CN106680239A - Device for performing in-situ infrared characterization on gas hydrate production and decomposition process and using method of device - Google Patents
Device for performing in-situ infrared characterization on gas hydrate production and decomposition process and using method of device Download PDFInfo
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- CN106680239A CN106680239A CN201710104036.8A CN201710104036A CN106680239A CN 106680239 A CN106680239 A CN 106680239A CN 201710104036 A CN201710104036 A CN 201710104036A CN 106680239 A CN106680239 A CN 106680239A
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- 238000011065 in-situ storage Methods 0.000 title claims abstract description 209
- 238000012512 characterization method Methods 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 49
- 230000008569 process Effects 0.000 title claims abstract description 36
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000007789 gas Substances 0.000 claims description 67
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 230000008676 import Effects 0.000 claims description 26
- 239000000110 cooling liquid Substances 0.000 claims description 25
- 238000002347 injection Methods 0.000 claims description 24
- 239000007924 injection Substances 0.000 claims description 24
- 238000003860 storage Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 230000008859 change Effects 0.000 claims description 10
- 238000001514 detection method Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 7
- 238000004452 microanalysis Methods 0.000 claims description 5
- 238000006073 displacement reaction Methods 0.000 claims description 4
- 238000002474 experimental method Methods 0.000 claims description 4
- 230000036760 body temperature Effects 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000002826 coolant Substances 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 150000004677 hydrates Chemical class 0.000 abstract description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 30
- 229910002092 carbon dioxide Inorganic materials 0.000 description 15
- 239000001569 carbon dioxide Substances 0.000 description 15
- VTVVPPOHYJJIJR-UHFFFAOYSA-N carbon dioxide;hydrate Chemical compound O.O=C=O VTVVPPOHYJJIJR-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 210000005056 cell body Anatomy 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000155 in situ X-ray diffraction Methods 0.000 description 1
- 238000010249 in-situ analysis Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- -1 structure type Chemical class 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3577—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing liquids, e.g. polluted water
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- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The invention relates to a device for performing in-situ infrared characterization on a gas hydrate production and decomposition process. The device comprises an in-situ infrared characterization part, a temperature control part connected with the in-situ infrared characterization part, and a gas circuit control part, wherein the in-situ infrared characterization part comprises an in-situ infrared cell, an in-situ infrared cell cover arranged on the top of the an in-situ infrared cell, and an infrared spectrometer connected with the in-situ infrared cell; an infrared light inlet and an infrared light outlet are symmetrically formed in two sides of the outer wall of the in-situ infrared cell; zinc selenide window flakes are arranged at the infrared light inlet and the infrared light outlet; the infrared light emitted from the infrared spectrometer passes through the zinc selenide window flakes of the infrared light inlet, penetrates through the detected samples arranged in the in-situ infrared cell, penetrates out of the zinc selenide window flakes of the infrared light outlet, and reaches a detector for detecting. According to the characterization device provided by the invention, in-situ infrared characterization of hydrates can be realized, and hydrates samples can be taken out for performing other micro-characterizations.
Description
Technical field
The invention belongs to In-situ Infrared Characterization technical field, and in particular to a kind of In-situ Infrared Characterization gas hydrate is generated
With the device and its using method of decomposable process.
Background technology
Gas hydrates are formed under the conditions of cryogenic high pressure, and extensive preservation is in the sea-bottom deposit of continental margin Deep Water Basins
Thing and the permafrost area on land, are a kind of unconventional gas resources, with the spy such as distribution is wide, reserves are big and energy density is high
Levy, be considered one of the alternative energy source in future, cause the highest attention of national governments and scientific circles.Gas hydrate can be stored
A large amount of gases, can be used to store and transport gas, and learning gas hydrate is generated and decomposition mechanism is for gas hydrates
Reservoiring mechanism, exploitation and storage and transportation gas are significant.
The micro-analysis of gas hydrate can provide the hydrates such as structure type, guest molecule composition, cage occupation rate
Many-sided nature parameters, for hydrate research valuable information is provided.Gas hydrate is taken out when characterizing at ambient pressure,
Easily decompose.The in-situ characterization of gas hydrate, can take out sample, and hydrate generation decomposable process is analyzed,
At present the means of the microstructure change of in-situ characterization gas hydrate have in situ X-ray diffraction diffractometer, in-situ Raman spectrometer.This
A little in-situ characterization means, can provide hydrate generation and the real-time in-situ analysis of decomposable process, but for carbon dioxide cage type
The analysis of structure has been short of.
The content of the invention
It is an object of the invention to provide a kind of In-situ Infrared Characterization gas hydrate generate and decomposable process device and
Its using method, the present invention proposes the In-situ Infrared analysis that gas hydrate can be realized under the conditions of cryogenic high pressure, obtains gas
The structure of matter and composition change information of the structural information, generation and decomposable process of gas hydrate, explores hydrate and generates and divide
Solution mechanism.
In order to realize foregoing invention purpose, technical scheme is as follows：
It is an object of the invention to provide a kind of In-situ Infrared Characterization gas hydrate generates the device with decomposable process, including
The temprature control unit and gas circuit control section of In-situ Infrared Characterization part and described In-situ Infrared Characterization part connection；Institute
The In-situ Infrared Characterization part stated includes In-situ Infrared pond body, the In-situ Infrared pond being arranged at the top of described In-situ Infrared pond body
Body lid and the infrared spectrometer being connected with described In-situ Infrared pond body, described In-situ Infrared pond body outer wall both sides are symmetrical arranged
There are infrared light import and infrared light exit, described infrared light import and infrared light exit is provided with zinc selenide window, institute
The zinc selenide window that the infrared light of the infrared spectrometer transmitting stated passes through infrared light import, is disposed through described In-situ Infrared
The sample that pond body inside is detected, passes from the zinc selenide window of infrared light exit, reaches detector detection；Described is in situ red
External cell body top is provided with pond injection port in situ and pond in situ outlet, and it is cold that described In-situ Infrared pond body outer wall is provided with circulation
But liquid import and circulating cooling liquid are exported, and the temprature control unit includes low temperature thermostat bath and temperature sensor, and described is low
Warm thermostat is connected respectively with described circulating cooling liquid import and described circulating cooling liquid outlet, described temperature sensor
One end is connected with described low temperature thermostat bath, and the other end gos deep into the In-situ Infrared pond body through described In-situ Infrared pond body lid
Inside is arranged in the middle of two zinc selenide windows, and the gas circuit control section includes the pressure sensing being sequentially communicated by pipeline
Device, flowmeter and source of the gas storage tank, described pressure sensor is connected with described pond injection port in situ.
Preferably, described In-situ Infrared pond body bottom is provided with the bottom for adjusting the In-situ Infrared pond body direction and height
Seat.
Preferentially, described In-situ Infrared pond body outside is provided with the muff for insulation.
Preferably, described gas circuit control section also includes vavuum pump, and described vavuum pump goes out sample with described pond in situ
Mouth is connected by the first stop valve.
Preferably, described gas circuit control section also includes source of the gas tank, described source of the gas tank and described source of the gas storage tank
Between be provided with pressure-reducing valve, be provided with the second stop valve, described stream between described source of the gas storage tank and described flowmeter
The 3rd stop valve is provided between gauge and described pressure sensor.
Preferably, described detector is MCT detectors or DGTS detectors.The aqueous solution selects DGTS detectors, reachable
To the purpose of detection, if with ice powder synthesized hydrate, detector is MCT detectors.
Preferably, described infrared light import and described infrared light exit it is highly identical.
The upper end of temperature sensor proposed by the present invention and pressure sensor infrared pond body in the original location, In-situ Infrared pond body lid
Sealing ring is provided between In-situ Infrared pond body so that good sealing effect, infrared spectrometer transmitting infrared light can be by original position
The zinc selenide window of one end of infrared pond body, through sample, infrared light is passed from other end zinc selenide, reaches detector detection.
Source of the gas tank sequentially passes through flowmeter and the 3rd cut-off by input pipe and source of the gas storage tank UNICOM, the flue of source of the gas storage tank
Valve, is connected with In-situ Infrared pond body, and flowmeter and high-pressure stop valve control gas input flow amount.Outlet end in pond in situ is by the
One stop valve UNICOM vacuum diaphragm pump.First stop valve, the second stop valve and the 3rd stop valve are high-pressure stop valve, flowmeter
For high pressure mass flowmenter.
In-situ Infrared pond body is made up of the stainless steel material for being resistant to be depressed into 20Mpa, infrared light import and infrared light exit
There is zinc selenide window respectively, the upper lid of In-situ Infrared pond body is provided with detachable stainless steel flue, pressure sensor, detachable
Temperature sensor, the pond injection port in situ of removable strip stop valve and pond in situ outlet.In-situ Infrared pond body bottom is provided with
Can the movement of tri- directions of XYZ the stainless steel base for fixing reaction in-situ pond body, by the movement of base can detect gas-
The material information of liquid or gas-solid interface, liquid or solid.The outermost layer of In-situ Infrared pond body has individual muff, outer end both sides
There are circulating cooling liquid import and circulating cooling liquid outlet, for providing the temperature environment needed for hydrate is generated and decomposed.It is in situ
The temperature sensor covered in infrared pond body is used to detect hydrate generation and decomposition temperature, temperature sensor in In-situ Infrared pond body
The length in In-situ Infrared pond body is stretched into just in two zinc selenide window central authorities, the temperature information of reaction center is measured, with temperature
What degree sensing element was connected is that temperature shows and memory.The pressure sensing component covered in In-situ Infrared pond body is used to monitor original
The change of pressure in position pool inner water compound generation and decomposable process, what is be connected with pressure sensing component is that pressure shows and stores
Device, first specified pressure is added to before reaction by required reacting gas, in course of reaction, can be judged by the change of temperature and pressure
Whether reaction completes.
Another object of the present invention is to propose the dress that a kind of In-situ Infrared Characterization gas hydrate is generated with decomposable process
The using method put, comprises the following steps：
(1) the pond injection port in situ of In-situ Infrared pond body is opened, closes pond in situ outlet, poured nitrogen and do background,
Preserve background paper；The temperature of low temperature thermostat bath is adjusted to into experiment temperature required, opens circulating cooling liquid import and circulating cooling
Liquid outlet makes In-situ Infrared pond body constant in temperature required, opening In-situ Infrared pond body lid, adds white or water-soluble needed for reaction
Liquid, In-situ Infrared pond body lid is covered；
(2) source of the gas storage tank is opened, source of the gas is passed through in In-situ Infrared pond body, close pond in situ injection port, open in situ
Pond outlet, vacuumizes, and after vacuum is taken out, closes pond in situ outlet, opens pond in situ injection port, treats that pressure increases to 2 greatly
Air pressure, closes pond in situ injection port, opens pond in situ outlet, vacuumizes, and repeatedly several times, realizes inside In-situ Infrared pond body
Gas displacement, opens pond in situ injection port, closes pond in situ outlet, and source of the gas is entered in In-situ Infrared pond body by flowmeter
Portion, treats that pressure increases to desirable pressure, closes pond in situ injection port, after question response stable system, coolant temperature is adjusted to into experiment
Temperature carries out hydrate reaction of formation；In hydrate formation, follow-on test sequential file gathers whole hydrate and generated
Cheng Zhong, obtains structure of matter change information, and In-situ Infrared pond body temperature and pressure are reached after stablizing, and are closed infrared sequence and are adopted
Collection, can gather sample, the hydrate spectrogram after collection generation.
Preferably, the using method of described situ high pressure IR Characterization device also includes step (3)：Using cryogenic thermostat
The temperature programming of groove, is arranged to temperature required, makes decomposition of hydrate, and temperature and pressure data in collection decomposable process are continuous to survey
Examination sequential file, during gathering whole decomposition of hydrate, obtains structure of matter change information.
Preferably, in step (2), after the completion of hydrate reaction of formation, pressure in In-situ Infrared pond body is unloaded to normal pressure, plus
Protection of liquid nitrogen, takes out sample, for other micro-analysis.
The invention has the beneficial effects as follows：
1st, the infrared reaction pond body simple structure proposed in the present invention, is easy to operation and maintenance；
2nd, the reaction unit can adjust test point by base, be capable of achieving solution-air or gas-solid interface, liquid or water
The infrared detection of compound solid, to meet the demand of in situ detection；
3rd, the reactor is simple to operate, can realize the continuous microscopic sdIBM-2+2q.p.approach of In-situ Infrared；
4th, the reactor not only can realize the In-situ Infrared Characterization of hydrate, and can also take out in hydrate sample is carried out
Other microscopic sdIBM-2+2q.p.approach；
5th, for the characteristic of gas hydrate, devising low temperature high-temp in-situ infrared facility can continuously characterize gas to the present invention
The generation of hydrate and decomposable process；
6th, with In-situ Infrared Characterization device proposed by the present invention, can be with in-situ characterization hydrate formation, particularly
The cage modle for making up the carbon dioxide hydrate that LR laser raman cannot be realized is characterized, and is characterized without the need for taking out, and hydrate is greatly lowered
Take out and characterize the possibility decomposed, and realize the In-situ Infrared Characterization of hydrate.
Description of the drawings
Fig. 1 is the structure and flow process of the device of a kind of In-situ Infrared Characterization gas hydrate generation of the invention and decomposable process
Schematic diagram；
Fig. 2 is the infrared transmission spectrogram of the carbon dioxide in embodiment 1 before hydrate generation；
Fig. 3 is the infrared transmission spectrogram of the carbon dioxide in embodiment 1 after hydrate generation；
Reference：1st, In-situ Infrared pond body；2nd, pond in situ air inlet；3rd, pressure sensor；4th, the 3rd stop valve；5th, it is high
Pressure mass flowmenter；6th, the second stop valve；7th, source of the gas storage tank；8th, pressure-reducing valve；9th, source of the gas tank；10th, circulating cooling liquid import；
11st, infrared light import；12nd, the first zinc selenide window；13rd, base；14th, the second zinc selenide window；15th, infrared light exit；16th, follow
Ring cooling liquid outlet；17th, pond in situ gas outlet；18th, the first stop valve；19th, vavuum pump；20th, temperature sensor；21st, it is in situ red
External cell body lid；22nd, low temperature thermostat bath.
Specific embodiment
With reference to instantiation, the present invention is further elucidated.It should be understood that these embodiments are merely to illustrate this
It is bright, rather than limit protection scope of the present invention.Improvement and tune that in actual applications technical staff makes according to the present invention
It is whole, still fall within protection scope of the present invention.
The equipment used except special instruction, the present invention and reagent are the art routine commercial products.Arrow in Fig. 1
Direction represents the direction of infrared light.
A kind of In-situ Infrared Characterization gas hydrate generation and the device of decomposable process, including In-situ Infrared Characterization part,
The temprature control unit being connected with In-situ Infrared Characterization part and gas circuit control section；In-situ Infrared Characterization part includes in situ red
External cell body 1, the In-situ Infrared pond body lid 21 for being arranged at the top of In-situ Infrared pond body 1 and infrared with what In-situ Infrared pond body 1 was connected
Spectrometer, the outer wall both sides of In-situ Infrared pond body 1 are symmetrically arranged with infrared light import 11 and infrared light exit 15, In-situ Infrared pond body
The first zinc selenide window 12 is provided with 1 infrared light import 11, the second zinc selenide window 14 is provided with infrared light exit 15,
The infrared light of infrared spectrometer transmitting by the first zinc selenide window 12 of infrared light import, through the sample for being detected, from red
Second zinc selenide window 14 of outer light exit is passed, and reaches detector detection；The top of In-situ Infrared pond body 1 is provided with pond in situ and enters
Sample mouth and pond in situ outlet, the outer wall of In-situ Infrared pond body 1 is provided with circulating cooling liquid import 10 and circulating cooling liquid outlet 16,
Temprature control unit includes low temperature thermostat bath 22 and temperature sensor 20, low temperature thermostat bath 22 and circulating cooling liquid import 10 and follows
Ring cooling liquid outlet 16 connects respectively, and the one end of temperature sensor 20 is connected with low temperature thermostat bath 22, and the other end runs through In-situ Infrared
Pond body lid 21 gos deep into being arranged inside In-situ Infrared pond body 1 in the middle of first zinc selenide window 12 and the second zinc selenide window 14, gas
Road control section includes pressure sensor 3, flowmeter, the gentle carrying shield 9 of source of the gas storage tank 7 being sequentially communicated by pipeline, pressure
Sensor 3 is connected with pond in situ injection port.In-situ Infrared pond body bottom is provided with and adjusts In-situ Infrared pond body direction and height
Base 13.In-situ Infrared pond body outside is provided with the muff for insulation.Gas circuit control section also includes vavuum pump 19, vacuum
Pump 19 is connected with pond in situ outlet by the first stop valve 18.Pressure-reducing valve 8 is provided between source of the gas tank 9 and source of the gas storage tank 7,
The second stop valve 6 is provided between source of the gas storage tank 7 and flowmeter, the 3rd section is provided between flowmeter and pressure sensor 3
Only valve 4.
The upper end of temperature sensor proposed by the present invention 20 and pressure sensor 3 infrared pond body 1 in the original location, In-situ Infrared pond
Sealing ring is provided between body lid 21 and In-situ Infrared pond body 1 so that good sealing effect, infrared spectrometer transmitting infrared light can be with
By the first zinc selenide window 12 of one end of In-situ Infrared pond body, through sample, transmitted light is from the other end the second zinc selenide window
Piece 14 is passed, and reaches detector detection.Source of the gas tank 9 is by input pipe and the UNICOM of source of the gas storage tank 7, the gas of source of the gas storage tank 7
Pipe sequentially passes through flowmeter and the 3rd stop valve 6, is connected with In-situ Infrared pond body 1, and flowmeter and high-pressure stop valve control gas
Input flow rate.Outlet end in pond in situ passes through the UNICOM's vacuum diaphragm pump 19 of the first stop valve 18.First stop valve 18, second ends
The stop valve 4 of valve 6 and the 3rd is high-pressure stop valve, and pressure limit is 0~25MPa, and flow is calculated as high pressure mass flowmenter 5, is pressed
Power scope is 0~25MPa.In course of reaction, by the reaction temperature inside temperature sensor feedback In-situ Infrared pond body, pressure is passed
Gas pressure in the feedback In-situ Infrared pond body of sensor, in collecting data acquisition unit.
The thickness of In-situ Infrared pond body and the thickness of muff are depending on actual conditions.
In-situ Infrared Characterization gas hydrate proposed by the present invention generates the using method with the device of decomposable process, including
Following steps：
(1) the pond injection port in situ of In-situ Infrared pond body 1 is opened, closes pond in situ outlet, poured nitrogen and do background,
Preserve background paper；The temperature of low temperature thermostat bath 22 is adjusted to into experiment temperature required, opens circulating cooling liquid import 10 and circulation
Cooling liquid outlet 16 makes In-situ Infrared pond body 1 constant in temperature required, opening In-situ Infrared pond body lid 21, adds frost needed for reaction
Or the aqueous solution, In-situ Infrared pond body lid 21 is covered；
(2) source of the gas storage tank 7 is opened, source of the gas is passed through in In-situ Infrared pond body 1, close pond in situ injection port, open former
Position pond outlet, vacuumizes, and after vacuum is taken out, closes pond in situ outlet, opens pond in situ injection port, treats that pressure increases to 2
Atmospheric pressure, closes pond in situ injection port, opens pond in situ outlet, vacuumizes, and repeatedly several times, realizes In-situ Infrared pond body 1
Internal gas are replaced, and open pond in situ injection port, close pond in situ outlet, and source of the gas enters In-situ Infrared pond body by flowmeter
Inside 1, treat that pressure increases to desirable pressure, close pond in situ injection port, after question response stable system, coolant temperature is adjusted to into reality
Testing temperature carries out hydrate reaction of formation；In hydrate formation, follow-on test sequential file gathers whole hydrate and generates
During, structure of matter change information is obtained, In-situ Infrared pond body temperature and pressure are reached after stablizing, and are closed infrared sequence and are adopted
Collection, can gather sample, the hydrate spectrogram after collection generation, after the completion of hydrate reaction of formation, by In-situ Infrared pond body internal pressure
Power is unloaded to normal pressure, plus protection of liquid nitrogen, sample is taken out, for other micro-analysis.
(3) using the temperature programming of low temperature thermostat bath, arrange to temperature required, make decomposition of hydrate, gather decomposable process
Middle temperature and pressure data, follow-on test sequential file during gathering whole decomposition of hydrate, obtains structure of matter change letter
Breath.
Embodiment 1
The gas hydrate generation of the present embodiment and the performance parameter of the cryogenic high pressure In-situ Infrared Characterization device for decomposing are：
0.1~10MPa of operating pressure, operating temperature is -40 DEG C~40 DEG C, 4000~6000cm of spectral region-1。
With reference to Fig. 1, so that carbon dioxide hydrate in the aqueous solution is generated as an example, In-situ Infrared Characterization gas hydrate generate and
The using method of the device of decomposable process, comprises the steps：
(1) low temperature thermostat bath 22 is cooled in advance -10 DEG C, connects In-situ Infrared pond body circulating cooling liquid import 10 and circulation is cold
But liquid outlet 16, opens circulation, and circulating cooling liquid flows to circulating cooling liquid outlet 16 via circulating cooling liquid import 10, and then controls
The temperature of In-situ Infrared pond body 1 processed, temperature range：- 40 DEG C~40 DEG C；
(2) thickness of In-situ Infrared pond body 1 is 10mm, and DGTS detectors are selected for the aqueous solution in the present embodiment, after stable
Background paper is surveyed, background paper is preserved；If with ice powder synthesized hydrate, detector from infrared spectrometer MCT detectors,
Liquid nitrogen is filled, background paper has been surveyed after stable, preserved background paper；
(3) carbon dioxide gas carrying shield 9 is opened, opens pressure-reducing valve 8, to high-pressure air source surge tank 7 pressure 25MPa is flushed to, closed
Pressure-reducing valve 8 is closed, source of the gas tank 9 is closed, adds pure water in In-situ Infrared pond body 1, tighten 8 spiral shells of In-situ Infrared pond body lid 21
Silk；
(4) the 3rd stop valve 4 on the top of pond in situ air inlet 2 is closed, open the top of pond in situ gas outlet 17 first section
Only valve 18, open vavuum pump 19, treat that vacuum is evacuated to required 0.01MPa, close the first stop valve 18, open the 3rd stop valve 4, punching
Enter carbon dioxide to 0.2MPa, carry out second time displacement, close the 3rd stop valve 4, open the first stop valve 18, open true
Empty pump 19, is evacuated to 0.01MPa, closes the first stop valve 18, opens the 3rd stop valve 4, adds carbon dioxide extremely
0.2MPa, carries out the 3rd time displacement, closes the 3rd stop valve 4, opens the first stop valve 18, opens vavuum pump 19, is evacuated to
0.01MPa, close the first stop valve 18, open the 3rd stop valve 4, by the carbon dioxide in high-pressure air source storage tank 7 according to
It is secondary to pass through to be added to In-situ Infrared pond body 1 after the second stop valve 6, the stop valve 4 of high pressure mass flowmenter 5 and the 3rd, to reaction
0.1~10MPa of desirable pressure, closes the 3rd stop valve 4；
(5) data acquisition unit is opened, collects the information such as temperature sensor Pt100 and pressure transmitter in In-situ Infrared pond,
Balance is after 6 hours, the adjustment temperature of low temperature thermostat bath 22 to -40 DEG C~40 DEG C of reaction temperature；
(6) infrared spectrometer is opened, adjusts base 13, to adjust infrared signal and adjust to the point for needing observation, clicked on
Sequential file is gathered, and can gather the relevant information in carbon dioxide hydrate generating process, the titanium dioxide before reaction in the aqueous solution
Carbon peak occurs in 2343cm-1And 2360cm-1It is bimodal, as hydrate formation peak slowly becomes 2346cm-1Main peak and
2360cm-1Ride peak, peak gradually strengthens, finally only 2346cm-1Main peak, represent carbon dioxide molecule dense in little cage
Degree strengthens；
(7) in reaction tank temperature and pressure reach it is stable after, close infrared sequence collection, sample can be gathered, collection is generated
Carbon dioxide hydrate spectrogram afterwards；
(8) after the completion of reacting, the first stop valve 18 is opened, pressure is unloaded to normal pressure, plus protection of liquid nitrogen, sample is taken out, can
For other micro-analysis；
(9) decomposition of hydrate process is characterized, using the temperature programming of low temperature thermostat bath 22, is arranged to temperature required, adopted
Temperature and pressure data in collection decomposable process, acquisition sequence file observes hydrate decomposable process, there is carbon dioxide gas before reaction
Body peak and the carbon dioxide peak being dissolved in the aqueous solution, gas peak slowly weakens, until carbon dioxide occur forms hydrate
Peak and a small amount of gas peak, last only carbon dioxide hydrate peak, collection closes data acquisition unit, low temperature thermostat bath after finishing,
Complete this time operation.
As shown in Figures 2 and 3, table is carried out using this situ high pressure IR Characterization device in-situ preparation carbon dioxide hydrate
Levy, the spectrogram that carbon dioxide is dissolved in the aqueous solution before reaction is shown in Fig. 2, and carbon dioxide peak occurs in 2360cm-1With
2343cm-12338cm is occurred in carbon dioxide peak in the aqueous solution-1, see Fig. 3 after the completion of reaction, hydrate complete be after generating
2346cm-1Peak of the carbon dioxide in the little cage of II type hydrates.
Reaction medium in above-described embodiment is 90% water (molar fraction)+10% (molar fraction) pentamethylene-titanium dioxide
Carbon-gas, pentamethylene as accelerator, is generated in the reaction with accelerating hydrate.Device proposed by the present invention also is adapted for ice
The reaction of powder and other gases (methane, ethane) and the sign of the reaction of addition accelerator and inhibitor.
At present carbon dioxide hydrate is mainly analyzed by infrared diffusing reflection, can only be taken from reactor after hydrate generation
Out analyze, it is impossible to realize in-situ study.With In-situ Infrared Characterization device proposed by the present invention, can be with in-situ characterization hydrate
Generating process, the cage modle for particularly making up the carbon dioxide hydrate that LR laser raman cannot be realized is characterized, and is characterized without the need for taking out, greatly
Amplitude reduction hydrate takes out and characterizes the possibility decomposed, and realizes the In-situ Infrared Characterization of hydrate.
Device proposed by the present invention is especially suitable for the cryogenic high pressure In-situ Infrared that gas hydrate generates decomposition mechanism research
Pond, is specifically designed for the condition of the generation decomposition of gas hydrate, overcomes existing low temperature diffusing reflection IR Characterization gas
Hydrate cannot realize that in-situ preparation and decomposable process are characterized.Using transmission mode, more suitable for gas-liquid reaction process.
With In-situ Infrared Characterization device proposed by the present invention, can be with in-situ characterization hydrate formation, particularly more
The cage modle for mending the carbon dioxide hydrate that LR laser raman cannot be realized is characterized, and is characterized without the need for taking out, and hydrate is greatly lowered and takes
Go out to characterize the possibility decomposed, and realize the In-situ Infrared Characterization of hydrate.
A kind of situ high pressure IR Characterization device that the present invention is provided is described in detail above, it is used herein
Specific case is set forth to the principle and embodiment of the present invention, and the explanation of above example is only intended to help and understands
The method of the present invention and its core concept, it is noted that to those of ordinary skill in the art, without departing from the present invention
On the premise of principle, some improvement and modification can also be carried out to the present invention, these are improved and modification also falls into right of the present invention
In the protection domain of requirement.
Claims (10)
1. a kind of In-situ Infrared Characterization gas hydrate generates the device with decomposable process, it is characterised in that including In-situ Infrared
Characterize temprature control unit and the gas circuit control section of part and described In-situ Infrared Characterization part connection；Described original position
IR Characterization part include In-situ Infrared pond body, the In-situ Infrared pond body lid being arranged at the top of described In-situ Infrared pond body and with
The infrared spectrometer of described In-situ Infrared pond body connection, described In-situ Infrared pond body outer wall both sides are symmetrically arranged with infrared light
Import and infrared light exit, described infrared light import and infrared light exit is provided with zinc selenide window, the infrared light
The zinc selenide window that the infrared light of spectrometer transmitting passes through infrared light import, is disposed through described In-situ Infrared pond body inside institute
The sample of detection, passes from the zinc selenide window of infrared light exit, reaches detector detection；Described In-situ Infrared pond body top
Be provided with pond injection port in situ and pond outlet in situ, described In-situ Infrared pond body outer wall be provided with circulating cooling liquid import and
Circulating cooling liquid is exported, and the temprature control unit includes low temperature thermostat bath and temperature sensor, described low temperature thermostat bath with
Described circulating cooling liquid import and described circulating cooling liquid outlet connect respectively, described temperature sensor one end with it is described
Low temperature thermostat bath connection, the other end gos deep into being arranged inside the In-situ Infrared pond body through described In-situ Infrared pond body lid
In the middle of two zinc selenide windows, pressure sensor that the gas circuit control section includes being sequentially communicated by pipeline, flowmeter and
Source of the gas storage tank, described pressure sensor is connected with described pond injection port in situ.
2. In-situ Infrared Characterization gas hydrate according to claim 1 generates the device with decomposable process, and its feature exists
In described In-situ Infrared pond body bottom is provided with the base of the In-situ Infrared pond body direction described in adjusting and height.
3. In-situ Infrared Characterization gas hydrate according to claim 1 and 2 generates the device with decomposable process, its feature
It is that described In-situ Infrared pond body outside is provided with the muff for insulation.
4. In-situ Infrared Characterization gas hydrate according to claim 1 and 2 generates the device with decomposable process, its feature
It is that described gas circuit control section also includes vavuum pump, described vavuum pump passes through first with described pond outlet in situ
Stop valve connects.
5. In-situ Infrared Characterization gas hydrate according to claim 1 and 2 generates the device with decomposable process, its feature
It is that described gas circuit control section also includes source of the gas tank, is provided between described source of the gas tank and described source of the gas storage tank
It is provided with the second stop valve between pressure-reducing valve, described source of the gas storage tank and described flowmeter, described flowmeter and described
Pressure sensor between be provided with the 3rd stop valve.
6. In-situ Infrared Characterization gas hydrate according to claim 1 and 2 generates the device with decomposable process, its feature
It is that described detector is MCT detectors or DGTS detectors.
7. In-situ Infrared Characterization gas hydrate according to claim 1 and 2 generates the device with decomposable process, its feature
Be, described infrared light import and described infrared light exit it is highly identical.
8. the In-situ Infrared Characterization gas hydrate described in a kind of claim 1 generates the user with the device of decomposable process
Method, it is characterised in that comprise the following steps：
(1) the pond injection port in situ of In-situ Infrared pond body is opened, closes pond in situ outlet, poured nitrogen and do background, preserved
Background paper；The temperature of low temperature thermostat bath is adjusted to into experiment temperature required, opens circulating cooling liquid import and circulating cooling liquid and go out
Mouth makes In-situ Infrared pond body constant in temperature required, opening In-situ Infrared pond body lid, adds the white or aqueous solution needed for reaction, by
In-situ Infrared pond body lid is covered；
(2) source of the gas storage tank is opened, source of the gas is passed through in In-situ Infrared pond body, close pond in situ injection port, opened pond in situ and go out
Sample mouth, vacuumizes, and after vacuum is taken out, closes pond in situ outlet, opens pond in situ injection port, treats that pressure increases to 2 atmospheric pressure,
Pond in situ injection port is closed, pond in situ outlet is opened, is vacuumized, repeatedly several times, realize In-situ Infrared pond body internal gas
Displacement, opens pond in situ injection port, closes pond in situ outlet, and source of the gas is entered inside In-situ Infrared pond body by flowmeter, treated
Pressure increases to desirable pressure, closes pond in situ injection port, after question response stable system, coolant temperature is adjusted to into experimental temperature and is entered
Water-filling compound reaction of formation；In hydrate formation, follow-on test sequential file, in gathering whole hydrate formation,
Structure of matter change information is obtained, In-situ Infrared pond body temperature and pressure are reached after stablizing, and close infrared sequence collection, can be adopted
Collection sample, the hydrate spectrogram after collection generation.
9. In-situ Infrared Characterization gas hydrate according to claim 8 generates the user with the device of decomposable process
Method, it is characterised in that the using method of the device of described situ high pressure IR Characterization also includes step (3)：It is permanent using low temperature
The temperature programming of warm groove, is arranged to temperature required, makes decomposition of hydrate, gathers temperature and pressure data in decomposable process, continuously
Test sequence file, during gathering whole decomposition of hydrate, obtains structure of matter change information.
10. In-situ Infrared Characterization gas hydrate according to claim 8 generates the user with the device of decomposable process
Method, it is characterised in that in step (2) after the completion of reaction, pressure in In-situ Infrared pond body is unloaded to normal pressure, plus protection of liquid nitrogen, take
Go out sample, for other micro-analysis.
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| US11796526B2 (en) | 2019-08-31 | 2023-10-24 | Dalian University Of Technology | Device and method of gas hydrate pressure maintaining replacement for in-situ Raman analysis |
| WO2021035753A1 (en) * | 2019-08-31 | 2021-03-04 | 大连理工大学 | Gas hydrate pressure-maintaining replacement apparatus and method used for in-situ raman analysis |
| CN110487771A (en) * | 2019-08-31 | 2019-11-22 | 大连理工大学 | Gas hydrate generation/decomposing system and method for in-situ Raman analysis |
| CN112748073A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Material in-situ characterization sample cell and use method thereof |
| CN112748073B (en) * | 2019-10-31 | 2024-05-31 | 中国石油化工股份有限公司 | Material in-situ characterization sample cell and use method thereof |
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