CN1318845C - Solid phase extraction sample bottle and thermal analysis apparatus - Google Patents
Solid phase extraction sample bottle and thermal analysis apparatus Download PDFInfo
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- CN1318845C CN1318845C CNB2004100692047A CN200410069204A CN1318845C CN 1318845 C CN1318845 C CN 1318845C CN B2004100692047 A CNB2004100692047 A CN B2004100692047A CN 200410069204 A CN200410069204 A CN 200410069204A CN 1318845 C CN1318845 C CN 1318845C
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Abstract
本发明一种固相萃取样品瓶和热解析装置涉及样品检测技术，是一种液-固萃取和气-固吸附技术，用于气体样品、液体样品和均质样品的预处理和目标组份的萃取富集，特别是用于色谱分析和仪器分析中的样品预处理和目标组份的萃取富集。本发明一种固相萃取样品瓶和热解析装置，包括一萃取样品瓶，为圆柱体状，一端开口，另一端封闭成底，其容腔内，于圆柱体部位的内壁中部固连有一层萃取固定相；一热解析器和一萃取样品瓶吹扫器。本发明同时处理上百个甚至更多的样品，并且省去了采样之后的保存、分装、分别预处理等步骤。极大地提高了样品预处理效率，提高了分析结果的准确性和重复精度，改善了不同实验室之间的数据重复性。
A solid-phase extraction sample bottle and a thermal analysis device of the present invention relate to sample detection technology, which is a liquid-solid extraction and gas-solid adsorption technology, and is used for pretreatment of gas samples, liquid samples and homogeneous samples and detection of target components Extraction enrichment, especially for sample pretreatment and extraction enrichment of target components in chromatographic analysis and instrumental analysis. A solid-phase extraction sample bottle and a thermal analysis device of the present invention include an extraction sample bottle, which is in the shape of a cylinder, one end is open, and the other end is closed to form a bottom. In the cavity, a layer is fixedly connected to the middle of the inner wall of the cylinder. Extraction stationary phase; a thermal desorber and an extraction vial purger. The invention processes hundreds or even more samples at the same time, and saves the steps of preservation, subpackaging and separate pretreatment after sampling. It greatly improves the efficiency of sample pretreatment, improves the accuracy and repeatability of analysis results, and improves the repeatability of data between different laboratories.
Description
Technical field
The present invention relates to the sample detection technology, be a kind of liquid-solid extraction and gas-solid adsorption technology, the extracting and enriching that is used for gaseous sample, fluid sample and homogeneous The pretreatment and target component is especially for the extracting and enriching of sample pretreatment in stratographic analysis and the instrumental analysis and target component.
Background technology
In environmental surveys, environmental protection and food security monitoring, all need composition in contained organic contaminant in a large amount of samples and the animals and plants extract is analyzed.The gas-solid adsorption technology that sample pretreatment during these are analyzed adopts multi-form liquid-liquid, liquid-solid extraction and static headspace gas to extract always, with functions such as the phase transfer that realizes target component in the sample, selective enrichments, satisfy analytical instrument to entering the sample requirement of instrument.
So far, having developed the sample pretreating method that all is serial mode, and both sample was processing one by one, can not handle up to a hundred samples on same device simultaneously.The condition that more can not guarantee processing sample in the different experiments chamber is the same.
The demand for development analytic process of modern society does not have or seldom has secondary pollution to environment.Develop for this reason and liquid-liquid micro-extraction technique and solid phase micro-extraction technique.The former uses the organic solvent extraction of about 0.1mL, and the latter avoids with an organic solvent.But the former still has discarded solvent, and the latter's shortcoming is serviceable life≤30 time of solid-phase micro-extraction fibre, stationary phase consumption≤1 μ L, make the enrichment multiple restricted, repeatability is not high, can not handle the high slightly fluid sample of viscosity, can not satisfy the requirement of many trace analysises.
Summary of the invention
The objective of the invention is provides a kind of solid phase extraction sample bottle and thermal analysis apparatus for overcoming the deficiencies in the prior art.
For achieving the above object, technical solution of the present invention is: a kind of solid phase extraction sample bottle and thermal analysis apparatus, it comprises
One extraction sample bottle is cylindrical shape, an end opening, and the other end seals into the end, and in its cavity volume, inwall middle part bonding or coated in the right cylinder position have one deck extraction stationary phase;
One hot parser is made up of obstruction, calandria, resolver seat and joint, and wherein, calandria is a right cylinder, and a room is arranged in it, and room is cylindrical, and the lower end is uncovered, and there is a spring on the top; On the calandria lower end, the uncovered outer circle groove that is with is provided with O-ring seal in the groove; There is a female adapter at calandria end face center, and joint bottom centre has a microtubule to communicate with room, purges protection effective fastening nut of gas circuit and cutting ferrule and is fixed in the female adapter; The calandria lower end is connected with the resolver seat;
The resolver seat is discoid, there is a dimple at the center, upper surface, dimple is with two annular grooves outward, be provided with second O-ring seal in the inner groovy, second O-ring seal is suitable with the bottleneck of extraction sample bottle, O-ring seal in outer groove and the calandria lower end groove is suitable, and the dimple bottom side is provided with thermal desorption carrier gas pipe; Resolver seat lower end central part has a projection cylinder, there is first male connection at center, cylinder lower end, the affixed capillary of this male connection and second hermetic collar and fastening pressure cap, this kapillary is positioned on the central shaft of the resolver seat and second hermetic collar, is used as thermal desorption gas escape pipe; The gas of thermal desorption in the extraction sample bottle is derived and entered in the analyzer; The sweep gas escape pipe protrudes upward, and its inlet is positioned at the room top of calandria, and length just in time is positioned at the bottom of extraction sample bottle; The cylinder of resolver seat lower end is connected with fastening pressure cap;
Fastening pressure cap is the notch cuttype cylinder, upper end nozzle external diameter is littler than lower end nozzle external diameter, the outer rib-loop of the cylinder of rib-loop and resolver seat lower end is suitable in the nozzle of upper end, and lower end nozzle internal diameter and gas chromatograph injector cap external diameter are suitable, and fastening pressure cap is connected with the gas chromatograph injector;
One extraction sample bottle purging device, it has a plinth, its side is provided with the gentle connecting pipe of heater tube, circumference is connected to square gas circuit divider on the base, one cavity is arranged in it, and the length of side of the side ratio base of gas circuit divider is short, and its upper surface vertically is connected with a plurality of gas outlet tubes, gas outlet tube stretches out the length of upper surface, less than the length of extraction sample bottle; But extract the sample bottle reversed stream on gas outlet tube, and place the upper surface of gas circuit divider; The upper end of all gas outlet is outlet, and the lower end all is communicated with the gas circuit connecting pipe respectively in the gas circuit dispenser cavity; Well heater is inlaid in the base, adds cavity and all extraction sample bottles of heat distributor; One square lid, the outside appearance of its outer length of side and base with, in it outside appearance of length of side and gas circuit divider with, in the lid room height greater than the summation of gas circuit divider and extraction sample bottle length, but its driving fit be placed on the gentle distributor of base; Lid and base cover and after, can with gas outlet tube with the extraction sample bottle be placed in the lid room.
Described solid phase extraction sample bottle and thermal analysis apparatus, its described extraction stationary phase, it focuses between 2～150mg, and thick is 0.1～100 μ m, is colloid, solid or porous layer organic polymer or inorganic adsorbent.
Described solid phase extraction sample bottle and thermal analysis apparatus, its described extraction sample bottle is to be made by quartz or glass, its end, is conical, semisphere or flat.
Described solid phase extraction sample bottle and thermal analysis apparatus, its described colloid, solid or porous layer organic polymer or inorganic adsorbent, for polymethyl siloxane, polystyrene porous coating, acticarbon and molecular sieve, for the organic polymer stationary phase, should be crosslinked and be bonded on the inwall of bottle.
Described solid phase extraction sample bottle and thermal analysis apparatus, its described thermal desorption gas escape pipe is quartz capillary or platinum pipe, its outlet is inserted the gas chromatograph injector or is kept in the spacer.
The method of operating of described solid phase extraction sample bottle and thermal analysis apparatus, its step is as follows:
A) earlier resolver seat lower end and fastening pressure cap are coupled together, the thermal desorption carrier gas pipe and the auxiliary carrier gas of resolver seat coupled together, protect gas circuit pipe and auxiliary constant current carrier gas to couple together the purging of calandria end face;
B) to liquid or equal quality samples, sample is injected the extraction sample bottle and to seal, target components is extracted the stationary phase extraction on the sample bottle inwall, will extract sample bottle and be put into and rocked in the constant temperature rocker 10～240 minutes;
C) extraction is opened bottle cap after reaching balance, topples over sample, dries the extraction sample bottle, to extract sample bottle again is inverted in the room of calandria of hot parser, the calandria lower end is connected with the resolver seat fastening, under the pressure of spring, heated sealed body lower end uncovered and extraction sample bottleneck;
D) be blown into gas by thermal desorption carrier gas pipe, add thermal desorption simultaneously, the component of desorption directly is transferred to the injector of gas chromatograph or is kept in the spacer by desorption gas escape pipe and analyzed, and perhaps is collected in the fraction collector;
Another road gas is blown into by purging protection gas circuit pipe, enters room by microtubule, be full of and purges extract the sample bottle periphery after, emptying; The effect that purges protection gas is to avoid air to enter in the chromatographic analysis gas circuit by the sealing position seepage between extraction sample bottle and the resolver seat;
E) will be on the gas outlet tube on the purging device with the extraction sample bottle reversed stream of crossing, cover the lid of purging device, under 250～300 ℃ of temperature, with inert gas purge extraction sample bottle inner chamber, extraction sample bottle after the processing is equipped with to be reused to remove residual component in aging 4～24 hours.
Described method of operating, in its thermal desorption process, carrier gas enters the extraction sample bottle continuously, derive the component and the carrier gas of desorption through the kapillary that is inserted into the bottle bottom, be incorporated into it in the chromatograph injector or in the fraction collector, avoided the component of extraction sample bottle outer wall pickup to enter the thermal desorption gas circuit fully, and do not used valve member and avoided sample absorption.
Described method of operating, if sample saliferous, particle or colloid material are at b) in the step, after sample and an amount of distilled water put into the extraction sample bottle and sealing, be put into and rocked in the constant temperature rocker 10～240 minutes, target components is extracted the stationary phase extraction on the sample bottle inwall.After the balance, open bottle cap, get extraction sample bottle 1～2 time express developed with distilled water again, get rid of in the clean extraction sample bottle behind the residual water droplet, continue c), d), e) step.
Described method of operating, if sample is contained half volatile and a difficult volatilization organic component in liquid and the equal quality sample, after a) going on foot, do pre-service: sample is placed the head space bottle, the constant temperature stirred sample, and bottom the head space bottle, be blown into gas, draw gas at head space bottle top and enter extraction sample bottle bottom, treat head space purge finish after, shut-down purge gas, to extract sample bottle and put on the pyrolysis haustorium, continue c), d), e) step.
The present invention utilizes the solubleness of target component in stationary phase in the sample greater than this character of solubleness in the former medium of sample, make the target component from sample media, transfer in the stationary phase on the sample bottle inwall and in stationary phase, be adsorbed, dissolving and enrichment.Be used for other purpose with heating the method desorption target components of resolving, enter to do in chromatograph or other analytic system to collect in further compartment analysis or the fraction collector then.It can handle up to a hundred even more sample simultaneously, and has saved steps such as the preservation afterwards of sampling, packing, difference pre-service.Greatly improve sample pretreatment efficient, improved the data repeatability between the different experiments chamber.
Different with existing fiber formula solid phase micro-extraction technique or solid-state absorption rod technology, the characteristics of solid phase extraction sample bottle method and apparatus of the present invention are: sample is encapsulated in (for liquid and equal quality sample) in the extraction sample bottle, and stationary phase is coated with stain or is linked on the sample bottle inwall, so the specific surface area of stationary phase is very big.Change the internal diameter and the length that are coated with stain thickness and sample bottle of stationary phase, stationary phase volume and sample size can change.This technology energy adsorb volatile, half volatile and difficult volatile component, fixedly being on good terms is easy to the damage that cleaning and extraction and desorption process can not be subjected to mechanical force, the extraction sample bottle can repeat repeatedly to use and also serviceable life than fiber formula solid-phase microextraction head length more than 10 times.
The desorption of solid phase extraction sample bottle method and apparatus of the present invention is resolved and is used the thermal desorption pattern, also can use the solvent desorption.Thermal desorption is to the heating of extraction sample bottle, blows in the injector of gas chromatograph with the component of auxiliary carrier gas with desorption; The solvent desorption is to use suitable desorption solvent to inject the extraction sample bottle, takes out solution behind the ready to balance and further concentrates, then compartment analysis.
Method and apparatus of the present invention is just sample to be packed into to extract in the sample bottle when sampling, and the volume of each bottle only is the milliliter level, thus can gather hundreds and thousands of samples, with adopting with sealing.Sample begins to have extracted in the bottle of packing into, comprise transportation and quicken balance on the constant temperature rocker behind the laboratory, so all samples all is to extract under the same conditions that whole process does not have extraneous contamination or sample loss.Can not only guarantee that like this pre-service to all samples is a term harmonization in the laboratory, the condition that can also guarantee different sample pretreatments between the different experiments chamber is consistent, has therefore improved precision of analysis and repeatable accuracy.
Description of drawings
Fig. 1 is a solid phase extraction sample bottle synoptic diagram of the present invention;
Fig. 2 is the synoptic diagram after the present invention extracts sample bottle and hot parser combination;
Fig. 3 is that the present invention extracts sample bottle purging device synoptic diagram;
Fig. 4 is the analysis of spectra of surface water, and wherein Fig. 4 A is that actual sample is analyzed chromatogram, and Fig. 4 B is the chromatogram of standard model solution;
Fig. 5 carries adsorption and enrichment device synoptic diagram for the static headspace gas of the component that partly volatilizees in the fluid sample.
Embodiment
Be coated with extraction sample bottle 1, hot parser 2 and the extraction sample bottle purging device 3 of stationary phase in the inventive system comprises.
Asking for an interview Fig. 1, is the synoptic diagram of solid phase extraction sample bottle of the present invention.Extraction sample bottle 1 is a cylindrical shape, is to be made by quartz or glass, an end opening 102, and the other end seals into the end, and its end, can be taper shape, semisphere or flat.In its cavity volume, be fixed with one deck extraction stationary phase 101 in the inwall at right cylinder position middle part, stationary phase 101 can be used coating method, and is crosslinked and be bonded on the tube wall.The bottle end and bottleneck position are not coated with the stain stationary phase and are beneficial to pyrolysis and analyse.
Asking for an interview Fig. 2, is that the present invention extracts the synoptic diagram after sample bottle 1 makes up with hot parser 2.Hot parser 2 is made up of obstruction 214, calandria 202, resolver seat 208 and fastening pressure cap 210, wherein, calandria 202 is a right cylinder, one room 211 is arranged in it, room 211 is cylindrical, the lower end is uncovered 212, and room 211 tops are conical, semisphere or flat-top, and there is a spring 203 on the top.On calandria 202 lower ends, the uncovered 212 outer circle grooves that are with are provided with O-ring seal 205 in the groove.Calandria 202 end face centers have one to stop up groove 213, and stopping up groove 213 bottoms is taper shape or semisphere, and bottom centre has a microtubule 215 to communicate with room 211.Stop up groove 213 and stop up 214 close proximity, stop up 214 belows and be connected with hermetic collar 209, be connected with on the central shaft of obstruction 214 and hermetic collar 209 and purge protection gas circuit pipe 201,201 outlets of protection gas circuit pipe are stretched out slightly by the center of hermetic collar 209.Calandria 202 lower ends are connected with resolver seat 208.
Resolver seat 208 is discoid, and there is a dimple 215 at the center, upper surface, is with two annular grooves 216,217 outside the dimple 215, is provided with O-ring seal 206 in the groove 216.Dimple 215 bottom sides are provided with thermal desorption carrier gas pipe 207.Resolver seat 208 lower end central parts have a projection cylinder 218, and center, cylinder 218 lower end also has one to stop up groove 220, stops up groove 220 and hermetic collar 219 close proximity.On the central shaft of resolver seat 208 and hermetic collar 219, be connected with thermal desorption sweep gas escape pipe 204.Sweep gas escape pipe 204 protrudes upward, and its inlet is positioned at room 211 tops of calandria 202.Sweep gas escape pipe 204 is a quartz capillary, and its outlet communicates with gas chromatograph injector or reservation spacer.The cylinder 218 of resolver seat 208 lower ends is connected with fastening pressure cap 210.
Fastening pressure cap 210 is the notch cuttype cylinder, and upper end nozzle external diameter is littler than lower end nozzle external diameter, and cylinder 218 external diameters of upper end nozzle internal diameter and resolver seat 208 lower ends are suitable, and lower end nozzle internal diameter and gas chromatograph injector cap external diameter are suitable.Fastening pressure cap 210 is connected with the gas chromatograph injector.
During assembling, extraction sample bottle 1 is inverted in the room 211 of calandria 202, extraction 1 end of sample bottle and room 211 tops are suitable, and by spring 203 contacts.At this moment, resolver seat 208 is linked to each other with calandria 202 lower ends, when calandria 202 lower ends with after resolver seat 208 links to each other, the O-ring seal 206 in the annular groove 216 and the bottleneck close proximity of extraction sample bottle 1, annular groove 217 and interior O-ring seal 205 close proximity of calandria 202 lower end grooves, resolver seat 208 is with uncovered 212 sealings of calandria 202 lower ends, and escape pipe 204 stretches into extraction sample bottle 1, and its inlet is positioned at the bottom of extraction sample bottle 1.
Ask for an interview Fig. 3, be extraction sample bottle purging device 3 structural representations.Extraction sample bottle purging device 3 has a plinth 301, and its side is provided with heater tube 302 gentle connecting pipes 303.Base 301 tops are connected with square gas circuit divider 304, one cavity (not illustrating among the figure) is arranged in it, the length of side of the side ratio base 301 of gas circuit divider 304 is short, its upper surface vertically is connected with a plurality of gas outlet tubes 305, gas outlet tube 305 stretches out the length of upper surface, less than the length of extraction sample bottle 1.But extract sample bottle 1 reversed stream gas outlet tube 305, and place the upper surface of gas circuit divider 304.The upper end of all gas outlet 305 is outlet, and the lower end all is communicated with gas circuit connecting pipe 303 respectively in gas circuit divider 304 cavitys.Heater tube 302 communicates with the cavity of gas circuit divider 304.One square lid 306, the outside appearance of its outer length of side and base 301 together, the outside appearance of length of side and gas circuit divider 304 is with, the summation of room height and extraction sample bottle 1 length high greater than gas circuit divider 304 in the lid 306 in it, but its driving fit be placed on the base 301 gentle distributors 304.Lid 306 and base 301 lids and after, gas outlet tube 305 and extraction sample bottle 1 can be placed in lid 306 rooms.
Tens gas outlet tubes 305 to up to a hundred metals can be installed on the gas circuit divider 304.
Method of operating of the present invention is as follows:
A) earlier resolver seat 208 lower ends and fastening pressure cap 210 are coupled together, the thermal desorption carrier gas pipe 207 and the attached auxiliary carrier gas of resolver seat 208 coupled together, the purging protection gas circuit pipe 201 and the attached auxiliary constant current carrier gas of calandria 202 end faces coupled together.
B) to liquid or equal quality samples, sample is injected extraction sample bottle 1 and to seal, target components is extracted stationary phase 101 extractions on sample bottle 1 inwall.Be to quicken extraction equilibrium and guarantee repeatability, will extract sample bottle 1 and be put into and rocked in the constant temperature rocker 10-240 minute, specifically the time decides on properties of samples.
C) extraction reaches the balance hypsokinesis and pours out sample, to extract sample bottle 1 again is inverted in the room 211 of calandria 202 of hot parser 2, be connected calandria 202 lower ends fastening with resolver seat 208, under holddown spring 203 effect, calandria 202 lower ends uncovered with 212 and 1 mouthful of sealing of extraction sample bottle.
D) be blown into thermal desorption gas by thermal desorption carrier gas pipe 207, add thermal desorption, the component of desorption directly is transferred to the injector of gas chromatograph by sweep gas escape pipe 204 or is kept in the spacer, perhaps in the fraction collector.If sample saliferous, particle or colloid material are got the extraction sample bottle express developed 1-2 time with redistilled water behind the extraction equilibrium, pyrolysis is analysed then.To gaseous sample, directly extraction sample bottle 1 is put in the hot parser 2 and adds thermal desorption behind the extraction equilibrium.
Another road gas is blown into by purging protection gas circuit pipe 201, enters room 211 by microtubule 215, be full of and purges extract sample bottle 1 periphery after, emptying.The effect that purges protection gas is to avoid air to enter in the chromatographic analysis gas circuit by the sealing position seepage between extraction sample bottle 1 and the resolver seat 208.
E) will be with put upside down gas circuit divider 304 upper surfaces of purging device 3 of the extraction sample bottle of crossing 1, on the reversed stream gas outlet tube 305, cover the lid 306 of purging device 3, under 250-300 ℃ of temperature, with inert gas purge extraction sample bottle 1 inner chamber, the inert gas that flows out from gas outlet tube 305 enters the extraction sample bottle 1, overflow from the slit between extraction sample bottle 1 bottleneck and gas circuit divider 304 upper surfaces, enter in the room of lid 306, then from the slit effusion emptying between lid 306 and the base 301.Extraction sample bottle 1 after the processing is equipped with to be reused to remove residual component in aging 4-24 hour.
When thermal desorption, for fear of the absorption of transfer conduit to sample, designed the thermal desorption gas escape pipe 204 made of quartz capillary or platinum pipe directly the transmission samples to chromatic spectrum sample feeder or directly enter and keep in the spacer, as shown in Figure 2.The characteristics of apparatus of the present invention are: auxiliary carrier gas purges extraction sample bottle 1 inner chamber, another road gas purging sample bottle outer wall emptying then continuously in the thermal desorption process.Be airproof between outer wall and the inwall, seal with high temperature resistant O-ring seals 205,206 at bottle mouth position.Therefore, any component of extraction sample bottle 1 outer wall absorption can not enter in extraction sample bottle 1 inner chamber or the chromatograph, has avoided cross pollution.
Embodiment 1:
The volatilization and the organic contaminant that partly volatilizees in the extracting and enriching surface water.
1.5mL sample sorption extraction sample bottle at the bottom of the internal diameter 8mm garden, inwall are coated with the crosslinked OV-1 stationary phase 30mg of stain, the about 20 μ m of film thickness.The 1mL water sample is added in the bottle, rubber cushion and aluminum cap seal mouth with the inner liner polytetrafluoroethylene film, be placed on the constant temperature rocker, hunting frequency 20Hz, 40 ℃ of temperature, uncork lid after the extraction 10min, get rid of residual water droplet in the clean extraction sample bottle after pouring out sample, to extract sample bottle and put into the pyrolysis haustorium, 260 ℃ of permanent 6min of resolution temperature close heating power supply then.As the sweep gas escape pipe, the rubber blanket by the chromatograph injector directly inserts and keeps in the spacer with the elastic quartz capillary tube of internal diameter 120 μ m.The temperature of chromatic spectrum sample feeder is 250 ℃, and keeping spacer is 10m * 0.53mm I.D., and analytical column is 30m * 0.53mm I.D. * 1.2 μ m SE-54, analyzes with Agilent 6890-Plus gas chromatograph, detects with flame ionization ditector.Chromatographic condition is: 30 ℃ of permanent 8min, and then with 6 ℃/min temperature programme to 250 ℃, permanent 10min, the analysis of spectra that obtains is as shown in Figure 4.Wherein Fig. 4 A is the sample analysis chromatogram, and Fig. 4 B is the chromatogram of standard model solution.
Embodiment 2:
Residues of pesticides in the extracting and enriching soil.
The extraction sample bottle is with embodiment 1, get 0.25 gram pedotheque in the extraction sample bottle, add redistilled water 0.8mL, seal by the method for embodiment 1, allow water logging steep soil 5min, be put into then and under 45 ℃, shake 60min uncork afterwards lid on the constant temperature rocker, again sample is poured out, wash fast with redistilled water and extract sample bottle, get rid of residual water droplet in the clean extraction sample bottle, to extract sample bottle and put into the pyrolysis haustorium, 280 ℃ of permanent 6min of resolution temperature close heating power supply then.Other analysis condition is with embodiment 1, but temperature programme to 275 ℃ is done qualitative analysis with GC-MS.
Embodiment 3:
Residues of pesticides in the extracting and enriching yogurt sample.
With 1.5mL conical bottom extraction sample bottle, inwall is coated with the crosslinked 20mg SE-54 stationary phase of stain, the about 14 μ m of thickness.Get yoghurt 1mL and add in the 1.5mL extraction sample bottle, seal by the method for embodiment 1, be placed on then on the constant temperature rocker, 40 ℃ of constant temperature wave 60min, frequency 10Hz.Step afterwards is identical with embodiment 2, analyzes with GC-MS.
Embodiment 4:
The static headspace gas of component of partly volatilizing in the fluid sample is carried adsorption and enrichment.
With 1.5mL circular base extraction sample bottle, inwall is coated with the crosslinked 50mg OV-1 stationary phase of stain, the about 35 μ m of thickness.Fluid sample 20mL inserts in the head space bottle, and gas from liquid bottom is blown into, and collect from the bottle top and draw gas to extracting the sample bottle bottom, the contained organic component that partly volatilizees in the adsorbed gas, waste gas is overflowed naturally, as shown in Figure 5.Overflow from fluid sample for quickening component, can be to headspace sample heated constant temperature and stirring.Behind the 10min, stop to purge, take off the extraction sample bottle, be put into and resolve target components on the hot parser.Remaining step is identical with embodiment 1.
Embodiment 5:
The enrichment of micro-volatile component in the gaseous sample.
With extraction sample bottle at the bottom of the shape of 1.5mL garden, inwall is coated with the crosslinked expanded polystyrene of stain, the about 20 μ m of thickness.Gas to be measured is fed extraction sample bottle bottom continuously, and gas is overflowed naturally.Other condition is with embodiment 1.
Embodiment 6:
Organic component partly volatilizees in the extraction vegetable slurries sample.
With round bottom 1.5mL extraction sample bottle, inwall is coated with the crosslinked OV-1 stationary phase 30mg of stain, the about 20 μ m of film thickness.Get vegetable slurries 1mL pack into the extraction sample bottle in, seal the back carry out according to the step of embodiment 2.Other condition is with embodiment 2.
Claims (5)
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| CNB2004100692047A CN1318845C (en) | 2004-07-14 | 2004-07-14 | Solid phase extraction sample bottle and thermal analysis apparatus |
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| CNB2004100692047A CN1318845C (en) | 2004-07-14 | 2004-07-14 | Solid phase extraction sample bottle and thermal analysis apparatus |
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Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009003429B3 (en) | 2009-02-04 | 2010-07-01 | Joint Analytical Systems Gmbh | Apparatus and method for preparing samples for gas chromatography |
| US8490466B2 (en) * | 2009-12-20 | 2013-07-23 | Agilent Technologies, Inc. | Capsule injection system for gas chromatography |
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| CN102207433B (en) * | 2011-03-10 | 2012-09-26 | 长沙开元仪器股份有限公司 | Device for sealing sample |
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| US9913924B2 (en) * | 2016-05-25 | 2018-03-13 | S. C. Johnson & Son, Inc. | Dispensing device |
| CN105911197B (en) * | 2016-05-25 | 2018-06-29 | 延边大学 | Automatic sample thermal desorption and liquid phase microemulsion preconcentrate device |
| CN106053288B (en) * | 2016-08-11 | 2018-11-30 | 北京市环境保护科学研究院 | Using the method for spherical passive sample devices measurement soil gas volatilization flux |
| CN108072720B (en) * | 2016-11-11 | 2024-09-20 | 成都青山利康药业股份有限公司 | Device for keeping sample injection bottle clean and dry |
| CN109839295A (en) * | 2017-11-27 | 2019-06-04 | 中国科学院大连化学物理研究所 | One kind being enriched with absorption-thermal desorption device for trace samplings |
| CN111141858B (en) * | 2018-11-06 | 2021-07-27 | 中国科学院大连化学物理研究所 | A device for thermal analyzer interface |
| CN109350995A (en) * | 2018-12-26 | 2019-02-19 | 济南大学 | A kind of solid phase extraction column loaded with SBA-15 adsorbent and preparation method thereof |
| CN110411800B (en) * | 2019-08-02 | 2021-09-14 | 河北大学 | Integrated dispersed solid phase extraction device and sample pretreatment method |
| CN110988009B (en) * | 2019-11-22 | 2021-03-09 | 浙江大学 | Pyrolysis reaction resonant cavity for EPR spectrometer and EPR spectrometer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001081912A1 (en) * | 2000-04-27 | 2001-11-01 | Sofia Softwareentwicklung Und Intelligente Analytik Gmbh | Metal cannula for extracting organic substances |
| CN1405560A (en) * | 2002-10-31 | 2003-03-26 | 上海交通大学 | Active-carbon-fiber type solid-phase adsorption method for gas-phase chromatogram |
-
2004
- 2004-07-14 CN CNB2004100692047A patent/CN1318845C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001081912A1 (en) * | 2000-04-27 | 2001-11-01 | Sofia Softwareentwicklung Und Intelligente Analytik Gmbh | Metal cannula for extracting organic substances |
| CN1405560A (en) * | 2002-10-31 | 2003-03-26 | 上海交通大学 | Active-carbon-fiber type solid-phase adsorption method for gas-phase chromatogram |
Non-Patent Citations (2)
| Title |
|---|
| 固相微萃取新技术 马继平等，色谱，第20卷第1期 2002 * |
| 热解析GC用的大容量固相萃取器的开发及其基本特征的探讨 王丽丽等，浙江科技学院学报，第15卷 2003 * |
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