CN109932276A - The measurement method and system of solid sample solubility in a kind of supercritical carbon dioxide - Google Patents
The measurement method and system of solid sample solubility in a kind of supercritical carbon dioxide Download PDFInfo
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- CN109932276A CN109932276A CN201910331675.7A CN201910331675A CN109932276A CN 109932276 A CN109932276 A CN 109932276A CN 201910331675 A CN201910331675 A CN 201910331675A CN 109932276 A CN109932276 A CN 109932276A
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- autoclave
- carbon dioxide
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- pressure
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 252
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 126
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 126
- 239000007787 solid Substances 0.000 title claims abstract description 100
- 238000000691 measurement method Methods 0.000 title claims abstract description 11
- 238000010926 purge Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- 238000003860 storage Methods 0.000 claims description 14
- 239000003990 capacitor Substances 0.000 claims description 12
- 238000001514 detection method Methods 0.000 claims description 11
- 230000003321 amplification Effects 0.000 claims description 8
- 238000003199 nucleic acid amplification method Methods 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 241000790917 Dioxys <bee> Species 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 4
- 230000002000 scavenging effect Effects 0.000 claims description 4
- -1 gas source Chemical compound 0.000 claims description 2
- 238000012360 testing method Methods 0.000 abstract description 21
- 238000007599 discharging Methods 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 10
- 238000005259 measurement Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- 239000000523 sample Substances 0.000 description 113
- 229910000831 Steel Inorganic materials 0.000 description 11
- 238000005070 sampling Methods 0.000 description 11
- 239000010959 steel Substances 0.000 description 11
- WUBBRNOQWQTFEX-UHFFFAOYSA-N 4-aminosalicylic acid Chemical compound NC1=CC=C(C(O)=O)C(O)=C1 WUBBRNOQWQTFEX-UHFFFAOYSA-N 0.000 description 6
- 229960004909 aminosalicylic acid Drugs 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000012530 fluid Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 238000013022 venting Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Abstract
The present invention relates to the measurement methods and system of solid sample solubility in a kind of supercritical carbon dioxide, belong to chemical industry measurement equipment technical field.Method includes the following steps: injecting carbon dioxide gas into autoclave, the air in autoclave is discharged；Autoclave is evacuated, makes to form negative pressure in autoclave；Quantitative solid sample is sucked into autoclave using the negative pressure in autoclave；Carbon dioxide is injected into autoclave；The pressure and/or temperature in autoclave are adjusted, keeps carbon dioxide in a supercritical state, is dissolved in all solid samples in carbon dioxide；Adjust the pressure and/or temperature in autoclave, solid sample be precipitated from carbon dioxide, the record pressure and temperature in autoclave at this time, calculate the solid sample the pressure and at a temperature of supercritical carbon dioxide in solubility.The present invention realizes first air-discharging in testing and is loaded product again, avoids loss of the sample in air-discharging operation, improves the accuracy of measurement result.
Description
Technical field
The present invention relates to the measurement methods and system of solid sample solubility in a kind of supercritical carbon dioxide, belong to chemical industry
Detection device technical field.
Background technique
Supercritical fluid refers to that temperature and pressure is above the fluid of critical point.Studying at present more is carbon dioxide,
It is excellent that supercritical carbon dioxide fluid has that nontoxic, non-combustible, relatively cheap, solvability is higher, recyclable, critical point is low etc.
Point.The good characteristic as possessed by supercritical carbon dioxide fluid, so that it is in polymer science, pharmacy and prepares ultra-fine
The fields such as particle have obtained extensive research application, and solubility of the substance in supercritical carbon dioxide is the basis in these fields
Data, therefore solubility of the test substances in supercritical carbon dioxide is with regard to particularly important.
In the prior art, such as the Chinese invention of a kind of entitled " a method of add fat-soluble nutrients ingredient in rice "
Patent application (application publication number is 108112876 A of CN) and paper " supercritical carbon dioxide-polymeric system cloud point pressure
The photosensitive method of power measures " scheme disclosed in (" chinese scientific papers ", in November, 2016, Zhu Teng etc.) is all using overcritical
It is molten in supercritical carbon dioxide that the solvability of CO 2 fluid with pressure change this characteristic carrys out test sample substance
Xie Du.Test philosophy is to be dissolved in quantitative test sample in the supercritical carbon dioxide of high pressure, then gradually decreases dioxy
The pressure for changing carbon makes it dissolve ability reduction, and when dioxide solution supersaturation, test sample in carbon dioxide will be by
It is precipitated, molten solid system is in cloudy state, and the pressure of carbon dioxide is cloud-point pressure at this time, finally according to the test sample of addition
The information such as quality, system bulk, cloud-point pressure, system temperature, it will be able to calculate current pressure, at a temperature of the test sample
Solubility in supercritical carbon dioxide.
Existing supercritical carbon dioxide solubility test method is usually to utilize the autoclave for having form, test process
It first to open autoclave and sample material is added, turn off autoclave and open exhaust valve, be passed through excessive carbon dioxide and carry out body
It is air-discharging operation.During this, some test samples belong to volatile substance, and the granularity of some test samples is smaller,
It is easy diffusion, therefore some test sample that is bound to causes test sample as the flowing of air-flow is discharged from exhaust valve
Loss, meanwhile, reduce autoclave in pressure during also will cause the loss of sample to outlet carbon dioxide,
But it is last not consider this loss when calculating solubility, cause the solubility of the supercritical carbon dioxide actually calculated relative to
True value is higher, causes the untrue inaccuracy of test result.
Therefore, how to improve the accuracy of the measurement result of solid sample solubility in supercritical carbon dioxide is to need to solve
Technical problem certainly.
Summary of the invention
The object of the present invention is to provide the measurement method and system of solid sample solubility in a kind of supercritical carbon dioxide,
To solve the problems, such as current supercritical carbon dioxide solubility measurement inaccuracy.
The present invention provides a kind of survey of solid sample solubility in supercritical carbon dioxide to solve above-mentioned technical problem
Amount method, comprising the following steps:
Step 1: injecting carbon dioxide gas into autoclave, the air in autoclave is discharged；
Step 2: autoclave being evacuated, makes to form negative pressure in autoclave；
Step 3: quantitative solid sample being sucked into autoclave using the negative pressure in autoclave；
Step 4: carbon dioxide is injected into autoclave；
Step 5: pressure and/or temperature in adjustment autoclave keep carbon dioxide in a supercritical state, make all solid samples
It is dissolved in carbon dioxide；
Step 6: pressure and/or temperature in adjustment autoclave are precipitated solid sample from carbon dioxide, record high pressure at this time
Pressure and temperature in kettle, calculate the solid sample the pressure and at a temperature of supercritical carbon dioxide in solubility.
Quantitative solid sample is first packed into sample inlet in test by this programme, is opened purging gas circuit later, is used gas source
Directly to purging air-discharging is carried out in autoclave, vacuum pump suction is reused to reduce the pressure in autoclave, finally opens sample
Solid sample in sample inlet is blown into autoclave by quality control road using gas source and draught head.This programme whole process is real
The operation for having showed sample introduction after first air-discharging avoids loss of the solid sample in air-discharging operation, to improve test knot
The accuracy of fruit.Meanwhile the subnormal ambient in autoclave can further decrease the content of air plankton in kettle, improve autoclave
The purity of interior carbon dioxide further improves the accuracy of test result.
Further, in steps of 5, the temperature in autoclave is first adjusted to setting constant temperature, then adjusts the pressure in autoclave
By force, keep carbon dioxide in a supercritical state, be dissolved in all solid samples in carbon dioxide.
This programme gives a kind of more excellent Adjusted Option for making carbon dioxide conversion supercriticality.
Further, in step 6, it keeps the temperature in autoclave in setting constant temperature, and reduces the pressure in autoclave,
Solid sample is precipitated from carbon dioxide.
This programme gives a kind of more excellent Adjusted Option that solid sample is precipitated from carbon dioxide.
Further, in step 6, according to the change in signal strength for the detection light for passing through carbon dioxide in autoclave, sentence
Whether disconnected solid sample is precipitated from supercritical carbon dioxide.
This programme judges whether solid sample is precipitated according to the detection light light intensity variation by supercritical carbon dioxide,
Instead of the conventional mode with human eye direct viewing, the reliability and authenticity of cloud-point pressure judgement are improved.
The present invention also provides a kind of measuring system of solid sample solubility in supercritical carbon dioxide, including gas source,
Cooling system and autoclave, the autoclave are equipped with intake valve and exhaust valve, which further includes purging gas circuit, sample
Pipeline, solid sample storage device, temperature-adjusting device, plunger pump and vacuum pump, the gas source pass through cooling system, plunger pump
It is connected to the intake valve of autoclave, the temperature-adjusting device is used to adjust the temperature in autoclave, the purging gas circuit, described
Sample inlet is equipped with opening and closing valve, and the gas source is connected to autoclave by the opening and closing valve of the purging gas circuit, the purging gas circuit,
Described sample inlet one end opens and closes valve by sample inlet and is connected to autoclave, and the other end connects the gas by gas circuit valve
Source, the vacuum pump connect the exhaust valve of the autoclave.
Preferably, described sample inlet one end opens and closes valve by sample inlet and is connected to autoclave, and the other end is separable
It is tightly connected the solid sample storage device.
This programme is first packed into solid sample in test in solid sample storage device, then controls blow down valve and uses gas
Source reduces the pressure in autoclave using vacuum pump suction later, finally opens directly to purging air-discharging is carried out in autoclave
Sample feeding-passage is added in autoclave under the drive of air pressure, and whole process realizes the operation of sample introduction after first air-discharging, keeps away
Loss of the solid sample in air-discharging operation is exempted from, to improve the accuracy of test result.Meanwhile it is negative in autoclave
Pressure ring border can further decrease the content of air plankton in kettle, improve the purity of carbon dioxide in kettle, further improve survey
The accuracy of test result.
Further, the opening and closing valve of the purging gas circuit and the opening and closing valve of the sample inlet are same opening and closing valve, the survey
Amount system further includes three-way magnetic valve, and the air inlet of the three-way magnetic valve is separately connected the sample inlet or scavenging pipeline,
The gas outlet of the three-way magnetic valve connects the opening and closing valve, for sample inlet or scavenging pipeline to be connected.
Specifically, the three-way magnetic valve be equipped with the first air inlet, the second air inlet and air outlet, for be connected first into
The access between access or the second air inlet and gas outlet between port and gas outlet；The gas source is separately connected the gas circuit
Second air inlet of one end of valve and the three-way magnetic valve；The solid sample storage device removable seal is connected to described
Between the other end of gas circuit valve and the first air inlet of the three-way magnetic valve；Described opening and closing valve one end and the three-way magnetic valve
Gas outlet connection, the other end is connected to the autoclave body.
This programme gives a kind of more preferably piping connection scheme, keeps air circuit connection more succinct efficient, in the system of reduction
The working efficiency of measuring system is improved while cost.
Further, which further includes light source, photodetector, signal amplification circuit, processing unit, the height
Pressing kettle includes two watch windows, and the photodetector is connect by the signal amplification circuit with the processing unit, is used
In the detection light across two watch windows of autoclave for receiving the light source sending, the processing unit is used for according to detection light
Strength Changes judge whether solid sample is precipitated.
This programme judges whether solid sample is precipitated according to the detection light light intensity variation by supercritical carbon dioxide,
Instead of the conventional mode with human eye direct viewing, the reliability and authenticity of cloud-point pressure judgement are improved.
Further, which further includes piston and motor, and the piston slides close along autoclave autoclave body central axes
Envelope is set in autoclave autoclave body, and for changing the volume of autoclave, the motor is for driving the piston up and down.
Autoclave in this programme can control moving up and down for piston by motor, pass through the variation of autoclave volume
Kettle internal pressure is powerful small changing, and avoids the operation using exhaust valve pressure release, and then avoid the loss of solid sample.
Further, solid sample storage device surface is set there are two port, and two ports are deposited by solid sample
Run-though space in storage device penetrates through connection, and the run-though space in the solid sample storage device is for placing solid sample.
This programme gives a kind of preferably solid sample memory device structure.
Further, two ports of the solid sample storage device respectively with the other end of the gas circuit valve, described
First air inlet thread seal of three-way magnetic valve connects.
This programme gives a kind of preferably solid sample storage device connection type.
Further, the photodetector is photodiode, and the processing unit is single-chip microcontroller, the signal amplification
Circuit includes operational amplifier, first resistor, second resistance, first capacitor, the second capacitor, third capacitor；
The plus earth of the photodiode, the cathode of the photodiode connect the operational amplifier reverse input end,
The operational amplifier positive input ground connection, the operational amplifier output terminal pass sequentially through first resistor, point A and third electricity
Hold ground connection, the first capacitor is connected between the reverse input end and output end of the operational amplifier, the second resistance with
The second capacitor parallel connection is followed by between the operational amplifier reverse input end and point A, and the point A and the single-chip microcontroller are believed
The connection of number input pin.
This programme gives a kind of circuit connection scheme that turbidity is detected using photodiode.
The invention has the benefit that
The present invention purges gas circuit and all the way sample inlet by special configuration all the way, is formed in autoclave using vacuum pump negative
Pressure ring border, cooperation gas source enters the solid sample in solid sample storage device in autoclave, so that the solution of the present invention
The operation that can be realized sample introduction after first air-discharging finally avoids sample in test and is lost because of air-discharging operation, improves most
The accuracy of whole measurement result, meanwhile, during manufacturing subnormal ambient in autoclave, further decrease remaining in autoclave
The content of air improves the degree of purity of carbon dioxide in autoclave, further improves the accuracy of final measurement, solution
Having determined in the prior art, the volatile sample easily spread is easy to be discharged with the flowing of air-flow from exhaust valve in air-discharging operation
And cause the technical problem of final measurement inaccuracy.
Detailed description of the invention
Fig. 1 is the measurement method embodiment flow chart of solid sample solubility in supercritical carbon dioxide of the present invention；
Fig. 2 is the structural schematic diagram of the measuring system embodiment 1 of solid sample solubility in supercritical carbon dioxide of the present invention:
Fig. 3 is the structural schematic diagram of the measuring system embodiment 2 of solid sample solubility in supercritical carbon dioxide of the present invention:
Fig. 4 is the structural schematic diagram of the measuring system embodiment 3 of solid sample solubility in supercritical carbon dioxide of the present invention:
Fig. 5 is the structural schematic diagram of the measuring system embodiment 4 of solid sample solubility in supercritical carbon dioxide of the present invention:
Fig. 6 is the photoelectric sensor electricity of the measuring system embodiment 4 of solid sample solubility in supercritical carbon dioxide of the present invention
Road connection schematic diagram.
Specific embodiment
Embodiment of the method 1
It is as shown in Figure 1 the measurement method embodiment flow chart of solid sample solubility in supercritical carbon dioxide of the present invention, tool
Body the following steps are included:
Step 1: injecting carbon dioxide gas into autoclave, air is discharged from exhaust outlet；
Step 2: manufacture subnormal ambient is evacuated to autoclave；
Step 3: opening sample inlet, the quantitative solid sample in sample inlet is blown into autoclave using gas source；
Step 4: closing sample inlet, carbon dioxide is injected into autoclave；
Step 5: first adjusting the temperature in autoclave to setting constant temperature, then adjust the pressure in autoclave, be in carbon dioxide
Supercriticality, stirring are dissolved in all solid samples in carbon dioxide；
Step 6: keeping the temperature in autoclave in setting constant temperature, and reduce the pressure in autoclave, make solid sample from dioxy
Change and be precipitated in carbon, record pressure and temperature in autoclave at this time, calculate the solid sample the pressure and at a temperature of it is overcritical
Solubility in carbon dioxide.
Wherein, according to the change in signal strength for the detection light for passing through carbon dioxide in autoclave, whether judge solid sample
It is precipitated from supercritical carbon dioxide.
Subnormal ambient in autoclave refers to the air pressure that the air pressure in autoclave is less than outside autoclave.
Present invention measurement solid sample is illustrated in supercritical carbon dioxide below with reference to following system embodiment
The detailed process of solubility.
System embodiment 1
It is illustrated in figure 2 the measuring system embodiment of solid sample solubility in a kind of supercritical carbon dioxide of the present invention, specifically
Including carbon dioxide steel cylinder 1, cooling system 2, plunger pump 3, intake valve 4, autoclave 5, preceding watch window 5-1, rear watch window
5-2, magnetic stirring apparatus 5-3, exhaust valve 6, solenoid valve 7, sample cell 8, blow down valve 9-1, sampling valve 10 and vacuum pump 11.
Intake valve 4, exhaust valve 6, blow down valve 9-1,10 one end of sampling valve are connected to inside autoclave autoclave body, and being all made of can
Control the solenoid valve of switch；Sample cell 8 is hollow tube, has sealing screw thread at nozzle；Preceding watch window 5-1 and rear watch window 5-2
It is symmetricly set on the autoclave body outer wall of 5 autoclave body central axes two sides of autoclave, material is sapphire, and 5 inner wall of kettle of autoclave is also set
It is equipped with temperature sensor, pressure transducer and heating sheet, be respectively used to detection autoclave body internal temperature, pressure and adjusts temperature in kettle
Degree.
Carbon dioxide steel cylinder 1 is separately connected 2 one end of cooling system, 7 one end of solenoid valve and the one end blow down valve 9-1, cooling system
2 other ends of uniting are connect by plunger pump with intake valve 4, and 7 other end of solenoid valve is connect by sample cell 8 with sampling valve 10, are vented
6 outlet side of valve is connect with 11 inlet end of vacuum pump.Wherein, sample cell 8 is a hollow tube, internal diameter and solenoid valve 7 and purging
The valve port internal diameter of valve 9-1 is identical, and two nozzles of sample cell 8 are connect with solenoid valve 7, blow down valve 9-1 thread seal respectively, in pipe
To place the solid sample powder for weighing up weight.Cooling system specifically used refrigeration compressor cools down the titanium dioxide flowed through
Carbon.
Specifically, the present embodiment includes that three carbon dioxide enter channel, it is respectively as follows:
1, the carbon dioxide injection main channel being made of 1-cooling system of carbon dioxide steel cylinder, 2-plunger pump-intake valve 4 is used
To pour into solid carbon dioxide；
2, the purging air-discharging channel being made of 1-blow down valve of carbon dioxide steel cylinder 9-1, to the air in venting autoclave 5；
3, the sample intake passage being made of 8-sampling valve of carbon dioxide steel cylinder 1-solenoid valve, 7-sample cell 10, in vacuum pump
With the help of, solid sample is added into autoclave 5.
Below by taking aminosalicylic acid (solid) as an example, illustrate the workflow of the present embodiment:
Firstly, sample cell 8 is removed, inserts the 0.005g aminosalicylic acid weighed up and reuse sealing nut and solenoid valve 7 and blow
It sweeps in valve 9-1 connection；
Then, it opens and sweeps air-discharging channel, carbon dioxide is blown into autoclave 5 and from exhaust valve 6 by carbon dioxide steel cylinder 1
Blowout, squeezes out air therein, in general, when the carbon dioxide volume of addition reaches autoclave volume 2 times or more, that is, thinks
Air has been drained in autoclave；
Later, intake valve 4 and sampling valve 10 are closed, exhaust valve 6 and vacuum pump 11 is opened, low-pressure state will be pumped into autoclave 5
Exhaust valve 6 is closed afterwards, sample intake passage is then turned on, is all blown into the solid sample in sample cell 8 in autoclave with draught head, is closed
Close sampling valve 10；The low-pressure state is for the atmospheric pressure outside autoclave, and optimal situation is to be evacuated to vacuum；
Then, open carbon dioxide injection main channel, using cooling system 2 by the carbon dioxide flowed through be cooled to 5 degrees Celsius with
Under, it is allowed to be converted into solid-state, solid carbon dioxide is pumped into autoclave using plunger pump, the amount for controlling carbon dioxide injection is come
Pressure in kettle is adjusted to adjust temperature in the kettle by the heating sheet on the outside of autoclave body to 20MPa to 45 degrees Celsius, turn carbon dioxide
It is changed to supercriticality；
Finally, accelerate dissolution of the solid sample in carbon dioxide using magnetic stirring apparatus 5-3, later by exhaust valve 6 to
Outer exhaust reduces pressure in kettle, when observing that solute precipitation causes carbon dioxide to become cloudy from preceding watch window 5-1, closes
Exhaust valve 6, cloud-point pressure is 18MPa to record at this time, temperature in the kettle is 45 degrees Celsius, knows current carbon dioxide by reading up the literature
Density is 789.24g/L, and in conjunction with the volume 100mL of autoclave, this kind of solid sample is calculated in current cloud-point pressure and temperature
The solubility spent in lower supercritical carbon dioxide is 0.0000671(mass), that is, indicate every gram of dioxy under Current Temperatures and pressure
0.0000671 gram of aminosalicylic acid can be dissolved by changing carbon, and circular is the prior art, is not repeated herein.
System embodiment 2
It is illustrated in figure 3 the measuring system embodiment of solid sample solubility in a kind of supercritical carbon dioxide of the present invention, the reality
The difference for applying example and system implementation 1 is that the present embodiment has used three-way magnetic valve 9-2 as blow down valve, three-way magnetic valve 9-2
There are two air inlet and a gas outlet, for be connected access between the first air inlet and gas outlet or the second air inlet with out
Access between port.
Carbon dioxide steel cylinder 1 is separately connected the second air inlet of 2 one end of cooling system, 7 one end of solenoid valve and three-way magnetic valve 9-2
Mouthful, 2 other end of cooling system is connect by plunger pump with intake valve 4, and 7 other end of solenoid valve passes through sample cell 8 and threeway electromagnetism
The connection of the first air inlet of valve 9-2, the gas outlet of three-way magnetic valve 9-2 are connect with sampling valve 10,6 outlet side of exhaust valve and vacuum pump
The connection of 11 inlet ends.Wherein, sample cell 8 is in the valve port of a hollow tube, internal diameter and solenoid valve 7 and three-way magnetic valve 9-2
Diameter is identical, and two nozzles of sample cell 8 are close with the first air inlet screw thread of the other end of solenoid valve 7, three-way magnetic valve 9-2 respectively
Envelope connection, pipe are interior to place the solid sample powder for weighing up weight.The specifically used refrigeration compressor of cooling system flows to cool down
The carbon dioxide crossed.
Specifically, the present embodiment includes that three carbon dioxide enter channel, it is respectively as follows:
1, the carbon dioxide injection main channel being made of 1-cooling system of carbon dioxide steel cylinder, 2-plunger pump-intake valve 4 is used
To pour into solid carbon dioxide；
2, the purging air-discharging channel being made of 1-three-way magnetic valve of carbon dioxide steel cylinder 9-2-sampling valve 10, to venting height
Press the air in kettle 5；
3, the sample introduction being made of carbon dioxide steel cylinder 1-solenoid valve, 7-sample cell, 8-three-way magnetic valve 9-2-sampling valve 10 is logical
Road, solid sample is added into autoclave 5 with the help of vacuum pump.
Below by taking aminosalicylic acid (solid) as an example, illustrate the workflow of the present embodiment:
Firstly, sample cell 8 is removed, inserts the 0.005g aminosalicylic acid weighed up and reuse sealing nut and solenoid valve 7 and blow
It sweeps in valve 9-1 connection；
Then, it opens and sweeps air-discharging channel, carbon dioxide is blown into autoclave 5 and from exhaust valve 6 by carbon dioxide steel cylinder 1
Blowout, squeezes out air therein, in general, when the carbon dioxide volume of addition reaches autoclave volume 2 times or more, that is, thinks
Air has been drained in autoclave；
Later, intake valve 4 and sampling valve 10 are closed, exhaust valve 6 and vacuum pump 11 is opened, low-pressure state will be pumped into autoclave 5
Exhaust valve 6 is closed afterwards, sample intake passage is then turned on, is all blown into the solid sample in sample cell 8 in autoclave with draught head, is closed
Close sampling valve 10；The low-pressure state is for the atmospheric pressure outside autoclave, and optimal situation is to be evacuated to vacuum；
Then, open carbon dioxide injection main channel, using cooling system 2 by the carbon dioxide flowed through be cooled to 5 degrees Celsius with
Under, it is allowed to be converted into solid-state, solid carbon dioxide is pumped into autoclave using plunger pump, the amount for controlling carbon dioxide injection is come
Pressure in kettle is adjusted to adjust temperature in the kettle by the heating sheet on the outside of autoclave body to 20MPa to 45 degrees Celsius, turn carbon dioxide
It is changed to supercriticality；
Finally, accelerate dissolution of the solid sample in carbon dioxide using magnetic stirring apparatus 5-3, later by exhaust valve 6 to
Outer exhaust reduces pressure in kettle, when observing that solute precipitation causes carbon dioxide to become cloudy from preceding watch window 5-1, closes
Exhaust valve 6, cloud-point pressure is 18MPa to record at this time, temperature in the kettle is 45 degrees Celsius, knows current carbon dioxide by reading up the literature
Density is 789.24g/L, and in conjunction with the volume 100mL of autoclave, this kind of solid sample is calculated in current cloud-point pressure and temperature
The solubility spent in lower supercritical carbon dioxide is 0.0000671(mass), that is, indicate every gram of dioxy under Current Temperatures and pressure
0.0000671 gram of aminosalicylic acid can be dissolved by changing carbon, and circular is the prior art, is not repeated herein.
System embodiment 3
It is illustrated in figure 4 the measuring system embodiment of solid sample solubility in a kind of supercritical carbon dioxide of the present invention, the reality
That applies example and system embodiment 2 is different only in that the present embodiment further includes autoclave piston 5-4, piston rod 5-5, motor 5-6
With crank block slider structure 5-7, wherein autoclave piston 5-4 is slidably and sealingly connected with autoclave inner-wall, the one end piston rod 5-5 with
The 5-4 connection of autoclave piston, one end are connect with by crank block slider structure 5-7 with motor 5-6, and the rotation of motor 5-6 is turned round
Square is converted into the pulling force for driving piston rod 5-5 to move up and down, certain crank block slider structure 5-7 can also for eccentric wheel structure or its
It can convert the rotation displacement of motor to the structure of piston rod upper and lower displacement.
The present embodiment directly can control autoclave piston 5-4 by motor 5-6 and move up and down, to change in autoclave
Pressure avoids the loss of sample so that not needing to carry out decompression of losing heart by exhaust valve 6 again in test.
System embodiment 4
It is illustrated in figure 5 the measuring system embodiment of solid sample solubility in a kind of supercritical carbon dioxide of the present invention, the reality
That applies example and system embodiment 3 is different only in that the present embodiment further includes LED light source 12, photodiode 13, signal amplification electricity
Road, MCU and host computer, LED light source 12 are located at the side preceding watch window 5-1, and photodiode 13 is located at rear watch window 5-2 mono-
Side.Wherein, LED light source 13 is sentenced by signal amplification circuit and MCU, strong and weak variation of the MCU for based on the received electrical signal
Whether disconnected solid sample is precipitated.MCU in addition also with each solenoid valve, three-way magnetic valve, motor, temperature pressure transducer, heating
Piece, cooling system connection, for controlling their working condition, while MCU also pass through RS-485 communication module and host computer into
Row communication receives the control command of host computer, and sends result data to host computer.Specific connection belongs to known in this field
Common sense is not repeated herein.
It is illustrated in figure 6 the present embodiment photoelectric sensor circuit connection schematic diagram, wherein A1 is operational amplifier, and D1 is light
Electric diode, R1, R2 are resistance, and C1, C2, C3 are electrolytic capacitor, and MCU is the S32K144 chip of NXP, the photodiode
Plus earth, the cathode of the photodiode connect the operational amplifier reverse input end, which connects
Ground, the operational amplifier output terminal pass sequentially through first resistor, point A and third capacity earth, which is connected to the operation
Between the reverse input end and output end of amplifier, the second resistance is in parallel with second capacitor be followed by it is anti-in the operational amplifier
To between input terminal and point A, which connect with the single-chip microcomputer signal input pin.Specific component parameter is needed according to letter
Number enlargement ratio selects, and specific to select rule be general knowledge known in this field, is not repeated herein.
In above-described embodiment, specifically used solenoid valve as valve positioner, certainly can also using mechanical valve come with
Identical function is instead of using this kind deformation should be fallen under the scope of the present invention.
It in above-described embodiment, has used LED light source as probe source, other lasers etc. can also be used certainly
As light source, this kind deformation should be fallen under the scope of the present invention.
It in above-described embodiment, has used photodiode as photodetector, other such as light can also be used certainly
Electric probe, phototriode etc. are used as photoelectric sensor, this kind deformation should be fallen under the scope of the present invention.
In above-described embodiment, give a kind of specific amplifying circuit, specifically can according to the difference of photodetector,
Using existing different amplifying circuit, this kind deformation should be fallen under the scope of the present invention.
Finally it should be noted that: the above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof；To the greatest extent
The present invention is described in detail with reference to preferred embodiments for pipe, it should be understood by those ordinary skilled in the art that: still
It can modify to a specific embodiment of the invention or some technical features can be equivalently replaced；Without departing from this hair
The spirit of bright technical solution should all cover within the scope of the technical scheme claimed by the invention.
Claims (10)
1. the measurement method of solid sample solubility in a kind of supercritical carbon dioxide, which comprises the following steps:
Step 1: injecting carbon dioxide gas into autoclave, the air in autoclave is discharged；
Step 2: autoclave being evacuated, makes to form negative pressure in autoclave；
Step 3: quantitative solid sample being sucked into autoclave using the negative pressure in autoclave；
Step 4: carbon dioxide is injected into autoclave；
Step 5: pressure and/or temperature in adjustment autoclave keep carbon dioxide in a supercritical state, make all solid samples
It is dissolved in carbon dioxide；
Step 6: pressure and/or temperature in adjustment autoclave are precipitated solid sample from carbon dioxide, record high pressure at this time
Pressure and temperature in kettle, calculate the solid sample the pressure and at a temperature of supercritical carbon dioxide in solubility.
2. the measurement method of solid sample solubility in supercritical carbon dioxide according to claim 1, which is characterized in that
In steps of 5, the temperature in autoclave is first adjusted to setting constant temperature, then adjusts the pressure in autoclave, is in carbon dioxide
Supercriticality is dissolved in all solid samples in carbon dioxide.
3. the measurement method of solid sample solubility in supercritical carbon dioxide according to claim 2, which is characterized in that
In step 6, it keeps the temperature in autoclave in setting constant temperature, and reduces the pressure in autoclave, make solid sample from dioxy
Change and is precipitated in carbon.
4. the measurement method of solid sample solubility in supercritical carbon dioxide according to claim 1 to 3, special
Sign is, in step 6, according to the change in signal strength for the detection light for passing through carbon dioxide in autoclave, judges solid sample
Whether it is precipitated from supercritical carbon dioxide.
5. the measuring system of solid sample solubility in a kind of supercritical carbon dioxide, including gas source, cooling system and autoclave,
The autoclave is equipped with intake valve and exhaust valve, which is characterized in that
The measuring system further include purging gas circuit, sample inlet, solid sample storage device, temperature-adjusting device, plunger pump and
Vacuum pump, the gas source are connected to the intake valve of autoclave by cooling system, plunger pump, and the temperature-adjusting device is for adjusting
The temperature in autoclave is saved, the purging gas circuit, the sample inlet are equipped with opening and closing valve, and the gas source passes through the purge gass
Road, the opening and closing valve for purging gas circuit are connected to autoclave, and described sample inlet one end passes through sample inlet and opens and closes valve connection high pressure
Inside kettle, the other end connects the gas source by gas circuit valve, and the vacuum pump connects the exhaust valve of the autoclave.
6. the measuring system of solid sample solubility in supercritical carbon dioxide according to claim 5, which is characterized in that
The opening and closing valve of the purging gas circuit and the opening and closing valve of the sample inlet are same opening and closing valve, which further includes three energizations
Magnet valve, the air inlet of the three-way magnetic valve are separately connected the sample inlet or scavenging pipeline, and the three-way magnetic valve goes out
Port connects the opening and closing valve, for sample inlet or scavenging pipeline to be connected.
7. the measuring system of solid sample solubility in supercritical carbon dioxide according to claim 6, which is characterized in that
The measuring system further includes light source, photodetector, signal amplification circuit, processing unit, and the autoclave includes two observations
Window, the photodetector are connect by the signal amplification circuit with the processing unit, for receiving the light source hair
The detection light across two watch windows of autoclave out, the processing unit are used to be judged according to the Strength Changes of detection light solid
Whether aspect product are precipitated.
8. special according to the measuring system of solid sample solubility in any supercritical carbon dioxide of claim 5-7
Sign is that the measuring system further includes piston and motor, and the piston is slidingly sealed along autoclave autoclave body central axes and is set to height
It presses in kettle autoclave body, for changing the volume of autoclave, the motor is for driving the piston up and down.
9. the measuring system of solid sample solubility in supercritical carbon dioxide according to claim 8, which is characterized in that
Solid sample storage device surface is set there are two port, and two ports pass through the run-though space in solid sample storage device
Perforation connects, and the run-though space in the solid sample storage device is for placing solid sample.
10. the measuring system of solid sample solubility, feature exist in supercritical carbon dioxide according to claim 7
In the photodetector is photodiode, and the processing unit is single-chip microcontroller, and the signal amplification circuit includes that operation is put
Big device, first resistor, second resistance, first capacitor, the second capacitor, third capacitor；
The plus earth of the photodiode, the cathode of the photodiode connect the operational amplifier reverse input end,
The operational amplifier positive input ground connection, the operational amplifier output terminal pass sequentially through first resistor, point A and third electricity
Hold ground connection, the first capacitor is connected between the reverse input end and output end of the operational amplifier, the second resistance with
The second capacitor parallel connection is followed by between the operational amplifier reverse input end and point A, and the point A and the single-chip microcontroller are believed
The connection of number input pin.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113522214A (en) * | 2021-08-11 | 2021-10-22 | 首都医科大学宣武医院 | Reaction device and method |
| CN114646603A (en) * | 2022-03-01 | 2022-06-21 | 湖北西塞山发电有限公司 | Method for measuring concentration of carbon dioxide in flue gas of thermal power generating unit |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5908995A (en) * | 1996-06-28 | 1999-06-01 | Institut Francais Du Petrole | System for measuring the solubility of solid compounds in supercritical fluids |
| JP2003270126A (en) * | 2002-03-19 | 2003-09-25 | Jasco Corp | Instrument for measuring solubility |
| US20050201904A1 (en) * | 2003-12-01 | 2005-09-15 | Drugrisk Solutions | Specimen collection and processing device |
| CN103212340A (en) * | 2013-04-07 | 2013-07-24 | 中国计量科学研究院 | Supercritical fluid extracting, spraying and granulating system and method |
| CN105259083A (en) * | 2014-07-16 | 2016-01-20 | 上海征鸿传感器测控技术有限公司 | Dry laser particle size analyzer cyclone feeding apparatus |
| CN106984370A (en) * | 2017-05-08 | 2017-07-28 | 北京旌准医疗科技有限公司 | A kind of automatic sample handling system based on micro-fluidic chip |
| CN108548887A (en) * | 2018-06-22 | 2018-09-18 | 上海辽誉机电科技有限公司 | A kind of gas chromatograph sampling system and device |
| CN209784116U (en) * | 2019-04-24 | 2019-12-13 | 中国烟草总公司郑州烟草研究院 | system for measuring solubility of solid sample in supercritical carbon dioxide |
-
2019
- 2019-04-24 CN CN201910331675.7A patent/CN109932276A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5908995A (en) * | 1996-06-28 | 1999-06-01 | Institut Francais Du Petrole | System for measuring the solubility of solid compounds in supercritical fluids |
| JP2003270126A (en) * | 2002-03-19 | 2003-09-25 | Jasco Corp | Instrument for measuring solubility |
| US20050201904A1 (en) * | 2003-12-01 | 2005-09-15 | Drugrisk Solutions | Specimen collection and processing device |
| CN103212340A (en) * | 2013-04-07 | 2013-07-24 | 中国计量科学研究院 | Supercritical fluid extracting, spraying and granulating system and method |
| CN105259083A (en) * | 2014-07-16 | 2016-01-20 | 上海征鸿传感器测控技术有限公司 | Dry laser particle size analyzer cyclone feeding apparatus |
| CN106984370A (en) * | 2017-05-08 | 2017-07-28 | 北京旌准医疗科技有限公司 | A kind of automatic sample handling system based on micro-fluidic chip |
| CN108548887A (en) * | 2018-06-22 | 2018-09-18 | 上海辽誉机电科技有限公司 | A kind of gas chromatograph sampling system and device |
| CN209784116U (en) * | 2019-04-24 | 2019-12-13 | 中国烟草总公司郑州烟草研究院 | system for measuring solubility of solid sample in supercritical carbon dioxide |
Non-Patent Citations (2)
| Title |
|---|
| 李入林;王琳;陈开勋;: "超临界二氧化碳与叔丁醇二元体系气液溶解度模型研究", 化学通报, no. 10, 18 October 2009 (2009-10-18) * |
| 闻利群;张同来;秦清风;: "TNT在超临界二氧化碳中的溶解特性", 含能材料, no. 03, 15 June 2010 (2010-06-15) * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113522214A (en) * | 2021-08-11 | 2021-10-22 | 首都医科大学宣武医院 | Reaction device and method |
| CN114646603A (en) * | 2022-03-01 | 2022-06-21 | 湖北西塞山发电有限公司 | Method for measuring concentration of carbon dioxide in flue gas of thermal power generating unit |
| CN114646603B (en) * | 2022-03-01 | 2023-08-11 | 湖北西塞山发电有限公司 | Method for measuring concentration of carbon dioxide in flue gas of thermal power generating unit |
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