CN105973937B - A kind of hydrate thermophysical property measurement system and its measurement method - Google Patents
A kind of hydrate thermophysical property measurement system and its measurement method Download PDFInfo
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- CN105973937B CN105973937B CN201610566181.3A CN201610566181A CN105973937B CN 105973937 B CN105973937 B CN 105973937B CN 201610566181 A CN201610566181 A CN 201610566181A CN 105973937 B CN105973937 B CN 105973937B
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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
A kind of hydrate thermophysical property measurement system and its measurement method, thermophysical property measurement system include autoclave, temperature regulating device, compression-molding apparatus, feeder, measuring device and data collector.Temperature regulating device includes constant water bath box, and autoclave is placed in constant water bath box.Compression-molding apparatus includes piston, is provided with inlet on the autoclave inner wall at piston rear portion, inlet is connected with booster pump.Measuring device includes thermal analyzer, and the probe of thermal analyzer is inserted into two sleeve middle positions.When being measured by a kind of above-mentioned hydrate thermophysical property measurement system, sample is put into sleeve first, then piston press sleeve, subsequently passes through the hot physical property that thermal analyzer measures hydrate.A kind of above-mentioned hydrate thermophysical property measurement system and its measurement method, hydrate two sides are squeezed simultaneously, and probe will not be bent, and can be reduced tip damage.Meanwhile hydrate consistency is good, measurement accuracy is high.
Description
Technical field
The present invention relates to a kind of thermophysical property measurement system and its measurement methods, and in particular to a kind of measurement accuracy is high, probe
The measurement method of non-damageable hydrate thermophysical property measurement system and its hydrate thermophysical property measurement system.
Background technique
Since starting the capacity of heat transmission to solid 18th century mid-term Benjamin Franklin and carrying out experimental study,
The measurement method of a variety of thermal coefficients is developed, the measurement of thermal coefficient is broadly divided into steady state method and cold store enclosure two major classes.
The research of hydrate thermal coefficient in recent years achieves certain progress, but due to the difference of measurement method and laboratory facilities, surveys
Amount result is not quite similar.In measurement process, it is contemplated that the metastability of hydrate, scientific research personnel are more likely to using unstable state
Method, such as probe method, heat-pole method, transition plane heat source method etc..When the thermal coefficient progress survey in situ using probe method to hydrate
When amount, probe can be radially arranged, can also axially arrange probe, when radially arrangement probe it is difficult to ensure that adding to sample
Probe form does not change when pressure is fine and close, and cannot effectively drive away residual gas in sample；And then cannot when axially arrangement probe
Carry out axial pressure.The thermal coefficient of transition plane heat source method measurement hydrate can also be used, the advantages of this method is measurement
Speed faster, and is not influenced by thermal contact resistance, but probe vertical is inserted into autoclave, the lid installation of autoclave
When probe can rotate, pop one's head in and is easily damaged in deposition medium, in addition, popping one's head in flexible damage when piston compacting sample
It is bad.
Summary of the invention
Easy to damage in order to solve the problems, such as to pop one's head in the prior art, the present invention provides a kind of hydrate thermophysical property measurement system
And its measurement method.
A kind of hydrate thermophysical property measurement system provided by the invention, including autoclave, temperature regulating device, compression forming
Device, feeder, measuring device and data collector.The autoclave lower part is provided with base support, base support
There are two sleeve, two sleeves are symmetrical for upper setting, and center of each sleeve transversely on axis wall surface is provided with charging aperture；
Pressure sensor and the first temperature sensor are additionally provided in autoclave, the first temperature sensor protrudes into set by charging aperture
In cylinder.The temperature regulating device includes constant water bath box, and autoclave is placed in constant water bath box, setting in constant water bath box
There is coil pipe, there is refrigerant circulation flowing in the coil pipe.Second temperature sensor and blender are additionally provided in constant water bath box；
Constant water bath box is connected with temperature controller.The compression-molding apparatus includes two work for being separately positioned on two sleeve rear portions
It fills in, also has inlet on the autoclave inner wall at two piston rear portions, two inlets are connected separately with the first liquid
Branch pipe and the second hydraulic branch pipe are pressed, the first hydraulic branch pipe and the second hydraulic branch pipe are connected to hydraulic supervisor, and the hydraulic supervisor connects
Logical booster pump；Hydraulic main valve is additionally provided on the hydraulic supervisor.Feeder includes leak detection channel, evacuation passageway, reaction
Gas air supply channel and emptying channel；Channel, evacuation passageway, reaction gas air supply channel and emptying channel hunt leak and high pressure
Reaction kettle is connected；The evacuation passageway is also connected with vacuum pump；Reaction gas air supply channel is connected to reaction gas gas cylinder；It puts
Safety valve and vent valve are provided on empty channel.The measuring device includes thermal analyzer, is provided on the probe of thermal analyzer
The protective film made of polymethyl methacrylate；The groove of Relative distribution is provided on two sleeves, when two sleeves fasten
When together, two grooves form probe mounting holes, and the probe is inserted into two sleeve middle positions by probe mounting holes.It is described
Data collector is connected with thermal analyzer, pressure sensor, the first temperature sensor, and data collector, which is also exported by data, to be believed
Number line is connected with computer.
Preferably, the compression-molding apparatus further includes pressure control assembly, and pressure control assembly includes being used for measuring unit
The rangefinder of cylinder and plunger distance, the rangefinder are connected with hydraulic controller, and it is electronic that the hydraulic controller is connected with first
Hydraulic valve and the second electro-hydraulic valve, first electro-hydraulic valve and the second electro-hydraulic valve are separately mounted to the first hydraulic branch
On pipe and the second hydraulic branch pipe.By distance between stadia surveying piston and sleeve, signal is delivered to hydraulic control by rangefinder
Device processed, hydraulic controller judge two-piston respectively apart from corresponding sleeve distance, and by adjusting the first electro-hydraulic valve and the
Two electro-hydraulic valve regulating piston movement velocitys make two pistons while abutting two sleeves respectively and being compressed, guarantee pressing
It pops one's head in and is not destroyed in compression process.
Further preferably, the rangefinder includes two infrared signal components, and the infrared signal component includes infrared emission
Device and infrared remote receiver, described two infrared signal components are separately fixed in the rear groove of sleeve.Pass through infrared signal group
Part measures sleeve and plunger distance, and measurement accuracy is high.
Preferably, piston and autoclave inner wall contact position are provided with seal washer.In piston and autoclave
Seal washer, the autoclave cavity that can prevent piston rear fluid from leaking between two-piston is arranged in wall contact position.
Preferably, at least two support rods are also provided with by articulation piece inside the autoclave, probe is fixed on
The upper end of support rod, articulation piece are threadedly attached on reaction kettle inner wall.When needing to be removed or placed into sleeve, only need to rotate
Support rod, the setting of support rod will not influence the taking-up of sleeve and be put into.It, can also be by screw thread when sleeve is excessive
The articulation piece of connection is dismantled, and is then removed support rod, is finally removed or placed into sleeve, the setting of the support rod can fix spy
Head, meanwhile, nor affect on being removed or placed into for sleeve.
A kind of hydrate thermophysical property measurement system provided by the invention has the advantages that compared with prior art
A kind of above-mentioned hydrate thermophysical property measurement system, can make deposit and solution original position high-pressure synthesis hydrate, can
With in situ measurement thermal physical property parameter, hydrate thermal physical property parameter can also be measured with ex situ, tip damage can be reduced, improved real
Test accuracy of measurement.
The sleeve can guarantee the consistency of sample, reduce sample and tie to measurement by sample compression at typical cylindrical body
The influence of fruit.The setting of sleeve prevents hydrate to be extruded in the autoclave tubular lid of top；It can also subtract to greatest extent
Few deposit or hydrate are scattered on autoclave inner wall, to reduce piston motion resistance, reduce piston as far as possible
Two sides pressure difference.It is provided with charging aperture on sleeve, charging aperture can be used to that loose dry deposit is added, and also can be convenient insertion the
One temperature sensor.
Autoclave is placed in constant water bath box, and refrigerant realizes temperature control, constant water bath box in coil pipe internal circulation flow
Interior temperature is regulated and controled by temperature controller, can be carried out program cooling and heating to bath temperature, i.e., be made by temperature oscillation
Substance fast reaction in autoclave；The first temperature sensor, second temperature sensor and blender is arranged in water bath with thermostatic control, the
For one temperature sensor to measure temperature in sleeve, second temperature sensor is warm in real time for measuring water-bath in constant water bath box
Degree, blender make in constant water bath box that temperature is uniform everywhere.
Compression-molding apparatus includes the piston of booster pump and autoclave both ends by hydraulic-driven, when judging that hydrate is anti-
It after answering, is pressurizeed by booster pump, the piston at autoclave both ends is moved to sleeve direction, piston press sleeve, is completed
Compression forming to sample can guarantee that probe will not using two-sided compression since probe is fixed on autoclave center
It is subjected to displacement because of squeezing, can effectively protect probe, be destroyed probe not.
Due to the extruding of piston in autoclave, pressure rise in kettle must be led to, to guarantee that pressure is in safety pressure in kettle
Under power, safety valve is set, pressure is arranged hydrate in a little higher than autoclave and generates pressure on antiaircraft channel.Work as piston press
When pressure being caused in autoclave to be more than safety valve setting pressure, safety valve is opened, and is released stress, when autoclave internal pressure
When power reaches safety valve setting pressure, safety valve is closed, and is guaranteed that autoclave works under safe pressure with this, is kept high pressure anti-
It answers kettle internal pressure power to keep constant, reduces the influence generated by pressure change to hydrate sample.
The present invention also provides a kind of hydrate thermophysical property measurement method, the measurement method need to use a kind of above-mentioned hydrate
Thermophysical property measurement system, specific measuring process are as follows:
The protective film of probe is stuck in the groove of two sleeves by the first step, the sleeve for then snapping together two
It is put into horizontal autoclave.
Second step installs the tubular lid of autoclave, carries out system leak detection by leak detection channel, guarantees reaction under high pressure
Kettle does not have leak source.
The leak detection valve being then shut off on leak detection channel, opens vacuum-pumping valve, starts vacuum pump, autoclave is taken out
Vacuum after vacuumizing, closes vacuum-pumping valve and autoclave is put into constant water bath box；According to requirement of experiment,
Adjust water bath with thermostatic control the temperature inside the box.
Third step opens reaction gas gas cylinder, the air-supplying valve of reaction gas air supply channel is opened, into autoclave
Reaction gas is passed through to requirement of experiment pressure, bath temperature is adjusted after standing a period of time to requirement of experiment temperature, is hydrated
Object generates reaction.
4th step keeps hydrate reaction complete using temperature oscillation, and staff can react institute by calculated hydration object
Amount of reactant gases is needed, gas pressure in amount of reactant gases and autoclave is added is confirmed whether fully reacting.After fully reacting,
Hydraulic main valve is opened, starting hand increasing pressure pump pressurization, when pressure reaches required pressure, piston squeezes two sleeve two sides simultaneously
Pressure obtains compressed hydrate sample.
5th step, after sample compression, starting thermal analyzer carries out the measurement of the hot physical property of hydrate, and thermal analyzer is logical
It crosses probe to heat sample, while recording temperature and raised resistance value and being fed back to thermal analyzer at any time, by heat
Metrical information is passed to data collector and carries out real-time data acquisition by analyzer, and hydrate sample finally is calculated by computer
The thermal physical property parameter of product.
Preferably, when hydrate sample in-situ preparation, a certain proportion of deposit is weighed first and solution is filled in two
In a sleeve, it is compacted smooth out surface, then snaps together two sleeves.
Preferably, when hydrate sample in-situ preparation and when sample is discrete particles shape, it will be equipped with the two of probe first
A sleeve is placed in horizontal autoclave, then slowly injects deposit and solution from the charging aperture on sleeve.
Compared with the prior art, the present invention has the following beneficial effects:
Hydrate or deposit and solution need to be only placed in sleeve by a kind of above-mentioned hydrate thermophysical property measurement method,
Two pistons squeeze two sleeves from two sides respectively, and hydrate two sides are squeezed simultaneously, and probe will not move, will not be curved
Folding, can reduce tip damage.Meanwhile two sides hydrate consistency after extruding is good, experiment measurement accuracy is high.Sample is added to
In sleeve, it can prevent sample from falling and adhering on the inner wall of autoclave.
Autoclave is placed in constant water bath box, and water bath with thermostatic control the temperature inside the box is regulated and controled by temperature controller, is passed through
Temperature oscillation changes temperature constantly, can accelerate the generation reaction of hydrate.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of hydrate thermophysical property measurement system.
Fig. 2 is the sectional view 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 reaction gas gas cylinder；9
Vacuum pump；10 gas flowmeters；11,12 gas pressure reducer；13 pressure sensors；14 first temperature sensors；15 safety valves；16
Vent valve；The first electro-hydraulic valve of 17a；The second electro-hydraulic valve of 17b；18 hydraulic main valves；19,20 first pressure gauge；21, it 22 supplies
Air valve, 23 vacuum-pumping valves；24 hydraulic controllers；25 second temperature sensors；26 blenders；27 seal washers；28 pedestals
Bracket；29 coil pipes；30 constant water bath box；31 rangefinders；32 computers；33 data collectors；34 thermal analyzers；35 signals electricity
Cable；36 charging apertures；37 infrared signal components；38 support rods；39 probe cables；40 second pressure gauges.
Specific embodiment
Embodiment 1
A kind of hydrate thermophysical property measurement system, including autoclave 1, temperature regulating device, compression-molding apparatus, gas supply dress
It sets, measuring device and data collector.1 lower part of autoclave is provided with base support 28, is arranged on base support 28
There are two sleeve 2, two sleeves 2 are symmetrical, and center of each sleeve 2 transversely on axis wall surface is provided with charging aperture 36；
Pressure sensor 13 and the first temperature sensor 14 are additionally provided in autoclave 1, the first temperature sensor 14 passes through charging
Hole 36 is inserted into sleeve 2.
The temperature regulating device includes constant water bath box 30, and autoclave 1 is placed in constant water bath box 30, water bath with thermostatic control
It is provided with coil pipe 29 in case 30, has refrigerant circulation flowing in the coil pipe 29.The second temperature is additionally provided in constant water bath box 30
Degree sensor 25 and blender 26, constant water bath box 30 are connected with temperature controller.
The compression-molding apparatus includes two pistons 3 for being separately positioned on two 2 rear portions of sleeve, and piston 3 and high pressure are anti-
1 inner wall contact position of kettle is answered to be provided with seal washer 27.Also had on 1 inner wall of autoclave at two 3 rear portions of piston into
Liquid mouth, two inlets are connected separately with the first hydraulic branch pipe and the second hydraulic branch pipe, the first hydraulic branch pipe and the second hydraulic branch
Pipe is connected to hydraulic supervisor, and the hydraulic supervisor is connected to booster pump, and the booster pump can be hand increasing pressure pump 6；It is described hydraulic
Hydraulic main valve 18 is additionally provided on supervisor.Compression-molding apparatus further includes pressure control assembly, and pressure control assembly includes being used for
The rangefinder 31 of sleeve 2 and 3 distance of piston is measured, rangefinder 31 includes two infrared signal components 37, the infrared signal group
Part 37 includes infrared transmitter and infrared remote receiver, and the rear portion that described two infrared signal components 37 are separately fixed at sleeve 2 is recessed
In slot.Sleeve 2 and 3 distance of piston are measured by infrared signal component 37, measurement accuracy is high.Rangefinder 31 is also connected with hydraulic control
Device 24 processed, the hydraulic controller 24 are connected with the first electro-hydraulic valve 17a and the second electro-hydraulic valve 17b, the first electronic liquid
Pressure valve 17a and the second electro-hydraulic valve 17b are separately mounted on the first hydraulic branch pipe and the second hydraulic branch pipe.Pass through rangefinder 31
Distance between piston 3 and sleeve 2 is measured, signal is delivered to hydraulic controller 24 by rangefinder 31, and hydraulic controller 24 judges two
Piston 3 passes through the first electro-hydraulic valve 17a of adjusting and the second electro-hydraulic valve 17b regulating piston respectively apart from 2 distance of sleeve
3 movement velocitys make two pistons 3 while abutting two sleeves 2 respectively；Piston 3 abut sleeve 2 after, 31 ranging of rangefinder away from
From being zero, distance signal is passed into hydraulic controller 24 at this time, hydraulic controller 24 controls the first electro-hydraulic valve 17a and the
It is identical that two electro-hydraulic valve 17b turn on degree, guarantees that 3 extruding force of two-piston is essentially identical, to guarantee in compression process
Probe 4 is not destroyed.
Feeder includes leak detection channel, evacuation passageway, reaction gas air supply channel and emptying channel；Leak detection channel,
Evacuation passageway, reaction gas air supply channel and emptying channel are connected with autoclave 1.The evacuation passageway also connects
It is connected to vacuum pump 9；The reaction gas air supply channel is connected to reaction gas gas cylinder 7,8；Safety is provided on the emptying channel
Valve 15 and vent valve 16.
The measuring device includes thermal analyzer 34, and the thermal analyzer 34 can be Hot Disk thermal constant analyzer,
The protective film made of polymethyl methacrylate is provided on the probe 4 of thermal analyzer 34；It is provided on two sleeves 2 opposite
The groove of distribution, when two sleeves 2 snap together, two grooves form 4 mounting holes of probe, and the probe 4 passes through probe 4
Mounting hole is inserted into two sleeves, 2 middle position.
The data collector 33 is connected with thermal analyzer 34, pressure sensor 13, the first temperature sensor 14, and data are adopted
Storage 33 is also connected with computer 32 by data-out signal line；Wherein, Agilent data can be used in data collector 33
Acquisition Instrument.
Further, at least two support rods 38, probe 4 are also provided with by articulation piece inside the autoclave 1
It is fixed on the upper end of support rod 38, articulation piece is threadedly attached on reaction kettle inner wall.When needing to be removed or placed into sleeve 2
When, only it need to rotate support rod 38, the setting of support rod 38 will not influence the taking-up of sleeve 2 and be put into.When 2 mistake of sleeve
When big, the articulation piece of threaded connection can also be dismantled, then remove support rod 38, finally be removed or placed into sleeve 2, the branch
The setting of strut 38 can fix probe 4, meanwhile, nor affect on being removed or placed into for sleeve 2.
A kind of above-mentioned hydrate thermophysical property measurement system, can make deposit and solution original position high-pressure synthesis hydrate, can
With in situ measurement thermal physical property parameter, ex situ measurement thermal physical property parameter can also be carried out, 4 damage of probe can be reduced, improved real
Test accuracy of measurement.
The sleeve 2 can guarantee the consistency of sample, reduce sample and survey to experiment by sample compression at typical cylindrical body
Measure the influence of result.The setting of sleeve 2 prevents hydrate sample to be extruded in 1 tubular lid 5 of top autoclave；It can also be with
Sediment sample is reduced to greatest extent to be scattered on 1 inner wall of autoclave, to reduce 3 resistance of motion of piston, is subtracted as far as possible
3 two sides pressure difference of piston is lacked.Charging aperture 36 is provided on sleeve 2, charging aperture 36 can be used to that loose dry deposit is added,
The first temperature sensor 14 of insertion can be facilitated.
Autoclave 1 is placed in constant water bath box 30, and refrigerant recycles in coil pipe 29 realizes temperature control, constant water bath box
Temperature is regulated and controled by temperature controller in 30, can carry out program cooling and heating, setting in autoclave 1 to bath temperature
First temperature sensor 14, water bath with thermostatic control are arranged second temperature sensor 25 and blender 26, the first temperature sensor 14 to
Temperature in sleeve 2 is measured, for measuring water-bath real time temperature in constant water bath box 30, blender 26 makes second temperature sensor 25
Temperature is uniform everywhere in constant water bath box 30.
Compression-molding apparatus includes the piston 3 of booster pump and 1 both ends of autoclave by hydraulic-driven, when judging hydrate
After reaction, it is pressurizeed by booster pump, the piston 3 at 1 both ends of autoclave is moved to 2 direction of sleeve, and piston 3 squeezes sleeve
2, the compression forming of complete paired samples can guarantee that probe 4 will not be subjected to displacement because of extruding using two-sided compression, can effectively protect
Shield probe 4 is not destroyed.
Due to the extruding of piston 3 in autoclave 1, pressure rise in kettle must be led to, to guarantee that pressure is in safety in kettle
Under pressure, safety valve 15 is set, pressure is arranged hydrate in a little higher than autoclave 1 and generates pressure, works as work on antiaircraft channel
Plug 3 squeezes and causes in autoclave 1 pressure when being more than that safety valve 15 sets pressure, and safety valve 15 is opened, and is released stress, is worked as height
When pressure reaches the setting pressure of safety valve 15 in pressure reaction kettle 1, safety valve 15 is closed, and guarantees autoclave 1 in safety with this
It works under pressure, keeps constant 1 internal pressure power of autoclave, reduce the influence generated by pressure change to hydrate sample.
Embodiment 2
A kind of hydrate thermophysical property measurement method, the measurement method need to use a kind of hydrate heat described in embodiment 1
Physical measurement system, specific measuring process are 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
Two sleeves 2 are snapped together.Probe 4 with protective film is stuck in the groove of two sleeves 2, is then fastened two
Sleeve 2 together is put into horizontal autoclave 1.
Second step installs the tubular lid 5 of autoclave 1, is connected to nitrogen cylinder and autoclave by leak detection channel
1, the leak detection valve on leak detection channel is opened, nitrogen is filled with and carries out system leak detection, guarantees that autoclave 1 does not have leak source.
It is then shut off leak detection valve, opens vacuum-pumping valve 23, starts vacuum pump 9, autoclave 1 is vacuumized, is taken out
After vacuum, closes vacuum-pumping valve 23 and autoclave 1 is put into constant water bath box 30；According to requirement of experiment, adjust
Temperature in whole constant water bath box 30.
Third step opens reaction gas gas cylinder 7,8, the air-supplying valve 21,22 of reaction gas air supply channel is opened, to high pressure
It is passed through reaction gas in reaction kettle 1 to requirement of experiment pressure, bath temperature is adjusted after standing a period of time to requirement of experiment temperature,
It carries out hydrate and generates reaction.
4th step keeps hydrate reaction complete using temperature oscillation, and staff can react institute by calculated hydration object
Amount of reactant gases is needed, gas pressure in amount of reactant gases and autoclave 1 is added is confirmed whether fully reacting.Open Hydraulic Main
Valve 18, starting hand increasing pressure pump 6 pressurizes, and when pressure reaches required pressure, piston 3 squeezes two 2 two sides of sleeve simultaneously and obtains
Obtain compressed hydrate sample.
5th step, after sample compression, starting thermal analyzer 34 starts the measurement of the hot physical property of hydrate, thermal analyzer
34 are heated by 4 pairs of samples of popping one's head in, while recording temperature raised resistance value and by measuring signal feedback backheat point at any time
Analyzer 34 carries out real-time data acquisition measuring signal is passed to data collector 33 by thermal analyzer 34, finally by calculating
The thermal physical property parameter of hydrate sample is calculated in machine 32.
Embodiment 3
A kind of hydrate thermophysical property measurement method, the measurement method need to use a kind of hydrate heat described in embodiment 1
Physical measurement system, specific measuring process are as follows:
The first step when hydrate sample in-situ preparation and when sample is discrete particles shape, will be equipped with the two of probe 4 first
A sleeve 2 is placed in horizontal autoclave 1, then by deposit and solution from the charging aperture 36 on sleeve 2 slowly
Injection.
Second step installs the tubular lid 5 of autoclave 1, is connected to nitrogen cylinder and autoclave by leak detection channel
1, the leak detection valve on leak detection channel is opened, nitrogen is filled with and carries out system leak detection, guarantees that autoclave 1 does not have leak source.
It is then shut off leak detection valve, opens vacuum-pumping valve 23, starts vacuum pump 9, autoclave 1 is vacuumized, is taken out
After vacuum, closes vacuum-pumping valve 23 and autoclave 1 is put into constant water bath box 30；According to requirement of experiment, adjust
Temperature in whole constant water bath box 30.
Third step opens reaction gas gas cylinder 7,8, the air-supplying valve 21,22 of reaction gas air supply channel is opened, to high pressure
It is passed through reaction gas in reaction kettle 1 to requirement of experiment pressure, bath temperature is adjusted after standing a period of time to requirement of experiment temperature,
Carry out hydrate reaction.
4th step keeps hydrate reaction complete using temperature oscillation, and staff can react institute by calculated hydration object
Amount of reactant gases is needed, gas pressure in amount of reactant gases and autoclave 1 is added is confirmed whether fully reacting.Open Hydraulic Main
Valve 18, starting hand increasing pressure pump 6 pressurizes, and when pressure reaches required pressure, piston 3 squeezes two 2 two sides of sleeve simultaneously and obtains
Obtain compressed hydrate sample.
5th step, after sample compression, starting thermal analyzer 34 starts the measurement of the hot physical property of hydrate, thermal analyzer
34 are heated by 4 pairs of samples of popping one's head in, while recording temperature raised resistance value and by measuring signal feedback backheat point at any time
Analyzer 34 carries out real-time data acquisition measuring signal is passed to data collector 33 by thermal analyzer 34, finally by calculating
The thermal physical property parameter of hydrate sample is calculated in machine 32.
Embodiment 4
A kind of hydrate thermophysical property measurement method, the measurement method need to use a kind of ex situ water described in embodiment 1
Object thermophysical property measurement system is closed, specific measuring process is as follows:
Collected hydrate sample is pressed into the sample of two pieces of same specifications first, can put set by the first step
In cylinder 2, polished with 4 contact surfaces of probe.Then two sleeves 2 are snapped together.Probe 4 with protective film is stuck in two
In the groove of sleeve 2, subsequently the sleeve 2 that two snap together is put into horizontal autoclave 1.
Second step installs the tubular lid 5 of autoclave 1, is connected to nitrogen cylinder and autoclave by leak detection channel
1, the leak detection valve on leak detection channel is opened, nitrogen is filled with and carries out system leak detection, guarantees that autoclave 1 does not have leak source.
It is then shut off leak detection valve, opens vacuum-pumping valve 23, starts vacuum pump 9, autoclave 1 is vacuumized, is taken out
After vacuum, closes vacuum-pumping valve 23 and autoclave 1 is put into constant water bath box 30；According to requirement of experiment, adjust
Temperature in whole constant water bath box 30.
Third step opens reaction gas gas cylinder 7,8, the air-supplying valve 21,22 of reaction gas air supply channel is opened, to high pressure
It is passed through required reaction gas in reaction kettle 1 to requirement of experiment pressure, bath temperature is adjusted after standing a period of time to requirement of experiment
Temperature carries out hydrate reaction.
4th step opens hydraulic main valve 18, and starting hand increasing pressure pump 6 pressurizes, when pressure reaches required pressure, piston 3
Two 2 two sides of sleeve are squeezed simultaneously and obtain compressed hydrate sample.
5th step, after sample compression, starting thermal analyzer 34 starts the measurement of the hot physical property of hydrate, thermal analyzer
34 are heated by 4 pairs of samples of popping one's head in, while being recorded temperature and raised resistance value and being fed back to thermal analyzer 34 at any time,
Real-time data acquisition is carried out passing to data collector 33 by it, the heat of hydrate sample is finally calculated by computer 32
Physical parameter.
Above-described embodiment 2, only need to be by hydrate or deposition to a kind of hydrate thermophysical property measurement method as described in example 4
Object and solution are placed in sleeve 2, and two pistons 3 squeeze two sleeves 2 from two sides respectively, and hydrate two sides are simultaneously by crowded
Pressure, probe 4 will not be moved, will not be bent, and can reduce 4 damage of probe.Meanwhile two sides hydrate consistency after extruding
Good, experiment measurement accuracy is high.Sample is added in sleeve 2, can prevent sample from falling and adhere to the inner wall of autoclave 1
On.
Autoclave 1 is placed in constant water bath box 30, and temperature is regulated and controled by temperature controller in constant water bath box 30,
It by temperature oscillation, changes temperature constantly, the generation reaction of hydrate can be accelerated.
Certainly, the above description is not a limitation of the present invention, and the present invention is also not limited to the example above, this technology neck
The variations, modifications, additions or substitutions that the technical staff in domain is made within the essential scope of the present invention also should belong to of the invention
Protection scope.
Claims (9)
1. a kind of hydrate thermophysical property measurement system, which is characterized in that including autoclave, temperature regulating device, compression forming dress
It sets, feeder, measuring device and data collector；
The autoclave lower part is provided with base support, and there are two sleeves, two sleeves symmetrically to divide for setting on base support
Cloth, center of each sleeve transversely on axis wall surface are provided with charging aperture；The first temperature biography is additionally provided in autoclave
Sensor and pressure sensor, first temperature sensor are protruded into sleeve by charging aperture；
The temperature regulating device includes constant water bath box, and autoclave is placed in constant water bath box；It is also set in constant water bath box
It is equipped with second temperature sensor and blender；Constant water bath box is connected with temperature controller；
The compression-molding apparatus includes the piston for being separately positioned on two sleeve rear portions, the autoclave at two piston rear portions
Inlet is also had on inner wall, two inlets are connected separately with the first hydraulic branch pipe and the second hydraulic branch pipe, the first liquid
Pressure branch pipe and the second hydraulic branch pipe are connected to hydraulic supervisor, and the hydraulic supervisor is connected to booster pump；It is also set on the hydraulic supervisor
It is equipped with hydraulic main valve；
The feeder includes leak detection channel, evacuation passageway, reaction gas air supply channel and emptying channel；Leak detection channel,
Evacuation passageway, reaction gas air supply channel and emptying channel are connected with autoclave；The evacuation passageway also connects
It is connected to vacuum pump；Reaction gas air supply channel is connected to reaction gas gas cylinder；Safety valve and deflation are provided on the emptying channel
Valve；
The measuring device includes thermal analyzer, is provided with the guarantor made of polymethyl methacrylate on the probe of thermal analyzer
Cuticula；The groove of Relative distribution is provided on two sleeves, when two sleeves snap together, two grooves form probe peace
Hole is filled, the probe is inserted into two sleeve middle positions by probe mounting holes；
The data collector is connected with thermal analyzer, pressure sensor, the first temperature sensor, and data collector also passes through number
Computer is connected with according to output signal line.
2. a kind of hydrate thermophysical property measurement system as described in claim 1, which is characterized in that the compression-molding apparatus is also
Including pressure control assembly, pressure control assembly includes the rangefinder for measuring sleeve and plunger distance, and the rangefinder connects
It is connected to hydraulic controller, the hydraulic controller is connected with the first electro-hydraulic valve and the second electro-hydraulic valve, first electricity
Hydraulic valve and the second electro-hydraulic valve are separately mounted on the first hydraulic branch pipe and the second hydraulic branch pipe.
3. a kind of hydrate thermophysical property measurement system as claimed in claim 2, which is characterized in that the rangefinder includes two
Infrared signal component, the infrared signal component include infrared transmitter and infrared remote receiver, described two infrared signal components
It is separately fixed in the rear groove of sleeve.
4. a kind of hydrate thermophysical property measurement system as described in claim 1, which is characterized in that in piston and autoclave
Wall contact position is provided with seal washer.
5. a kind of hydrate thermophysical property measurement system as described in claim 1, which is characterized in that inside the autoclave
At least two support rods are also provided with by articulation piece, probe is fixed on the upper end of support rod, and articulation piece is threadedly attached in
On reaction kettle inner wall.
6. a kind of hydrate thermophysical property measurement method, which is characterized in that pass through one as described in claim 1 to 5 any one
Kind hydrate thermophysical property measurement system measures, and specific measuring process is as follows:
The first step, by the probe card with protective film in the groove of two sleeves, the sleeve that then snaps together two
It is put into horizontal autoclave；
Second step installs the tubular lid of autoclave, by leak detection channel system leak detection, guarantees that autoclave does not leak
Point；
The leak detection valve being then shut off on leak detection channel, opens vacuum-pumping valve, starts vacuum pump, autoclave is taken out true
Sky after vacuumizing, closes vacuum-pumping valve and autoclave is put into constant water bath box；According to requirement of experiment, adjust
Whole water bath with thermostatic control the temperature inside the box；
Third step opens the air-supplying valve of reaction gas air supply channel, reaction gas to experiment is passed through into autoclave and is wanted
Pressure is sought, regulating thermostatic bath temperature carries out hydrate and generate reaction to requirement of experiment temperature after standing a period of time；
4th step keeps hydrate reaction complete using temperature oscillation；Hydraulic main valve is opened, starting hand increasing pressure pump pressurizes, to
When pressure reaches required pressure, piston squeezes two sleeve two sides simultaneously and obtains compressed hydrate sample；
5th step, after sample compression, starting thermal analyzer carries out the measurement of the hot physical property of hydrate, and thermal analyzer passes through spy
Head heats sample, while recording temperature raised resistance value at any time, and metrical information is fed back to thermal analyzer, by
Thermal analyzer passes to data collector and carries out real-time data acquisition, and the hot object of hydrate sample is finally calculated by computer
Property parameter.
7. a kind of hydrate thermophysical property measurement method as claimed in claim 6, which is characterized in that when hydrate sample is raw in situ
Cheng Shi, weighs a certain proportion of deposit first and solution is filled in two sleeves, is compacted smooth out surface, then covers two
Cylinder snaps together.
8. a kind of hydrate thermophysical property measurement method as claimed in claim 6, which is characterized in that when hydrate sample is raw in situ
At and sample be discrete particles shape when, two sleeves for being equipped with probe are placed in horizontal autoclave first, so
Deposit and solution are slowly injected from the charging aperture on sleeve afterwards.
9. a kind of hydrate thermophysical property measurement method as claimed in claim 6, which is characterized in that when hydrate sample ex situ
When generation, hydrate sample is pressed into the sample of two pieces of same specifications first, can be put into sleeve, with probe contacts face
It polishes.
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| CN108169448B (en) * | 2017-12-06 | 2020-06-12 | 中国科学院广州能源研究所 | Hydrate in-situ synthesis and comprehensive physical property testing device thereof |
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| 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 |
| CN112546962B (en) * | 2020-12-01 | 2022-02-18 | 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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