquisition in this process.
For reaching the purpose of continuous running, the reactant mixture that comes out from tubular reactor enters separation equipment behind cooling heat exchanger, and hydrate, remaining unreacted gas and the unreacted water that generates is separated continuously.Separation equipment connects and composes gas or liquid circulation loop with bubble generator gas access or liquid inlet respectively.Wherein, the hydrate of separating is derived separation equipment, and the gas of separating enters gas circulation loop; The water of separating enters liquid circulation loop.
The high speed production device of gas hydrate of the present invention comprises successively the source of the gas, heat exchanger, bubble generator, tubular reactor, cooling heat exchanger, separation equipment and the various connecting pipe that connect and valve, water pump.Separation equipment connects and composes gas or liquid circulation loop with bubble generator gas access or liquid inlet respectively.Meanwhile cooling heat exchanger connects heat exchanger, condensing tower and cooling water pump formation heat of cooling exchange system.
Described bubble generator is made up of inner and outer pipes, and interior Guan Jingyi contraction flow region is communicated with generator exports, and casing pipe sleeve is communicated with outside interior pipe and with generator exports.When bubble generator uses, generate the required water of hydrate and enter generator, behind a contraction flow region, penetrate at a high speed, form high-speed jet thus from anterior interior pipe.Because flow velocity improves, and partly forms lower pressure at jet, in the natural gas suction jet with the outside sleeve pipe.Gas fully mixes with water, forms the water that has a large amount of micro-bubbles thus at the generator exports place.
Described tubular reactor is a tubular structure, there is spiral blade inside, the gas that comes from bubble generator during use and the mixture of liquid carry out helical form and flow tubular reactor, gas and liquid obtain fully to mix the hydrate that generates with continuous acquisition in this process.
The present invention has compared with prior art avoided the using gases compressor, not only greatly reduces the energy consumption of hydrate generation system, and makes that bubble size is littler, Size Distribution is more even.
Description of drawings
Fig. 1 is an embodiment of the invention apparatus structure schematic diagram;
Fig. 2 is an embodiment of the invention bubble generator structural representation;
Fig. 3 is an embodiment of the invention tubular reactor structural representation.
Description of reference numerals
Source of the gas 1, heat exchanger 2, bubble generator 3, tubular reactor 4, cooling heat exchanger 5, separation equipment 6, water tank 7, water pump 8, cooling water pump 9, interior pipe 10, contraction flow region 11, sleeve pipe 12, spiral blade 13
The specific embodiment
Below in conjunction with drawings and Examples content of the present invention is described in further details:
As shown in Figure 1, the high speed production device of present embodiment hydrate is made up of through over-heat-exchanger 2 connection bubble generators 3, tubular reactor 4, cooling heat exchanger 5, separation equipment 6 source of the gas 1 usefulness pipeline, separation equipment 6 usefulness pipelines are connected to bubble generator 3 liquid inlets and form a liquid circulation loop through water tank 7, water pump 8, heat exchanger 2, and separation equipment 6 usefulness pipelines are connected to heat exchanger 2 and are connected to bubble generator 3 gas accesses and form a gas circulation loop.
Described bubble generator 3 structures as described in Figure 2, bubble generator 3 is made up of inner and outer pipes, interior pipe 10 is communicated with generator exports through a contraction flow region 11, pipe 10 was outer and be communicated with generator exports in sleeve pipe 12 was enclosed within.Described tubular reactor 4 structures as shown in Figure 3, tubular reactor 4 is a tubular structure, there is spiral blade 13 inside.
Described separation equipment 6 is a sieve texture, and the solid water compound is constantly separated from mixture, derives separation equipment; The water that filters out flows out below screen cloth, returns liquid circulation loop; Unreacted gas returns gas circulation loop.
Described cooling heat exchanger 5 is made up of internal and external casing.What flow in the interior pipe is to be cooling medium (as cold-producing medium, non freezing solution etc.) between hydrate-water-AIR MIXTURES, interior pipe and the outer tube.Heat exchange is carried out in the interior outside, and the heat in the hydrate generative process is taken away.
The present embodiment device enters the interior pipe 10 of bubble generator 3 from the water of water pump 7 in use after heat exchanger 2 coolings, ejaculation at a high speed forms high-speed jet thus through a contraction flow region 11 after.Because flow velocity improves, and partly forms lower pressure at jet, will suck the jet from the natural gas via outside sleeve pipe 12 of source of the gas 1.Gas fully mixes with water, forms the water that has a large amount of micro-bubbles thus in bubble generator 3 exits.
Then, the mixture of above-mentioned gas and water enters tubular reactor 4.This tubular reactor 4 is a tubular structure, and there is spiral blade 13 inside, and the gas that comes from bubble generator and the mixture of water carry out helical form and flow tubular reactor 4, and gas and water obtain fully to mix in this process.Portion gas and water generation chemical reaction form gas hydrates.
Owing to the exothermic process that forms of hydrate, therefore need to import cooling heat exchanger 5 from the mixture that has hydrate that tubular reactor 4 comes out and cool off, and further generate hydrate herein.
The mixture that has water and thing that comes out from cooling heat exchanger 5 enters separation equipment 6, and hydrate, remaining responseless gas and the responseless water that generates is separated continuously.Wherein, the hydrate of separating is derived separation equipment and is entered the dry and formation system (not marking among the figure) of hydrate.The gas of separating returns the gas access of bubble generator 3 through heat exchanger 2 with pipeline; The liquid of separating enters water tank 7, squeezes into bubble generator by water pump 8 with supplementing water behind heat exchanger 2 then, carries out next one circulation.
Present embodiment has compared with prior art been avoided the using gases compressor, not only greatly reduces the energy consumption of hydrate generation system, and makes that bubble size is littler, Size Distribution is more even.

Claims (10)

1, a kind of high-speed preparation method of gas hydrate, the first level that the water and the gas of hydration reaction needs are cooled to hydrate-formation temperature under the corresponding pressure, enter bubble generator then, the mixture of water and gas enters tubular reactor after mixing in the bubble generator, in tubular reactor, mix the hydrate that the back obtains generation continuously, enter in the separation equipment through cooling heat exchanger and separate, it is characterized in that: the negative pressure that gas produces when flowing through bubble generator by water directly sucks bubble generator.
2, the high-speed preparation method of gas hydrate as claimed in claim 1, it is characterized in that: described bubble generator is made up of inner and outer pipes, generate the required water of hydrate and enter generator, behind a contraction flow region, penetrate at a high speed, form high-speed jet thus from anterior interior pipe; Because flow velocity improves, and partly forms lower pressure at jet, in the natural gas suction jet with the outside sleeve pipe; Gas fully mixes with water, forms the water that has a large amount of micro-bubbles thus in the bubble generator exit.
3, the high-speed preparation method of gas hydrate as claimed in claim 1, it is characterized in that: described tubular reactor is a tubular structure, there is spiral blade inside, the gas that comes from bubble generator and the mixture of water carry out helical form and flow tubular reactor, gas and water obtain fully to mix the hydrate that generates with continuous acquisition in this process.
4, the high-speed preparation method of gas hydrate as claimed in claim 1 is characterized in that: described separation equipment connects and composes gas or liquid circulation loop with bubble generator gas access or liquid inlet respectively.
5, the high-speed preparation method of gas hydrate as claimed in claim 4, it is characterized in that: the hydrate that described separation equipment is separated is derived separation equipment, the unreacted gas of separating enters gas circulation loop, and unreacted water enters liquid circulation loop.
6, a kind of high speed production device of gas hydrate comprises successively the source of the gas, heat exchanger, bubble generator, tubular reactor, cooling heat exchanger, separation equipment and the connecting pipe that connect and valve, water pump; It is characterized in that: described bubble generator is made up of inner and outer pipes, and interior Guan Jingyi contraction flow region is communicated with generator exports, and casing pipe sleeve is communicated with outside interior pipe and with the bubble generator outlet.
7, the high speed production device of gas hydrate according to claim 6, it is characterized in that: described tubular reactor is a tubular structure, and there is spiral blade inside.
8, the high speed production device of gas hydrate according to claim 6 is characterized in that: described separation equipment connects and composes gas or liquid circulation loop with bubble generator gas access or liquid inlet respectively.
9, according to the high speed production device of claim 6 or 8 described gas hydrates, it is characterized in that: described separation equipment is a sieve texture.
10, the high speed production device of gas hydrate according to claim 6 is characterized in that: described cooling heat exchanger connects heat exchanger, condensing tower and cooling water pump etc. and constitutes heat of cooling exchange system.
CNB2006101230561A 2006-10-27 2006-10-27 A gas hydrate high-speed preparation method and device Expired - Fee Related CN100534604C (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101862632A (en) * 2010-06-03 2010-10-20 常州大学 Semi-circulation type gas-liquid multiphase flow contact method
CN101543736B (en) * 2009-04-24 2011-05-18 华南理工大学 Visualization device for preparing gas hydrate in a spraying way
CN101415802B (en) * 2006-04-05 2013-02-06 三井造船株式会社 Apparatus for manufacturing and dewatering gas hydrate
CN103160351A (en) * 2012-01-09 2013-06-19 中国科学院理化技术研究所 Method and device for recovering methane in low-concentration coal bed gas by using hydrate method
CN103992829A (en) * 2014-05-16 2014-08-20 上海理工大学 Natural gas hydrate preparation system based on compressed gas refrigeration cycle
CN108289475A (en) * 2015-11-30 2018-07-17 荷兰联合利华有限公司 The production method of frozen product
CN109097120A (en) * 2018-08-27 2018-12-28 华南理工大学 A kind of gas hydrates static state strengthens quick continuous generation device and method
CN110577851A (en) * 2019-09-12 2019-12-17 华南理工大学 device and method for quickly and continuously hydrating and separating coal bed gas
WO2020118782A1 (en) * 2018-12-14 2020-06-18 中国科学院广州能源研究所 Gas-hydrate slurry separating device and method based on air flotation and siphon synergistic effect
CN111603952A (en) * 2019-07-09 2020-09-01 中建材创新科技研究院有限公司 Novel foam generator capable of preparing stable and size-controllable foam
CN112535998A (en) * 2019-09-20 2021-03-23 中国石油化工股份有限公司 Gas hydrate preparation system
CN114432977A (en) * 2020-10-31 2022-05-06 中国石油化工股份有限公司 Loop type gas hydrate reaction device and reaction method

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6028234A (en) * 1996-12-17 2000-02-22 Mobil Oil Corporation Process for making gas hydrates
CN1570458A (en) * 2004-05-09 2005-01-26 中国科学院广州能源研究所 Gas hydrate high-speed preparing method and apparatus
JP4559898B2 (en) * 2005-03-31 2010-10-13 独立行政法人産業技術総合研究所 Gas hydrate production equipment

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101415802B (en) * 2006-04-05 2013-02-06 三井造船株式会社 Apparatus for manufacturing and dewatering gas hydrate
CN101543736B (en) * 2009-04-24 2011-05-18 华南理工大学 Visualization device for preparing gas hydrate in a spraying way
CN101862632A (en) * 2010-06-03 2010-10-20 常州大学 Semi-circulation type gas-liquid multiphase flow contact method
CN101862632B (en) * 2010-06-03 2013-03-13 常州大学 Semi-circulation type gas-liquid multiphase flow contact method
CN103160351A (en) * 2012-01-09 2013-06-19 中国科学院理化技术研究所 Method and device for recovering methane in low-concentration coal bed gas by using hydrate method
CN103992829A (en) * 2014-05-16 2014-08-20 上海理工大学 Natural gas hydrate preparation system based on compressed gas refrigeration cycle
US10932479B2 (en) 2015-11-30 2021-03-02 Conopeo, Inc. Process for the manufacture of a frozen product
CN108289475A (en) * 2015-11-30 2018-07-17 荷兰联合利华有限公司 The production method of frozen product
CN109097120A (en) * 2018-08-27 2018-12-28 华南理工大学 A kind of gas hydrates static state strengthens quick continuous generation device and method
CN109097120B (en) * 2018-08-27 2020-09-22 华南理工大学 Static strengthening rapid continuous generation device and method for natural gas hydrate
WO2020118782A1 (en) * 2018-12-14 2020-06-18 中国科学院广州能源研究所 Gas-hydrate slurry separating device and method based on air flotation and siphon synergistic effect
CN111603952A (en) * 2019-07-09 2020-09-01 中建材创新科技研究院有限公司 Novel foam generator capable of preparing stable and size-controllable foam
CN110577851A (en) * 2019-09-12 2019-12-17 华南理工大学 device and method for quickly and continuously hydrating and separating coal bed gas
CN112535998A (en) * 2019-09-20 2021-03-23 中国石油化工股份有限公司 Gas hydrate preparation system
CN114432977A (en) * 2020-10-31 2022-05-06 中国石油化工股份有限公司 Loop type gas hydrate reaction device and reaction method
CN114432977B (en) * 2020-10-31 2023-05-05 中国石油化工股份有限公司 Loop type gas hydrate reaction device and reaction method

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