CN106544070A - A kind of gas hydrates generate the method and device with displacement - Google Patents

A kind of gas hydrates generate the method and device with displacement Download PDF

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CN106544070A
CN106544070A CN201611111609.1A CN201611111609A CN106544070A CN 106544070 A CN106544070 A CN 106544070A CN 201611111609 A CN201611111609 A CN 201611111609A CN 106544070 A CN106544070 A CN 106544070A
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gas
reactor
stop valve
valve
hydrate
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CN106544070B (en
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郎雪梅
操原
樊栓狮
王燕鸿
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South China University of Technology SCUT
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South China University of Technology SCUT
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L3/00Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08Production of synthetic natural gas
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/04Pressure vessels, e.g. autoclaves

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of gas hydrates generate the method and device with displacement.Described device includes mixing CO2/N2Gas cylinder, CH4Gas cylinder, gas flowmeter, wet type gas mass flowmenter, surge tank, thermostatic water bath, reactor, circulator bath, hand pump, feed liquor funnel, data collecting instrument and computer;Methods described refers to that natural gas hydrate generates the method with displacement.The invention provides a kind of method and device that is simple, quickly generating gas hydrates and displacer gas hydrate, to overcome the shortcomings of in porous media that gas hydrates generation content is few, displacement efficiency is low.

Description

A kind of gas hydrates generate the method and device with displacement
Technical field
The present invention relates to gas hydrates generation method and experimental provision, and in particular to a kind of gas hydrates are generated With the method and device of displacement.
Background technology
Gas hydrates are the Fossil fuels for most cleaning, and it is the most potential energy for taking over oil and coal to have been found to Source resource.Gas hydrates be a kind of energy resources its carbon contents be all Fossil fuels twice, be distributed in all over the world. Huge reserves are attracted attention in the exploitation of gas hydrates, and natural gas exploiting method traditional at present is main Including voltage drop method, heat injection method, chemical-agent technique or joint both the above method.But above method exploitation of gas hydrate meeting Cause caving in for geological stratification, cause the destruction serious to natural environment.
Existing gas displacement exploitation of gas hydrate method, mainly has CO2Replacement exploitation and mixing CO2/N2Displacement is opened Adopt, wherein CO2The methane recovery of replacement exploitation is than mixing CO2/N2The methane recovery of replacement exploitation is low, therefore preferential employing Mixing CO2/N2Gas displacement exploitation of gas hydrate.
At present, mix CO2/N2Gas displacement exploitation of gas hydrate is mostly in the laboratory research stage.It is accurate before displacement Standby a certain amount of manually generated gas hydrates, and in order to simulate natural hydrate geological environment, experimentation is typically adopted Hydrate is generated in how empty medium, conventional method is the ice powder using first milled, is then transferred in reactor, often Cause caking or the thawing of ice powder, the gas hydrates content obtained after being filled with methane gas is low, be unfavorable for follow-up opening Adopt experiment.
The shortcomings of gas hydrates content is low, and time-consuming is generated in many sky media for more than, the present invention provides a kind of Quickly generate in many sky media and exploitation of gas hydrate device and method, realization quickly generates gas hydrates, and And on the basis of hydrate is generated, carry out mixing CO2/N2Gas displacement, improves replacement rate and replacement rate, and operation is simple, knot Structure is simple and clear, low cost.
The content of the invention
The invention provides a kind of gas hydrates generate the method and device with displacement, to overcome day in porous media So gas hydrate generates the deficiency that content is few, displacement efficiency is low.
The present invention is achieved through the following technical solutions:
A kind of gas hydrates generate the device with displacement, including mixing CO2/N2Gas cylinder, CH4Gas cylinder, gas flow Meter, wet gas flow meter, surge tank, thermostatic water bath, reactor, circulator bath, hand pump and feed liquor funnel;
The hand pump and reactor, surge tank, gas flowmeter, mix CO2/N2Gas cylinder is sequentially connected with;The feed liquor leakage Bucket is connected with hand pump;The thermostatic water bath is arranged at outside the surge tank;The circulator bath is connected with reactor;It is described CH4Gas cylinder is sequentially connected with wet gas flow meter, reactor.
In said apparatus, the reactor includes kettle, the gas inlet and outlet positioned at kettle side, is connected in kettle The kettle cover at top, the support for supporting autoclave body bottom, the agitator and sand export that are placed in autoclave body bottom;
Pressure detecting interface, temperature detection interface and the inlet for being connected to kettle inner chamber is additionally provided with the kettle cover;Institute Draw point is provided with stating inlet.
In said apparatus, the kettle cover is connected by screw thread or flange with kettle.
In said apparatus, also including the first temperature sensor, second temperature sensor, first pressure sensor, the second pressure Force transducer, data collecting instrument and computer;First temperature sensor is connected on the temperature survey interface of surge tank, described Second temperature sensor is connected on the temperature survey interface of reactor;The first pressure sensor connects the output of surge tank Mouthful, on the pressure detecting mouth of the second pressure sensor coupled reaction kettle;Above sensor connects data by holding wire Acquisition Instrument, the data collecting instrument connect computer, and the reading of each temperature and pressure is shown on computer.
In said apparatus, also including CH4Air relief valve, mixed gas CO2/N2Air relief valve, the first hydralic pressure gauge, the second hydralic pressure gauge, First three-way valve, the second three-way valve, the 3rd three-way valve, check valve, the first stop valve, the second stop valve, the 3rd stop valve and Four stop valves;The CH4Air relief valve is arranged at CH4On the pipeline connected between gas cylinder and wet gas flow meter;The gaseous mixture Body CO2/N2Air relief valve is arranged at mixed gas CO2/N2On the pipeline connected between gas cylinder and gas flowmeter;First liquid Pressure table is arranged on the pipeline that check valve is connected with hand pump;Second hydralic pressure gauge is arranged at the 3rd stop valve and the 3rd threeway On the pipeline of valve connection;
First three-way valve is arranged on the pipeline of surge tank and first pressure sensor, and is connected with reactor;Institute State the second three-way valve to be arranged on the pipeline of the first stop valve and reactor air inlet, and be connected with wet gas flow meter;Institute State the 3rd three-way valve to be arranged on the pipeline that the second stop valve is connected with the second hydralic pressure gauge;The check valve be arranged at hand pump and On pipeline between reactor;First stop valve is arranged on the pipeline of the first three-way valve and the connection of the second three-way valve;Institute State on the connecting pipe that the second stop valve is arranged between wet gas flow meter and the 3rd three-way valve;3rd stop valve sets It is placed in the second hydralic pressure gauge and CH4On connecting pipe between air relief valve;4th stop valve is arranged at hand pump and feed liquor leakage On pipeline between bucket.
A kind of gas hydrates generate the method with displacement, add 15-20 DEG C of water to feed liquor funnel, by hand pump Water is pressed into reactor, water is entered in drop in the reactor of the band stirring for having been filled with methane gas, water is quickly generated with this Compound;Then, after hydrate is generated, enter line replacement reaction by being passed through substitution gas.
Further, the volume for generating the water used by hydrate, injects water to reactor using hand pump, according to note Enter the volume of water so as to obtain the volume of the water used for generating hydrate.
Further, comprise the steps:
(1) in reactor quartz sand, evacuation is added to open CH4Air relief valve, the 3rd stop valve and the second stop valve, CH is filled into reactor4It is 4MPa~12MPa, the CH being filled with wet type mass flow meter measurement in reactor to pressure4Amount, note Record is filled with the CH in reactor4Gas volume be V1, circulator bath and thermostatic water bath are opened, the temperature -7 of circulator bath is set DEG C -- 2 DEG C, the temperature of thermostatic water bath is 0 DEG C -2 DEG C, while opening the agitating device of reactor;
(2) the 4th stop valve is opened, aqueous solution is injected into reactor using hand pump, keep water along draw point to reaction At the uniform velocity to flow down in drop state in kettle, and record the volume of injection water;
(3) when hydrate is generated, close CH4Air relief valve, the first stop valve, the second stop valve and the 3rd stop valve, will Mixing CO2/N2 gases are filled with surge tank, and the volume of surge tank is 100~800ml;Wherein mix in CO2/N2 gases, CO2With N2 Volume ratio be 0.25~4;
(4) after hydrate is generated, the second stop valve is opened, by the CH in reactor for reaction4Gas is discharged, and uses wet type The CH that mass flow meter measurement is discharged4Amount, record volume are V2
(5) close the second stop valve, open the first stop valve, by the mixed gas in surge tank by gas inlet, Second three-way valve is filled with reactor, after the mixture pressure for being filled with reactor reaches 6MPa~12MPa, closes first section To valve, while it is 0 DEG C -2 DEG C to adjust circulator bath temperature;
(6) response time is 70h~200h, every the 2-6 hour component of gas chromatographic measurement gas, up to measuring CH4Content constant it is constant;
(7) work as CH4The temperature of circulator bath when content no longer changes, is raised, reacted hydrate is decomposed completely, is beaten The second stop valve is opened, volume V of the mixed gas produced after the decomposition of hydrate with wet type mass flow meter measurement remnants3, And with gas chromatographic measurement decompose after gas component, CH in the mixed gas for measuring4Gas proportion is yCH4, and pass through The constant CH measured with step (6)4Content compares, and obtains final exploitation of gas hydrates rate data;
(8) disposal data calculate, the CH of generation4Volume V of hydrateH
Wherein, ρ H are CH4 hydrate density;
Final displacement efficiency η:
Further, draw point used by the present invention is with different length type and demarcates the draw point of volume.
Further, injecting water to reactor used by the present invention is injected to reactor using hand pump.
Compared with prior art, the present invention has advantages below:
1 by the way of bottom is stirred continuously, and can accelerate methane hydrate generation, and stir during replacing again Gas-solid contact area can be updated, so as to improve methane recovery.
2 bottom opening mode, experiment complete after facilitate pouring out for quartz sand.
Description of the drawings
Fig. 1 be the present invention quickly generate and replacement exploitation of gas hydrate device structural representation.
Fig. 2 is the structure diagram of reactor.
Specific embodiment
Below in conjunction with the accompanying drawings and specific embodiment is described in further detail to present disclosure.
As shown in figure 1, a kind of gas hydrates generate the device with displacement, including mixing CO2/N2Gas cylinder 1, CH4Gas cylinder 29th, gas flowmeter 3, wet gas flow meter 23, surge tank 5, thermostatic water bath 4, reactor 10, circulator bath 14, hand pump 16 and feed liquor funnel 18;The hand pump 16 and reactor 10, surge tank 5, gas flowmeter 3, mix CO2/N2Gas cylinder 1 is sequentially Connection;The feed liquor funnel 18 is connected with hand pump 16;The thermostatic water bath 4 is arranged at outside the surge tank 5;The circulation Water-bath 14 is connected with reactor 10;The CH4Gas cylinder 29 is sequentially connected with wet gas flow meter 23, reactor 10.It is described anti- Kettle 10 is answered to include kettle 37, the gas inlet and outlet 9 positioned at kettle side, the kettle cover 36 being connected at the top of kettle 37, support The support 38 of 37 bottom of kettle, the agitator 11 and sand export 12 that are placed in 37 bottom of kettle;It is additionally provided with the kettle cover 36 and connects Pressure detecting interface 33, temperature detection interface 35 and inlet 34 to 37 inner chamber of kettle;Steel is provided with the inlet 34 Pin 8.The kettle cover 36 is connected by screw thread or flange with kettle 37.Also sense including the first temperature sensor 6, second temperature Device 13, first pressure sensor 19, second pressure sensor 20, data collecting instrument 21 and computer 22;First temperature sensing Device 6 is connected on the temperature survey interface of surge tank, and the second temperature sensor 13 is connected to the temperature survey of reactor 10 On interface;The first pressure sensor 19 connects the delivery outlet of surge tank 5,20 coupled reaction kettle of the second pressure sensor On 10 pressure detecting mouth;Above sensor connects data collecting instrument 21 by holding wire, and the data collecting instrument 21 connects Computer 22, shows the reading of each temperature and pressure on computer.Also include CH4Air relief valve 28, mixed gas CO2/N2Air relief valve 2, First hydralic pressure gauge 15, the second hydralic pressure gauge 26, the first three-way valve 32, the second three-way valve 31, the 3rd three-way valve 25, check valve 30, One stop valve 7, the second stop valve 24, the 3rd stop valve 27 and the 4th stop valve 17;The CH4Air relief valve 28 is arranged at CH4Gas cylinder On the pipeline connected between 29 and wet gas flow meter 23;Mixed gas CO2/N2Air relief valve 2 is arranged at mixed gas CO2/N2On the pipeline connected between gas cylinder 1 and gas flowmeter 3;First hydralic pressure gauge 15 be arranged at check valve 30 with it is hand On the pipeline of the connection of pump 16;Second hydralic pressure gauge 26 is arranged at the pipeline that the 3rd stop valve 27 is connected with the 3rd three-way valve 25 On;First three-way valve 32 is arranged on the pipeline of surge tank 5 and first pressure sensor 19, and is connected with reactor 10; Second three-way valve 31 is arranged on the first stop valve 7 and the pipeline of reactor air inlet 9, and with wet gas flow meter 23 Connection;3rd three-way valve 25 is arranged on the pipeline that the second stop valve 24 is connected with the second hydralic pressure gauge 26;The check valve 30 are arranged on the pipeline between hand pump 16 and reactor 10;First stop valve 7 is arranged at the first three-way valve 32 and On the pipeline of the connection of two three-way valve 31;Second stop valve 24 be arranged at wet gas flow meter 23 and the 3rd three-way valve 25 it Between connecting pipe on;3rd stop valve 27 is arranged at the second hydralic pressure gauge 26 and CH4Connecting pipe between air relief valve 28 On;4th stop valve 17 is arranged on the pipeline between hand pump 16 and feed liquor funnel 18.
The method that gas hydrates are quickly generated and replaced, comprises the steps:
(1) in reactor 10 a certain amount of quartz sand, evacuation is added to open CH4Air relief valve 28, the 3rd stop valve 27 With the second stop valve 24, CH is filled into reactor 104Be 12MPa to pressure, reaction is filled with the measurement of wet type mass flowmenter 23 CH in kettle 104Amount, record are filled with the CH in reactor 104Gas volume be V1, circulator bath 14 and thermostatic water bath 4 are opened, The temperature of setting circulator bath 14 and thermostatic water bath 4, while opening the agitating device 11 of reactor 10;
(2) open the 4th stop valve 17, be slowly injected into aqueous solution into reactor 10 using hand pump 16, keep water along Draw point 8 is interior at the uniform velocity to flow down in drop state to reactor 10, and records the volume of injection water;
(3) when hydrate is generated, close CH4Air relief valve 28, the first stop valve 7, the second stop valve 24 and the 3rd by Valve 27, will mixing CO2/N2 gas (CO2:N2=0.25~4) be filled with surge tank 5, the volume of surge tank 5 is 300ml;
(4) after hydrate is generated, the second stop valve 24 is opened, by the CH in reactor 10 for reaction4Gas is discharged, and is used in combination The CH that the measurement of wet type mass flowmenter 23 is discharged4Amount, record volume are V2
(5) the second stop valve 24 is closed, opens the first stop valve 7, the mixed gas in surge tank 5 are injected by gas Mouthful, the second three-way valve 31 be filled with reactor 10, after the mixture pressure for being filled with reactor 10 reaches 10MPa, close the One stop valve 7;
(6) response time is 70h~200h, every 6 hours component of gas chromatographic measurement gas, until measure CH4Content constant it is constant;
(7) work as CH4The temperature of circulator bath 14 when content no longer changes, is raised, reacted hydrate is decomposed completely, Open the second stop valve 24, the body of the mixed gas produced after the decomposition of hydrate with 23 measurement remnant of wet type mass flowmenter Product V3, and with gas chromatographic measurement decompose after gas component, CH in the mixed gas for measuring4Gas proportion is yCH4, and By the constant CH measured with step 64Content compares, and obtains final exploitation of gas hydrates rate data;
(8) disposal data calculate, the CH of generation4Volume V of hydrateH
Final displacement efficiency η:
Embodiment 1
In order to verify this method and device, two groups of contrast experiments are carried out respectively, 1 process of experiment is as follows:
(1) in reactor 10, add the quartz sand of 110.2g, evacuation to open CH4Air relief valve 28, the 3rd stop valve 27 With the second stop valve 24, CH is filled into reactor 104It is 12.3MPa to pressure, is filled with the measurement of wet type mass flowmenter 23 anti- Answer the CH in kettle 104Amount, record are filled with the CH in reactor 104Gas volume be V1For 185.6ml, circulator bath 14 is opened With thermostatic water bath 4, the temperature of circulator bath 14 is set as -4.0 DEG C and 1.0 DEG C of the temperature of thermostatic water bath 4.
(2) open the 4th stop valve 17, be slowly injected into aqueous solution into reactor 10 using hand pump 16, keep water along To in reactor 10 at the uniform velocity to flow down in drop state, and to record volume V of injection water be 50.3ml to draw point 8;
(3) when hydrate is generated, close CH4Air relief valve 28, the first stop valve 7, the second stop valve 24 and the 3rd by Valve 27, will mixing CO2/N2 gas (volume ratios CO2:N2=0.89 surge tank 5) is filled with, the volume of surge tank 5 is 300.6ml;
(4) after hydrate is generated, the second stop valve 24 is opened, by the CH in reactor 10 for reaction4Gas is discharged, and is used in combination The CH that the measurement of wet type mass flowmenter 23 is discharged4Amount, record volume are V2For 179.9ml.
(5) the second stop valve 24 is closed, opens the first stop valve 7, the mixed gas in surge tank 5 are injected by gas Mouthful, the second three-way valve 31 be filled with reactor 10, after the mixture pressure for being filled with reactor 10 reaches 10MPa, close the One stop valve 7, while it is 1 DEG C to adjust circulator bath temperature;
(6) response time is 102h, every 6 hours component of gas chromatographic measurement gas, until the CH for measuring4's Content constant is constant;
(7) work as CH4The temperature of circulator bath 14 when content no longer changes, is raised, reacted hydrate is decomposed completely, Open the second stop valve 24, the body of the mixed gas produced after the decomposition of hydrate with 23 measurement remnant of wet type mass flowmenter Product V3For 49.0ml, and after being decomposed with gas chromatographic measurement gas component, CH in the mixed gas for measuring4Gas proportion For yCH4For 0.059, and the constant CH by measuring with step 64Content compares, and obtains final exploitation of gas hydrates rate Data;
(8) disposal data calculate, the CH of generation4Volume V of hydrateH1For 33.32ml, it is that injection water 50.3ml is obtained Generation hydrate volume 62.874ml 53%
In formula:M(CH4·5.75H2O)For CH4The molal weight (119.5g/mol) of hydrate, ρ H are CH4Hydrate density is 0.918g/cm3
Calculate final displacement efficiency η1For 49.83%
Embodiment 2
(1) in reactor 10, add the quartz sand of 110.4g, evacuation to open CH4Air relief valve 28, the 3rd stop valve 27 With the second stop valve 24, CH is filled into reactor 104It is 12.6MPa to pressure, is filled with the measurement of wet type mass flowmenter 23 anti- Answer the CH in kettle 104Amount, record are filled with the CH in reactor 104Gas volume be V1For 189.3ml, circulator bath 14 is opened With thermostatic water bath 4, the temperature of circulator bath 14 is set as -4.0 DEG C and 1.0 DEG C of the temperature of thermostatic water bath 4, while opening reactor 10 agitating device 11.
(2) open the 4th stop valve 17, be slowly injected into aqueous solution into reactor 10 using hand pump 16, keep water along To in reactor 10 at the uniform velocity to flow down in drop state, and to record volume V of injection water be 50.6ml to draw point 8;
(3) when hydrate is generated, close CH4Air relief valve 28, the first stop valve 7, the second stop valve 24 and the 3rd by Valve 27, will mixing CO2/N2 gas (volume ratios CO2:N2=0.89 surge tank 5) is filled with, the volume of surge tank 5 is 300.4ml;
(4) after hydrate is generated, the second stop valve 24 is opened, by the CH in reactor 10 for reaction4Gas is discharged, and is used in combination The CH that the measurement of wet type mass flowmenter 23 is discharged4Amount, record volume are V2For 180.1ml.
(5) the second stop valve 24 is closed, opens the first stop valve 7, the mixed gas in surge tank 5 are injected by gas Mouthful, the second three-way valve 31 be filled with reactor 10, after the mixture pressure for being filled with reactor 10 reaches 10MPa, close the One stop valve 7, while it is 1 DEG C to adjust circulator bath temperature;
(6) response time is 87h, every 6 hours component of gas chromatographic measurement gas, until the CH for measuring4's Content constant is constant;
(7) work as CH4The temperature of circulator bath 14 when content no longer changes, is raised, reacted hydrate is decomposed completely, Open the second stop valve 24, the body of the mixed gas produced after the decomposition of hydrate with 23 measurement remnant of wet type mass flowmenter Product V3For 56.8ml, and after being decomposed with gas chromatographic measurement gas component, CH in the mixed gas for measuring4Gas proportion For yCH4For 0.053, and the constant CH by measuring with step 64Content compares, and obtains final exploitation of gas hydrates rate Data;
(8) disposal data calculate, the CH of generation4Volume V of hydrateH2For 53.44ml, inject water 50ml and obtain The 85% of hydrate volume 62.874ml of generation
In formula:M(CH4·5.75H2O)For CH4The molal weight (119.5g/mol) of hydrate, ρ H are CH4Hydrate density is 0.918g/cm3
Calculate final displacement efficiency η2For 67.36%
The CH that embodiment 1 is generated4Volume V of hydrateH1For 33.32ml, final displacement efficiency η1For 49.83%;Do not open Agitating device 12, remaining is identical with 1 condition of embodiment, the CH that embodiment 2 is generated4Volume V of hydrateH2For 53.44ml, finally Displacement efficiency η2For 67.36%.
Embodiment 3
Hydrate is carried out by this device and method to generate and the experiment of mixed gas replacement exploitation, experimentation is as follows:
(1) in reactor 10, add the quartz sand of 50.8g, evacuation to open CH4Air relief valve 28, the 3rd stop valve 27 With the second stop valve 24, CH is filled into reactor 104It is 12.9MPa to pressure, is filled with the measurement of wet type mass flowmenter 23 anti- Answer the CH in kettle 104Amount, record are filled with the CH in reactor 104Gas volume be V1For 221.4ml, circulator bath 14 is opened With thermostatic water bath 4, the temperature of circulator bath 14 is set as -4.0 DEG C and 0 DEG C of the temperature of thermostatic water bath 4, while opening reactor 10 Agitating device 11;
(2) open the 4th stop valve 17, be slowly injected into aqueous solution into reactor 10 using hand pump 16, keep water along To in reactor 10 at the uniform velocity to flow down in drop state, and to record volume V of injection water be 50.8ml to draw point 8;
(3) when hydrate is generated, close CH4Air relief valve 28, the first stop valve 7, the second stop valve 24 and the 3rd by Valve 27, will mixing CO2/N2 gas (volume ratios CO2:N2=surge tank 5 0.89) is filled with, the volume of surge tank 5 is 300.4ml;
(4) after hydrate is generated, the second stop valve 24 is opened, by the CH in reactor 10 for reaction4Gas is discharged, and is used in combination The CH that the measurement of wet type mass flowmenter 23 is discharged4Amount, record volume are V2For 212.0ml.
(5) the second stop valve 24 is closed, opens the first stop valve 7, the mixed gas in surge tank 5 are injected by gas Mouthful, the second three-way valve 31 be filled with reactor 10, after the mixture pressure for being filled with reactor 10 reaches 11MPa, close the One stop valve 7, while it is 0 DEG C to adjust circulator bath temperature;
(6) response time is 78h, every 6 hours component of gas chromatographic measurement gas, until the CH for measuring4's Content constant is constant;
(7) work as CH4The temperature of circulator bath 14 when content no longer changes, is raised, reacted hydrate is decomposed completely, Open the second stop valve 24, the body of the mixed gas produced after the decomposition of hydrate with 23 measurement remnant of wet type mass flowmenter Product V3For 52.73ml, and after being decomposed with gas chromatographic measurement gas component, CH in the mixed gas for measuring4Gas proportion For yCH4For 0.053, and the constant CH by measuring with step 64Content compares, and obtains final exploitation of gas hydrates rate Data;
(8) disposal data calculate, the CH of generation4Volume V of hydrateHFor 54.37ml, inject water 50ml and obtain The 86.47% of hydrate volume 62.87ml of generation
In formula:M(CH4·5.75H2O)For CH4The molal weight (119.5g/mol) of hydrate, ρ H are CH4Hydrate density is 0.918g/cm3
Final displacement efficiency η is calculated for 70.02%
Embodiment 4
Hydrate is carried out by this device and method to generate and the experiment of mixed gas replacement exploitation, experimentation is as follows:
(1) in reactor 10, add the quartz sand of 110.7g, evacuation to open CH4Air relief valve 28, the 3rd stop valve 27 With the second stop valve 24, CH is filled into reactor 104It is 14.6MPa to pressure, is filled with the measurement of wet type mass flowmenter 23 anti- Answer the CH in kettle 104Amount, record are filled with the CH in reactor 104Gas volume be V1For 175.5ml, circulator bath 14 is opened With thermostatic water bath 4, the temperature of circulator bath 14 is set as -4.0 DEG C and 1.0 DEG C of the temperature of thermostatic water bath 4, while opening reactor 10 agitating device 11;
(2) open the 4th stop valve 17, be slowly injected into aqueous solution into reactor 10 using hand pump 16, keep water along To in reactor 10 at the uniform velocity to flow down in drop state, and to record volume V of injection water be 70.2ml to draw point 8;
(3) when hydrate is generated, close CH4 air relief valve 28, the first stop valve 7, the second stop valve 24 and the 3rd by Valve 27, will mixing CO2/N2 gas (volume ratios CO2:N2=surge tank 5 0.89) is filled with, the volume of surge tank 5 is 300.3ml;
(4) after hydrate is generated, the second stop valve 24 is opened, the CH4 gases in reactor 10 for reaction is discharged, is used in combination The CH that the measurement of wet type mass flowmenter 23 is discharged4Amount, record volume are V2For 161.9ml.
(5) the second stop valve 24 is closed, opens the first stop valve 7, the mixed gas in surge tank 5 are injected by gas Mouth, the second three-way valve 31 are filled with reactor 10, after the mixture pressure for being filled with reactor 10 reaches 12.5MPa, are closed First stop valve 7, while it is 1.0 DEG C to adjust 14 temperature of circulator bath;
(6) response time is 67h, every 4 hours component of gas chromatographic measurement gas, until the CH for measuring4's Content constant is constant;
(7) work as CH4The temperature of circulator bath 14 when content no longer changes, is raised, reacted hydrate is decomposed completely, Open the second stop valve 24, the body of the mixed gas produced after the decomposition of hydrate with 23 measurement remnant of wet type mass flowmenter Product V3 be 70.9ml, and with gas chromatographic measurement decompose after gas component, CH in the mixed gas for measuring4Gas proportion For yCH4For 0.055, and the constant CH by measuring with step 64Content compares, and obtains final exploitation of gas hydrates rate Data;
(8) disposal data calculate, the CH of generation4Volume V of hydrateHFor 78.46ml, inject water 70ml and obtain The 89.12% of hydrate volume 88.04ml of generation;
In formula:M(CH4·5.75H2O)For CH4The molal weight (119.5g/mol) of hydrate, ρ H are CH4Hydrate density is 0.918g/cm3
Final displacement efficiency η is calculated for 71.26%

Claims (8)

1. a kind of gas hydrates generate the device with displacement, it is characterised in that including mixing CO2/N2Gas cylinder (1), CH4Gas Bottle (29), gas flowmeter (3), wet gas flow meter (23), surge tank (5), thermostatic water bath (4), reactor (10), circulation Water-bath (14), hand pump (16) and feed liquor funnel (18);
The hand pump (16) and reactor (10), surge tank (5), gas flowmeter (3), mix CO2/N2Gas cylinder (1) sequentially connects Connect;The feed liquor funnel (18) is connected with hand pump (16);It is outside that the thermostatic water bath (4) is arranged at the surge tank (5);Institute State circulator bath (14) to be connected with reactor (10);The CH4Gas cylinder (29) and wet gas flow meter (23), reactor (10) It is sequentially connected with.
2. device according to claim 1, it is characterised in that the reactor (10) is including kettle (37), positioned at kettle side The gas inlet and outlet (9) on side, the kettle cover (36) being connected at the top of kettle (37), the support for supporting kettle (37) bottom (38) agitator (11) and sand export (12) of kettle (37) bottom, are placed in;
Pressure detecting interface (33), the temperature detection interface (35) for being connected to kettle (37) inner chamber is additionally provided with the kettle cover (36) With inlet (34);Draw point (8) is provided with the inlet (34).
3. device according to claim 1, it is characterised in that the kettle cover (36) and kettle (37) are by screw thread or flange phase Connection.
4. device according to claim 1, it is characterised in that also including the first temperature sensor (6), second temperature sensor (13), first pressure sensor (19), second pressure sensor (20), data collecting instrument (21) and computer (22);Described first Temperature sensor (6) is connected on the temperature survey interface of surge tank, and the second temperature sensor (13) is connected to reactor (10) on temperature survey interface;The delivery outlet of the first pressure sensor (19) connection surge tank (5), the second pressure On the pressure detecting mouth of sensor (20) coupled reaction kettle (10);Above sensor connects data collecting instrument by holding wire (21), the data collecting instrument (21) connection computer (22), shows the reading of each temperature and pressure on computer.
5. device according to claim 1, it is characterised in that also including CH4Air relief valve (28), mixed gas CO2/N2Decompression Valve (2), the first hydralic pressure gauge (15), the second hydralic pressure gauge (26), the first three-way valve (32), the second three-way valve (31), the 3rd three-way valve (25), check valve (30), the first stop valve (7), the second stop valve (24), the 3rd stop valve (27) and the 4th stop valve (17); The CH4Air relief valve (28) is arranged at CH4On the pipeline being connected between gas cylinder (29) and wet gas flow meter (23);It is described mixed Close gas CO2/N2Air relief valve (2) is arranged at mixed gas CO2/N2The pipeline being connected between gas cylinder (1) and gas flowmeter (3) On;First hydralic pressure gauge (15) is arranged on the pipeline that check valve (30) is connected with hand pump (16);Second hydralic pressure gauge (26) it is arranged on the pipeline that the 3rd stop valve (27) is connected with the 3rd three-way valve (25);
First three-way valve (32) is arranged on the pipeline of surge tank (5) and first pressure sensor (19), and and reactor (10) connect;Second three-way valve (31) is arranged on the pipeline of the first stop valve (7) and reactor air inlet (9), and with Wet gas flow meter (23) connects;3rd three-way valve (25) is arranged at the second stop valve (24) and the second hydralic pressure gauge (26) On the pipeline of connection;The check valve (30) is arranged on the pipeline between hand pump (16) and reactor (10);Described first Stop valve (7) is arranged on the pipeline that the first three-way valve (32) and the second three-way valve (31) connect;Second stop valve (24) It is arranged on the connecting pipe between wet gas flow meter (23) and the 3rd three-way valve (25);3rd stop valve (27) sets It is placed in the second hydralic pressure gauge (26) and CH4On connecting pipe between air relief valve (28);4th stop valve (17) is arranged at handss Shake on the pipeline between pump (16) and feed liquor funnel (18).
6. a kind of gas hydrates generate the method with displacement, it is characterised in that add 15-20 DEG C of water to feed liquor funnel, Water is pressed into reactor by hand pump, water is entered in drop in the reactor of the band stirring for having been filled with methane gas, with this Quickly generate hydrate;Then, after hydrate is generated, enter line replacement reaction by being passed through substitution gas.
7. gas hydrates according to claim 6 generate the method with displacement, it is characterised in that the generation hydration The volume of the water used by thing, using hand pump to reactor inject water, according to injection water volume so as to obtain generate hydrate Water used volume.
8. gas hydrates according to claim 6 generate the method with displacement, it is characterised in that including following step Suddenly:
(1) in reactor quartz sand, evacuation is added to open CH4Air relief valve, the 3rd stop valve and the second stop valve, to reaction CH is filled in kettle4It is 4MPa~12MPa, the CH being filled with wet type mass flow meter measurement in reactor to pressure4Amount, record are filled with CH in reactor4Gas volume be V1, circulator bath and thermostatic water bath are opened, -7 DEG C of the temperature of circulator bath is set -- 2 DEG C, the temperature of thermostatic water bath is 0 DEG C -2 DEG C, while opening the agitating device of reactor;
(2) the 4th stop valve is opened, aqueous solution is injected into reactor using hand pump, keep water along draw point in reactor At the uniform velocity to flow down in drop state, and record the volume of injection water;
(3) when hydrate is generated, close CH4Air relief valve, the first stop valve, the second stop valve and the 3rd stop valve, will mixing CO2/N2 gases are filled with surge tank, and the volume of surge tank is 100~800ml;Wherein mix in CO2/N2 gases, CO2With N2Body Product is than being 0.25~4;
(4) after hydrate is generated, the second stop valve is opened, by the CH in reactor for reaction4Gas is discharged, and uses wet type quality The CH that effusion meter measurement is discharged4Amount, record volume are V2
(5) close the second stop valve, open the first stop valve, by the mixed gas in surge tank by gas inlet, second Three-way valve is filled with reactor, after the mixture pressure for being filled with reactor reaches 6MPa~12MPa, close first by Valve, while it is 0 DEG C -2 DEG C to adjust circulator bath temperature;
(6) response time is 70h~200h, every the 2-6 hour component of gas chromatographic measurement gas, up to the CH for measuring4 Content constant it is constant;
(7) work as CH4The temperature of circulator bath when content no longer changes, is raised, reacted hydrate is decomposed completely, open the Two stop valves, volume V of the mixed gas produced after the decomposition of hydrate with wet type mass flow meter measurement remnants3, it is used in combination The component of gas, CH in the mixed gas for measuring after gas chromatographic measurement decomposition4Gas proportion is yCH4, and by with step Suddenly the constant CH that (6) measure4Content compares, and obtains final exploitation of gas hydrates rate data;
(8) disposal data calculate, the CH of generation4Volume V of hydrateH
V H = V 1 - V 2 22.4 × M ( CH 4 · 5.75 H 2 O ) ρ H .
Wherein, ρ H are CH4 hydrate density;
Final displacement efficiency η:
η = V 1 - V 2 - y CH 4 × V 3 V 1 - V 2 .
CN201611111609.1A 2016-12-06 2016-12-06 Method and device for generating and replacing natural gas hydrate Active CN106544070B (en)

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