JP2007167815A - Solid-phase extraction cartridge and solid-phase extraction method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid-phase extraction cartridge which is stable in a medium in a wide pH region ranging from acidity to alkalinity and enables efficient, rapid and convenient fractionation, purification, concentration etc. of an object material and a fractionation method, a sample-purifying method and a method of recovering an object material which enable rapid, convenient and highly reproductive fractionation, purification, concentration, etc. of an object material by the use of the solid-phase cartridge. <P>SOLUTION: The solid-phase extraction cartridge is charged with at least a porous silicon carbide type filler in its inside. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a solid-phase extraction cartridge and a method for separating a substance to be collected using the same, a method for purifying a sample, and a method for collecting a substance to be collected. More specifically, the present invention relates to a solid-phase extraction cartridge filled with a porous silicon carbide-based filler, a fractionation target substance separation method using the same, a sample purification method, and a recovery subject substance recovery method.

  Conventionally, the liquid absorption method has been used to extract organic substances from gases and the liquid-liquid extraction method has been used to extract organic substances and heavy metals from liquids. However, the work is complicated and requires time and experience. There were problems such as using a large amount of organic solvent.

  In contrast, the solid-phase extraction method has features that it is easy to work, requires a short time, and uses a small amount of organic solvent. Therefore, it is very advantageous when a large number of specimens must be processed in a short time, and automation is also easy.

  Applications of the solid phase extraction method include, for example, measurement of pollutants contained in environmental water such as rivers, soil and air. In particular, for the measurement of pesticides and pesticide degradation products contained in environmental water, laws and regulations often stipulate that the solid-phase extraction method be used for the separation of substances to be measured from samples.

  There are inorganic and organic fillers used in the solid-phase extraction method. As the base material for the inorganic filler, silica gel or chemically bonded silica gel whose surface is chemically modified is used. As the base material for the organic filler, synthetic polymer systems typified by styrene-divinylbenzene copolymer and those obtained by chemically modifying the surface thereof are used (see Patent Document 1 and Patent Document 2). .

  However, silica gel-based fillers are weak against strong acids and alkalis having a pH of about 8 or more. Particularly, the porous material easily disintegrates when subjected to mechanical stress in an acidic medium or an alkaline medium. The solid phase extraction cartridge is not suitable for separating, purifying, concentrating, etc. a stable substance only in an acidic medium or an alkaline medium.

For example, to deproteinize in a matrix in a fluid-related medium, basically C18
Although solid phase (ODS) is used, it may be purified or concentrated by shifting the pH to extremely acidic or alkaline side. That is, when an acidic compound is made acidic and a basic compound is made alkaline, dissociation is suppressed and extraction becomes easy. In such a case, the use of a silica-based filler is not suitable.

  Therefore, a solid-phase extraction cartridge that can separate, purify, and concentrate a substance to be separated from a sample in a medium in a wide pH range from acidic to alkaline, and a solid-phase extraction cartridge that can remove the object to be removed and purify the sample. Therefore, development of a solid-phase extraction cartridge capable of recovering a recovery object has been desired.

By the way, silicon carbide (SiC) is a compound that maintains its structure stably in a medium in a wide pH range from acidic to alkaline. The porous body of silicon carbide has been reported to be used as an adsorbent, a liquid chromatography carrier or a catalyst carrier (Patent Document 3, Patent Document 4, Non-Patent Document 1). However, use for a solid phase extraction cartridge has not been studied.
JP 59-147606 A JP-A-4-334546 JP-A-2-191542 JP-A-6-294788 Satoshi Takeuchi, “Properties of Porous Materials and Their Applied Technologies”, first edition, Fuji Techno System Co., Ltd., 1999, p62-67

  The present invention has been made in view of such a situation, and a solid-phase extraction cartridge capable of eliminating the above-described drawbacks of the prior art, as well as a method for separating a substance to be sorted using the solid-phase extraction cartridge, It is an object of the present invention to provide a sample purification method and a recovery method of a recovery target substance.

  That is, the present invention provides a solid-phase extraction cartridge capable of efficiently, quickly and simply separating, purifying, and concentrating a target substance even in a medium in a wide pH range from acidic to alkaline. Is an issue.

  Further, the present invention provides a fractionation method, a sample purification method, and a collection target that can quickly, easily, and reproducibly sort, purify, and concentrate a substance to be sorted using the solid-phase extraction cartridge. The problem is to provide a method for collecting substances.

  As a result of intensive studies to solve the above problems, the inventors of the present invention are stable only in an acidic or alkaline medium at least according to a solid-phase extraction cartridge in which a porous silicon carbide filler is filled in the cartridge. It was found that even a simple compound could be efficiently and reliably separated, purified and concentrated, and the present invention was completed.

That is, the present invention relates to the following matters.
(1) A solid-phase extraction cartridge characterized in that at least a porous silicon carbide-based filler is filled in the cartridge.

(2) The porous silicon carbide based filler is in the form of particles, the number average particle diameter is in the range of 10 μm to 1000 μm, and the specific surface area by the BET method is 10 m ² / g or more. The solid phase extraction cartridge according to (1) above.

(3) The solid phase extraction cartridge according to (2), wherein the porous silicon carbide-based filler is crushed particles obtained by crushing a porous sintered body of silicon carbide.
(4) A sample containing the substance to be sorted and the coexisting substance is circulated through the solid phase extraction cartridge according to any one of (1) to (3), and the substance to be sorted is placed in the solid phase extraction cartridge. A method for fractionating a substance to be fractionated, wherein the substance to be fractionated is eluted by passing the eluent through the solid-phase extraction cartridge after being adsorbed by the porous silicon carbide-based filler therein.

  (5) The sample containing the substance to be separated and the coexisting substance is circulated through the solid phase extraction cartridge according to any one of (1) to (3), whereby the coexisting substance is placed in the solid phase extraction cartridge. A method for fractionating a substance to be fractionated, wherein the substance to be fractionated is adsorbed on the porous silicon carbide filler and the substance to be fractionated is allowed to flow out.

(6) The above (4), wherein the substance to be sorted is one or more compounds selected from dioxins, polychlorinated biphenyls, agricultural chemicals, environmental hormones, heavy metals, and proteins.
) Or (5).

  (7) Removing the substance to be removed from the sample by circulating the sample containing the substance to be removed and the coexisting substance through the solid-phase extraction cartridge according to any one of (1) to (3) above. A method for purifying a sample.

  (8) Collecting the sample to be collected from the sample by circulating the sample containing the substance to be collected and the coexisting substance through the solid-phase extraction cartridge according to any one of (1) to (3) above. A method for recovering a substance to be recovered.

  According to the solid-phase extraction cartridge of the present invention, a target substance can be efficiently, rapidly and simply separated, purified, concentrated, and the like stably in a medium in a wide pH range from acidic to alkaline.

  In addition, according to the method for separating a substance to be separated, the method for purifying a sample, and the method for collecting a substance to be collected according to the present invention, the target substance can be separated, collected or removed quickly, easily and with good reproducibility. The object to be separated or the sample can be purified and concentrated.

Hereinafter, embodiments of the present invention will be described in detail.
<Solid phase extraction cartridge>
First, a solid phase extraction cartridge to which the present invention is applied will be described in detail with reference to the drawings as necessary. In addition, in order to make the feature easy to understand, the drawing may show the feature portion in an enlarged manner for the sake of convenience, and the dimensional ratios and the like of the respective constituent elements are not always the same.

  A solid-phase extraction cartridge to which the present invention is applied includes a cartridge main body 10a formed in a substantially cylindrical shape, for example, like the solid-phase extraction cartridge 10 of FIG. 1, and both end portions in the longitudinal direction of the cartridge main body 10a. Are provided with nozzles 10b and 10c, respectively. The solid-phase extraction cartridge 10 includes a filler 11 and a pair of filters 12a and 12b arranged so as to sandwich the filler 11 from the longitudinal direction inside the cartridge body 10a. Since the cartridge body 10a accommodates the filler 11 and the filters 12a and 12b, the cartridge body 10a can be divided between a lid portion provided with the nozzle 10b and a container portion provided with the nozzle 10c. .

  The material of the cartridge body 10a is not particularly limited as long as it is insoluble in the solvent used and does not leak the filler 11 during the sample collection, purification, and concentration operations. Specifically, for example, those made of glass, stainless steel, or resin (for example, polypropylene or polyethylene) are preferably mentioned.

  The shape of the cartridge main body 10a is not particularly limited, and may be cylindrical, syringe barrel (syringe), barrel, or disk. The size of the cartridge body 10a can be selected appropriately depending on the amount of sample to be used, but usually has a volume of 0.1 to 500 ml, preferably 2 to 100 ml, more preferably about 3 to 6 ml. Is preferable in terms of handling.

  The filler 11 is filled in the cartridge body 10a and is held by a pair of filters 12a and 12b so as not to leak outside from the nozzles 10b and 10c of the cartridge body 10a.

  In the solid-phase extraction cartridge of the present invention, at least a porous silicon carbide filler is used as the filler 11. This porous silicon carbide-based filler may be a silicon carbide porous body itself, or a silicon carbide porous body modified (coated) with an organic compound for controlling the surface adsorptivity. But you can.

  The porous body of silicon carbide constituting the porous silicon carbide filler that can be used in the present invention can be produced by a known method, and the method is not particularly limited. That is, depending on the shape, size, specific surface area, etc. of the porous silicon carbide filler to be obtained, a commercially available silicon carbide porous body may be used, and a known production method may be used. You may employ | adopt suitably and manufacture. The silicon carbide contained in the porous silicon carbide filler may be α-SiC, β-SiC, or a mixture thereof.

Specifically, for example, Atchison method; silica carbon reduction method; silicon / carbon direct reaction method; sol / gel silica carbon reduction method; gas phase reaction method (CVD method); thermal decomposition of CH ₃ SiCl ₃ or polycarbosilane When silicon carbide, which is produced by a known production method such as pyrolysis and is commercially available, is a porous body, it is used as a porous silicon carbide filler as it is or after being pulverized as necessary May be.

  Moreover, as described in Patent Document 4, after mixing polycarbosilane, carbon black, and a solvent to obtain a slurry, and granulating the obtained slurry, it is 1450 to 1650 ° C. in an inert atmosphere. The silicon carbide obtained by firing may be used as a porous silicon carbide filler.

  Further, commercially available silicon carbide or silicon carbide produced by the above-mentioned known method is pulverized as necessary, and then dispersed in a dispersion medium such as water together with a binder polymer and a dispersant to obtain a slurry. The resulting slurry is impregnated into an organic foamed molded article such as polyurethane foam, dried, and heated to about 2000 ° C. for 2 to 3 hours under normal pressure and inert atmosphere to sinter silicon carbide and organic foam. It is also possible to obtain a block-like porous body of silicon carbide by burning out the molded body. The obtained block-like porous body of silicon carbide can be used as a porous silicon carbide filler as it is depending on the shape, size, specific surface area, etc. of the porous silicon carbide filler to be obtained. Alternatively, it may be used as a porous silicon carbide filler after being subjected to grinding treatment or pulverizing as appropriate.

  The porous body of silicon carbide obtained in this way may be used as a porous silicon carbide filler as it is. However, when it is desired to change the adsorption characteristics of the surface, an organic compound is added to the surface of the porous body. It is preferable to coat (modify).

  Examples of the coating method include a monomer adsorption polymerization method (a method in which a monomer is polymerized on the surface of the silicon carbide porous body), a coupling reaction, and the like. Absent.

  The shape of the filler 11, particularly the porous silicon carbide filler, is rod-shaped (the filler is the same size as the inside of the cartridge body as one lump), bulk-shaped (lump of about 1 mm to 5 cm) Any of a particulate form and a fibrous form may be used, but a rod form or a particulate form is preferable, and a particulate form is more preferable from the viewpoint that a space can be filled with less gap when filling a container.

The number average particle diameter in the form of particles is preferably in the range of 10 μm to 1000 μm, more preferably in the range of 30 μm to 700 μm, and most preferably in the range of 50 μm to 500 μm. When the average particle size is less than 10 μm, when the flow rate of the sample such as liquid or gas flowing through the solid-phase extraction cartridge 10 is increased, the difference in static pressure before and after the filler layer made of the filler 11 (pressure loss) And the sample cannot flow at a high flow rate. On the other hand, if the average particle diameter exceeds 1000 μm, the adsorption efficiency of the target substance is deteriorated.

  In addition, the average particle diameter of the filler 11, especially the porous silicon carbide based filler is measured in accordance with JIS Z8815 sieving test method general rules using a test sieve defined in JIS Z8801.

Furthermore, the specific surface area of the filler 11, particularly the specific surface area of the porous silicon carbide-based filler described above, is preferably 10 m ² / g or more, more preferably 30 m ² / g or more. When the specific surface area is less than 10 m ² / g, the adsorption efficiency of the target substance is deteriorated. The specific surface area is measured by the BET method.

  Further, as the filler 11, particularly the porous silicon carbide-based filler, those having the above shapes can be used in combination. For example, it is also possible to use a filler in the form of particles or fibers in the gaps between the bulk fillers.

  Further, if necessary, in addition to the porous silicon carbide-based filler described above, another filler, that is, another organic or inorganic porous material may be mixed and used as the filler 11, Further, the inside of the cartridge main body 10a may be filled so as to form a multilayer structure with the porous silicon carbide filler and other fillers or base materials.

  Examples of other porous materials or other fillers that can be used as the filler 11 in addition to the porous silicon carbide filler include polystyrene beads, ODS, and alumina beads.

<Solid-phase extraction method; method for fractionating target substance, sample purification method, and target substance recovery method>
Next, a solid phase extraction method using the above-described solid phase extraction cartridge to which the present invention is applied, that is, a fractionation target substance sorting method, a sample purification method, and a recovery target substance using the solid phase extraction cartridge A method of collecting the above will be described.

  In the present invention, a sample such as gas or liquid is allowed to flow through the above-described solid phase extraction cartridge, and the target substance contained in this sample is once adsorbed on the filler and then eluted, or the coexisting substance is adsorbed on the filler. By flowing out the target substance, the target substance can be collected and recovered. The sample can also be purified. Here, the “target substance” means a chemical substance that is a target of sorting, recovery, or the like.

Hereinafter, the method for separating the target substance will be described as an example, and will be described with reference to the drawings as necessary.
2 and 3, the solid-phase extraction cartridge 10 is the same as the solid-phase extraction cartridge 10 of FIG. 1, and is a schematic cross-sectional view schematically showing this. Therefore, the same parts are denoted by the same reference numerals, and the description thereof is omitted. 2 and 3, in order to simplify and describe the solid-phase extraction cartridge 10 of FIG. 1, the lid portion provided with the upper nozzle 10 b and the filters 12 a and 12 b are not shown and omitted.

As shown in FIG. 2, a solid phase extraction cartridge 10 filled with a filler 11 is prepared, and a sample 20 is caused to flow down to the solid phase extraction cartridge 10. This sample 20 contains a substance 15 to be sorted and a coexisting substance 17 that is not to be sorted. When the sample 20 is caused to flow down, the fractionation target substance 15 is adsorbed on the filler 11, and the coexisting substance 17 that is not subject to fractionation is allowed to flow down without being adsorbed. Thereafter, the eluent is allowed to flow down to desorb the fractionation target substance 15 from the filler 11 and elute it.

  As the eluent, any organic solvent can be used according to the target substance to be collected. Specific examples include acetone, acetonitrile, methanol, ethanol, tetrahydrofuran, ethyl acetate, and n-hexane.

In this manner, the separation target substance 15 contained in the sample 20 can be separated.
FIG. 3 shows another example of a method for separating a target substance using the solid-phase extraction cartridge 10.
As shown in FIG. 3, a solid phase extraction cartridge 10 filled with a filler 11 is prepared, and a sample 20 is caused to flow down to the solid phase extraction cartridge 10. When the sample 20 is caused to flow down, in the example of FIG. 3, the coexisting substance 17 that is not to be sorted is adsorbed by the filler 11, and the substance to be sorted 15 flows down without being adsorbed. In the flowed-down solution, the amount of the coexisting substance 17 is greatly reduced, while the fractionation target substance 15 flows almost as it is. In this manner, the separation target substance 15 contained in the sample 20 can be separated.

  Here, in order to adsorb the target substance 15 on the filler 11 or not, for example, an organic compound to be coated on the surface of the filler 11, particularly the porous silicon carbide-based filler, may be selected appropriately. Preferably mentioned.

  Although the method for separating the target substance has been described above, in the present invention, the above-described sorting method can be directly applied to the method for removing the target substance to be removed from the sample and the method for collecting the target substance to be collected.

  Specific target substances of the above-described solid phase extraction method include incinerator exhaust gas, various manufacturing facility exhaust gas, environmental air such as air collected on the main road, indoor air, factory wastewater, river water, lake water, Examples include trace substances contained in samples selected from human and livestock excrement, etc. that require high concentration, and the solid-phase extraction cartridge of the present invention can be suitably used as a pretreatment of these samples. However, it is not particularly limited.

  These trace substances include compounds that accumulate in the human body and livestock and cause harm, compounds excreted in the urine of the human body and livestock and their metabolites, or compounds useful for the human body and livestock, environmental pollutants, toxic substances, physiological Active substances.

  Specifically, dioxins; polychlorinated biphenyls; pesticides or pesticide degradation products such as disulfides; environmental hormones; petrochemical derivatives; nutritional components; products from microorganisms; toxins; heavy metals; Can be mentioned.

  Examples of these compounds include dioxins, dibenzofurans, polycyclic aromatic hydrocarbons (including PAHs, benzo (a) pyrene), polychlorinated biphenyls, polybrominated biphenyls, tetramethylthiuram disulfide, DDT, chlorpyrifos, aldrin, Dildoline, Endrin, Chlorden, Heptachlor, Trichlorobenzene, Tetrachlorobenzene, Hexachlorobenzene (HCB), Milex, Toxaphene (Camphechlor), Hexachlorocyclohexane (Lindene (γ-HCH), etc.), Chlordecone (Kepon), Octachlorostyrene (OCS) ), Ashram, simazine, 1,4-dioxane, nonylphenol, surfactant, female hormone, male hormone, other hormones, polyphenols, antibiotics, antibacterial agents, Proteins, peptides, lipids, sugars, nucleic acid-related substance, vitamins, neurotransmitters, natural toxins typified by mycotoxins and marine toxins, arsenic, selenium and their metabolites can be mentioned.

  Among these, when a compound that is stable only in an acidic or alkaline medium is used as a target substance, or when a coexisting substance is removed from a sample containing the compound, the effect of the present invention is exhibited more greatly. Therefore, the present invention is preferably applied to such fractionation, purification, concentration, recovery, etc., but is not particularly limited thereto.

FIG. 1 is a perspective view showing an example of a solid-phase extraction cartridge according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view illustrating an example of a solid phase extraction method using a solid phase extraction cartridge according to an embodiment of the present invention. FIG. 3 is a schematic cross-sectional view for explaining another example of the solid phase extraction method using the solid phase extraction cartridge according to the embodiment of the present invention.

Explanation of symbols

10: Solid phase extraction cartridge 10a: Cartridge body 10b, 10c: Nozzle 11: Filler 12a, 12b: Filter 15: Sorting target substance 17: Non-sorting target substance (coexisting substance)
20: Sample

Claims (8)

  A solid-phase extraction cartridge characterized in that at least a porous silicon carbide-based filler is filled in the cartridge. The porous silicon carbide-based filler is particulate, its number average particle diameter is in the range of 10 µm to 1000 µm, and the specific surface area by the BET method is 10 m ² / g or more. 2. The solid phase extraction cartridge according to 1.   The solid phase extraction cartridge according to claim 2, wherein the porous silicon carbide-based filler is crushed particles obtained by crushing a porous sintered body of silicon carbide.   A sample containing the substance to be sorted and the coexisting substance is circulated through the solid-phase extraction cartridge according to any one of claims 1 to 3 so that the substance to be sorted is porous silicon carbide in the solid-phase extraction cartridge. A method for fractionating a substance to be sorted, wherein the substance to be sorted is eluted by allowing an eluent to flow through the solid-phase extraction cartridge after being adsorbed on a system filler.   A sample containing the substance to be separated and the coexisting substance is circulated through the solid-phase extraction cartridge according to any one of claims 1 to 3 so that the coexisting substance is porous silicon carbide in the solid-phase extraction cartridge. A method for sorting a substance to be sorted, wherein the substance to be sorted is caused to flow out while being adsorbed by a filler.   6. The substance to be sorted according to claim 4 or 5, wherein the substance to be sorted is at least one compound selected from dioxins, polychlorinated biphenyls, agricultural chemicals, environmental hormones, heavy metals, and proteins. Sorting method.   A sample containing the substance to be removed and the coexisting substance is passed through the solid-phase extraction cartridge according to any one of claims 1 to 3 to remove the substance to be removed from the sample. Purification method.   A recovery target, wherein the recovery target substance is recovered from the sample by circulating the sample containing the recovery target substance and the coexisting substance through the solid-phase extraction cartridge according to claim 1. Material recovery method.

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