CN217033175U - Continuous measurement system for organic matter solubility in supercritical carbon dioxide - Google Patents
Continuous measurement system for organic matter solubility in supercritical carbon dioxide Download PDFInfo
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- CN217033175U CN217033175U CN202220243506.5U CN202220243506U CN217033175U CN 217033175 U CN217033175 U CN 217033175U CN 202220243506 U CN202220243506 U CN 202220243506U CN 217033175 U CN217033175 U CN 217033175U
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Abstract
The utility model provides a continuous measuring system for the solubility of organic matters in supercritical carbon dioxide, which comprises a sampling system and an analysis system, wherein the sampling system comprises a high-pressure balance kettle, a sampling bottle and a first pipeline, the sampling bottle is connected with or separated from the high-pressure balance kettle through the first pipeline, the high-pressure balance kettle provides the temperature, the pressure and the place required for dissolving the organic matters in supercritical carbon dioxide fluid, and the supercritical carbon dioxide fluid in which saturated organic matters are dissolved in the high-pressure balance kettle enters the sampling bottle through the first pipeline at the specified temperature and the specified pressure; the first pipeline is provided with a first regulating valve, and the first regulating valve closes and seals the inlet end of the sampling bottle after the sampling of the sampling bottle is finished; the analysis system comprises a sampling bottle and an absorption bottle which are separated from the high-pressure balance kettle after sampling is finished. The utility model can realize the continuous measurement of the solubility of the organic matters in the supercritical carbon dioxide under the specified pressure and temperature, and has high measurement efficiency and short measurement procedure.
Description
Technical Field
The utility model relates to the technical field of supercritical fluid extraction, in particular to a continuous measuring system for the solubility of organic matters in supercritical carbon dioxide.
Background
A supercritical fluid refers to a fluid having a temperature and pressure above the critical point. The supercritical fluid is in a gas-liquid nondividing state, has no obvious gas-liquid interface, has the properties of gas and liquid, has the density similar to that of the liquid, the viscosity similar to that of the gas and the diffusion coefficient between the liquid and the gas. This allows the supercritical fluid to have good flow, heat transfer, mass transfer and dissolution properties.
Because the carbon dioxide has the characteristics of stability, no toxicity, flame retardance, low cost, low critical temperature and critical pressure and the like, the carbon dioxide is widely applied to various industries, such as carbon dioxide oil displacement, carbon dioxide extraction and the like. The supercritical carbon dioxide fluid extraction technology is a green, environment-friendly, efficient and clean separation technology, and the principle of the technology is to utilize the influence of pressure and temperature on the fluid dissolving capacity. Under supercritical conditions, carbon dioxide selectively dissolves different components. Then converting the supercritical fluid into common gas by a series of methods such as decompression, temperature rise and the like, and sequentially separating extracted substances, thereby achieving the purpose of separation and purification. Therefore, measuring the solubility of a substance in supercritical carbon dioxide is of great significance for practical production.
The existing method for measuring the solubility of supercritical carbon dioxide is to put solute components with known mass into a high-pressure balance kettle with a transparent visual window, and to introduce supercritical carbon dioxide fluid into the kettle to dissolve the solute components. During the measurement, the temperature and pressure in the kettle are changed to make the phase system have cloud point, i.e. the solubility at the temperature and pressure. However, the method cannot determine the solubility of the organic matters in the supercritical carbon dioxide under the specified pressure and temperature, has long dissolution equilibrium time, is difficult to capture the cloud point moment of the system, and has the defects that part of solutes flow out of an exhaust valve along with the flow of air flow in the air exhaust process, so that the calculated supercritical carbon dioxide solubility result is large, and the measurement result is distorted. In the prior art, in the sampling step, the high-pressure balance kettle is usually opened to sample, and air is introduced into the high-pressure balance kettle every time of opening, so that pipeline purging is required once after the high-pressure balance kettle is opened every time to sample, errors caused by introduced air are reduced, the measurement efficiency is reduced, and the measurement process is prolonged.
SUMMERY OF THE UTILITY MODEL
In order to solve the problems, the utility model provides a continuous measurement system for the solubility of organic matters in supercritical carbon dioxide, which can be used for sampling at any time by detachably connecting a sampling bottle and a high-pressure balance kettle without the limitation of temperature and pressure in the high-pressure balance kettle, separating the high-pressure balance kettle from the sampling bottle after sampling is finished, connecting the separated sampling bottle with an absorption bottle, and conveniently and quickly calculating the solubility of the organic matters according to the quality of carbon dioxide or organic matter samples absorbed by the absorption bottle, thereby solving the technical problems that the existing measurement system cannot realize the measurement of the solubility of the organic matters in the supercritical carbon dioxide under the specified pressure and temperature, has low measurement efficiency and more measurement procedures.
The utility model provides a continuous measuring system for the solubility of organic matters in supercritical carbon dioxide, which comprises a sampling system and an analysis system, wherein the sampling system comprises a high-pressure balance kettle, a sampling bottle and a first pipeline for connecting an outlet of the high-pressure balance kettle with an inlet of the sampling bottle, the sampling bottle is connected with or separated from the high-pressure balance kettle through the first pipeline, the high-pressure balance kettle provides the temperature, the pressure and the place required for dissolving the organic matters in the supercritical carbon dioxide fluid, and the high-pressure balance kettle is internally provided with a temperature sensor, a pressure sensor and a temperature sensorThe supercritical carbon dioxide fluid dissolved with saturated organic matters enters a sampling bottle through a first pipeline at specified temperature and pressure; the first pipeline is provided with a first regulating valve, and the first regulating valve closes the inlet end of the sealed sampling bottle after the sampling of the sampling bottle is finished; the analysis system comprises a sampling bottle separated from the high-pressure balance kettle after sampling and an absorption bottle connected with the outlet of the sampling bottle, wherein the absorption bottle is an organic matter absorption bottle or CO2And (4) an absorption bottle.
According to the technical scheme, the excessive organic matter sample is added into the high-pressure balance kettle, so that the organic matter sample in the supercritical carbon dioxide can be ensured to be in a saturated state, and errors caused by cloud point capturing moments are avoided; because the organic matter sample in the high-pressure balance kettle is in an excessive state, the sampling under another specified pressure and temperature can be realized only by adjusting the pressure and the temperature in the high-pressure balance kettle, and the problem that the system pipeline contains impurity gas due to repeated injection of the organic matter is avoided.
The sampling bottle is detachably connected with the high-pressure balance kettle, so that sampling can be carried out at any time, continuous sampling and continuous measurement are realized, the high-pressure balance kettle does not need to be opened in the sampling process, air is prevented from entering the high-pressure balance kettle, purging of a pipeline is reduced, the sampling process is shortened, and the sampling efficiency is improved; and the phenomenon that part of solute flows out along with the flow of the air flow in the pipeline purging process is avoided, and the accuracy of the solubility calculation is improved; after the sampling is finished, the high-pressure balance kettle and the sampling bottle are separated, the separated sampling bottle is connected with the absorption bottle, and the solubility of the organic matters can be conveniently and quickly calculated according to the mass of carbon dioxide or organic matter samples absorbed by the absorption bottle.
The first regulating valve can control the flow of the supercritical carbon dioxide fluid dissolved with saturated organic matters into the sampling bottle, and can seal the inlet end of the sampling bottle after sampling is finished, so that impurities are prevented from entering the sampling bottle to bring about measurement errors, and the accuracy of a measurement result is further improved.
In an optional technical scheme of the utility model, the first pipeline comprises a first pipe section and a second pipe section, an inlet of the first pipe section is connected with an outlet of the high-pressure balance kettle, an outlet of the first pipe section is detachably connected with an inlet of the second pipe section, an outlet of the second pipe section is connected with the sampling bottle, after sampling of the sampling bottle is finished, the second pipe section is disconnected with the first pipe section, and an outlet of the first pipe section is connected with another sampling bottle.
According to the technical scheme, high pressure balance cauldron and sampling bottle are through dismantling the first pipeline section and the separable connection of second pipeline section of being connected, moreover, the steam generator is simple in structure, easily preparation, low cost, and can be convenient, realize being connected and separating of high pressure balance cauldron and sampling bottle in a flexible way, after once taking a sample, can realize the sample under another temperature and the pressure parameter through the export lug connection at first pipeline section another sampling bottle and the temperature and the pressure of adjusting in the high pressure balance cauldron, it is convenient, the continuous measurement of organic matter solubility in the swift supercritical carbon dioxide of realizing, and can avoid impurity to get into the sampling bottle through first pipeline section, the accuracy of measuring result is improved.
In the optional technical scheme of the utility model, a second pipeline is arranged between the outlet of the sampling bottle and the inlet of the absorption bottle, and a second regulating valve for regulating the outlet flow of the sampling bottle and a pressure reducing valve for reducing the inlet pressure of the absorption bottle are sequentially arranged on the second pipeline.
According to the technical scheme, the outlet flow of the sampling bottle is adjusted through the fifth adjusting valve, the inlet pressure is reduced through the pressure reducing valve, and the situation that the supercritical carbon dioxide fluid with dissolved organic matters is incompletely absorbed by the absorption bottle due to the fact that the supercritical carbon dioxide fluid quickly passes through the absorption bottle and the accuracy of a calculation result of the solubility is influenced can be avoided.
In an alternative embodiment of the utility model, in the analysis system, the inlet of the second tube section is connected to a protective gas supply, and the first control valve is opened when the protective gas supply supplies protective gas.
According to the technical scheme, the protective gas supply device is used for providing a gas source for the analysis system and ensuring that the organic matter sample or the carbon dioxide in the sampling bottle completely enters the absorption bottle.
In an optional technical scheme of the utility model, the sampling system further comprises a carbon dioxide supply device, a third regulating valve, a cooling device, a high-pressure pump, a preheating device and a fourth regulating valve which are sequentially connected through a third pipeline, wherein the carbon dioxide supply device provides carbon dioxide gas required by measurement, the cooling device is used for cooling the carbon dioxide gas at the outlet of the carbon dioxide supply device into liquid carbon dioxide, the high-pressure pump is used for conveying the liquid carbon dioxide to the preheating device, the preheating device heats the liquid carbon dioxide to a specified temperature, the third regulating valve is used for controlling the outlet flow of the carbon dioxide gas, and the fourth regulating valve is used for controlling the outlet flow of the carbon dioxide preheated to the specified temperature.
According to the technical scheme, carbon dioxide gas provided by the carbon dioxide supply device is cooled to be below the saturation temperature after being cooled by the cooling device to form liquid carbon dioxide, and after the liquid carbon dioxide is conveyed by the high-pressure pump and preheated by the preheating device, the pressure and the temperature of the liquid carbon dioxide are increased to be above the critical pressure and the critical temperature to reach a supercritical state. The gaseous carbon dioxide before entering the high-pressure balance kettle is pretreated to reach a supercritical state, so that the treatment of the carbon dioxide in the high-pressure balance kettle is simplified, the measurement efficiency is improved, and the flexibility of the system is improved.
In the optional technical scheme, the high-pressure balance kettle is provided with the first pressure sensor and the first temperature sensor, the sampling bottle is provided with the second pressure sensor and the second temperature sensor, the readings of the first pressure sensor and the second pressure sensor are the same and are the experiment specified pressure, and the readings of the first temperature sensor and the second temperature sensor are the same and are the experiment specified temperature.
According to the technical scheme, the temperature and the pressure of the balance kettle and the sampling bottle can be conveniently obtained, the temperature and the pressure in the balance kettle and the sampling bottle are ensured to be the same during sampling, the reduction of experimental errors is facilitated, and the measuring accuracy is improved.
In an optional technical scheme of the utility model, the sampling system further comprises a vacuum pump, an outlet of the vacuum pump is connected to the third pipeline and is positioned between the high-pressure pump and the preheating device, and a fifth regulating valve is arranged at an outlet of the vacuum pump.
According to the setting of this technical scheme vacuum pump, can detach the impure gas in the system's pipeline, improve the measuring accuracy.
Drawings
Fig. 1 is a schematic structural diagram of a sampling system in a system for continuously measuring the solubility of organic substances in supercritical carbon dioxide according to a first embodiment of the present invention.
Fig. 2 is a schematic structural view of an analysis system in the continuous measurement system for the solubility of organic substances in supercritical carbon dioxide according to the first embodiment of the present invention.
FIG. 3 is a schematic diagram showing the structure of a sampling system in the system for continuously measuring the solubility of organic substances in supercritical carbon dioxide according to the second embodiment of the present invention.
Fig. 4 is a schematic structural diagram of a sampling system in a system for continuously measuring the solubility of organic substances in supercritical carbon dioxide according to a third embodiment of the present invention.
Fig. 5 is a schematic structural view of an analysis system in a continuous measurement system for the solubility of organic substances in supercritical carbon dioxide according to a fourth embodiment of the present invention.
Reference numerals:
a sampling system 1; a thermostatic vessel 10; a high-pressure balance kettle 11; a first pressure sensor 111; a first temperature sensor 112; a piston 113; a sampling bottle 12; a second pressure sensor 121; a second temperature sensor 122; a carbon dioxide supply device 13; a cooling device 14; a high-pressure pump 15; a preheating device 16; a buffer device 17; an injector 18; a vacuum pump 19; an analysis system 2; an absorption bottle 21; a shielding gas supply device 22; a first pipe 31; a first pipe section 311; a second tube section 312; a ferrule type pipe joint 313; a second conduit 32; a third pipeline 33; a branch pipe 331; a relief valve 332; a first regulating valve 41; a second regulating valve 42; a third regulating valve 42; a fourth regulating valve 44; a fifth regulating valve 45; a pressure reducing valve 5; an exhaust valve 51; a third pressure sensor 131; a third temperature sensor 132; and a pressure bottle 23.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
[ first embodiment ] A
Referring to fig. 1 and 2, the present invention provides a continuous measurement system for the solubility of organic compounds in supercritical carbon dioxide, including a sampling system 1 and an analysis system 2, wherein the sampling system 1 includes a high-pressure equilibrium kettle 11, a sampling bottle 12 and a first pipeline 31 connecting an outlet of the high-pressure equilibrium kettle 11 and an inlet of the sampling bottle 12, the sampling bottle 12 is connected to or separated from the high-pressure equilibrium kettle 11 through the first pipeline 31, the high-pressure equilibrium kettle 11 provides the temperature, pressure and location required for dissolving the organic compounds in the supercritical carbon dioxide fluid, and the supercritical carbon dioxide fluid in the high-pressure equilibrium kettle 11, in which the saturated organic compounds are dissolved, enters the sampling bottle 12 through the first pipeline 31 at a specified temperature and pressure; the first pipeline 31 is provided with a first regulating valve 41, and the first regulating valve 41 closes and seals the inlet end of the sampling bottle 12 after the sampling of the sampling bottle 12 is finished; the analysis system 2 comprises a sampling bottle 12 separated from the high-pressure balance kettle 11 after sampling and an absorption bottle 21 connected with the outlet of the sampling bottle 12, wherein the absorption bottle 21 is an organic matter absorption bottle or CO2And (4) an absorption bottle.
In the embodiment of the utility model, the excessive organic matter sample is added into the high-pressure balance kettle 11, so that the organic matter sample in the supercritical carbon dioxide can be ensured to be in a saturated state, and the error caused by capturing the cloud point moment is avoided; because the organic matter sample in the high-pressure balance kettle 11 is in an excessive state, the sampling under another specified pressure and temperature can be realized only by adjusting the pressure and temperature in the high-pressure balance kettle 11, and the problem that the system pipeline contains impurity gas due to repeated injection of the organic matter is avoided.
The sampling bottle 12 is detachably connected with the high-pressure balance kettle 11, so that sampling can be carried out at any time, continuous sampling and continuous measurement are realized, the high-pressure balance kettle 11 does not need to be opened in the sampling process, air is prevented from entering the high-pressure balance kettle 11, purging of a pipeline is reduced, the sampling process is shortened, and the sampling efficiency is improved; and the phenomenon that part of solute flows out along with the flow of the air flow in the pipeline purging process is avoided, and the accuracy of the calculation of the solubility of the organic matter sample is improved; after sampling is finished, the high-pressure balance kettle 11 and the sampling bottle 12 are separated, the separated sampling bottle 12 is connected with the absorption bottle 21, and the solubility of the organic matters can be conveniently and quickly calculated according to the mass of the carbon dioxide or the organic matter sample absorbed by the absorption bottle 21.
The first regulating valve 41 can control the flow of the supercritical carbon dioxide fluid dissolved with saturated organic matters entering the sampling bottle 12, and can seal the inlet end of the sampling bottle 12 after sampling is finished, so that the phenomenon that impurities enter the sampling bottle 12 to bring measurement errors is avoided, and the accuracy of a measurement result is further improved.
In the preferred embodiment of the present invention, the first pipeline 31 comprises a first pipe section 311 and a second pipe section 312, the inlet of the first pipe section 311 is connected with the outlet of the high pressure equilibrium still 11, the outlet of the first pipe section 311 is detachably connected with the inlet of the second pipe section 312, the outlet of the second pipe section 312 is connected with the sampling bottle 12, after the sampling of the sampling bottle 12 is finished, the second pipe section 312 is disconnected from the first pipe section 311, and the outlet of the first pipe section 311 is connected with another sampling bottle 12.
In this way, high pressure balance cauldron 11 and sampling bottle 12 are through dismantling the first pipeline section 311 and the separable connection of second pipeline section 312 of connection, moreover, the steam generator is simple in structure, easily make, low cost, and can be convenient, realize the connection and the separation of high pressure balance cauldron 11 and sampling bottle 12 in a flexible way, after once taking a sample, through another sampling bottle 12 of export lug connection at first pipeline section 311, and adjust the temperature in the high pressure balance cauldron 11 and the sample that can realize under another temperature and the pressure parameter, conveniently, swiftly realize the continuous measurement of organic matter solubility in the supercritical carbon dioxide, and can avoid impurity to get into sampling bottle 12 through first pipeline section 311, improve the accuracy of measuring result. In the specific embodiment of the present invention, the first pipe section 311 and the second pipe section 312 are detachably connected through the ferrule type pipe joint 313, so that the connection and the separation of the first pipe section 311 and the second pipe section 312 can be conveniently achieved, the sealing performance of the connection node between the first pipe section 311 and the second pipe section 312 can be ensured, and impurities are prevented from entering a pipeline.
In the preferred embodiment of the present invention, the high pressure equilibrium still 11 is provided with the first pressure sensor 111 and the first temperature sensor 112, and the sampling bottle 12 is provided with the second pressure sensor 121 and the second temperature sensor 122. The first pressure sensor 111 and the first temperature sensor 112 are respectively used for measuring the pressure and the temperature in the high-pressure balance kettle 11, and the second pressure sensor 121 and the second temperature sensor 122 are respectively used for measuring the pressure and the temperature in the sampling bottle 12; the continuous measurement process ensures that the readings of the first pressure sensor 111 and the second pressure sensor 121 are the same and are experimentally specified pressure, and the readings of the first temperature sensor 112 and the second temperature sensor 122 are the same and are experimentally specified temperature.
In the preferred embodiment of the present invention, a second pipeline 32 is provided between the outlet of the sampling flask 12 and the inlet of the absorption flask 21, and a second regulating valve 42 for regulating the outlet flow rate of the sampling flask 12 and a pressure reducing valve 5 for reducing the inlet pressure of the absorption flask 21 are sequentially provided in the second pipeline 32.
In the embodiment of the utility model, the outlet flow of the sampling bottle 12 is adjusted by the second adjusting valve 42, the inlet pressure is reduced by the pressure reducing valve 5, and the high-pressure carbon dioxide and the organic matter sample in the sampling bottle 12 slowly enter the absorption bottle 21 to be absorbed, so that the problem that the absorption of the organic matter sample or the carbon dioxide by the absorption bottle 21 is incomplete due to the fact that the supercritical carbon dioxide fluid with the dissolved organic matter rapidly passes through the absorption bottle 21, and the accuracy of the calculation result of the solubility is influenced can be avoided.
In the preferred embodiment of the present invention, in the analysis system 2, the inlet of the second pipe section 312 is connected to the shielding gas supply device 22, and the first regulating valve 31 is opened when the shielding gas supply device 22 supplies the shielding gas. The shielding gas supply device 22 is used for supplying a gas source to the analysis system 2 to ensure that the organic sample or carbon dioxide in the sampling bottle 12 completely enters the absorption bottle 21, and the first regulating valve 41 is also used for regulating the flow of the shielding gas entering the analysis system 2. The shielding gas supply 22 is preferably a shielding gas reservoir, and the shielding gas is typically an inert gas that does not react with the carbon dioxide or organic sample and does not affect the measurement results.
In a preferred embodiment of the present invention, the sampling system 1 further includes a carbon dioxide supply device 13, a third regulating valve 43, a cooling device 14, a high-pressure pump 15, a preheating device 16, and a fourth regulating valve 44 connected in series via a third pipeline 33, wherein the carbon dioxide supply device 14 supplies carbon dioxide gas required for measurement, the cooling device 14 cools the carbon dioxide gas into liquid carbon dioxide, the high-pressure pump 15 is used to deliver the liquid carbon dioxide to the preheating device 16, the preheating device 16 preheats the received liquid carbon dioxide to a prescribed temperature, the third regulating valve 43 is used to control an outlet flow rate of the carbon dioxide gas, and the fourth regulating valve 44 is used to control an outlet flow rate of the carbon dioxide preheated to the prescribed temperature. In the embodiment of the present invention, the carbon dioxide supply device 13 is a carbon dioxide storage tank, the carbon dioxide gas provided by the carbon dioxide supply device 13 is cooled by the cooling device 14 and then cooled to a temperature below the saturation temperature to form liquid carbon dioxide, and after being delivered by the high pressure pump 15 and preheated by the preheating device 16, the pressure and temperature of the liquid carbon dioxide are raised to a critical pressure and a critical temperature, so as to reach a supercritical state. The gaseous carbon dioxide before entering the high-pressure balance kettle 11 is pretreated to reach a supercritical state, so that the treatment of the carbon dioxide in the high-pressure balance kettle 11 is simplified, the measurement efficiency is improved, and the flexibility of the system is improved.
In a preferred embodiment of the present invention, in order to reduce the heat dissipation between the carbon dioxide in the pipeline and the external environment and ensure that the temperature of the carbon dioxide entering the high-pressure equilibrium tank 11 is consistent with the temperature of the carbon dioxide at the outlet of the preheating device 16, the outside of the third pipeline 33 between the preheating device 16 and the high-pressure equilibrium tank 11 is covered with heat preservation cotton (not shown in the figure).
In a preferred embodiment of the present invention, in order to alleviate the pressure and flow fluctuation in the pipeline caused by the reciprocating and circulating motion of the high-pressure pump 15 and to make the data acquisition during the system operation more stable, a buffer device 17 is disposed on the third pipeline 33 between the high-pressure pump 15 and the preheating device 16, and specifically, the buffer device 17 is a pulsation damper.
In the preferred embodiment of the present invention, an injector 18 is further included, and the organic sample is injected into the autoclave 11 through the injector 18.
In the preferred embodiment of the present invention, the sampling system further comprises a vacuum pump 19 disposed on the third pipeline 33 and between the pulsation damper and the preheating device 16, and an outlet of the vacuum pump 19 is provided with a fifth regulating valve 45. The vacuum pump 19 is used for exhausting air introduced in the system pipeline, and measuring errors are reduced.
Furthermore, the third pipe 33 is further provided with a branch pipe 331 and a safety valve 332 provided on the branch pipe 331, the safety valve 332 plays a safety protection role in the system, and when the system pressure exceeds a predetermined value, the safety valve 332 is opened to discharge a part of the fluid in the system to the atmosphere so that the system pressure does not exceed an allowable value.
In the preferred embodiment of the present invention, the sampling system 1 further comprises a thermostatic vessel 10, and the high-pressure autoclave 11 and the sampling bottle 12 are disposed in the thermostatic vessel 10.
The above description specifically describes the continuous measurement system for the solubility of organic substances in supercritical carbon dioxide according to the first embodiment of the present invention, and the following description specifically describes the measurement method including the steps of:
s1: injecting a supercritical carbon dioxide fluid and an excessive organic matter sample into the high-pressure balance kettle 11, wherein at least part of the organic matter sample is dissolved in the supercritical carbon dioxide fluid;
s2: adjusting the temperature and the pressure in the high-pressure balance kettle 11 to reach a specified temperature and a specified pressure respectively, opening the first adjusting valve 41 after the dissolution time of the organic matter sample reaches the specified time, so that the supercritical carbon dioxide fluid dissolved with the saturated organic matter in the high-pressure balance kettle 11 enters the sampling bottle 12, wherein the temperature and the pressure in the sampling bottle 12 are the same as those in the high-pressure balance kettle 11, completing sampling and closing the first adjusting valve 41;
s3: separating the sample bottle 12 from the high pressure balance kettle 11, and connecting the outlet of the separated sample bottle 12 with the inlet of the absorption bottle 21 to make the organic matter sample and CO in the sample bottle 122Entering the absorption bottle 21; in particular, a separate sampling vial12 are connected to the analysis system 2 together with the second pipe section 312 and the first regulating valve 41;
s4: when the absorption bottle is a carbon dioxide absorption bottle, absorbing carbon dioxide from the sampling bottle, obtaining the total mass m of the carbon dioxide and the organic matter sample by weighing the mass of the sampling bottle before and after sampling, and calculating the mass m' of the carbon dioxide according to the formula (4) by measuring the change of the pH value of the absorption bottle before and after absorbing the carbon dioxide gas; calculating the solubility S of the organic matter sample at a specified temperature and a specified pressure according to the formula (1) and the formula (2);
or when the absorption bottle is an organic matter absorption bottle, weighing the mass of the sampling bottle before and after sampling to obtain the total mass m of the carbon dioxide and the organic matter sample, weighing the mass of the absorption bottle before and after absorbing the organic matter sample to obtain the mass m' of the organic matter, and calculating the solubility S of the organic matter sample at the specified temperature and the specified pressure according to the formula (1) and the formula (3);
m＝m0-m1 (1)
in the formula, m0Mass m of the sample bottle after sampling1The mass of the sample bottle before sampling; c0To absorb OH in the bottle before carbon dioxide is absorbed-Concentration of ion, C1V is the concentration of OH-ions in the absorption flask before and after carbon dioxide absorption, and V is the volume of the solution in the absorption flask. The carbon dioxide absorption bottle is filled with alkaline solution.
By the mode, the sampling bottle 12 is detachably connected with the high-pressure balance kettle 11, so that sampling can be carried out at any time, continuous sampling and continuous measurement are realized, the high-pressure balance kettle 11 does not need to be opened in the sampling process, air is prevented from entering the high-pressure balance kettle 11, pipeline purging is reduced, the sampling process is shortened, and the sampling efficiency is improved; the mass of the carbon dioxide or organic matter sample is calculated by adopting an absorption method, and the solubility of the organic matter is calculated by combining the mixed mass before and after sampling, so that the problems of measurement error and the like of a flowmeter under low flow are avoided, and the rapid, continuous and reliable measurement of the solubility of the organic matter in the supercritical carbon dioxide is realized.
Specifically, before step S1, a purge system piping step S0 is also included;
s01: adjusting the fourth adjusting valve 44, the first adjusting valve 41 and the second adjusting valve 42 to be in an open state, opening the third adjusting valve 43 and starting the high-pressure pump 15 to purge the system pipeline with carbon dioxide;
s02: closing the regulating valves (41,42,43 and 44) and opening a fifth regulating valve 45, starting the vacuum pump 19 to discharge and vacuumize gas in the system pipeline;
s03: closing the fifth regulating valve 45 and the vacuum pump 19; and repeating the steps S01 and S02 two to three times to ensure that the system pipeline does not contain impurity gases such as air and the like.
In step S1, the step of injecting the excess organic sample into the autoclave 11 includes: after the system purges the lines, the high pressure autoclave 11 is filled with an excess of organic sample via injector 18. Preferably, a magnetic stirrer (not shown) is disposed in the high pressure equilibrium tank 11 to accelerate the dissolution process of the organic substances.
The step of injecting carbon dioxide into the high-pressure balance tank 11 includes:
adjusting the fourth adjusting valve 44 to be in an open state, the cooling device 14 and the preheating device 16 to be in a working state, and the preheating device 16 heating the carbon dioxide to the experiment set temperature; the third regulating valve 43 is opened and the high-pressure pump 15 is started to inject carbon dioxide into the high-pressure equilibrium tank 11.
In step S2, after the reading of the first pressure sensor 11 is stable and is the experimental set pressure value and the reading of the first temperature sensor 12 is stable and is the experimental set temperature value, the third regulating valve 43 and the fourth regulating valve 44 are closed; after the dissolving time reaches the experimental set time, opening the first regulating valve 41 to make the supercritical carbon dioxide in which the saturated organic matters are dissolved in the high-pressure balance kettle 7 flow into the sampling bottle 12; after the readings of the second pressure sensor 13 and the first pressure sensor 11 are the same, the first regulating valve 41 is closed after the readings of the second temperature sensor 14 and the first temperature sensor 12, and the sampling is completed.
In the preferred embodiment of the present invention, the volume of the sampling bottle 12 should be much smaller than the volume of the high pressure balance tank 11, and when the first regulating valve 41 is opened for sampling, the readings of the first pressure sensor 11 and the first temperature sensor 12 are not changed. Further, in order to prevent the fluid temperature from dropping sharply due to adiabatic expansion at the opening moment of the first control valve 41, causing some organic matter or carbon dioxide to condense at the outlet of the first control valve 41, the first pipeline 31 is covered with a constant temperature electric heating belt.
In a preferred embodiment of the present invention, the absorption bottle 21 is a carbon dioxide absorption bottle, the absorption bottle 21 contains an alkaline solution, the carbon dioxide absorption bottle contains an alkaline solution, cations of the alkaline solution and carbon dioxide form carbonate precipitates, and the mass m' of carbon dioxide in the sampling bottle is calculated according to formula (5) by weighing the mass of the precipitates generated in the absorption bottle;
in the formula (5), M' represents the mass of the precipitate formed in the absorption flask, M represents the molar mass of the precipitate, and X represents the molar mass of the precipitate contained in one precipitate molecule
The number of the cells.
The solubility of the organic matters is calculated by adopting the modes of weighing and measuring pH, so that the problems of measurement errors and the like caused by the fact that a flow meter measures the gas flow under low flow are solved, and the quick, continuous and reliable measurement of the solubility of the organic matters in the supercritical carbon dioxide is realized. In some embodiments, the absorption bottle 21 may also be an organic absorption bottle, the absorption bottle 21 contains organic substances for absorbing the organic sample, the weight of the organic sample can be obtained by measuring the change in weight of the absorption bottle 21 before and after absorption based on the principle that the organic absorption bottle only absorbs the organic sample and does not absorb carbon dioxide, and the solubility of the organic substances in the supercritical carbon dioxide fluid can be calculated by combining the total mass of the carbon dioxide obtained before and after sampling and the total mass of the organic sample.
In the preferred embodiment of the present invention, after the sampling bottle 12 is separated from the high pressure equilibrium reactor 11, another sampling bottle 12 (including a new second pipe section 312 and a first regulating valve 41) is connected to the outlet of the high pressure equilibrium reactor 11, and the temperature and pressure in the high pressure equilibrium reactor 11 are regulated to realize sampling under another temperature and pressure parameter. Specifically, the sample bottle 12 can be connected to the analysis system 2 by disconnecting the high pressure autoclave 11 and the sample bottle 12 through the ferrule type fitting 313. A new sample vial 12 including a new second tube section 312 and first regulator valve 41) can be sealingly connected to autoclave 11 again by ferrule fitting 313. Repeating the above step S2 can complete the sampling at the specified pressure and temperature.
[ second embodiment ]
Referring to fig. 3, a second embodiment of the present invention provides a continuous measurement system for the solubility of organic substances in supercritical carbon dioxide, which has a structure substantially the same as that of the continuous measurement system of the first embodiment, except that a piston 113 is installed above the high pressure balance kettle 11, the piston 113 can move up and down in the high pressure balance kettle 11, and the pressure in the high pressure balance kettle 11 can be increased or decreased by moving the piston 113. The pressure in the high-pressure balance kettle 11 is flexibly controlled by moving the piston 113, the starting and stopping of the high-pressure pump 15 are reduced, and the high-pressure balance kettle 11 can reach higher pressure through the movement of the piston 113 when the experiment set pressure is higher.
[ third embodiment ] A
Referring to fig. 4, a third embodiment of the present invention provides a continuous measurement system for the solubility of organic matters in supercritical carbon dioxide, which has a structure substantially the same as that of the continuous measurement system of the first embodiment, except that a carbon dioxide storage tank supplies liquid carbon dioxide, and the carbon dioxide storage tank is inclined, so that the liquid carbon dioxide in the carbon dioxide storage tank can flow out through a bottle mouth and be delivered to a preheating device 16 by a high-pressure pump 15, thereby omitting a cooling device 14, simplifying the system structure, reducing the system energy consumption, shortening the measurement time, and improving the measurement efficiency.
[ fourth embodiment ] A
Referring to fig. 5, a fourth embodiment of the present invention provides a continuous measurement system for the solubility of organic matters in supercritical carbon dioxide, which has a structure substantially the same as that of the continuous measurement system in the first embodiment, except that in the analysis system, carbon dioxide and organic matter samples in the sampling bottle 12 are introduced into a pressure-resistant bottle 23 with a known volume, carbon dioxide and organic matter samples in the sampling bottle 12 are introduced into the pressure-resistant bottle 23 through a second regulating valve 42, wherein the carbon dioxide exists in the pressure-resistant bottle 23 in a gas form, and the organic matter samples are in a liquid form, and the volume occupied by the organic matter samples is ignored. The pressure sensor 131 and the temperature sensor 132 are mounted on the pressure-resistant bottle 23, and the mass m' of the carbon dioxide can be obtained by inquiring the density of the carbon dioxide under the corresponding pressure and temperature and combining the volume of the pressure-resistant bottle 23.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalents and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A continuous measuring system for the solubility of organic substances in supercritical carbon dioxide is characterized by comprising a sampling system and an analyzing system, wherein,
the sampling system comprises a high-pressure balance kettle, a sampling bottle and a first pipeline which is connected with an outlet of the high-pressure balance kettle and an inlet of the sampling bottle, the sampling bottle is connected with or separated from the high-pressure balance kettle through the first pipeline, the high-pressure balance kettle provides temperature, pressure and place required by dissolving organic matters in supercritical carbon dioxide fluid, and the supercritical carbon dioxide fluid in which saturated organic matters are dissolved in the high-pressure balance kettle enters the sampling bottle through the first pipeline at a specified temperature and at a specified pressure; the first pipeline is provided with a first regulating valve, and the first regulating valve closes and seals the inlet end of the sampling bottle after the sampling of the sampling bottle is finished;
the analysis system comprises a sampling bottle and an absorption bottle connected with an outlet of the sampling bottle, wherein the sampling bottle is separated from the high-pressure balance kettle after sampling is finished, and the absorption bottle is an organic matter absorption bottle or CO (carbon monoxide) absorption bottle2And (4) an absorption bottle.
2. The system for continuously measuring the solubility of organic matters in supercritical carbon dioxide according to claim 1, wherein the first pipeline comprises a first pipe section and a second pipe section, the inlet of the first pipe section is connected with the outlet of the high-pressure balance kettle, the outlet of the first pipe section and the inlet of the second pipe section are detachably connected, the outlet of the second pipe section is connected with the sampling bottle, after the sampling of the sampling bottle is finished, the second pipe section is disconnected from the first pipe section, and the outlet of the first pipe section is connected with another sampling bottle.
3. The system for continuously measuring the solubility of organic matters in supercritical carbon dioxide as claimed in claim 2, wherein a second pipeline is arranged between the outlet of the sampling bottle and the inlet of the absorption bottle, and a second regulating valve for regulating the flow rate of the outlet of the sampling bottle and a pressure reducing valve for reducing the pressure of the inlet of the absorption bottle are sequentially arranged on the second pipeline.
4. The system of claim 3, wherein a shielding gas supply is connected to an inlet of the second pipe segment in the analysis system, and the first control valve is opened when the shielding gas supply supplies shielding gas.
5. The continuous measurement system for organic matter solubility in supercritical carbon dioxide according to any one of claims 1 to 4, it is characterized in that the sampling system also comprises a carbon dioxide supply device, a third regulating valve, a cooling device, a high-pressure pump, a preheating device and a fourth regulating valve which are sequentially connected through a third pipeline, the carbon dioxide supply device provides carbon dioxide gas required by measurement, the cooling device is used for cooling the carbon dioxide gas at the outlet of the carbon dioxide supply device into liquid carbon dioxide, the high-pressure pump is used for conveying liquid carbon dioxide to the preheating device, the preheating device heats the liquid carbon dioxide to a specified temperature, the third regulating valve is used for controlling the outlet flow of the carbon dioxide gas, and the fourth regulating valve is used for controlling the outlet flow of the carbon dioxide preheated to the specified temperature.
6. The continuous measurement system for the solubility of organic matters in supercritical carbon dioxide according to any one of claims 1 to 4, wherein a first pressure sensor and a first temperature sensor are installed on the high-pressure equilibrium still, and a second pressure sensor and a second temperature sensor are installed on the sampling bottle; in the sampling process, the readings of the first pressure sensor and the second pressure sensor are the same and are set pressure, and the readings of the first temperature sensor and the second temperature sensor are the same and are set temperature.
7. The system for continuously measuring the solubility of organic matters in supercritical carbon dioxide according to claim 5, wherein the sampling system further comprises a vacuum pump, an outlet of the vacuum pump is connected to the third pipeline and is located between the high-pressure pump and the preheating device, and an outlet of the vacuum pump is provided with a fifth regulating valve.
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