CN105973937A - Thermo-physical property measurement system and method of hydrate - Google Patents
Thermo-physical property measurement system and method of hydrate Download PDFInfo
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- CN105973937A CN105973937A CN201610566181.3A CN201610566181A CN105973937A CN 105973937 A CN105973937 A CN 105973937A CN 201610566181 A CN201610566181 A CN 201610566181A CN 105973937 A CN105973937 A CN 105973937A
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- G01N25/00—Investigating or analyzing materials by the use of thermal means
- G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
- G01N25/48—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation
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Abstract
The invention provides a thermo-physical property measurement system and method of a hydrate. The thermo-physical property measurement system comprises a high-pressure reaction kettle, a temperature control device, a compression and molding device, a gas supply device, a measurement device and a data acquisition device. The temperature control device comprises a constant-temperature water bath box; and the high-pressure reaction kettle is arranged in the constant-temperature water bath box. The compression and molding device comprises a piston; a liquid inlet is formed in an inner wall of the high-pressure reaction kettle at the rear part of the piston; and the liquid inlet is connected with a pressurizing pump. The measurement device comprises a thermal analyzer; and a probe of the thermal analyzer is inserted into the middle position between two sleeves. When the thermo-physical property measurement system of the hydrate is used for measuring, a sample is firstly put into the sleeve, the sleeve is squeezed through the piston, and then thermo-physical properties of the hydrate are measured through the thermal analyzer. According to the thermo-physical property measurement system and method of the hydrate, provided by the invention, the two sides of the hydrate are squeezed at the same time and the probe is not bent, so that the damages of the probe can be reduced. Meanwhile, the consistency of the hydrate is good and the measurement precision is high.
Description
Technical field
The present invention relates to a kind of thermophysical property measurement system and measuring method thereof, be specifically related to a kind of certainty of measurement height, not rapid wear of popping one's head in
Bad hydrate thermophysical property measurement system and the measuring method of this hydrate thermophysical property measurement system thereof.
Background technology
Since mid-term in 18th century Benjamin Franklin start since the capacity of heat transmission to solid carries out experimentation, to have studied
Going out the measuring method of multiple heat conductivity, the measurement of heat conductivity is broadly divided into steady state method and the big class of cold store enclosure two.In the last few years
The research of hydrate heat conductivity achieves certain progress, but due to measuring method and the difference of laboratory facilities, measurement result is not to the utmost
Identical.During measurement, it is contemplated that the metastability of hydrate, scientific research personnel is more likely to use cold store enclosure, such as probe method,
Heat-pole method, transition plane heat source method etc..When using probe method that the heat conductivity of hydrate is carried out in site measurement, can be radially
Arrange probe, it is also possible to axial arranged probe, when radial arrangement pop one's head in it is difficult to ensure that sample is pressurizeed densification time pop one's head in shape
State does not changes, and can not effectively drive away residual gas in sample；Axial pressure then can not be carried out when axial arranged probe.Also
Transition plane heat source method can be used to measure the heat conductivity of hydrate, the advantage of this method be measuring speed faster, and do not connect
Touching the impact of thermal resistance, but probe vertical inserts autoclave, when the lid of autoclave is installed, probe can rotate, heavy
Long-pending thing medium is popped one's head in and is easily damaged, it addition, flexible damage of popping one's head in when piston compacting sample.
Summary of the invention
In order to solve flimsy problem of popping one's head in prior art, the present invention provides a kind of hydrate thermophysical property measurement system and survey thereof
Metering method.
The present invention provide a kind of hydrate thermophysical property measurement system, including autoclave, temperature regulating device, compression-molding apparatus,
Feeder, measurement apparatus and data acquisition unit.Described autoclave bottom is provided with base support, and base support sets
Being equipped with two sleeves, two sleeves are symmetrical, and the center on each sleeve transversely axis wall has charging aperture；High pressure
Being additionally provided with pressure transducer and the first temperature sensor in reactor, the first temperature sensor is stretched in sleeve by charging aperture.
Described temperature regulating device includes that constant water bath box, autoclave are placed in constant water bath box, is provided with coil pipe in constant water bath box,
Refrigerant cycle is had to flow in described coil pipe.The second temperature sensor and agitator it is additionally provided with in constant water bath box；Water bath with thermostatic control
Case connects temperature controller.Described compression-molding apparatus includes two pistons being separately positioned on two sleeve rear portions, two work
Also having inlet on the autoclave inwall at plug rear portion, two inlets are connected to the first hydraulic pressure arm and second
Hydraulic pressure arm, the first hydraulic pressure arm and the second hydraulic pressure arm all connect hydraulic main, and described hydraulic main connects booster pump；Described
Hydraulic main valve it is additionally provided with on hydraulic main.Feeder include hunt leak passage, evacuation passageway, reacting gas air supply channel and
Emptying passage；Leak detection passage, evacuation passageway, reacting gas air supply channel are all connected with autoclave with emptying passage；
Described evacuation passageway is also associated with vacuum pump；Reacting gas air supply channel connection reacting gas gas cylinder；It is provided with on emptying passage
Relief valve and vent valve.Described measurement apparatus includes thermal analyzer, and the probe of thermal analyzer is provided with by poly-methyl methacrylate
The protecting film that ester is made；The groove of Relative distribution it is provided with on two sleeves, when two sleeves snap together, two grooves
Forming probe mounting holes, described probe inserts two sleeve centre positions by probe mounting holes.Described data acquisition unit connects heat
Analyser, pressure transducer, the first temperature sensor, data acquisition unit connects also by data-out signal line computer.
Preferably, described compression-molding apparatus also includes pressure control assembly, and pressure control assembly includes for measuring sleeve and work
The diastimeter of plug distance, described diastimeter connects a hydraulic controller, described hydraulic controller connect have the first electro-hydraulic valve and
Second electro-hydraulic valve, described first electro-hydraulic valve and the second electro-hydraulic valve are separately mounted to the first hydraulic pressure arm and the second liquid
On pressure arm.By the spacing of stadia surveying piston Yu sleeve, signal is delivered to hydraulic controller, hydraulic pressure control by diastimeter
Device processed judges that two-piston, respectively apart from corresponding sleeve distance, and is adjusted by regulating the first electro-hydraulic valve and the second electro-hydraulic valve
Joint piston movement speed, make two pistons abut two sleeves the most respectively and be compressed, it is ensured that pop one's head in compression process not by
Destroy.
Further preferably, described diastimeter includes that two infrared signal assemblies, described infrared signal assembly include infrared transmitter and red
Outer receptor, said two infrared signal assembly is separately fixed in the rear groove of sleeve.By infrared signal assembly measuring unit
Cylinder and plunger distance, certainty of measurement is high.
Preferably, it is provided with seal washer at piston and autoclave contact internal walls.At piston and autoclave contact internal walls
Place arranges seal washer, is possible to prevent piston rear fluid to leak into the autoclave cavity between two-piston.
Preferably, inside described autoclave, articulated elements being provided with at least two support bar, probe is fixed on support bar
Upper end, articulated elements is threadedly attached on reactor inwall.When needs are removed or placed into sleeve, only support bar need to be rotated
Can, the setting of support bar does not interferes with the taking-up of sleeve and puts into.When sleeve is excessive, it is also possible to by threaded
Articulated elements is dismantled, and then takes off support bar, is finally removed or placed into sleeve, and arranging of described support bar can fix probe, with
Time, nor affect on being removed or placed into of sleeve.
A kind of hydrate thermophysical property measurement system that the present invention provides, compared with prior art, has the advantages that
Above-mentioned a kind of hydrate thermophysical property measurement system, can make deposit and solution high-pressure synthesis hydrate in situ, can be in situ
Measure thermal physical property parameter, it is also possible to ex situ measures hydrate thermal physical property parameter, it is possible to reduce tip damage, improve experiment and measure
Precision.
Sample compression can be become typical cylindrical body by described sleeve, it is ensured that the concordance of sample, reduces the sample shadow to measurement result
Ring.The setting of sleeve prevents hydrate to be extruded in the autoclave tubular lid of top；Deposit can also be reduced to greatest extent
Or hydrate is scattered on autoclave inwall, thus reduce piston movement resistance, decrease piston both sides pressure reduction as far as possible.
Having charging aperture on sleeve, charging aperture can be used to add loose dry deposit, it is also possible to convenient insertion the first temperature sensing
Device.
Autoclave is inserted in constant water bath box, and cold-producing medium realizes temperature control, water bath with thermostatic control the temperature inside the box at coil pipe internal circulation flow
Regulated and controled by temperature controller, bath temperature can be carried out programmed cooling and intensification, i.e. make reaction under high pressure by temperature oscillation
Material fast reaction in still；Water bath with thermostatic control arranges the first temperature sensor, the second temperature sensor and agitator, and the first temperature passes
Sensor is in order to measure temperature in sleeve, and the second temperature sensor is used for measuring water-bath real time temperature in constant water bath box, and agitator makes
Homogeneous temperature everywhere in constant water bath box.
Compression-molding apparatus include booster pump and autoclave two ends by hydraulically powered piston, when judging that hydrate reaction terminates
After, being pressurizeed by booster pump, the piston at autoclave two ends moves to sleeve direction, piston press sleeve, complete paired samples
Compression forming, owing to probe is fixed on autoclave center, use two-sided compression can ensure that probe will not be because of extruding
And be subjected to displacement, can effectively protect probe, make probe not be destroyed.
Due to the extruding of piston in autoclave, in must causing still, pressure raises, for pressure in ensureing still under safe pressure,
Arranging relief valve on air defense passage, in pressure arranges a little higher than autoclave, hydrate generates pressure.When piston press causes height
When pressure reacting kettle inner pressure exceedes safety valve setting pressure, relief valve is opened, and discharges pressure, when in autoclave, pressure reaches
During safety valve setting pressure, relief valve cuts out, and ensures that autoclave works under safe pressure, in making autoclave with this
Pressure keeps constant, reduces the impact produced hydrate sample because of pressure change.
The present invention also provides for a kind of hydrate thermophysical property measurement method, and described measuring method need to use above-mentioned a kind of hot physical property of hydrate
Measurement system, concrete measuring process is as follows:
The first step, is stuck in the protecting film of probe in the groove of two sleeves, then the sleeve that two snap together is put into horizontal stroke
In the autoclave put.
Second step, installs the tubular lid of autoclave, carries out system leak detection by leak detection passage, it is ensured that autoclave does not has
There is leak source.
It is then shut off the leak detection valve on passage of hunting leak, opens vacuum-pumping valve, start vacuum pump, by autoclave evacuation,
After evacuation, close vacuum-pumping valve and autoclave is put in constant water bath box；According to requirement of experiment, adjust perseverance
Tepidarium the temperature inside the box.
3rd step, opens reacting gas gas cylinder, opens the air-supplying valve of reacting gas air supply channel, is passed through in autoclave
Reacting gas is to requirement of experiment pressure, and after standing a period of time, regulation bath temperature is to requirement of experiment temperature, carries out hydrate generation
Reaction.
4th step, uses temperature oscillation to make hydrate reaction complete, and staff can be by the required reaction of calculated hydration thing reaction
In gas flow, addition amount of reactant gases and autoclave, gas pressure is confirmed whether that reaction is completely.After reaction completely, open liquid
Pressure main valve, starts hand increasing pressure pump pressurization, and when pressure reaches desirable pressure, piston extrudes acquisition to two sleeve both sides simultaneously
Hydrate sample after compression.
5th step, after treating sample compression, starts thermal analyzer and carries out the measurement of the hot physical property of hydrate, and thermal analyzer is by visiting
Sample is heated by head, simultaneously the record resistance that raises in time of temperature be fed back to thermal analyzer, by thermal analyzer
Metrical information is passed to data acquisition unit and carries out real-time data acquisition, finally calculated the hot thing of hydrate sample by computer
Property parameter.
Preferably, when hydrate sample in-situ generates, first weigh a certain proportion of deposit and solution is filled in two sleeves
In, it is compacted smooth out surface, then two sleeves is snapped together.
Preferably, when hydrate sample in-situ generates and sample is discrete particles shape, first two sleeves of probe will be installed
It is placed in horizontal autoclave, then deposit and solution is slowly injected in the charging aperture from sleeve.
The present invention compared with prior art, has the advantages that
A kind of above-mentioned hydrate thermophysical property measurement method, only need to be placed on hydrate or deposit in sleeve with solution, two work
Plug extrudes two sleeves respectively from both sides, and hydrate both sides are squeezed simultaneously, and probe will not move, and also will not bend, it is possible to
Reduce tip damage.Meanwhile, the hydrate concordance after the extruding of both sides is good, and experiment certainty of measurement is high.Sample adds in sleeve,
It is possible to prevent sample to drop and adheres on the inwall of autoclave.
Autoclave is inserted in constant water bath box, and water bath with thermostatic control the temperature inside the box is regulated and controled by temperature controller, is shaken by temperature
Swing method, make temperature constantly change, the reaction of formation of hydrate can be accelerated.
Accompanying drawing explanation
Fig. 1 is the structural representation of a kind of hydrate thermophysical property measurement system.
Fig. 2 is the profile of two sleeves.
Fig. 3 is the sectional side view of autoclave.
1, autoclave；2 sleeves；3 pistons；4 probes；5 tubular lids；6 hand increasing pressure pumps；7,8 reacting gas gas cylinder；
9 vacuum pumps；10 gas flowmeters；11,12 gas pressure reducer；13 pressure transducers；14 first temperature sensors；15 peaces
Full valve；16 vent valves；17a the first electro-hydraulic valve；17b the second electro-hydraulic valve；18 hydraulic main valves；19,20 first pressure
Power table；21,22 air-supplying valves, 23 vacuum-pumping valves；24 hydraulic controllers；25 second temperature sensors；26 agitators；
27 seal washers；28 base supports；29 coil pipes；30 constant water bath box；31 diastimeters；32 computers；33 data acquisitions
Device；34 thermal analyzers；35 signal cables；36 charging apertures；37 infrared signal assemblies；38 support bars；39 probe cables；40
Second Pressure gauge.
Detailed description of the invention
Embodiment 1
A kind of hydrate thermophysical property measurement system, including autoclave 1, temperature regulating device, compression-molding apparatus, feeder,
Measurement apparatus and data acquisition unit.Described autoclave 1 bottom is provided with base support 28, and base support 28 is arranged
Having two sleeves 2, two sleeves 2 are symmetrical, and the center on each sleeve 2 transversely axis wall has charging aperture 36；
Being additionally provided with pressure transducer 13 and the first temperature sensor 14 in autoclave 1, the first temperature sensor 14 is by charging
Hole 36 is inserted in sleeve 2.
Described temperature regulating device includes that constant water bath box 30, autoclave 1 are placed in constant water bath box 30, constant water bath box
It is provided with coil pipe 29 in 30, in described coil pipe 29, has refrigerant cycle to flow.The second temperature it is additionally provided with in constant water bath box 30
Sensor 25 and agitator 26, constant water bath box 30 connects temperature controller.
Described compression-molding apparatus includes two pistons 3 being separately positioned on two sleeve 2 rear portions, piston 3 and autoclave 1
Seal washer 27 it is provided with at contact internal walls.Inlet is also had on autoclave 1 inwall at two piston 3 rear portions,
Two inlets are connected to the first hydraulic pressure arm and the second hydraulic pressure arm, the first hydraulic pressure arm and the second hydraulic pressure arm and all connect
Hydraulic main, described hydraulic main connects booster pump, and described booster pump can be hand increasing pressure pump 6；Described hydraulic main is upper also
It is provided with hydraulic main valve 18.Compression-molding apparatus also includes pressure control assembly, and pressure control assembly includes for measuring sleeve 2
With the diastimeter 31 of piston 3 distance, diastimeter 31 includes that two infrared signal assemblies 37, described infrared signal assembly 37 include
Infrared transmitter and infrared remote receiver, said two infrared signal assembly 37 is separately fixed in the rear groove of sleeve 2.Pass through
Infrared signal assembly 37 measures sleeve 2 and piston 3 distance, and certainty of measurement is high.Diastimeter 31 is also associated with hydraulic controller 24,
Described hydraulic controller 24 connects the first electro-hydraulic valve 17a and the second electro-hydraulic valve 17b, the first electro-hydraulic valve 17a
It is separately mounted on the first hydraulic pressure arm and the second hydraulic pressure arm with the second electro-hydraulic valve 17b.Piston is measured by diastimeter 31
3 with the spacing of sleeve 2, signal is delivered to hydraulic controller 24 by diastimeter 31, and hydraulic controller 24 judges two-piston 3
Distance sleeve 2 distance respectively, and transport by regulating the first electro-hydraulic valve 17a and the second electro-hydraulic valve 17b regulating piston 3
Dynamic speed, makes two pistons 3 abut two sleeves 2 the most respectively；After piston 3 abuts sleeve 2, diastimeter 31 find range away from
From for zero, now distance signal is passed to hydraulic controller 24, hydraulic controller 24 control the first electro-hydraulic valve 17a and
It is identical that second electro-hydraulic valve 17b turns on degree, it is ensured that two-piston 3 extruding force is essentially identical, to ensure in compression process
Middle probe 4 is not destroyed.
Feeder includes hunt leak passage, evacuation passageway, reacting gas air supply channel and emptying passage；Leak detection passage, take out true
Empty passage, reacting gas air supply channel are all connected with autoclave 1 with emptying passage.Described evacuation passageway is also associated with
Vacuum pump 9；Described reacting gas air supply channel connection reacting gas gas cylinder 7,8；It is provided with relief valve 15 on described emptying passage
With vent valve 16.
Described measurement apparatus includes that thermal analyzer 34, described thermal analyzer 34 can be Hot Disk thermal constant analysers, heat point
It is provided with, on the probe 4 of analyzer 34, the protecting film being made up of polymethyl methacrylate；It is provided with Relative distribution on two sleeves 2
Groove, when two sleeves 2 snap together, two grooves form probe 4 installing holes, and described probe 4 is by probe 4
Installing hole inserts two sleeve 2 centre positions.
Described data acquisition unit 33 connects thermal analyzer 34, pressure transducer the 13, first temperature sensor 14, data acquisition
Device 33 connects also by data-out signal line computer 32；Wherein, data acquisition unit 33 can use Agilent data acquisition
Collection instrument.
Further, described autoclave 1 is internal is provided with at least two support bar 38 also by articulated elements, and probe 4 is fixed
In the upper end of support bar 38, articulated elements is threadedly attached on reactor inwall.When needs are removed or placed into sleeve 2, only
Need to rotate support bar 38 can, the setting of support bar 38 does not interferes with the taking-up of sleeve 2 and puts into.When sleeve 2 is excessive
Time, it is also possible to by threaded articulated elements dismounting, then take off support bar 38, be finally removed or placed into sleeve 2, described
Arranging of strut 38 can fix probe 4, meanwhile, nor affects on being removed or placed into of sleeve 2.
Above-mentioned a kind of hydrate thermophysical property measurement system, can make deposit and solution high-pressure synthesis hydrate in situ, can be in situ
Measure thermal physical property parameter, it is also possible to carry out ex situ and measure thermal physical property parameter, it is possible to reduce probe 4 damage, improve experiment and measure
Precision.
Sample compression can be become typical cylindrical body by described sleeve 2, it is ensured that the concordance of sample, reduces sample and experiment is measured knot
The impact of fruit.The setting of sleeve 2 prevents hydrate sample to be extruded in top autoclave 1 tubular lid 5；Can also be
Limits reduces sediment sample and is scattered on autoclave 1 inwall, thus reduces piston 3 resistance of motion, reduces as far as possible
Piston 3 both sides pressure reduction.Having charging aperture 36 on sleeve 2, charging aperture 36 can be used to add loose dry deposit,
Also the first temperature sensor 14 can conveniently be inserted.
Autoclave 1 is inserted in constant water bath box 30, and cold-producing medium circulates in coil pipe 29 and realizes temperature control, constant water bath box 30
Interior temperature is regulated and controled by temperature controller, and bath temperature can be carried out programmed cooling and intensification, arranges in autoclave 1
One temperature sensor 14, water bath with thermostatic control arranges the second temperature sensor 25 and agitator 26, and the first temperature sensor 14 is in order to survey
Temperature in amount sleeve 2, the second temperature sensor 25 is used for measuring water-bath real time temperature in constant water bath box 30, and agitator 26 makes
Homogeneous temperature everywhere in constant water bath box 30.
Compression-molding apparatus include booster pump and autoclave 1 two ends by hydraulically powered piston 3, when judging hydrate reaction
After end, being pressurizeed by booster pump, the piston 3 at autoclave 1 two ends moves to sleeve 2 direction, piston 3 compression sleeve
2, the compression forming of complete paired samples, use two-sided compression can ensure to pop one's head in and 4 will not be subjected to displacement because of extruding, can effectively protect
Protect probe 4 not to be destroyed.
Due to the extruding of piston 3 in autoclave 1, in must causing still, pressure raises, for pressure in ensureing still at safe pressure
Under, air defense passage arranges relief valve 15, in pressure arranges a little higher than autoclave 1, hydrate generates pressure, when piston 3
Extruding causes pressure in autoclave 1 to exceed relief valve 15 when setting pressure, and relief valve 15 is opened, and discharges pressure, works as height
In pressure reactor 1, pressure reaches relief valve 15 when setting pressure, and relief valve 15 cuts out, and ensures that autoclave 1 is in peace with this
Work under total pressure, make intrinsic pressure the trying hard to keep of autoclave 1 hold constant, that hydrate sample is produced because of pressure change by minimizing impact.
Embodiment 2
A kind of hydrate thermophysical property measurement method, described measuring method need to use the hot physical property of a kind of hydrate described in embodiment 1 to survey
Amount system, concrete measuring process is as follows:
The first step, weighs a certain proportion of deposit and solution is filled in two sleeves 2, is compacted smooth out surface, then by two
Individual sleeve 2 snaps together.Probe 4 with protecting film is stuck in the groove of two sleeves 2, then two is fastened on
Sleeve 2 together is put in horizontal autoclave 1.
Second step, installs the tubular lid 5 of autoclave 1, by leak detection channel connection nitrogen cylinder and autoclave 1, beats
Open the leak detection valve on leak detection passage, be filled with nitrogen and carry out system leak detection, it is ensured that autoclave 1 does not has leak source.
It is then shut off valve of hunting leak, opens vacuum-pumping valve 23, start vacuum pump 9, by autoclave 1 evacuation, take out true
After sky, close vacuum-pumping valve 23 and autoclave 1 is put in constant water bath box 30；According to requirement of experiment, adjust
Temperature in whole constant water bath box 30.
3rd step, opens reacting gas gas cylinder 7,8, opens the air-supplying valve 21,22 of reacting gas air supply channel, anti-to high pressure
Answer and still 1 is passed through reacting gas to requirement of experiment pressure, regulate bath temperature after standing a period of time to requirement of experiment temperature, enter
Row hydrate reaction of formation.
4th step, uses temperature oscillation to make hydrate reaction complete, and staff can be by the required reaction of calculated hydration thing reaction
In gas flow, addition amount of reactant gases and autoclave 1, gas pressure is confirmed whether that reaction is completely.Open hydraulic main valve 18,
Starting hand increasing pressure pump 6 to pressurize, when pressure reaches desirable pressure, piston 3 extrudes acquisition pressure to two sleeve 2 both sides simultaneously
Hydrate sample after contracting.
5th step, after treating sample compression, starts thermal analyzer 34 and starts the measurement of the hot physical property of hydrate, thermal analyzer 34
Being heated sample by probe 4, record temperature raises in time simultaneously resistance general measure signal back thermal analyzer
34, carry out real-time data acquisition, finally by computer 32 measurement signal being passed to data acquisition unit 33 by thermal analyzer 34
Calculate the thermal physical property parameter of hydrate sample.
Embodiment 3
A kind of hydrate thermophysical property measurement method, described measuring method need to use the hot physical property of a kind of hydrate described in embodiment 1 to survey
Amount system, concrete measuring process is as follows:
The first step, when hydrate sample in-situ generates and sample is discrete particles shape, first will be provided with two sets of probe 4
Cylinder 2 is placed in horizontal autoclave 1, then deposit and solution is slowly injected in the charging aperture 36 from sleeve 2.
Second step, installs the tubular lid 5 of autoclave 1, by leak detection channel connection nitrogen cylinder and autoclave 1, beats
Open the leak detection valve on leak detection passage, be filled with nitrogen and carry out system leak detection, it is ensured that autoclave 1 does not has leak source.
It is then shut off valve of hunting leak, opens vacuum-pumping valve 23, start vacuum pump 9, by autoclave 1 evacuation, take out true
After sky, close vacuum-pumping valve 23 and autoclave 1 is put in constant water bath box 30；According to requirement of experiment, adjust
Temperature in whole constant water bath box 30.
3rd step, opens reacting gas gas cylinder 7,8, opens the air-supplying valve 21,22 of reacting gas air supply channel, anti-to high pressure
Answer and still 1 is passed through reacting gas to requirement of experiment pressure, regulate bath temperature after standing a period of time to requirement of experiment temperature, enter
Row hydrate reaction.
4th step, uses temperature oscillation to make hydrate reaction complete, and staff can be by the required reaction of calculated hydration thing reaction
In gas flow, addition amount of reactant gases and autoclave 1, gas pressure is confirmed whether that reaction is completely.Open hydraulic main valve 18,
Starting hand increasing pressure pump 6 to pressurize, when pressure reaches desirable pressure, piston 3 extrudes acquisition pressure to two sleeve 2 both sides simultaneously
Hydrate sample after contracting.
5th step, after treating sample compression, starts thermal analyzer 34 and starts the measurement of the hot physical property of hydrate, thermal analyzer 34
Being heated sample by probe 4, record temperature raises in time simultaneously resistance general measure signal back thermal analyzer
34, carry out real-time data acquisition, finally by computer 32 measurement signal being passed to data acquisition unit 33 by thermal analyzer 34
Calculate the thermal physical property parameter of hydrate sample.
Embodiment 4
A kind of hydrate thermophysical property measurement method, described measuring method need to use a kind of ex situ hydrate heat described in embodiment 1
Physical measurement system, concrete measuring process is as follows:
The first step, is first pressed into the sample of two pieces of same specifications by the hydrate sample collected so that it is can put in sleeve 2,
4 contact surfaces polish with popping one's head in.Then two sleeves 2 are snapped together.Probe 4 with protecting film is stuck in two sleeves
In the groove of 2, subsequently two sleeves snapped together 2 are put in horizontal autoclave 1.
Second step, installs the tubular lid 5 of autoclave 1, by leak detection channel connection nitrogen cylinder and autoclave 1, beats
Open the leak detection valve on leak detection passage, be filled with nitrogen and carry out system leak detection, it is ensured that autoclave 1 does not has leak source.
It is then shut off valve of hunting leak, opens vacuum-pumping valve 23, start vacuum pump 9, by autoclave 1 evacuation, take out true
After sky, close vacuum-pumping valve 23 and autoclave 1 is put in constant water bath box 30；According to requirement of experiment, adjust
Temperature in whole constant water bath box 30.
3rd step, opens reacting gas gas cylinder 7,8, opens the air-supplying valve 21,22 of reacting gas air supply channel, anti-to high pressure
Answer and still 1 be passed through required reacting gas to requirement of experiment pressure, regulate bath temperature after standing a period of time to requirement of experiment temperature,
Carry out hydrate reaction.
4th step, opens hydraulic main valve 18, starts hand increasing pressure pump 6 and pressurizes, and when pressure reaches desirable pressure, piston 3 is right
Two sleeve 2 both sides extrude the hydrate sample after obtaining compression simultaneously.
5th step, after treating sample compression, starts thermal analyzer 34 and starts the measurement of the hot physical property of hydrate, thermal analyzer 34
4 being heated sample by probe, record temperature raises in time simultaneously resistance is also fed back to thermal analyzer 34,
Passed to data acquisition unit 33 by it and carry out real-time data acquisition, finally calculated the hot thing of hydrate sample by computer 32
Property parameter.
A kind of hydrate thermophysical property measurement method described in above-described embodiment 2 to embodiment 4, only need to by hydrate or deposit with
Solution is placed in sleeve 2, and two pistons 3 extrude two sleeves 2 respectively from both sides, and hydrate both sides are squeezed simultaneously,
Probe 4 will not move, and also will not bend, it is possible to reduces probe 4 damage.Meanwhile, the hydrate concordance after the extruding of both sides is good,
Experiment certainty of measurement is high.Sample adds in sleeve 2, is possible to prevent sample to drop and adheres on the inwall of autoclave 1.
Autoclave 1 is inserted in constant water bath box 30, and in constant water bath box 30, temperature is regulated and controled by temperature controller, logical
Excess temperature succusion, makes temperature constantly change, and can accelerate the reaction of formation of hydrate.
Certainly, described above is not limitation of the present invention, and the present invention is also not limited to the example above, the art
Change that technical staff is made in the essential scope of the present invention, retrofit, add or replace, also should belong to the protection of the present invention
Scope.
Claims (9)
1. a hydrate thermophysical property measurement system, it is characterised in that include autoclave, temperature regulating device, compression forming dress
Put, feeder, measurement apparatus and data acquisition unit；
Described autoclave bottom is provided with base support, and base support is provided with two sleeves, and two sleeves are symmetrical,
Center on each sleeve transversely axis wall has charging aperture；Be additionally provided with in autoclave the first temperature sensor and
Pressure transducer, described first temperature sensor is stretched in sleeve by charging aperture；
Described temperature regulating device includes that constant water bath box, autoclave are placed in constant water bath box；Also set up in constant water bath box
There are the second temperature sensor and agitator；Constant water bath box connects temperature controller；
Described compression-molding apparatus includes the piston being separately positioned on two sleeve rear portions, in the autoclave at two piston rear portions
Also having inlet on wall, two inlets are connected to the first hydraulic pressure arm and the second hydraulic pressure arm, and the first hydraulic pressure props up
Pipe all connects hydraulic main with the second hydraulic pressure arm, and described hydraulic main connects booster pump；It is additionally provided with liquid on described hydraulic main
Pressure main valve；
Described feeder includes hunt leak passage, evacuation passageway, reacting gas air supply channel and emptying passage；Leak detection passage,
Evacuation passageway, reacting gas air supply channel are all connected with autoclave with emptying passage；Described evacuation passageway is also connected with
There is vacuum pump；Reacting gas air supply channel connection reacting gas gas cylinder；It is provided with relief valve and vent valve on described emptying passage；
Described measurement apparatus includes thermal analyzer, and the probe of thermal analyzer is provided with the protection being made up of polymethyl methacrylate
Film；Being provided with the groove of Relative distribution on two sleeves, when two sleeves snap together, two grooves form probe and install
Hole, described probe inserts two sleeve centre positions by probe mounting holes；
Described data acquisition unit connects thermal analyzer, pressure transducer, the first temperature sensor, and data acquisition unit is also by number
Connect according to output signal line and have computer.
2. a kind of hydrate thermophysical property measurement system as claimed in claim 1, it is characterised in that described compression-molding apparatus is also
Including pressure control assembly, pressure control assembly includes the diastimeter for measuring sleeve and plunger distance, and described diastimeter connects
Having hydraulic controller, described hydraulic controller connects the first electro-hydraulic valve and the second electro-hydraulic valve, described first electronic liquid
Pressure valve and the second electro-hydraulic valve are separately mounted on the first hydraulic pressure arm and the second hydraulic pressure arm.
3. a kind of hydrate thermophysical property measurement system as claimed in claim 2, it is characterised in that described diastimeter includes two
Infrared signal assembly, described infrared signal assembly includes that infrared transmitter and infrared remote receiver, said two infrared signal assembly divide
It is not fixed in the rear groove of sleeve.
4. a kind of hydrate thermophysical property measurement system as claimed in claim 1, it is characterised in that in piston and autoclave
Wall contact position is provided with seal washer.
5. a kind of hydrate thermophysical property measurement system as claimed in claim 1, it is characterised in that inside described autoclave
Articulated elements is provided with at least two support bar, and probe is fixed on the upper end of support bar, and articulated elements is threadedly attached in instead
Answer on still inwall.
6. a hydrate thermophysical property measurement method, it is characterised in that by a kind of water as described in right 1 to 5 any one
Compound thermophysical property measurement system measures, and concrete measuring process is as follows:
The first step, by the probe card with protecting film in the groove of two sleeves, then puts the sleeve that two snap together
In horizontal autoclave；
Second step, installs the tubular lid of autoclave, is hunted leak by leak detection channel system, it is ensured that autoclave does not leak
Point；
It is then shut off the leak detection valve on passage of hunting leak, opens vacuum-pumping valve, start vacuum pump, by autoclave evacuation,
After evacuation, close vacuum-pumping valve and autoclave is put in constant water bath box；According to requirement of experiment, adjust perseverance
Tepidarium the temperature inside the box；
3rd step, opens the air-supplying valve of reacting gas air supply channel, is passed through reacting gas to requirement of experiment in autoclave
Pressure, after standing a period of time, regulating thermostatic bath temperature is to requirement of experiment temperature, carries out hydrate reaction of formation；
4th step, uses temperature oscillation to make hydrate reaction complete；Open hydraulic main valve, start hand increasing pressure pump pressurization, treat
When pressure reaches desirable pressure, piston extrudes the hydrate sample after obtaining compression to two sleeve both sides simultaneously；
5th step, after treating sample compression, starts thermal analyzer and carries out the measurement of the hot physical property of hydrate, and thermal analyzer is by visiting
Sample is heated by head, simultaneously the record resistance that raises in time of temperature, and metrical information is fed back to thermal analyzer, by
Thermal analyzer passes to data acquisition unit and carries out real-time data acquisition, is finally calculated the hot physical property of hydrate sample by computer
Parameter.
7. a kind of hydrate thermophysical property measurement method as claimed in claim 6, it is characterised in that when hydrate sample in-situ is raw
Cheng Shi, first weighs a certain proportion of deposit and solution is filled in two sleeves, is compacted smooth out surface, then by two sets
Cylinder snaps together.
8. a kind of hydrate thermophysical property measurement method as claimed in claim 6, it is characterised in that when hydrate sample in-situ is raw
When one-tenth and sample are discrete particles shape, first two sleeves being provided with probe are placed in horizontal autoclave, then
Deposit and solution are slowly injected in the charging aperture from sleeve.
9. a kind of hydrate thermophysical property measurement method as claimed in claim 6, it is characterised in that when hydrate sample ex situ
During generation, first hydrate sample is pressed into the sample of two pieces of same specifications so that it is can put in sleeve, with probe contacts face
Polish.
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| CN112577991A (en) * | 2020-06-24 | 2021-03-30 | 山东科技大学 | Device and method for measuring heat conductivity coefficient of hydrate by means of ex-situ pressure maintaining and fidelity |
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| CN112577991A (en) * | 2020-06-24 | 2021-03-30 | 山东科技大学 | Device and method for measuring heat conductivity coefficient of hydrate by means of ex-situ pressure maintaining and fidelity |
| CN112577991B (en) * | 2020-06-24 | 2023-03-14 | 山东科技大学 | Device and method for ex-situ pressure-maintaining fidelity measurement of heat conductivity coefficient of hydrate |
| CN112362690A (en) * | 2020-11-06 | 2021-02-12 | 西南石油大学 | Hydrate generation induction time measuring device |
| CN112546962A (en) * | 2020-12-01 | 2021-03-26 | 中国科学院广州能源研究所 | Device and method for quickly preparing gas hydrate cylinder |
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