CN107345894B - A kind of the high pressure cold bench device and application method of in-situ observation gas hydrate size distribution - Google Patents

A kind of the high pressure cold bench device and application method of in-situ observation gas hydrate size distribution Download PDF

Info

Publication number
CN107345894B
CN107345894B CN201710439791.1A CN201710439791A CN107345894B CN 107345894 B CN107345894 B CN 107345894B CN 201710439791 A CN201710439791 A CN 201710439791A CN 107345894 B CN107345894 B CN 107345894B
Authority
CN
China
Prior art keywords
pressure
storehouse
pressure resistant
reaction warehouse
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710439791.1A
Other languages
Chinese (zh)
Other versions
CN107345894A (en
Inventor
陈佩丽
周雪冰
苏秋成
付娟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Technical Institute of Physics and Chemistry of CAS
Original Assignee
Guangzhou Institute of Energy Conversion of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangzhou Institute of Energy Conversion of CAS filed Critical Guangzhou Institute of Energy Conversion of CAS
Priority to CN201710439791.1A priority Critical patent/CN107345894B/en
Publication of CN107345894A publication Critical patent/CN107345894A/en
Application granted granted Critical
Publication of CN107345894B publication Critical patent/CN107345894B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00Investigating characteristics of particles; Investigating permeability, pore-volume, or surface-area of porous materials
    • G01N15/02Investigating particle size or size distribution
    • G01N15/0205Investigating particle size or size distribution by optical means, e.g. by light scattering, diffraction, holography or imaging

Abstract

The invention discloses a kind of high pressure cold bench devices of in-situ observation gas hydrate size distribution, the granule size of gas hydrate crystal and the measurement of size distribution in fluid are completed in the device and laser particle analyzer cooperation, which includes high pressure resistant perspective storehouse, high pressure resistant reaction warehouse, temperature control system, control pressurer system, computer data acquisition system;The present invention has expanded the use and measuring condition range of existing laser particle analyzer as the accessory device of laser particle analyzer, allows to carry out the solid-liquid two-phase fluid under high pressure low temperature environment the measurement of granule size and size distribution.Its measurement method is simple, and measurement accuracy is significantly larger than the similar experimental provision that international other countries are developed.The present invention is to processes such as generation, the decomposition of quantitative analysis gas hydrate and discloses the dependent dynamics mechanism of gas hydrate and plays important directive function.

Description

A kind of high pressure cold bench device of in-situ observation gas hydrate size distribution and use Method
Technical field:
The present invention relates to hydrate particle size lambda characterization techniques fields, and in particular to a kind of in-situ observation gas hydrate granularity point The high pressure cold bench device and application method of cloth.
Background technique:
Gas hydrate is generated under low temperature and condition of high voltage by gas molecule and hydrone in the mixed of ice-like substance Close object.The gas hydrate of self-assembling formation is distributed widely in the sanidal deposit layer in shallow sea and plateau permafrost layer.In recent years Carry out a large amount of discoveries in the world with gas hydrates, becomes a kind of fungible energy source of great exploitation potential And obtain the attention of countries in the world.Currently, the gas hydrates reserves verified in the world reach 2.1 × 1015m3, it is traditional fossil energy total amount more than twice.At the same time, the gas storage density of gas hydrate is big.1 normal volume Gas hydrate can store the gas of up to 160 normal volumes.Temperature and pressure condition needed for it is stored compares liquefied gas again Body temperature and, therefore can be widely applied to natural gas storage and transportation and the fixation of carbon dioxide and seal up for safekeeping.Therefore, learning gas hydrate Kinetic characteristics and Related Mechanism for realize gas hydrates exploitation, storage and transportation and the trapping of greenhouse gases with seal up for safekeeping It has a very important significance.
Gas hydrate plays pendulum under normal temperature and pressure conditions, is extremely easy in decomposition into gas and liquid water.And it ties up Water holding solvate crystal stable structure then needs lower temperature and higher pressure.Such as at 1 DEG C, methane gas hydration is kept Minimum pressure required for object crystalchecked is about 2.9MPa.Therefore, under the conditions of cryogenic high pressure, gas hydrate in liquid phase is completed The observation of object crystal growth and analysis are extremely difficult.Currently, main institution of scientific research is mainly first in reaction kettle both at home and abroad Interior synthesized hydrate sample, then sieve under the conditions of cryogenic high pressure using different meshes carried out in high-pressure solution screening and Acquisition hydrate particle is removed high-pressure bottle and carries out the measurement of partial size and quality under the conditions of liquid nitrogen by filtering;Or it utilizes Portable laser particle size analyzer, by the visual windows on autoclave to the gas hydrate particle diameter distribution in solution change into Row in situ measurement.The above method can not the actual reaction under high pressure process of real simulation hydrate, there are large error or needs Instrument and equipment is greatly improved, required higher cost.Therefore, to the particle size growth of gas hydrate crystal and change in solution Change process, which carries out quantitative measurment and analysis, becomes the main bugbear for restricting gas hydrate kinetic mechanism study.
Summary of the invention:
The purpose of the invention is to overcome above-mentioned the deficiencies in the prior art, a kind of in-situ observation gas water is provided The high pressure cold bench device and application method of object size distribution are closed, which can simulate the rings such as different temperatures, pressure, fluid flow rate The generation in the liquid phase of gas hydrate crystal, decomposable process, the change of the real time measure sample size and size distribution are carried out in border Change, realizes the in situ measurement of gas hydrate crystal growing process in liquid phase.
The present invention is achieved by the following technical programs:
A kind of high pressure cold bench device of in-situ observation gas hydrate size distribution, the device have cooperated with laser particle analyzer At the measurement of the granule size of gas hydrate crystal and size distribution in fluid, which includes high pressure resistant perspective storehouse, resistance to height Press reaction warehouse, temperature control system, control pressurer system, computer data acquisition system;The high pressure resistant perspective storehouse is that have The high-pressure-resistant vessel of sapphire glass form is laser particle size using the sapphire glass of anti-reflection film is covered with as visual window Instrument provides sample to be tested;The high pressure resistant perspective storehouse is fixed on the retainer inside laser particle analyzer, which passes through resistance to Upper and lower two fixed hangers of the fixed hanger in high pressure perspective storehouse fix high pressure resistant perspective storehouse, the fixed hanger packet in high pressure resistant perspective storehouse Fixed hanger, quartz glass cover and lower fixed hanger are included, quartz glass cover is located between fixed hanger up and down, high pressure resistant perspective Storehouse is enclosed in by fixing in the airtight vacuum environment that hanger and quartz glass cover form up and down;High pressure resistant reaction warehouse is gas hydrate Object formed main device, be located at outside laser particle analyzer, for it is high pressure resistant perspective storehouse store and provide continuous-stable to flow measurement Body;Temperature control system, control pressurer system, computer data acquisition system are respectively high pressure resistant perspective storehouse and high pressure resistant reaction Storehouse provides stationary temperature and pressure environment, and carries out real-time measurement and record to the temperature and pressure parameter of fluid to be measured.
It is high pressure chest that the high pressure resistant perspective storehouse, which includes as the high-pressure chamber of watch window and the outside of high-pressure chamber, Fluid to be measured in body provides the annular coolant liquid collet of stationary temperature and pressure;The high-pressure chamber is by two panels sapphire glass Glass and observation storehouse pedestal are formed, and are allowed to detect laser and are passed through along two pieces of sapphire glass surfaces;Operational process mesohigh cavity stream Fluid to be measured is moved, the detection laser emitted in laser particle analyzer is injected by different angular illumination to sapphire glass surface High-pressure chamber, in fluid grain graininess and size distribution measure;The annular coolant liquid collet is by observing storehouse pedestal It is closed with observation storehouse end cap, wherein coolant liquid, which continuously flows, provides stationary temperature environment for high-pressure chamber;Coolant liquid into Outlet is located at observation storehouse end cap sidewall;The high pressure resistant perspective storehouse coolant liquid collet bottom is equipped with thermal resistance temperature sensor, uses In the environment temperature of real-time measurement high-pressure chamber.
Observation storehouse pedestal and pressure ring observe storehouse end cap and are all made of screw or spiral is fixed.
Particularly, two pieces of sapphire glass are fixed by pressure ring and interior hexagonal spiral, gasket seal, and with observation storehouse pedestal Form closed high-pressure chamber.
It is fixed between observation storehouse pedestal and observation storehouse end cap using O-ring sealing, a word screw.
Observation storehouse pedestal, observation storehouse end cap and pressure ring are all made of corrosion-resistant high voltage bearing Stainless steel 316 L manufacture.
The high pressure resistant perspective storehouse is on the retainer being fixed on inside laser particle analyzer, which passes through high pressure resistant The upper and lower two fixed hangers depending on the fixed hanger in storehouse fix high pressure resistant perspective storehouse, and the fixed hanger in high pressure resistant perspective storehouse includes upper solid Determine hanger, quartz glass cover and lower fixed hanger, quartz glass cover is located between fixed hanger up and down, high pressure resistant perspective storehouse closing By fixing in the airtight vacuum environment that hanger and quartz glass cover form up and down, strengthened using vacuum environment in closed cavity exhausted Thermal effect, which does not influence to detect laser simultaneously, penetrates effect, condenses for reducing vapor in heat transfer and environment in glass surface, Prevent water vapor in air in high pressure resistant perspective storehouse surface sweating or solidifying frost.
Fixation is bolted in the upper and lower fixed hanger of the high pressure resistant fixed hanger in perspective storehouse, and upper fixed hanger symmetrically divides Several through-holes of cloth are for connecting high-pressure liquid line and coolant line;Lower fixed hanger bottom side is used for connection thermal resistor temperature Degree meter conducting wire.Fixed hanger uses foamed plastic with the pedestal that high pressure resistant perspective storehouse directly contacts above and below, reduces and high pressure resistant Depending on the heat exchange between storehouse.Fixed hanger uses aluminum alloy materials up and down, reduces integrally-built quality.
The high pressure resistant reaction warehouse is visual high pressure resistant mechanical stirring kettle, and top is observed equipped with circular sapphire glass Hole, for observing high pressure resistant reaction warehouse hydrate particle formational situation, prevent hydrate particle quantity excessive and caused by high pressure Fluid circuit blocking;Meanwhile high pressure resistant reaction warehouse shape is conical round table, reduce top peep hole it is internally thermally conductive caused by High pressure resistant reaction warehouse internal temperature fluctuation;Pressure sensor interface is symmetrically arranged with above high pressure resistant reaction warehouse side and air inlet pipe connects Mouthful;The pressure sensor interface connects pressure sensor;The intake pipe connection is connected to the air inlet pipe being connected to high pressure gas cylinder Road is successively arranged back pressure regulating valve, needle-valve and pressure reducing valve on air inlet pipeline;High pressure resistant reaction warehouse side middle and lower part is symmetrically arranged with company The testing liquid interface of the turnover pipeline of fluid measured is received, the turnover pipeline is connected to high pressure resistant perspective storehouse respectively, forms one A circulation loop, the circulation loop are equipped with high pressure resistant circulating pump;High pressure resistant reaction warehouse side is equipped with coolant liquid collet, is anti- Storehouse is answered to provide stationary temperature environment;The inlet and outlet of coolant liquid are symmetrical in the bottom outside of high pressure resistant reaction warehouse;It is high pressure resistant Reaction warehouse bottom centre is equipped with stirring blade, by the adjustable motor drive of revolving speed outside high pressure resistant reaction warehouse.
The temperature control system includes low temperature thermostat bath and two independent coolant liquids being built in low temperature thermostat bath Circulating pump and the water-bath collet for being coated on high pressure resistant perspective storehouse and high pressure resistant reaction warehouse outer layer, to gas hydrate reaction system Temperature realize control quickly and precisely, for high pressure resistant perspective storehouse and high pressure resistant reaction warehouse provide the constant coolant liquid of temperature with Realize that temperature is constant.For providing the coolant liquid of constant initial temperature, two coolant recirculation pumps are separately connected low temperature thermostat bath High pressure resistant perspective storehouse and high pressure resistant reaction warehouse provide constant for the coolant liquid collet in high pressure resistant perspective storehouse and high pressure resistant reaction warehouse The flow of the coolant liquid of initial temperature, two coolant recirculation pumps is adjustable, and coolant recirculation pump can be according to high pressure resistant perspective storehouse With the locating environment temperature of high pressure resistant reaction warehouse, controlled in high pressure resistant perspective storehouse and high pressure resistant reaction warehouse by adjusting flow Actual temperature, guarantee that the temperature in two devices is consistent substantially.
The control pressurer system includes pressure reducing valve, the needle-valve, back pressure regulating valve, pressure sensor with high pressure gas cylinder connection With high pressure resistant circulating pump, the control pressurer system by back pressure regulating valve, needle-valve and subtracts using high pressure gas cylinder as high-pressure air source Pressure valve provides constant gaseous pressure for high pressure resistant reaction warehouse, while realizing fluid to be measured using the power that high pressure resistant circulating pump provides Continuous circulation in high pressure resistant reaction warehouse and high pressure resistant perspective storehouse.The circulation line is covered with the resistance to of heat-insulating material using surface High-pressure hose.
Particularly, the output end of high pressure resistant circulating pump is provided with pressure relief device, prevents from being expanded suddenly in fluid to be measured to resistance to High-pressure circulation pump damages.
Computer data acquisition system is by the thermal resistance temperature sensor and Nai Gao in data collecting instrument, high pressure resistant perspective storehouse Press the pressure sensor composition in reaction warehouse;In measurement process, data collection system is responsible for acquiring high pressure resistant perspective storehouse in real time In thermal resistance temperature sensor temperature and the pressure sensor in high pressure resistant reaction warehouse pressure, to the temperature in reaction system Degree and pressure are monitored in real time, and carry out alarm to the temperature and pressure parameter beyond measurement codomain.
Computer data acquisition system uses recording instrument without paper, can real-time records store data and easy to remove.
The application method of the high pressure cold bench device of the in-situ observation gas hydrate size distribution, comprising the following steps:
1) it is hunted leak respectively to the coolant liquid circulation line of device and fluid to be measured circulation pipe using liquids and gases, In the case where water clock, opens computer data acquisition system and ensure that experiment parameter is normally measured and acquired, and pass through resistance to height Pressure reaction warehouse injects solution into device, guarantees that liquid level does not exceed intake pipe connection in injection process, is not less than simultaneously The height of stirring blade;And the air in high pressure resistant circulating pump discharger is opened, realize the stable circulation of solution in a device Flowing;
2) then cooled down by temperature control system to device, while utilizing control pressurer system to high pressure resistant reaction The gas of injection setting initial pressure, when below the Phase Equilibrium Temperature under the conditions of temperature drops to corresponding pressure, is opened in storehouse Laser particle analyzer and in fluid granule size and size distribution measure.
Beneficial effects of the present invention are as follows:
Structure of the invention is compact, is moved easily, and has preferable safety, is able to bear the up to pressure of 12MPa and can To provide stationary temperature environment in the range of -20 DEG C to 50 DEG C, generated in solution suitable for most of gas hydrate Or hydrate particle is distributed in decomposable process and the measurement of growth rate rate, the present invention are filled as the accessory of laser particle analyzer The use and measuring condition range for having expanded existing laser particle analyzer are set, is allowed to the solid-liquid two under high pressure low temperature environment The measurement of phase fluid progress granule size and size distribution.Its measurement method is simple, and measurement accuracy is significantly larger than its international other country The similar experimental provision that family is developed.The present apparatus uses measure that is more complete heat-insulated and preventing Water vapor condensation, can be with Influence of the ambient temperature fluctuation to fluid to be measured is effectively reduced, improves the continuity and accuracy of measurement process.The present invention The processes such as generation, decomposition to quantitative analysis gas hydrate and the dependent dynamics mechanism for disclosing gas hydrate play important Directive function.
Detailed description of the invention:
Fig. 1 is the working principle of the invention figure;
Fig. 2 is structural schematic diagram of the invention;
Fig. 3 is the bulk junction composition in high pressure resistant perspective storehouse.
Fig. 4 is the fixation hanging rack structure figure in high pressure resistant perspective storehouse.
Wherein: 1, high pressure resistant perspective storehouse;2, low temperature thermostat bath;3, high pressure resistant reaction warehouse;4, high pressure gas cylinder;5, thermal resistance temperature Spend sensor;6, pressure sensor;7, back pressure regulating valve;8, needle-valve;, 9 high pressure resistant circulating pumps;10, pressure reducing valve;11, data are adopted Collect instrument;1a, observation storehouse pedestal;2a, sapphire glass;3a, pressure ring;4a, observation storehouse end cap;5a, O-ring;6a, gasket;7a, one Word screw;8a, hexagon socket head cap screw.
Specific embodiment:
It is to further explanation of the invention, rather than limiting the invention below.
Embodiment 1:
A kind of high pressure cold bench device of in-situ observation gas hydrate size distribution as shown in Figure 2, the device and laser The granule size of gas hydrate crystal and the measurement of size distribution in fluid are completed in particle size analyzer cooperation, which includes high pressure resistant Have an X-rayed storehouse 1, high pressure resistant reaction warehouse 3, temperature control system, control pressurer system, computer data acquisition system;As Fig. 2-4 institute Show, the high pressure resistant perspective storehouse 1 is the high-pressure-resistant vessel with sapphire glass form, using the sapphire for being covered with anti-reflection film Glass 2a provides sample to be tested as visual window, for laser particle analyzer;The high pressure resistant perspective storehouse 1 is fixed in laser particle analyzer On the retainer in portion, which fixes hangers for high pressure resistant perspective storehouse 1 by upper and lower the two of the high pressure resistant fixed hanger in perspective storehouse Fixed, the fixed hanger in high pressure resistant perspective storehouse includes that upper fixed hanger, quartz glass cover and lower fixed hanger, quartz glass cover are located at Up and down between fixed hanger, high pressure resistant perspective storehouse is enclosed in the airtight vacuum ring formed by fixing hanger and quartz glass cover up and down In border;High pressure resistant reaction warehouse 3 is the main device that gas hydrate is formed, and is located at outside laser particle analyzer, is high pressure resistant perspective Storehouse 1 stores and provides the fluid to be measured of continuous-stable;Temperature control system, control pressurer system, computer data acquisition system Respectively high pressure resistant perspective storehouse 1 and high pressure resistant reaction warehouse 3 provide stationary temperature and pressure environment, and to the temperature of fluid to be measured Real-time measurement and record are carried out with pressure parameter.
The high pressure resistant perspective storehouse 1 includes the outside of the high-pressure chamber and high-pressure chamber as watch window for being high The fluid to be measured in cavity is pressed to provide the annular coolant liquid collet of stationary temperature and pressure;The high-pressure chamber is blue precious by two panels Stone glass 2a and observation storehouse pedestal 1a are formed, and are allowed to detect laser and are passed through along two pieces of surfaces sapphire glass 2a;In operational process High-pressure chamber flows fluid to be measured, and the detection laser emitted in laser particle analyzer passes through different angular illumination to sapphire glass Glass surface inject high-pressure chamber, in fluid grain graininess and size distribution measure;It is described annular coolant liquid collet by Observation storehouse pedestal 1a and observation storehouse end cap 4a are closed, and wherein coolant liquid, which continuously flows, provides stationary temperature for high-pressure chamber Environment;The high pressure resistant 1 coolant liquid collet bottom of perspective storehouse is equipped with thermal resistance temperature sensor 5, is used for real-time measurement high pressure chest The environment temperature of body.
Particularly, two pieces of sapphire glass 2a are fixed by pressure ring 3a and interior hexagonal spiral 8a, gasket 6a sealing, and with sight It examines storehouse pedestal 1a and forms closed high-pressure chamber.
It is fixed between observation storehouse pedestal 1a and observation storehouse end cap 4a using O-ring 5a sealing, a word screw 7a.
Coolant liquid inlet and outlet are located at the observation side storehouse end cap 4a.Wherein observe storehouse pedestal 1a, observation storehouse end cap 4a and pressure ring 3a is all made of corrosion-resistant high voltage bearing Stainless steel 316 L manufacture.
The high pressure resistant perspective storehouse 1 is on the retainer being fixed on inside laser particle analyzer, which passes through high pressure resistant Upper and lower two fixed hangers of the fixed hanger in perspective storehouse fix high pressure resistant perspective storehouse, and the fixed hanger in high pressure resistant perspective storehouse includes upper Fixed hanger, quartz glass cover and lower fixed hanger, quartz glass cover are located between fixed hanger up and down, high pressure resistant perspective storehouse envelope It closes by fixing in the airtight vacuum environment that hanger and quartz glass cover form above and below, it is strong using vacuum environment in closed cavity Change insulation effect and do not influence to detect laser simultaneously and penetrates effect, it is solidifying in glass surface for reducing vapor in heat transfer and environment Knot prevents water vapor in air in high pressure resistant perspective storehouse surface sweating or solidifying frost, improves the accuracy of measurement.
Fig. 4 is the fixed hanging rack structure figure in high pressure resistant perspective storehouse.The fixed hanger in high pressure resistant perspective storehouse is mainly used for will be high pressure resistant Perspective storehouse be fixed on the retainer of laser particle analyzer, while reduce the high pressure resistant perspective storehouse in operational process under cryogenic conditions with Heat exchange between environment prevents the vapor in air from condensing on sapphire glass surface, improves the accuracy of measurement.It is high pressure resistant The fixed hanger in perspective storehouse includes upper fixed hanger, quartz glass cover and lower fixed hanger, and quartz glass cover is located at fixed up and down hang Between frame, fixation is bolted in upper and lower fixed hanger, and the upper fixed symmetrical several through-holes of hanger are for connecting high-pressure spray Body pipeline and coolant line;Lower fixed hanger bottom side is used for connection thermal resistor thermometer conducting wire.Upper and lower fixed hanger with Using foamed plastic, the heat reduced between high pressure resistant perspective storehouse exchanges the pedestal that high pressure resistant perspective storehouse directly contacts.Up and down Fixed hanger uses aluminum alloy materials, reduces integrally-built quality.
The high pressure resistant reaction warehouse 3 is visual high pressure resistant mechanical stirring kettle, and top is seen equipped with circular sapphire glass Examine hole, for observing high pressure resistant reaction warehouse hydrate particle formational situation, prevent hydrate particle quantity excessive and caused by height Press fluid circuit blocking;Meanwhile high pressure resistant 3 shape of reaction warehouse is conical round table, reduction top peep hole is internally thermally conductive and draws The high pressure resistant reaction warehouse internal temperature fluctuation risen;Be symmetrically arranged with above high pressure resistant 3 side of reaction warehouse pressure sensor interface and into Air pipe interface;The pressure sensor interface connects pressure sensor 6;The intake pipe connection connection is connected to high pressure gas cylinder 4 Air inlet pipeline, be successively arranged back pressure regulating valve 7, needle-valve 8 and pressure reducing valve 10 on air inlet pipeline;In high pressure resistant 3 side of reaction warehouse Lower part is symmetrically arranged with the testing liquid interface of the turnover pipeline of connection fluid to be measured, and the turnover pipeline is respectively with high pressure resistant perspective Storehouse 1 is connected to, and forms a circulation loop, and the circulation loop is equipped with high pressure resistant circulating pump 9;High pressure resistant 3 side of reaction warehouse is set There is coolant liquid collet, provides stationary temperature environment for reaction warehouse;The inlet and outlet of coolant liquid are outside the bottom of high pressure resistant reaction warehouse 3 Side is symmetrical;High pressure resistant 3 bottom centre of reaction warehouse is equipped with stirring blade, adjustable electronic by the revolving speed outside high pressure resistant reaction warehouse Machine driving.
The temperature control system includes low temperature thermostat bath 2 and two independent coolings being built in low temperature thermostat bath 2 Liquid circulating pump and the water-bath collet for being coated on high pressure resistant perspective storehouse 1 and 3 outer layer of high pressure resistant reaction warehouse, react gas hydrate The temperature of system realizes control quickly and precisely, provides temperature constant cold for high pressure resistant perspective storehouse 1 and high pressure resistant reaction warehouse 3 But liquid is to realize that temperature is constant.Low temperature thermostat bath 2 is for providing the coolant liquid of constant initial temperature, two coolant recirculation pumps point High pressure resistant perspective storehouse 1 and high pressure resistant reaction warehouse 3 are not connected, for the coolant liquid folder in high pressure resistant perspective storehouse 1 and high pressure resistant reaction warehouse 3 Set provides the coolant liquid of constant initial temperature, and the flow of two coolant recirculation pumps is adjustable, and coolant recirculation pump can be according to resistance to High pressure has an X-rayed the locating environment temperature in storehouse 1 and high pressure resistant reaction warehouse 3, controls high pressure resistant 1 He of perspective storehouse by adjusting flow Actual temperature in high pressure resistant reaction warehouse 3 guarantees that the temperature in two devices is consistent substantially.
The control pressurer system includes passing with the pressure reducing valve 10 of high pressure gas cylinder connection, needle-valve 8, back pressure regulating valve 7, pressure Sensor 6 and high pressure resistant circulating pump 9, the control pressurer system by high pressure gas cylinder 4 be used as high-pressure air source, by back pressure regulating valve 7, Needle-valve 8 and pressure reducing valve 10 are that high pressure resistant reaction warehouse 3 provides constant gaseous pressure, while being moved using what high pressure resistant circulating pump 9 provided Power realizes continuous circulation of the fluid to be measured in high pressure resistant reaction warehouse 3 and high pressure resistant perspective storehouse 1.The circulation line uses surface It is covered with the high pressure resistant hose of heat-insulating material.
Particularly, the output end of high pressure resistant circulating pump 9 is provided with pressure relief device, prevents from being expanded suddenly in fluid to be measured to resistance to High-pressure circulation pump 9 damages.
Computer data acquisition system is by 5 and of thermal resistance temperature sensor in data collecting instrument 11, high pressure resistant perspective storehouse 1 Pressure sensor 6 in high pressure resistant reaction warehouse 3 forms;In measurement process, data collection system is responsible for acquiring in real time high pressure resistant The pressure for having an X-rayed the pressure sensor 6 in the temperature and high pressure resistant reaction warehouse 3 of the thermal resistance temperature sensor 5 in storehouse 1, to reaction Temperature and pressure in system is monitored in real time, and carries out alarm to the temperature and pressure parameter beyond measurement codomain.
Computer data acquisition system uses recording instrument without paper, can real-time records store data and easy to remove.
The working principle diagram of the high pressure cold bench device of the in-situ observation gas hydrate size distribution as shown in Figure 1, its General work process, comprising the following steps: first turn on data collecting instrument and inject one into device by high pressure resistant reaction warehouse Quantitative solution, and open high pressure resistant circulating pump and realize solution circulating in a device, then pass through temperature control system Cool down to device, while injecting the gas of setting initial pressure into high pressure resistant reaction warehouse using control pressurer system, when When temperature drops to the Phase Equilibrium Temperature under the conditions of corresponding pressure or less, laser particle analyzer is opened and to the granule size in fluid It is measured with size distribution.
It is illustrated below by each system function:
1. the course of work of temperature control system are as follows: low temperature thermostat bath 2 is opened, when coolant temperature drops to set temperature Afterwards, while the coolant recirculation pump that high pressure resistant perspective storehouse 1 and high pressure resistant reaction warehouse 3 are separately connected in thermostat is opened.When resistance to height After the temperature of pressure perspective storehouse 1 and high pressure resistant reaction warehouse 3 is stablized, slowly adjusting coolant recirculation pump flow makes high pressure resistant perspective storehouse 1 It is consistent with high pressure resistant 3 internal temperature of reaction warehouse.
2. the course of work of control pressurer system are as follows: when injecting a certain amount of reaction solution in high pressure resistant reaction warehouse 3 and open Begin after cooling, opening high pressure resistant circulating pump 9 makes fluid to be measured continue to follow between high pressure resistant perspective storehouse 1 and high pressure resistant reaction warehouse 3 Circulation is dynamic.Then high pressure gas cylinder 4, pressure reducing valve 10 and needle-valve 8 are successively opened, using the reaction gas in high pressure gas cylinder in device Air purged, adjust back pressure regulating valve 7 to setting value simultaneously continue to reaction under high pressure storehouse 3 inject reaction gas.Work as reaction After pressure reaches setting value in storehouse, needle-valve 8, pressure reducing valve 10 and high pressure gas cylinder gas cylinder are successively closed, stops injection reaction gas.It opens The mechanical stirring of high pressure resistant 3 bottom of reaction warehouse is opened, and fluid to be measured is observed by the watch window at high pressure resistant 3 top of reaction warehouse The generation situation of mobility status and hydrate.
3. the course of work in high pressure resistant perspective storehouse 1 are as follows: will first connect the high pressure resistant retainer for having an X-rayed storehouse 1 from laser particle analyzer Middle taking-up simultaneously observes mobility status of the fluid to be measured in observation storehouse.Determine fluid proper flow in observation storehouse, resistance and temperature Sensor 5 read it is basicly stable after, retainer is put into laser particle analyzer and starts to measure.Before hydrate crystal generation And under the metastable environment of thermodynamic condition, 3 measurements are carried out to fluid to be measured, to determine the initial environment of hydrate generation The granule size of middle fluid to be measured and distribution.
4. the course of work of computer data acquisition system are as follows: check thermal resistance temperature sensor 5 before experiment starts Installation, sealing with pressure sensor 6 and the connection with data collecting instrument 11.It is then turned on data collecting instrument 11, to resistance to Temperature and pressure parameter are measured and are recorded in high pressure perspective storehouse 1 and high pressure resistant reaction warehouse 3.
5. the course of work of high pressure resistant reaction warehouse 3 are as follows: the glass window for opening 3 top of high pressure resistant reaction warehouse, to high pressure resistant The appropriate solution of injection in reaction warehouse 3.Meanwhile high pressure resistant circulating pump 9 is opened, make solution full of high pressure resistant perspective storehouse 1 and to flow measurement Simultaneously air therein is discharged in body circulation pipeline.It is then turned on high pressure gas cylinder 4, pressure reducing valve 10 and needle-valve 8, is purged using reaction gas Air in reaction warehouse.Finally close the glass window at 3 top of high pressure resistant reaction warehouse, and to continuing inside high pressure resistant reaction warehouse 3 Injection reaction gas is to setting pressure.Mechanical stirring is opened in pressure process to accelerate gas rate of dissolution in the solution and strong Change the conduction of heat of solution.After hydrate generates, coolant temperature is adjusted in time or adjusts back pressure regulating valve 7 to control hydration The generation total amount of object.
Hereafter it is applied to methane hydrate crystal with apparatus of the present invention to be formed in 2 DEG C of pure water and the measurement of size distribution For experiment, its application method is described.The methane gas of experiment composes source gas Co., Ltd from Guangzhou, and purity is not less than 99.9%.Water used is distilled water, is prepared by laboratory.First respectively to the coolant liquid circulation line and fluid to be measured of device Circulation pipe is hunted leak using liquids and gases.In the case where ensuring no water clock, turn-on data Acquisition Instrument simultaneously ensures to test ginseng Number normally can be measured and be acquired.It opens the circular sapphire glass peep hole of high pressure resistant 3 top of reaction warehouse and infuses thereto Enter a certain amount of pure water, guarantees that the liquid level of pure water does not exceed intake pipe connection in injection process, while not less than stirring The height of blade.Later on high pressure resistant circulating pump 9 all arranges the air in fluid to be measured pipeline and high pressure resistant perspective storehouse 1 Out.When flowing of the pure water in high pressure resistant reaction warehouse 3 reaches stable, the window of high pressure resistant 3 top of reaction warehouse is sealed.First The mechanical agitator of high pressure resistant reaction warehouse bottom, bottle valve 4, pressure reducing valve 10 and needle-valve 8 are opened afterwards, into high pressure resistant reaction warehouse 3 A small amount of low pressure reaction gas is injected, is then discharged by counterbalance valve 7, to purge the air in gas phase.High pressure resistant perspective storehouse 1 is put Enter in laser particle analyzer.It opens laser particle analyzer and background measurement is carried out to initial liquid phase.The back pressure value of counterbalance valve is turned up extremely 6MPa is simultaneously slowly injected into reaction gas into high pressure resistant reaction warehouse.When pressure reaches setting pressure 6MPa in reaction warehouse and holding is steady After fixed, low temperature thermostat bath 2 and two coolant recirculation pumps are opened, start to be cooled to 2 DEG C.In temperature-fall period, again to fluid to be measured Carry out 2 measurements, it has been determined that primary particles distribution.When stable to 2 DEG C of temperature, corresponding pressure parameter at this time is recorded, Start to carry out one-shot measurement to fluid to be measured and observe hydrate in liquid phase by high pressure resistant 3 top window of reaction warehouse for every 10 minutes Whether particle generates.The generation moment of hydrate, which measures fluid to be measured and records, generates the time.Subsequent hydrate crystal Quantity and volume in the liquid phase starts rapid growth, the pressure in high pressure resistant reaction warehouse 3 as reaction gas consumption And it is gradually reduced.Instantly when near vapor pressure, the pressure remained steady of high pressure resistant reaction warehouse 3, the generating process of hydrate Also terminate therewith.Continue to measure 1 hour to fluid to be measured and completes the measurement of hydrate formation.

Claims (10)

1. a kind of high pressure cold bench device of in-situ observation gas hydrate size distribution, which is characterized in that the device and laser grain It spends instrument cooperation and completes the granule size of gas hydrate crystal and the measurement of size distribution in fluid, which includes high pressure resistant Depending on storehouse, high pressure resistant reaction warehouse, temperature control system, control pressurer system, computer data acquisition system;The high pressure resistant perspective Storehouse is the high-pressure-resistant vessel with sapphire glass form, provides sample to be tested for laser particle analyzer;The high pressure resistant perspective storehouse It is fixed on the retainer inside laser particle analyzer, which fixes by upper and lower the two of the high pressure resistant fixed hanger in perspective storehouse Hanger fixes high pressure resistant perspective storehouse, the fixed hanger in the high pressure resistant perspective storehouse include upper fixed hanger, quartz glass cover and under Fixed hanger, quartz glass cover are located between fixed hanger up and down, and high pressure resistant perspective storehouse is enclosed in by fixing hanger and stone up and down In the airtight vacuum environment of English cloche composition;High pressure resistant reaction warehouse is the device that gas hydrate is formed, and is located at laser particle size Outside instrument, stores for high pressure resistant perspective storehouse and the fluid to be measured of continuous-stable is provided;Temperature control system, control pressurer system, Computer data acquisition system is respectively high pressure resistant perspective storehouse and high pressure resistant reaction warehouse provides stationary temperature and pressure environment, and Real-time measurement and record are carried out to the temperature and pressure parameter of fluid to be measured.
2. the high pressure cold bench device of in-situ observation gas hydrate size distribution according to claim 1, which is characterized in that To include as the high-pressure chamber of watch window and the outside of high-pressure chamber be in the high pressure resistant perspective storehouse in high-pressure chamber to The annular coolant liquid collet of fluid measured offer stationary temperature and pressure;The high-pressure chamber is by two panels sapphire glass and observation Storehouse pedestal is formed, and is allowed to detect laser and is passed through along two pieces of sapphire glass surfaces;Operational process mesohigh cavity flows to be measured Fluid, the detection laser irradiation emitted in laser particle analyzer to sapphire glass surface injects high-pressure chamber, in fluid Grain granularity and size distribution measure;The annular coolant liquid collet is closed by observation storehouse pedestal and observation storehouse end cap; Coolant liquid inlet and outlet are located at observation storehouse end cap sidewall;The high pressure resistant perspective storehouse coolant liquid collet bottom is passed equipped with resistance and temperature Sensor.
3. the high pressure cold bench device of in-situ observation gas hydrate size distribution according to claim 2, which is characterized in that Observation storehouse pedestal is all made of screw with observation storehouse end cap or spiral is fixed.
4. the high pressure cold bench device of in-situ observation gas hydrate size distribution according to claim 2 or 3, feature exist In two pieces of sapphire glass are fixed by pressure ring and interior hexagonal spiral, gasket seal, and form closed height with observation storehouse pedestal Press cavity;It is fixed between observation storehouse pedestal and observation storehouse end cap using O-ring sealing, a word screw;Observe storehouse pedestal, observation storehouse End cap and pressure ring are all made of Stainless steel 316 L manufacture.
5. the high pressure cold bench device of in-situ observation gas hydrate size distribution according to claim 1, which is characterized in that Fixation is bolted in the upper and lower fixed hanger of the high pressure resistant fixed hanger in perspective storehouse, and upper fixed hanger is symmetrical several logical Hole is for connecting high-pressure liquid line and coolant line;Lower fixed hanger bottom side is led for connection thermal resistor thermometer Line;Upper and lower fixed hanger uses foamed plastic with the pedestal that high pressure resistant perspective storehouse directly contacts;Upper and lower fixed hanger uses aluminium Alloy material.
6. the high pressure cold bench device of in-situ observation gas hydrate size distribution according to claim 1 or 2, feature exist In the high pressure resistant reaction warehouse is visual high pressure resistant mechanical stirring kettle, and top is equipped with circular sapphire glass peep hole, resistance to Reaction under high pressure storehouse shape is conical round table, is symmetrically arranged with pressure sensor interface above high pressure resistant reaction warehouse side and air inlet pipe connects Mouthful;The pressure sensor interface connects pressure sensor;The intake pipe connection is connected to the air inlet pipe being connected to high pressure gas cylinder Road is successively arranged back pressure regulating valve, needle-valve and pressure reducing valve on air inlet pipeline;High pressure resistant reaction warehouse side middle and lower part is symmetrically arranged with company The testing liquid interface of the turnover pipeline of fluid measured is received, the turnover pipeline is connected to high pressure resistant perspective storehouse respectively, forms one A circulation loop, the circulation loop are equipped with high pressure resistant circulating pump;High pressure resistant reaction warehouse side is equipped with coolant liquid collet, is anti- Storehouse is answered to provide stationary temperature environment;The inlet and outlet of coolant liquid are symmetrical in the bottom outside of high pressure resistant reaction warehouse;It is high pressure resistant Reaction warehouse bottom centre is equipped with stirring blade, by the adjustable motor drive of revolving speed outside high pressure resistant reaction warehouse.
7. the high pressure cold bench device of in-situ observation gas hydrate size distribution according to claim 1 or 2, feature exist In two independent coolant recirculation pumps that, the temperature control system includes low temperature thermostat bath and is built in low temperature thermostat bath And it is coated on the coolant liquid collet in high pressure resistant perspective storehouse and high pressure resistant reaction warehouse outer layer, the flow of two coolant recirculation pumps can It adjusts, is separately connected high pressure resistant perspective storehouse and high pressure resistant reaction warehouse, for the coolant liquid in high pressure resistant perspective storehouse and high pressure resistant reaction warehouse Collet provides the coolant liquid of constant initial temperature.
8. the high pressure cold bench device of in-situ observation gas hydrate size distribution according to claim 1 or 2, feature exist In, the control pressurer system include with the pressure reducing valve of high pressure gas cylinder connection, needle-valve, back pressure regulating valve, pressure sensor and resistance to High-pressure circulation pump, the control pressurer system pass through back pressure regulating valve, needle-valve and pressure reducing valve using high pressure gas cylinder as high-pressure air source Constant gaseous pressure is provided for high pressure resistant reaction warehouse, while the power provided using high pressure resistant circulating pump realizes fluid to be measured resistance to Continuous circulation in reaction under high pressure storehouse and high pressure resistant perspective storehouse;The circulation line is covered with the high pressure resistant of heat-insulating material using surface Hose.
9. the high pressure cold bench device of in-situ observation gas hydrate size distribution according to claim 1 or 2, feature exist In, computer data acquisition system by thermal resistance temperature sensor in data collecting instrument, high pressure resistant perspective storehouse and high pressure resistant anti- The pressure sensor of Ying Cangzhong forms;In measurement process, data collection system is responsible for acquiring in real time in high pressure resistant perspective storehouse The pressure of the temperature of thermal resistance temperature sensor and the pressure sensor in high pressure resistant reaction warehouse, in reaction system temperature and Pressure is monitored in real time, and carries out alarm to the temperature and pressure parameter beyond measurement codomain.
10. the high pressure cold bench device of in-situ observation gas hydrate size distribution described in any claim in claim 6 or 8 Application method, which comprises the following steps:
1) it is hunted leak respectively to the coolant liquid circulation line of device and fluid to be measured circulation pipe using liquids and gases, in no drop It in the case where leakage, opens computer data acquisition system and ensures that experiment parameter is normally measured and acquired, and by high pressure resistant anti- Fluid is injected in Ying Cangxiang device, and opens the air in high pressure resistant circulating pump discharger, realizes fluid following in a device Ring steady flow;
2) then cooled down by temperature control system to device, while using control pressurer system into high pressure resistant reaction warehouse The gas of injection setting initial pressure, when below the Phase Equilibrium Temperature under the conditions of temperature drops to corresponding pressure, opens laser Particle size analyzer and in fluid granule size and size distribution measure.
CN201710439791.1A 2017-06-12 2017-06-12 A kind of the high pressure cold bench device and application method of in-situ observation gas hydrate size distribution Active CN107345894B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710439791.1A CN107345894B (en) 2017-06-12 2017-06-12 A kind of the high pressure cold bench device and application method of in-situ observation gas hydrate size distribution

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710439791.1A CN107345894B (en) 2017-06-12 2017-06-12 A kind of the high pressure cold bench device and application method of in-situ observation gas hydrate size distribution

Publications (2)

Publication Number Publication Date
CN107345894A CN107345894A (en) 2017-11-14
CN107345894B true CN107345894B (en) 2019-07-09

Family

ID=60253509

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710439791.1A Active CN107345894B (en) 2017-06-12 2017-06-12 A kind of the high pressure cold bench device and application method of in-situ observation gas hydrate size distribution

Country Status (1)

Country Link
CN (1) CN107345894B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108195858A (en) * 2017-12-04 2018-06-22 中国科学院广州能源研究所 A kind of high pressure cold bench device and application method suitable for cryogenic high pressure material X-ray diffraction measurement
CN108130146B (en) * 2017-12-07 2020-07-21 中国科学院广州能源研究所 Gas hydrate crystal culture device
CN108519384A (en) * 2018-04-17 2018-09-11 中国石油大学(华东) A kind of normal pressure visualization device and method generated in porous media for simulating hydrate with decomposition
CN109668891A (en) * 2018-12-25 2019-04-23 中海石油(中国)有限公司深圳分公司 The sample observation device and microscopic observation module and microscopic observation system of hydrate
CN109839336B (en) * 2019-04-24 2019-07-19 江苏一夫科技股份有限公司 Cytochrome P--450 on-line checking analyzer

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007238826A (en) * 2006-03-10 2007-09-20 Mitsui Eng & Shipbuild Co Ltd Method and apparatus for producing gas hydrate
CN102445371A (en) * 2011-11-10 2012-05-09 大连理工大学 Integrated device for in-situ generation and decomposition of hydrate sediments and permeability measurement thereof
WO2013095192A2 (en) * 2011-12-20 2013-06-27 Шлюмберже Холдингс Лимитед Method for examining samples of unconsolidated porous media
CN105004849A (en) * 2015-08-14 2015-10-28 西南石油大学 Laboratory experiment device and method for solid fluidization exploitation of gas hydrate
CN105445437A (en) * 2016-01-11 2016-03-30 西南石油大学 Natural gas hydrate particle synthesis and gas-liquid-solid three-phase flow experimental device
CN205786187U (en) * 2016-02-01 2016-12-07 青岛海洋地质研究所 A kind of gas hydrates borehole axis is to the one-dimensional physical simulating device that shakes out

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105548137A (en) * 2015-12-25 2016-05-04 中国科学院广州能源研究所 High-pressure cooling-heating table device for in-situ observation of aquo-complex microscopic reaction kinetics process and application method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007238826A (en) * 2006-03-10 2007-09-20 Mitsui Eng & Shipbuild Co Ltd Method and apparatus for producing gas hydrate
CN102445371A (en) * 2011-11-10 2012-05-09 大连理工大学 Integrated device for in-situ generation and decomposition of hydrate sediments and permeability measurement thereof
WO2013095192A2 (en) * 2011-12-20 2013-06-27 Шлюмберже Холдингс Лимитед Method for examining samples of unconsolidated porous media
CN105004849A (en) * 2015-08-14 2015-10-28 西南石油大学 Laboratory experiment device and method for solid fluidization exploitation of gas hydrate
CN105445437A (en) * 2016-01-11 2016-03-30 西南石油大学 Natural gas hydrate particle synthesis and gas-liquid-solid three-phase flow experimental device
CN205786187U (en) * 2016-02-01 2016-12-07 青岛海洋地质研究所 A kind of gas hydrates borehole axis is to the one-dimensional physical simulating device that shakes out

Also Published As

Publication number Publication date
CN107345894A (en) 2017-11-14

Similar Documents

Publication Publication Date Title
Song et al. Evaluation of gas production from methane hydrates using depressurization, thermal stimulation and combined methods
CN103033442B (en) A kind of gas adsorption test device for desorption
Quick et al. Hydrogen and deuterium in iron, 49–506 C
Mraw et al. Vapor-liquid equilibrium of the methane-carbon dioxide system at low temperatures
Fitzgerald et al. Subnanogram determination of mercury by two-stage gold amalgamation and gas phase detection applied to atmospheric analysis
Stryjek et al. Low-temperature vapor-liquid equilibriums of nitrogen-methane system
Cropper et al. Analytical Separation of the Methyl Esters of the C 12–C 22 Fatty Acids by Vapour-Phase Chromatography
Long et al. Measurement of CO 2 assimilation by plants in the field and the laboratory
CN104267172B (en) A kind of multifunctional all formula soil body freezing-thawing test system
CN203287337U (en) Soil body freezing-thawing process visualized testing device
Mohammadi et al. Semi-clathrate hydrate phase equilibrium measurements for the CO2+ H2/CH4+ tetra-n-butylammonium bromide aqueous solution system
CN103196945B (en) Condensation heat-transfer experiment device capable of realizing coupling of natural circulation and forced circulation
Holste et al. Experimental (p, Vm, T) for pure CO2 between 220 and 450 K
Bergeron et al. CO2 and CH4 mole fraction measurements during hydrate growth in a semi-batch stirred tank reactor and its significance to kinetic modeling
AU648075B2 (en) A method of and an apparatus for measuring the adsorption and the desorption of a gas adsorbed by a solid sample and the use thereof
Ludwig et al. An open gas-exchange system for the simultaneous measurement of the CO2 and 14CO2 fluxes from leaves
Bollengier et al. Phase equilibria in the H2O–CO2 system between 250–330 K and 0–1.7 GPa: Stability of the CO2 hydrates and H2O-ice VI at CO2 saturation
CN104729948A (en) Water-gas two-phase percolation experimental system and method of gas-containing coal
CN105588782B (en) High/low temperature High Pressure Absorption test device for desorption and method
CN102141529B (en) Vacuum contact thermal conduction measurement device of fixed junction surface
CN105547907B (en) The servo measurement pilot system and method for coal sample gas adsorption desorption
US10801942B2 (en) Multi-functional multi-field coupling seepage experiment device and testing method thereof
CN203011791U (en) Gas absorption/desorption testing device
CN102012246B (en) Device for measuring in-situ flow rate change of marine cold seep gas seepage
Zhao et al. In situ observations by magnetic resonance imaging for formation and dissociation of tetrahydrofuran hydrate in porous media

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20210301

Address after: 2 / F, No.2, courtyard 88, Shuangying West Road, Nanshao Town, Changping District, Beijing

Patentee after: Physicochemical Lianke (Beijing) Instrument Technology Co.,Ltd.

Address before: Guangzhou City, Guangdong province 510640 energy road No. 2 Tianhe District Wushan

Patentee before: GUANGZHOU INSTITUTE OF ENERGY CONVERSION, CHINESE ACADEMY OF SCIENCES

TR01 Transfer of patent right