Continuous supercritical extraction device for multi-polar components of sample and use method of continuous supercritical extraction device

Abstract

The invention discloses a continuous supercritical extraction device for multi-polar components of a sample. The continuous supercritical extraction device for the multi-polar components of the sample mainly comprises an entrainer conveying unit, a supercritical CO2 fluid conveying unit, a pipeline cleaning unit, a multi-channel extraction unit and a gas-liquid separation unit. The invention further discloses a using method of the continuous supercritical extraction device for the multi-polar components of the sample. Compared with the prior art, the continuous supercritical extraction device for the multi-polar component of the sample has the advantages that the residual entrainer in a pipeline can be accurately removed, and meanwhile, the same-batch continuous extraction of full-spectrum pollutants from non-polar pollutants to strong-polar pollutants is supported.

Description

Technical Field

[0001] The present invention relates to the technical field of environmental monitoring and chemical analysis instruments, and particularly relates to a continuous supercritical extraction device for multi-polar components of a sample and a using method thereof. Background Art

[0002] In the field of environmental pollutant analysis, the supercritical fluid extraction (SFE) technology has been widely used in the enrichment and separation of pollutants in water quality, soil and biological samples due to its advantages such as high efficiency and environmental protection.

[0003] The existing technologies are mainly optimized for single polarity design, and the same type of pollutants are extracted through multiple extraction channels simultaneously, making it difficult to be compatible with the synchronous treatment of wide-spectrum pollutants (such as C8-C24 alkanes, polycyclic aromatic hydrocarbons, phenolic compounds). In addition, the traditional devices adopt normal temperature or single temperature zone control, and cannot optimize the phase change conditions according to the solvent polarity difference, resulting in solidification residues in the pipeline before the valve for high-boiling solvents, and frequent disassembly and cleaning are required. Moreover, when the existing devices extract pollutants with different polarities, different conditions and solvents with large polarity differences need to be switched, but due to the lack of a dynamic phase change regulation mechanism in the pipeline before the valve, the phenomenon of "solvent bridging" occurs for the residual liquid column under the action of gravity. For example, when switching from a non-polar solvent (such as n-hexane) to a strongly polar solvent (such as methanol), the residual liquid column in the pipeline before the valve will be miscible with the new solvent, resulting in deviation of the recovery rate of the target pollutant.

[0004] Therefore, how to provide a continuous supercritical extraction device for multi-polar components of a sample, so as to achieve the technical effect of eliminating the residue in the pipeline before the valve and realizing the extraction of pollutants with different polarities through different extraction channels, is a technical problem that needs to be urgently solved by those skilled in the art. Summary of the Invention

[0005] In view of the problems existing in the prior art, the technical problem to be solved by the present invention is to provide a continuous supercritical extraction device for multi-polar components of a sample, so as to achieve the technical effect of eliminating the residue in the pipeline before the valve and realizing the extraction of pollutants with different polarities through different extraction channels.

[0006] To achieve the above object, the present invention provides a continuous supercritical extraction device for multi-polar components of a sample. The continuous supercritical extraction device for multi-polar components of the sample includes: an entrainer conveying unit, which includes a plurality of entrainer tanks and a liquid path assembly. One end of each entrainer tank is connected to one end of the liquid path assembly through a corresponding entrainer pipeline; a supercritical CO2 fluid conveying unit, one end of which is connected to the other end of the liquid path assembly; a pipeline cleaning unit, one end of which is connected to the connection end of the supercritical CO2 fluid conveying unit and the liquid path assembly; a multi-channel extraction unit, one end of which is connected to the other end of the pipeline cleaning unit; a gas-liquid separation unit, one end of which is connected to the other end of the multi-channel extraction unit.

[0007] In the first aspect, the liquid path assembly includes: a liquid path distributor, and each entrainer pipeline is connected to the inlet end of the liquid path distributor; two liquid pipelines, one end of one liquid pipeline is connected to the outlet end of the liquid path distributor; a first high-pressure plunger pump, the inlet end of which is connected to the other end of one liquid pipeline, and the outlet end of the first high-pressure plunger pump is connected to one end of the other liquid pipeline; a first one-way valve, which is arranged in the middle of the other liquid pipeline; wherein, the other end of the other liquid pipeline is connected to one end of the supercritical CO2 fluid conveying unit; one end of the pipeline cleaning unit is connected to the connection end of the other liquid pipeline and the supercritical CO2 fluid conveying unit.

[0008] In the first aspect, the supercritical CO2 fluid conveying unit includes: a CO2 liquid storage tank; two CO2 fluid conveying pipelines, one end of one CO2 fluid conveying pipeline is connected to one end of the CO2 liquid storage tank; a pre-pump cooling device, which is arranged around one CO2 fluid conveying pipeline; a second high-pressure plunger pump, the inlet end of which is connected to the other end of one CO2 fluid conveying pipeline, and the outlet end of the second high-pressure plunger pump is connected to one end of the other CO2 fluid conveying pipeline; a second one-way valve, which is arranged in the middle of the other CO2 fluid conveying pipeline; wherein, the other end of the other CO2 fluid conveying pipeline is connected to the other end of the other liquid pipeline, and one end of the pipeline cleaning unit is connected to the connection end of the other CO2 fluid conveying pipeline and the other liquid pipeline.

[0009] In a first aspect, the pipeline cleaning unit includes: a purging gas source tank; a purging pipeline, one end of the purging pipeline is connected to the purging gas source tank; a purging gas control valve, the purging gas control valve is arranged on the purging pipeline; a pipeline temperature control module, a first end of the pipeline temperature control module is connected to the other end of the purging pipeline; a purging discharge port control valve, the purging discharge port control valve is arranged at a second end of the pipeline temperature control module; wherein, a connection end of the pipeline temperature control module and the purging pipeline is connected to a connection end of another CO2 fluid delivery pipeline and another liquid pipeline; one end of the multi-channel extraction unit is connected to a third end of the pipeline temperature control module.

[0010] In a first aspect, the pipeline temperature control module includes: a plurality of high thermal conductivity and high pressure resistant pipelines, each of the high thermal conductivity and high pressure resistant pipelines has a T-shaped structure, a first end of each of the high thermal conductivity and high pressure resistant pipelines is sequentially connected to a second end of an adjacent one of the high thermal conductivity and high pressure resistant pipelines to form a high thermal conductivity and high pressure resistant multi-pass pipeline; a first end of one of the high thermal conductivity and high pressure resistant pipelines at one end of the high thermal conductivity and high pressure resistant multi-pass pipeline is connected to the other end of the purging pipeline, and a second end of one of the high thermal conductivity and high pressure resistant pipelines at the other end of the high thermal conductivity and high pressure resistant multi-pass pipeline is provided with the purging discharge port control valve; a plurality of rapid heating devices, the plurality of rapid heating devices are distributed corresponding to the plurality of high thermal conductivity and high pressure resistant pipelines one by one, and a heating component of each of the rapid heating devices is arranged on the periphery of a corresponding one of the high thermal conductivity and high pressure resistant pipelines; an in-pipe temperature sensor, a detection end of the in-pipe temperature sensor is located inside a main pipeline of the high thermal conductivity and high pressure resistant multi-pass pipeline; a plurality of rapid cooling devices, the plurality of rapid cooling devices are distributed corresponding to the plurality of high thermal conductivity and high pressure resistant pipelines one by one, and a cooling component of each of the rapid cooling devices is arranged on the periphery of a corresponding one of the high thermal conductivity and high pressure resistant pipelines, and a cooling component of one of the rapid cooling devices located on the periphery of the same high thermal conductivity and high pressure resistant pipeline is arranged adjacent and spaced apart from a heating component of one of the rapid heating devices; wherein, a connection end of one of the high thermal conductivity and high pressure resistant pipelines at one end of the high thermal conductivity and high pressure resistant multi-pass pipeline and the purging pipeline is connected to a connection end of another CO2 fluid delivery pipeline and another liquid pipeline; a third end of each of the high thermal conductivity and high pressure resistant pipelines is connected to one end of the multi-channel extraction unit.

[0011] In a first aspect, the multi-channel extraction unit includes: a high-pressure valve array, the high-pressure valve array assembly includes a plurality of high-pressure valves, and the plurality of high-pressure valves are distributed in one-to-one correspondence with a plurality of the high-thermal-conductivity and high-pressure-resistant pipelines. One end of each high-pressure valve is connected to the third end of a corresponding one of the high-thermal-conductivity and high-pressure-resistant pipelines; a high-pressure extraction kettle array, the high-pressure extraction kettle array includes a plurality of high-pressure extraction kettles, and the plurality of high-pressure extraction kettles are distributed in one-to-one correspondence with the plurality of high-pressure valves. The inlet end of each high-pressure extraction kettle is connected to the other end of a corresponding high-pressure valve; an extraction kettle temperature control module, the extraction kettle temperature control module includes a plurality of extraction kettle temperature control devices, and the plurality of extraction kettle temperature control devices are distributed in one-to-one correspondence with the plurality of high-pressure extraction kettles. Each extraction kettle temperature control device is located around a corresponding high-pressure extraction kettle; a back-pressure valve array, the back-pressure valve array includes a plurality of back-pressure valves, and the plurality of back-pressure valves are distributed in one-to-one correspondence with the plurality of high-pressure extraction kettles. One end of each back-pressure valve is connected to the outlet end of a corresponding high-pressure extraction kettle.

[0012] In a first aspect, the gas-liquid separation unit includes: a plurality of pipeline switching valves, the plurality of pipeline switching valves are distributed in one-to-one correspondence with the plurality of back-pressure valves. The first end of each pipeline switching valve is connected to the other end of a corresponding back-pressure valve; a plurality of waste liquid discharge pipes, the plurality of waste liquid discharge pipes are distributed in one-to-one correspondence with the plurality of pipeline switching valves. One end of each waste liquid discharge pipe is connected to the second end of a corresponding pipeline switching valve; a gas-liquid separator array, the gas-liquid separator array includes a plurality of gas-liquid separators, and the plurality of gas-liquid separators are distributed in one-to-one correspondence with the plurality of pipeline switching valves. The inlet of each gas-liquid separator is connected to the third end of a corresponding pipeline switching valve; a plurality of entrainer collection bottles, the plurality of entrainer collection bottles are distributed in one-to-one correspondence with the plurality of gas-liquid separators. The inlet of each entrainer collection bottle is connected to the outlet of a corresponding gas-liquid separator.

[0013] The present invention also provides a usage method of a sample multi-polarity component continuous supercritical extraction device for the usage of the above-mentioned sample multi-polarity component continuous supercritical extraction device. The usage method includes a sample multi-polarity component sequential continuous extraction mode, or a sample multi-polarity component multi-channel synchronous extraction mode, or a conventional multi-channel single-time simultaneous extraction mode;

[0014] The sequential continuous extraction mode of the multi-polar components of the sample includes: S1-1: Before extraction, different samples are respectively placed in the high-pressure extraction autoclaves of each channel, different formula entrainers are respectively placed in the entrainer tanks, supercritical CO2 fluid is injected into the CO2 liquid storage tank, and the temperature control device of the extraction autoclave of each channel is turned on; S1-2: With the high-pressure valve array and the back-pressure valve array of each channel in the normally closed state, the high-pressure valves corresponding to the high-pressure extraction autoclaves of each channel are sequentially opened, and the first formula entrainer is sequentially injected into the high-pressure extraction autoclaves of each channel through the first high-pressure plunger pump and the liquid path distributor, and the first high-pressure plunger pump and the liquid path distributor are closed; then the second high-pressure plunger pump is turned on to sequentially inject supercritical CO2 fluid into the high-pressure extraction autoclaves of each channel. When the high-pressure extraction autoclaves of each channel reach the set critical pressure and temperature in sequence, the corresponding high-pressure valves are closed, and static extraction is started using the first formula entrainer; S1-3: After the high-pressure extraction autoclaves of all channels start static extraction, the purge gas control valve and the discharge port control valve are opened, and the rapid heating device is started to discharge the first formula entrainer remaining in the pipeline before the high-pressure valve array. After the remaining first formula entrainer is purified, the purge gas control valve and the discharge port control valve are closed, and the rapid cooling device is started until the temperature drops to an acceptable temperature for injecting the next formula entrainer; S1-4: After extraction is completed, the pipeline switching valves of each channel are all switched to communicate with the gas-liquid separator. The back-pressure valves of each channel are sequentially opened and the pressure in the high-pressure extraction autoclave is slowly reduced to atmospheric pressure. The first formula entrainer carrying the extract in the high-pressure extraction autoclaves of each channel is separated from CO2 after passing through the gas-liquid separator, and then is sequentially collected into the entrainer collection bottles; S1-5: Repeat S1-1 to S1-4 without taking out the samples in the high-pressure extraction autoclaves of each channel, replace with the second formula entrainer for extraction, and then repeat S1-1 to S1-4 without taking out the samples in the high-pressure extraction autoclaves of each channel, replace with the third formula entrainer for extraction until the samples in the high-pressure extraction autoclaves of each channel complete the extraction cycle of the set several formula entrainers; S1-6: After all extraction cycles are completed, after taking out the samples in the high-pressure extraction autoclaves of each channel, the pipeline switching valves of each channel are all switched to be connected to the gas-liquid separator, then the first high-pressure plunger pump is turned on and the flow path of the liquid path distributor is switched, and the extraction autoclave array and its corresponding channel pipelines are cleaned with the formula entrainer used in the next extraction cycle; S1-7: Put a new batch of samples in the high-pressure extraction autoclaves of each channel, repeat S1-1 to S1-6, and perform sequential continuous extraction of the multi-polar components of the new batch of samples.

[0015] In the second aspect, the multi-polarity component multi-channel synchronous extraction mode of the sample includes: S2-1: Before extraction, the same sample is respectively placed in the high-pressure extraction autoclaves of each channel, different formula entrainers are respectively placed in the entrainer tanks, supercritical CO2 fluid is injected into the CO2 liquid storage tank, and the temperature control device of the extraction autoclave of each channel is turned on; S2-2: With the high-pressure valve array and the back-pressure valve array of each channel in the normally closed state, the high-pressure valve corresponding to the high-pressure extraction autoclave of the first channel is opened, and the first formula entrainer is injected into the high-pressure extraction autoclave of the first channel through the first high-pressure plunger pump and the liquid path distributor, and the first high-pressure plunger pump and the liquid path distributor are closed; then the second high-pressure plunger pump is turned on to inject supercritical CO2 fluid into the high-pressure extraction autoclave of the first channel. When the high-pressure extraction autoclave of the first channel reaches the set critical pressure and temperature, the corresponding high-pressure valve is closed, and static extraction begins; S2-3: After the sample in the high-pressure extraction autoclave of the first channel starts to be extracted, the purge gas control valve and the discharge port control valve are opened, and the rapid heating device is started to discharge the remaining first formula entrainer in the pipeline before the high-pressure valve array. After the remaining first formula entrainer is purified, the purge gas control valve and the discharge port control valve are closed, and the rapid cooling device is started until the temperature drops to the acceptable temperature for injecting the next formula entrainer; S2-4: The high-pressure valve corresponding to the high-pressure extraction autoclave of the second channel is opened, and the second formula entrainer is injected into the high-pressure extraction autoclave of the second channel through the first high-pressure plunger pump and the liquid path distributor, and the first high-pressure plunger pump and the liquid path distributor are closed; then the second high-pressure plunger pump is turned on to inject supercritical CO2 fluid into the high-pressure extraction autoclave of the second channel. When the high-pressure extraction autoclave of the second channel reaches the set critical pressure and temperature, the corresponding high-pressure valve is closed, and static extraction begins; S2-5: Repeat the process of S2-1 to S2-4 to inject different formula entrainers into the high-pressure extraction autoclaves of the remaining channels and start static extraction; if the entrainer formulas set between adjacent channels are the same, the process of S2-3 is not repeated when switching this channel; S2-6: After the extraction in the high-pressure extraction autoclave of the first channel is completed, the pipeline switching valve corresponding to the high-pressure extraction autoclave of the first channel is switched to communicate with the gas-liquid separator, the back-pressure valve corresponding to the high-pressure extraction autoclave of the first channel is opened, and the pressure in the high-pressure extraction autoclave is slowly reduced to atmospheric pressure. The first entrainer carrying the extract is separated from CO2 after passing through the gas-liquid separator, and then is collected into the entrainer collection bottle; S2-7: After the collection of the first formula entrainer corresponding to the first channel of the high-pressure extraction autoclave of the first channel is completed, the corresponding pipeline switching valve is switched to communicate with the waste liquid discharge pipe, then the first high-pressure plunger pump is turned on to clean the high-pressure extraction autoclave of the first channel and its corresponding channel pipeline with the entrainer. After the cleaning is completed, the pipeline switching valve is switched to communicate with the gas-liquid separator, and the high-pressure extraction autoclave of the first channel is removed and waiting for re-sampling;S2-8: Repeat the processes of S2-6 and S2-7 until the extraction, entrainer collection, and pipeline cleaning of the high-pressure extraction autoclaves for all channels are completed; then place a new batch of samples in the high-pressure extraction autoclave array, and repeat steps S2-1 to S2-7 to perform multi-channel synchronous extraction of the new batch of samples.;

[0016] In the second aspect, the conventional multi-channel single simultaneous extraction mode includes: S3-1: Before extraction, place samples in the high-pressure extraction autoclaves of each channel respectively, place the entrainer with the same formula in the entrainer tank respectively, inject supercritical CO2 fluid into the CO2 liquid storage tank, and turn on the temperature control device of the extraction autoclave for each channel; S3-2: With the high-pressure valve array and the back-pressure valve array of each channel in the normally closed state, sequentially open the high-pressure valves corresponding to the high-pressure extraction autoclaves of each channel, and inject the formulated entrainer into the high-pressure extraction autoclaves of each channel in sequence through the first high-pressure plunger pump and the liquid path distributor, and then turn off the first high-pressure plunger pump and the liquid path distributor; then turn on the second high-pressure plunger pump and inject supercritical CO2 fluid into the high-pressure extraction autoclaves of each channel in sequence. After the high-pressure extraction autoclaves of each channel reach the set critical pressure and temperature in sequence, close the corresponding high-pressure valves and start static extraction using the first formulated entrainer; S3-3: After the high-pressure extraction autoclaves of all channels start static extraction, open the purge gas control valve and the discharge port control valve, and start the rapid heating device to discharge the residual formulated entrainer in the pipeline before the high-pressure valve array. After the residual formulated entrainer is purified, close the purge gas control valve and the discharge port control valve, and start the rapid cooling device until the temperature drops to the acceptable temperature of the formulated entrainer; S3-4: After extraction is completed, switch the pipeline switching valves of each channel to communicate with the gas-liquid separator, sequentially open the back-pressure valves of each channel and slowly reduce the pressure in the high-pressure extraction autoclave to atmospheric pressure. The formulated entrainer carrying the extract in the high-pressure extraction autoclaves of each channel is separated from CO2 after passing through the gas-liquid separator, and then is sequentially collected into the entrainer collection bottle; S3-5: After all extraction cycles are completed, after taking out the samples in the high-pressure extraction autoclaves of each channel, switch the pipeline switching valves of each channel to be connected to the gas-liquid separator, then turn on the first high-pressure plunger pump and switch the flow path of the liquid path distributor, and clean the extraction autoclave array and its corresponding channel pipelines with the formulated entrainer used in the next round of extraction; S3-6: Place a new batch of samples in the high-pressure extraction autoclave array, and repeat S3-1 to S3-5 to perform multi-channel single simultaneous extraction of the new batch.;

[0017] Beneficial effects:

[0018] The present invention provides a continuous supercritical extraction device for multi-polar components of a sample. The continuous supercritical extraction device for multi-polar components of a sample mainly includes an entrainer delivery unit, a supercritical CO2 fluid delivery unit, a pipeline cleaning unit, a multi-channel extraction unit, and a gas-liquid separation unit. Among them, the entrainer delivery unit is used to provide and deliver the entrainer of the formula used in extraction, and the liquid path component is used to selectively deliver the entrainer of the required formula; the supercritical CO2 fluid delivery unit is used to provide and deliver supercritical CO2 fluid to make the high-pressure extraction kettle reach a certain pressure; the pipeline cleaning unit is used to remove the residual entrainer in the pipeline passed through during the entrainer delivery process to avoid affecting the extraction experimental data; the multi-channel extraction unit is used to extract the sample. The multi-channel extraction unit includes a number of high-pressure valves with independent channels, a number of high-pressure extraction kettles with independent channels, a number of back-pressure valves with independent channels, and an extraction kettle temperature control module, so that each channel can control the opening and closing of the high-pressure extraction kettle passage in the extraction experiment through independent high-pressure valves and back-pressure valves. At the same time, combined with the liquid path component, entrainers with different polarities in different channels and supercritical CO2 fluid are mixed and then enter the high-pressure extraction reaction kettle; the structural composition and connection of the continuous supercritical extraction device for multi-polar components of a sample of the present invention enable the extraction mode of the continuous supercritical extraction device for multi-polar components of a sample of the present invention to have three types, namely, different samples are placed in different high-pressure extraction kettles, and each channel sequentially uses entrainers with different formulas for cyclic extraction, that is, the sequential continuous extraction mode of multi-polar components of the sample; the same sample is placed in different high-pressure extraction kettles, and each channel uses entrainers with different formulas for synchronous extraction, that is, the multi-channel synchronous extraction mode of multi-polar components of the sample; the high-pressure extraction kettles of each channel use the same formula entrainer for single extraction at the same time, that is, the conventional multi-channel single simultaneous extraction mode; the continuous supercritical extraction device for multi-polar components of a sample of the present invention can target the polar characteristics of the sample to select the extraction mode, greatly improving the extraction efficiency; in summary, the continuous supercritical extraction device for multi-polar components of a sample of the present invention contains multiple independent extraction channels. By combining multiple parallel independent extraction channels with the selection change of the formula entrainer, the accurate removal of the residual entrainer in the pipeline can be realized, and at the same time, it supports the simultaneous continuous extraction of the full-spectrum pollutants from non-polar pollutants to strongly polar pollutants in the same batch. Brief Description of the Drawings

[0019] In order to more clearly illustrate the technical solutions in the embodiments of the present specification or the prior art, the following will briefly introduce the drawings required for use in the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0020] Figure 1 It is a simplified connection diagram of the continuous supercritical extraction device for multi-polar components of a sample of the present invention;

[0021] Figure 2 It is the front view of the internal structure of the continuous supercritical extraction device for multi-polar components of samples of the present invention;

[0022] Figure 3 It is the front view of the overall structure of the continuous supercritical extraction device for multi-polar components of samples of the present invention;

[0023] Figure 4 It is the side view of the overall structure of the continuous supercritical extraction device for multi-polar components of samples of the present invention;

[0024] Figure 5 It is the side view of the internal structure of the continuous supercritical extraction device for multi-polar components of samples of the present invention;

[0025] Figure 6 It is the schematic structural view of the pipeline cleaning unit of the present invention;

[0026] Figure 7 It is the recovery rate graph of each dioxin compound obtained by extracting standard soil by the present invention in the conventional multi-channel single-time simultaneous extraction mode;

[0027] Figure 8 It is the recovery rate graph of organochlorine pesticides obtained by extracting standard soil by the present invention in the conventional multi-channel single-time simultaneous extraction mode;

[0028] Figure 9 It is the recovery rate graph of imidaclothiz obtained by extracting standard soil by the present invention in the conventional multi-channel single-time simultaneous extraction mode;

[0029] Figure 10 It is the recovery rate graph of dioxin compounds, organochlorine pesticides, imidaclothiz and polychlorinated biphenyls obtained by extracting standard soil samples by the present invention in the sequential continuous extraction mode of multi-polar components of samples;

[0030] Figure 11 It is the recovery rate graph of dioxin compounds, organochlorine pesticides, imidaclothiz and polychlorinated biphenyls obtained by extracting actual soil samples by the present invention in the sequential continuous extraction mode of multi-polar components of samples.

[0031] Reference numerals:

[0032] 1. Entrainer delivery unit; 11. Entrainer tank; 12. Liquid path assembly; 121. Liquid path distributor; 122. First high-pressure plunger pump; 123. First one-way valve;

[0033] 2. Supercritical CO2 fluid delivery unit; 21. CO2 liquid storage tank; 22. Pre-pump cooling device; 23. Second high-pressure plunger pump; 24. Second one-way valve;

[0034] 3. Pipeline cleaning unit; 31. Purge gas source tank; 32. Purge gas control valve; 33. Pipeline temperature control module; 331. High thermal conductivity and high pressure resistance pipeline; 332. Quick heating device; 333. In-pipe temperature sensor; 334. Quick cooling device; 34. Purge discharge port control valve;

[0035] 4. Multi-channel extraction unit; 41. High-pressure valve; 42. High-pressure extraction kettle; 43. Extraction kettle temperature control module; 44. Back pressure valve;

[0036] 5. Gas-liquid separation unit; 51. Pipeline switching valve; 52. Waste liquid discharge pipe; 53. Gas-liquid separator; 54. Entrainer collection bottle. Specific embodiments

[0037] Next, the technical solutions in the embodiments of this specification will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of this specification. Obviously, the described embodiments are only a part of the embodiments of this specification, rather than all the embodiments. Based on the embodiments in this specification, all other embodiments obtained by those of ordinary skill in the art belong to the scope of protection of the present invention.

[0038] Embodiment 1

[0039] As Figures 1 - 6 shown, Embodiment 1 provides a continuous supercritical extraction device for multi-polar components of a sample. The continuous supercritical extraction device for multi-polar components of the sample includes: an entrainer delivery unit 1, the entrainer delivery unit 1 includes a plurality of entrainer tanks 11 and a liquid path assembly 12, and one end of each entrainer tank 11 is connected to one end of the liquid path assembly 12 through a corresponding entrainer pipeline; a supercritical CO2 fluid delivery unit 2, one end of the supercritical CO2 fluid delivery unit 2 is connected to the other end of the liquid path assembly 12; a pipeline cleaning unit 3, one end of the pipeline cleaning unit 3 is connected to the connection end of the supercritical CO2 fluid delivery unit 2 and the liquid path assembly 12; a multi-channel extraction unit 4, one end of the multi-channel extraction unit 4 is connected to the other end of the pipeline cleaning unit 3; a gas-liquid separation unit 5, one end of the gas-liquid separation unit 5 is connected to the other end of the multi-channel extraction unit 4.

[0040] The present invention provides a continuous supercritical extraction device for multi-polar components of a sample. The continuous supercritical extraction device for multi-polar components of a sample mainly includes an entrainer delivery unit, a supercritical CO2 fluid delivery unit, a pipeline cleaning unit, a multi-channel extraction unit, and a gas-liquid separation unit. Among them, the entrainer delivery unit is used to provide and deliver the entrainer of the formula used in extraction, and the liquid path assembly is used to selectively deliver the entrainer of the required formula; the supercritical CO2 fluid delivery unit is used to provide and deliver supercritical CO2 fluid to make the high-pressure extraction kettle reach a certain pressure; the pipeline cleaning unit is used to remove the residual entrainer in the pipeline passed through during the entrainer delivery process to avoid affecting the extraction experimental data; the multi-channel extraction unit is used to extract the sample. The multi-channel extraction unit includes a number of high-pressure valves with independent channels, a number of high-pressure extraction kettles with independent channels, a number of back-pressure valves with independent channels, and an extraction kettle temperature control module, so that each channel can control the opening and closing of the high-pressure extraction kettle passage in the extraction experiment through independent high-pressure valves and back-pressure valves. At the same time, in combination with the liquid path assembly, entrainers with different polarities in different channels are mixed with supercritical CO2 fluid and then enter the high-pressure extraction reaction kettle; the structural composition and connection of the continuous supercritical extraction device for multi-polar components of a sample according to the present invention enable the extraction mode of the continuous supercritical extraction device for multi-polar components of a sample according to the present invention to have three types, namely, different samples are placed in different high-pressure extraction kettles, and each channel sequentially uses different formula entrainers for cyclic extraction, that is, the sequential continuous extraction mode of multi-polar components of the sample; the same sample is placed in different high-pressure extraction kettles, and each channel uses different formula entrainers for synchronous extraction, that is, the multi-channel synchronous extraction mode of multi-polar components of the sample; the high-pressure extraction kettles of each channel use the same formula entrainer for single extraction at the same time, that is, the conventional multi-channel single simultaneous extraction mode; the continuous supercritical extraction device for multi-polar components of a sample according to the present invention can target the polarity characteristics of the sample to select the extraction mode, greatly improving the extraction efficiency; in summary, the continuous supercritical extraction device for multi-polar components of a sample according to the present invention contains multiple independent extraction channels. By combining multiple parallel independent extraction channels with the selection change of the formula entrainer, accurate removal of the residual entrainer in the pipeline can be achieved, and at the same time, continuous extraction of the whole spectrum of pollutants from non-polar pollutants to strongly polar pollutants in the same batch is supported.

[0041] In some possible implementations, the liquid path component 12 includes: a liquid path distributor 121, with each entrainer pipeline connected to the inlet end of the liquid path distributor 121; two liquid pipelines, one end of one liquid pipeline connected to the outlet end of the liquid path distributor 121; a first high-pressure plunger pump 122, the inlet end of the first high-pressure plunger pump 122 connected to the other end of one liquid pipeline, and the outlet end of the first high-pressure plunger pump 122 connected to one end of the other liquid pipeline; a first one-way valve 123, the first one-way valve 123 disposed in the middle of the other liquid pipeline; wherein, the other end of the other liquid pipeline is connected to one end of the supercritical CO2 fluid delivery unit 2; one end of the pipeline cleaning unit 3 is connected to the connection end of the other liquid pipeline and the supercritical CO2 fluid delivery unit 2.

[0042] Specifically, the liquid path distributor is used to select and connect the entrainer tank containing the required formula of entrainer, so that the entrainer of the required formula is output and mixed with the supercritical CO2 fluid to enter the high-pressure extraction kettle.

[0043] In some possible implementations, the supercritical CO2 fluid delivery unit 2 includes: a CO2 liquid storage tank 21; two CO2 fluid delivery pipelines, one end of one CO2 fluid delivery pipeline connected to one end of the CO2 liquid storage tank 21; a pre-pump cooling device 22, the pre-pump cooling device 22 disposed around one CO2 fluid delivery pipeline; a second high-pressure plunger pump 23, the inlet end of the second high-pressure plunger pump 23 connected to the other end of one CO2 fluid delivery pipeline, and the outlet end of the second high-pressure plunger pump 23 connected to one end of the other CO2 fluid delivery pipeline; a second one-way valve 24, the second one-way valve 24 disposed in the middle of the other CO2 fluid delivery pipeline; wherein, the other end of the other CO2 fluid delivery pipeline is connected to the other end of the other liquid pipeline, and one end of the pipeline cleaning unit 3 is connected to the connection end of the other CO2 fluid delivery pipeline and the other liquid pipeline.

[0044] Specifically, the pre-pump cooling device is used to prevent the supercritical CO2 fluid from gasifying.

[0045] In some possible implementation manners, the pipeline cleaning unit 3 includes: a purging gas source tank 31; a purging pipeline, one end of the purging pipeline is connected to the purging gas source tank 31; a purging gas control valve 32, the purging gas control valve 32 is arranged on the purging pipeline; a pipeline temperature control module 33, a first end of the pipeline temperature control module 33 is connected to the other end of the purging pipeline; a purging discharge port control valve 34, the purging discharge port control valve 34 is arranged at a second end of the pipeline temperature control module 33; wherein, a connection end of the pipeline temperature control module 33 and the purging pipeline is connected to a connection end of another CO2 fluid delivery pipeline and another liquid pipeline; one end of the multi-channel extraction unit 4 is connected to a third end of the pipeline temperature control module 33.

[0046] Specifically, after the entrainer and the supercritical CO2 fluid are delivered to the high-pressure extraction kettle, in order to avoid the difference in the formula of the entrainer input next time, it is necessary to remove the residual entrainer in the pipeline; the pipeline temperature control module is used for heating to volatilize the entrainer, and then the purging gas in the purging gas source tank is used to carry out the volatilized entrainer out of the pipeline, so as to achieve the effect of removing the residual entrainer.

[0047] In some possible implementation manners, the pipeline temperature control module 33 includes: a plurality of high thermal conductivity and high pressure resistant pipelines 331, each of the high thermal conductivity and high pressure resistant pipelines 331 has a T-shaped structure, and the first end of each high thermal conductivity and high pressure resistant pipeline is sequentially connected to the second end of an adjacent high thermal conductivity and high pressure resistant pipeline to form a high thermal conductivity and high pressure resistant multi-pass pipeline; the first end of one of the high thermal conductivity and high pressure resistant pipelines 331 at one end of the high thermal conductivity and high pressure resistant multi-pass pipeline is connected to the other end of the purging pipeline, and a purging discharge port control valve 34 is arranged at the second end of one of the high thermal conductivity and high pressure resistant pipelines 331 at the other end of the high thermal conductivity and high pressure resistant multi-pass pipeline; a plurality of rapid heating devices 332, the plurality of rapid heating devices 332 are distributed in one-to-one correspondence with the plurality of high thermal conductivity and high pressure resistant pipelines 331, and the heating component of each rapid heating device 332 is arranged on the periphery of a corresponding high thermal conductivity and high pressure resistant pipeline 331; an in-pipe temperature sensor 333, the detection end of the in-pipe temperature sensor 333 is located inside the main pipeline of the high thermal conductivity and high pressure resistant multi-pass pipeline; a plurality of rapid cooling devices 334, the plurality of rapid cooling devices 334 are distributed in one-to-one correspondence with the plurality of high thermal conductivity and high pressure resistant pipelines 331, and the cooling component of each rapid cooling device 334 is arranged on the periphery of a corresponding high thermal conductivity and high pressure resistant pipeline 331, and the cooling component of a rapid cooling device 334 arranged on the periphery of the same high thermal conductivity and high pressure resistant pipeline 331 is arranged adjacent to and spaced from the heating component of a rapid heating device 332; wherein, the connection end of one of the high thermal conductivity and high pressure resistant pipelines 331 at one end of the high thermal conductivity and high pressure resistant multi-pass pipeline and the purging pipeline is connected to the connection end of another CO2 fluid delivery pipeline and another liquid pipeline; the third end of each high thermal conductivity and high pressure resistant pipeline 331 is connected to one end of the multi-channel extraction unit 4.

[0048] Specifically, the high thermal conductivity and high pressure resistant pipeline with a T-shaped structure includes three unobstructed ports. After several high thermal conductivity and high pressure resistant pipelines with a T-shaped structure are connected in sequence, a high thermal conductivity and high pressure resistant multi-way pipeline containing several branch channels is formed. The high thermal conductivity and high pressure resistant multi-way pipeline is integrally formed by a high thermal conductivity and high pressure resistant material. The high thermal conductivity and high pressure resistant multi-way pipeline containing several branch channels enables several branch channels to be subsequently connected to their respective corresponding high pressure valves, thus constituting the multi-channel transmission of the entrainer in the subsequent multi-channel extraction unit; the rapid heating device is used to heat the high thermal conductivity and high pressure resistant pipeline to volatilize the residual entrainer, and the rapid cooling device is used to cool the high thermal conductivity and high pressure resistant pipeline to a temperature at which the entrainer will not be adversely affected after the entrainer is removed; the in-pipe temperature sensor is used to monitor the temperature of the high thermal conductivity and high pressure resistant pipeline, determine whether the heating temperature reaches the volatilization temperature of the entrainer, and determine whether the cooling temperature reaches the temperature at which the entrainer is not affected; the connection end of the CO2 fluid delivery pipeline and the liquid pipeline can be connected to any position other than the third end of any high thermal conductivity and high pressure resistant pipeline of the pipeline temperature control module of the pipeline cleaning unit, such as the connection end of the first end and the second end of two adjacent high thermal conductivity and high pressure resistant pipelines, or the first end of one of the high thermal conductivity and high pressure resistant pipelines at one end of the high thermal conductivity and high pressure resistant multi-way pipeline.

[0049] In some possible implementation manners, the multi-channel extraction unit 4 includes: a high pressure valve array, the high pressure valve array assembly includes several high pressure valves 41, and several of the high pressure valves 41 are distributed in one-to-one correspondence with several of the high thermal conductivity and high pressure resistant pipelines 331. One end of each of the high pressure valves 41 is connected to the third end of a corresponding one of the high thermal conductivity and high pressure resistant pipelines 331; a high pressure extraction kettle array, the high pressure extraction kettle array includes several high pressure extraction kettles 42, and several of the high pressure extraction kettles 42 are distributed in one-to-one correspondence with several of the high pressure valves 41. The inlet end of each of the high pressure extraction kettles 42 is connected to the other end of a corresponding one of the high pressure valves 41; an extraction kettle temperature control module 43, the extraction kettle temperature control module includes several extraction kettle temperature control devices, and several of the extraction kettle temperature control devices are distributed in one-to-one correspondence with several of the high pressure extraction kettles 42. Each of the extraction kettle temperature control devices is located on the periphery of a corresponding one of the high pressure extraction kettles 42; a back pressure valve array, the back pressure valve array includes several back pressure valves 44, and several of the back pressure valves 44 are distributed in one-to-one correspondence with several of the high pressure extraction kettles 42. One end of each of the back pressure valves 44 is connected to the outlet end of a corresponding one of the high pressure extraction kettles 42.

[0050] Specifically, each high-pressure valve and each back-pressure valve are independent. The opening and closing of each high-pressure extraction kettle passage in the extraction experiment can be controlled by the independent high-pressure valve and back-pressure valve. At the same time, the combined liquid path component enables the entrainer with different polarities in different channels to be mixed with the supercritical CO2 fluid and then enter the high-pressure extraction reactor; the temperature control module of the extraction kettle can not only include several extraction kettle temperature control devices corresponding to several high-temperature extraction kettles respectively, but also be an overall extraction kettle temperature control device, so that all the high-temperature extraction kettles are located in the extraction kettle temperature control device to control the temperature of all the high-pressure extraction kettles.

[0051] In some possible implementation manners, the gas-liquid separation unit 5 includes: several pipeline switching valves 51, several of the pipeline switching valves 51 are distributed in one-to-one correspondence with several of the back-pressure valves 44, and the first end of each pipeline switching valve 51 is connected to the other end of a corresponding back-pressure valve 44; several waste liquid discharge pipes 52, several of the waste liquid discharge pipes 52 are distributed in one-to-one correspondence with several of the pipeline switching valves 51, and one end of each waste liquid discharge pipe 52 is connected to the second end of a corresponding pipeline switching valve 51; a gas-liquid separator array, the gas-liquid separator array includes several gas-liquid separators 53, several of the gas-liquid separators 53 are distributed in one-to-one correspondence with several of the pipeline switching valves 51, and the inlet of each gas-liquid separator 53 is connected to the third end of a corresponding pipeline switching valve 51; several entrainer collection bottles 54, several of the entrainer collection bottles 54 are distributed in one-to-one correspondence with several of the gas-liquid separators 53, and the inlet of each entrainer collection bottle 54 is connected to the outlet of a corresponding gas-liquid separator 53.

[0052] Specifically, the gas-liquid separator is used to separate CO2 gas and liquid.

[0053] Embodiment 2

[0054] As Figures 1 - 6As shown in the figure, Embodiment 2 of the present invention provides a method for using a continuous supercritical extraction device for multi-polar components of a sample, which is used for the use of the continuous supercritical extraction device for multi-polar components of the sample described in Embodiment 1. The method for using includes a sequential continuous extraction mode for multi-polar components of the sample, or a multi-channel synchronous extraction mode for multi-polar components of the sample, or a conventional multi-channel single-time simultaneous extraction mode; the sequential continuous extraction mode for multi-polar components of the sample includes: S1-1: Before extraction, different samples are respectively placed in the high-pressure extraction autoclaves of each channel, different formula entrainers are respectively placed in the entrainer tank, supercritical CO2 fluid is injected into the CO2 liquid storage tank, and the temperature control device of the extraction autoclave of each channel is turned on; S1-2: With the high-pressure valve array and the back-pressure valve array of each channel in a normally closed state, the high-pressure valves corresponding to the high-pressure extraction autoclaves of each channel are sequentially opened, and the first formula entrainer is sequentially injected into the high-pressure extraction autoclaves of each channel through the first high-pressure plunger pump and the liquid path distributor, and the first high-pressure plunger pump and the liquid path distributor are closed; then the second high-pressure plunger pump is turned on to sequentially inject supercritical CO2 fluid into the high-pressure extraction autoclaves of each channel. When the high-pressure extraction autoclaves of each channel reach the set critical pressure and temperature in sequence, the corresponding high-pressure valves are closed, and static extraction is started using the first formula entrainer; S1-3: After the high-pressure extraction autoclaves of all channels start static extraction, the purge gas control valve and the discharge port control valve are opened, and the rapid heating device is started to discharge the first formula entrainer remaining in the pipeline before the high-pressure valve array. After the remaining first formula entrainer is purified, the purge gas control valve and the discharge port control valve are closed, and the rapid cooling device is started until the temperature drops to an acceptable temperature for injecting the next formula entrainer; S1-4: After extraction is completed, the pipeline switching valves of each channel are all switched to be connected to the gas-liquid separator. The back-pressure valves of each channel are sequentially opened and the pressure in the high-pressure extraction autoclave is slowly reduced to atmospheric pressure. The first formula entrainer carrying the extract in the high-pressure extraction autoclaves of each channel is separated from CO2 after passing through the gas-liquid separator, and then is sequentially collected into the entrainer collection bottle; S1-5: Repeat S1-1 to S1-4 without taking out the samples in the high-pressure extraction autoclaves of each channel, replace with the second formula entrainer for extraction, and then repeat S1-1 to S1-4 without taking out the samples in the high-pressure extraction autoclaves of each channel, replace with the third formula entrainer for extraction until the samples in the high-pressure extraction autoclaves of each channel complete the extraction cycle of several set formula entrainers; S1-6: After all extraction cycles are completed, after taking out the samples in the high-pressure extraction autoclaves of each channel, the pipeline switching valves of each channel are all switched to be connected to the gas-liquid separator, then the first high-pressure plunger pump is turned on and the flow path of the liquid path distributor is switched, and the extraction autoclave array and its corresponding channel pipelines are cleaned with the formula entrainer used in the next extraction cycle;S1-7: Put a new batch of samples into the high-pressure extraction autoclaves of each channel, repeat S1-1 to S1-6, and perform sequential continuous extraction of multi-polar components of the new batch of samples; The multi-channel synchronous extraction mode of the multi-polar components of the sample includes: S2-1: Before extraction, put the same sample into the high-pressure extraction autoclaves of each channel, put different formulated entrainers into the entrainer tanks respectively, inject supercritical CO2 fluid into the CO2 liquid storage tank, and turn on the temperature control device of the extraction autoclave of each channel; S2-2: With the high-pressure valve array and the back pressure valve array of each channel in the normally closed state, open the high-pressure valve corresponding to the high-pressure extraction autoclave of the first channel, inject the first formulated entrainer into the high-pressure extraction autoclave of the first channel through the first high-pressure plunger pump and the liquid path distributor, and close the first high-pressure plunger pump and the liquid path distributor; Then turn on the second high-pressure plunger pump to inject supercritical CO2 fluid into the high-pressure extraction autoclave of the first channel. When the high-pressure extraction autoclave of the first channel reaches the set critical pressure and temperature, close the corresponding high-pressure valve and start static extraction; S2-3: After the sample in the high-pressure extraction autoclave of the first channel starts to be extracted, open the purge gas control valve and the discharge port control valve, and start the rapid heating device to discharge the remaining first formulated entrainer in the pipeline before the high-pressure valve array. After the remaining first formulated entrainer is purified, close the purge gas control valve and the discharge port control valve, and start the rapid cooling device until the temperature drops to an acceptable temperature for injecting the next formulated entrainer; S2-4: Open the high-pressure valve corresponding to the high-pressure extraction autoclave of the second channel, inject the second formulated entrainer into the high-pressure extraction autoclave of the second channel through the first high-pressure plunger pump and the liquid path distributor, and close the first high-pressure plunger pump and the liquid path distributor; Then turn on the second high-pressure plunger pump to inject supercritical CO2 fluid into the high-pressure extraction autoclave of the second channel. When the high-pressure extraction autoclave of the second channel reaches the set critical pressure and temperature, close the corresponding high-pressure valve and start static extraction; S2-5: Repeat the process of S2-1 to S2-4 to inject different formulated entrainers into the high-pressure extraction autoclaves of the remaining channels and start static extraction; If the entrainer formulations set between adjacent channels are the same, the process of S2-3 is not repeated when switching this channel; S2-6: After the extraction in the high-pressure extraction autoclave of the first channel is completed, switch the pipeline switching valve corresponding to the high-pressure extraction autoclave of the first channel to communicate with the gas-liquid separator, open the back pressure valve corresponding to the high-pressure extraction autoclave of the first channel and slowly reduce the pressure in the high-pressure extraction autoclave to atmospheric pressure. The first entrainer carrying the extract is separated from CO2 after passing through the gas-liquid separator, and then is collected into the entrainer collection bottle;S2-7: After the collection of the first formula entrainer corresponding to the first channel of the high-pressure extraction kettle is completed, switch the corresponding pipeline switching valve to communicate with the waste liquid discharge pipe, then turn on the first high-pressure plunger pump to wash the high-pressure extraction kettle of the first channel and its corresponding channel pipeline with the entrainer. After the washing is completed, switch the pipeline switching valve to communicate with the gas-liquid separator, remove the high-pressure extraction kettle of the first channel and wait for re-sampling; S2-8: Repeat the processes of S2-6 and S2-7 until the high-pressure extraction kettles of all channels complete extraction, entrainer collection and pipeline cleaning; then put a new batch of samples in the high-pressure extraction kettle array, and repeat steps S2-1 to S2-7 to perform multi-channel synchronous extraction of the new batch of samples; The conventional multi-channel single-time simultaneous extraction mode includes: S3-1: Before extraction, put samples in the high-pressure extraction kettles of each channel respectively, put the same formula entrainer in the entrainer tank respectively, inject supercritical CO2 fluid into the CO2 liquid storage tank, and turn on the temperature control device of the extraction kettle of each channel; S3-2: With the high-pressure valve array and the back pressure valve array of each channel in the normally closed state, sequentially open the high-pressure valves corresponding to the high-pressure extraction kettles of each channel, and inject the formula entrainer into the high-pressure extraction kettles of each channel through the first high-pressure plunger pump and the liquid path distributor in sequence, and then turn off the first high-pressure plunger pump and the liquid path distributor; then turn on the second high-pressure plunger pump to inject supercritical CO2 fluid into the high-pressure extraction kettles of each channel in sequence. When the high-pressure extraction kettles of each channel reach the set critical pressure and temperature in sequence, close the corresponding high-pressure valves and start static extraction with the first formula entrainer; S3-3: After the high-pressure extraction kettles of all channels start static extraction, open the purge gas control valve and the discharge port control valve, and start the rapid heating device to discharge the residual formula entrainer in the pipeline before the high-pressure valve array. After the residual formula entrainer is purified, close the purge gas control valve and the discharge port control valve, and start the rapid cooling device until the temperature drops to the acceptable temperature of the formula entrainer; S3-4: After extraction is completed, switch the pipeline switching valves of each channel to communicate with the gas-liquid separator, sequentially open the back pressure valves of each channel and slowly reduce the pressure in the high-pressure extraction kettle to atmospheric pressure. The formula entrainer carrying the extract in the high-pressure extraction kettles of each channel is separated from CO2 after passing through the gas-liquid separator, and then is sequentially collected into the entrainer collection bottle; S3-5: After all extraction cycles are completed, after taking out the samples in the high-pressure extraction kettles of each channel, switch the pipeline switching valves of each channel to be connected to the gas-liquid separator, then turn on the first high-pressure plunger pump and switch the flow path of the liquid path distributor to wash the extraction kettle array and its corresponding channel pipeline with the formula entrainer used in the next round of extraction; S3-6: Put a new batch of samples in the high-pressure extraction kettle array, and repeat S3-1 to S3-5 to perform multi-channel single-time simultaneous extraction of a new batch.

[0055] Specifically, the extraction of the multi-polarity component continuous supercritical extraction device of the present invention has three extraction modes, which can be selected according to experimental requirements. The three extraction modes are as follows: different samples are placed in different high-pressure extraction autoclaves, and each channel sequentially uses different formula entrainers for cyclic extraction, that is, the sequential continuous extraction mode of multi-polarity components of the sample; the same sample is placed in different high-pressure extraction autoclaves, and each channel uses different formula entrainers for synchronous extraction, that is, the multi-channel synchronous extraction mode of multi-polarity components of the sample; the high-pressure extraction autoclaves of each channel use the same formula entrainer for single extraction at the same time, that is, the conventional multi-channel single-time simultaneous extraction mode. The use of the multi-polarity component continuous supercritical extraction device of the present invention can target the polarity characteristics of the sample to select the extraction mode, greatly improving the extraction efficiency. In the sequential continuous extraction mode of multi-polarity components of the sample, the number of high-pressure extraction autoclaves depends on the ratio of the duration of a single extraction cycle to the duration of the mixed injection of the entrainer and supercritical CO2 fluid, so that in the sequential continuous extraction mode of multi-polarity components of the sample, after the mixed injection of the required formula entrainer and supercritical CO2 fluid into the high-pressure extraction autoclave of the last channel is completed, the static extraction in the high-pressure extraction autoclave of the first channel is just completed, improving the system operation efficiency. It should be noted that the usage method of the multi-polarity component continuous supercritical extraction device in the second embodiment is used for the usage of the multi-polarity component continuous supercritical extraction device described in the first embodiment. Therefore, the performance principle of the multi-polarity component continuous supercritical extraction device will not be elaborated here, and the unelaborated part can be referred to in the first embodiment.

[0056] In order to further elaborate on the technical solution of the present application to support the technical problem to be solved by the present application, a multi-polarity component continuous supercritical extraction device of the present invention is used below to extract dioxin-like compounds, organochlorine pesticides, clothianidin, and polychlorinated biphenyls in soil, specifically as shown in Examples 1 to 4.

[0057] Example 1

[0058] The conventional multi-channel single-time simultaneous extraction mode is adopted to perform conventional multi-channel single-time simultaneous extraction of dioxin-like compounds in standard soil under different temperature and pressure conditions, and the recovery rates of each component of dioxin-like compounds are tested, specifically including:

[0059] S3-1: Before extraction, a standard soil sample containing dioxin-like compounds is placed in a 20 mL stainless steel high-pressure extraction autoclave respectively, an entrainer of Formula A is placed in the entrainer tank, and supercritical CO2 fluid is injected into the CO2 liquid storage tank. The temperature control device of the extraction autoclave is turned on. The entrainer of Formula A is a volume ratio: n-hexane:dichloromethane:acetone = 4:4:7;

[0060] S3-2: With the high-pressure valve array and the back-pressure valve arrays of each channel in the normally closed state, open the high-pressure valve corresponding to the high-pressure extraction kettle of this channel, inject the Formulation A entrainer into the high-pressure extraction kettle of this channel through the first high-pressure piston pump and the liquid path distributor, and then close the first high-pressure piston pump and the liquid path distributor; then turn on the second high-pressure piston pump and inject supercritical CO2 fluid into the high-pressure extraction kettles of each channel in turn. When the pressure value and temperature in the high-pressure extraction kettle of this channel reach 12 Mpa and 40 °C, close the corresponding high-pressure valve, and start static extraction using the Formulation A entrainer. The extraction time is 20 min;

[0061] S3-3: After the high-pressure extraction kettle of this channel starts static extraction, open the purge gas control valve and the discharge port control valve, and start the rapid heating device to heat to 160 °C to remove the residual Formulation A entrainer in the pipeline before the high-pressure valve array. After the residual Formulation A entrainer is purified, close the purge gas control valve and the discharge port control valve, and start the rapid cooling device until the temperature drops below 60 °C;

[0062] S3-4: After extraction is completed, switch the pipeline switching valves of this channel to be connected to the gas-liquid separator, open the back-pressure valve corresponding to the channel and slowly reduce the pressure in the high-pressure extraction kettle to atmospheric pressure at a pressure drop rate of 5 MPa / min. The Formulation A entrainer carrying the extract in the high-pressure extraction kettles of each channel is separated from CO2 after passing through the gas-liquid separator, and then is sequentially collected into the entrainer collection bottle;

[0063] S3-5: After the extraction cycle is completed, after taking out the sample in the high-pressure extraction kettle of this channel, switch the pipeline switching valves of each channel to be connected to the gas-liquid separator, and then turn on the first high-pressure piston pump and switch the flow path of the liquid path distributor;

[0064] S3-6: Repeat S3-1 to S3-5, change the pressure and temperature in the high-pressure extraction kettle during static extraction for extraction, and the pressure and temperature combinations are 15 Mpa and 45 °C, 16 Mpa and 48 °C, 18 Mpa and 50 °C respectively. Measure the content of each component of the dioxin-like compounds in the Formulation A entrainer carrying the extract after extraction respectively, and obtain the recovery rates of each component of the dioxin-like compounds. The results are shown in Figure 7 。

[0065] Example 2

[0066] Adopt the conventional multi-channel single-time simultaneous extraction mode, conduct conventional multi-channel single-time simultaneous extraction of organochlorine pesticides in standard soil under different temperature and pressure conditions, and test the recovery rate of organochlorine pesticides, specifically including:

[0067] S3-1: Before extraction, place a standard soil sample containing organochlorine pesticides in a 20 mL stainless-steel high-pressure extraction autoclave respectively, place the entrainer of Formula B in the entrainer tank, inject supercritical CO2 fluid into the liquid storage tank of CO2, and turn on the temperature control device of the extraction autoclave. The entrainer of Formula B is in a volume ratio of n-hexane: acetone = 1:1;

[0068] S3-2: With the high-pressure valve array and the back-pressure valve array of each channel in a normally closed state, open the high-pressure valve corresponding to the high-pressure extraction autoclave of this channel, inject the entrainer of Formula A into the high-pressure extraction autoclave of this channel through the first high-pressure plunger pump and the liquid path distributor, and close the first high-pressure plunger pump and the liquid path distributor; then turn on the second high-pressure plunger pump and inject supercritical CO2 fluid into the high-pressure extraction autoclaves of each channel in turn. When the pressure value and temperature in the high-pressure extraction autoclave of this channel reach 12 Mpa and 55 °C, close the corresponding high-pressure valve, and start static extraction using the entrainer of Formula B. The extraction time is 15 min;

[0069] S3-3: After the high-pressure extraction autoclave of this channel starts static extraction, open the purge gas control valve and the discharge port control valve, and start the rapid heating device to heat to 160 °C to remove the entrainer of Formula B remaining in the pipeline before the high-pressure valve array. After the remaining entrainer of Formula B is purified, close the purge gas control valve and the discharge port control valve, and start the rapid cooling device until the temperature drops below 60 °C;

[0070] S3-4: After extraction is completed, switch the pipeline switching valves of this channel to be connected to the gas-liquid separator, open the back-pressure valve corresponding to the channel and slowly reduce the pressure in the high-pressure extraction autoclave to atmospheric pressure at a pressure drop rate of 5 MPa / min. The entrainer of Formula B carrying the extract in the high-pressure extraction autoclaves of each channel is separated from CO2 after passing through the gas-liquid separator, and then is collected into the entrainer collection bottle in turn;

[0071] S3-5: After the extraction cycle is completed, after taking out the sample in the high-pressure extraction autoclave of this channel, switch the pipeline switching valves of each channel to be connected to the gas-liquid separator, and then turn on the first high-pressure plunger pump and switch the flow path of the liquid path distributor;

[0072] S3-6: Repeat S3-1 to S3-5, change the pressure in the high-pressure extraction autoclave during static extraction for extraction, the pressures are 14 Mpa, 16 Mpa, 18 Mpa respectively, and measure the content of organochlorine pesticides in the entrainer of Formula B carrying the extract after extraction to obtain the recovery rate of organochlorine pesticides. The results are shown in Figure 8 。

[0073] Example 3

[0074] Using the conventional multi-channel single-shot simultaneous extraction mode, imidaclothizol in standard soil was respectively subjected to conventional multi-channel single-shot simultaneous extraction under different temperature and pressure conditions, and the recovery rate of imidaclothizol was tested. Specifically, it includes:

[0075] S3-1: Before extraction, put the standard soil sample containing imidaclothizol into a 20 mL stainless steel high-pressure extraction autoclave respectively, put the entrainer of Formula C into the entrainer tank, inject supercritical CO2 fluid into the CO2 liquid storage tank, and turn on the temperature control device of the extraction autoclave. The entrainer of Formula C is a volume ratio: acetonitrile: acetone = 1:1;

[0076] S3-2: With the high-pressure valve array and the back pressure valve array of each channel in the normally closed state, open the high-pressure valve corresponding to the high-pressure extraction autoclave of this channel, inject the entrainer of Formula C into the high-pressure extraction autoclave of this channel through the first high-pressure plunger pump and the liquid path distributor, and close the first high-pressure plunger pump and the liquid path distributor; then turn on the second high-pressure plunger pump and inject supercritical CO2 fluid into the high-pressure extraction autoclave of each channel in turn. When the pressure value and temperature in the high-pressure extraction autoclave of this channel reach 15 Mpa and 43 °C, close the corresponding high-pressure valve and start static extraction with the entrainer of Formula C. The extraction time is 15 min;

[0077] S3-3: After the high-pressure extraction autoclave of this channel starts static extraction, open the purge gas control valve and the discharge port control valve, and start the rapid heating device to heat to 160 °C to remove the residual entrainer of Formula C in the pipeline before the high-pressure valve array. After the residual entrainer of Formula C is purified, close the purge gas control valve and the discharge port control valve, and start the rapid cooling device until the temperature drops below 60 °C;

[0078] S3-4: After extraction is completed, switch the pipeline switching valves of this channel to be connected to the gas-liquid separator, open the corresponding back pressure valve of the channel and slowly reduce the pressure in the high-pressure extraction autoclave to atmospheric pressure at a pressure drop rate of 5 MPa / min. The entrainer of Formula C carrying the extract in the high-pressure extraction autoclave of each channel is separated from CO2 after passing through the gas-liquid separator and then is sequentially collected into the entrainer collection bottle;

[0079] S3-5: After the extraction cycle is completed, after taking out the sample in the high-pressure extraction autoclave of this channel, switch the pipeline switching valves of each channel to be connected to the gas-liquid separator, then turn on the first high-pressure plunger pump and switch the flow path of the liquid path distributor;

[0080] S3-6: Repeat S3-1 to S3-5, change the pressure and temperature in the high-pressure extraction kettle during static extraction for extraction, and the pressure and temperature combinations are 15 Mpa and 47 °C, 14 Mpa and 45 °C, 16 Mpa and 45 °C, 15 Mpa and 45 °C respectively. Measure the content of imidacloprid in the C-formula entrainer carrying the extract after extraction respectively, and obtain the recovery rate of imidacloprid. The results are shown in Figure 9 .

[0081] Figures 7 - 9 Dioxin-like compounds, organochlorine pesticides, and imidacloprid are represented by PCDD / Fs, OCPs, and IMZ respectively.

[0082] It can be seen from Figures 7 - 9 that when the conventional multi-channel single-time simultaneous extraction mode of the multi-polar component continuous supercritical extraction device of the present invention is used to extract dioxin-like compounds, organochlorine pesticides, and imidacloprid in standard soil respectively, the recovery rates of each component of dioxin-like compounds are all higher than 40%, and the highest is above 90%. The recovery rates of organochlorine pesticides are all higher than 70%, and the recovery rates of imidacloprid are all higher than 60%. The extraction recovery rates of these three substances are all higher than those of the prior art.

[0083] Example 4

[0084] Use the sequential continuous extraction mode of multi-polar components of the sample to sequentially extract dioxin-like compounds, organochlorine pesticides, imidacloprid, and polychlorinated biphenyls in the standard soil respectively, and test the recovery rates of dioxin-like compounds, organochlorine pesticides, imidacloprid, and polychlorinated biphenyls. Specifically, it includes:

[0085] S1-1: Before extraction, put standard soil samples containing dioxin-like compounds, organochlorine pesticides, imidacloprid, and polychlorinated biphenyls into a 20 mL stainless steel high-pressure extraction kettle respectively, put A-formula entrainer, B-formula entrainer, and C-formula entrainer into the entrainer tank respectively, inject supercritical CO2 fluid into the CO2 liquid storage tank, and turn on the temperature control device of the extraction kettle in this channel; the A-formula entrainer is a volume ratio: n-hexane:dichloromethane:acetone = 4:4:7, the B-formula entrainer is a volume ratio: n-hexane:acetone = 1:1, and the C-formula entrainer is a volume ratio: acetonitrile:acetone = 1:1;

[0086] S1-2: With the high-pressure valve array and the corresponding back-pressure valve array in the normally closed state, open the high-pressure valve corresponding to the high-pressure extraction kettle of this channel, inject 5 mL of entrainer of formulation A into the high-pressure extraction kettle of this channel through the first high-pressure plunger pump and the liquid path distributor, and close the first high-pressure plunger pump and the liquid path distributor; then open the second high-pressure plunger pump to inject supercritical CO2 fluid into the high-pressure extraction kettle of this channel. When the pressure and temperature in the high-pressure extraction kettle reach 15 MPa and 45 °C respectively, close the corresponding high-pressure valve and start static extraction with the entrainer of formulation A for 20 minutes;

[0087] S1-3: After the high-pressure extraction kettle of this channel starts static extraction, open the purge gas control valve and the discharge port control valve, and start the rapid heating device to heat to 160 °C to purge the residual entrainer of formulation A in the pipeline before the high-pressure valve array. After the residual entrainer of formulation A is purified, close the purge gas control valve and the discharge port control valve, and start the rapid cooling device until the temperature drops below 60 °C;

[0088] S1-4: After extraction is completed, switch all the pipeline switching valves of this channel to connect with the gas-liquid separator, open the corresponding back-pressure valve of the channel and slowly reduce the pressure in the high-pressure extraction kettle to atmospheric pressure at a pressure drop rate of 5 MPa / min. The first formulation entrainer carrying the extract in the high-pressure extraction kettles of each channel is separated from CO2 after passing through the gas-liquid separator and then is successively collected into the entrainer collection bottles;

[0089] S1-5: Repeat S1-1 to S1-4 without taking out the samples in the high-pressure extraction kettle, and use the entrainer of formulation B for extraction. The entrainer of formulation B is subjected to static extraction for 15 minutes at 18 MPa and 55 °C and the entrainer is successively collected; then repeat S1-1 to S1-4 again without taking out the samples in the high-pressure extraction kettle of this channel, and use the entrainer of formulation C for extraction. The entrainer of formulation C is subjected to static extraction for 15 minutes at 14 MPa and 60 °C and the entrainer is successively collected to complete the extraction cycle of the three formulation entrainers for the samples in the high-pressure extraction kettle;

[0090] S1-6: After all extraction cycles are completed, take out the samples in the high-pressure extraction kettle of this channel, then switch all the pipeline switching valves of this channel to connect with the gas-liquid separator, then turn on the first high-pressure plunger pump and switch the flow path of the liquid path distributor, and use the entrainer of the formulation for the next extraction cycle to clean the extraction kettle array and its corresponding channel pipeline.

[0091] Detect the contents of dioxin-like compounds, organochlorine pesticides, imidaclothiz, and polychlorinated biphenyls in the entrainer collection bottle, and combine with the contents of dioxin-like compounds, organochlorine pesticides, imidaclothiz, and polychlorinated biphenyls in the standard soil to obtain the recovery rates of dioxin-like compounds, organochlorine pesticides, imidaclothiz, and polychlorinated biphenyls. The results are shown in Figure 10 .

[0092] Replace the standard soil in Example 1 with actual soil containing dioxin-like compounds, organochlorine pesticides, imidaclothiz, and polychlorinated biphenyls, and perform extraction using the extraction mode steps of Example 1. Before extraction, determine the contents of dioxin-like compounds, organochlorine pesticides, imidaclothiz, and polychlorinated biphenyls in the actual soil. After extraction, detect the contents of dioxin-like compounds, organochlorine pesticides, imidaclothiz, and polychlorinated biphenyls in the entrainer collection bottle, and combine with the contents of dioxin-like compounds, organochlorine pesticides, imidaclothiz, and polychlorinated biphenyls in the actual soil determined before extraction to obtain the recovery rates of dioxin-like compounds, organochlorine pesticides, imidaclothiz, and polychlorinated biphenyls. The results are shown in Figure 11 .

[0093] Figure 10 and Figure 11 The dioxin-like compounds, organochlorine pesticides, imidaclothiz, and polychlorinated biphenyls in are represented by PCDD / Fs, OCPs, IMZ, and PCBs respectively.

[0094] From Figure 10 and Figure 11 it can be seen that for the standard soil sample, the sample multi-polar component continuous supercritical extraction device of the present invention has good extraction effects on the sample multi-polar components. In the sequential continuous extraction mode of the sample multi-polar components, the recovery rates of dioxin-like compounds, organochlorine pesticides, imidaclothiz, and polychlorinated biphenyls are all above 80%. For the actual soil sample, in the case of complex components in the actual soil, the recovery rate of dioxin-like compounds is higher than 70%, the recovery rate of organochlorine pesticides is higher than 90%, the recovery rate of imidaclothiz is higher than 80%, and the recovery rate of polychlorinated biphenyls is higher than 25%. The recovery rate is significantly higher than that in the prior art, and has remarkable effects.

[0095] The preferred specific embodiments of the present invention have been described in detail above. It should be understood that those of ordinary skill in the art can make many modifications and variations according to the concept of the present invention without creative work. Therefore, all technical solutions that can be obtained by those skilled in the art in the technical field of the present invention based on the concept of the present invention through logical analysis, reasoning, or limited experiments on the basis of the prior art should be within the protection scope determined by the claims.

Claims

1. A continuous supercritical extraction device for multi-polar components of a sample, characterized in that, The continuous supercritical extraction device for multi-polar components of the sample includes: An entrainer delivery unit (1), which includes a number of entrainer tanks (11) and a liquid path assembly (12). One end of each entrainer tank (11) is connected to one end of the liquid path assembly (12) through a correspondingly adapted entrainer pipeline. A supercritical CO2 fluid delivery unit (2), one end of which is connected to the other end of the liquid path assembly (12). A pipeline cleaning unit (3), one end of which is connected to the connection end of the supercritical CO2 fluid delivery unit (2) and the liquid path assembly (12). A multi-channel extraction unit (4), one end of which is connected to the other end of the pipeline cleaning unit (3). A gas-liquid separation unit (5), one end of which is connected to the other end of the multi-channel extraction unit (4).

2. The continuous supercritical extraction device for multi-polar components of a sample according to claim 1, wherein, The liquid path assembly (12) includes: A liquid path distributor (121), and each entrainer pipeline is connected to the inlet end of the liquid path distributor (121). Two liquid pipelines, one end of one liquid pipeline is connected to the outlet end of the liquid path distributor (121). A first high-pressure plunger pump (122), the inlet end of which is connected to the other end of one liquid pipeline, and the outlet end of the first high-pressure plunger pump (122) is connected to one end of the other liquid pipeline. A first check valve (123), which is arranged in the middle of the other liquid pipeline. Wherein, the other end of the other liquid pipeline is connected to one end of the supercritical CO2 fluid delivery unit (2); one end of the pipeline cleaning unit (3) is connected to the connection end of the other liquid pipeline and the supercritical CO2 fluid delivery unit (2).

3. The continuous supercritical extraction device for multi-polar components of a sample according to claim 2, characterized in that, The supercritical CO2 fluid delivery unit (2) includes: A CO2 liquid storage tank (21); Two CO2 fluid delivery pipelines, one end of one CO2 fluid delivery pipeline is connected to one end of the CO2 liquid storage tank (21). A pre-pump cooling device (22), which is arranged around one CO2 fluid delivery pipeline. A second high-pressure plunger pump (23), the inlet end of which is connected to the other end of one CO2 fluid delivery pipeline, and the outlet end of the second high-pressure plunger pump (23) is connected to one end of the other CO2 fluid delivery pipeline. A second check valve (24), which is arranged in the middle of the other CO2 fluid delivery pipeline. Wherein, the other end of the other CO2 fluid delivery pipeline is connected to the other end of the other liquid pipeline, and one end of the pipeline cleaning unit (3) is connected to the connection end of the other CO2 fluid delivery pipeline and the other liquid pipeline.

4. The continuous supercritical extraction device for multi-polar components of a sample according to claim 3, characterized in that, The pipeline cleaning unit (3) includes: A purge gas source tank (31); A purge pipeline, one end of the purge pipeline is connected to the purge gas source tank (31); A purge gas control valve (32), the purge gas control valve (32) is arranged on the purge pipeline; A pipeline temperature control module (33), the first end of the pipeline temperature control module (33) is connected to the other end of the purge pipeline; A purge discharge port control valve (34), the purge discharge port control valve (34) is arranged at the second end of the pipeline temperature control module (33); Wherein, the connection end of the pipeline temperature control module (33) and the purge pipeline is connected to the connection end of the other CO2 fluid delivery pipeline and the other liquid pipeline; One end of the multi-channel extraction unit (4) is connected to the third end of the pipeline temperature control module (33).

5. The continuous supercritical extraction device for multi-polar components of a sample according to claim 4, characterized in that, The pipeline temperature control module (33) includes: A number of high thermal conductivity and high pressure resistant pipelines (331), each of the high thermal conductivity and high pressure resistant pipelines (331) has a T-shaped structure, and the first end of each high thermal conductivity and high pressure resistant pipeline is sequentially connected to the second end of an adjacent high thermal conductivity and high pressure resistant pipeline to form a high thermal conductivity and high pressure resistant multi-pass pipeline; The first end of a high thermal conductivity and high pressure resistant pipeline (331) at one end of the high thermal conductivity and high pressure resistant multi-pass pipeline is connected to the other end of the purge pipeline, and the second end of a high thermal conductivity and high pressure resistant pipeline (331) at the other end of the high thermal conductivity and high pressure resistant multi-pass pipeline is provided with the purge discharge port control valve (34); A number of rapid heating devices (332), a number of the rapid heating devices (332) are distributed corresponding to a number of the high thermal conductivity and high pressure resistant pipelines (331), and the heating component of each rapid heating device (332) is arranged outside the corresponding high thermal conductivity and high pressure resistant pipeline (331); An in-pipe temperature sensor (333), the detection end of the in-pipe temperature sensor (333) is located inside the main pipeline of the high thermal conductivity and high pressure resistant multi-pass pipeline; A number of rapid cooling devices (334), a number of the rapid cooling devices (334) are distributed corresponding to a number of the high thermal conductivity and high pressure resistant pipelines (331), and the cooling component of each rapid cooling device (334) is arranged outside the corresponding high thermal conductivity and high pressure resistant pipeline (331), and the cooling component of a rapid cooling device (334) outside the same high thermal conductivity and high pressure resistant pipeline (331) is arranged adjacent and spaced from the heating component of a rapid heating device (332); Wherein, the connection end of a high thermal conductivity and high pressure resistant pipeline (331) at one end of the high thermal conductivity and high pressure resistant multi-pass pipeline and the purge pipeline is connected to the connection end of the other CO2 fluid delivery pipeline and the other liquid pipeline; The third end of each high thermal conductivity and high pressure resistant pipeline (331) is connected to one end of the multi-channel extraction unit (4).

6. The continuous supercritical extraction device for multi-polar components of a sample according to claim 5, wherein, The multi-channel extraction unit (4) includes: High-pressure valve array, the high-pressure valve array assembly includes a number of high-pressure valves (41), and the number of the high-pressure valves (41) is distributed in one-to-one correspondence with a number of the high-thermal-conductivity and high-pressure-resistant pipelines (331). One end of each high-pressure valve (41) is connected to the third end of a corresponding high-thermal-conductivity and high-pressure-resistant pipeline (331); High-pressure extraction kettle array, the high-pressure extraction kettle array includes a number of high-pressure extraction kettles (42), and the number of the high-pressure extraction kettles (42) is distributed in one-to-one correspondence with a number of the high-pressure valves (41). The inlet end of each high-pressure extraction kettle (42) is connected to the other end of a corresponding high-pressure valve (41); Extraction kettle temperature control module (43), the extraction kettle temperature control module includes a number of extraction kettle temperature control devices, and the number of the extraction kettle temperature control devices is distributed in one-to-one correspondence with a number of the high-pressure extraction kettles (42). Each extraction kettle temperature control device is located on the periphery of a corresponding high-pressure extraction kettle (42); Back-pressure valve array, the back-pressure valve array includes a number of back-pressure valves (44), and the number of the back-pressure valves (44) is distributed in one-to-one correspondence with a number of the high-pressure extraction kettles (42). One end of each back-pressure valve (44) is connected to the outlet end of a corresponding high-pressure extraction kettle (42).

7. The continuous supercritical extraction device for multi-polar components of a sample according to claim 6, characterized in that, The gas-liquid separation unit (5) includes: A number of pipeline switching valves (51), and the number of the pipeline switching valves (51) is distributed in one-to-one correspondence with a number of the back-pressure valves (44). The first end of each pipeline switching valve (51) is connected to the other end of a corresponding back-pressure valve (44); A number of waste liquid discharge pipes (52), and the number of the waste liquid discharge pipes (52) is distributed in one-to-one correspondence with a number of the pipeline switching valves (51). One end of each waste liquid discharge pipe (52) is connected to the second end of a corresponding pipeline switching valve (51); Gas-liquid separator array, the gas-liquid separator array includes a number of gas-liquid separators (53), and the number of the gas-liquid separators (53) is distributed in one-to-one correspondence with a number of the pipeline switching valves (51). The inlet of each gas-liquid separator (53) is connected to the third end of a corresponding pipeline switching valve (51); A number of entrainer collection bottles (54), and the number of the entrainer collection bottles (54) is distributed in one-to-one correspondence with a number of the gas-liquid separators (53). The inlet of each entrainer collection bottle (54) is connected to the outlet of a corresponding gas-liquid separator (53).

8. A method for using a continuous supercritical extraction device for multi-polar components of a sample, which is used for the use of a continuous supercritical extraction device for multi-polar components of a sample as described in any one of claims 1 to 7, characterized in that, The usage method includes the sequential continuous extraction mode of sample multi-polar components, or the multi-channel synchronous extraction mode of sample multi-polar components, or the conventional multi-channel single-time simultaneous extraction mode; The sequential continuous extraction mode of the sample multi-polar components includes: S1-1: Before extraction, different samples are respectively placed in the high-pressure extraction kettles of each channel, different formula entrainers are respectively placed in the entrainer tanks, supercritical CO2 fluid is injected into the CO2 liquid storage tank, and the extraction kettle temperature control devices of each channel are turned on; S1-2: With the high-pressure valve arrays and the back-pressure valve arrays of each channel in the normally closed state, the high-pressure valves corresponding to the high-pressure extraction autoclaves of each channel are sequentially opened, and the first formulation entrainer is sequentially injected into the high-pressure extraction autoclaves of each channel through the first high-pressure plunger pump and the liquid path distributor, and the first high-pressure plunger pump and the liquid path distributor are closed; then the second high-pressure plunger pump is turned on to sequentially inject supercritical CO2 fluid into the high-pressure extraction autoclaves of each channel. When the high-pressure extraction autoclaves of each channel reach the set critical pressure and temperature in sequence, the corresponding high-pressure valves are closed, and static extraction is started using the first formulation entrainer; S1-3: After the high-pressure extraction autoclaves of all channels start static extraction, the purge gas control valve and the discharge port control valve are opened, and the rapid heating device is started to discharge the remaining first formulation entrainer in the pipeline in front of the high-pressure valve array. After the remaining first formulation entrainer is purified, the purge gas control valve and the discharge port control valve are closed, and the rapid cooling device is started until the temperature drops to an acceptable temperature for injecting the next formulation entrainer; S1-4: After the extraction is completed, the pipeline switching valves of each channel are switched to be connected to the gas-liquid separator. The back-pressure valves of each channel are sequentially opened and the pressure in the high-pressure extraction autoclave is slowly reduced to atmospheric pressure. The first formulation entrainer carrying the extract in the high-pressure extraction autoclaves of each channel is separated from CO2 after passing through the gas-liquid separator, and then is sequentially collected into the entrainer collection bottle; S1-5: Repeat S1-1 to S1-4 without taking out the samples in the high-pressure extraction autoclaves of each channel, use the second formulation entrainer for extraction, and then repeat S1-1 to S1-4 without taking out the samples in the high-pressure extraction autoclaves of each channel, use the third formulation entrainer for extraction until the samples in the high-pressure extraction autoclaves of each channel complete the extraction cycle of the set several formulation entrainers; S1-6: After all the extraction cycles are completed, after taking out the samples in the high-pressure extraction autoclaves of each channel, the pipeline switching valves of each channel are switched to be connected to the gas-liquid separator, then the first high-pressure plunger pump is turned on and the flow path of the liquid path distributor is switched, and the extraction autoclave array and its corresponding channel pipelines are cleaned with the formulation entrainer used in the next extraction cycle; S1-7: Put a new batch of samples in the high-pressure extraction autoclaves of each channel, repeat S1-1 to S1-6, and perform sequential continuous extraction of multi-polar components of the new batch of samples.

9. The usage method of a continuous supercritical extraction device for multi-polar components of a sample as claimed in claim 8, characterized in that, The multi-channel synchronous extraction mode of the multi-polar components of the sample includes: S2-1: Before extraction, the same samples are respectively placed in the high-pressure extraction autoclaves of each channel, different formulation entrainers are respectively placed in the entrainer tanks, supercritical CO2 fluid is injected into the CO2 liquid storage tank, and the temperature control device of the extraction autoclave of each channel is turned on; S2-2: With the high-pressure valve arrays and the back-pressure valve arrays of each channel in the normally closed state, open the high-pressure valve corresponding to the high-pressure extraction kettle of the first channel, inject the first formulation entrainer into the high-pressure extraction kettle of the first channel through the first high-pressure plunger pump and the liquid path distributor, and close the first high-pressure plunger pump and the liquid path distributor; then turn on the second high-pressure plunger pump to inject supercritical CO2 fluid into the high-pressure extraction kettle of the first channel. When the high-pressure extraction kettle of the first channel reaches the set critical pressure and temperature, close the corresponding high-pressure valve and start static extraction; S2-3: After the sample in the high-pressure extraction kettle of the first channel starts to be extracted, open the purge gas control valve and the discharge port control valve, and start the rapid heating device to discharge the remaining first formulation entrainer in the pipeline before the high-pressure valve array. After the remaining first formulation entrainer is purified, close the purge gas control valve and the discharge port control valve, and start the rapid cooling device until the temperature drops to an acceptable temperature for injecting the next formulation entrainer; S2-4: Open the high-pressure valve corresponding to the high-pressure extraction kettle of the second channel, inject the second formulation entrainer into the high-pressure extraction kettle of the second channel through the first high-pressure plunger pump and the liquid path distributor, and close the first high-pressure plunger pump and the liquid path distributor; then turn on the second high-pressure plunger pump to inject supercritical CO2 fluid into the high-pressure extraction kettle of the second channel. When the high-pressure extraction kettle of the second channel reaches the set critical pressure and temperature, close the corresponding high-pressure valve and start static extraction; S2-5: Repeat the process of S2-1 to S2-4 to inject different formulation entrainers into the high-pressure extraction kettles of the remaining channels and start static extraction; if the entrainer formulations set between adjacent channels are the same, do not repeat the process of S2-3 when switching this channel; S2-6: After the extraction in the high-pressure extraction kettle of the first channel is completed, switch the pipeline switching valve corresponding to the high-pressure extraction kettle of the first channel to communicate with the gas-liquid separator, open the back-pressure valve corresponding to the high-pressure extraction kettle of the first channel and slowly reduce the pressure in the high-pressure extraction kettle to atmospheric pressure. The first entrainer carrying the extract is separated from CO2 after passing through the gas-liquid separator and then collected in the entrainer collection bottle; S2-7: After the collection of the first formulation entrainer in the corresponding channel of the high-pressure extraction kettle of the first channel is completed, switch the corresponding pipeline switching valve to communicate with the waste liquid discharge pipe, then turn on the first high-pressure plunger pump to wash the high-pressure extraction kettle of the first channel and its corresponding channel pipeline with the entrainer. After the washing is completed, switch the pipeline switching valve to communicate with the gas-liquid separator, remove the high-pressure extraction kettle of the first channel and wait for re-sampling; S2-8: Repeat the processes of S2-6 and S2-7 until the extraction, entrainer collection, and pipeline cleaning of all high-pressure extraction kettles are completed; then put a new batch of samples in the high-pressure extraction kettle array and repeat the steps of S2-1 to S2-7 to perform multi-channel synchronous extraction of the new batch of samples.

10. The method for using a continuous supercritical extraction device for multi-polar components of a sample according to claim 8, characterized in that, The described conventional multi-channel single-time simultaneous extraction mode includes: S3-1: Before extraction, place samples in the high-pressure extraction autoclaves of each channel respectively, place the same-formula entrainer in the entrainer tanks respectively, inject supercritical CO2 fluid into the CO2 liquid storage tank, and turn on the temperature control device of the extraction autoclave of each channel; S3-2: With the high-pressure valve arrays and the back-pressure valve arrays of each channel in a normally closed state, sequentially open the high-pressure valves corresponding to the high-pressure extraction autoclaves of each channel, inject the formula entrainer into the high-pressure extraction autoclaves of each channel in sequence through the first high-pressure plunger pump and the liquid path distributor, and close the first high-pressure plunger pump and the liquid path distributor; then turn on the second high-pressure plunger pump to inject supercritical CO2 fluid into the high-pressure extraction autoclaves of each channel in sequence. After the high-pressure extraction autoclaves of each channel reach the set critical pressure and temperature in sequence, close the corresponding high-pressure valves and start static extraction with the first formula entrainer; S3-3: After the high-pressure extraction autoclaves of all channels start static extraction, open the purge gas control valve and the discharge port control valve, and start the rapid heating device to discharge the residual formula entrainer in the pipeline before the high-pressure valve array. After the residual formula entrainer is purified, close the purge gas control valve and the discharge port control valve, and start the rapid cooling device until the temperature drops to the acceptable temperature of the formula entrainer; S3-4: After extraction is completed, switch the pipeline switching valves of each channel to communicate with the gas-liquid separator, sequentially open the back-pressure valves of each channel and slowly reduce the pressure in the high-pressure extraction autoclave to atmospheric pressure. The formula entrainer carrying the extract in the high-pressure extraction autoclaves of each channel is separated from CO2 after passing through the gas-liquid separator and then is sequentially collected into the entrainer collection bottles; S3-5: After all extraction cycles are completed, after taking out the samples in the high-pressure extraction autoclaves of each channel, switch the pipeline switching valves of each channel to be connected to the gas-liquid separator, then turn on the first high-pressure plunger pump and switch the flow path of the liquid path distributor, and clean the extraction autoclave array and its corresponding channel pipelines with the formula entrainer used in the next extraction round; S3-6: Place a new batch of samples in the high-pressure extraction autoclave array, repeat S3-1 to S3-5 to perform a new batch of multi-channel single-time simultaneous extraction.

Images