CN106544070B - Method and device for generating and replacing natural gas hydrate - Google Patents

Method and device for generating and replacing natural gas hydrate Download PDF

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CN106544070B
CN106544070B CN201611111609.1A CN201611111609A CN106544070B CN 106544070 B CN106544070 B CN 106544070B CN 201611111609 A CN201611111609 A CN 201611111609A CN 106544070 B CN106544070 B CN 106544070B
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reaction kettle
stop valve
hydrate
valve
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CN106544070A (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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    • 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
    • C10L3/08—Production of synthetic natural gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/04—Pressure vessels, e.g. autoclaves

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Abstract

The invention discloses a method and a device for generating and replacing natural gas hydrate. The device comprises a mixing deviceSynthetic CO2/N2Gas cylinder, CH4The system comprises a gas cylinder, a gas flowmeter, a wet gas mass flowmeter, a buffer tank, a constant-temperature water tank, a reaction kettle, a circulating water bath, a hand pump, a liquid inlet funnel, a data acquisition instrument and a computer; the method refers to a method for generating and replacing natural hydrate. The invention provides a method and a device for simply and quickly generating natural gas hydrate and replacing the natural gas hydrate, which overcome the defects of low generation content and low replacement efficiency of the natural gas hydrate in a porous medium.

Description

Method and device for generating and replacing natural gas hydrate
Technical Field
The invention relates to a natural gas hydrate generation method and an experimental device, in particular to a natural gas hydrate generation and replacement method and a device.
Background
Natural gas hydrate is the cleanest fossil fuel and has proven to be the most promising energy resource to replace petroleum and coal. Natural gas hydrate is an energy resource with twice the carbon content of all fossil fuels and is distributed around the world. The huge reserves attract people to pay attention to the exploitation of the natural gas hydrate, and the traditional natural gas exploitation method at present mainly comprises a depressurization method, a heat injection method, a chemical reagent method or a combination of the two methods. However, the above method for extracting natural gas hydrates causes collapse of geological formations, resulting in serious damage to the natural environment.
The existing method for exploiting natural gas hydrate by gas displacement mainly comprises CO2Displacement mining and mixing CO2/N2Displacement mining of CO2Methane recovery ratio mixed CO for displacement mining2/N2The methane recovery rate of displacement mining is low, so mixed CO is preferentially adopted2/N2And (4) gas displacement exploitation of natural gas hydrate.
At present, CO is mixed2/N2Gas displacement production of natural gas hydrates is mainly in the laboratory research phase. A certain amount of artificially generated natural gas hydrate is prepared before replacement, and in order to simulate the geological environment of the natural gas hydrate, the conventional method for generating the hydrate in a porous medium is generally adopted in experimental researchThe method is characterized in that the ice powder which is ground firstly is transferred into a reaction kettle, the ice powder is often caked or melted, and the natural gas hydrate obtained after filling methane gas has low content, so that the subsequent exploitation experiment is not facilitated.
Aiming at the defects of low content, long time consumption and the like of the natural gas hydrate generated in the multi-space medium, the invention provides a device and a method for quickly generating and exploiting the natural gas hydrate in the multi-space medium, which realize the quick generation of the natural gas hydrate and carry out CO mixing on the basis of generating the hydrate2/N2The gas replacement improves the replacement rate and the replacement rate, and has simple operation, simple structure and low cost.
Disclosure of Invention
The invention provides a method and a device for generating and replacing natural gas hydrate, which overcome the defects of low generation content and low replacement efficiency of the natural gas hydrate in a porous medium.
The invention is realized by the following technical scheme:
a natural gas hydrate generating and displacing device comprises mixed CO2/N2Gas cylinder, CH4The device comprises a gas cylinder, a gas flowmeter, a wet gas flowmeter, a buffer tank, a constant-temperature water tank, a reaction kettle, a circulating water bath, a hand pump and a liquid inlet funnel;
the hand pump, the reaction kettle, the buffer tank, the gas flowmeter and the mixed CO2/N2The gas cylinders are connected in sequence; the liquid inlet funnel is connected with the hand pump; the constant-temperature water tank is arranged outside the buffer tank; the circulating water bath is connected with the reaction kettle; the CH4The gas cylinder is connected with the wet gas flowmeter and the reaction kettle in sequence.
In the device, the reaction kettle comprises a kettle body, a gas inlet and a gas outlet which are positioned on the side edge of the kettle body, a kettle cover which is connected and arranged on the top of the kettle body, a bracket for supporting the bottom of the kettle body, a stirrer arranged at the bottom of the kettle body and a sand outlet;
the kettle cover is also provided with a pressure detection interface, a temperature detection interface and a liquid inlet which are connected to the inner cavity of the kettle body; a steel needle is arranged in the liquid inlet.
In the device, the kettle cover is connected with the kettle body through threads or flanges.
The device also comprises a first temperature sensor, a second temperature sensor, a first pressure sensor, a second pressure sensor, a data acquisition instrument and a computer; the first temperature sensor is connected to the temperature measuring interface of the buffer tank, and the second temperature sensor is connected to the temperature measuring interface of the reaction kettle; the first pressure sensor is connected with the output port of the buffer tank, and the second pressure sensor is connected with the pressure detection port of the reaction kettle; the sensors are connected with a data acquisition instrument through signal wires, the data acquisition instrument is connected with a computer, and the computer displays the readings of the temperatures and the pressures.
In the above device, CH is further included4Pressure reducing valve, mixed gas CO2/N2The hydraulic control system comprises a pressure reducing valve, a first hydraulic gauge, a second hydraulic gauge, a first three-way valve, a second three-way valve, a third three-way valve, a one-way valve, a first stop valve, a second stop valve, a third stop valve and a fourth stop valve; the CH4The pressure reducing valve is arranged on the CH4The gas cylinder is connected with the wet gas flowmeter through a pipeline; the mixed gas CO2/N2The pressure reducing valve is arranged on the mixed gas CO2/N2The pipeline is connected between the gas cylinder and the gas flowmeter; the first hydraulic gauge is arranged on a pipeline connecting the one-way valve and the hand pump; the second hydraulic gauge is arranged on a pipeline connecting the third stop valve and the third three-way valve;
the first three-way valve is arranged on a pipeline between the buffer tank and the first pressure sensor and is connected with the reaction kettle; the second three-way valve is arranged on the pipeline between the first stop valve and the gas inlet of the reaction kettle and is connected with the wet gas flowmeter; the third three-way valve is arranged on a pipeline connecting the second stop valve and the second hydraulic gauge; the one-way valve is arranged on a pipeline between the hand pump and the reaction kettle; the first stop valve is arranged on a pipeline connected with the first three-way valve and the second three-way valve; the second stop valve is arranged on a connecting pipeline between the wet gas flowmeter and the third three-way valve; the third stop valve is arranged between the second hydraulic gauge and the CH4Pressure reducing valveThe connecting pipeline between the two pipes; the fourth stop valve sets up on the pipeline between hand pump and feed liquor funnel.
A method for generating and replacing natural gas hydrate comprises adding water of 15-20 deg.C into a liquid inlet funnel, pressing water into a reaction kettle by a hand pump to make water drop-wise enter the reaction kettle filled with methane gas and with stirring to generate hydrate rapidly; then, after the hydrate is formed, a displacement reaction is carried out by introducing a displacement gas.
And further, injecting water into the reaction kettle by using a hand pump according to the volume of the water used for generating the hydrate, and obtaining the volume of the water used for generating the hydrate according to the volume of the injected water.
Further, the method comprises the following steps:
(1) adding quartz sand into the reaction kettle, vacuumizing, and opening CH4A pressure reducing valve, a third stop valve and a second stop valve, and CH is filled in the reaction kettle4Measuring CH filled in the reaction kettle by a wet mass flowmeter until the pressure is 4-12 MPa4Measuring, recording CH filled in the reaction kettle4Has a gas volume of V1Opening a circulating water bath and a constant-temperature water tank, setting the temperature of the circulating water bath to be-7-2 ℃, and the temperature of the constant-temperature water tank to be 0-2 ℃, and simultaneously opening a stirring device of the reaction kettle;
(2) opening a fourth stop valve, injecting water solution into the reactor by using a hand pump, keeping water flowing into the reaction kettle along the steel needle in a liquid drop state at a constant speed, and recording the volume of the injected water;
(3) closing CH when hydrate is formed4The mixed CO2/N2 gas is filled into a buffer tank, and the volume of the buffer tank is 100-800 ml; wherein CO is mixed in CO2/N2 gas2And N2The volume ratio of (A) to (B) is 0.25-4;
(4) after the hydrate is generated, the second stop valve is opened, and the CH for reaction is in the reactor4Gas exhaust and measurement of exhausted CH with a wet mass flow meter4Volume, recording volume V2；
(5) Closing the second stop valve, opening the first stop valve, filling the mixed gas in the buffer tank into the reaction kettle through the gas filling port and the second three-way valve, closing the first stop valve when the pressure of the mixed gas filled into the reaction kettle reaches 6-12 MPa, and simultaneously adjusting the temperature of the circulating water bath to 0-2 ℃;
(6) the reaction time is 70 h-200 h, and the gas components are measured by gas chromatography every 2-6 hours until the measured CH4The content of (A) is constant;
(7) when CH is present4When the content is not changed any more, the temperature of the circulating water bath is raised to completely decompose the reacted hydrate, the second stop valve is opened, and the volume V of the mixed gas generated after the decomposition of the residual hydrate is measured by a wet mass flowmeter3And measuring the components of the decomposed gas by gas chromatography to obtain CH in the mixed gas4Proportion of gas yCH4And by constant CH determined in step (6)4Comparing the contents to obtain final natural gas hydrate production rate data;
(8) sorting data and calculating generated CH4Volume V of hydrateH：
Figure BDA0001172615270000051
Wherein rho H is CH4 hydrate density;
final substitution efficiency η:
Figure BDA0001172615270000052
further, the steel needle used in the present invention is a steel needle having different length types and calibrated volume.
Furthermore, the water used for injecting into the reaction kettle is injected into the reaction kettle by a hand pump.
Compared with the prior art, the invention has the following advantages:
1, the mode of continuously stirring at the bottom is adopted, the generation of methane hydrate can be accelerated, and the gas-solid contact area can be updated by stirring in the replacement process, so that the methane recovery rate is improved.
2, the bottom is opened, so that the quartz sand can be poured out conveniently after the experiment is finished.
Drawings
Fig. 1 is a schematic structural diagram of the device for rapidly generating and replacing and exploiting natural gas hydrate.
FIG. 2 is a schematic diagram of the structure of a reaction vessel.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
As shown in figure 1, a natural gas hydrate generation and replacement device comprises mixed CO2/N2Gas cylinder 1, CH4The device comprises a gas cylinder 29, a gas flowmeter 3, a wet gas flowmeter 23, a buffer tank 5, a constant-temperature water tank 4, a reaction kettle 10, a circulating water bath 14, a hand pump 16 and a liquid inlet funnel 18; the hand pump 16, the reaction kettle 10, the buffer tank 5, the gas flowmeter 3 and the mixed CO2/N2The gas cylinders 1 are connected in sequence; the liquid inlet funnel 18 is connected with a hand pump 16; the constant-temperature water tank 4 is arranged outside the buffer tank 5; the circulating water bath 14 is connected with the reaction kettle 10; the CH4The gas cylinder 29 is connected to the wet gas flowmeter 23 and the reaction vessel 10 in this order. The reaction kettle 10 comprises a kettle body 37, a gas inlet and outlet 9 positioned on the side edge of the kettle body, a kettle cover 36 connected and arranged on the top of the kettle body 37, a bracket 38 for supporting the bottom of the kettle body 37, a stirrer 11 arranged at the bottom of the kettle body 37 and a sand outlet 12; the kettle cover 36 is also provided with a pressure detection interface 33, a temperature detection interface 35 and a liquid inlet 34 which are connected to the inner cavity of the kettle body 37; a steel needle 8 is arranged in the liquid inlet 34. The kettle cover 36 and the kettle body 37 are connected through threads or flanges. The device also comprises a first temperature sensor 6, a second temperature sensor 13, a first pressure sensor 19, a second pressure sensor 20, a data acquisition instrument 21 and a computer 22; the first temperature sensor 6 is connected to a temperature measuring interface of the buffer tank, and the second temperature sensor 13 is connected to a temperature measuring interface of the reaction kettle 10; the first pressure sensor 19 is connected with the output port of the buffer tank 5, and the second pressure sensor 20 is connected with the reaction kettle 10The pressure detection port; the sensors are connected with a data acquisition instrument 21 through signal lines, the data acquisition instrument 21 is connected with a computer 22, and the computer displays the readings of the temperatures and the pressures. And also includes CH4 Pressure reducing valve 28, mixed gas CO2/N2The pressure reducing valve 2, the first hydraulic pressure gauge 15, the second hydraulic pressure gauge 26, the first three-way valve 32, the second three-way valve 31, the third three-way valve 25, the check valve 30, the first stop valve 7, the second stop valve 24, the third stop valve 27, and the fourth stop valve 17; the CH4A pressure reducing valve 28 is arranged at CH4The gas cylinder 29 and the wet gas flowmeter 23; the mixed gas CO2/N2The pressure reducing valve 2 is arranged in the mixed gas CO2/N2The pipeline is connected between the gas cylinder 1 and the gas flowmeter 3; the first hydraulic gauge 15 is arranged on a pipeline connecting the one-way valve 30 and the hand pump 16; the second hydraulic pressure gauge 26 is arranged on a pipeline connecting the third stop valve 27 and the third three-way valve 25; the first three-way valve 32 is arranged on the pipeline between the buffer tank 5 and the first pressure sensor 19 and is connected with the reaction kettle 10; the second three-way valve 31 is arranged on the pipeline between the first stop valve 7 and the reaction kettle gas inlet 9 and is connected with the wet gas flowmeter 23; the third three-way valve 25 is arranged on a pipeline connecting the second stop valve 24 and the second hydraulic pressure meter 26; the check valve 30 is arranged on a pipeline between the hand pump 16 and the reaction kettle 10; the first stop valve 7 is arranged on a pipeline connected with the first three-way valve 32 and the second three-way valve 31; the second stop valve 24 is arranged on a connecting pipeline between the wet gas flowmeter 23 and the third three-way valve 25; the third stop valve 27 is disposed between the second hydraulic gauge 26 and the CH4The connecting pipe between the pressure reducing valves 28; the fourth stop valve 17 is arranged on the pipeline between the hand pump 16 and the liquid inlet funnel 18.
The method for quickly generating and replacing the natural gas hydrate comprises the following steps:
(1) adding a certain amount of quartz sand into the reaction kettle 10, vacuumizing, and opening CH4A pressure reducing valve 28, a third stop valve 27 and a second stop valve 24, and CH is filled in the reaction kettle 104Until the pressure is 12MPa, measuring the pressure in the reaction kettle 10 by a wet mass flowmeter 23CH4Measuring, recording CH filled in the reaction vessel 104Has a gas volume of V1Opening the circulating water bath 14 and the constant-temperature water tank 4, setting the temperature of the circulating water bath 14 and the constant-temperature water tank 4, and simultaneously opening the stirring device 11 of the reaction kettle 10;
(2) opening a fourth stop valve 17, slowly injecting water solution into the reaction kettle 10 by using a hand-operated pump 16, keeping water flowing into the reaction kettle 10 along the steel needle 8 at a constant speed in a liquid drop state, and recording the volume of the injected water;
(3) closing CH when hydrate is formed4A pressure reducing valve 28, a first stop valve 7, a second stop valve 24 and a third stop valve 27, wherein the buffer tank 5 is filled with mixed CO2/N2 gas (CO2: N2 is 0.25-4), and the volume of the buffer tank 5 is 300 ml;
(4) after the hydrate is generated, the second stop valve 24 is opened, and the CH for reaction is filled in the reaction kettle 104Gas is discharged and the discharged CH is measured by a wet mass flow meter 234Volume, recording volume V2。
(5) Closing the second cut-off valve 24, opening the first cut-off valve 7, filling the mixed gas in the buffer tank 5 into the reaction kettle 10 through the gas injection port and the second three-way valve 31, and closing the first cut-off valve 7 when the pressure of the mixed gas filled into the reaction kettle 10 reaches 10 MPa;
(6) the reaction time is 70 h-200 h, and the gas components are measured by gas chromatography every 6 hours until the measured CH4The content of (A) is constant;
(7) when CH is present4When the content is not changed any more, the temperature of the circulating water bath 14 is raised to completely decompose the hydrate after the reaction, the second stop valve 24 is opened, and the volume V of the mixed gas generated after the decomposition of the residual hydrate is measured by the wet mass flow meter 233And measuring the components of the decomposed gas by gas chromatography to obtain CH in the mixed gas4The proportion of gas is yCH4And by constant CH measured in step 64Comparing the contents to obtain final natural gas hydrate production rate data;
(8) sorting data and calculating generated CH4Volume V of hydrateH：
Figure BDA0001172615270000081
Final substitution efficiency η:
Figure BDA0001172615270000082
example 1
In order to verify the method and the device, two sets of comparative experiments were performed, respectively, and the experiment 1 process was as follows:
(1) 110.2g of quartz sand is added into a reaction kettle 10, vacuum pumping is carried out, CH is opened4A pressure reducing valve 28, a third stop valve 27 and a second stop valve 24, and CH is filled in the reaction kettle 104Until the pressure became 12.3MPa, CH filled in the reaction vessel 10 was measured by a wet mass flow meter 234Measuring, recording CH filled in the reaction vessel 104Has a gas volume of V1The volume was 185.6ml, the circulating water bath 14 and the constant temperature water tank 4 were opened, and the temperature of the circulating water bath 14 was set to-4.0 ℃ and the temperature of the constant temperature water tank 4 was set to 1.0 ℃.
(2) Opening a fourth stop valve 17, slowly injecting water solution into the reaction kettle 10 by using a hand pump 16, keeping water flowing into the reaction kettle 10 along the steel needle 8 at a constant speed in a liquid drop state, and recording the volume V of the injected water as 50.3 ml;
(3) closing CH when hydrate is formed4A pressure reducing valve 28, a first stop valve 7, a second stop valve 24 and a third stop valve 27, wherein the buffer tank 5 is filled with mixed CO2/N2 gas (the volume ratio of CO2: N2 is 0.89), and the volume of the buffer tank 5 is 300.6 ml;
(4) after the hydrate is generated, the second stop valve 24 is opened, and the CH which is reacted in the reaction kettle 10 is4Gas is discharged and the discharged CH is measured by a wet mass flow meter 234Volume, recording volume V2179.9 ml.
(5) Closing the second stop valve 24, opening the first stop valve 7, filling the mixed gas in the buffer tank 5 into the reaction kettle 10 through the gas injection port and the second three-way valve 31, closing the first stop valve 7 when the pressure of the mixed gas filled into the reaction kettle 10 reaches 10MPa, and simultaneously adjusting the temperature of the circulating water bath to 1 ℃;
(6) the reaction time was 102h and the gas composition was measured by gas chromatography every 6 hours until the CH was measured4The content of (A) is constant;
(7) when CH is present4When the content is not changed any more, the temperature of the circulating water bath 14 is raised to completely decompose the hydrate after the reaction, the second stop valve 24 is opened, and the volume V of the mixed gas generated after the decomposition of the residual hydrate is measured by the wet mass flow meter 23349.0ml, and the composition of the decomposed gas was measured by gas chromatography to determine CH in the mixed gas4The proportion of gas is yCH4Is 0.059 and passes the constant CH measured in step 64Comparing the contents to obtain final natural gas hydrate production rate data;
(8) sorting data and calculating generated CH4Volume V of hydrateH133.32ml, 53% of the volume of the formed hydrate obtained by injecting 50.3ml of water, 62.874ml
Figure BDA0001172615270000101
In the formula: m(CH4·5.75H2O)Is CH4Molar mass of hydrate (119.5g/mol) (. rho.H) is CH4The density of the hydrate is 0.918g/cm3；
Calculating the final substitution efficiency eta1Is 49.83 percent
Figure BDA0001172615270000102
Example 2
(1) Adding 110.4g of quartz sand into the reaction kettle 10, vacuumizing, and opening CH4A pressure reducing valve 28, a third stop valve 27 and a second stop valve 24, and CH is filled in the reaction kettle 104Until the pressure became 12.6MPa, CH filled in the reaction vessel 10 was measured by a wet mass flow meter 234Measuring, recording CH filled in the reaction vessel 104Has a gas volume of V1189.3ml, the circulating water bath was opened14 and a constant temperature water tank 4, setting the temperature of the circulating water bath 14 to be-4.0 ℃ and the temperature of the constant temperature water tank 4 to be 1.0 ℃, and simultaneously opening a stirring device 11 of the reaction kettle 10.
(2) Opening a fourth stop valve 17, slowly injecting water solution into the reaction kettle 10 by using a hand pump 16, keeping water flowing into the reaction kettle 10 along the steel needle 8 at a constant speed in a liquid drop state, and recording the volume V of the injected water as 50.6 ml;
(3) closing CH when hydrate is formed4A pressure reducing valve 28, a first stop valve 7, a second stop valve 24 and a third stop valve 27, wherein the buffer tank 5 is filled with mixed CO2/N2 gas (the volume ratio of CO2: N2 is 0.89), and the volume of the buffer tank 5 is 300.4 ml;
(4) after the hydrate is generated, the second stop valve 24 is opened, and the CH for reaction is filled in the reaction kettle 104Gas is discharged and the discharged CH is measured by a wet mass flow meter 234Volume, recorded volume, V2It was 180.1 ml.
(5) Closing the second stop valve 24, opening the first stop valve 7, filling the mixed gas in the buffer tank 5 into the reaction kettle 10 through the gas injection port and the second three-way valve 31, closing the first stop valve 7 when the pressure of the mixed gas filled into the reaction kettle 10 reaches 10MPa, and simultaneously adjusting the temperature of the circulating water bath to 1 ℃;
(6) the reaction time was 87h and the gas composition was measured by gas chromatography every 6 hours until the CH was determined4The content of (A) is constant;
(7) when CH is present4When the content is not changed any more, the temperature of the circulating water bath 14 is raised to completely decompose the hydrate after the reaction, the second stop valve 24 is opened, and the volume V of the mixed gas generated after the decomposition of the residual hydrate is measured by the wet mass flow meter 23356.8ml, and the composition of the decomposed gas was measured by gas chromatography to determine CH in the mixed gas4The proportion of gas is yCH4Is 0.053 and passes the constant CH measured in step 64Comparing the contents to obtain final natural gas hydrate production rate data;
(8) sorting data and calculating generated CH4Volume V of hydrateH253.44ml, and 50ml of water was injected to obtain raw materialThe volume of the formed hydrate is 85 percent of that of 62.874ml
Figure BDA0001172615270000111
In the formula: m(CH4·5.75H2O)Is CH4Molar mass of hydrate (119.5g/mol) (. rho.H) is CH4The density of the hydrate is 0.918g/cm3；
Calculating the final substitution efficiency eta2Is 67.36 percent
Figure BDA0001172615270000112
CH generated in example 14Volume V of hydrateH133.32ml, final replacement efficiency η149.83 percent; CH produced in example 2 under the same conditions as in example 1 except that the stirring apparatus 12 was not opened4Volume V of hydrateH253.44ml, final replacement efficiency η2The content was 67.36%.
Example 3
The device and the method are used for carrying out hydrate generation and mixed gas displacement exploitation experiments, and the experimental process is as follows:
(1) 50.8g of quartz sand is added into a reaction kettle 10, vacuum pumping is carried out, CH is opened4A pressure reducing valve 28, a third stop valve 27 and a second stop valve 24, and CH is filled in the reaction kettle 104Until the pressure became 12.9MPa, CH filled in the reaction vessel 10 was measured by a wet mass flow meter 234Measuring, recording CH filled in the reaction vessel 104Has a gas volume of V1221.4ml, opening the circulating water bath 14 and the constant-temperature water tank 4, setting the temperature of the circulating water bath 14 to be-4.0 ℃ and the temperature of the constant-temperature water tank 4 to be 0 ℃, and simultaneously opening the stirring device 11 of the reaction kettle 10;
(2) opening a fourth stop valve 17, slowly injecting water solution into the reaction kettle 10 by using a hand pump 16, keeping water flowing into the reaction kettle 10 along the steel needle 8 at a constant speed in a liquid drop state, and recording the volume V of the injected water as 50.8 ml;
(3) closing CH when hydrate is formed4The pressure reducing valve 28, the first stop valve 7, the second stop valve 24 and the third stop valve 27 mix the CO2/N2 gas (volume ratio CO)2:N20.89) is filled into the buffer tank 5, and the volume of the buffer tank 5 is 300.4 ml;
(4) after the hydrate is generated, the second stop valve 24 is opened, and the CH which is reacted in the reaction kettle 10 is4Gas is discharged and the discharged CH is measured by a wet mass flow meter 234Volume, recording volume V2212.0 ml.
(5) Closing the second stop valve 24, opening the first stop valve 7, filling the mixed gas in the buffer tank 5 into the reaction kettle 10 through the gas injection port and the second three-way valve 31, closing the first stop valve 7 when the pressure of the mixed gas filled into the reaction kettle 10 reaches 11MPa, and simultaneously adjusting the temperature of the circulating water bath to be 0 ℃;
(6) the reaction time was 78h and the gas composition was measured by gas chromatography every 6 hours until the CH was determined4The content of (A) is constant;
(7) when CH is present4When the content is not changed any more, the temperature of the circulating water bath 14 is raised to completely decompose the hydrate after the reaction, the second stop valve 24 is opened, and the volume V of the mixed gas generated after the decomposition of the residual hydrate is measured by the wet mass flow meter 23352.73ml, and measuring the composition of the decomposed gas by gas chromatography to obtain CH in the mixed gas4The gas accounts for yCH4Is 0.053 and passes the constant CH measured in step 64Comparing the contents to obtain final natural gas hydrate production rate data;
(8) sorting data and calculating generated CH4Volume V of hydrateH54.37ml, 86.47% of the volume of the hydrate formed when 50ml of water was injected, 62.87ml
Figure BDA0001172615270000131
In the formula: m(CH4·5.75H2O)Is CH4Molar mass of hydrate (119.5g/mol) (. rho.H) is CH4The density of the hydrate is 0.918g/cm3；
The final replacement efficiency eta was calculated to be 70.02%
Figure BDA0001172615270000132
Example 4
The device and the method are used for carrying out hydrate generation and mixed gas displacement exploitation experiments, and the experimental process is as follows:
(1) 110.7g of quartz sand was charged into the reaction vessel 10, and vacuum-pumping was performed to turn on CH4A pressure reducing valve 28, a third stop valve 27 and a second stop valve 24, and CH is filled in the reaction kettle 104Until the pressure became 14.6MPa, CH charged in the reaction vessel 10 was measured by a wet mass flow meter 234Measuring, recording CH filled in the reaction vessel 104Has a gas volume of V1Opening the circulating water bath 14 and the constant-temperature water tank 4 when the volume is 175.5ml, setting the temperature of the circulating water bath 14 to be minus 4.0 ℃ and the temperature of the constant-temperature water tank 4 to be 1.0 ℃, and simultaneously opening the stirring device 11 of the reaction kettle 10;
(2) opening a fourth stop valve 17, slowly injecting water solution into the reaction kettle 10 by using a hand pump 16, keeping water flowing into the reaction kettle 10 along the steel needle 8 at a constant speed in a liquid drop state, and recording the volume V of the injected water as 70.2 ml;
(3) when hydrate is generated, the CH4 pressure reducing valve 28, the first stop valve 7, the second stop valve 24 and the third stop valve 27 are closed, and mixed CO2/N2 gas (volume ratio CO)2:N20.89) is filled into the buffer tank 5, and the volume of the buffer tank 5 is 300.3 ml;
(4) after the hydrate is formed, the second cut-off valve 24 is opened, the CH4 gas which is reacted in the reaction vessel 10 is discharged, and the discharged CH is measured by the wet mass flow meter 234Volume, recorded volume, V2161.9 ml.
(5) Closing the second stop valve 24, opening the first stop valve 7, filling the mixed gas in the buffer tank 5 into the reaction kettle 10 through the gas injection port and the second three-way valve 31, closing the first stop valve 7 when the pressure of the mixed gas filled into the reaction kettle 10 reaches 12.5MPa, and simultaneously adjusting the temperature of the circulating water bath 14 to be 1.0 ℃;
(6) inverse directionThe gas composition was measured by gas chromatography at 4 hour intervals for a period of 67 hours until the CH was measured4The content of (A) is constant;
(7) when CH is generated4When the content no longer changed, the temperature of the circulating water bath 14 was raised to completely decompose the hydrate after the reaction, the second cut-off valve 24 was opened, the volume V3 of the mixed gas produced after the decomposition of the remaining hydrate was measured to be 70.9ml by the wet mass flow meter 23, and the composition of the gas after the decomposition was measured by gas chromatography to measure CH in the mixed gas4The proportion of gas is yCH4Is 0.055 and by comparison with the constant CH determined in step 64Comparing the contents to obtain final natural gas hydrate production rate data;
(8) sorting data and calculating generated CH4Volume V of hydrateH78.46ml, 89.12% of the resulting hydrate volume 88.04ml obtained for 70ml of water injected;
Figure BDA0001172615270000151
in the formula: m(CH4·5.75H2O)Is CH4Molar mass of hydrate (119.5g/mol) (. rho.H) is CH4The density of the hydrate is 0.918g/cm3；
The final replacement efficiency eta was calculated to be 71.26%
Figure BDA0001172615270000152

Claims (2)

1. The device for generating and replacing the natural gas hydrate is characterized by comprising CO mixture2/N2Gas cylinder (1), CH4The device comprises a gas cylinder (29), a gas flowmeter (3), a wet gas flowmeter (23), a buffer tank (5), a constant-temperature water tank (4), a reaction kettle (10), a circulating water bath (14), a hand pump (16) and a liquid inlet funnel (18);
the hand pump (16), the reaction kettle (10), the buffer tank (5), the gas flowmeter (3) and the mixed CO2/N2The gas cylinders (1) are connected in sequence; what is needed isThe liquid inlet funnel (18) is connected with a hand pump (16); the constant-temperature water tank (4) is arranged outside the buffer tank (5); the circulating water bath (14) is connected with the reaction kettle (10); the CH4The gas cylinder (29) is connected with the wet gas flowmeter (23) and the reaction kettle (10) in sequence;
the reaction kettle (10) comprises a kettle body (37), a reaction kettle air inlet (9) positioned on the side edge of the kettle body, a kettle cover (36) connected and arranged on the top of the kettle body (37), a support (38) for supporting the bottom of the kettle body (37), a stirrer (11) arranged at the bottom of the kettle body (37) and a sand outlet (12);
the kettle cover (36) is also provided with a pressure detection interface (33), a temperature detection interface (35) and a liquid inlet (34) which are connected to the inner cavity of the kettle body (37); a steel needle (8) is arranged in the liquid inlet (34);
the kettle cover (36) is connected with the kettle body (37) through threads or flanges;
the device also comprises a first temperature sensor (6), a second temperature sensor (13), a first pressure sensor (19), a second pressure sensor (20), a data acquisition instrument (21) and a computer (22); the first temperature sensor (6) is connected to a temperature measuring interface of the buffer tank, and the second temperature sensor (13) is connected to a temperature measuring interface of the reaction kettle (10); the first pressure sensor (19) is connected with an output port of the buffer tank (5), and the second pressure sensor (20) is connected with a pressure detection port of the reaction kettle (10); the sensors are connected with a data acquisition instrument (21) through signal lines, the data acquisition instrument (21) is connected with a computer (22), and the computer displays the readings of all temperatures and pressures;
and also includes CH4Pressure reducing valve (28) and mixed gas CO2/N2The hydraulic control system comprises a pressure reducing valve (2), a first hydraulic pressure meter (15), a second hydraulic pressure meter (26), a first three-way valve (32), a second three-way valve (31), a third three-way valve (25), a one-way valve (30), a first stop valve (7), a second stop valve (24), a third stop valve (27) and a fourth stop valve (17); the CH4A pressure reducing valve (28) is arranged at CH4A pipeline connected between the gas cylinder (29) and the wet gas flowmeter (23); the mixed gas CO2/N2The pressure reducing valve (2) is arranged on the mixed gas CO2/N2On the pipeline connected between the gas cylinder (1) and the gas flowmeter (3)(ii) a The first hydraulic gauge (15) is arranged on a pipeline connecting the one-way valve (30) and the hand pump (16); the second hydraulic gauge (26) is arranged on a pipeline connected with the third stop valve (27) and the third three-way valve (25);
the first three-way valve (32) is arranged on the pipelines of the buffer tank (5) and the first pressure sensor (19) and is connected with the reaction kettle (10); the second three-way valve (31) is arranged on the pipeline of the first stop valve (7) and the reaction kettle gas inlet (9) and is connected with the wet gas flowmeter (23); the third three-way valve (25) is arranged on a pipeline connecting the second stop valve (24) and the second hydraulic pressure meter (26); the check valve (30) is arranged on a pipeline between the hand pump (16) and the reaction kettle (10); the first stop valve (7) is arranged on a pipeline connected with the first three-way valve (32) and the second three-way valve (31); the second stop valve (24) is arranged on a connecting pipeline between the wet gas flowmeter (23) and the third three-way valve (25); the third stop valve (27) is arranged between the second hydraulic gauge (26) and the CH4A connecting pipeline between the pressure reducing valves (28); the fourth stop valve (17) is arranged on a pipeline between the hand pump (16) and the liquid inlet funnel (18);
adding water with the temperature of 15-20 ℃ into a liquid inlet funnel, pressing water into a reaction kettle through a hand pump, and allowing the water to enter the reaction kettle filled with methane gas in a liquid drop manner and provided with a stirrer, so as to quickly generate a hydrate; then, after generating the hydrate, carrying out displacement reaction by introducing displacement gas;
and the volume of the water for generating the hydrate is obtained by adopting a hand pump to inject water into the reaction kettle according to the volume of the injected water.
2. The natural gas hydrate generation and replacement device according to claim 1, wherein the natural gas hydrate generation and replacement method comprises the following specific steps:
(1) adding quartz sand into the reaction kettle, vacuumizing, and opening CH4A pressure reducing valve, a third stop valve and a second stop valve, and CH is filled in the reaction kettle4Until the pressure is 4-12 MPa, a wet mass flowmeter is usedMeasuring CH filled in the reaction kettle4Measuring, recording CH filled in the reaction kettle4Has a gas volume of V1Opening a circulating water bath and a constant-temperature water tank, setting the temperature of the circulating water bath to be-7-2 ℃, and the temperature of the constant-temperature water tank to be 0-2 ℃, and simultaneously opening a stirring device of the reaction kettle;
(2) opening a fourth stop valve, injecting water solution into the reactor by using a hand pump, keeping water flowing into the reaction kettle along a steel needle in a liquid drop state at a constant speed, and recording the volume of the injected water;
(3) closing CH when hydrate is formed4A pressure reducing valve, a first stop valve, a second stop valve and a third stop valve for mixing CO2/N2Filling the gas into a buffer tank, wherein the volume of the buffer tank is 100-800 ml; wherein CO is mixed2/N2In the gas, CO2And N2The volume ratio of (A) to (B) is 0.25-4;
(4) after the hydrate is generated, the second stop valve is opened, and the CH for reaction is in the reactor4Gas exhaust and wet mass flow meter measurement of exhausted CH4Volume, recording volume V2；
(5) Closing the second stop valve, opening the first stop valve, filling the mixed gas in the buffer tank into the reaction kettle through the gas filling port and the second three-way valve, closing the first stop valve when the pressure of the mixed gas filled into the reaction kettle reaches 6 MPa-12 MPa, and simultaneously adjusting the temperature of the circulating water bath to 0-2 ℃;
(6) the reaction time is 70 h-200 h, and the gas components are measured by gas chromatography every 2-6 hours until the measured CH4The content of (A) is constant;
(7) when CH is present4When the content is not changed any more, the temperature of the circulating water bath is raised to completely decompose the reacted hydrate, the second stop valve is opened, and the volume V of the mixed gas generated after the decomposition of the residual hydrate is measured by a wet mass flowmeter3And measuring the components of the decomposed gas by gas chromatography to obtain CH in the mixed gas4The proportion of gas is yCH4And by constant CH determined in step (6)4Comparing the contents to obtain the final natural gas hydrateMining rate data;
(8) sorting data and calculating generated CH4Volume V of hydrateH：
Figure FDA0003587710130000041
Where ρ H is CH4Density of hydrate;
final substitution efficiency η:
Figure FDA0003587710130000042
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