WO2013073693A1 - Vapor-liquid contact extraction method and device - Google Patents
Vapor-liquid contact extraction method and device Download PDFInfo
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- WO2013073693A1 WO2013073693A1 PCT/JP2012/079865 JP2012079865W WO2013073693A1 WO 2013073693 A1 WO2013073693 A1 WO 2013073693A1 JP 2012079865 W JP2012079865 W JP 2012079865W WO 2013073693 A1 WO2013073693 A1 WO 2013073693A1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4055—Concentrating samples by solubility techniques
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/065—Preparation using different phases to separate parts of sample
Definitions
- the present invention relates to a dissolved substance in a liquid (hereinafter referred to as “GC”) or a gas chromatograph mass spectrometer (hereinafter sometimes referred to as “GC / MS”).
- GC gas chromatograph mass spectrometer
- the present invention relates to a method and apparatus for efficiently gas-liquid extraction of analytical species in the analysis of “analytical species”.
- P & T purge and trap
- HS headspace
- P & T method an analyte dissolved in a solution is forcibly extracted into a gas phase by flowing a gas having a low solubility in the solution, and the extracted analyte is temporarily used as an adsorbent.
- This is a method of concentrating the analyte by holding it. Thereafter, the adsorbent is rapidly heated, the analyte is heated and desorbed from the adsorbent, and the analyte is introduced into the GC analytical column.
- Equation 1 The purge efficiency R in the ideal state can be obtained from Equation 1 for extracting the analysis species from the water in the P & T method.
- F is the flow rate of the purge gas
- t is the purge time
- K is the partition coefficient
- V L is the volume of the sample
- V G is the gas phase volume of the vessel
- m 0 is the amount of analyte in the original solution
- M a is the amount of the analyte that has entered the gas phase.
- the total purge flow must be increased to increase the recovery rate.
- it is the process of holding the analyte in the extracted purge gas with the adsorbent. Since the adsorbent used has a breakthrough volume for each analyte, consider the total flow rate of the purge gas. There is a need.
- the purge efficiency increases by increasing the purge gas flow rate, decreasing the distribution coefficient K, decreasing the volume of the sample, and decreasing the gas phase portion of the purge vessel.
- the musty odor component in tap water is said to have a threshold of 1 ppt. That is, even if 1 pg of analytical species exists in 1 ml of tap water, a person recognizes it as a musty odor. It is said that the olfactory threshold of trichloroanisole caused by the hypochlorous acid sterilization residue and phenols is 0.03ppt.
- the measurement sensitivity of GC / MS does not reach human sensations. Although it depends on the amount of impurities, etc. that are not to be measured, the analytical species cannot be detected unless several pg of analytical species are introduced into the GC separation column and reach the mass spectrometer.
- frit fine mesh sintered filter
- cryofocus P & T method Since the cryofocus P & T method has poor extraction efficiency, a cryofocus using liquid nitrogen is used in order to introduce the entire amount of the extracted analyte into GC or GC / MS.
- a cryofocus using liquid nitrogen is used in order to introduce the entire amount of the extracted analyte into GC or GC / MS.
- Equation 2 The concentration in the gas phase by the HS method can be obtained from Equation 2.
- C G is analyte concentration in the gas phase (g / cm 3)
- C L is analyte concentration in the liquid phase (g / cm 3)
- V G is the volume of gas-phase
- V L is the volume of the liquid phase
- C L 0 is the sample concentration before equilibration.
- Equation 2 when the water-soluble component has a large partition coefficient K, the recovery rate of the analyte extracted in the gas phase is poor.
- K increases the vial temperature (for water samples) to salting perform, it is understood that the addition of an acid or a base is effective.
- reducing ⁇ increasing the amount of sample, decreasing the gas phase portion is not very effective in improving sensitivity.
- the multiple HS method in which the headspace gas after gas-liquid equilibration is concentrated and collected in the adsorbent many times, or the P & T method in which gas-liquid equilibria are created with microbubbles and extracted continuously.
- the HS method is different in batch processing and the P & T method is different in continuous extraction.
- the HS method and the P & T method are the same in principle, and the extraction amount depends on the distribution coefficient.
- the big problem of both is that the gas concentration of the analyte immediately after starting the extraction operation after putting the sample in the container or the purge pipe is high, the analyte is extracted from the liquid and the concentration of the solution is low, Since the distribution coefficient (ratio of concentration in solution to gas) is constant, the concentration in gas also decreases.
- the second half of the extraction operation is that the amount of extracted analyte is reduced while the P & T method consumes a large amount of extracted gas.
- Gas-liquid countercurrent contact extraction is known as a gas-liquid extraction operation that has the potential to solve the problems of the conventional method. This technique is employed when a predetermined component is recovered or removed from a large amount of liquid in the chemical industry field such as a plant (see Japanese Patent Application Laid-Open No. 10-57947 and Japanese Patent No. 3006894). .
- a wick is installed on the inner wall surface of the tube, and the liquid is moved in the liquid phase by capillary action.
- this liquid phase transfer by capillary action can be used when the amount of liquid is large, but the time control is not effective in the analysis process of a small amount of liquid sample, and fine particles are present in the sample liquid. If present, the fine particles may accumulate on the rotating member or wick and contaminate the inner wall surface of the tube, which is not suitable for continuous operation of the apparatus.
- a surfactant is mixed into a liquid sample, or when the liquid sample is an effervescent beverage, there is foaming, and the sample itself may be difficult to extract, making practical use impossible.
- the P & T method and the HS method are methods in which analysis is performed using a liquid sample stored in a fixed space, and it is impossible to supply and analyze a continuous sample over a long period of time.
- samples of “specimens with a high partition coefficient in vapor-liquid equilibrium”, “species with high water solubility”, or “species with low olfactory threshold” are collected 24 hours a day, unattended and continuously.
- the sample liquid is continuously supplied to the gas-liquid extraction part, the supply balance between the purge gas and the sample liquid is ensured, the analyte is rapidly transferred to the gas phase, and is led to the collection tube.
- a method and apparatus for introducing a sample into a GC or GC / MS i.e., a method and apparatus for performing extraction at all times of continuous sample flow.
- the present invention uses a gas-liquid contact extractor that continuously introduces sample liquid from above and purge gas from below, and makes the sample liquid and purge gas come into gas-liquid contact to extract the analyte in the sample liquid.
- the sample liquid is discharged through the liquid reservoir provided in the discharge pipe connected to the lower part of the gas-liquid contact extractor, and the purge gas is prevented from flowing out from the liquid reservoir.
- a gas-liquid contact extraction method is provided.
- the sample liquid is preheated to an extraction temperature in the gas-liquid contact extractor before supplying the sample liquid to the gas-liquid contact extractor.
- An extraction method is provided.
- the gas-liquid contact extraction method is characterized in that a water-soluble component having a partition coefficient K greater than 1 or an analyte present in a liquid having an olfactory threshold lower than 10 ppt (pg / ml) is gas-liquid contact extracted.
- a gas-liquid contact extraction method is provided.
- the gas-liquid contact extractor is installed in a temperature-controllable oven, and the flow path to the collection tube where the gas-liquid contact-extracted analyte is concentrated is set to the oven temperature (
- a gas-liquid contact extraction method characterized in that an analytical species extracted by gas-liquid extraction is concentrated in the collection tube at a temperature equal to or higher than the gas-liquid extraction temperature).
- a gas-liquid contact extractor for supplying a liquid sample from above and a purge gas from below is provided, and a discharge pipe is connected to the lower portion of the gas-liquid contact extractor while discharging the sample liquid to the discharge pipe.
- a gas-liquid contact extraction device provided with a liquid reservoir for preventing discharge of purge gas.
- a gas-liquid contact extraction device wherein the contact surface with the sample liquid of the gas-liquid contact extractor is subjected to surface treatment, and the contact surface is in an extended wet state. To do.
- the gas-liquid contact extraction device is characterized in that the surface treatment is either hydrophilic treatment or water repellent treatment.
- liquid sample supply unit is connected to the gas-liquid contact extraction device via a syringe pump and a selector valve for switching the flow path, and the analytes extracted by the gas-liquid contact extraction device are collected.
- an automatic liquid sample supply device characterized by being sent to a tube.
- the liquid sample in supplying the liquid sample to the gas-liquid contact extractor, the liquid sample is supplied at the extraction temperature, and the gas-liquid contact at the gas-liquid boundary surface is sufficiently and rapidly performed.
- the liquid sample can achieve gas-liquid equilibrium in a short time, and the analyte can be secured quickly and reliably.
- the purge gas is prevented from being discharged from the discharge part, and the supply amount of the sample liquid to the gas-liquid contact extractor, the purge gas pressure, and the purge gas flow rate are matched. It is possible to increase the gas-liquid contact rate, increase the extraction efficiency of the analyte, and reliably carry out the flow of the analyte to a concentrating tube having a constant flow rate.
- the analyte concentration in the gas phase can be made closer to the theoretical value, and the analysis species with a high partition coefficient, high water solubility, and low olfactory threshold, which have been difficult in the past, can be obtained. It became easy to analyze.
- Fig. 1 shows an online connection of GC or GC / MS that can be used for quality control in tap water and beverage factories, which can supply river water and tap water by flow from a source such as a large storage tank.
- This system 500 includes the gas-liquid contact extractor 2, the gas-liquid contact extraction device 200, and the automatic liquid sample supply device 100 of the present invention, and is a system that performs the gas-liquid contact extraction method of the present invention.
- the tube 1 constitutes the main body of the gas-liquid contact extractor 2 and is installed in a slanting manner.
- the tube 1 is preferably a spiral tube, but a straight tube, a bent tube or the like can also be used.
- the automatic liquid sample supply apparatus 100 includes a gas-liquid contact extractor 2 and a gas-liquid contact extraction apparatus 200.
- the gas-liquid contact extractor 2 is made of glass, metal, synthetic resin, or the like, and has an inner diameter of 3 to 10 mm and an inclination angle of 15 ° to 45 ° with respect to the horizontal.
- the gas-liquid contact extractor 2 is formed of a spiral tube, its length and winding diameter are not particularly limited, but it is preferable that the length is 500 to 1500 mm and the winding diameter is 50 to 200 mm.
- the gas-liquid contact extractor 2 performs surface treatment on the contact surface with the sample liquid, that is, the inner surface of the gas-liquid contact extractor 2 to improve the “wetting property” when contacting with the sample liquid. It is preferable to make a gas-liquid contact area large by adopting the form of "".
- the wetness of the liquid on the inner surface of the gas-liquid contact extractor 2 there are extended wetness, immersion wetness, and adhesion wetness as shown in the science chronology. It is preferable.
- the treatment contents differ depending on the sample.
- Water samples such as rivers, tap water, soft drinks and alcohol are subjected to hydrophilic treatment, and oil samples such as vegetable oil and industrial oil are subjected to water repellent treatment.
- hydrophilic treatment super-hydrophilization by plasma treatment, super-hydrophilization by sol-gel method, super-hydrophilization by photocatalyst, super-hydrophilization by additives, super-hydrophilic treatment by inorganic nanoparticle coating, hot water treatment of gel film
- Techniques such as hydrophilization by graft copolymerization, hydrophilization by hydrophilic micelle crosslinking, hydrophilization by corona discharge, hydrophilization by laser irradiation, and hydrochloric acid treatment can be used.
- water repellency treatment includes super water repellency by plasma treatment, super water repellency by fluorine surface modifier, super water repellency by chemical adsorption method, super water repellency by sol-gel method, fluorine Super water-repellent treatment by electrodeposition coating with a fluorine-based graft copolymer / fluorine resin fine particles, water repellency by a silane coupling agent, water repellency by an acrylic silicone / silica composite film, water repellency by a chemical adsorption monomolecular film , Coating with chemicals with functional groups such as super water repellency by ion beam modification and saturated fluoroalkyl group (especially trifluoromethyl group), alkylsilyl group, fluoroacyl group, long chain alkyl group There is a technique such as, and it can be selected and used corresponding to each sample.
- An opening 4 for connecting a sample supply pipe 3 for supplying a sample liquid to the pipe 1 and an opening 6 for connecting a purge gas discharge pipe 5 to the pipe 1 are provided at the upper end of the pipe 1. Further, at the lower end of the pipe 1, an opening 8 for connecting a purge gas supply pipe 7 provided with a pressure controller 30 to the pipe 1 and an opening 10 for connecting a discharge pipe 9 for discharging a sample liquid to the pipe 1. Is provided.
- a purge gas such as helium is sent from below through the gas supply pipe 7 and the opening 8 to the gas-liquid contact extractor 2 in which the openings 4, 6, 8, and 10 are formed, and the sample supply pipe 3 and the opening are opened from above. Through 4, the sample liquid is dropped. Therefore, the gas (purge gas) and the liquid (sample liquid) are brought into contact with each other by countercurrent, and the analyte present in the liquid phase is rapidly moved to the gas phase.
- the sample supply pipe 3 communicates with the syringe pump 11, and a predetermined amount of sample liquid calibrated by the syringe pump 11 is supplied to the gas-liquid contact extractor 2 via the selector valve 31 and the sample supply pipe 3.
- a preheat pipe 12 is installed in the sample supply pipe 3.
- the gas supply pipe 7 is also provided with a preheat pipe 13.
- the gas-liquid contact extractor 2 is installed in the oven 14 and is temperature-controlled.
- the purge gas discharge pipe 5 communicates with a valve 15, and the valve 15 is connected to a vent 16 and a second valve 17.
- the valve 17 is provided with connection paths 19 and 20 to the GC or GC / MS 18, a vent 21, and connection paths 23 and 24 to the concentration tube 22. Further, a heater 25 and a fan 26 are installed opposite to the concentration tube 22.
- a connecting pipe 28 is connected to the valve 15, and the connecting pipe 28 is connected to the gas supply pipe 7 through a needle valve 27.
- a predetermined number of sample tanks 32 are connected to the syringe pump 11 via a line 30 and a selector valve 31.
- the automatic liquid sample supply device 100 includes a gas-liquid contact extraction device.
- the gas-liquid contact extraction device includes the gas-liquid contact extractor 2, a discharge pipe 9 that discharges the sample liquid, and a liquid reservoir 34.
- the liquid reservoir 34 is a mechanism for maintaining a constant liquid level in order to prevent the purge gas from flowing out from the discharge pipe 9 connected to the lower part of the gas-liquid contact extractor 2.
- the liquid reservoir 34 is provided in the discharge pipe 9.
- the liquid reservoir 34 employs a mechanism using the principle of a U-tube manometer, for example, a U-tube structure or a structure in which a part of the sample liquid flowing out from the discharge tube 9 is formed in a large diameter. I can do it.
- a pipe is connected to the opening 10 of the gas-liquid contact extractor 2 or the discharge pipe 9 for discharging the sample liquid instead of a manometer, and a liquid level sensor and a solenoid valve (not shown) are connected here.
- the sample liquid that is provided and discharged may be configured to maintain a constant liquid level in the pipe. Further, a load corresponding to a water column may be applied to the discharge portion of the U-shaped tube so that the sample liquid can maintain the water surface in the pipe.
- the sample liquid is supplied to the gas-liquid contact extractor 2 by the syringe pump 11 through the selector valve 31 and the sample supply pipe 3.
- the sample liquid is heated to the sample extraction temperature by the preheat pipe 12 in the sample supply pipe 3 in order to achieve a rapid gas-liquid equilibrium state in the gas-liquid contact extractor 2.
- the flow path of the entire system in particular, the oven 14 in which the gas-liquid contact extractor 2 is housed and the flow path between the oven 14 and the GC or GC / MS 18 are temperature-controlled so that the temperature is equal to or higher than the sample extraction temperature. It is good to set. By such temperature setting, it is possible to prevent water vapor condensation and analyte adsorption caused by the following purge.
- the container 32 is a container containing a sample liquid, and containers containing different sample liquids can be installed in parallel and connected to the selector valve 31 respectively.
- the container 33 is a container containing a standard sample liquid having a known concentration of analytical species, and the container 35 is a container containing cleaning water.
- the selector valve 31 is operated to open the port a connected to the container 32 containing the sample liquid.
- the valve 29-1 moves to a position connecting the port b and the port c, and the valve 29-2 moves to a position connecting the port a and the port b.
- the container 32 containing the sample liquid and the pipe 30 are connected, and the sample liquid can be sucked by the syringe pump 11-1 and the syringe pump 11-2.
- the syringe pump 11-1 moves to a position where the port a and the port b of the valve 29-1 are connected, and the sample liquid is gas-liquid through the pipe 3. Feed to contact extractor 2. At this time, the syringe pump 11-2 stops the sample liquid supply operation. Before the sample liquid supplied by the syringe pump 11-1 runs out, the valve 29-1 moves to a position connecting the port b and the port c and sucks the sample liquid again.
- the sample liquid sucked by the syringe pump 11-2 is evacuated from the pipe 3 by moving to a position where the port b and the port c of the valve 29-2 are connected.
- the liquid contact extractor 2 is supplied.
- the sample liquid is continuously supplied to the gas-liquid contact extractor 2 by interlocking the syringe pump 11-1 with the valve 29-1, and the syringe pump 11-2 with the valve 29-2.
- the liquid sample warmed in the sample supply pipe 3 and adapted to the extraction temperature always enters the gas-liquid contact extractor 2 through the opening 4 and flows down along the bottom surface of the pipe 1 installed in an oblique shape.
- the purge gas is supplied to the gas-liquid contact extractor 2 at a constant flow rate, warmed to an appropriate temperature by the preheat pipe 13 in the gas supply pipe 7, and continuously enters the gas-liquid contact extractor 2 through the lower opening 8 and rises. To do. Therefore, the sample liquid and the purge gas are always in countercurrent and contact with each other.
- the flow rate of the sample liquid is 0.01 to 5 ml / min
- the purge gas flow rate is 0.1 to 100 ml / min
- the extraction temperature is within the range where the liquid sample is not frozen and the target analyte is not thermally decomposed.
- the extraction is performed at a temperature suitable for extraction, and the extraction time is set according to the liquid sample.
- the liquid phase and the gas phase heated in the gas-liquid contact extractor 2 are continuously subjected to mass transfer at the boundary. What is required here is an improvement in the contact efficiency between the gas and the liquid, and the rapid movement of the substance in the liquid, that is, the analyte, into the gas phase by the gas-liquid contact.
- the sample liquid is always discharged from the gas-liquid contact extractor 2 to which the sample liquid is supplied at a constant flow rate via the liquid reservoir 34 utilizing the principle of the U-tube manometer. Outflow from the liquid reservoir 34 is prevented, and supply of purge gas at a constant flow rate is ensured in the concentration tube 22 for concentrating the gas-liquid extracted analyte.
- the purge gas pressure is adjusted to a pressure necessary to supply the purge gas containing the extracted analyte at a constant flow rate to the concentrating tube 22.
- the sample liquid stored in and discharged from the liquid reservoir 34 prevents the purge gas from flowing out from the lower part of the gas-liquid contact extractor 2 and maintains the supply pressure of the purge gas. As a result, a stable supply of the gas phase in the gas-liquid contact extractor 2 is performed, and a balance with the sample liquid supply can be achieved. As a result, gas-liquid contact is sufficiently performed, contributing to gas-liquid equilibrium.
- the gas-liquid contact extractor 2 moves to the gas phase portion based on the above equation 2 that defines the distribution coefficient.
- the amount of analytical species can be calculated.
- the thickness of the liquid phase is formed thin as described above due to the wettability of the inner surface of the tube 1 constituting the gas-liquid contact extractor 2.
- Mass transfer in the liquid phase is governed by the diffusion coefficient. It is known that the diffusion coefficient of molecules in water is on the order of 10 ⁇ 5 cm 2 / sec. And as the thickness of the liquid phase is thinner, the time for the moving substance, that is, the analyte to reach the gas-liquid boundary surface is earlier, and the number of times that the analyte in the liquid phase contacts the gas phase increases. That is, the thinner the liquid phase, the greater the amount of analyte that moves to the gas phase, which means that the time to reach the vapor-liquid equilibrium state is shorter.
- the diffusion coefficient of benzene in water is 1.02 ⁇ 10 ⁇ 5 cm 2 / sec.
- one molecule of benzene will be present somewhere within the range of 18 ⁇ m after 1 second.
- the thickness of the liquid phase is 0.22 mm (220 ⁇ m)
- the time to reach the liquid surface from the bottom is approximately 10 seconds (12.2 seconds in calculation).
- the pipe 1 falls for 30 seconds at a water flow rate of 2 ml / min
- the benzene molecule can reach the gas-liquid contact surface twice, and the benzene molecule has two chances to move to the gas phase. Will be.
- the flow of liquid and the thickness of the water channel in the pipe 1 can be analyzed by the speed theory of the open channel.
- the mixing effect (displacement of lower and upper water) of the fluid is promoted by the generation of the secondary flow, and the driving force for causing efficient mass transfer from the liquid phase to the gas phase It has become.
- the gas-liquid contact extractor 2 may be a box-type water channel having a flat bottom surface, and has a channel through which the sample liquid can flow from the upstream and the purge gas can be introduced from the downstream, and the introduced purge gas is captured.
- the tube shape is not limited to the above as long as it is not discharged to any place other than the collecting tube.
- the distribution coefficient K can be reduced by preheating the sample liquid, and the liquid phase is formed thin due to the wettability of the inner surface of the tube 1, so that the analysis species into the gas phase can be reduced. Mass transfer was fast and purge efficiency increased.
- the analyte concentration (theoretical value) in the gas phase theoretically calculated based on the definition of the distribution coefficient (Equation 2) is substantially the same as the analyte concentration (experimental value) obtained in the actual experiment. It has become.
- the sample water containing 2-MIB and Geosimin was analyzed by the conventional P & T method and the gas-liquid contact extraction method of the present invention using the system including the gas-liquid contact extraction device of the present invention and the automatic liquid sample supply device shown in FIG. .
- An experimental example for comparing the amount of mass transfer of 2-MIB and Geosimin into the gas phase is shown.
- Table 2 shows the theoretical mass transfer amounts of 2-MIB and Geosimin that move from the liquid phase of the concentration 5ppt (5 pg / mL) to the gas phase, and the respective extraction for the conventional P & T method and the gas-liquid contact extraction method of the present invention. Shows efficiency.
- the amount of sample water in the conventional P & T method is 20 ml, and in the method of the present invention, water is passed for 20 minutes at a water flow rate of 2 ml / min, so the total amount is 40 ml.
- the theoretical mass transfer amount to the gas phase is from formula 1 to 2-MIB: 72.0 pg, Geosimin: 76.3 pg, and the experimental values are 2-MIB: 44.6 pg, Geosimin: 59. It was 9 pg. The experimental value is far below the theoretical value. This means that mass transfer from the liquid phase to the gas phase by the conventional P & T method is not performed rapidly, and the vapor-liquid equilibrium state has not been reached.
- the theoretical mass transfer amount to the gas phase of the method of the present invention is from formula 2 to 2-MIB: 132.1 pg, Geosimin: 150.0 pg, and the experimental values are 2-MIB: 139.6 pg, Geosimin: It was 157.2 pg.
- the experimental and theoretical values were almost equal. This means that the mass transfer from the liquid phase to the gas phase according to the method of the present invention is performed rapidly, and a vapor-liquid equilibrium state is reached at the purge gas outlet.
- the “spiral tube (counterflow) method” based on the principle of gas-liquid countercurrent contact extraction of the present invention has been found to be a method that can obtain the extraction efficiency as theoretically. Furthermore, the method of the present invention extends the gas-liquid countercurrent contact extraction operation time, so that it can be concentrated as long as it does not exceed the breakthrough capacity of the adsorbent for the analyte, so detection sensitivity is improved in GC and GC / MS analysis. it can.
- Sample water extraction conditions 1) Sample water extraction temperature: 60 ° C 2) Sample water: Conventional P & T: 20 ml, method flow rate of the present invention: 2 ml / min 3) Purge gas flow rate: Conventional P & T: 80 ml / min (120 kPa), method flow rate of the present invention: 80 ml / min (120 kPa) 4) Extraction time: 20 min 5) Sample flow path temperature: 60 ° C 6) Spiral tube shape: inner diameter 4 mm, length 1200 mm, installation angle 30 ° Pyrex (registered trademark) glass 7) Spiral tube inner surface treatment: 18% HCl was sealed in a spiral tube, washed and dried.
- the extraction efficiency of 2-MIB and Geosimin was compared by changing the purge gas flow rate and the sample water flow rate.
- the extraction efficiency conditions for 2-MIB and Geosimin due to differences in purge gas flow rate and sample water flow rate are: A: Sample water flow rate: 4 ml / min, purge gas flow rate: 160 ml / min, extraction time: 10 minutes B: sample water flow rate: 2 ml / min, purge gas flow rate: 80 ml / min, extraction time: 20 minutes C: sample water flow rate: 1 ml / min, purge gas flow rate: 40 ml / min, extraction time: 40 minutes, and extraction temperature was 60 ° C. The results are shown in FIG. It was found that the condition for obtaining high extraction efficiency for both components was B in the figure.
- Sample water extraction conditions 1) Sample water extraction temperature: 60 ° C 2) Sample water flow rate: 1, 2, 4 ml / min 3) Purge gas flow rate: 40 ml / min (60 kPa), 80 ml / min (120 kPa), 160mlmin (240kPa) 4) Sample flow path temperature: 60 ° C min 5) Extraction time: 10, 20, 40 min 6) Spiral tube shape: inner diameter 4 mm, length 1200 mm, installation angle 30 degrees Pyrex (registered trademark) glass 7) Spiral tube inner surface treatment: 18% HCL is sealed in a spiral tube, washed and dried.
- Sample water extraction conditions 1) Sample water extraction temperature: 60 ° C 2) Sample water flow rate: 2 ml / min 3) Purge gas flow rate: 80 ml / min (120 kPa) 4) Sample flow path temperature: 60 ° C 5) Extraction time: 20 min 6) Spiral tube shape: inner diameter 4 mm, length 1200 mm, installation angle 30 ° Pyrex (registered trademark) glass 7) Spiral tube inner surface treatment: 18% HCl was sealed in a spiral tube, washed and dried. As a result, the glass surface was decontaminated and the silanol groups on the glass surface were activated to improve the hydrophilicity of the glass surface.
- Sample water extraction conditions 1) Sample water extraction temperature: 60 ° C 2) Sample water flow rate: 2 ml / min 3) Purge gas flow rate: 80 ml / min (120 kPa) 4) Sample flow path temperature: 60 ° C 5) Extraction time: 20 min 6) Spiral tube shape: inner diameter 4 mm, length 1200 mm, installation angle 30 ° Pyrex (registered trademark) glass 7) Spiral tube inner surface treatment: 18% HCl was sealed in a spiral tube, washed and dried. As a result, the glass surface was decontaminated and the silanol groups on the glass surface were activated to improve the hydrophilicity of the glass surface.
- TCA 2,4,6-Trichloroanisole
- TCP 2,4,6-trichlorophenol
- TCP contamination occurs during chlorination of raw water or during transport using a water distribution system. In this way, there is a need for thorough management not only in water sources but also in manufacturing factories that handle water.
- 2,4,6-trichloroanisole with a concentration of 30 ppq was prepared, and analysis was performed using the same gas-liquid contact extraction method as in Example 1 above with a sample flow rate of 2 ml / min and an extraction time of 100 minutes (total flow rate of 200 ml). .
- MS was measured in SIM mode, and monitor ions were set to m / z 210 and 212.
- Other analysis conditions are the same as in Example 1.
- Sample water extraction conditions 1) Sample water extraction temperature: 60 ° C 2) Sample water flow rate: 2 ml / min 3) Purge gas flow rate: 80 ml / min (120 kPa) 4) Sample flow path temperature: 60 ° C 5) Extraction time: 20 min 6) Spiral tube shape: inner diameter 4 mm, length 1200 mm, installation angle 30 ° Pyrex (registered trademark) glass 7) Spiral tube inner surface treatment: 18% HCl was sealed in a spiral tube, washed and dried. As a result, the glass surface was decontaminated and the silanol groups on the glass surface were activated to improve the hydrophilicity of the glass surface.
- Sample concentration condition 1 Collection agent: Tenax TA 200 mg (collection tube 3.2 mm ID ⁇ 200 mm) 2) Collection temperature: 60 ° C 3) Collection tube heating temperature: 220 (10 minutes) 4) Desorption flow rate during heating: 11 ml / min 5) Valve temperature: 150 ° C 6) Transfer line temperature: 150 ° C (3) GCMS measurement conditions 1) Collection tube temperature during sampling: 60 ° C 2) Collection tube heating temperature during sample introduction: 220 ° C. (5 ° C./second), (holding time 10 min) 3) Analytical column flow rate: 1 ml / min 4) Split flow rate: 10 ml / min 5) GC oven temperature: 40 ° C. (12 min) -20 ° C./min-250° C.
- 1,4-Dioxane was added on November 30, 2009 to environmental standards related to the protection of human health related to water pollution in public water areas and environmental standards related to water pollution in groundwater.
- the environmental standard is 0.05 mg / L or less
- the groundwater environmental standard is 0.05 mg / L or less.
- the establishment of drainage standards is currently under deliberation by the Central Council Water Environment Subcommittee, etc. It is.
- the standard value for tap water for 1,4-dioxane is also 0.05 mg / L.
- the lower limit of detection is required to be 1/10 or less of the reference value.
- the analysis method of 1,4-dioxane in the water supply method is a solid phase extraction / solvent extraction-GC / MS method.
- 1 / 4-dioxane 0.05 mg / L 1 / 10 ⁇ g / L (5 ppb) was examined.
- MS under measurement conditions was measured in SIM mode, and monitor ions were set to m / z 58 and 64.
- the other conditions were the analysis conditions described in Example 1.
- Sample water extraction conditions 1) Sample water extraction temperature: 60 ° C 2) Sample water flow rate: 2 ml / min 3) Purge gas flow rate: 80 ml / min (120 kPa) 4) Sample channel temperature: 60 ° C) 5) Extraction time: 20 min 6) Spiral tube shape: inner diameter 4 mm, length 1200 mm, installation angle 30 ° Pyrex (registered trademark) glass 7) Spiral tube inner surface treatment: 18% HCl was sealed in a spiral tube, washed and dried. As a result, the glass surface was decontaminated and the silanol groups on the glass surface were activated to improve the hydrophilicity of the glass surface.
- Sesame oil is produced by a process of roasting and pressing at a high temperature. At this time, sugar and protein in the component cause a Maillard reaction to generate a pyrazine compound that is an aroma component. These pyrazines have been proposed to exhibit physiological activity, and there are many research reports.
- Sample water extraction conditions 1) Sample water extraction temperature: 60 ° C 2) Sample water flow rate: 2 ml / min 3) Purge gas flow rate: 80 ml / min (120 kPa) 4) Sample flow path temperature: 60 ° C 5) Extraction time: 20 min 6) Spiral tube shape: inner diameter 4 mm, length 1200 mm, installation angle 30 degrees Pyrex (registered trademark) glass 7) Spiral tube inner surface treatment: After activating hydroxyl groups on the glass surface, a toluene solution in which octadecyldimethylchlorosilane was dissolved Put it in, reflux for a predetermined time, wash with toluene and dry.
- Sample water extraction conditions 1) Sample water extraction temperature: 60 ° C 2) Sample water flow rate: 2 ml / min 3) Purge gas flow rate: 80 ml / min (120 kPa) 4) Sample flow path temperature: 60 ° C 5) Extraction time: 20 min 6) Spiral tube shape: inner diameter 4 mm, length 1200 mm, installation angle 30 ° Pyrex (registered trademark) glass 7) Spiral tube inner surface treatment: 18% HCl was sealed in a spiral tube, washed and dried. As a result, the glass surface was decontaminated and the silanol groups on the glass surface were activated to improve the hydrophilicity of the glass surface.
- FIG. 15 shows a SIM chromatogram (18.3-20 ⁇ 3 min: m / z 95, 20.3) comparing the 10 ppt mold odor standard water (a) and the river water (b) having a turbidity of 150 degrees (kaolin). -22.5 min: m / z 112).
- peak 1 is 2-MIB
- peak 2 is Geosmin.
- the SIM chromatogram of (b) many contaminant components were confirmed around the peaks of 2-MIB and Geosmin due to the influence of the contaminant components, and the rise in the baseline was remarkable. It turns out that analysis of river water is possible enough.
- Tea contains a lot of substances called saponins, and these have high foaming properties.
- saponins substances called saponins, and these have high foaming properties.
- bubbles are blown up together with the purge gas and enter the collection tube, making it impossible to analyze tea.
- FIG. 16 shows a total ion current chromatogram (hereinafter abbreviated as TICC) in which a commercially available tea beverage was compared with respect to aroma components immediately after opening and after 10 days.
- TICC total ion current chromatogram
- Sample (a) 10 days after opening contains 1-octen-3-ol of peak 1 and 2-Heptenal, (E)-of peak 2 which are off-flavor components not detected immediately after opening (b). Remarkably confirmed. It was also found that the flavor component 1,6,10-Dodecatrien-3-ol, 3,7,11-trimethyl- (also known as nerolidol) detected immediately after opening was not detected after 10 days. Both (5E) -3,4-dimethyl-5-pentylidenefuran-2-one (also called boride) at peak 3 were confirmed. It was proved that tea can be analyzed by the gas-liquid contact extraction method of the present invention.
- Milk has high foaming properties due to casein protein and whey protein.
- foam is blown up with purge gas and enters the collection tube, making it impossible to analyze milk.
- milk can be analyzed by the gas-liquid contact extraction method of the present invention. Therefore, the present invention was analyzed for volatile organic compounds in commercial milk. TICC is shown in the chromatogram of FIG.
- analyte having a large partition coefficient an analyte having a high water solubility, or an analyte having a low olfactory threshold, which has been difficult in the past.
- an analyte having a large partition coefficient an analyte having a high water solubility, or an analyte having a low olfactory threshold, which has been difficult in the past.
- in quality control of tap water, river water, and beverages it has become possible to introduce samples unattended from sampling to extraction and analysis continuously for a long time without manual operation.
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Abstract
Description
P&T法は、溶液中に溶存する分析種を、溶液への溶解度の小さなガスを流して強制的にガス相に抽出させ、抽出した分析種を一旦吸着剤に保持させることにより、分析種を濃縮させる方法である。その後、吸着剤を急速加熱して、分析種を加熱して吸着材から脱着し、分析種をGCの分析カラムに導入する。 (1) P & T method and its problems In the P & T method, an analyte dissolved in a solution is forcibly extracted into a gas phase by flowing a gas having a low solubility in the solution, and the extracted analyte is temporarily used as an adsorbent. This is a method of concentrating the analyte by holding it. Thereafter, the adsorbent is rapidly heated, the analyte is heated and desorbed from the adsorbent, and the analyte is introduced into the GC analytical column.
(式1)
(Formula 1)
1)分配係数が大きい水溶性成分の回収率
P&T法では、トータルパージ流量を増やしても水中に共存する分配係数の小さな無極性成分が主に回収され、分配係数Kが大きい水溶性成分の回収率を向上させることは困難である。 Problems of the P & T method 1) Recovery rate of water-soluble components with a large distribution coefficient In the P & T method, nonpolar components with a small distribution coefficient that coexist in water are mainly recovered even if the total purge flow rate is increased, and the distribution coefficient K is large. It is difficult to improve the recovery rate of water-soluble components.
従来P&T法のパージ管は、パージ流速の増大とともに液滴が飛散する。実試料においては金属、錆、微生物、細菌などが配管に堆積し装置トラブルの原因となる。また、パージによる試料の泡立ちが気液抽出効率を低下させるといわれている。パージ流速が遅いと、パージガスの総量を増やそうとしたときに、分析の時間が長くなる(Anal.Chem.,58(1986)1822,James F.Pankow参照)。 2) Occurrence of problems due to increase in purge flow rate In the conventional P & T purge tube, droplets scatter as the purge flow rate increases. In the actual sample, metal, rust, microorganisms, bacteria, etc. accumulate on the pipe and cause trouble of the equipment. In addition, it is said that bubbling of the sample due to purging reduces gas-liquid extraction efficiency. When the purge flow rate is slow, the analysis time becomes long when trying to increase the total amount of purge gas (see Anal. Chem., 58 (1986) 1822, James F. Pankow).
P&T法において、気液平衡に時間を要する原因は、a)気泡内の気相濃度の均一化、b)気液(気泡)界面の物質移動、c)水中の物質移動が考えられ、最も寄与が大きいのはc)である。 3) In the P & T method, where the mass transfer of analyte species in water to the gas phase is slow, the cause of the time required for gas-liquid equilibration is: a) uniform gas phase concentration in the bubble, b) material at the gas-liquid (bubble) interface Movement, c) Mass movement in water can be considered, and c) has the largest contribution.
P&T法は抽出効率が悪いので、抽出した分析種を全量、GC又はGC/MSに導入するため、液体窒素を利用するクライオフォーカスが用いられる。浄水場などで24時間の連続自動分析を実施する場合、液体窒素の供給作業が必要となり完全無人化は困難で又分析コストでも不利である。 4) Since the cryofocus P & T method has poor extraction efficiency, a cryofocus using liquid nitrogen is used in order to introduce the entire amount of the extracted analyte into GC or GC / MS. When continuous automatic analysis for 24 hours is carried out at a water purification plant or the like, it is necessary to supply liquid nitrogen, and it is difficult to completely unmanned, and the analysis cost is also disadvantageous.
HS法は試料を密栓したバイアルに入れ、一定温度で一定時間加熱し、そして保温し、気液平衡状態とした後、気相部分の一定量を採取し、分析する方法である。 (2) HS method and its problems In the HS method, a sample is placed in a tightly sealed vial, heated at a constant temperature for a certain time, and kept warm to obtain a gas-liquid equilibrium state. It is a method of analysis.
HS法による気相中の濃度は、式2により求めることができる。
(式2)
(Formula 2)
また、βを小さくすること(試料量の増加、気相部の減少)は、感度向上に実際にはあまり効果がない。 From
In addition, reducing β (increasing the amount of sample, decreasing the gas phase portion) is not very effective in improving sensitivity.
この従来法の問題を解決する可能性を有する気液抽出操作として、気液向流接触抽出がある。この手法は、プラントなどの化学工業分野で大量の液体から所定の成分の回収や除去を行う場合に採用されている(日本国特開平10‐57947号公報及び日本国特許第3006894号公報参照)。[Correction based on Rule 91 27.12.2012]
Gas-liquid countercurrent contact extraction is known as a gas-liquid extraction operation that has the potential to solve the problems of the conventional method. This technique is employed when a predetermined component is recovered or removed from a large amount of liquid in the chemical industry field such as a plant (see Japanese Patent Application Laid-Open No. 10-57947 and Japanese Patent No. 3006894). .
又、日本国特許第3006894号公報に於いては、液体を上方から、気体を下方から流す管路を鉛直方向に於いて屈曲して立設する構成と、管の構成として管内壁部に毛管現象により液相移動させるウィックを設置する構成が示されている。[Correction based on Rule 91 27.12.2012]
Further, in Japanese Patent No. 3006894, a structure in which a pipe for flowing a liquid from above and a gas from below is bent in a vertical direction, and a capillary is formed on the inner wall of the pipe as a structure of the pipe. A configuration is shown in which a wick for liquid phase transfer is installed depending on the phenomenon.
液接触抽出器2に於ける気相の安定供給が行われ、又、試料液体供給とのバランスが取れるようになる。これにより気液接触が充分に行われ、気液平衡に資することになる。 The sample liquid stored in and discharged from the
(1)試料水抽出条件
1)試料水抽出温度:60℃
2)試料水・・従来P&T:20ml、本発明方法流量:2ml/min
3)パージガス流量・・従来P&T:80ml/min(120kPa)、本発明方法流量:80ml/min(120kPa)
4)抽出時間:20min
5)サンプル流路温度:60℃
6)スパイラル管形状:内径4mm、長さ1200mm、設置角度30度 パイレックス(登録商標)ガラス製
7)スパイラル管内面処理:18%HClをスパイラル管に封入後、洗浄、乾燥。これによりガラス表面の汚染除去と、ガラス表面のシラノール基の活性化を実施し、ガラス表面の親水性を向上させた。
(2)試料濃縮条件
1)捕集剤:Tenax TA 200mg(捕集管3.2mmI.D.×200mm)
2)捕集時温度:60℃
3)捕集管加熱温度:220℃(10分間)
4)加熱時脱着流量:11ml/min
5)バルブ温度:150℃
6)トランスファーライン温度:150℃
(3)GCMS測定条件
1)サンプリング時捕集管温度:60℃
2)試料導入時捕集管加熱温度:220℃(5℃/秒)、(保持時間10min)
3)分析カラム流量:1ml/min
4)スプリット流量:10ml/min
5)GCオーブン温度:40℃(12min)-20℃/min-250℃(5min)
6)キャピラリーカラム:InertCap 5MS/Sil、0.25mmI.D.×30m、df=0.25μm
7)イオン源:EI、70eV
8)SIMモード:2-MIB:m/z95,107、Geosimin:m/z112,125 <Experimental conditions>
(1) Sample water extraction conditions 1) Sample water extraction temperature: 60 ° C
2) Sample water: Conventional P & T: 20 ml, method flow rate of the present invention: 2 ml / min
3) Purge gas flow rate: Conventional P & T: 80 ml / min (120 kPa), method flow rate of the present invention: 80 ml / min (120 kPa)
4) Extraction time: 20 min
5) Sample flow path temperature: 60 ° C
6) Spiral tube shape:
(2) Sample concentration condition 1) Collection agent:
2) Collection temperature: 60 ° C
3) Collection tube heating temperature: 220 ° C. (10 minutes)
4) Desorption flow rate during heating: 11 ml / min
5) Valve temperature: 150 ° C
6) Transfer line temperature: 150 ° C
(3) GCMS measurement conditions 1) Collection tube temperature during sampling: 60 ° C
2) Collection tube heating temperature during sample introduction: 220 ° C. (5 ° C./second), (holding
3) Analytical column flow rate: 1 ml / min
4) Split flow rate: 10 ml / min
5) GC oven temperature: 40 ° C. (12 min) −20 ° C./min−250° C. (5 min)
6) Capillary column: InertCap 5MS / Sil, 0.25 mmI. D. × 30m, df = 0.25μm
7) Ion source: EI, 70 eV
8) SIM mode: 2-MIB: m / z 95, 107, Geosimin: m / z 112, 125
A:試料水流量:4ml/分、パージガス流量:160ml/分、抽出時間:10分
B:試料水流量:2ml/分、パージガス流量:80ml/分、抽出時間:20分
C:試料水流量:1ml/分、パージガス流量:40ml/分、抽出時間:40分
であり、抽出温度は60℃で行った。結果を図3に示す。両成分とも高抽出効率が得られる条件は図中Bであることが判明した。 In the gas-liquid contact extraction method of the present invention using the automatic liquid sample supply device of the present invention, the extraction efficiency of 2-MIB and Geosimin was compared by changing the purge gas flow rate and the sample water flow rate. The extraction efficiency conditions for 2-MIB and Geosimin due to differences in purge gas flow rate and sample water flow rate are:
A: Sample water flow rate: 4 ml / min, purge gas flow rate: 160 ml / min, extraction time: 10 minutes B: sample water flow rate: 2 ml / min, purge gas flow rate: 80 ml / min, extraction time: 20 minutes C: sample water flow rate: 1 ml / min, purge gas flow rate: 40 ml / min, extraction time: 40 minutes, and extraction temperature was 60 ° C. The results are shown in FIG. It was found that the condition for obtaining high extraction efficiency for both components was B in the figure.
(1)試料水抽出条件
1)試料水抽出温度:60℃
2)試料水流量:1、2、4ml/min
3)パージガス流量:40ml/min(60kPa)、80ml/min(120kPa)、
160mlmin(240kPa)
4)サンプル流路温度:60℃min
5)抽出時間:10、20、40min
6)スパイラル管形状:内径4mm、長さ1200mm、設置角度30度 パイレックス(登録商標)ガラス製
7)スパイラル管内面処理:18%HCLをスパイラル管に封入後、洗浄、乾燥。これによりガラス表面の汚染除去と、ガラス表面のシラノール基の活性化を実施し、ガラス表面の親水性を向上させた。
(2)試料濃縮条件
1)捕集剤:Tenax TA 200mg(捕集管3.2mmI.D.×200mm)
2)捕集時温度:60℃
3)捕集管加熱温度:220(10分間)
4)加熱時脱着流量:11ml/min
5)バルブ温度:150℃
6)トランスファーライン温度:150℃
(3)GCMS測定条件
1)サンプリング時捕集管温度:60℃
2)試料導入時捕集管加熱温度:220℃(5℃/秒)、(保持時間10min)
3)分析カラム流量:1ml/min
4)スプリット流量:10ml/min
5)GCオーブン温度:40℃(12min)-20℃/min-250℃(5min)
6)キャピラリーカラム:InertCap 5MS/Sil、0.25mmI.D.×30m、df=0.25μm
7)イオン源:EI、70eV
8)SIMモード:2-MIB:m/z95,107、Geosimin:m/z112,125 <Experimental conditions>
(1) Sample water extraction conditions 1) Sample water extraction temperature: 60 ° C
2) Sample water flow rate: 1, 2, 4 ml / min
3) Purge gas flow rate: 40 ml / min (60 kPa), 80 ml / min (120 kPa),
160mlmin (240kPa)
4) Sample flow path temperature: 60 ° C min
5) Extraction time: 10, 20, 40 min
6) Spiral tube shape:
(2) Sample concentration condition 1) Collection agent:
2) Collection temperature: 60 ° C
3) Collection tube heating temperature: 220 (10 minutes)
4) Desorption flow rate during heating: 11 ml / min
5) Valve temperature: 150 ° C
6) Transfer line temperature: 150 ° C
(3) GCMS measurement conditions 1) Collection tube temperature during sampling: 60 ° C
2) Collection tube heating temperature during sample introduction: 220 ° C. (5 ° C./second), (holding
3) Analytical column flow rate: 1 ml / min
4) Split flow rate: 10 ml / min
5) GC oven temperature: 40 ° C. (12 min) −20 ° C./min−250° C. (5 min)
6) Capillary column: InertCap 5MS / Sil, 0.25 mmI. D. × 30m, df = 0.25μm
7) Ion source: EI, 70 eV
8) SIM mode: 2-MIB: m / z 95, 107, Geosimin: m / z 112, 125
(1)試料水抽出条件
1)試料水抽出温度:60℃
2)試料水流量:2ml/min
3)パージガス流量:80ml/min(120kPa)
4)サンプル流路温度:60℃
5)抽出時間:20min
6)スパイラル管形状:内径4mm、長さ1200mm、設置角度30度 パイレックス(登録商標)ガラス製
7)スパイラル管内面処理:18%HClをスパイラル管に封入後、洗浄、乾燥。これによりガラス表面の汚染除去と、ガラス表面のシラノール基の活性化を実施し、ガラス表面の親水性を向上させた。
(2)試料濃縮条件
1)捕集剤:Tenax TA 200mg(捕集管3.2mmI.D.×200mm)
2)捕集時温度:60℃
3)捕集管加熱温度:220(10分間)
4)加熱時脱着流量:11ml/min
5)バルブ温度:150℃
6)トランスファーライン温度:150℃
(3)GCMS測定条件
1)サンプリング時捕集管温度:60℃
2)試料導入時捕集管加熱温度:220℃(5℃/秒)、(保持時間10min)
3)分析カラム流量:1ml/min
4)スプリット流量:10ml/min
5)GCオーブン温度:40℃(12min)-20℃/min-250℃(5min)
6)キャピラリーカラム:InertCap 5MS/Sil、0.25mmI.D.×30m、df=0.25μm
7)イオン源:EI、70eV
8)SIMモード:2-MIB:m/z95,107、Geosimin:m/z112,125 <Experimental conditions>
(1) Sample water extraction conditions 1) Sample water extraction temperature: 60 ° C
2) Sample water flow rate: 2 ml / min
3) Purge gas flow rate: 80 ml / min (120 kPa)
4) Sample flow path temperature: 60 ° C
5) Extraction time: 20 min
6) Spiral tube shape:
(2) Sample concentration condition 1) Collection agent:
2) Collection temperature: 60 ° C
3) Collection tube heating temperature: 220 (10 minutes)
4) Desorption flow rate during heating: 11 ml / min
5) Valve temperature: 150 ° C
6) Transfer line temperature: 150 ° C
(3) GCMS measurement conditions 1) Collection tube temperature during sampling: 60 ° C
2) Collection tube heating temperature during sample introduction: 220 ° C. (5 ° C./second), (holding
3) Analytical column flow rate: 1 ml / min
4) Split flow rate: 10 ml / min
5) GC oven temperature: 40 ° C. (12 min) −20 ° C./min−250° C. (5 min)
6) Capillary column: InertCap 5MS / Sil, 0.25 mmI. D. × 30m, df = 0.25μm
7) Ion source: EI, 70 eV
8) SIM mode: 2-MIB: m / z 95, 107, Geosimin: m / z 112, 125
(1)試料水抽出条件
1)試料水抽出温度:60℃
2)試料水流量:2ml/min
3)パージガス流量:80ml/min(120kPa)
4)サンプル流路温度:60℃
5)抽出時間:20min
6)スパイラル管形状:内径4mm、長さ1200mm、設置角度30度 パイレックス(登録商標)ガラス製
7)スパイラル管内面処理:18%HClをスパイラル管に封入後、洗浄、乾燥。これによりガラス表面の汚染除去と、ガラス表面のシラノール基の活性化を実施し、ガラス表面の親水性を向上させた。
(2)試料濃縮条件
1)捕集剤:Tenax TA 200mg(捕集管3.2mmI.D.×200mm)
2)捕集時温度:60℃
3)捕集管加熱温度:220(10分間)
4)加熱時脱着流量:11ml/min
5)バルブ温度:150℃
6)トランスファーライン温度:150℃
(3)GCMS測定条件
1)サンプリング時捕集管温度:60℃
2)試料導入時捕集管加熱温度:220℃(5℃/秒)、(保持時間10min)
3)分析カラム流量:1ml/min
4)スプリット流量:10ml/min
5)GCオーブン温度:40℃(12min)-20℃/min-250℃(5min)
6)キャピラリーカラム:InertCap 5MS/Sil、0.25mmI.D.×30m、df=0.25μm
7)イオン源:EI、70eV
8)SIMモード:2-MIB:m/z95,107、Geosimin:m/z112,125 <Experimental conditions>
(1) Sample water extraction conditions 1) Sample water extraction temperature: 60 ° C
2) Sample water flow rate: 2 ml / min
3) Purge gas flow rate: 80 ml / min (120 kPa)
4) Sample flow path temperature: 60 ° C
5) Extraction time: 20 min
6) Spiral tube shape:
(2) Sample concentration condition 1) Collection agent:
2) Collection temperature: 60 ° C
3) Collection tube heating temperature: 220 (10 minutes)
4) Desorption flow rate during heating: 11 ml / min
5) Valve temperature: 150 ° C
6) Transfer line temperature: 150 ° C
(3) GCMS measurement conditions 1) Collection tube temperature during sampling: 60 ° C
2) Collection tube heating temperature during sample introduction: 220 ° C. (5 ° C./second), (holding
3) Analytical column flow rate: 1 ml / min
4) Split flow rate: 10 ml / min
5) GC oven temperature: 40 ° C. (12 min) −20 ° C./min−250° C. (5 min)
6) Capillary column: InertCap 5MS / Sil, 0.25 mmI. D. × 30m, df = 0.25μm
7) Ion source: EI, 70 eV
8) SIM mode: 2-MIB: m / z 95, 107, Geosimin: m / z 112, 125
そして、TCAによる汚染は木材のTCP汚染のほか、原水の塩素処理時、あるいは配水システムを用いた輸送時に発生することなどが報告されている。このように水源だけでなく水を扱う製造工場などにおいても管理を徹底する必要性がある。 2,4,6-Trichloroanisole (hereinafter TCA) has a very small olfactory sense and is said to be 30 ppq. This compound is a causative substance of mold odor and detoxifies 2,4,6-trichlorophenol (hereinafter referred to as “TCP”), which is an antifungal agent for wood, by O-methylation of some molds. Became widely known as occurring during the breeding process.
In addition to TCP contamination of wood, it has been reported that TCA contamination occurs during chlorination of raw water or during transport using a water distribution system. In this way, there is a need for thorough management not only in water sources but also in manufacturing factories that handle water.
(1)試料水抽出条件
1)試料水抽出温度:60℃
2)試料水流量:2ml/min
3)パージガス流量:80ml/min(120kPa)
4)サンプル流路温度:60℃
5)抽出時間:20min
6)スパイラル管形状:内径4mm、長さ1200mm、設置角度30度 パイレックス(登録商標)ガラス製
7)スパイラル管内面処理:18%HClをスパイラル管に封入後、洗浄、乾燥。これによりガラス表面の汚染除去と、ガラス表面のシラノール基の活性化を実施し、ガラス表面の親水性を向上させた。
試料濃縮条件
1)捕集剤:Tenax TA 200mg(捕集管3.2mmI.D.×200mm)
2)捕集時温度:60℃
3)捕集管加熱温度:220(10分間)
4)加熱時脱着流量:11ml/min
5)バルブ温度:150℃
6)トランスファーライン温度:150℃
(3)GCMS測定条件
1)サンプリング時捕集管温度:60℃
2)試料導入時捕集管加熱温度:220℃(5℃/秒)、(保持時間10min)
3)分析カラム流量:1ml/min
4)スプリット流量:10ml/min
5)GCオーブン温度:40℃(12min)-20℃/min-250℃(5min)
6)キャピラリーカラム:InertCap 5MS/Sil、0.25mm I.D.×30m、df=0.25μm
7)イオン源:EI、70eV
8)SIMモード:TCA:m/z210、212 <Experimental conditions>
(1) Sample water extraction conditions 1) Sample water extraction temperature: 60 ° C
2) Sample water flow rate: 2 ml / min
3) Purge gas flow rate: 80 ml / min (120 kPa)
4) Sample flow path temperature: 60 ° C
5) Extraction time: 20 min
6) Spiral tube shape:
Sample concentration condition 1) Collection agent:
2) Collection temperature: 60 ° C
3) Collection tube heating temperature: 220 (10 minutes)
4) Desorption flow rate during heating: 11 ml / min
5) Valve temperature: 150 ° C
6) Transfer line temperature: 150 ° C
(3) GCMS measurement conditions 1) Collection tube temperature during sampling: 60 ° C
2) Collection tube heating temperature during sample introduction: 220 ° C. (5 ° C./second), (holding
3) Analytical column flow rate: 1 ml / min
4) Split flow rate: 10 ml / min
5) GC oven temperature: 40 ° C. (12 min) -20 ° C./min-250° C. (5 min)
6) Capillary column: InertCap 5MS / Sil, 0.25 mm D. × 30m, df = 0.25μm
7) Ion source: EI, 70 eV
8) SIM mode: TCA: m / z 210, 212
(1)試料水抽出条件
1)試料水抽出温度:60℃
2)試料水流量:2ml/min
3)パージガス流量:80ml/min(120kPa)
4)サンプル流路温度:60℃)
5)抽出時間:20min
6)スパイラル管形状:内径4mm、長さ1200mm、設置角度30度 パイレックス(登録商標)ガラス製
7)スパイラル管内面処理:18%HClをスパイラル管に封入後、洗浄、乾燥。これによりガラス表面の汚染除去と、ガラス表面のシラノール基の活性化を実施し、ガラス表面の親水性を向上させた。
(2)試料濃縮条件
1)捕集剤:Tenax TA 200mg(捕集管3.2mmI.D.×200mm)
2)捕集時温度:60℃
3)捕集管加熱温度:220℃(10分間)
4)加熱時脱着流量:11ml/min
5)バルブ温度:150℃
6)トランスファーライン温度:150℃
(3)GCMS測定条件
1)サンプリング時捕集管温度:60℃
2)試料導入時捕集管加熱温度:220℃(5℃/秒)、(保持時間10min)
3)分析カラム流量:1ml/min
4)スプリット流量:10ml/min
5)GCオーブン温度:40℃(12min)-20℃/min-250℃(5min)
6)キャピラリーカラム:InertCap 5MS/Sil、0.25mmI.D.×30m、df=0.25μm
7)イオン源:EI、70eV
8)SIMモード:1,4Dioxan:m/z58,64 <Experimental conditions>
(1) Sample water extraction conditions 1) Sample water extraction temperature: 60 ° C
2) Sample water flow rate: 2 ml / min
3) Purge gas flow rate: 80 ml / min (120 kPa)
4) Sample channel temperature: 60 ° C)
5) Extraction time: 20 min
6) Spiral tube shape:
(2) Sample concentration condition 1) Collection agent:
2) Collection temperature: 60 ° C
3) Collection tube heating temperature: 220 ° C. (10 minutes)
4) Desorption flow rate during heating: 11 ml / min
5) Valve temperature: 150 ° C
6) Transfer line temperature: 150 ° C
(3) GCMS measurement conditions 1) Collection tube temperature during sampling: 60 ° C
2) Collection tube heating temperature during sample introduction: 220 ° C. (5 ° C./second), (holding
3) Analytical column flow rate: 1 ml / min
4) Split flow rate: 10 ml / min
5) GC oven temperature: 40 ° C. (12 min) −20 ° C./min−250° C. (5 min)
6) Capillary column: InertCap 5MS / Sil, 0.25 mmI. D. × 30m, df = 0.25μm
7) Ion source: EI, 70 eV
8) SIM mode: 1, 4 Dioxan: m / z 58, 64
ゴマ油は高い温度で焙煎後圧搾する工程で製造される。このとき、成分中の糖とタンパク質がメイラード(Maillard)反応を起こして香気成分であるピラジン(pyrazine)化合物を生成する。このピラジン類は、生理活性をあらわす可能性が提唱され、研究報告も多い。 Analysis of volatile organic compounds in sesame oil Sesame oil is produced by a process of roasting and pressing at a high temperature. At this time, sugar and protein in the component cause a Maillard reaction to generate a pyrazine compound that is an aroma component. These pyrazines have been proposed to exhibit physiological activity, and there are many research reports.
(1)試料水抽出条件
1)試料水抽出温度:60℃
2)試料水流量:2ml/min
3)パージガス流量:80ml/min(120kPa)
4)サンプル流路温度:60℃
5)抽出時間:20min
6)スパイラル管形状:内径4mm、長さ1200mm、設置角度30度 パイレックス(登録商標)ガラス製
7)スパイラル管内面処理:ガラス表面の水酸基を活性化後に、オクタデシルジメチルクロロシランを溶解させたトルエン溶液を入れ、所定時間還流後、トルエンで洗浄、乾燥。これにより、ガラス表面のオクタデシル基の化学修飾を実施し、ガラス表面の疎水性を向上させた。
(2)試料濃縮条件
1)捕集剤:Tenax TA 200mg(捕集管3.2mmI.D.×200mm)
2)捕集時温度:60℃
3)捕集管加熱温度:220(10分間)
4)加熱時脱着流量:11ml/min
5)バルブ温度:150℃
6)トランスファーライン温度:150℃
(3)GCMS測定条件
1)サンプリング時捕集管温度:60℃
2)試料導入時捕集管加熱温度:220℃(5℃/秒)、(保持時間10min)
3)分析カラム流量:1ml/min
4)スプリット流量:10ml/min
5)GCオーブン温度:40℃(12min)-20℃/min-250℃(5min)
6)キャピラリーカラム:InertCap Pure-WAX、0.25mmI.D.x30m、df=0.25μm
7)イオン源:EI、70eV
8)Scanモード:m/z10-450 <Experimental conditions>
(1) Sample water extraction conditions 1) Sample water extraction temperature: 60 ° C
2) Sample water flow rate: 2 ml / min
3) Purge gas flow rate: 80 ml / min (120 kPa)
4) Sample flow path temperature: 60 ° C
5) Extraction time: 20 min
6) Spiral tube shape:
(2) Sample concentration condition 1) Collection agent:
2) Collection temperature: 60 ° C
3) Collection tube heating temperature: 220 (10 minutes)
4) Desorption flow rate during heating: 11 ml / min
5) Valve temperature: 150 ° C
6) Transfer line temperature: 150 ° C
(3) GCMS measurement conditions 1) Collection tube temperature during sampling: 60 ° C
2) Collection tube heating temperature during sample introduction: 220 ° C. (5 ° C./second), (holding
3) Analytical column flow rate: 1 ml / min
4) Split flow rate: 10 ml / min
5) GC oven temperature: 40 ° C. (12 min) −20 ° C./min−250° C. (5 min)
6) Capillary column: InertCap Pure-WAX, 0.25 mm I.D. D. x30m, df = 0.25μm
7) Ion source: EI, 70 eV
8) Scan mode: m / z 10-450
(1)試料水抽出条件
1)試料水抽出温度:60℃
2)試料水流量:2ml/min
3)パージガス流量:80ml/min(120kPa)
4)サンプル流路温度:60℃
5)抽出時間:20min
6)スパイラル管形状:内径4mm、長さ1200mm、設置角度30度 パイレックス(登録商標)ガラス製
7)スパイラル管内面処理:18%HClをスパイラル管に封入後、洗浄、乾燥。これによりガラス表面の汚染除去と、ガラス表面のシラノール基の活性化を実施し、ガラス表面の親水性を向上させた。
(2)試料濃縮条件
1)捕集剤:Tenax TA 200mg(捕集管3.2mmI.D.×200mm)
2)捕集時温度:60℃
3)捕集管加熱温度:220(10分間)
4)加熱時脱着流量:11ml/min
5)バルブ温度:150℃
6)トランスファーライン温度:150℃
(3)GCMS測定条件
1)サンプリング時捕集管温度:60℃
2)試料導入時捕集管加熱温度:220℃(5℃/秒)、(保持時間10min)
3)分析カラム流量:1ml/min
4)スプリット流量:10ml/min
5)GCオーブン温度:40℃(12min)-20℃/min-250℃(5min)
6)キャピラリーカラム:InertCap 5MS/Sil、0.25mmI.D.×30m、df=0.25μm
7)イオン源:EI、70eV
8)SIMモード:2-MIB:m/z95,107、Geosimin:m/z112,125 <Experimental conditions>
(1) Sample water extraction conditions 1) Sample water extraction temperature: 60 ° C
2) Sample water flow rate: 2 ml / min
3) Purge gas flow rate: 80 ml / min (120 kPa)
4) Sample flow path temperature: 60 ° C
5) Extraction time: 20 min
6) Spiral tube shape:
(2) Sample concentration condition 1) Collection agent:
2) Collection temperature: 60 ° C
3) Collection tube heating temperature: 220 (10 minutes)
4) Desorption flow rate during heating: 11 ml / min
5) Valve temperature: 150 ° C
6) Transfer line temperature: 150 ° C
(3) GCMS measurement conditions 1) Collection tube temperature during sampling: 60 ° C
2) Collection tube heating temperature during sample introduction: 220 ° C. (5 ° C./second), (holding
3) Analytical column flow rate: 1 ml / min
4) Split flow rate: 10 ml / min
5) GC oven temperature: 40 ° C. (12 min) −20 ° C./min−250° C. (5 min)
6) Capillary column: InertCap 5MS / Sil, 0.25 mmI. D. × 30m, df = 0.25μm
7) Ion source: EI, 70 eV
8) SIM mode: 2-MIB: m / z 95, 107, Geosimin: m / z 112, 125
(1)高濁度河川水抽出条件
1)抽出温度:60℃
2)流量:2mL/min
3)パージガス流量:80mL/min
4)抽出時間:2.5min
5)スパイラル管形状:内径4mm、長さ1200mm、設置角度30度 パイレックス(登録商標)ガラス製
6)スパイラル管内面処理:18%HCLをスパイラル管に封入後、洗浄、乾燥。これによりガラス表面の汚染除去と、ガラス表面のシラノール基の活性化を実施し、ガラス表面の親水性を向上させた。
(2)試料濃縮条件
1)捕集剤:Tenax TA 50mg(捕集管3.2mmI.D.×300mm)
2)サンプリング時捕集管温度:60℃
2)捕集管加熱温度:220℃(5℃/sec、10分間)
3)加熱時脱着流量:2.4mL/min
4)バルブ温度:150℃
5)トランスファーライン温度:150℃
(3)GCMS測定条件
1)分析カラム流量:2.4mL/min
2)スプリット流量:0mL/min(スプリットレス)
3)GCオーブン温度:40℃(12min)-20℃/min-250℃(5min)
4)キャピラリーカラム:InertCap 5MS/Sil、0.25mmI.D.×30m、df=1.0μm
5)イオン源:EI、70eV
6)SIMモード:2-MIB:m/z95,107、Geosimin:m/z112,125 <Experimental conditions>
(1) High turbidity river water extraction conditions 1) Extraction temperature: 60 ° C
2) Flow rate: 2 mL / min
3) Purge gas flow rate: 80 mL / min
4) Extraction time: 2.5 min
5) Spiral tube shape:
(2) Sample concentration condition 1) Collection agent:
2) Collection tube temperature during sampling: 60 ° C
2) Collection tube heating temperature: 220 ° C. (5 ° C./sec, 10 minutes)
3) Desorption flow rate during heating: 2.4 mL / min
4) Valve temperature: 150 ° C
5) Transfer line temperature: 150 ° C
(3) GCMS measurement conditions 1) Analytical column flow rate: 2.4 mL / min
2) Split flow rate: 0 mL / min (splitless)
3) GC oven temperature: 40 ° C (12min) -20 ° C / min-250 ° C (5min)
4) Capillary column: InertCap 5MS / Sil, 0.25 mmI. D. × 30m, df = 1.0μm
5) Ion source: EI, 70 eV
6) SIM mode: 2-MIB: m / z 95, 107, Geosimin: m / z 112, 125
(1)市販お茶飲料抽出条件
1)抽出温度:40℃
2)流量:2mL/min
3)パージガス流量:60mL/min
4)抽出時間:10min
5)スパイラル管形状:内径4mm、長さ1200mm、設置角度30度 パイレックス(登録商標)ガラス製
6)スパイラル管内面処理:18%HCLをスパイラル管に封入後、洗浄、乾燥。これによりガラス表面の汚染除去と、ガラス表面のシラノール基の活性化を実施し、ガラス表面の親水性を向上させた。
(2)試料濃縮条件
1)捕集剤:Tenax TA 100mg(捕集管3.2mmI.D.×300mm)
2)サンプリング時捕集管温度:40℃
3)捕集管加熱温度:220℃(5℃/sec、10分間)
4)バルブ温度:150℃
5)トランスファーライン温度:150℃
(3)GCMS測定条件
1)分析カラム流量:1mL/min
2)スプリット流量:5mL/min
3)GCオーブン温度:40℃(12min)-20℃/min-250℃(5min)
4)キャピラリーカラム:InertCap 5MS/Sil、0.25mmI.D.×30m、df=1.0μm
5)イオン源:EI、70eV
6)Scanモード:m/z15-450 <Experimental conditions>
(1) Commercial tea beverage extraction conditions 1) Extraction temperature: 40 ° C
2) Flow rate: 2 mL / min
3) Purge gas flow rate: 60 mL / min
4) Extraction time: 10 min
5) Spiral tube shape:
(2) Sample concentration condition 1) Collection agent:
2) Collection tube temperature during sampling: 40 ° C
3) Collection tube heating temperature: 220 ° C. (5 ° C./sec, 10 minutes)
4) Valve temperature: 150 ° C
5) Transfer line temperature: 150 ° C
(3) GCMS measurement conditions 1) Analytical column flow rate: 1 mL / min
2) Split flow rate: 5 mL / min
3) GC oven temperature: 40 ° C (12min) -20 ° C / min-250 ° C (5min)
4) Capillary column: InertCap 5MS / Sil, 0.25 mmI. D. × 30m, df = 1.0μm
5) Ion source: EI, 70 eV
6) Scan mode: m / z 15-450
(1)市販牛乳抽出条件
1)抽出温度:40℃
2)流量:2mL/min
3)パージガス流量:60mL/min
4)抽出時間:10min
5)スパイラル管形状:内径4mm、長さ1200mm、設置角度30度 パイレックス(登録商標)ガラス製
6)スパイラル管内面処理:18%HCLをスパイラル管に封入後、洗浄、乾燥。これによりガラス表面の汚染除去と、ガラス表面のシラノール基の活性化を実施し、ガラス表面の親水性を向上させた。
(2)試料濃縮条件
1)捕集剤:Tenax TA 100mg(捕集管3.2mmI.D.×300mm)
2)サンプリング時捕集管温度:40℃
3)捕集管加熱温度:220℃(5℃/sec、10分間)
4)バルブ温度:150℃
5)トランスファーライン温度:150℃
(3)GCMS測定条件
1)分析カラム流量:1mL/min
2)スプリット流量:5mL/min
3)GCオーブン温度:40℃(12min)-20℃/min-250℃(5min)
4)キャピラリーカラム:InertCap AQUATIC-2、0.25mmI.D.x40m、df=1.4μm
5)イオン源:EI、70eV
6)Scanモード:m/z15-450 <Experimental conditions>
(1) Commercial milk extraction conditions 1) Extraction temperature: 40 ° C
2) Flow rate: 2 mL / min
3) Purge gas flow rate: 60 mL / min
4) Extraction time: 10 min
5) Spiral tube shape:
(2) Sample concentration condition 1) Collection agent:
2) Collection tube temperature during sampling: 40 ° C
3) Collection tube heating temperature: 220 ° C. (5 ° C./sec, 10 minutes)
4) Valve temperature: 150 ° C
5) Transfer line temperature: 150 ° C
(3) GCMS measurement conditions 1) Analytical column flow rate: 1 mL / min
2) Split flow rate: 5 mL / min
3) GC oven temperature: 40 ° C (12min) -20 ° C / min-250 ° C (5min)
4) Capillary column: InertCap AQUATIC-2, 0.25 mm I.D. D. x40m, df = 1.4μm
5) Ion source: EI, 70 eV
6) Scan mode: m / z 15-450
Claims (8)
- 上方から試料液体を、下方からパージガスを各々連続導入する気液接触抽出器を用い、当該試料液体とパージガスとを気液接触させ、該試料液体中の分析種を抽出する気液接触抽出方法であって、前記気液接触抽出器の下部に接続した排出管に設けた液溜め部を介して試料液体を排出しつつ、該液溜め部からのパージガスの流出を阻止したことを特徴とする気液接触抽出方法。 A gas-liquid contact extraction method that uses a gas-liquid contact extractor that continuously introduces a sample liquid from above and a purge gas from below, makes the sample liquid and purge gas contact each other, and extracts an analyte in the sample liquid. The gas liquid is discharged through the liquid reservoir provided in the discharge pipe connected to the lower part of the gas-liquid contact extractor, and the purge gas is prevented from flowing out of the liquid reservoir. Liquid contact extraction method.
- 前記気液接触抽出器に試料液体を供給する前に、試料液体を前記気液接触抽出器内での抽出温度にプレヒートすることを特徴とする請求項1に記載の気液接触抽出方法。 The gas-liquid contact extraction method according to claim 1, wherein the sample liquid is preheated to an extraction temperature in the gas-liquid contact extractor before supplying the sample liquid to the gas-liquid contact extractor.
- 分配係数Kが1より大きい水溶性成分、あるいは嗅覚閾値が10ppt(pg/ml)より低い液中に存在する分析種を気液接触抽出することを特徴とする請求項1又は2に記載の気液接触抽出方法。 3. A gas-liquid contact extraction of a water-soluble component having a partition coefficient K greater than 1 or an analyte present in a liquid having an olfactory threshold lower than 10 ppt (pg / ml). Liquid contact extraction method.
- 前記気液接触抽出器を温度制御可能なオーブン内に設置し、気液接触抽出された分析種が濃縮される捕集管までの流路をオーブン温度(気液抽出温度)と同じかそれよりも高い温度に設定し、気液抽出により抽出された分析種を捕集管にて濃縮することを特徴とする請求項1から3のうち何れか1項に記載の気液接触抽出方法。 The gas-liquid contact extractor is installed in a temperature-controllable oven, and the flow path to the collection tube where the analytes extracted by gas-liquid contact extraction are concentrated is the same as or higher than the oven temperature (gas-liquid extraction temperature) The gas-liquid contact extraction method according to any one of claims 1 to 3, wherein an analytical species extracted by gas-liquid extraction is concentrated in a collection tube at a higher temperature.
- 上方から液体試料を、下方からパージガスを夫々供給する気液接触抽出器を備え、当該気液接触抽出器の下部に排出管を接続し、当該排出管に、前記試料液体を排出しつつパージガスの排出を阻止する液溜め部を設けたことを特徴とする気液接触抽出装置。 A gas-liquid contact extractor that supplies a liquid sample from above and a purge gas from below is provided. A discharge pipe is connected to the lower part of the gas-liquid contact extractor, and the purge gas is discharged into the discharge pipe while discharging the sample liquid. A gas-liquid contact extraction device comprising a liquid reservoir for preventing discharge.
- 前記気液接触抽出器の試料液体との接触面に表面処理を行い、当該接触面を拡張ぬれ状態としたことを特徴とする請求項5に記載の気液接触抽出装置。 6. The gas-liquid contact extraction device according to claim 5, wherein the contact surface with the sample liquid of the gas-liquid contact extractor is subjected to a surface treatment so that the contact surface is in an expanded wet state.
- 前記表面処理が親水処理あるいは撥水処理の何れかであることを特徴とする請求項6に記載の気液接触抽出装置。 The gas-liquid contact extraction device according to claim 6, wherein the surface treatment is either hydrophilic treatment or water repellent treatment.
- 液体試料供給部を流路切換えのためのシリンジポンプ及びセレクターバルブを介して請求項5から7の何れか1項に記載の前記気液接触抽出装置に連結し、該気液接触抽出装置にて気液接触抽出された分析種を捕集管に送ることを特徴とする自動液体試料供給装置。 A liquid sample supply unit is connected to the gas-liquid contact extraction device according to any one of claims 5 to 7 via a syringe pump and a selector valve for switching a flow path, and the gas-liquid contact extraction device An automatic liquid sample supply device for sending an analytical species extracted by gas-liquid contact to a collection tube.
Priority Applications (3)
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JP2013544354A JP5731010B2 (en) | 2011-11-17 | 2012-11-16 | Gas-liquid contact extraction method and apparatus |
CN201280056306.8A CN103946683B (en) | 2011-11-17 | 2012-11-16 | Gas-to-liquid contact extracting method and device |
US14/358,744 US9347919B2 (en) | 2011-11-17 | 2012-11-16 | Gas-liquid contact extraction method and apparatus |
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JP2011-252022 | 2011-11-17 | ||
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Cited By (4)
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CN106443031A (en) * | 2016-09-30 | 2017-02-22 | 中南林业科技大学 | Bionic smell detection and analysis device based on dynamic gas distribution and detection and analysis method of bionic smell detection and analysis device |
CN111453908A (en) * | 2020-04-15 | 2020-07-28 | 大连百傲化学股份有限公司 | Treatment method of phenol-containing wastewater |
JP2021501313A (en) * | 2017-10-25 | 2021-01-14 | エンテック インスツルメンツ インコーポレイテッド | Sample pre-concentration system and method for use in gas chromatography |
US11946912B2 (en) | 2020-06-30 | 2024-04-02 | Entech Instruments Inc. | System and method of trace-level analysis of chemical compounds |
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CN109844519B (en) * | 2016-10-11 | 2022-06-03 | 株式会社岛津制作所 | Gas chromatograph |
IT201800004825A1 (en) * | 2018-04-24 | 2019-10-24 | Headspace sampling procedure and device | |
WO2020022226A1 (en) * | 2018-07-23 | 2020-01-30 | ジーエルサイエンス株式会社 | Column hardware and separation column, and method for manufacturing same |
CN111562320B (en) * | 2020-01-09 | 2021-04-02 | 北京理工大学 | Method for simultaneously measuring characteristic parameters of semi-volatile organic compounds in source-sink material |
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JPWO2013073693A1 (en) | 2015-04-02 |
JP5731010B2 (en) | 2015-06-10 |
CN103946683B (en) | 2016-12-07 |
CN103946683A (en) | 2014-07-23 |
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