CN112608775A - Device and method for rapid cycle generation of gas hydrate - Google Patents
Device and method for rapid cycle generation of gas hydrate Download PDFInfo
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- CN112608775A CN112608775A CN202011391490.4A CN202011391490A CN112608775A CN 112608775 A CN112608775 A CN 112608775A CN 202011391490 A CN202011391490 A CN 202011391490A CN 112608775 A CN112608775 A CN 112608775A
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- 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 discloses a device and a method for quickly and circularly generating gas hydrate, which comprises an upper chamber, a middle chamber and a lower chamber, wherein the upper chamber is used for mixing slurry, the middle chamber is used for generating the gas hydrate, the lower chamber is used for containing the gas hydrate slurry, the upper part of the middle chamber is provided with a spraying device which is communicated with the upper chamber and is used for spraying the slurry of the upper chamber to the middle chamber, and the lower chamber is internally provided with a leakage pipe which is used for guiding the gas hydrate slurry generated in the middle chamber to the lower chamber. The gas-water separation device is used for separating gas hydrate, gas, water phase and oil phase in the gas hydrate slurry and repeatedly utilizing the gas, the water phase and the oil phase. The gas hydrate synthesizer has three layers, namely an upper layer, a middle layer and a lower layer, so that rapid hydration is facilitated, and gas-liquid separation and oil-water separation are convenient to recycle; the method eliminates a series of inherent defects that the existing hydrate gas storage method has low gas storage density and is difficult to realize rapid production and the like.
Description
Technical Field
The invention belongs to the field of gas hydrate synthesis, and particularly relates to a device and a method for rapid cycle generation of a gas hydrate.
Background
Gas hydrates are ice-like crystals consisting of water-hydrogen bonds forming cages surrounding gas molecules, such as methane, carbon dioxide or other hydrocarbons. The gas can be stored by generating the gas hydrate by the gas and water or solution, the gas hydrate has high gas storage density, the natural gas hydrate in unit volume can store 180 volumes of natural gas, the generation condition of the natural gas hydrate is simple, and only the temperature and the pressure need to be controlled by the generation condition of the azinphos hydrate. Therefore, the gas storage and transportation by using the hydrate method has extremely high economic value and application potential. However, in the current research situation, the rapid synthesis process of natural gas hydrate is still not mature, and the problems hindering the commercialization of the technology are mainly that the hydrate formation step is slow and the storage is difficult, and in addition, when the natural gas hydrate is synthesized by adopting an aqueous solution, the generated hydrate is aggregated into blocks, the mobility is poor, and the wall climbing phenomenon is caused, so that the hydrate product is not easy to take out and further collect and transport after the reaction is finished, which is another defect that the gas storage of the hydration method is limited to realize large-scale industrial application. Compared with an aqueous solution, the existing research reports show that when gas is contacted with a water/oil emulsion added with a proper polymerization inhibitor at low temperature and high pressure to generate hydrate, the hydrate is dispersed in an oil phase in a granular form, so that the aqueous solution has better fluidity, the separation effect is obviously improved, and the reaction time is obviously shortened.
Disclosure of Invention
The invention provides a device and a method for rapid cycle generation of gas hydrate, aiming at the key problems of low natural gas storage density, low hydration conversion rate and the like of the existing hydration method.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: an apparatus for rapid cyclic generation of gas hydrates, comprising:
the gas hydrate synthesizer comprises an upper chamber, a middle chamber and a lower chamber, wherein the upper chamber, the middle chamber and the lower chamber are sequentially arranged from top to bottom and are mutually sealed and isolated, the upper chamber is used for mixing slurry, the lower chamber is used for containing gas hydrate slurry, the top of the middle chamber is provided with a spraying device which is communicated with the upper chamber and is used for spraying the slurry in the upper chamber to the middle chamber, and the lower chamber is internally provided with a leakage pipe which is used for guiding the gas hydrate slurry generated in the middle chamber to the lower chamber; the upper chamber is also provided with a magnetic stirring device for mixing and stirring the slurry;
the gas supply system is connected with the middle chamber and is used for supplying required gas to the middle chamber;
a diesel-emulsifier mixing system connected to the upper chamber for providing a diesel-emulsifier to the upper chamber;
the water supply system is connected with the upper chamber and is used for supplying water to the upper chamber;
the refrigerating system is connected with the gas hydrate synthesizer and is used for cooling the interior of the gas hydrate synthesizer;
the solid-phase particle separation device is communicated with the lower chamber and is used for receiving the gas hydrate slurry discharged from the lower chamber;
the gas-liquid separator is connected with the solid-phase particle separation device and used for receiving the gas-containing liquid after the solid-phase particle separation device filters the gas hydrate and separating gas in the gas-containing liquid; the gas-liquid separator is connected with the middle cavity and is used for sending the separated gas back to the middle cavity;
the oil-water separation system is connected with the gas-liquid separator and is used for receiving liquid after the gas is separated by the gas-liquid separator and separating oil and water in the liquid; the oil-water separation system is connected with the diesel oil-emulsifier mixing system and is used for sending the separated oil into the diesel oil-emulsifier mixing system; the oil-water separation system is connected with the water supply system and is used for sending the separated water into the water supply system.
The top of the upper chamber is provided with a water injection port and a diesel-emulsifier mixed solution injection port, the diesel-emulsifier mixed system is connected with the upper chamber through the diesel-emulsifier mixed solution injection port, and the water supply system is connected with the upper chamber through the water injection port;
a gas injection port and a gas return port are arranged at the upper part of the middle chamber, the gas supply system is connected with the middle chamber through the gas injection port, the gas injection port is connected with a gas inlet nozzle, and the gas-liquid separator is connected with the middle chamber through the gas return port;
the utility model provides a lower cavity structure, the bottom of cavity is equipped with gas hydrate thick liquid export down, solid phase particle separator passes through gas hydrate thick liquid export and is connected with lower cavity.
The spraying device comprises a nozzle arranged on the partition plate I in a penetrating way and an electromagnetic valve I connected with the nozzle and used for controlling the on-off of the nozzle;
the device further provides a sealing and separating method between the middle chamber and the lower chamber and the arrangement of the leakage pipes, wherein a partition plate II is arranged between the middle chamber and the lower chamber and used for sealing and separating the middle chamber and the lower chamber, the leakage pipes are provided with a plurality of electromagnetic valve electromagnetic valves II which are arranged on the partition plate II in a sealing and penetrating mode at intervals, and the leakage pipes are provided with electromagnetic valve electromagnetic valves II used for controlling the on-off of the leakage pipes. More specifically, a plurality of orifices penetrating through the upper end face and the lower end face of the partition plate II are formed in the partition plate II, leakage pipes are hermetically penetrated in the orifices, the leakage pipes correspond to the orifices one by one, the diameter of each leakage pipe is 1/8 of the diameter of the partition plate II, the number of the leakage pipes is 4, the leakage pipes are uniformly distributed on the partition plate II, and the leakage pipes are provided with electromagnetic valves II for realizing the on-off of the leakage pipes;
furthermore, the upper chamber and the middle chamber are both provided with pressure gauges, so that the generation of gas hydrate is facilitated through the regulation and control of the internal pressure.
In order to facilitate the cleaning of the gas hydrate, the device further comprises a hydrate filtering and flushing unit which is connected with the solid phase particle separating device and is used for washing the gas hydrate particles filtered by the solid phase particle separating device. The solid-phase particle separation device is internally provided with a sieve plate, the sieve plate is provided with filtering holes with the diameter smaller than 1 mu m, the sieve plate can be directly lifted out, so that the subsequent filtering, cleaning and conveying are convenient, hydrate crystals are left on the sieve plate after the hydrate oil slurry passes through the solid-phase particle separation device, the liquid phase is filtered out from the lower part of the sieve plate, and the liquid phase is collected at the bottom of the separation device and is discharged from a liquid discharge port.
Furthermore, the solid-phase particle separation device is connected with the lower cavity through a pipeline provided with a throttle valve and a delivery pump, and the throttle valve is used for decompressing gas hydrate slurry discharged from the gas hydrate synthesizer into the normal-pressure solid-phase particle separation device, so that the temperature of the gas hydrate slurry is further reduced.
Furthermore, the gas supply system adopts a plurality of high-pressure gas cylinders connected in parallel.
Further, the gas-liquid separator is connected with the middle cavity through a gas return pipeline, and a gas collecting tank, a compressor I and a flowmeter I are sequentially arranged on the gas return pipeline along the gas flowing direction;
and/or the gas supply system is connected with the middle chamber through a gas supply pipeline, and a buffer tank and a compressor II are sequentially arranged on the gas supply pipeline along the gas flowing direction. The gas injection port is connected with the buffer tank, gas enters the compressor after being stabilized, high-pressure control in the gas hydrate synthesizer is facilitated after the gas is compressed, the gas inlet nozzle is further arranged at the injection port, then the gas is sprayed into the middle cavity, fluid disturbance in the middle cavity is further promoted, and hydration reaction efficiency is improved. The mixed emulsion is dispersed to the middle chamber by combining the spraying device and is combined with the gas, so that the contact area of the gas and the emulsion is increased, and the hydration reaction rate is accelerated.
Furthermore, the volume of the upper chamber and the volume of the middle chamber of the gas hydrate synthesizer are not less than the volume of the lower chamber, and the volume of the upper chamber and the volume of the middle chamber are approximately equal.
Furthermore, in order to increase the oil-water separation effect and better recycle, the oil-water separation system comprises a water separation storage tank and an oil separation storage tank, wherein a lipophilic hydrophobic membrane is arranged in the water separation storage tank and divides the interior of the water separation storage tank into an upper layer and a lower layer, the upper layer is provided with an oil-water inlet connected with the gas-liquid separator and a water phase outlet connected with the water supply system, and the lower layer is provided with an oil phase outlet connected with the oil separation storage tank;
a hydrophilic oleophobic membrane is arranged in the oil separation storage tank, the hydrophilic oil delivery membrane divides the interior of the oil separation storage tank into an upper layer and a lower layer, wherein the upper layer is provided with an oil outlet connected with the diesel oil-emulsifier mixing system and an oil phase inlet connected with the oil phase outlet, and the lower layer is provided with a waste liquid outlet;
furthermore, the diesel oil-emulsifier mixed solution injection port is connected with a high-pressure liquid injection pump I through a pipeline, and low-pressure liquid in the diesel oil-emulsifier mixed container is pumped into the high-pressure hydrate synthesizer.
Furthermore, the water injection port is connected with a high-pressure injection pump II through a pipeline, and low-pressure liquid in the water container is pumped into the high-pressure hydrate synthesizer.
A gas hydrate rapid cycle generation method is carried out based on the gas hydrate rapid cycle generation device, and comprises the following steps:
injecting a set amount of water and diesel oil-emulsifier mixed solution into the upper cavity of the gas hydrate synthesizer according to a set proportion, dispersing the system uniformly to form water/oil-emulsifier mixed emulsion through a magnetic stirring device, and simultaneously starting a refrigeration system to cool the gas hydrate synthesizer;
vacuumizing a middle chamber of a gas hydrate synthesizer, injecting gas with set pressure from a gas supply system, maintaining the middle chamber at the set pressure, starting a spraying device, injecting the water/oil-emulsifier mixed emulsion into the middle chamber, and hydrating the water/oil-emulsifier mixed emulsion with the gas to generate gas hydrate slurry;
when the gas hydrate slurry method of the middle chamber reaches the set volume, opening a leakage pipe to introduce the hydrate slurry into the lower chamber, then performing solid-liquid separation by a solid-phase particle separation device, and then collecting the gas hydrate in a solid phase;
and the gas-containing liquid from the solid-phase particle separation device enters an oil-water separation system for gas-liquid separation, the separated gas enters a middle chamber for reuse, the liquid after the gas is separated enters the oil-water separation system for oil-water separation, the separated oil is sent to a diesel-emulsifier mixing system for reuse, and the separated water is sent to a water supply system for reuse.
Further, the volume ratio of water to the diesel oil-emulsifier mixed solution in the upper chamber of the gas hydrate synthesizer is 1: 4-9;
and/or the emulsifier adopts span-20, the content is 1% -6% of the volume of the mixed solution of water and diesel oil-emulsifier;
and/or the temperature control range of the refrigerating system is 1-10 ℃;
and/or controlling the working pressure in the gas hydrate synthesizer to be 0-7 Mpa;
and/or the gas is natural gas.
Compared with the prior art, the gas and the water/oil-emulsifier mixed solution are contacted at low temperature and high pressure to generate hydrate slurry, and then the slurry is subjected to gas-liquid-solid three-phase separation to obtain hydrate crystals, gas phase and liquid phase, so that the continuous production operation of realizing rapid hydration, filtering the hydrate crystals for storage and transportation and recycling the filtered and recovered oil and gas phase is facilitated; the method eliminates a series of inherent defects that the existing hydrate gas storage method has low gas storage density, is difficult to realize rapid production and the like, meets the requirements of efficient natural gas storage and continuous and batch production of natural gas hydrate products, is convenient for large-scale industrial application, and has important significance for the practical application of the gas storage technology.
Drawings
Fig. 1 is a schematic structural diagram of an apparatus for rapid cycle gas hydrate generation according to an embodiment of the present invention.
Fig. 2 is a schematic structural diagram of a gas hydrate synthesizer in the apparatus for rapid cycle generation of gas hydrates in the embodiment of the present invention.
The reference numbers in the figures are: 1-a gas hydrate synthesizer; 2-a solid phase particle separation device; 3-a gas-liquid separator; 4-oil-water separation system; 5-a refrigeration system; 6-a gas supply system; 7-magnetic stirring device; 8-a separator I; 9-a spraying device; 10-electromagnetic valve I; 11-a buffer tank; 12-a separator II; 13-a leakage pipe; 14-electromagnetic valve II; 15-a pressure gauge; 16-a water container; 17-a diesel-emulsifier mixing vessel; 18-high pressure liquid injection pump I; 19-high pressure liquid injection pump II; 20-a pulling device; 21-compressor I; 22-flow meter I; 23-pump I; 24-pump II; 25-flow meter II; 26-flow meter III; 27-a water separation tank; 28-lipophilic hydrophobic membrane; 29-oil separation storage tank; 30-a hydrophilic oleophobic membrane; 31-a waste liquid recovery tank; 32-sieve plate; 33-a gas collection tank; 34-compressor II; 35-air inlet nozzle.
Detailed Description
The invention is further illustrated below with reference to the figures and examples in order to facilitate the understanding of the invention by a person skilled in the art. It is to be understood that the invention is not limited in scope to the specific embodiments, but is intended to cover various modifications within the spirit and scope of the invention as defined and defined by the appended claims, as would be apparent to one of ordinary skill in the art.
As shown in fig. 1, the device for rapid cycle generation of gas hydrate comprises a gas hydrate synthesizer 1, a solid-phase particle separation device 2, a gas-liquid separator 3, an oil-water separation system 4, a refrigeration system 5, a gas supply system 6 and other units.
The gas hydrate synthesizer 1 comprises three layers of cavities, wherein the upper cavity is a mixed slurry synthesis cavity, the middle cavity is a gas hydrate synthesis cavity, and the lower cavity is a hydrate slurry storage cavity. The top of the container is provided with a water injection port and a diesel-emulsifier mixed solution injection port, the top of the upper chamber is provided with a magnetic stirring device 7, the bottom of the upper chamber is provided with a partition plate I8 which is hermetically separated from the middle chamber, a hole is arranged on the partition plate I8 and is provided with a spraying device 9, the spraying device 9 is controlled to be opened and closed by a solenoid valve I10 at the top, the solenoid valve I10 is electrically connected with a control device, the side surface of the middle chamber is provided with a gas injection port, the gas injection port is connected with a gas supply system 6 through a buffer tank 11, the middle chamber is separated from the lower chamber by a partition plate II 12, the partition plate II 12 is provided with a plurality of leakage pipes 13, the leakage pipes 13 are provided with a solenoid valve II 14, the solenoid valve II 14 is electrically connected with the control device, the gas hydrate synthesizer 1 is a high-pressure cavity, the refrigeration system 5 is externally coated, the upper chamber and the, The high-pressure liquid injection pump II 19 is connected with the water container 16 and the diesel-emulsifier mixed solution container 17, a slurry outlet is formed in the bottom of the lower chamber and is connected with the solid-phase particle separation device 2 through the slurry outlet, the solid-phase particle separation device 2 is connected with the hydrate filtering and flushing unit, the bottom of the lower chamber is connected with the gas-liquid separator 3 through the water-oil mixed solution outlet, the upper outlet of the gas-liquid separator 3 is connected with the upper chamber of the gas hydrate through a compressor I21 and a flowmeter I22, the lower outlet of the gas-liquid separator 3 is connected with the oil-water separation system 4, the oil-water separation system 4 is respectively connected with the water container 16 and the diesel-emulsifier mixed container 17 through a pump I23 and;
the volumes of an upper chamber, a middle chamber and a lower chamber of the gas hydrate synthesizer 1 are equal;
the partition plates between the chambers of the gas hydrate synthesizer 1 are made of stainless steel materials and are mechanically and fixedly arranged on the container;
the spraying device 9 is hermetically connected with the upper chamber through an upper orifice of a partition plate I8, is mechanically fixed on the partition plate, and is opened and closed by controlling an electromagnetic valve I10 through a control system;
the orifice of the second partition plate 12 is provided with 4 leakage pipes 13, the diameter of each leakage pipe 13 is selected to be 1/8 of the diameter of the second partition plate 12, the leakage pipes 13 are uniformly distributed on the second partition plate 12, the leakage pipes 13 and the second partition plate 12 are sealed, and the electromagnetic valve II 14 is controlled by a control system to be opened and closed;
valve groups are arranged between the pipelines and between the containers for flow regulation and reaction flow control;
the refrigerating system 5 adopts water bath refrigeration, a heat insulation sleeve is arranged outside the gas hydrate synthesizer 1, and the refrigerating medium carrying water/ethylene glycol mixed liquid is used for temperature control.
A sieve plate 32 is arranged in the solid-phase particle separation device 1, filter holes with the pore diameter smaller than 1 are formed in the sieve plate 32, slurry from a lower cavity of the gas hydrate synthesizer 1 is filtered by the sieve plate 32, hydrate crystals are collected by the sieve plate, and liquid phase flows through the sieve plate like a gas-liquid separator 3;
the oil-water separation system 4 is composed of a water separation storage tank 27, an oleophylic hydrophobic membrane 28, an oil separation storage tank 29, an oleophylic oleophobic membrane 30 and a waste liquid recovery tank 31. The water and the oil obtained by separation enter the water container 16 and the diesel oil-emulsifier mixing container 17 for repeated use through pipelines;
the upper chamber and the middle chamber of the gas hydrate synthesizer 1 are both provided with pressure gauges;
flow meters are arranged between the water container 16 and the water injection port, between the diesel oil-emulsifier mixed solution container 17 and the diesel oil-emulsifier mixed solution injection port, and between the gas collection tank 33 and the recycled gas injection port, and are used for monitoring the flow rate;
example 1, the selected gas was natural gas;
the method for realizing the circular rapid synthesis of the natural gas hydrate by using the system comprises the following steps:
and starting the refrigerating system 5 to cool the gas hydrate synthesizer 1 so as to meet the low-temperature condition required by the generation of the natural gas hydrate in the hydrate synthesizer 1.
A certain amount of water is injected into the hydrate synthesizer 1 from a water injection port through a conveying high-pressure injection pump II 19, a prepared diesel oil-emulsifier (a mixed oil phase of diesel oil and an emulsifier Span-20 in the embodiment) is injected into the hydrate synthesizer 1 through a conveying high-pressure injection pump I18, and the volume ratio of the injected water phase and the injected oil phase is controlled through a flowmeter.
And (3) starting a magnetic stirring device 7 of the hydrate synthesizer 1 to mix the water phase and the oil phase into emulsion, then starting a vacuum pumping device of a middle chamber of the hydrate synthesizer 1 to completely pump air in the middle chamber, starting an air supply system 5, and injecting a certain amount of natural gas into the middle chamber through a high-pressure gas bottle group.
When the temperature and the pressure in the upper chamber of the hydrate synthesizer 1 are stable, the electromagnetic valve I10 is opened, the spraying device 9 is opened, the emulsion is injected into the middle chamber from the middle chamber, and water, the diesel oil-Span 20 mixed oil phase and the natural gas phase are supplemented to the hydrate synthesizer 1 in time in the emulsion injection process. The emulsion is combined with natural gas to be converted into hydrate oil slurry, and the pressure of the natural gas in the hydrate synthesizer 1 is reduced after the natural gas is converted into hydrate in the hydration reaction process, so that the natural gas is required to be supplemented into the hydrate synthesizer 1 from the gas supply system 5 in time to keep the pressure basically stable.
When the volume of the cavity slurry in the gas hydrate synthesizer 1 accounts for about 4/5 of the total volume, a liquid outlet at the bottom of the hydrate synthesizer 1 is opened, the high-pressure environment in the hydrate synthesizer 1 pushes the hydrate oil slurry out of the bottom of the synthesizer to flow to the solid particle separation device 2, hydrate crystals are enriched on the sieve plate 32, the sieve plate 32 is taken out, and the collected natural gas hydrate crystals are poured into other collection containers or transportation equipment to be directly transported at low temperature and normal pressure or low pressure. The gas phase and the liquid phase enter the gas-liquid separator 3, and the gas phase is discharged from the top of the gas-liquid separator 3 to enter a gas collecting tank 33 and returns to the gas hydrate synthesizer 1 through a compressor I21 for reuse.
And the liquid phase coming out from the bottom of the gas-liquid separator 3 passes through an oil-water separation system 4 to realize the separation of water and oil, and the water and the oil obtained by the separation respectively enter a water container and a diesel oil-emulsifier mixing container through a delivery pump to be stored for reuse. Realizes the synthesis of the natural gas hydrate in a rapid cycle.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and their concepts should be equivalent or changed within the technical scope of the present invention.
The present invention is not limited to the above embodiments, and those skilled in the art can implement the present invention in other embodiments according to the disclosure of the present invention, or make simple changes or modifications on the design structure and idea of the present invention, and fall into the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention. Furthermore, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first," "second," etc. may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art through specific situations.
Claims (10)
1. A gas hydrate rapid cycle generation device is characterized in that: the method comprises the following steps:
the gas hydrate synthesizer (1) comprises an upper chamber, a middle chamber and a lower chamber, wherein the upper chamber, the middle chamber and the lower chamber are sequentially arranged from top to bottom and are mutually sealed and isolated, the middle chamber is used for generating gas hydrate, the lower chamber is used for containing gas hydrate slurry, a spraying device (9) which is communicated with the upper chamber and is used for spraying the slurry in the upper chamber to the middle chamber is arranged at the top of the middle chamber, and a leakage pipe (13) which is used for guiding the gas hydrate slurry generated in the middle chamber to the lower chamber is arranged in the lower chamber; the upper chamber is also provided with a magnetic stirring device (7) for mixing and stirring the slurry;
the gas supply system (6) is connected with the middle chamber and is used for supplying required gas to the middle chamber;
a diesel-emulsifier mixing system connected to the upper chamber for providing a diesel-emulsifier to the upper chamber;
the water supply system is connected with the upper chamber and is used for supplying water to the upper chamber;
the refrigerating system (5) is connected with the gas hydrate synthesizer (1) and is used for cooling the interior of the gas hydrate synthesizer (1);
a solid phase particle separation device (2) communicated with the lower chamber and used for receiving the gas hydrate slurry discharged from the lower chamber;
the gas-liquid separator (3) is connected with the solid-phase particle separating device (2) and is used for receiving the gas-containing liquid after the gas hydrate is filtered by the solid-phase particle separating device (2) and separating gas in the gas-containing liquid; the gas-liquid separator (3) is connected with the middle chamber and is used for sending the separated gas back to the middle chamber;
the oil-water separation system (4) is connected with the gas-liquid separator (3) and is used for receiving the liquid after the gas is separated by the gas-liquid separator (3) and separating oil and water in the liquid; the oil-water separation system (4) is connected with the diesel oil-emulsifier mixing system and is used for sending the separated oil into the diesel oil-emulsifier mixing system; the oil-water separation system (4) is connected with the water supply system and is used for sending the separated water into the water supply system.
2. A gas hydrate rapid cycle generating apparatus as claimed in claim 1 wherein: the top of the upper chamber is provided with a water injection port and a diesel-emulsifier mixed solution injection port, the diesel-emulsifier mixed system is connected with the upper chamber through the diesel-emulsifier mixed solution injection port, and the water supply system is connected with the upper chamber through the water injection port;
and/or the upper part of the middle cavity is provided with a gas injection port and a gas return port, the gas supply system (6) is connected with the middle cavity through the gas injection port, the gas injection port is connected with a gas inlet nozzle (35), the gas inlet nozzle (35) is positioned in the middle cavity, and the gas-liquid separator (3) is connected with the middle cavity through the gas return port;
and/or the bottom of the lower chamber is provided with a gas hydrate slurry outlet, and the solid-phase particle separation device (2) is connected with the lower chamber through the gas hydrate slurry outlet.
3. A gas hydrate rapid cycle generating apparatus as claimed in claim 1 wherein: a partition plate I (8) is arranged between the upper chamber and the middle chamber and is used for sealing and separating the upper chamber from the lower chamber, and the spraying device (9) comprises a nozzle penetrating through the partition plate I (8) and an electromagnetic valve I (10) connected with the nozzle and used for controlling the on-off of the nozzle;
and/or be equipped with baffle II (12) between well cavity and the lower cavity for airtight the wall between well cavity and the lower cavity, leak pipe (13) have a plurality ofly and the interval is airtight wear to establish on baffle II (12), be equipped with solenoid valve II (14) that are used for controlling leak pipe (13) break-make on leak pipe (13).
4. A gas hydrate rapid cycle generating apparatus as claimed in claim 1 wherein: the upper chamber and the middle chamber are both provided with pressure gauges (15).
5. A gas hydrate rapid cycle generating apparatus as claimed in claim 1 wherein: the device also comprises a hydrate filtering and flushing unit which is connected with the solid-phase particle separating device (2) and is used for washing the gas hydrate particles filtered by the solid-phase particle separating device (2).
6. A gas hydrate rapid cycle generating apparatus as claimed in claim 1 wherein: the gas-liquid separator (3) is connected with the middle cavity through a gas return pipeline, and a gas collecting tank (33), a compressor I (21) and a flowmeter I (22) are sequentially arranged on the gas return pipeline along the gas flowing direction;
and/or the gas supply system (6) is connected with the middle chamber through a gas supply pipeline, and a buffer tank (11) and a compressor II (34) are sequentially arranged on the gas supply pipeline along the gas flowing direction.
7. A gas hydrate rapid cycle generating apparatus as claimed in claim 1 wherein: the volume of an upper chamber and a middle chamber of the gas hydrate synthesizer (1) is not less than the volume of a lower chamber, and the volume of the upper chamber and the volume of the middle chamber are equal;
and/or a sieve plate is arranged in the solid-phase particle separation device (2), the sieve plate is provided with filtering holes with the diameter less than 1 mu m, and the sieve plate can be lifted upwards from the solid-phase particle separation device (2);
and/or the solid-phase particle separation device (2) is connected with the lower cavity through a pipeline provided with a throttle valve and a delivery pump.
8. A gas hydrate rapid cycle generating apparatus as claimed in claim 1 wherein: the oil-water separation system (4) comprises a water separation storage tank (27) and an oil separation storage tank (29), wherein a lipophilic hydrophobic membrane (28) is arranged in the water separation storage tank (27), the lipophilic hydrophobic membrane (28) divides the interior of the water separation storage tank (27) into an upper layer and a lower layer, the upper layer is provided with an oil-water inlet connected with the gas-liquid separator (3) and a water phase outlet connected with a water supply system, and the lower layer is provided with an oil phase outlet connected with the oil separation storage tank (29);
a hydrophilic oleophobic membrane (30) is arranged in the oil separation storage tank (29), the hydrophilic oil delivery membrane divides the interior of the oil separation storage tank (29) into an upper layer and a lower layer, wherein the upper layer is provided with an oil outlet connected with the diesel oil-emulsifier mixing system and an oil phase inlet connected with the oil phase outlet, and the lower layer is provided with a waste liquid outlet;
and/or the diesel oil-emulsifier mixing system is connected with the upper chamber through a pipeline provided with a high-pressure liquid injection pump I;
and/or the water supply system is connected with the upper chamber through a pipeline provided with a high-pressure liquid injection pump II.
9. A gas hydrate rapid cycle generation method is characterized in that: the method is carried out based on the device for the rapid cycle generation of the gas hydrate as claimed in any one of claims 1 to 8, and comprises the following steps:
injecting a set amount of water and diesel oil-emulsifier mixed solution into the upper cavity of the gas hydrate synthesizer (1) according to a set proportion, uniformly dispersing the system to form water/oil-emulsifier mixed emulsion through a magnetic stirring device (7), and simultaneously starting a refrigeration system (5) to cool the gas hydrate synthesizer (1);
vacuumizing a middle chamber of a gas hydrate synthesizer (1), injecting gas with set pressure from a gas supply system (6), maintaining the middle chamber at the set pressure, starting a spraying device (9), injecting the water/oil-emulsifier mixed emulsion into the middle chamber, and hydrating the water/oil-emulsifier mixed emulsion with the gas to generate gas hydrate slurry;
when the gas hydrate slurry method of the middle chamber reaches the set volume, the leakage pipe (13) is opened to introduce the hydrate slurry into the lower chamber, then the solid-liquid separation is carried out by the solid-phase particle separation device (2), and then the gas hydrate is collected in the solid phase;
gas-containing liquid from the solid-phase particle separation device (2) enters an oil-water separation system (4) for gas-liquid separation, the separated gas enters a middle chamber for reuse, the liquid after the gas is separated enters the oil-water separation system (4) for oil-water separation, the separated oil is sent to a diesel-emulsifier mixing system for reuse, and the separated water is sent to a water supply system for reuse.
10. A gas hydrate rapid cycle production method as claimed in claim 9 wherein:
the volume ratio of water to the diesel oil-emulsifier mixed solution in the upper chamber of the gas hydrate synthesizer (1) is 1: 4-9;
and/or the emulsifier adopts span-20, the content is 1% -6% of the volume of the mixed solution of water and diesel oil-emulsifier;
and/or the temperature control range of the refrigerating system (5) is 1-10 ℃;
and/or the working pressure in the gas hydrate synthesizer (1) is controlled to be 0-7 Mpa;
and/or the gas is natural gas.
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| CN112844275A (en) * | 2020-11-05 | 2021-05-28 | 东北石油大学 | Reaction kettle for preparing layered multistage hydrate slurry and preparation method |
| CN113175767A (en) * | 2021-04-26 | 2021-07-27 | 常州大学 | Split type grid type refrigeration heating device based on hydrate effect |
| CN114814156A (en) * | 2022-06-23 | 2022-07-29 | 中国地质大学（北京） | Decomposition device for simulating evolution law of natural gas hydrate |
| CN115264679A (en) * | 2022-06-29 | 2022-11-01 | 中南大学 | With CO2Seasonal cold accumulation system with hydrate as cold accumulation material |
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