CN100362347C - Solvent quenching accelerating device online co-operated with gas phase chromatography and method thereof - Google Patents
Solvent quenching accelerating device online co-operated with gas phase chromatography and method thereof Download PDFInfo
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- CN100362347C CN100362347C CNB2005100470116A CN200510047011A CN100362347C CN 100362347 C CN100362347 C CN 100362347C CN B2005100470116 A CNB2005100470116 A CN B2005100470116A CN 200510047011 A CN200510047011 A CN 200510047011A CN 100362347 C CN100362347 C CN 100362347C
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Abstract
The related extraction device applied with gas phase chromatogram on-line comprises: a small extraction pond, a heating unit, a ten-way valve, a six-way valve, a dosing tube, an assist carrier gas, a stead valve, a pressure sensor, a high-pressure pump for solvent, and a capillary transmission pipe. Compared with prior art, this invention improves sample utility up to 50-100 times with less solvent and high repeating precision, and has wide application.
Description
Technical field
The present invention relates to a kind of extraction equipment that is used for the analytic sample pre-service, a kind of specifically accelerated solvent extraction device of and gas chromatography on-line coupling.
The invention still further relates to a kind of method that realizes accelerated solvent extraction and gas chromatography on-line coupling.
Background technology
In analytical chemistry, solid and colloid sample are carried out method of extraction has soxhlet extraction, ultrasonic extraction method, microwave extraction method and accelerated solvent extraction to follow the example of.The simplest liquid-solid extraction is exactly that the solid of desire extraction is put into extraction solvent, is shaken, and can heat in case of necessity, utilizes method centrifugal or that filter to make liquid, the solid separation then, desires extracted component and enters solvent.
The most frequently used liquid-solid extraction is that Soxhlet is extracted, and its extraction equipment comprises condensing reflux pipe, tube, flask and the electric furnace that is linked in sequence from top to bottom.The solid of desire extraction is placed in the tube, and solvent is put into flask, lights electric furnace, and to the heating of the solvent in the flask, the solvent in the flask carries out the circulating reflux extraction.Simultaneously, open the temperature of condensing reflux pipe with control device.Soxhlet is extracted commercial prod, but its solvent load is big, and the used time is long, wants tens hours usually, could analyze after need concentrating extract.
Other are as methods such as ultrasonic extraction method, microwave extraction method and accelerated solvent extractions, and ultimate principle all is the liquid-solid extraction principle, just adopt diverse ways to shorten the sample preparation time, reduce solvent load and improve extraction efficiency.
The ultrasonic extraction method is that the solid and the solvent of desire extraction are put into the ultrasonic oscillation instrument jointly, centrifuging after ultrasonic concussion preset time.Microwave extraction method is a kind of extracting process that utilizes microwave energy to improve extraction efficiency in airtight sample pot and shorten the extraction time.
The notion of accelerated solvent extraction proposed in nineteen ninety-five, was also referred to as pressurized liquid extraction, pressure fluid extraction or the solvent extraction that strengthens.Accelerated solvent extraction is to utilize under uniform temperature and pressure, and the specific physical chemical property that solvent had comes solid and colloidal material are extracted.It is fast that this method has speed, and the solvent use amount is few, characteristics such as good reproducibility.Dai An company (Dionex) develops it and this technology commercialization, the registered trademark of its product is ASE.Dai An company to employed abstraction pool application in the own instrument United States Patent (USP) (U.S.Pat.No.5647976).But the accelerated solvent extraction device of Dai An company is a kind of sample pre-treatments technology, and the sample utilization factor is still very low, and greatly about 0.1%～2%, the solvent for use amount is still bigger, can not be applied in the gas chromatography on-line analysis.
Summary of the invention
The object of the present invention is to provide a kind of and the accelerated solvent extraction device and method gas chromatography on-line coupling.This device will speed up solvent-extracted sample-pretreating method and combines with gas chromatography large volume sample injection technology, realize gas chromatography to trace organic substance on-line extraction direct injection analysis in solid and the colloid sample, can be widely used in the gas chromatography on-line analysis of micro-solid and colloid sample in atmosphere fine particle (gasoloid), soil, environment, food, criminal investigation and the forensic medical examination.
The objective of the invention is to be achieved through the following technical solutions:
Extraction equipment of the present invention comprise solvent delivery high-pressure pump, extraction cells, pressure transducer,
First quantity tube, ten-way valve, second flow stabilizing valve, six-way valve, capillary transfer pipe and second auxiliary carrier gas; Wherein ten-way valve links to each other with six-way valve, is connected with solvent delivery high-pressure pump, extraction cells, pressure transducer and first quantity tube on the ten-way valve, is connected with the capillary transfer pipe on the six-way valve, and second auxiliary carrier gas is connected on the six-way valve by second flow stabilizing valve.
Wherein: first auxiliary carrier gas is connected on the ten-way valve by first flow stabilizing valve; On six-way valve, be equipped with second quantity tube; Described extraction cells comprises abstraction pool and heating unit, has through hole on the heating unit, and abstraction pool is placed in the through hole, forms extraction cells with heating unit; Described abstraction pool comprises induction pipe, first nut, abstraction pool body, filter, liner, second nut, bolt and outlet; One end of induction pipe is connected with first cutting ferrule, the other end inserts first nut, the below of first nut is threaded with the upper end of abstraction pool body, and first cutting ferrule that is positioned in first nut is stuck on the abstraction pool body, and the bottom of abstraction pool body is connected with the threaded one end of second nut; The bottom of abstraction pool body is provided with filter, and filter below is equipped with the liner that connects with it, the other end of second nut bolt that has been threaded, and outlet passes bolt and is connected on the liner; Be equipped with second cutting ferrule and the 3rd cutting ferrule respectively between the abstraction pool body and second nut and between liner and bolt; The polishing of abstraction pool body inwall adopts the good stainless steel material of inertia to make 0～300 ℃ of heatproof, withstand voltage 0～30MPa; Described heating unit comprises heating block, heating rod, thermopair and temperature controller, and an end of heating rod and thermopair is inserted in the heating block, and the other end links to each other with temperature controller by lead, by the temperature of temperature controller regulation and control heating block; The solvent delivery high-pressure pump is connected to No. 1 position of ten-way valve, the induction pipe of abstraction pool and outlet are connected to No. 10 positions and No. 3 positions of ten-way valve, pressure transducer is connected to No. 2 positions of ten-way valve, the two ends of first quantity tube are connected to No. 9 positions and No. 6 positions of ten-way valve, No. 8 positions and No. 7 positions of ten-way valve are respectively the inlet and the outlet of injecting solution to first quantity tube, and No. 4 positions and No. 5 positions of ten-way valve are connected with No. 1 position and No. 4 positions of six-way valve respectively; No. 2 positions of six-way valve connect the capillary transfer pipes, and second auxiliary carrier gas is connected No. 3 positions of six-way valve by second flow stabilizing valve, and No. 6 positions of six-way valve and No. 5 positions are respectively the inlet and the outlet of rinse solvent; The solvent delivery high-pressure pump is connected to No. 1 position of ten-way valve, the induction pipe of abstraction pool and outlet are connected to No. 10 positions and No. 3 positions of ten-way valve, pressure transducer is connected to No. 2 positions of ten-way valve, the two ends of first quantity tube are connected to No. 9 positions and No. 6 positions of ten-way valve, No. 8 positions and No. 7 positions of ten-way valve are respectively the inlet and the outlet of injecting solution to first quantity tube, first auxiliary carrier gas is connected No. 5 positions of ten-way valve by first flow stabilizing valve, No. 4 positions of ten-way valve are connected with No. 6 positions of six-way valve, No. 2 positions of six-way valve connect the capillary transfer pipe, second auxiliary carrier gas is connected No. 3 positions of six-way valve by second flow stabilizing valve, No. 1 position of six-way valve is connected second quantity tube with No. 4 interdigits, the outlet that No. 5 positions of six-way valve are extract.Accelerated solvent extraction device of the present invention and gas chromatography coupling, sample is carried out the method for online and gas chromatographic analysis after the pre-service, all or part of the transferring in the gas chromatography of extract that to flow out from the accelerated solvent extraction device analyzed, operation steps is: sample is packed in the abstraction pool body in the abstraction pool, sealing, ten-way valve places the solvent extraction position; Introduce in the abstraction pool body in the abstraction pool solvent and the 5～20MPa that pressurizes with the solvent delivery high-pressure pump, be heated to 80～200 ℃ simultaneously, heated 2 minutes～2 hours, carry out accelerated solvent extraction; After extraction is finished, all or part of the transferring in the gas chromatography of extract analyzed.
Wherein: for the whole input modes of extract, after extraction is finished, ten-way valve and six-way valve are switched to the sample introduction position, second auxiliary carrier gas promotes extract and standard specimen enters gas chromatography analysis; Mode for extract part sample introduction, after extraction is finished, at first six-way valve is switched to the sampling location, first auxiliary carrier gas pushes extract in second quantity tube and finishes sampling process, then six-way valve is placed the sample introduction position, second auxiliary carrier gas promotes extract and enters gas chromatography analysis.
Advantage of the present invention and good effect are:
1. improve the sensitivity that detects.Device of the present invention uses large volume sample injection, can make sample size be increased to 50～100 μ L or more by traditional gas chromatography sample size 1～5 μ L, therefore can improve detection sensitivity, simplifies The pretreatment.
2. reduced the consumption of extraction solvent.The present invention is realizing on the microminiaturized basis of accelerated solvent extraction (ASE) device, in conjunction with gas chromatography large volume sample injection technology, having invented the sample pretreatment apparatus and the method for accelerated solvent extraction and gas chromatography on-line coupling, the consumption of extraction solvent is reduced, is 50～500 μ L.
3. be widely used.The present invention can transfer to gas chromatographic analysis with all extracts are all or part of, method is simple and reliable, highly sensitive, can be widely used in the gas chromatography on-line analysis of micro-solid, colloid sample in atmosphere fine particle (gasoloid), soil, environment, food, criminal investigation and the forensic medical examination.
Description of drawings
Figure 1A is the structural representation of apparatus of the present invention whole sample introductions in the accelerated solvent extraction process;
Figure 1B is the structural representation of apparatus of the present invention whole sample introductions in the gas chromatographic analysis process;
Fig. 1 C is the structural representation of apparatus of the present invention whole sample introductions in system's cleaning process;
Fig. 2 A is the structural representation of apparatus of the present invention part sample introduction in the accelerated solvent extraction process;
Fig. 2 B is the structural representation of apparatus of the present invention part sample introduction in sampling process;
Fig. 2 C is the structural representation of apparatus of the present invention part sample introduction in the gas chromatographic analysis process;
Fig. 3 is the structural representation of abstraction pool of the present invention;
Fig. 4 is the structural representation of abstraction pool body in the abstraction pool of the present invention;
Fig. 5 is the structural representation of liner in the abstraction pool of the present invention;
Fig. 6 is the structural representation of heating unit of the present invention;
Fig. 7 is the chromatogram of 16 kinds of palycyclic aromatics in the atmospheric aerosol samples;
Fig. 8 is the chromatogram of 16 kinds of palycyclic aromatics.
Embodiment
The invention will be further described below in conjunction with accompanying drawing.
The inventive system comprises solvent delivery high-pressure pump 102, extraction cells 103, pressure transducer 104, first quantity tube 1051, ten-way valve 106, second flow stabilizing valve 1072, six-way valve 108, capillary transfer pipe 109 and second auxiliary carrier gas 1162; Wherein ten-way valve 106 links to each other with six-way valve 108, be connected with solvent delivery high-pressure pump 102, extraction cells 103, pressure transducer 104 and first quantity tube 1051 on the ten-way valve 106, being connected with capillary transfer pipe 109, the second auxiliary carrier gas 1162 on the six-way valve 108 is connected on the six-way valve 108 by second flow stabilizing valve 1072.First auxiliary carrier gas 1161 is connected on the ten-way valve 106 by first flow stabilizing valve 1071; On six-way valve 108, be equipped with second quantity tube 1052.
Shown in Figure 1A～Fig. 1 C, be accelerated solvent extraction and the whole sampling device synoptic diagram of gas chromatography coupling.Solvent delivery high-pressure pump 102 is connected to No. 1 position of ten-way valve 106, the induction pipe 201 of abstraction pool 2 adopts the stainless-steel tube of fine inner diameter to be connected to No. 10 positions and No. 3 positions of ten-way valve 106 with outlet 211, pressure transducer 104 is connected to No. 2 positions of ten-way valve 106, the two ends of first quantity tube 1051 are connected to No. 9 positions and No. 6 positions of ten-way valve 106, No. 8 positions and No. 7 positions of ten-way valve 106 are respectively the inlet and the outlet of injecting solution to first quantity tube 1051, and No. 4 positions and No. 5 positions of ten-way valve 106 are connected with No. 1 position and No. 4 positions of six-way valve 108 respectively; No. 2 positions of six-way valve 108 connect an end of capillary transfer pipe 109, and the other end of capillary transfer pipe 109 links to each other with gas chromatography 110.Second auxiliary carrier gas 1162 is connected No. 3 positions of six-way valve 108 by second flow stabilizing valve 1072, and No. 6 positions of six-way valve 108 and No. 5 positions are respectively the inlet and the outlet of rinse solvent.
At first be the accelerated solvent extraction process:
Shown in Figure 1A, in the process, No. 1 position of ten-way valve 106 communicates with No. 10 positions, No. 2 positions communicate with No. 3 positions, No. 4 positions communicate with No. 5 positions, No. 6 positions communicate with No. 7 positions, No. 8 positions communicate with No. 9 positions.No. 1 position of six-way valve 108 communicates with No. 2 positions, No. 3 positions communicate with No. 4 positions, No. 5 positions communicate with No. 6 positions.After abstraction pool 2 installs, with sample from abstraction pool body 204 is packed on abstraction pool 2 tops into, first-class first nut 202.Again the induction pipe 201 of abstraction pool 2 and outlet 211 are connected to No. 10 positions and No. 3 positions of ten-way valve 106.Opening solution carries high-pressure pump 102 that the solvent in the solvent bottle 101 is squeezed in the abstraction pool 2 and by pressure transducer 104 by No. 10 positions, No. 1 position of ten-way valve 106 through No. 2 positions of ten-way valve 106 abstraction pool 2 to be pressurized to requirement of experiment pressure, by heating unit 3 heating abstraction pools 2, realize online accelerated solvent extraction simultaneously.In extraction, if needed, can add solvent by No. 8 positions of ten-way valve 106, make in first quantity tube 1051 to be full of solvent, the solvent of surplus is by No. 7 position emptying of ten-way valve 106.
Secondly be the gas chromatographic analysis process:
After extraction finishes, switch position shown in ten-way valve 106 and the six-way valve 108 to Figure 1B, No. 1 position of ten-way valve 106 communicates with No. 2 positions, No. 3 positions communicate with No. 4 positions, No. 5 positions communicate with No. 6 positions, No. 7 positions communicate with No. 8 positions, No. 9 positions communicate with No. 10 positions.No. 1 position of six-way valve 108 communicates with No. 2 positions, No. 3 positions communicate with No. 4 positions, No. 5 positions communicate with No. 6 positions.Second auxiliary carrier gas 1162 through No. 3 positions of second flow stabilizing valve 1072 order by six-way valve 108, No. 3 positions of No. 9 positions of No. 5 positions of No. 4 positions, ten-way valve 106, No. 6 positions, first quantity tube 1051, ten-way valve 106, No. 10 positions, extraction cells 103, ten-way valve 106, No. 4 positions, No. 1 position of six-way valve 108, No. 2 positions, promote to carry out stratographic analysis in the solvent and the pre-columns 112 of the extract in the abstraction pool 2 in capillary transfer pipe 109 direct introducing gas chromatographies 110 in first quantity tube 105 1.Gas chromatography 110 is used for the separation detection of material, and it has a column sample injection device 111 and a flame ionization ditector 115; The effect of pre-column 112 is that solvent focuses on, and it links to each other with analytical column 114 by a quartzy crimp head 113.
Be system's cleaning process at last:
After sample introduction finishes, switch position shown in ten-way valve 106 and six-way valve 108 to Fig. 1 C, No. 1 position of ten-way valve 106 communicates with No. 2 positions, No. 3 positions communicate with No. 4 positions, No. 5 positions communicate with No. 6 positions, No. 7 positions communicate with No. 8 positions, No. 9 positions communicate with No. 10 positions.No. 1 position of six-way valve 108 communicates with No. 6 positions, No. 2 positions communicate with No. 3 positions, No. 4 positions communicate with No. 5 positions.Enter system with the neat solvent cleaning fluid by No. 6 positions of six-way valve 108, No. 4 positions of No. 6 positions of No. 10 positions of No. 4 positions of No. 1 position of order by six-way valve 108, ten-way valve 106, No. 3 positions, extraction cells 103, ten-way valve 106, No. 9 positions, first quantity tube 1051, ten-way valve 106, No. 5 positions, six-way valve 108, No. 5 position emptying by six-way valve 108, system pipeline and abstraction pool are cleaned, prepare to analyze next time and use.
The effect of six-way valve 108 is:
1. after each extract is transferred to pre-column, directly switch carrier gas and enter in the pre-column;
2. after each extraction is finished, valve and pipeline are washed.
Extraction pressure in the abstraction pool is controlled by the solvent delivery high-pressure pump, and can be by changing the heating-up temperature fine setting of abstraction pool.The employed temperature range of abstraction pool can be within 0～300 ℃; Pressure limit can be within 0～30MPa; It is 42MPa that solution is carried the maximum working pressure (MOP) of high-pressure pump.
Adopt homemade liquid chromatography pump in the device, be used for abstraction pool 2 is pressurizeed.Stainless steel abstraction pool 2 volumes are 180 μ L, and the filter 205 in one 1 μ m apertures is equipped with in the bottom of abstraction pool 2, and filter 205 is of a size of 4mm (diameter) * 1.5mm (thick).Induction pipe 201 and outlet 211 adopt the stainless-steel tube of a 0.25mm internal diameter to be used to connect abstraction pool 2 and ten-way valve 106.The firing rate of abstraction pool 2 is 100 ℃/min.The pressure transducer 104 that numeral shows, its pressure unit is Kgf/cm
2Gas chromatography 110 is furnished with a column sample injection device 111 and a flame ionization ditector 115.Analytical column 114 is a 30m * 0.53mm I.D. * 0.6 μ m quartz capillary columns.Pre-column 112 is that 10m * 0.53mm I.D deactivates quartz capillary, and it keeps the focusing that spacer techniques realizes solute as the retention gap post to utilize.Pre-column 112 is to be connected with quartzy crimp head 113 with analytical column 114.Adopt this device that the sucked solid particulate matter in the atmosphere is carried out pressure extraction, and carry out online detection by capillary gas chromatography, wherein 16 kinds of palycyclic aromatics are detected, extraction solvent adopts 9: 1 normal hexane: methylene chloride, extracting pressure is 10MPa, and extraction temperature is 140 ℃, and the extraction time is 10 minutes, gas chromatography sample introduction speed is 300L/min, and the stratographic analysis spectrogram as shown in Figure 7.Among the figure, the sample size of gas chromatography is 130 μ L; Sample introduction speed is 300 μ L/min; Initial furnace temperature is 70 ℃, and keeps 10min, and the speed journey with 6 ℃/min is raised to 290 ℃ then, and keeps 30 minutes.Each component among the figure is respectively: 1, naphthalene (2mg/L); 2, acenaphthene (4mg/L); 3, acenaphthene (2mg/L); 4, fluorenes (0.4mg/L); 5, luxuriant and rich with fragrance (0.2mg/L); 6, anthracene (0.2mg/L); 7, fluoranthene (0.4mg/L); 8, pyrene (0.2mg/L); 9,1,2-benzanthrene (0.2mg/L); 10, bend (0.2mg/L); 11, benzo (b) fluoranthene (0.4mg/L); 12, benzo (k) fluoranthene (0.2mg/L); 13, benzo (a) pyrene (0.2mg/L); 14, indeno (1,2,3-cd) pyrene (0.2mg/L); 15, dibenzo (a, h) anthracene (0.4mg/L); 16, benzo (g, h, i) north (0.4mg/L); IS1,1-chloronaphthalene (interior mark); IS2,2,4-dinitrotoluene (DNT) (interior mark).
Shown in Fig. 2 A～Fig. 2 C, be accelerated solvent extraction and gas chromatography coupling part sampling device synoptic diagram.Solvent delivery high-pressure pump 102 is connected to No. 1 position of ten-way valve 106, the induction pipe 201 and the outlet 211 of abstraction pool 2 is connected to No. 10 positions and No. 3 positions of ten-way valve 106, pressure transducer 104 is connected to No. 2 positions of ten-way valve 106, the two ends of first quantity tube 1051 are connected to No. 9 positions and No. 6 positions of ten-way valve 106, No. 8 positions and No. 7 positions of ten-way valve 106 are respectively the inlet and the outlet of injecting solution to first quantity tube 1051, first auxiliary carrier gas 1161 is connected No. 5 positions of ten-way valve 106 by first flow stabilizing valve 1071, No. 4 positions of ten-way valve 106 are connected with No. 6 positions of six-way valve 108, No. 2 positions of six-way valve 108 connect capillary transfer pipe 109, second auxiliary carrier gas 1162 is connected No. 3 positions of six-way valve 108 by second flow stabilizing valve 1072, No. 1 position of six-way valve 108 is connected second quantity tube 1052 with No. 4 interdigits, the outlet that No. 5 positions of six-way valve 108 are extract.
At first be the accelerated solvent extraction process:
Shown in Fig. 2 A, in the process, No. 1 position of ten-way valve 106 communicates with No. 10 positions, No. 2 positions communicate with No. 3 positions, No. 4 positions communicate with No. 5 positions, No. 6 positions communicate with No. 7 positions, No. 8 positions communicate with No. 9 positions.No. 1 position of six-way valve 108 communicates with No. 6 positions, No. 2 positions communicate with No. 3 positions, No. 4 positions communicate with No. 5 positions.After abstraction pool 2 installs, with sample from abstraction pool body 204 is packed on abstraction pool 2 tops into, first-class first nut 202.Again the induction pipe 201 of abstraction pool 2 and outlet 211 are connected to No. 10 positions and No. 3 positions of ten-way valve 106.Opening solution carries high-pressure pump 102 that the solvent in the solvent bottle 101 is squeezed in the abstraction pool 2 and by pressure transducer 104 by No. 10 positions, No. 1 position of ten-way valve 106 through No. 2 positions of ten-way valve 106 abstraction pool 2 to be pressurized to requirement of experiment pressure, by heating unit 3 heating abstraction pools 2, realize online accelerated solvent extraction simultaneously.In extraction, if needed, can add solvent by No. 8 positions of ten-way valve 106, make in first quantity tube 1051 to be full of solvent, the solvent of surplus is by No. 7 position emptying of ten-way valve 106.
Secondly be sampling process:
After extraction finishes, switch position shown in ten-way valve 106 and six-way valve 108 to Fig. 2 B, No. 1 position of ten-way valve 106 communicates with No. 2 positions, No. 3 positions communicate with No. 4 positions, No. 5 positions communicate with No. 6 positions, No. 7 positions communicate with No. 8 positions, No. 9 positions communicate with No. 10 positions.No. 1 position of six-way valve 108 communicates with No. 6 positions, No. 2 positions communicate with No. 3 positions, No. 4 positions communicate with No. 5 positions.First auxiliary carrier gas 1161 through first flow stabilizing valve 1071 with constant flow No. 3 positions of No. 9 positions of No. 5 positions by ten-way valve 106, No. 6 positions, first quantity tube 1051, ten-way valve, No. 10 positions, extraction cells 103, ten-way valve, No. 4 positions, No. 6 positions of six-way valve 108, No. 1 position in proper order, promote to finish the quantitative collection of extract in second quantity tube 1052 that extract in first quantity tube 1051 and the solvent in the abstraction pool 2 enter six-way valve 108.
Be the gas chromatographic analysis process at last:
After sampling finishes, switch position shown in ten-way valve 106 and six-way valve 108 to Fig. 2 C, No. 1 position of ten-way valve 106 communicates with No. 2 positions, No. 3 positions communicate with No. 4 positions, No. 5 positions communicate with No. 6 positions, No. 7 positions communicate with No. 8 positions, No. 9 positions communicate with No. 10 positions.No. 1 position of six-way valve 108 communicates with No. 2 positions, No. 3 positions communicate with No. 4 positions, No. 5 positions communicate with No. 6 positions.Second auxiliary carrier gas 1162 through No. 3 positions of second flow stabilizing valve 1072 order by six-way valve 108, No. 4 positions, second quantity tube 1052, No. 1 position of six-way valve 108, No. 2 positions, promote in second quantity tube 1052 in the pre-column 112 of extract in capillary transfer pipe 109 enters gas chromatography 110.
The effect of six-way valve 108 is:
1. after extraction is finished, the quantitative collection extract;
2. the sample in the quantity tube is sent in the gas chromatography and analyzed.
After sample introduction finished, repetitive operation block diagram 2A and Fig. 2 B prepared to analyze next time use with pipeline and abstraction pool in the neat solvent purging system.
Adopt homemade liquid chromatography pump in the device, be used for abstraction pool 2 is pressurizeed.Stainless steel abstraction pool 2 volumes are 180 μ L, and the filter 205 in one 1 μ m apertures is equipped with in the bottom of abstraction pool 2, and filter 205 is of a size of 4mm (diameter) * 1.5mm (thick).Induction pipe 201 and outlet 211 adopt the stainless-steel tube of a 0.25mm internal diameter to be used to connect abstraction pool 2 and ten-way valve 106.The firing rate of abstraction pool 2 is 100 ℃/min.The pressure transducer 104 that numeral shows, its pressure unit is Kgf/cm
2Gas chromatography 110 is furnished with a column sample injection device 111 and a flame ionization ditector 115.Analytical column 114 is a 30m * 0.53mm I.D. * 0.6 μ m quartz capillary columns.Pre-column 112 is that 10m * 0.53mm I.D deactivates quartz capillary, and it keeps the focusing that spacer techniques realizes solute as the retention gap post to utilize.Pre-column 112 is to be connected with quartzy crimp head 113 with analytical column 114.Adopt this device that 16 kinds of palycyclic aromatic standard models are carried out pressure extraction, and carry out online detection by capillary gas chromatography, extraction solvent adopts 9: 1 normal hexane: methylene chloride, extracting pressure is 10MPa, extraction temperature is 140 ℃, the extraction time is 10 minutes, and gas chromatography sample introduction speed is 300L/min, and the stratographic analysis spectrogram as shown in Figure 8.Among the figure, the sample size of gas chromatography is 20 μ L; Sample introduction speed is 300 μ L/min; Initial furnace temperature is 70 ℃, and keeps 10min, and the speed journey with 6 ℃/min is raised to 290 ℃ then, and keeps 30 minutes.Each component among the figure is respectively: 1, naphthalene (2mg/L); 2, acenaphthene (4mg/L); 3, acenaphthene (2mg/L); 4, fluorenes (0.4mg/L); 5, luxuriant and rich with fragrance (0.2mg/L); 6, anthracene (0.2mg/L); 7, fluoranthene (0.4mg/L); 8, pyrene (0.2mg/L); 9,1,2-benzanthrene (0.2mg/L); 10, bend (0.2mg/L); 11, benzo (b) fluoranthene (0.4mg/L); 12, benzo (k) fluoranthene (0.2mg/L); 13, benzo (a) pyrene (0.2mg/L); 14, indeno (1,2,3-cd) pyrene (0.2mg/L); 15, dibenzo (a, h) anthracene (0.4mg/L); 16, benzo (g, h, i) north (0.4mg/L); IS1,1-chloronaphthalene (interior mark); IS2,2,4-dinitrotoluene (DNT) (interior mark).
Experimental provision and method are carried out pressurized liquid extraction with embodiment 1 to the environmental contaminants in the soil.Solvent adopts 1: 1 normal hexane: acetone, and extracting pressure 10Mpa, 100 ℃ of extraction temperature, the extraction time is 10 minutes.
Accelerated solvent extraction device of the present invention and gas chromatography coupling, sample is carried out the method for online and gas chromatographic analysis after the pre-service, all or part of the transferring in the gas chromatography of extract that to flow out from the accelerated solvent extraction device analyzed, the concrete operations step is: sample is packed in the abstraction pool body 204 in the abstraction pool 2, sealing, ten-way valve 106 places the solvent extraction position; Introduce in the abstraction pool body 204 in the abstraction pool 2 solvent and the 5～20MPa that pressurizes with solvent delivery high-pressure pump 102, be heated to 80～200 ℃ simultaneously, heated 2 minutes～2 hours, carry out accelerated solvent extraction; After extraction is finished, all or part of the transferring in the gas chromatography of extract analyzed.
For the whole input modes of extract, after extraction is finished, ten-way valve 106 and six-way valve 108 are switched to the sample introduction position, second auxiliary carrier gas 1162 promotes extract and standard specimen enters gas chromatography analysis; Mode for extract part sample introduction, after extraction is finished, at first six-way valve 108 is switched to the sampling location, first auxiliary carrier gas 1161 pushes extract in second quantity tube 1052 and finishes sampling process, then six-way valve 108 is placed the sample introduction position, second auxiliary carrier gas 1162 promotes extract and enters gas chromatography analysis.
Claims (10)
1. the accelerated solvent extraction device with the gas chromatography on-line coupling is characterized in that: comprise solvent delivery high-pressure pump (102), extraction cells (103), pressure transducer (104), first quantity tube (1051), ten-way valve (106), second flow stabilizing valve (1072), six-way valve (108), capillary transfer pipe (109) and second auxiliary carrier gas (1162); Wherein ten-way valve (106) links to each other with six-way valve (108), be connected with solvent delivery high-pressure pump (102), extraction cells (103), pressure transducer (104) and first quantity tube (1051) on the ten-way valve (106), be connected with capillary transfer pipe (109) on the six-way valve (108), second auxiliary carrier gas (1162) is connected on the six-way valve (108) by second flow stabilizing valve (1072).
2. by the described accelerated solvent extraction device with the gas chromatography on-line coupling of claim 1, it is characterized in that: first auxiliary carrier gas (1161) is connected on the ten-way valve (106) by first flow stabilizing valve (1071); On six-way valve (108), be equipped with second quantity tube (1052).
3. by the accelerated solvent extraction device of claim 1 or 2 described and gas chromatography on-line couplings, it is characterized in that: described extraction cells (103) comprises abstraction pool (2) and heating unit (3), have through hole (305) on the heating unit (3), abstraction pool (2) is placed in the through hole (305), forms extraction cells (103) with heating unit (3).
4. by the described accelerated solvent extraction device with the gas chromatography on-line coupling of claim 3, it is characterized in that: described abstraction pool (2) comprises induction pipe (201), first nut (202), abstraction pool body (204), filter (205), liner (206), second nut (209), bolt (210) and outlet (211); One end of induction pipe (201) is connected with first cutting ferrule (203), the other end inserts first nut (202), the below of first nut (202) is threaded with the upper end of abstraction pool body (204), first cutting ferrule (203) that is positioned in first nut (202) is stuck on the abstraction pool body (204), and the bottom of abstraction pool body (204) is connected with the threaded one end of second nut (209); The bottom of abstraction pool body (204) is provided with filter (205), filter (205) below is equipped with the liner (206) that connects with it, the other end of second nut (209) bolt (210) that has been threaded, outlet (211) passes bolt (210) and is connected on the liner (206); Be equipped with second cutting ferrule (207) and the 3rd cutting ferrule (208) respectively between abstraction pool body (204) and second nut (209) and between liner (206) and bolt (210).
5. by the described accelerated solvent extraction device with the gas chromatography on-line coupling of claim 4, it is characterized in that: the polishing of described abstraction pool body (204) inwall, adopt the good stainless steel material of inertia to make 0～300 ℃ of heatproof, withstand voltage 0～30MPa.
6. by the described accelerated solvent extraction device with the gas chromatography on-line coupling of claim 3, it is characterized in that: described heating unit (3) comprises heating block (301), heating rod (302), thermopair (303) and temperature controller (304), one end of heating rod (302) and thermopair (303) is inserted in the heating block (301), the other end links to each other with temperature controller (304) by lead, by the temperature of temperature controller (304) regulation and control heating blocks (301).
7. by the described accelerated solvent extraction device with the gas chromatography on-line coupling of claim 1, it is characterized in that: solvent delivery high-pressure pump (102) is connected to No. 1 position of ten-way valve (106), the induction pipe (201) of abstraction pool (2) and outlet (211) are connected to No. 10 positions and No. 3 positions of ten-way valve (106), pressure transducer (104) is connected to No. 2 positions of ten-way valve (106), the two ends of first quantity tube (1051) are connected to No. 9 positions and No. 6 positions of ten-way valve (106), No. 8 positions and No. 7 positions of ten-way valve (106) are respectively the inlet and the outlet of injecting solution to first quantity tube (1051), and No. 4 positions and No. 5 positions of ten-way valve (106) are connected with No. 1 position and No. 4 positions of six-way valve (108) respectively; No. 2 positions of six-way valve (108) connect capillary transfer pipe (109), second auxiliary carrier gas (1162) is connected No. 3 positions of six-way valve (108) by second flow stabilizing valve (1072), and No. 6 positions of six-way valve (108) and No. 5 positions are respectively the inlet and the outlet of rinse solvent.
8. by the described accelerated solvent extraction device with the gas chromatography on-line coupling of claim 2, it is characterized in that: solvent delivery high-pressure pump (102) is connected to No. 1 position of ten-way valve (106), the induction pipe (201) of abstraction pool (2) and outlet (211) are connected to No. 10 positions and No. 3 positions of ten-way valve (106), pressure transducer (104) is connected to No. 2 positions of ten-way valve (106), the two ends of first quantity tube (1051) are connected to No. 9 positions and No. 6 positions of ten-way valve (106), No. 8 positions and No. 7 positions of ten-way valve (106) are respectively the inlet and the outlet of injecting solution to first quantity tube (1051), first auxiliary carrier gas (1161) is connected No. 5 positions of ten-way valve (106) by first flow stabilizing valve (1071), No. 4 positions of ten-way valve (106) are connected with No. 6 positions of six-way valve (108), No. 2 positions of six-way valve (108) connect capillary transfer pipe (109), second auxiliary carrier gas (1162) is connected No. 3 positions of six-way valve (108) by second flow stabilizing valve (1072), No. 1 position of six-way valve (108) is connected second quantity tube (1052) with No. 4 interdigits, the outlet that No. 5 positions of six-way valve (108) are extract.
9. using method by the described accelerated solvent extraction device of claim 1, it is characterized in that: accelerated solvent extraction device and gas chromatography coupling, sample is carried out the method for online and gas chromatographic analysis after the pre-service, all or part of the transferring in the gas chromatography of extract that to flow out from the accelerated solvent extraction device analyzed, operation steps is: sample is packed in the abstraction pool body (204) in the abstraction pool (2), sealing, ten-way valve (106) places the solvent extraction position; Introduce in the interior abstraction pool body (204) of abstraction pool (2) solvent and the 5～20MPa that pressurizes with solvent delivery high-pressure pump (102), be heated to 80～200 ℃ simultaneously, heated 2 minutes～2 hours, carry out accelerated solvent extraction; After extraction is finished, all or part of the transferring in the gas chromatography of extract analyzed.
10. press the using method of the described accelerated solvent extraction device of claim 9, it is characterized in that: for the whole input modes of extract, after extraction is finished, ten-way valve (106) and six-way valve (108) are switched to the sample introduction position, and second auxiliary carrier gas (1162) promotes extract and standard specimen enters gas chromatography analysis; Mode for extract part sample introduction, after extraction is finished, at first six-way valve (108) is switched to the sampling location, first auxiliary carrier gas (1161) pushes extract in second quantity tube (1052) and finishes sampling process, then six-way valve (108) is placed the sample introduction position, second auxiliary carrier gas (1162) promotes extract and enters gas chromatography analysis.
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| CN104280487B (en) * | 2014-10-24 | 2016-11-16 | 王峰 | A kind of pressed powder sampling device for liquid chromatograph |
| CN104436753B (en) * | 2014-12-09 | 2016-05-25 | 天津博纳艾杰尔科技有限公司 | A kind of solid-phase extracting instrument |
| CN109828050A (en) * | 2019-03-08 | 2019-05-31 | 中钢集团鞍山热能研究院有限公司 | A kind of method of 3,4- BaP content in quick measurement coal tar, coal tar pitch |
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