CN108426868A - The method of on-line determination carbon dioxide solubility in pure water in situ - Google Patents
The method of on-line determination carbon dioxide solubility in pure water in situ Download PDFInfo
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- 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
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- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
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Abstract
The present invention provides a kind of on-line determination CO in situ2The method of solubility in pure water, the method includes drawing standard curve, measure CO2Two parts of solubility in pure water；The method of the present invention has intuitive, low consumption, accurate, conveniently, and the advantages that can operating continuously, quartz capillary can be effectively reduced the temperature gradient of reaction, solve system under conditions of close to environment temperature, bulk temperature is less than set temperature, measured value defect bigger than normal；In addition, this method innovatively applies to situ Raman Spectroscopy on-line analysis in system, detect and counting system CO within a certain period of time2With the ratio of peak of pure water, compared by surveyed numerical value, judge whether system reaches thermodynamical equilibrium, ensure that surveyed CO2‑H2The accuracy of O system solubility, to measure CO under certain temperature, pressure condition2The research of dissolution characteristics in geological storage provides a kind of brand-new thinking.
Description
(1) technical field
The present invention relates to a kind of on-line determination CO in situ2The method of solubility in pure water.
(2) background technology
Contemporary society's rapid economic development, people largely use fossil fuel to accelerate expanding economy, and fossil fires
The burning of material causes a large amount of CO2The discharge of gas.CO2It is the arch-criminal for leading to global warming and environmental change, its longevity
The time limit is ordered compared with long, discharge capacity is big, maximum to the contribution of " greenhouse effects ".According to European Commission EC (European
Commission) and (Netherlands Environmental Assessment Agency) composition is affixed one's name in Holland's assessment
EDGAR reports claim, and world's CO2 emissions in 2015 are up to 35,300,000,000 tons, wherein Chinese CO2 emissions are up to
10300000000 tons, become the big CO2 emission state of the first in the world.Therefore, greenhouse gases CO is reduced2Discharge it is total as the whole mankind
With concern, significant problem urgently to be resolved hurrily.
Currently, carbon trapping is to realize CO with Plugging Technology Applied (Carbon Capture Storage, CCS)2Emission reduction is most real
One of effective method.Wherein, CO2Geological reservoir be considered as one have extensive CO2Emission Reduction Potential, control greenhouse gas
One of the important technology of body discharge, the optional place of storage include：It has discarded or the oil without business extraction value and natural
Salt water aquifer in gas field, sedimentary basin and the deep layer coal seam without commercial extraction value.CO2It is sealed in the geology of salt water aquifer
CO can not only be realized by depositing2It seals up for safekeeping, moreover it is possible to reach CO2The purpose of emission reduction, accurately measures CO2Solubility in pure water is one item
Important element task.
Traditional CO2Solubility test method is divided into two classes：Static analysis method and static synthetic method (Liu Y H, Hou M Q,
Yang G Y,et al.Solubility of CO2in aqueous solutions of NaCl,KCl,CaCl2and
their mixed salts at different temperatures and pressures；Yan W,Huang S L,
Stenby E H.Measurement and modeling of CO2 solubility in NaCl brine and CO2-
saturated NaCl brine density；Hou S X,Maitland G C,Trusler J P M.Phase
equilibria of(CO2+H2O+NaCl)and(CO2+H2O+KCl):Measurements and modeling).Static state point
Analysis method is by CO2It is passed through together in closed autoclave with brine and keeps specific temperature, pressure, after system reaches balance
It samples from autoclave, and is analyzed at normal temperatures and pressures using physical method or instrument, to obtain related soluble degrees of data；
Static synthetic method is to be passed through in autoclave and be heated to specific temperature by advance prepared a certain amount of brine, after be passed through high pressure
CO2, after system reaches balance, by measuring the front and back CO that balances each other2P-V-T parameters, calculate obtain related soluble degrees of data.
But we have found that there are certain defects for conventional method：Static analysis method is easily destroyed system balance, static monitor in sampling process
Rule is in CO2There are errors for quantitative aspect, and autoclave volume is larger, big so as to cause amount of samples, and equipment energy consumption is high, pass
Matter rate is slow, and mass transfer is not easy to balance.Thus the data illustrated are inaccurate.
Minisize capillary pipe microreactor/equilibrium still causes the concern of academia with Raman spectrum joint technology in recent years.
Centre National de la Recherche Scientifique S.Marre team (Liu N, Aymonier C, Lecoutre C, et
al.Microfluidic approach for studying CO2solubility in water and brine using
Confocal Raman spectroscopy) and Spain Compton Laura.J.Bonales team of this university (Bonales L
J,V,Prieto-Ballesteros O.Raman spectroscopy as a tool to study the
solubility of CO2in magnesium sulphate brines:application to the fluids of
Europa ' s cryomagmatic reservoirs) using microreactor combination Raman spectrum development CO2It is molten in brine layer
Xie Du is studied, but without quantitative analysis CO2Solubility；Team of Lv Wan armies (Guo H R, Chen Y, Hu Q C, et
al.Quantitative Raman spectroscopic investigation of geo-fluids high-pressure
phase equilibria:Part I.Accurate calibration and determination of
CO210 to 120MPa of solubility in water from 273.15to 573.15K and from) utilize Raman light
Measures and carried out CO to spectrum quantitative system2Solubility studies in water, but its operation needs that mercury seal technology is taken to prepare not
With known CO2The standard sample of concentration, data point complicated for operation and different cannot achieve continuous measurement.
Therefore, if can establish it is a set of have that data reliability is high, detection speed is fast, easy to operate and safe, and can measure
CO under high temperature and pressure2The assay method of solubility in water phase can not only overcome the defect of conventional method, and to developing CO2
Geological storage technology is of great significance.
(3) invention content
The object of the present invention is to provide a kind of on-line determination CO in situ2The method of solubility in pure water, this method can be
CO2Geological storage technology provides basic data and theory support.
Technical scheme is as follows：
A kind of original position on-line determination CO2The method of solubility in pure water, the method carries out in following device, described
Device includes：The burnt micro-Raman spectroscopy of copolymerization, pressure duct, circulation line, first pressure sensor, second pressure sensing
Device, cold and hot；
The burnt micro-Raman spectroscopy of the copolymerization includes Laser Scanning Confocal Microscope, display, objective table, and the copolymerization is burnt micro-
Raman spectrometer is equipped with changeable sample observation mode and Raman light path pattern：Burnt micro- drawing is copolymerized under sample observation mode
The Laser Scanning Confocal Microscope of graceful spectrometer is connect with DVD real-time recording systems, and real-time micro- amplification sample image is observed；It is drawing
Laser Scanning Confocal Microscope is connect with laser Raman spectrum instrument under graceful light path pattern, is carried out laser Raman spectroscopy and is measured detection；
N is equipped in the pressure duct2Steel cylinder, CO2Steel cylinder, vacuum pump, constant displacement pump, the vacuum pump and N2Steel cylinder and CO2
Steel cylinder connect, the constant displacement pump also with N2Steel cylinder and CO2Steel cylinder connects；
Balance each other kettle, circulating pump, quartz capillary, the kettle that balances each other, circulating pump, quartz are equipped in the circulation line
Capillary connection forming circuit；
The first pressure sensor is connect with the constant displacement pump in the pressure duct, the second pressure sensor and institute
The kettle connection that balances each other in circulation line is stated, the constant displacement pump in the pressure duct and the kettle company that balances each other in the circulation line
It connects, the quartz capillary in the circulation line is placed in described cold and hot, and described cold and hot to be fixed on the copolymerization burnt micro-
On the objective table of Raman spectrometer.
Further, in the pressure duct, the vacuum pump is successively through third triple valve, the second triple valve, the first threeway
Valve and N2Steel cylinder and CO2Steel cylinder connects, and the constant displacement pump is successively through the 4th triple valve, the second triple valve, the first triple valve and N2Steel
Bottle and CO2Steel cylinder connects；The third triple valve is also associated with the first two-port valve.
Further, in the circulation line, third two-port valve, the phase are equipped between the circulating pump and quartz capillary
The 4th two-port valve is equipped between equilibrium still and quartz capillary.
Further, the constant displacement pump in the pressure duct is successively through the 4th triple valve, the second two-port valve and the circulation pipe
The kettle connection that balances each other in road.
Further, first two-port valve, the second two-port valve, third two-port valve or the 4th two-port valve are the high pressure needle of two-way
Valve.
Further, first triple valve, the second triple valve, third triple valve or the 4th triple valve are the high pressure of threeway
Valve.
A kind of original position on-line determination CO2The method of solubility, the described method comprises the following steps in pure water：
(1) device pre-processes
The air-tightness that nitrogen check device is injected into circulation line, later vacuumizes pressure duct, circulation line；
(2) standard curve is drawn
Pure water is filled into the kettle that balances each other, CO is added using constant displacement pump2Gas makes gas and liquid by Manual pressurization pump
It is miscible, it stands, using circulating pump by the CO in the kettle that balances each other2-H2O systems are recycled in quartz capillary, the quartz capillary
It is equipped with one section of transparent observation window, it is burnt aobvious using copolymerization under the sample observation mode of the burnt micro-Raman spectroscopy of copolymerization
Micro mirror observes CO in quartz capillary2-H2The dissolving of O systems changes, and cold and hot temperature of adjustment is to T DEG C, by the burnt microscopic Raman of copolymerization
Spectrometer switches to Raman light path pattern, utilizes CO in laser Raman spectrum instrument detection quartz capillary2-H2The Raman light of O systems
Spectrogram, and by formulaObtain CO2-H2CO in O systems2With the ratio of peak of water quartz is indicated when ratio of peak is constant
Capillary CO2-H2O systems reach reaction balance, the ratio of peak numerical value of recording constant；(recommend 5 times) to add several times by constant displacement pump
Enter CO2, detect and record CO2CO under gradient concentration2-H2CO in O systems2With the constant ratio of peak numerical value of water, with CO2A concentration of cross
Coordinate, ratio of peak are that ordinate draws standard curve；
Described T DEG C of range is at 30~80 DEG C；
The CO2The range of gradient concentration is in 0~1.5mol/kg, preferably 0.2~1.0mol/kg；
The formulaIn, IrIndicate CO2-H2CO in O systems2With the Raman ratio of peak of water,For 1385cm-1Locate CO2The peak height of your double bond of Fermi, υO-HFor 2800~3800cm-1Locate the peak height of the O-H stretching vibration peaks of water；
(3) CO is obtained2Dissolubility data in pure water
Pure water is filled in the kettle that balances each other, excessive CO is added into pure water2Gas, by Manual pressurization pump make gas with
Liquid is miscible, stands, using circulating pump by the saturation CO in the kettle that balances each other2-H2O systems are recycled in quartz capillary, are being copolymerized
Under the sample observation mode of burnt micro-Raman spectroscopy, is observed in quartz capillary using Laser Scanning Confocal Microscope and be saturated CO2-H2O bodies
The dissolving of system changes, and for cold and hot temperature of adjustment to T DEG C, control Manual pressurization pump adjusts pressure to X MPa, observation saturation CO2-H2O
CO in system2The variation of bubble intercepts phase-state change figure, as saturation CO2-H2After O systems phase-state change is no longer apparent, it will be copolymerized
Burnt micro-Raman spectroscopy switches to Raman light path pattern, utilizes different positions in laser Raman spectrum instrument detection quartz capillary
It sets, the saturation CO of different time2-H2The Raman spectrogram of O systems determines the saturation CO in quartz capillary2-H2O systems reach
When reaction balance, then is detected with laser Raman spectrum instrument and be saturated CO in quartz capillary2-H2O systems are under the conditions of T DEG C, X MPa
Raman spectrogram, and by formulaObtain saturation CO2-H2The Raman ratio of peak of O systems, gained ratio of peak is substituted into
In the standard curve that step (2) is drawn, T DEG C is calculated, CO under the conditions of X Mpa2Dissolubility data in pure water；
Described T DEG C of range is at 30~80 DEG C；
The range of the X MPa is in 3~35MPa；
The formulaDefinition it is identical with step (2).
Pure water of the present invention is deionized water.
Observation window on quartz capillary of the present invention can remove the brown of capillary surface by using oxyhydrogen flame
Color polyimide layer obtains, and the observation window length is usually in 1~2cm.Specifically, quartz capillary example of the present invention
The quartz capillary that internal diameter is 300 μm, outer diameter is 665 μm, length is 28cm such as can be used.
Specifically, in step (1) of the present invention,
The operating procedure of air-tightness that nitrogen check device is injected into circulation line is：Adjust the first triple valve,
Second triple valve and the 4th triple valve are connected to N2Steel cylinder and constant displacement pump close above-mentioned 3 threeways after so that nitrogen is entered constant displacement pump
Valve then adjusts the 4th triple valve, the second two-port valve, third two-port valve and the 4th two-port valve connection constant displacement pump and circulation line,
Nitrogen is pressed into circulation line using Manual pressurization pump, passes through the airtight of the pressure change judgment means of second pressure sensor
Property；
The operating procedure that pressure duct, circulation line are vacuumized is：Adjust the first two-port valve isolation pressure duct,
Circulation line and extraneous air adjust the first triple valve isolation pressure duct, circulation line and N2Steel cylinder, CO2Steel cylinder, more than adjusting
Under all two-port valves so that vacuum pump is connected to pressure duct, circulation line with triple valve, vacuumized using vacuum pump, when first
When pressure above pressure sensor is shown as zero, third triple valve isolation vacuum pump and pressure duct, circulation line are adjusted, most
After turn off vacuum pump.
In step (3) of the present invention, CO2The variation of bubble can be judged by the size that bubble changes；The Raman swashs
Photothermal spectroscopic analyzer, which detects, is saturated CO in quartz capillary2-H2Raman spectrogram of O systems under the conditions of T DEG C, X MPa, is measured
Point be the point far from 200 μm of positions of bubble.
In step (3) of the present invention, different location, different time in laser Raman spectrum instrument detection quartz capillary are utilized
It is saturated CO2-H2The Raman spectrogram of O systems determines the saturation CO in quartz capillary2-H2O systems reach the behaviour of reaction balance
It is as method：
With the sample in laser Raman spectrum instrument irradiating and detecting quartz capillary, it is measured, is obtained not in different location
With the Raman spectrogram of the sample of position, according to formulaRatio of peak is calculated separately, when the ratio of peak one of different location
It causes and (generally refers to the ratio of peak data error of different location within ± 3%) after constant no longer variation, then detect its middle-end
The Raman spectrogram of the sample of position different time points, according to formulaRatio of peak is calculated separately, different time points are worked as
Ratio of peak it is consistent and it is constant no longer change after (generally refer to the ratio of peak data error of different time points within ± 3%),
Indicate the saturation CO in quartz capillary2-H2O systems reach reaction balance；
The different location is generally chosen along the front end of quartz capillary length direction, middle-end, end three, detects three
The ratio of peak data of different observation points are compared, and are generally sufficient to characterization saturation CO2-H2The equilibrium state of O systems can also be chosen
More multipoint observation point is used for detecting saturation CO2-H2The equilibrium state of O systems；
The different time points generally selection 0,10,20,30, this five time points of 40min (every 10min), detection five
The ratio of peak data of a different time points are compared, and are generally sufficient to characterization saturation CO2-H2The equilibrium state of O systems, it is also optional
The observation point of more different intervals is taken to be used for detecting saturation CO2-H2The equilibrium state of O systems.
The beneficial effects of the present invention are：The method of the present invention has intuitive, low consumption, accurate, conveniently, and can operate continuously
Advantage.Quartz capillary can be effectively reduced the temperature gradient of reaction, solve system under conditions of close to environment temperature, whole
Temperature is less than set temperature, measured value defect bigger than normal.In addition, this method innovatively divides situ Raman Spectroscopy online
Analysis applies in system, within a certain period of time detection and counting system CO2With the ratio of peak of pure water, pass through surveyed numeric ratio
Compared with judging whether system reaches thermodynamical equilibrium, ensure that surveyed CO2-H2The accuracy of O system solubility, be certain temperature,
CO is measured under pressure condition2The research of dissolution characteristics in geological storage provides a kind of brand-new thinking.
(4) it illustrates
Fig. 1：On-line determination CO in situ2The installation drawing of solubility in pure water, wherein 1- high pressures N2Steel cylinder；2- high pressure COs2
Steel cylinder；3- vacuum pumps；4- constant displacement pumps；5- first pressure sensors；6- balances each other kettle；7- second pressure sensors；8- circulating pumps；
9- quartz capillaries；Cold and hot of 10-；The Laser Scanning Confocal Microscope of the burnt micro-Raman spectroscopy of 11- copolymerization；12- displays；V-1 is
First triple valve；V-2 is the second triple valve；V-3 is third triple valve；V-4 is the 4th triple valve；V-5 is the first two-port valve；V-
6 second two-port valves；V-7 third two-port valves；The 4th two-port valves of V-8；
Fig. 2：On-line determination CO in situ2The method flow diagram of solubility in pure water；
Fig. 3：Under the conditions of 30 DEG C, 9MPa, CO in pure water2Raman spectrogram；
Fig. 4：Illustrate pure aquatic system observation point position along the three of the front end of quartz capillary length direction, middle-end and end
Figure；
Fig. 5 a：Front end, middle-end and end three at observation point Raman spectrogram；
Fig. 5 b are saturated CO2-H2O systems 0,10,20,30, the Raman spectrogram at five time points of 40min (40 DEG C,
9MPa)；
Fig. 6：In 30 DEG C, under the conditions of different pressures, CO2-H2The ratio of peak of O systems；
Fig. 7：Under condition of different temperatures, it is known that CO2The ratio of peak of the pure aquatic system of concentration；
Fig. 8：The CO of various concentration2With the CO measured2-H2The standard curve that the ratio of peak of O systems is drawn；
Fig. 9：It is saturated CO2The CO of pure aquatic system2Bubble variation diagram；
Figure 10：Under different temperatures pressure, saturation CO of the invention2-H2The tendency chart of O system ratio of peak；
Figure 11：Under different temperatures pressure, saturation CO of the invention2-H2The tendency chart of O system solubility；
Figure 12：Under different temperatures pressure, the saturation CO of the present invention and document 12-H2The comparison figure of O system solubility；
Figure 13：Under different temperatures pressure, the saturation CO of the present invention and document 22-H2The comparison figure of O system solubility；
Figure 14：The experimental result comparison diagram of the embodiment of the present invention and comparative example.
(5) specific implementation mode
With reference to specific embodiment, the present invention is described further, and but the scope of the present invention is not limited thereto.
Embodiment 1：
The on-line determination CO in situ that the present embodiment uses2The device of solubility is as shown in Figure 1, described device packet in pure water
It includes：The burnt micro-Raman spectroscopy of copolymerization (Horiba JobinYvon, HR800, France), pressure duct, circulation line, the first pressure
Force snesor, second pressure sensor, cold and hot；
The burnt micro-Raman spectroscopy of the copolymerization includes Laser Scanning Confocal Microscope 11, display 12, objective table, and the copolymerization is burnt
Micro-Raman spectroscopy is equipped with changeable sample observation mode and Raman light path pattern：It is copolymerized under sample observation mode burnt aobvious
The Laser Scanning Confocal Microscope of micro- Raman spectrometer is connect with DVD real-time recording systems, and real-time micro- amplification sample image is observed；
Laser Scanning Confocal Microscope is connect with laser Raman spectrum instrument under Raman light path pattern, is carried out laser Raman spectroscopy and is measured detection.
N is equipped in the pressure duct2Steel cylinder 1, CO2Steel cylinder 2, vacuum pump 3, constant displacement pump 4, the vacuum pump is successively through
Three triple valve V-3, the second triple valve V-2, the first triple valve V-1 and N2Steel cylinder 1 and CO2Steel cylinder 2 connects, and the constant displacement pump 4 is successively
Through the 4th triple valve V-4, the second triple valve V-2, the first triple valve V-1 and N2Steel cylinder 1 and CO2Steel cylinder 2 connects；Described 3rd 3
Port valve V-3 is also associated with the first two-port valve V-5.
Balance each other kettle 6, circulating pump 8, quartz capillary 9, kettle 6, the circulating pump of balancing each other are equipped in the circulation line
8, the connection of quartz capillary 9 forming circuit；It is described equipped with third two-port valve V-7 between the circulating pump 8 and quartz capillary 9
It balances each other and is equipped with the 4th two-port valve V-8 between kettle 6 and quartz capillary 9.
The first pressure sensor 5 is connect with the constant displacement pump 4 in the pressure duct, the second pressure sensor 7
It is connect with the kettle 6 that balances each other in the circulation line, the constant displacement pump 4 in the pressure duct is successively through the 4th triple valve V-4,
Two two-port valve V-6 are connect with the kettle 6 that balances each other in the circulation line, and the quartz capillary 9 in the circulation line is placed in institute
It states in cold and hot 10, described cold and hot 10 is fixed on the objective table of the burnt micro-Raman spectroscopy of the copolymerization.
The first two-port valve V-5, the second two-port valve V-6, third two-port valve V-7 or the 4th two-port valve V-8 are two-way
High pressure needle valve.
The first triple valve V-1, the second triple valve V-2, third triple valve V-3 or the 4th triple valve V-4 are threeway
High pressure valve.
9 internal diameter of the quartz capillary is 300 μm, outer diameter is 665 μm, length 28cm, in quartz capillary 9 against the right side
The transparent sight hole mouth of one section of long 1~2cm is equipped at the 4th two-port valve V-8 of side.
On-line determination CO in situ2The method of solubility is as follows in pure water：
(1) quartz capillary (300 μm of internal diameter, 665 μm of outer diameter) for intercepting one section of about 28cm removes capillary with oxyhydrogen flame
The brown polyimide layer of pipe both ends 0.1cm or so simultaneously seals, and the centre of quartz capillary is inserted in the high pressure of two sections of 2cm or so
The high pressure stainless steel tube sealing of stainless steel tube (fracture for preventing observation window), both ends AB glue and 2.5cm or so it is glued (to prevent
The only entrance of impurity), 24 hours are stood, after its fixation, extra quartz capillary is intercepted along the end of high pressure stainless steel tube,
Cutting ferrule and nut are set on high pressure stainless steel tube, can be connect with high pressure valve V-7, V-8.
(2) quartz capillary comprising observation window is placed in cold and hot sample cell (Linkam, CAP500, UK), and
Cold and hot is fixed on the objective table of the burnt micro-Raman spectroscopy of copolymerization.Laser Scanning Confocal Microscope light source is opened, adjusts cold and hot
With quartz capillary position, reach best observation effect, observation window is enable completely to be observed by microscope.By quartzy capillary
Pipe is connected to by high pressure valve in circulation line, is opened high pressure valve, is passed through high pressure N2A certain amount of N is added in steel cylinder2, close
High pressure valve, circulation line and pressure duct, which are in, at this time disconnects disconnected state.Then it is forced by Manual pressurization pump
30MPa or so stands 3-4 hours, according to the air-tightness of pressure change check device.
(3) high pressure valve is opened, vacuum pump is opened, all pipelines in device is vacuumized, the pressure above pressure sensor
Power is shown as zero；It is then shut off vacuum pump.
(4) pure water is filled into the kettle that balances each other, and opens high pressure CO2CO is added using constant displacement pump in steel cylinder2Gas is then shut off
High pressure CO2Steel cylinder.High pressure valve is closed, by Manual pressurization pump to the CO in circulation line2Gas, which carries out pressurization, makes gas and liquid
Body is miscible, stands 12 hours, using cycle pump circulation 15 minutes by the CO in the kettle that balances each other2-H2O systems are recycled to quartzy capillary
Guan Zhong maintains a period of time after temperature adjusting reaches preset condition, using known to the burnt micro-Raman spectroscopy detection of copolymerization not
Same CO2Under conditions of concentration, CO at 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C2-H2The Raman spectrogram of O systems, wherein
Influence of the pressure to ratio of peak is smaller (as shown in Figure 6), then calculates separately ratio of peakFurther according to CO2Concentration with
The average value of ratio of peak (as shown in Figure 7) draws standard curve (as shown in Figure 8) under measured different temperatures.
(5) high pressure CO is opened2Excessive CO is added in steel cylinder in pure water2Gas is then shut off high pressure CO2Steel cylinder.It closes
High pressure valve, by Manual pressurization pump to the CO in circulation line2Gas, which carries out pressurization, keeps gas miscible with liquid, and it is small to stand 12
When, using cycle pump circulation 15 minutes by the saturation CO in the kettle that balances each other2-H2O systems are recycled in quartz capillary, pass through increasing
Add cold and hot temperature to T DEG C, control Manual pressurization pump reduces pressure to X MPa, Laser Scanning Confocal Microscope-DVD real-time recording systems
It is observed that saturation CO2-H2CO in O systems2The variation of bubble, interception phase-state change figure (as shown in Figure 9)；When preset temperature,
Under pressure condition, the CO of saturation2-H2After O systems phase-state change is no longer apparent, instrument is switched into Raman light path pattern, uses laser
Different location different time is full in Raman spectrometers (Horiba JobinYvon, HR800, France) detection quartz capillary
And CO2The Raman spectrogram of pure aquatic system, the Raman spectrogram (shown in such as Fig. 5 (a)) of the system measured by different location, in
The Raman spectrogram (shown in such as Fig. 5 (b)) of system measured by end position different time, then calculates separately ratio of peakWhereinIt is 1385cm-1Locate CO2The peak height of your double bond of Fermi, υO-HFor 2800~3800cm-1The O-H of place's water stretches
The peak height of contracting vibration peak, the ratio of peak data of different location different time points as shown in table 1,2, the SD values of ratio of peak are 5.02 ×
10-4, ratio of peak it is consistent and it is constant no longer change, indicate quartz capillary in saturation CO2-H2O systems reach reaction balance.So
It uses again afterwards in laser Raman spectrum instrument detection quartz capillary and is saturated CO2-H2Raman spectrum under the conditions of T DEG C of O systems, X MPa
Figure, then by formulaCalculate separately saturation CO2The ratio of peak (as shown in Figure 10) of pure aquatic system, further according to standard
Saturation CO is calculated with measured ratio of peak in curve (Fig. 8)2The solubility (as shown in figure 11) of pure aquatic system.
Table 1
| Front end | Middle-end | End | |
| Ratio of peak | 0.17482 | 0.17362 | 0.17376 |
Table 2
| 0min | 10min | 20min | 30min | 40min | |
| Ratio of peak | 0.17026 | 0.17341 | 0.17354 | 0.17358 | 0.17362 |
Calculate value=5.02 × 10 SD of ratio of peak-4
Acquired results are shown in that Figure 12 and Figure 13, Figure 12 are the present invention and (Sun R, the Duan Z.An improved of document 1
model calculating CO2,solubility in pure water and aqueous NaCl solutions
0 to 2000bar of from 273to 533K and from) survey calculation obtains respectively different temperatures, the saturation under pressure
CO2The tendency chart of the solubility of pure aquatic system.
Figure 13 is this method and (Diamond LW, the Akinfiev N N.Solubility of CO of document 22,in
water from-1.5 to 100℃and from 0.1 to 100MPa:evaluation of literature data
And thermodynamic modelling) both the solubility trend comparison figure that is combined of data.
It can be seen that the solubility that this method measures is consistent with document from Figure 12,13, thus illustrate we
The correctness and feasibility of method data.
Comparative example
Currently, carrying out quantitative analysis measurement at high temperature under high pressure using Raman spectrum still faces huge challenge.Existing skill
The synthesis that art is developed is not applied for the temperature, pressure and constituent of wider range comprising method；And saturated concentration method is not
Certainty is too high, and experimental error is larger, and it is therefore necessary to develop a kind of quantitative study of new departure progress Raman spectrum.
Experimental procedure compares：
Team of Lv Wan armies (Guo H R, Chen Y, Hu Q C, et al.Quantitative Raman
spectroscopic investigation of geo-fluids high-pressure phase equilibria:Part
I.Accurate calibration and determination of CO2solubility in water from
273.15 to, 573.15 K and from, 10 to 120MPa) using mercury seal method prepare various concentration homogeneous sample
Product establish raman scattering intensity than being quantified with concentration of dissolved gas ratio and temperature by acquiring the raman spectra under different temperature and pressure
Functional relation obtains CO after the Raman spectrum under obtaining vapor liquid equilibrium by function2Solubility.
Experiment is divided into two parts：Raman was demarcated before this, the followed by measurement of solubility.
One, Raman is demarcated：Prepare known CO2The homogeneous aqueous solution of concentration
Experiment prepares CO known to difference using the method for mercury seal2The sample of concentration.It comprises the concrete steps that：1. by a root long 7~
The water column of 8cm is packed into the bottom end of coarse wool tubule (outer diameter 650mm, internal diameter 300mm, be about 30cm)；2. a fine capillary is (outer
Diameter 200mm, internal diameter 75mm, is about 50cm) it is connected to CO2Source simultaneously adjusts CO2Flow velocity；3. fine capillary is passed through coarse wool tubule, insert
To gas-liquid interface, the air in capillary is excluded, after 3~5min, fine capillary is inserted to coarse wool tubule bottom, in CO2Column
It is quickly drawn out fine capillary when being moved to required gas length；4. mercury column (9~10mm long) is injected coarse wool tubule, by water column point
At two parts, part sealing CO2Column, another part stay in the other side of mercury column；It is sealed by mercury 5. measuring at normal temperatures and pressures
Water column and CO2The length of column, passes through formulaCalculate CO2In pure water
In concentration；6. horizontal with capillary tube movement is mounted on cold and hot platform, pressure line is connected, CO is made by pressurization2It is completely dissolved
In water, system reaches uniform state；The CO under 273.15~573.15K, 15~70MPa is measured using Raman spectrometer2
The Raman spectrum of matter solution.Ratio of peak and CO are drawn according to measured ratio of peak2The pass of concentration proportion and temperature in pure water
It is curve, to obtain the relational expression of ratio of peak and concentration proportion and temperature.
The formulaIn, r indicates the radius of device, is fixed
Value；For CO2The length of column；For CO2Molal volume；For the density of pure water；For the length of water column.
Two, CO2Solubility in pure water measures
It is comprised the concrete steps that：1. water column (length ＜ 1cm) to be injected to the blind end of capillary, open end is connected to pressure pipe
The high pressure valve of line；2. moving horizontally capillary to be installed on cold and hot platform, it is passed through CO2, pressure is increased using pressure generator
20MPa is added to, temperature is reduced to 243.15K to form CO2Hydrate；3. raising the temperature to room temperature makes decomposition of hydrate, and
A large amount of bubbles are generated in aqueous solution；4. adjusting and keeping specific temperature and pressure, wait for 15~20min to ensure to reach flat
Weighing apparatus collects bubble CO nearby2The Raman spectrum of saturated solution.The ratio of peak measured is substituted into the formula obtained by step 1, you can
Obtain CO2Solubility in pure water.
Of the present invention is calibration curve method, and experiment is divided into two parts：One, draw standard curve, two, measure CO2
Solubility in pure water.
Experimental result comparison is as shown in figure 14.
The temperature and pressure range that team of Lv Wan armies measures is wide, but meets obtained data of practical geology storage condition and few,
Under the conditions of geological storage, the data of the data and Duan models that are measured through the invention with team of Lv Wan armies are compared hair
It is existing：Data deviation is little, but the data that this experimental data and Duan models are calculated are closer.
The method of the present invention is improved in the method used by team of Lv Wan armies, and mercury all deposits human body and environment first
In certain harm, invention removes the use of mercury, reduce the pollution to environment；Secondly team of Lv Wan armies is by drawing peak
Height ratio and CO2Concentration proportion and the curve of temperature are to obtain the complexity that its relational expression increases calculating in water, to drop
The low accuracy of data, and the present invention reduces the uncertainty of experiment by drawing standard curve, improve data can
By property；Method used by team of last Lv Wan armies requires strong operability, otherwise can reduce experiment success rate, and the present invention operates
Simply, it and can operate continuously, it is convenient succinct.
Claims (10)
1. a kind of original position on-line determination CO2The device of solubility in pure water, which is characterized in that described device includes：Copolymerization is burnt aobvious
Micro- Raman spectrometer, pressure duct, circulation line, first pressure sensor, second pressure sensor, cold and hot；
The burnt micro-Raman spectroscopy of the copolymerization includes Laser Scanning Confocal Microscope, display, objective table, the burnt microscopic Raman of the copolymerization
Spectrometer is equipped with changeable sample observation mode and Raman light path pattern：Burnt microscopic Raman light is copolymerized under sample observation mode
The Laser Scanning Confocal Microscope of spectrometer is connect with DVD real-time recording systems, and real-time micro- amplification sample image is observed；In Raman light
Laser Scanning Confocal Microscope is connect with laser Raman spectrum instrument under the pattern of road, is carried out laser Raman spectroscopy and is measured detection；
N is equipped in the pressure duct2Steel cylinder, CO2Steel cylinder, vacuum pump, constant displacement pump, the vacuum pump and N2Steel cylinder and CO2Steel cylinder
Connection, the constant displacement pump also with N2Steel cylinder and CO2Steel cylinder connects；
Balance each other kettle, circulating pump, quartz capillary, the kettle that balances each other, circulating pump, quartzy capillary are equipped in the circulation line
Pipe connection forming circuit；
The first pressure sensor is connect with the constant displacement pump in the pressure duct, and the second pressure sensor is followed with described
The kettle connection that balances each other in endless tube road, the constant displacement pump in the pressure duct are connect with the kettle that balances each other in the circulation line,
Quartz capillary in the circulation line is placed in described cold and hot, and described cold and hot is fixed on the burnt microscopic Raman of the copolymerization
On the objective table of spectrometer.
2. original position on-line determination CO as described in claim 12The device of solubility in pure water, which is characterized in that the high-voltage tube
Lu Zhong, the vacuum pump is successively through third triple valve, the second triple valve, the first triple valve and N2Steel cylinder and CO2Steel cylinder connects, institute
Constant displacement pump is stated successively through the 4th triple valve, the second triple valve, the first triple valve and N2Steel cylinder and CO2Steel cylinder connects；Described 3rd 3
Port valve is also associated with the first two-port valve.
3. original position on-line determination CO as described in claim 12The device of solubility in pure water, which is characterized in that the circulation pipe
Lu Zhong, is equipped with third two-port valve between the circulating pump and quartz capillary, described balance each other sets between kettle and quartz capillary
There is the 4th two-port valve.
4. original position on-line determination CO as described in claim 12The device of solubility in pure water, which is characterized in that the high-voltage tube
Constant displacement pump in road is connect through the 4th triple valve, the second two-port valve with the kettle that balances each other in the circulation line successively.
5. original position on-line determination CO as described in claim 12The device of solubility in pure water, which is characterized in that the described 1st
Port valve, the second two-port valve, third two-port valve or the 4th two-port valve are the high pressure needle valve of two-way；First triple valve, the two or three
Port valve, third triple valve or the 4th triple valve are the high pressure valve of threeway.
6. a kind of original position on-line determination CO2The method of solubility in pure water, which is characterized in that the described method comprises the following steps：
(1) device pre-processes
The air-tightness that nitrogen check device is injected into circulation line, later vacuumizes pressure duct, circulation line；
(2) standard curve is drawn
Pure water is filled into the kettle that balances each other, CO is added using constant displacement pump2Gas keeps gas miscible with liquid by Manual pressurization pump,
It stands, using circulating pump by the CO in the kettle that balances each other2-H2O systems are recycled in quartz capillary, are set on the quartz capillary
There is one section of transparent observation window, under the sample observation mode of the burnt micro-Raman spectroscopy of copolymerization, utilizes Laser Scanning Confocal Microscope
Observe CO in quartz capillary2-H2The dissolving of O systems changes, and cold and hot temperature of adjustment is to T DEG C, by the burnt micro Raman spectra of copolymerization
Instrument switches to Raman light path pattern, utilizes CO in laser Raman spectrum instrument detection quartz capillary2-H2The Raman spectrum of O systems
Figure, and by formulaObtain CO2-H2CO in O systems2With the ratio of peak of water quartz wool is indicated when ratio of peak is constant
Tubule CO2-H2O systems reach reaction balance, the ratio of peak numerical value of recording constant；CO is added several times by constant displacement pump2, detection
And record CO2CO under gradient concentration2-H2CO in O systems2With the constant ratio of peak numerical value of water, with CO2A concentration of abscissa, peak height
Than drawing standard curve for ordinate；
Described T DEG C of range is at 30~80 DEG C；
The CO2The range of gradient concentration is in 0~1.5mol/kg；
The formulaIn, IrIndicate CO2-H2CO in O systems2With the Raman ratio of peak of water,For 1385cm-1Place
CO2The peak height of your double bond of Fermi, υO-HFor 2800~3800cm-1Locate the peak height of the O-H stretching vibration peaks of water；
(3) CO is obtained2Dissolubility data in pure water
Pure water is filled in the kettle that balances each other, excessive CO is added into pure water2Gas makes gas and liquid by Manual pressurization pump
It is miscible, it stands, using circulating pump by the saturation CO in the kettle that balances each other2-H2O systems are recycled in quartz capillary, burnt aobvious in copolymerization
Under the sample observation mode of micro- Raman spectrometer, is observed in quartz capillary using Laser Scanning Confocal Microscope and be saturated CO2-H2O systems
Dissolving variation, for cold and hot temperature of adjustment to T DEG C, control Manual pressurization pump adjusts pressure to X MPa, observation saturation CO2-H2O systems
Interior CO2The variation of bubble intercepts phase-state change figure, as saturation CO2-H2After O systems phase-state change is no longer apparent, will copolymerization it is burnt aobvious
Micro- Raman spectrometer switches to Raman light path pattern, utilizes different location, no in laser Raman spectrum instrument detection quartz capillary
With the saturation CO of time2-H2The Raman spectrogram of O systems determines the saturation CO in quartz capillary2-H2O systems reach reaction
When balance, then is detected with laser Raman spectrum instrument and be saturated CO in quartz capillary2-H2Drawing of O systems under the conditions of T DEG C, X MPa
Graceful spectrogram, and by formulaObtain saturation CO2-H2Gained ratio of peak is substituted into step by the Raman ratio of peak of O systems
(2) in the standard curve drawn, T DEG C is calculated, CO under the conditions of X Mpa2Dissolubility data in pure water；
Described T DEG C of range is at 30~80 DEG C；
The range of the X MPa is in 3~35MPa；
The formulaDefinition it is identical with step (2).
7. original position on-line determination CO as claimed in claim 62The method of solubility in pure water, which is characterized in that in step (1),
The operating procedure of air-tightness that nitrogen check device is injected into circulation line is：Adjust the first triple valve, the second threeway
Valve and the 4th triple valve are connected to N2Steel cylinder and constant displacement pump are closed above-mentioned 3 triple valves, are then adjusted after so that nitrogen is entered constant displacement pump
The 4th triple valve, the second two-port valve, third two-port valve and the 4th two-port valve connection constant displacement pump and circulation line are saved, is added using manual
Nitrogen is pressed into circulation line by press pump, passes through the air-tightness of the pressure change judgment means of second pressure sensor.
8. original position on-line determination CO as claimed in claim 62The method of solubility in pure water, which is characterized in that in step (1),
The operating procedure that pressure duct, circulation line are vacuumized is：Adjust the first two-port valve isolation pressure duct, circulation line
And extraneous air, adjust the first triple valve isolation pressure duct, circulation line and N2Steel cylinder, CO2Steel cylinder is adjusted remaining all
Two-port valve makes vacuum pump be connected to pressure duct, circulation line with triple valve, is vacuumized using vacuum pump, when first pressure senses
When pressure above device is shown as zero, third triple valve isolation vacuum pump and pressure duct, circulation line are adjusted, is finally turned off true
Sky pump.
9. original position on-line determination CO as claimed in claim 62The method of solubility in pure water, which is characterized in that in step (3),
The saturation CO using different location, different time in laser Raman spectrum instrument detection quartz capillary2-H2The Raman of O systems
Spectrogram determines the saturation CO in quartz capillary2-H2O systems reach the operating method that reaction balances：
With the sample in laser Raman spectrum instrument irradiating and detecting quartz capillary, it is measured in different location, obtains different location
Sample Raman spectrogram, according to formulaRatio of peak is calculated separately, when the ratio of peak of different location is consistent and constant
After no longer changing, then the Raman spectrogram of the sample of wherein middle end position different time points is detected, according to formulaPoint
Do not calculate ratio of peak, when the ratio of peak of different time points it is consistent and it is constant no longer change after, indicate quartz capillary in saturation
CO2-H2O systems reach reaction balance.
10. original position on-line determination CO as claimed in claim 92The method of solubility in pure water, which is characterized in that the difference
Position is chosen along the front end of quartz capillary length direction, middle-end, end three, and the ratio of peak number of three different observation points is detected
According to being compared；The different time points selection 0,10,20,30, this five time points of 40min, detect five different time points
Ratio of peak data be compared.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109142161A (en) * | 2018-10-23 | 2019-01-04 | 武汉工程大学 | A kind of solid solubility automatic measuring system and measuring method in a liquid |
| CN111157510A (en) * | 2020-01-03 | 2020-05-15 | 浙江工业大学 | In-situ online CO determination2Method and apparatus for solubility in alkanes |
| CN114136874A (en) * | 2021-11-26 | 2022-03-04 | 浙江工业大学 | Device and method for measuring metal corrosion resistance under high temperature and high pressure |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004008091A1 (en) * | 2002-07-15 | 2004-01-22 | Microbar, Inc. | Method and system for analyte determination in metal plating baths |
| WO2005119219A2 (en) * | 2004-05-26 | 2005-12-15 | Real-Time Analyzers, Inc. | Method and apparatus for performing sers analysis using a chemical reference |
| CN1975381A (en) * | 2006-12-22 | 2007-06-06 | 浙江工业大学 | On-line testing method and equipment for solubility of disperse dye in supercritical CO2 |
| CN102621023A (en) * | 2012-03-06 | 2012-08-01 | 华东理工大学 | Method for measuring dissolvability of CO2-micromolecule-polymer system and quartz crystal microbalance |
| CN103454391A (en) * | 2013-08-22 | 2013-12-18 | 西南石油大学 | Testing method for solubility of high-CO2-content natural gas in formation water |
| CN104267059A (en) * | 2013-12-16 | 2015-01-07 | 浙江工业大学 | An apparatus and a method of measuring solubility of an inorganic salt in subcritical water by the apparatus |
| WO2016025929A1 (en) * | 2014-08-14 | 2016-02-18 | Parallume, Inc. | Porous medium with encoded regions |
-
2018
- 2018-03-13 CN CN201810203152.XA patent/CN108426868B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004008091A1 (en) * | 2002-07-15 | 2004-01-22 | Microbar, Inc. | Method and system for analyte determination in metal plating baths |
| WO2005119219A2 (en) * | 2004-05-26 | 2005-12-15 | Real-Time Analyzers, Inc. | Method and apparatus for performing sers analysis using a chemical reference |
| CN1975381A (en) * | 2006-12-22 | 2007-06-06 | 浙江工业大学 | On-line testing method and equipment for solubility of disperse dye in supercritical CO2 |
| CN102621023A (en) * | 2012-03-06 | 2012-08-01 | 华东理工大学 | Method for measuring dissolvability of CO2-micromolecule-polymer system and quartz crystal microbalance |
| CN103454391A (en) * | 2013-08-22 | 2013-12-18 | 西南石油大学 | Testing method for solubility of high-CO2-content natural gas in formation water |
| CN104267059A (en) * | 2013-12-16 | 2015-01-07 | 浙江工业大学 | An apparatus and a method of measuring solubility of an inorganic salt in subcritical water by the apparatus |
| WO2016025929A1 (en) * | 2014-08-14 | 2016-02-18 | Parallume, Inc. | Porous medium with encoded regions |
Non-Patent Citations (1)
| Title |
|---|
| 贝克 等: "石英毛细管反应器中研究超临界CO2在水中的溶解度", 《第十届全国超临界流体技术学术及应用研讨会暨第三届海峡两岸超临界流体技术研讨会论文集》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109142161A (en) * | 2018-10-23 | 2019-01-04 | 武汉工程大学 | A kind of solid solubility automatic measuring system and measuring method in a liquid |
| CN111157510A (en) * | 2020-01-03 | 2020-05-15 | 浙江工业大学 | In-situ online CO determination2Method and apparatus for solubility in alkanes |
| CN114136874A (en) * | 2021-11-26 | 2022-03-04 | 浙江工业大学 | Device and method for measuring metal corrosion resistance under high temperature and high pressure |
| CN114136874B (en) * | 2021-11-26 | 2023-08-08 | 浙江工业大学 | Device and method for measuring corrosion resistance of metal at high temperature and high pressure |
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