JP3740532B2 - Organic compound separation method and apparatus, and analysis method and analysis apparatus - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method and apparatus for separating an organic compound constituting a solid sample from a solid sample, and a method and apparatus for analyzing the obtained organic compound.
[0002]
[Prior art]
A substance constituting the solid sample, for example, an organic substance, is separated from the solid sample by an extraction operation, etc., and then the extracted component is analyzed by various analysis methods to confirm the substance of the extracted component and contain it. An amount is determined. As an operation means for extracting the constituent components, a solvent or water vapor has been used.
As a method for dissolving in an organic solvent or a solvent, extraction of components with an organic solvent using a Soxhlet extraction apparatus has been conventionally performed (for example, AM Cicero, E. Pietrantonio, G. Romanelli, A. Di Muccio (2000) Bull Environ. Contam. Toxicol., 65 , 307-313).
This device heats the solvent reservoir of the organic solvent provided at the bottom of the device, introduces the vapor of the generated organic solvent into the uppermost cooling unit, condenses the solvent, and the cylinder provided immediately below it. The organic solvent-soluble component contained in the solid sample is taken out by passing through the filter paper by bringing the liquid organic solvent into contact with the solid substance to be extracted placed on the filter paper, leading to the filtration section having the filter paper. Extract the contained components. Since the distilled solvent always comes into contact with the sample, the final recovery rate of the target substance is quite good and has been widely used as a pretreatment method such as chemical analysis. The Soxhlet extraction method generally consumes a large amount of several hundred mL of an organic solvent for sample extraction of several grams to 10 grams, and is a relatively low temperature extraction process from room temperature to the boiling point of the solvent used. Requires a long extraction time of 10 hours or more. A microwave extraction method has been developed as a method for solving this problem. An external heating means such as a mantle heater is used to heat the organic solvent in the Soxhlet extraction apparatus. In the microwave extraction method (for example, V. Camel (2001) Analyst, 126 , 1182-1193), heating by microwaves is used. Is adopted. In this method, the target component is extracted by irradiating the sample and solvent with microwaves in a container made of a microwave-permeable material such as glass (Pyrex (registered trademark), quartz, etc.) or fluororesin (PFA, etc.). It is a method to do. Although it has been proved that both solvent consumption and extraction time are small compared to the Soxhlet extraction method, it is necessary to separate the extraction residue and the extracted liquid by filtration and centrifugation after extraction, which requires complicated operations. Is done. Furthermore, as in the Soxhlet method, there is also known a method such as a microwave extraction method that can obtain an extract containing no extraction residue by holding the extract in a container separate from the solvent reservoir (specialty). Table 2000-510765 “Apparatus and equipment for extracting organic compounds from samples by the addition of microwaves”).
In this method, by sealing the container and placing it in a pressure-resistant outer cylinder, it becomes possible to perform the treatment at a temperature equal to or higher than the boiling point of the solvent under atmospheric pressure, so that more efficient extraction is possible. Become. In this case, extracting the target component with an organic solvent is the center of the operation, and comprehensive selection of the solvent, extraction temperature, required time, etc. is performed.
However, in any of these extraction methods, since the organic solvent and the sample are first brought into direct contact with each other, it is generally easy to extract substances other than the target component dissolved in the organic solvent. For this reason, the obtained solution with an organic solvent requires an operation to remove substances other than these target products or to use only the target organism as a solvent, and it takes time, labor, and an apparatus for that purpose. Since a solvent is required, even if the extraction process is rapid and solvent-saving, the features are not always utilized effectively.
[0003]
As a method different from the solvent extraction, there is a steam distillation method in which a sample material is heated to extract a material to be analyzed in the presence of water. When heated in the presence of water, boiling occurs when the sum of the vapor pressure of the substance to be taken out and the water becomes equal to atmospheric pressure, and the components generated at each temperature are separated according to the heating temperature. It is. Since the target component is separated by the vapor pressure, the selectivity is high.
As a result, each component by water vapor is taken out and analyzed. Since it is possible to vaporize and separate substances that are not very volatile at a relatively low temperature, it has long been used for extraction of aroma components from plant tissues and applied as an extraction method for analysis of organochlorine compounds. There are also examples.
In an example of applying this method to polychlorinated biphenyl extraction in soil (GD Veith & LM Kiwus (1977) Bull. Environ. Contam. Toxicol., 17 , 631-636) It has also been pointed out that components can be analyzed directly by a gas chromatograph without going through an up process. However, the amount of moisture used is large, the operation is complicated, and the extraction temperature is limited to about 100 ° C., so that the extraction rate is low.
In this method using steam distillation, a method of vaporizing and collecting aroma components together with water vapor by irradiating a plant sample containing water under reduced pressure with microwaves is disclosed (Japanese Patent Application Laid-Open No. 8-512337 “Solvent Method and apparatus for microwave extraction of natural products without the use of "". However, in this method, once all of the water contained in the sample has evaporated, no further distillation can occur, so extraction with water vapor is limited to one time. There is a problem that it is not done.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to analyze an analyte substance to be analyzed from a sample substance containing the analyte substance under conditions where the amount of water and organic solvent used is small and the operation can be completed in a short time. And a device therefor, and a method and device for analyzing an analysis target substance to be analyzed.
[0005]
[Means for Solving the Problems]
The present inventors have made extensive studies on the above problems and have obtained the following knowledge.
For solid samples containing various organic substances such as soil, biological tissue, organic polymer compound composition, etc., in the case of an extract containing moisture or a dried sample, the moisture sample should be appropriately added, and the liquid sample Is processed by adding an appropriate amount of an inert powdered solid substance. The upper sample is put in a container equipped with a filter made of a hydrophilic material at the bottom, and the container is placed in a container that can be further sealed, and an organic solvent that is hardly soluble in water and has a lower density than water is added. By irradiating it with microwaves, the moisture contained in the sample can be heated to 100 ° C. or higher, the target substance accompanying the generated water vapor can be taken out, and the target target substance can be separated. And the analysis means can analyze what the target substance is. That is, water is present, but not in the presence of a large excess of water as in the case of steam distillation, but the minimum amount that the sample and bottom filter are saturated with water shall be added. .
By embodying this knowledge, it is possible to obtain a method and an apparatus for separating an organic compound constituting these samples from a solid or liquid sample.
According to the present invention, the following inventions are provided.
[0006]
(1) In a method for extracting an analysis target substance from a sample substance containing an analysis target substance, the sample substance containing the analysis target substance is held in the presence of water, and an organic solvent is further added to the upper part of the water In the state, the water is heated by microwaves, and in the state accompanied by the analyte and organic solvent contained in the sample, the water vapor is taken out, and these are recovered in a liquid form. A method for extracting a substance to be analyzed from a contained sample substance.
(2) The liquid substance described in (1) 1 above is supplied to the analysis means, and the analysis target substance is extracted from the sample substance containing the analysis target substance and its content is measured. A method of analyzing the analyte.
(3) In an apparatus for extracting an analysis target substance from a sample substance containing an analysis target substance, an inner container is provided at a coaxial interval in an outer container kept in a closed state . The upper part is open in the outer container, the bottom part of the inner container is close to the outer container and is in communication with the outer container, and a filter made of a hydrophilic material is attached to the inner container bottom part. the sample material containing the analyte, the water soaking the sample material containing analyte has the capacity to further hold the organic solvent on the surface of the water, the microwave heating device on the outside of the outer container There consist structure is installed, the water is heated by microwave irradiation, to vaporize the analyte contained in the sample increases the water by heating operation, then the organic solvent Heating, feeding water vapor and organic solvent vapor in a state of being associated with the analyte from the open portion of the top of the inner container, lowers the portion between the outer container and the inner container, recovered in liquid material recovered An apparatus for extracting an analysis target substance from a sample substance containing the analysis target substance, wherein the section is installed between the inner container and the outer container.
(4) In an apparatus for extracting an analysis target substance from a sample substance containing an analysis target substance, an inner container is provided at a coaxial interval in an outer container kept in a closed state . The upper part is open in the outer container, the bottom part of the inner container is close to the outer container and is in communication with the outer container, and a filter made of a hydrophilic material is attached to the inner container bottom part. the sample material containing the analyte, the water soaking the sample material containing analyte has the capacity to further hold the organic solvent on the surface of the water, the microwave heating apparatus in the inside of the outer container There consist structure is installed, the water is heated by microwave irradiation, to vaporize the analyte contained in the sample increases the water by heating operation, then the organic solvent Heating, feeding water vapor and organic solvent vapor in a state of being associated with the analyte from the open portion of the top of the inner container, lowers the portion between the outer container and the inner container, recovered in liquid material recovered An apparatus for extracting an analysis target substance from a sample substance containing the analysis target substance, wherein the section is installed between the inner container and the outer container.
(5) The recovery unit in the apparatus for extracting the analysis target substance from the sample substance containing the analysis target substance described in (3) or (4) described above is an apparatus for measuring the analysis target substance contained in the liquid and the content thereof. An apparatus for extracting a substance to be analyzed from a sample substance containing the substance to be analyzed, which is characterized by being combined, and analyzing the substance to be analyzed.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
An apparatus for performing the separation method of the present invention is as shown in FIGS.
The outside of the apparatus of the present invention is provided with a lid (4) for entering and exiting in order to install an outer container (3) and a container (1) for filling a processing object in the container. It is designed to be sealed.
When microwave irradiation is performed from the outside of the outer container (3), the outer container (3), the container (1), and the lid of the outer container are made of a material that can transmit microwaves. Specifically, it is made of glass (Pyrex (registered trademark), quartz or the like), fluorine resin (PFA or the like), or the like. The container (1) when microwave irradiation is performed from the inside of the outer container is also made of glass (Pyrex (registered trademark), quartz, etc.) and fluororesin (PFA, etc.), which are materials that can also transmit microwaves. The
If the strength of the external container with respect to the internal pressure is insufficient, the container can be further heated in a pressure-resistant outer cylinder such as a glass fiber reinforced resin.
[0008]
A filter (5) made of a hydrophilic material is attached to the bottom of the container (1). The filter is a porous glass filter. Here, the porous pore diameter is 0.1 μm to 0.5 mm. The range of the pore diameter is determined in consideration of such fineness that water can permeate or pass therethrough, and at the same time, does not allow sample residue generated in some cases to pass through. Even if it is less than this range, it can be used if it does not matter that the processing speed is slow. Further, if the residue of the sample is a large particle, even if it exceeds this range, there is no problem. In the embodiment of the present invention, one having a thickness of about 0.1 mm was used.
As a material of the filter, other hydrophilic substances such as glass or those obtained by coating a hydrophilic substance with a hydrophobic substance (such as a fluororesin) can be used. Examples of hydrophilic substances include cellulose and nylon. The thickness is appropriately selected as long as water can pass through the inside and outside of the container through the bottom of the container and can withstand supporting the solid sample filled in the container. Generally, about 0.5 mm to 3 mm is sufficient.
A filter paper made of cellulose or glass fiber is placed on the surface of the filter so that the residue remaining after the extraction of the solid to be treated on the filter paper surface does not pass through the glass filter and permeate outside. it can.
[0009]
Samples include soils, biological tissues, organic polymer compound compositions, solid samples or various liquid samples containing various organic substances. The organic substances contained in these sample substances are extracted by an extraction operation, and the amount of substances contained is determined from the analysis results. In particular, it is preferable that a substance other than the measurement target substance is not extracted if possible, since the subsequent analysis operation can be easily performed.
Place the sample on the surface of the filter paper. The sample is supplied in powder form, granular form or the like. Even if it is in the form of a lump, there is no problem in the case of a substance that can sufficiently contact with water.
In the case of a solid sample that does not contain enough water, an amount of water necessary to permeate the sample and the bottom filter, generally from the same weight as the sample to several times the amount, is injected.
Microwaves act on this water. As a result, the water temperature rises and the sample can be heated. At that time, water vapor condenses on the lid of the outer container and the inner wall of the side surface where the temperature is relatively low, returns to the bottom, and further passes through the hydrophilic filter and permeates the sample. Will do.
[0010]
The solvent is filled above the water. An organic solvent is used as the solvent. In general, nonpolar or weakly polar ones, specifically hexane, heptane, octane, nonane, isooctane, toluene and the like are desirable in terms of microwave permeability and extraction selectivity. The organic solvent may be placed either inside or outside the inner container before the operation, but it is desirable to put the organic solvent inside in order to suppress scattering of the sample. This solvent must have a capacity that can dissolve the vaporized organic substance at the minimum, and at the same time, in order to suppress extraction of components other than the analyte by direct contact between the organic solvent and the sample, It is desirable not to exceed the capacity of the gap between the container and the outer container.
[0011]
In consideration of the required amount of water and the required amount of solvent, the ratio of the organic solvent and water can be appropriately determined from these ranges. Increasing the amount of water more than necessary is not preferable because it consumes excessive energy and contributes to a longer extraction time.
As an example, an amount of about 2 to 5 mL of water and 5 to 20 mL of an organic solvent is used for 0.5 to 5 g of a sample. This value is based on the experimental apparatus of the present invention. This value changes depending on the scale of the apparatus, and the range of this value changes by changing the sizes of the microwave irradiation apparatus, the microwave output, and the extraction container.
[0012]
Microwaves are irradiated from the outside of the outer container (3) or from the inside of the outer container (3).
A microwave generator is provided outside the outer container (3) or inside the outer container (3), and microwaves are introduced into the container (1) and heated.
Water that is in a state of coexisting with the sample is heated from the inside by microwaves and can be rapidly raised to a temperature of 100 ° C. or higher, which is a boiling point.
Along with the generated water vapor, the target substance in the sample is vaporized and then condensed and separated. Microwave heating is an induction heating method using electromagnetic waves in the range of 300 MHz to 300 GHz. Microwave heating is due to ion currents present in the medium caused by electromagnetic waves and dipole rotation of molecules.
Irradiation of microwaves is intermittent while controlling so that the temperature is kept at 150 ° C. per 100 to 200 W per apparatus (in the case of including 0.5 to 5 g of sample, 2 to 5 mL of water, and 10 mL of organic solvent). It is performed by irradiating for 30 to 60 minutes.
[0013]
The solvent vapor containing the substance to be extracted rises in the container 3, condenses on the lid provided on the upper part and the inner wall of the side surface, and descends while the temperature decreases, and the container (3) and the container ( Accumulate during 1).
At that time, only water permeates through the hydrophilic filter at the bottom of the inner container and penetrates into the sample, thereby contributing to repeated extraction. At that time, the target organic substance is dissolved and accumulated in the organic solvent phase. And if it cools after microwave irradiation and an inner container is removed, the extract which does not contain an extraction residue will be obtained. At that time, the slightly mixed water can be easily removed by a gradient method or the like.
The condensed organic solvent layer can be taken out, the target target substance can be separated, and the target substance can be analyzed by the analyzing means. In this invention, since the water layer is maintained above and below the sample, the sample and the organic solvent are not in direct contact with each other, so that highly polar and low volatile substances are hardly recovered. When this is applied to the analysis of polychlorinated biphenyls and the like, it produces an advantage that unnecessary substances need not be removed before the quantitative operation, and thus enables rapid analysis. For example, it is possible to directly analyze an extract obtained by the above-described operation only by removing mixed water by a gas chromatograph / mass spectrometer.
[0014]
【Example】
Example 1
In this example, an external container (3) (inner diameter: 40 mm, height: about 150 mm), pressure-resistant outer cylinder (1), and microwave irradiation apparatus (commercially available CEM MarsX, USA) were used.
The materials constituting these outer container (3) and pressure-resistant outer cylinder (1) were fluororesin (PFA) and glass fiber reinforced resin, respectively.
A container equipped with a hydrophilic filter (5) was used at the bottom of the container (1) (inner diameter 20 mm, height 50 mm) installed inside the container. The filter has a thickness of 2 mm and a pore diameter of 0.1 mm.
The microwave was irradiated from the outside of the external container (3) by a microwave irradiation device (maximum output 1200 W).
[0015]
Example 2
Using the results of the present invention, using a sediment reference material with a known PCB content (NIST SRM1944), the measurement results of the PCB content are compared to confirm that the measurement method of the present invention is effective. did.
The apparatus of Example 1 was used.
Sample (bottom standard substance) consumption 0.7g
Water injection volume 3mL
Solvent n-octane 10mL
3. Usage amount Extraction temperature 150 ° C., extraction time 60 minutes The results of analyzing the extract directly with a gas chromatograph / mass spectrometer, and the results and certified values obtained by Comparative Example 1 below are shown in FIG. It can be seen that the result of the present invention shows a good agreement with the value of the authentication value.
[0016]
Example 3
Analysis was performed in the same manner as in Example 2 using the harbor sediment as a sample.
Sample (bottom standard) consumption 2.5g
Water injection volume 3mL
Amount of solvent (specific name) n-octane 10mL
Heating conditions and heating time. FIG. 3 shows the results obtained by directly analyzing the extract with a gas chromatograph / mass spectrometer and the results obtained in Comparative Examples 2 and 3 at 150 ° C. for an extraction time of 60 minutes.
[0017]
Comparative Example 1
Sediment reference material with known PCB content (NIST SRM1944) is extracted by the usual microwave extraction method (extraction temperature 130 ° C, extraction time 10 minutes, acetone / hexane 20 mL) and cleaned up by high performance liquid chromatograph etc. After the treatment, it was analyzed with a gas chromatograph / mass spectrometer.
Sample (bottom standard substance) consumption 0.7g
Solvent Acetone / hexane (ratio 1/1) 20 mL
Amount used Extraction temperature 130 ° C, extraction time 10 minutes cleanup Removal of sulfur by adding copper powder, removal of highly polar components by silica gel,
Interference removal by high performance liquid chromatograph
Comparative Example 2
Port sediments are extracted by the usual microwave extraction method (extraction temperature 130 ° C, extraction time 10 minutes, acetone / hexane 20 mL), and after high-performance liquid chromatograph cleanup, gas chromatograph / mass spectrometry Analyzed in total.
Sample (bottom standard) consumption 2.5g
Solvent Acetone / hexane (ratio 1/1) 20 mL
Amount used Extraction temperature 130 ° C, extraction time 10 minutes cleanup Removal of sulfur by adding copper powder, removal of highly polar components by silica gel,
Interference component removal by high performance liquid chromatograph
Comparative Example 3
Port bottom sediment was extracted by a normal Soxhlet extraction method (extraction time 12 hours, acetone / hexane 300 mL), subjected to a cleanup process using a high performance liquid chromatograph, and then analyzed by a gas chromatograph / mass spectrometer.
Sample (bottom standard) consumption 2.5g
Solvent Acetone / hexane (ratio 1/1) 300 mL
Usage amount extraction temperature: about 60 ° C., extraction time: 12 hours Except for the numerical values described above, the other conditions are almost the same in Comparative Examples 1 and 2.
[0020]
【The invention's effect】
The present invention can provide a method and apparatus for extracting an analysis target substance from a sample substance containing the analysis target substance to be analyzed, and a method and apparatus for analyzing the analysis target substance to be analyzed. According to the present invention, the amount of water and organic solvent used is small, and the operation can be completed in a short time.
[Brief description of the drawings]
FIG. 1 is a schematic diagram of the present invention.
1: Glass cylinder 2: Porous glass filter 3: Fluororesin container 4: Fluororesin lid FIG. 2 is a diagram showing a process of organic substance extraction in the present invention using the apparatus of FIG.
1: Glass cylinder 2: Porous glass filter 3: Fluororesin container 4: Fluororesin lid 5: Filter paper or glass fiber filter paper 6: Sample and contained water 7: Water 8: Organic solvent 9: Water / organic solvent / FIG. 3 is a diagram showing a comparison between analytical values and certified values of polychlorinated biphenyls and organochlorine pesticides in seabed sediment sample A obtained by the apparatus of the present invention. .
FIG. 4 is a comparison of analytical values of polychlorinated biphenyls and organochlorine pesticides in seabed sample B obtained by the apparatus of the present invention and analytical values obtained by a conventional microwave extraction device / Soxhlet extraction device. FIG.
[Explanation of symbols]
Regarding FIG. 1: 1: Container 2: Porous glass filter 3: Outer container 4: Lid Regarding FIG. 2: 1: Container 2: Porous glass filter 3: Outer container 4: Outer container lid 5: Filter paper or glass fiber filter paper 6: Sample Moisture 7: Water 8: Organic solvent 9: Water, organic solvent, vapor of target substance and movement of condensate

Claims (5)

  In the method of extracting the analysis target substance from the sample substance containing the analysis target substance, the sample substance containing the analysis target substance is held in the presence of water, and further, an organic solvent is added to the upper part of the water, A sample containing an analysis target substance, characterized in that the water is heated by microwaves, the analysis target substance and the organic solvent contained in the sample are accompanied, and water vapor is taken out and recovered in a liquid form A method for extracting a substance to be analyzed from a substance.   The liquid substance according to claim 1 is supplied to an analysis means, and the analysis target substance is extracted from the sample substance containing the analysis target substance and the content thereof, and the analysis target substance is analyzed. how to. In an apparatus for extracting an analysis target substance from a sample substance containing an analysis target substance, an inner container is provided coaxially in an outer container that is kept closed , and the upper part of the inner container is an outer side. Open to the container, the bottom of the inner container is close to the outer container,
In addition, a filter made of a hydrophilic material is attached to the bottom of the inner container , and the upper part of the filter is a sample substance containing the analysis target substance, water for immersing the sample substance containing the analysis target substance, and It has a capacity to hold an organic solvent on the surface of water, and has a structure in which a microwave heating device is installed outside the outer container. The water is heated by microwave irradiation, Evaporate the analyte contained in the sample to raise the water, then heat the organic solvent, and send out the water vapor and organic solvent vapor with the analyte attached from the open part of the upper part of the inner container the portion between the outer container and the inner container is lowered, the recovery unit for recovering a liquid body, the analyte, characterized in that it is installed between the outer container and the inner container containing Device for taking out the analyte from the sample material to be. In an apparatus for extracting an analysis target substance from a sample substance containing an analysis target substance, an inner container is provided coaxially in an outer container that is kept closed , and the upper part of the inner container is an outer side. Open to the container, the bottom of the inner container is close to the outer container,
In addition, a filter made of a hydrophilic material is attached to the bottom of the inner container, and the upper part of the filter is a sample substance containing the analysis target substance, water for immersing the sample substance containing the analysis target substance, and It has a capacity to hold an organic solvent on the surface of water, and has a structure in which a microwave heating device is installed inside the outer container. The water is heated by microwave irradiation, Evaporate the analyte contained in the sample to raise the water, then heat the organic solvent, and send out the water vapor and organic solvent vapor with the analyte attached from the open part of the upper part of the inner container the portion between the outer container and the inner container is lowered, the recovery unit for recovering a liquid body, the analyte, characterized in that it is installed between the outer container and the inner container Device for taking out the analyte from the sample material with. The recovery unit in the apparatus for extracting the analysis target substance from the sample substance containing the analysis target substance according to claim 3 or 4 is coupled to the analysis target substance contained in the liquid and the apparatus for measuring the content thereof. An apparatus for extracting an analysis target substance from a sample substance containing the characteristic analysis target substance and analyzing the analysis target substance.

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