CN102445503B - Combined analytic device for subcritical fluid extraction-liquid chromatography (LC) - Google Patents

Abstract

The invention discloses a subcritical fluid extraction-liquid chromatography coupled analysis device, which comprises: R134a storage tank, two purifiers, a condenser, a high-pressure pump, a heat exchanger, three preheaters, an extraction kettle, Separator, restrictor, six-way valve, cleaning pump, solid phase trap, LC pump, LC column, UV detector, data collector, flow meter, coarse filter, two purifiers, compressor, Six pressure gauges, two pressure control monitors, seven temperature control monitors, transfer pump, solvent buffer tank, two-way valve, four-way valve, two one-way valves, restrictor valve, fifteen regulating valves, exhaust valve, two waste bottles. The extraction kettle is sealed with a sealing ring, the separation kettle is sealed with a sealing ring, and the outlet of the extraction kettle is connected with the inlet of the separation kettle and the SFE-LC interface through a four-way valve. The device is suitable for the analysis of hormone residues in animals, feed, chemical products and cosmetics. The analysis time is short, the amount of chemical reagents is small, the operation is convenient, the subcritical fluid can be recycled, and the energy consumption is low. It can achieve the purpose of fast and efficient detection.

Description

A subcritical fluid extraction-liquid chromatography coupled analysis device

technical field

The present invention relates to a subcritical fluid extraction-liquid chromatographic analysis device, to be precise, it uses R134a fluid in a subcritical state as an extraction agent to extract residual sex hormones from a sample, and then conducts online or offline detection. .

Background technique

Due to the long-term use of sex hormones, it is common for drug residues to exceed the standard, and the quality problems of food and cosmetics have become increasingly prominent. Drug residues have directly affected the quality of products and the health of consumers. Therefore, adding sex hormones to animal feed, food and cosmetics is currently strictly prohibited worldwide, and its detection methods have also matured accordingly.

With the continuous optimization and perfection of modern chromatographic technology and chromatographic mass spectrometry technology, the detection of sex hormone residues is becoming more and more simplified. Usually, it only takes a few minutes to tens of minutes to analyze a sample, and the sample treatment before analysis It takes hours. Therefore, sample pretreatment technology has increasingly become the key and development focus in the analysis of sex hormone residues, and it is also the main content of this project. The methods for the analysis of sex hormone residues at home and abroad are still in the stage of traditional extraction methods, including liquid-liquid extraction (LLE), accelerated solvent extraction (ASE), solid phase extraction (SPE) and supercritical CO ₂ extraction. However, these methods are time-consuming and labor-intensive, especially the traditional organic solvent extraction method, which consumes a large amount of organic solvents and causes serious pollution, which is not conducive to the health of operators. Although supercritical CO ₂ extraction has a series of significant advantages such as high efficiency, good selectivity, and environmental protection, it also has disadvantages such as high operating pressure, high equipment cost, and difficulty in popularization and application.

Because 1,1,1,2-tetrafluoroethane (R134a) has the characteristics of easy access to critical conditions (Tc=101.1°C, Pc=4.06MPa), low toxicity, inertness, non-flammability and no damage to the ozone layer, it has become a sub- First choice for critical fluids. According to the literature search, so far there is no report on the use of subcritical R134a extraction as a pretreatment technology for the analysis of sex hormone residues, and there is no literature on online detection, and there is no corresponding device.

Contents of the invention

The invention discloses a subcritical fluid extraction-liquid chromatography coupled analysis device, which has the advantages of low temperature, non-toxicity, simple process, convenient operation, realizes separation during the extraction process, has no adverse effects on production personnel and the environment, and solves the problem of Problems such as long analysis time, environmental pollution, and unfavorable health of operators in the prior art are eliminated.

The technical solution adopted by the present invention to solve its technical problems is:

A subcritical fluid R134a extraction-liquid chromatography analysis device, which includes: R134a storage tank (1), first purifier (2), condenser (3), high pressure pump (4), heat exchanger ( 5), preheater (6), extraction kettle (7), separation kettle (8), restrictor (9), six-way valve (10), cleaning pump (11), solid phase trap (12) , LC pump (13), LC chromatographic column (14), UV detector (15), data collector (16), flow meter (17), coarse filter (18), second purifier (19), compression machine (20), characterized in that: the R134a storage tank (1) is equipped with a pressure gauge, and there is a first regulating valve (22) and a second Three regulating valves (24), a temperature regulator (26) and a fourth regulating valve (27) are arranged between the condenser (3) and the high pressure pump (4), one end of the heat exchanger (5) and the solvent Buffer tank (28) is connected, and temperature control indicator (35), one-way valve (36) and the 6th regulating valve (37) are arranged on the passage of described preheater (6) to extraction kettle, and described extraction kettle (7 ) is equipped with a temperature control display (39), a pressure control display (40), a pressure gauge (41) and the seventh regulating valve (38), and the separation kettle is equipped with a pressure gauge (46), a pressure control display (47), Temperature control display (48) and the twelfth regulating valve (53), the ninth regulating valve (43), four-way valve (44), pressure Table (49) and the tenth regulating valve (45), one end of the restrictor (9) is connected to the two-way valve, one end is connected to the six-way valve (10), and one end is connected to the solid phase trap (12), The other end of the two-way valve connected to one end of the throttle (9) is connected to the eighth regulating valve (42), and the six-way valve (10) is connected to the throttle (9), cleaning pump (11), LC pump (13), LC chromatographic column (14), solid phase catcher (12) and waste liquid bottle (55) link to each other, there is a thirteenth adjustment between the six-way valve (10) and waste liquid bottle (55) Valve (56), the cleaning pump (11) is connected to the six-way valve (10), one end of the solid phase trap (12) is connected to the throttle (9), and one end is connected to the six-way valve (10) , the LC pump is connected to the six-way valve (10), one end of the LC chromatographic column (14) is connected to the six-way valve (10), and one end is connected to the UV detector (15), and the UV detector (15) One end is connected to the data collector (16), one end is connected to the waste liquid bottle (54), and one end is connected to the LC chromatographic column (14), and the data collector (16) is connected to the UV detector (15), and the flow A pressure gauge (60) and a fifteenth regulating valve (59) are arranged between the meter (17) and the six-way valve (10), and a pressure gauge (60) is arranged between the flow meter (17) and the separation tank (8). And the fourteenth regulating valve (57), there is a second purifier (19) between the coarse filter (18) and the compressor (20) , the passage from the compressor (20) to the high-pressure pump (4) is connected with a pressure gauge (61), a sixteenth regulating valve (62), an exhaust valve (63), a one-way valve (25) and a fourth Regulating valve (27), the passage from the compressor (20) to R134a (1) is connected with a pressure gauge (61), a sixteenth regulating valve (62), an exhaust valve (63), a second regulating valve ( 23) and the first regulating valve (22). The extraction kettle (7) has a jacket, and a pump (29), a preheater (32), a temperature control display (33) and a fifth regulating valve (34) are arranged between one end of the jacket and the solvent buffer tank (28). ), the other end links to each other with the separation kettle (8). The separation kettle (8) has a jacket, and the passage from the jacket of the separation kettle (8) to the jacket of the extraction kettle has a preheater (50), a temperature control display (52) and an eleventh regulating valve (51). The compressor (20) has a jacket, solvent pipes are connected at both ends of the jacket, and a restrictor (31) and a temperature controller (30) are arranged between one end of the jacket and the heat exchanger (5). The extraction kettle (7) is sealed with a sealing ring, the separation kettle (8) is sealed with a sealing ring, and the outlet seal of the extraction kettle (7) is connected with the (8) inlet of the separation kettle. This device can be used for both on-line monitoring and off-line detection. When performing online detection, the tenth regulating valve (45) is closed, and when performing offline detection, the eighth regulating valve (42) is closed.

The beneficial effects of the present invention are:

The subcritical fluid extraction-liquid chromatography combined analysis device disclosed by the invention can be automatically controlled, the analysis time for sex hormone residues is short, and the extraction and detection can be completed at one time. For some special sex hormones, offline detection can be performed. The whole process is easy to operate, R134a can be recycled, and the energy consumption is low. The heat generated by the compressor can not only preheat the R134a fluid, but also heat the extraction kettle and the separation kettle with the excess heat.

Description of drawings

Accompanying drawing 1 is the system flow chart of a kind of subcritical fluid extraction-liquid chromatography coupled analysis device of the present invention;

Accompanying drawing 2 is a schematic diagram of a subcritical fluid extraction-liquid chromatography coupled analysis device of the present invention.

In attached drawing 1:

1 is the R134a storage tank, 2 is the first purifier, 3 is the condenser, 4 is the high-pressure column pump, 5 is the heat exchanger, 6 is the preheater, 7 is the extraction tank, 8 is the separation tank, and 9 is throttling 10 is a six-way valve, 11 is a cleaning pump, 12 is a solid phase trap, 13 is an LC pump, 14 is an LC chromatographic column, 15 is a UV detector, 16 is a data collector, 17 is a flow meter, 18 Is a coarse filter, 19 is a second purifier, 20 is a compressor, 21 is a pressure gauge, 22 is a first regulating valve, 23 is a second regulating valve, 24 is a third regulating valve, 25 is a one-way valve, 26 is the temperature control display, 27 is the fourth regulating valve, 28 is the buffer tank, 29 is the pump, 30 is the temperature control display, 31 is the throttling device, 32 is the preheater, 33 is the temperature control display, 34 is the fifth adjustment Valve, 35 is a temperature control display, 36 is a one-way valve, 37 is the sixth regulating valve, 38 is the seventh regulating valve, 39 is a temperature control display, 40 is a pressure control display, 41 is a pressure gauge, 42 is the eighth regulating valve Valve, 43 is the ninth regulating valve, 44 is the four-way valve, 45 is the tenth regulating valve, 46 is the pressure gauge, 47 is the pressure control display, 48 is the temperature control display, 49 is the pressure gauge, 50 is the preheater, 51 is the eleventh regulating valve, 52 is the temperature control display, 53 is the twelfth regulating valve, 54 is the waste liquid bottle, 55 is the waste liquid bottle, 56 is the thirteenth regulating valve, 57 is the fourteenth regulating valve, 58 is a two-way valve, 59 is a fifteenth regulating valve, 60 is a pressure gauge, 61 is a pressure gauge, 62 is a sixteenth regulating valve, and 63 is an exhaust valve.

Detailed ways:

In order to simplify the technological process of sample hormone residue analysis, reduce energy consumption, and shorten the time of the entire work process, thereby reducing the labor intensity of analysts, and can perform pollution-free and efficient analysis of sample sex hormone residues, the present invention provides a Subcritical fluid extraction-liquid chromatography combined analysis device. When the subcritical fluid is in contact with the analysis sample, the residual sex hormones in it are selectively dissolved, and then the subcritical fluid is returned to normal state and rapidly volatilized by means of decompression and temperature rise, and the dissolved sex hormones are precipitated in solid form, and then can be carried out On-line or off-line detection, so as to achieve the purpose of analyzing the sex hormone residues in the sample.

In accompanying drawing 1, a kind of subcritical fluid R134a extraction-liquid chromatography coupling analysis device, it comprises: R134a storage tank (1), the first purifier (2), condenser (3), high-pressure pump (4 ), heat exchanger (5), preheater (6), extraction kettle (7), separation kettle (8), restrictor (9), six-way valve (10), cleaning pump (11), solid phase Trap (12), LC pump (13), LC chromatographic column (14), UV detector (15), data collector (16), flow meter (17), coarse filter (18), second purification device (19), compressor (20), characterized in that: the R134a storage tank (1) is equipped with a pressure gauge (21), and the first step between the R134a storage tank (1) and the first purifier (2) There is a regulating valve (22) and a third regulating valve (24), a temperature regulator (26) and a fourth regulating valve (27) are arranged between the condenser (3) and the high pressure pump (4), and the changing One end of the heater (5) is connected to the solvent buffer tank (28), and a temperature control display (35), a one-way valve (36) and a sixth A regulating valve (37), the extraction kettle (7) is equipped with a temperature control display (39), a pressure control display (40), a pressure gauge (41) and the seventh regulating valve (38), and the separation kettle is equipped with a pressure Table (46), pressure control display (47), temperature control display (48) and the twelfth regulating valve (53), there is a ninth regulating valve between the extraction kettle (7) and the separation kettle (8) (43), four-way valve (44), pressure gauge (49) and the tenth regulating valve (45), one end of the throttle (9) is connected to the two-way valve, and one end is connected to the six-way valve (10), One end is connected to the solid phase trap (12), the other end of the two-way valve connected to one end of the throttle (9) is connected to the eighth regulating valve (42), the six-way valve (10) and the throttle (9), cleaning pump (11), LC pump (13), LC chromatographic column (14), solid phase catcher (12) and waste liquid bottle (55) link to each other, described six-way valve (10) and waste liquid There is a thirteenth regulating valve (56) between the liquid bottles (55), the cleaning pump (11) is connected to the six-way valve (10), and one end of the solid phase trap (12) is connected to the throttle ( 9), one end is connected to the six-way valve (10), the LC pump is connected to the six-way valve (10), one end of the LC chromatographic column (14) is connected to the six-way valve (10), and one end is connected to the UV detector (15), one end of the UV detector (15) is connected to the data collector (16), one end is connected to the LC chromatographic column (14), one end is connected to the waste liquid bottle (54), and one end is connected to the LC chromatographic column (14 ), the data collector (16) links to each other with the UV detector (15), and there is a pressure gauge (60) between the flow meter (17) and the separation kettle (8), and the flow meter (17) and six There is a pressure gauge (60) and a fifteenth regulating valve (59) between the through valve (10), and the coarse filter (18) and pressure There is a second purifier (19) between the compressors (20), and the passage from the compressor (20) to the high-pressure pump (4) is connected with a pressure gauge (61), a sixteenth regulating valve (62), an exhaust Air valve (63), one-way valve (25) and the fourth regulating valve (27), the path from the compressor (20) to the R134a storage tank (1) is connected with a pressure gauge (61), the sixteenth regulating valve valve (62), exhaust valve (63), second regulating valve (23) and first regulating valve (22).

The extraction kettle (7) has a jacket, and a pump (29), a preheater (32), a temperature control display (33) and a fifth regulating valve (34) are arranged between one end of the jacket and the solvent buffer tank (28). ), the other end links to each other with the separation kettle (8). The separation kettle (8) has a jacket, and the passage from the jacket of the separation kettle to the jacket of the extraction kettle has a preheater (50), a temperature control display (52) and an eleventh regulating valve (51). The compressor (20) has a jacket, solvent pipes are connected at both ends of the jacket, and a restrictor (31) and a temperature controller (30) are arranged between one end of the jacket and the heat exchanger (5). The extraction kettle (7) is sealed with a sealing ring, the separation kettle (8) is sealed with a sealing ring, and the outlet seal of the extraction kettle (7) is connected with the (8) inlet of the separation kettle. This device can be used for both on-line monitoring and off-line detection. When performing online detection, the tenth regulating valve (45) is closed, and when performing offline detection, the eighth regulating valve (42) is closed.

The specific working principle is as follows:

The R134a in the R134a storage tank 1 is purified by the purifier 2 and then sent to the condenser 3, and the condenser 3 freezes the R134a into a liquid, which is sent to the heat exchanger 5 by the high-pressure pump 4 for preliminary preheating, and then sent to the preheating In the heater 6, the subcritical fluid heated to a certain temperature enters the extraction tank 7 heated to a certain temperature, and contacts with the sample therein to selectively dissolve the residual sex hormones in the sample. If online detection is performed, the tenth regulating valve 45 is closed, the eighth regulating valve 42 and the two-way valve 58 are opened, and the R134a fluid dissolved in sex hormone enters the solid phase trap 12 with lower pressure through the restrictor 9, due to The pressure decreases, the solubility decreases, the solute in R134a is precipitated, and is adsorbed by the solid phase trap 12, and R134a enters the coarse filter 18 and the purifier 19 for purification through the fifteenth regulating valve 59 and the flow meter 17, and then is sent to the compressor 20 middle compression, then through the sixteenth regulating valve 62, the check valve 25 and the fourth regulating valve 27, it is sent to the high-pressure pump 4 for recycling. The adsorbed sex hormones are eluted, sent to the LC chromatographic column 14 for separation, and finally sent to the UV detector 15 for detection, and the data is collected and analyzed by the data collector 16; if offline detection is performed, the eighth regulating valve 42 is closed and opened. The tenth regulating valve 45, the R134a fluid dissolved with sex hormone enters the separation tank 8 with lower pressure, due to the pressure drop, the solubility drops, the solute in R134a is precipitated, and stays in the separation tank 8, and R134a passes through the fourteenth regulating valve 57 and The flowmeter 17 enters the coarse filter 18 and the purifier 19 for purification in turn, and then is sent to the compressor 20 for compression, and the compressed R134a fluid is sent to the In the high-pressure pump 4, it is recycled, and when the extraction is completed, the sex hormones in the separation kettle 8 can be detected off-line. In order to reduce energy consumption, during the whole extraction process, the heat generated by the compressor is carried by the water to the heat exchanger 5 for preliminary preheating of the R134a fluid, and the hot water after the heat exchange is sent to the solvent buffer tank 28, and then the pump 29 Sent to the preheater 32, the hot water heated to a certain temperature is sent to the jacket of the extraction kettle 7 through the fifth regulating valve 34 to insulate the R134a fluid. The hot water flowing out from the inside is sent to the preheater 50, and the hot water heated to a certain temperature is sent to the jacket of the separation kettle 8 through the eleventh regulating valve 51 to keep the separation kettle 8 warm.

Claims (9)

1. a subcritical fluids R134a extraction-liquid chromatography combined analysis device, it comprises: R134a storage tank (1), the first clarifier (2), condenser (3), high-pressure pump (4), heat interchanger (5), primary heater (6), extraction kettle (7), separating still (8), flow controller (9), six-way valve (10), scavenging pump (11), solid phase drip catcher (12), LC pump (13), LC chromatographic column (14), UV detecting device (15), data acquisition unit (16), flowmeter (17), coarse filter (18), the second clarifier (19), compressor (20), it is characterized in that: described R134a storage tank (1) is furnished with tensimeter (21), between described R134a storage tank (1) and the first clarifier (2), there are the first variable valve (22) and the 3rd variable valve (24), between described condenser (3) and high-pressure pump (4), there are temperature regulator (26) and the 4th variable valve (27), one end of described heat interchanger (5) is connected with solvent surge tank (28), described primary heater (6) has temperature control display (35) to the path of extraction kettle, retaining valve (36) and the 6th variable valve (37), described extraction kettle (7) is furnished with temperature control display (39), pressure control display (40), tensimeter (41) and the 7th variable valve (38), described separating still is furnished with tensimeter (46), pressure control display (47), temperature control display (48) and the 12 variable valve (53), described extraction kettle (7) is to there being the 9th variable valve (43) between described separating still (8), four-way valve (44), tensimeter (49) and the tenth variable valve (45), described flow controller (9) one end is connected to two-port valve, one end is connected to six-way valve (10), one end is connected to solid phase drip catcher (12), the other end of the two-port valve being connected with flow controller (9) one end is connected with the 8th variable valve (42), described six-way valve (10) and flow controller (9), scavenging pump (11), LC pump (13), LC chromatographic column (14), solid phase drip catcher (12) is connected with waste liquid bottle (55), between described six-way valve (10) and waste liquid bottle (55), there is the 13 variable valve (56), described scavenging pump (11) is connected with six-way valve (10), described solid phase drip catcher (12) one end is connected to flow controller (9), one end is connected to six-way valve (10), described LC pump is connected with six-way valve (10), described LC chromatographic column (14) one end is connected to six-way valve (10), one end is connected to UV detecting device (15), described UV detecting device (15) one end is connected to data acquisition unit (16), one end is connected to waste liquid bottle (54), one end is connected to LC chromatographic column (14), described data acquisition unit (16) is connected with UV detecting device (15), between described flowmeter (17) and separating still (8), there are tensimeter (60) and the 14 variable valve (57), between described flowmeter (17) and six-way valve (10), there are tensimeter (60) and the 15 variable valve (59), between described coarse filter (18) and compressor (20), there is the second clarifier (19), described compressor (20) is connected with tensimeter (61) to the path of high-pressure pump (4), the 16 variable valve (62), vent valve (63), retaining valve (25) and the 4th variable valve (27), described compressor (20) is connected with tensimeter (61) to the path of the first clarifier (2), the 16 variable valve (62), vent valve (63), the second variable valve (23) and the 3rd variable valve (24).

2. a kind of subcritical fluids R134a extraction-liquid chromatography combined analysis device according to claim 1, it is characterized in that: described extraction kettle (7) is with chuck, between chuck one end and solvent surge tank (28), have pump (29), primary heater (32), temperature control display (33) and the 5th variable valve (34), the other end is connected with separating still (8).

3. a kind of subcritical fluids R134a extraction-liquid chromatography combined analysis device according to claim 1, is characterized in that: described separating still (8) is with chuck.

4. a kind of subcritical fluids R134a extraction-liquid chromatography combined analysis device according to claim 3, is characterized in that: the chuck of separating still has primary heater (50), temperature control display (52) and the 11 variable valve (51) on the set pattern of the chuck of extraction kettle.

5. a kind of subcritical fluids R134a extraction-liquid chromatography combined analysis device according to claim 1, it is characterized in that: described compressor (20) is with chuck, chuck two ends are connected with solvent conduit, have flow controller (31) and temperature controller (30) between one end of chuck and heat interchanger (5).

6. a kind of subcritical fluids R134a extraction-liquid chromatography combined analysis device according to claim 5, is characterized in that: in the solvent conduit at compressor chuck two ends, fluid used is water.

7. a kind of subcritical fluids R134a extraction-liquid chromatography combined analysis device according to claim 1, it is characterized in that: extraction kettle (7) seals with O-ring seal, separating still (8) seals with O-ring seal, and the exit seal place of extraction kettle (7) is connected with (8) entrance of separating still.

8. a kind of subcritical fluids R134a extraction-liquid chromatography combined analysis device according to claim 1, is characterized in that: in the time detecting online, close the tenth variable valve (45).

9. a kind of subcritical fluids R134a extraction-liquid chromatography combined analysis device according to claim 1, is characterized in that: in the time carrying out offline inspection, close the 8th variable valve (42).