JP2010197266A - Analysis method of sulfuric acid and sulfur trioxide within fuming sulfuric acid-impregnated carrier and method for manufacturing fuming sulfuric acid-impregnated carrier using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an analysis method for individually measuring the quantities of a sulfuric acid and a sulfur trioxide impregnated in a fuming sulfuric acid-impregnated carrier. <P>SOLUTION: The fuming sulfuric acid-impregnated carrier as a sample is immersed in water. The sulfur trioxide in the carrier reacts on the water. The total quantity of the sulfuric acid previously existing in the carrier and the sulfuric acid derived from the sulfur trioxide is measured as a measurement value A. The same sample as the previous sample is immersed in a dodecylbenzene solution. After the solution reacts on the sulfur trioxide, the content quantity of the sulfuric acid within the solution is measured as a measurement value B. The quantities of the sulfuric acid and the sulfur trioxide impregnated in the carrier are calculated from a measurement result (the measurement value A-the measurement value B). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for analyzing sulfuric acid and sulfur trioxide in a fuming sulfuric acid-impregnated carrier and a method for producing a fuming sulfuric acid-impregnated carrier using the same. Specifically, when quantifying polychlorinated biphenyls in a hydrophobic sample containing polychlorinated biphenyls, an analysis method for sulfuric acid and sulfur trioxide in a fuming sulfuric acid-impregnated support used for sample pretreatment and the like is described. The present invention relates to a method for producing the fuming sulfuric acid-impregnated carrier used.

Polychlorinated biphenyls contained in hydrophobic samples such as insulating oils used in transformers and the like [hereinafter sometimes abbreviated as PCBs. ], It is necessary to remove in advance the coexisting substances that interfere with the quantification of PCBs. However, such coexisting substances cannot be separated by ordinary processing methods such as column chromatography. Some are difficult. Therefore, Non-Patent Document 1 [Attached Table 2 “Special Management General Waste and Special Management Industry of July 3, 1992 revised by the Ministry of Health, Labor and Welfare Notification No. 633 on December 28, 2000” In the so-called official method described in “Standard Test Method for Waste”], after repeating the operation of bringing a hydrophobic sample into contact with concentrated sulfuric acid in liquid-liquid contact, the coexisting substances are subjected to the above column chromatographic treatment. And a method of treating a hydrophobic sample using fuming sulfuric acid having a free SO ₃ concentration of 25% by mass in place of concentrated sulfuric acid is also known. Hydrophobic samples after liquid-liquid contact with concentrated sulfuric acid or fuming sulfuric acid are separated from concentrated sulfuric acid or fuming sulfuric acid by a liquid separation operation, and this method of treatment removes difficult-to-separate interfering substances contained in hydrophobic samples. can do.

However, it is troublesome to repeat the operation of separating the hydrophobic sample after the liquid-liquid contact from concentrated sulfuric acid or fuming sulfuric acid.

From this demand, BET specific surface area of 250m ² / g~450m ² / g, the silica gel pore volume 1.4cm ³ /g~2.6cm ³ / g, free SO ₃ concentration is 5 mass% to 40 mass% A method using a fuming sulfuric acid-impregnated silica gel impregnated with a certain fuming sulfuric acid is known (Patent Document 1).

The method disclosed in Patent Document 1 is an excellent method capable of sufficiently removing an interfering substance that is difficult to separate from PCBs contained in a hydrophobic sample with good workability. For example, even if fuming sulfuric acid-impregnated silica gel is produced using fuming sulfuric acid having a free SO ₃ concentration of 25% by mass because it absorbs moisture in the air and changes to sulfuric acid in a short period of time, It is necessary for quality control to know how much free SO ₃ concentration the product has over time.

JP 2007-248270 A

December 28, 2000 Ministry of Health, Labor and Welfare Notification No. 633, revised on July 3, 1992 Ministry of Health, Labor and Welfare Notification No. 192, Appendix 2 “Examination Methods for Standards Related to Specially Managed General Waste and Specially Managed Industrial Waste” "

  However, as is apparent from JIS K1321 1994 “sulfuric acid” and JIS K8741 1996 “fuming sulfuric acid (reagent)”, the conventionally known measurement method is based on the premise that the measurement sample is composed only of sulfuric acid and sulfur trioxide. This is an analytical method, in which sulfur trioxide is reacted with water to form sulfuric acid, and then the total sulfuric acid concentration is measured, and the amount exceeding 100% is obtained as a sulfur trioxide content by a formula. Therefore, this method cannot be applied to a sample containing substances other than sulfuric acid and sulfur trioxide such as silica gel.

  In view of such circumstances, the present inventors have intensively studied to find out a method capable of correctly analyzing the amount of sulfuric acid and sulfur trioxide impregnated in the support even in the presence of a support such as silica gel. It came to be completed.

That is, the present invention provides: An object of the present invention is to provide a method for analyzing sulfuric acid and sulfur trioxide in a fuming sulfuric acid-impregnated carrier, characterized by analyzing by the following procedure.
(1) A step of immersing a fuming sulfuric acid-impregnated carrier in water and reacting sulfur trioxide in the carrier with water to obtain sulfuric acid, and measuring the total amount of sulfuric acid previously present in the carrier and sulfuric acid derived from sulfur trioxide ( 2) The fuming sulfuric acid impregnated carrier is immersed in a solvent that does not react with sulfuric acid but reacts only with sulfur trioxide to form a reaction product different from sulfuric acid, and the sulfur trioxide and the solvent are reacted with sulfuric acid in the solvent. Step of measuring content (3) Step of calculating the content of sulfuric acid and sulfur trioxide contained in the fuming sulfuric acid impregnated carrier from the amount of sulfuric acid obtained in (1) and the amount of sulfuric acid obtained in (2)

  The present invention also provides 2. 1. A solvent that reacts only with sulfur trioxide without reacting with sulfuric acid and forms a reactant different from sulfuric acid is an aromatic hydrocarbon. It is an object of the present invention to provide a method for analyzing sulfuric acid and sulfur trioxide in a fuming sulfuric acid-impregnated support.

  In the present invention, 3. 1. The above-mentioned 1. characterized in that the solvent which does not react with sulfuric acid but reacts only with sulfur trioxide and forms a reactant different from sulfuric acid is dodecylbenzene. Or 2. It provides a method for analyzing sulfuric acid and sulfur trioxide in the fuming sulfuric acid impregnated carrier described above.

  In addition, the present invention provides the above 1. ~ 3. A fuming sulfuric acid impregnated carrier characterized by adjusting the amount of sulfur trioxide supported on the carrier based on the analysis result of sulfuric acid and sulfur trioxide in the fuming sulfuric acid impregnated carrier obtained by the analysis method according to any one of the above The manufacturing method of this is provided.

  Since the present invention can correctly analyze the amount of sulfuric acid and sulfur trioxide even in the presence of a carrier and the like, when quantifying polychlorinated biphenyls in a hydrophobic sample containing polychlorinated biphenyls, sample pretreatment, etc. The amount of sulfuric acid and sulfur trioxide in the fuming sulfuric acid-impregnated carrier used in the present invention can be measured, and has an extremely great effect on the quality control of products.

  Further, the fuming sulfuric acid impregnated carrier obtained from the impregnation operation of fuming sulfuric acid to the carrier is usually produced as a product in which moisture or air such as glass is sealed in the non-permeable column, and sealed in the non-permeable column. Measure the time-dependent change of the fuming sulfuric acid impregnated carrier until it is done, and control the amount of fuming sulfuric acid impregnated more accurately by adjusting the amount of raw materials, working conditions, working environment, etc. based on the measurement results It is possible to provide a fuming sulfuric acid impregnated support column.

  The fuming sulfuric acid-impregnated support using the analysis method of the present invention, as described above, is obtained by contacting a sample with a hydrophobic sample containing PCBs by bringing the sample into contact with the sample in advance when the PCBs are quantified by chromatography or immunoassay. The purpose is to sufficiently remove interfering substances that are difficult to separate from PCBs contained in the above with good workability. The applied hydrophobic sample is a hydrophobic liquid sample, for example, an insulating oil that is sealed and used in an electrical device such as a transformer or a condenser for cooling, and the insulating oil is decomposed. Examples include oily samples such as cracked oils obtained. Such an oily sample may be used as it is without being diluted, or may be used after being diluted with a hydrophobic solvent such as n-hexane or cyclohexane.

  Examples of hydrophobic samples include solid samples such as soot discharged from incinerators, burning husks, soil samples collected from soil, water samples such as rainwater and drainage, n-hexane, toluene and the like. A hydrophobic solution containing PCBs extracted with a hydrophobic solvent is also mentioned.

  In order to extract PCBs from a solid sample or a water quality sample with a hydrophobic solvent, for example, the solid sample or the water quality sample may be brought into contact with the hydrophobic solvent as described above.

  The hydrophobic solvent extract obtained by extracting PCBs from a solid sample or a water quality sample with a hydrophobic solvent may be used as it is as a hydrophobic sample, but usually other coexistence extracted with PCBs. In order to separate the substances, PCBs are further extracted with a polar organic solvent from a hydrophobic solvent extract such as n-hexane or toluene, and the PCBs are transferred from the obtained polar organic solvent extract to a hydrophobic solvent. . Examples of such a polar organic solvent include dimethyl sulfoxide, acetonitrile, methanol, n-methylpyrrolidone and the like. In order to dissolve the polar organic solvent extract into the hydrophobic solvent, for example, water may be added to the polar organic solvent extract and then extracted with the hydrophobic solvent.

  The fuming sulfuric acid-impregnated carrier using the method of the present invention is usually obtained by impregnating fuming sulfuric acid into silica gel as a carrier.

The silica gel, BET specific surface area of 250m ² / g~450m ² / g, preferably from 250m ² / g~350m ² / g. A pore volume of 1.4cm ³ /g~2.6cm ³ / g, preferably is used as the 1.6cm ³ /g~2.6cm ³ / g.

Fuming sulfuric acid is obtained by absorbing sulfur trioxide [SO ₃ ] gas in concentrated sulfuric acid, and its free SO ₃ concentration is measured according to JIS K-1321-1994 and JIS K8741 1996. Since the concentration of free SO _{3 in} fuming sulfuric acid that is generally commercially available is 10% by mass to 60% by mass, fuming sulfuric acid having a free SO ₃ concentration as defined above can be obtained by adding concentrated sulfuric acid, that is, H, to commercial fuming sulfuric acid, for example. ₂ SO ₄ It can be prepared by a method of diluting by adding sulfuric acid having a concentration of 98% by mass or more, a method of absorbing sulfur trioxide gas by blowing it into commercially available fuming sulfuric acid or concentrated sulfuric acid, and the like.

The concentration of free SO _{3 in} fuming sulfuric acid is 5% by mass or more, preferably 15% by mass or more in terms of sufficiently removing interfering substances, and 40% by mass or less, preferably in terms of accurately quantifying PCBs. Is 30% by mass or less.

  The amount of the fuming sulfuric acid impregnated with respect to the silica gel may be an amount that can be impregnated and retained in the silica gel, and is usually 0.5 to 5 times by mass with respect to the silica gel. It is preferably 2.5 times by mass or less in that it hardly oozes out and the particles do not stick to each other and are easy to handle as a powdered and fluid fuming sulfuric acid silica gel.

  As a more specific form of use of the fuming sulfuric acid impregnated silica gel, the fuming sulfuric acid impregnated silica gel is accommodated in a portable sealed container in advance, and is opened during use, and the fuming sulfuric acid impregnated silica gel is packed in a column. The form which processes this hydrophobic sample by letting pass is mentioned. According to this form of use, since the fuming sulfuric acid impregnated silica gel is accommodated in the portable sealed container, it is preferable because it can be easily pretreated even at the collection site of the hydrophobic sample to be analyzed.

  Examples of the portable sealed container in which the fuming sulfuric acid impregnated silica gel is accommodated include those which are inert to fuming sulfuric acid and can seal the silica gel.

  Examples of such containers include cylinder-type sealed containers whose inner surfaces are coated by glass lining, fluororesin processing, etc., ampoules, etc., and are easy to obtain, lightweight and easy to handle, Ampoules are preferred.

  As the ampoule, a glass-made ampoule is usually used because it is easy to confirm the contents and easy to open.

  The sealed ampule is formed by sealing the above fuming sulfuric acid-impregnated silica gel with an ampule. For example, the ampule with an open inlet is prepared by charging the silica gel and fuming sulfuric acid and sealing the inlet. Can do. The silica gel and fuming sulfuric acid may be mixed in advance, or after being put into an ampoule, it may be stirred and mixed by shaking the ampoule.

  When using the fuming sulfuric acid impregnated silica gel, the fuming sulfuric acid impregnated silica gel sealed ampoule is usually opened, and the sealed fuming sulfuric acid impregnated carrier is packed into a column. In order to fill the column with the fumed sulfuric acid-impregnated carrier that has been sealed, the ampoule-impregnated carrier inside may be transferred to the column after the ampoule is opened by a normal method.

  The fuming sulfuric acid-impregnated silica gel obtained by impregnating the above silica gel with the fuming sulfuric acid of 2.5 mass times or less with respect to the silica gel is in the form of a fluid powder so that it can be easily transferred from the ampule to the column. It is preferable at this point.

  The amount of fuming sulfuric acid supported (impregnated) on silica gel is controlled as being approximately equal to the amount of fuming sulfuric acid charged to the silica gel as a raw material during production, but fuming sulfuric acid is extremely reactive and rich in volatility under atmospheric conditions. Therefore, it is difficult to grasp the amounts of sulfur trioxide and sulfuric acid constituting fuming sulfuric acid impregnated on a silica gel carrier as fuming sulfuric acid impregnated silica gel.

In the method of the present invention, the individual contents of sulfuric acid and sulfur trioxide can be calculated by analyzing the fuming sulfuric acid impregnated in the fuming sulfuric acid impregnated silica gel produced by the above-described method by the following procedure.
(1) A step of immersing a fuming sulfuric acid-impregnated carrier in water and reacting sulfur trioxide in the carrier with water to obtain sulfuric acid, and measuring the total amount of sulfuric acid previously present in the carrier and sulfuric acid derived from sulfur trioxide ( 2) The fuming sulfuric acid impregnated carrier is immersed in a solvent that does not react with sulfuric acid but reacts only with sulfur trioxide to form a reaction product different from sulfuric acid, and the sulfur trioxide and the solvent are reacted with sulfuric acid in the solvent. Step of measuring content (3) Step of calculating the content of sulfuric acid and sulfur trioxide contained in the fuming sulfuric acid impregnated carrier from the amount of sulfuric acid obtained in (1) and the amount of sulfuric acid obtained in (2)

By the method of the present invention, grasping the amount of fuming sulfuric acid actually impregnated on the silica gel carrier, that is, grasping the correct loading amount of sulfur trioxide and sulfuric acid, further, product inspection when outsourcing the production of the above products, etc. In addition, the present invention is applicable. In the present invention, the expressions sulfuric acid and sulfur trioxide impregnated in the fuming sulfuric acid impregnated carrier are used in the same meaning as sulfuric acid and sulfur trioxide possessed by the fuming sulfuric acid impregnated carrier.

  In carrying out the method of the present invention, although not particularly limited, for example, in the above step (1), 10 mL of water is placed in a container, and 2 g of fuming sulfuric acid impregnated silica gel as a sample is placed therein, and sulfur trioxide in the sample is added. Is reacted with water to form sulfuric acid, and the total amount of sulfuric acid impregnated from the beginning is measured by a neutralization titration method using a conventionally known aqueous caustic soda solution (titration value A). The treatment conditions are not particularly limited, but since the sample has volatility, a container having a sealing function may be used, and the treatment may be performed under conditions with little contact with the atmosphere.

  Next, put 10 mL of the “solvent that does not react with sulfuric acid but reacts only with sulfur trioxide and forms a reaction product different from sulfuric acid” into a container having a sealing function, and then the fuming sulfuric acid that is the same sample as used above 2 g of silica gel is immersed, and sulfur trioxide is reacted with the solvent out of sulfuric acid and sulfur trioxide constituting the fuming sulfuric acid impregnated in the carrier (2). Examples of such a solvent include aromatic hydrocarbons such as propylbenzene and dodecylbenzene. In particular, use of dodecylbenzene is recommended for reasons such as ease of handling and cost.

The contact (reaction) temperature and time of the sample and the solvent in the step (2) are selected such that substantially the total amount of sulfur trioxide present in the sample reacts with the solvent to form a reaction product different from sulfuric acid. Although these are not unambiguous depending on the type of solvent used, etc., the reaction temperature is usually below the boiling point of the solvent, the time is within 3 hours, usually within the range of 1 to 2 hours, and the optimum reaction temperature and time are simple. Can be easily determined by simple preliminary experiments. When dodecylbenzene is used as a solvent, the temperature is usually in the range of about 70 ° C. to 90 ° C. and time of about 90 minutes to 120 minutes. For the solvent after the reaction, the amount of sulfuric acid in the solvent is measured by a neutralization titration method using a conventionally known aqueous caustic soda solution (titration value B).

  By subtracting the titration value B (the amount of sulfuric acid excluding the reaction product of sulfur trioxide and solvent in the sample) from the titration value A (total amount of sulfuric acid in the sample) measured by such a method, the silica gel is impregnated. Since the content of sulfur trioxide contained in the silica gel is known, the amount of sulfuric acid and sulfur trioxide impregnated in the silica gel can be individually known (step (3)).

  The solvent used in step (2) reacts with almost the total amount of sulfur trioxide present in the sample, and the reaction product exhibits a substance that is not counted as sulfuric acid by a conventionally known neutralization titration operation of sulfuric acid. I just need it. Whether or not the solvent has such characteristics is determined by contacting and reacting a standard sample (commercially available reagent) with a clear fuming sulfuric acid concentration with the solvent, measuring the sulfuric acid concentration in the solvent after the reaction, and separately Measure the total sulfuric acid content of the standard sample by the method (1) above, and simply subtract the sulfuric acid amount obtained by the method (2) from the total sulfuric acid amount obtained by the method (1). Since the amount of sulfur can be determined, by comparing the value with the value of sulfur trioxide in the standard sample, the test solvent is defined in the present invention as “reacts with only sulfur trioxide without reacting with sulfuric acid. It can be seen whether or not the solvent corresponds to “a solvent that forms a reactant different from sulfuric acid”. In the selection of the solvent to be actually applied, the above requirements are selected in consideration of conditions such as ease of handling, safety, reaction time, and cost.

  By grasping the amount of fuming sulfuric acid actually supported on such a silica gel carrier, the analytical value obtained by the method of the present invention is fed back to the production conditions when the grade of raw materials used or lots are changed, etc. In addition, when the sealed ampule is opened and the column is filled with fuming sulfuric acid-impregnated silica gel, a fuming sulfuric acid is added to adjust the desired loading amount.

  The contact between the hydrophobic sample and the fuming sulfuric acid impregnated silica gel is usually carried out by contacting the hydrophobic sample with the fuming sulfuric acid impregnated silica gel packed in the column. Typically, the hydrophobic sample is impregnated with the fuming sulfuric acid impregnated silica gel. This is done by passing through a column packed with silica gel.

  The contact temperature when the hydrophobic sample is brought into contact with the fuming sulfuric acid-impregnated silica gel is usually about 0 ° C to 50 ° C. The contact time is usually about 1 minute to 20 minutes, and 3 minutes to 10 minutes is preferable in terms of high accuracy and efficient measurement.

  Depending on the viscosity of the hydrophobic sample, it may be difficult to pass through the fuming sulfuric acid impregnated silica gel column as it is, but in such a case, the hydrophobic sample is appropriately selected, for example, n-hexane, heptane, cyclohexane, etc. It may be used by lowering the viscosity by diluting with a hydrophobic solvent, or after placing a hydrophobic sample on a fuming sulfuric acid impregnated silica gel column and further passing it through diluted with a flowing hydrophobic solvent. Good.

  The hydrophobic solvent sample is preferably dehydrated in advance. In order to dehydrate, for example, it may be brought into contact with a dehydrating agent. As the fuming sulfuric acid impregnated silica gel column, a two-layered column composed of a fuming sulfuric acid impregnated silica gel layer further filled with a dehydrating agent on the upstream side and a dehydrating agent layer is used. The hydrophobic sample may be configured to pass through the dehydrating agent layer and then pass through the fuming sulfuric acid impregnated silica gel layer, or the upstream side of the fuming sulfuric acid impregnated silica gel column is filled with the dehydrating agent. The dehydrated column may be connected so that the hydrophobic sample passes through the fuming sulfuric acid impregnated silica gel column after passing through the dehydrated column. As the dehydrating agent, a dehydrating agent inert to fuming sulfuric acid and concentrated sulfuric acid such as anhydrous sodium sulfate is usually used.

  Interfering substances can be removed by subjecting the hydrophobic sample after contact with the fuming sulfuric acid-impregnated silica gel, for example, to silica gel column chromatography. In silica gel column chromatography, a silica gel column in which the column is filled with silica gel is usually used, and usually connected to the downstream side of the fuming sulfuric acid impregnated silica gel column.

  The hydrophobic sample after performing such a treatment operation may be concentrated by a method such as evaporation of the solvent, if necessary. Usually, PCBs are dissolved in a polar organic solvent such as dimethyl sulfoxide or acetone from the hydrophobic sample. Examples of the method of transferring the solvent to the polar organic solvent include a method in which the hydrophobic sample is distilled off and the residue is added to the above polar organic solvent and dissolved. However, other coexisting substances remaining in the hydrophobic sample can be used. Of these, substances that are insoluble in polar organic solvents can be separated from PCBs and removed, so polar organic solvents that are insoluble in hydrophobic samples are added, and the layers are separated into two layers: a hydrophobic solvent layer and a polar organic solvent layer. Then, a method of obtaining a hydrophilic solvent layer by liquid separation is preferably used, and the liquid sample may be separated after concentrating the hydrophobic sample by a method such as solvent distillation before liquid separation.

  In addition, after the above-described processing operation, other coexisting substances remaining in the hydrophobic sample can be removed by subjecting to purification treatment such as ordinary column chromatography as necessary.

  For example, among the above-mentioned other coexisting substances, lipophilic substances are obtained by extracting PCBs contained in a hydrophobic sample with a polar organic solvent, and using the obtained polar solvent extract as a column chromatography using a lipophilic adsorbent as a filler. By performing graph processing, it can be separated from PCBs. Examples of the polar organic solvent include those described above. The lipophilic adsorbent is a solid adsorbent composed of a material having at least a surface having affinity with an oily substance, and is usually in a granular form. Examples of such lipophilic adsorbents include those widely used as column chromatography packing materials, solid phase extraction packing materials, and column packing materials for reversed-phase liquid chromatography. Use the filler “C18”, which is commercially available from Waters, Inc. under the trade names of “SEP-PAK-C18”, “SEP-PAK-tC18”, “SEP-PAK-VactC18”, etc. Can do.

  The column chromatograph process is performed, for example, by using a column filled with a lipophilic adsorbent and using a polar organic solvent extract as the falling liquid. The polar solvent extract after flowing down may be concentrated as necessary.

  When the polar organic solvent extract after column chromatography with a lipophilic adsorbent contains hydrophilic substances as other coexisting substances, for example, PCBs contained in the polar organic solvent extract are treated with a hydrophobic solvent. The transferred solution dissolved in can be separated from PCBs by multilayer silica gel column chromatography.

  In order to dissolve PCBs contained in the polar organic solvent extract in a hydrophobic solvent, for example, water may be added to the polar organic solvent extract and then extracted with the hydrophobic solvent. Multi-layer silica gel column chromatography is performed, for example, by passing the transferred solution through a multi-layer silica gel column having a multi-layer structure in which the column is filled with a silica gel filler such as untreated silica gel, potassium hydroxide-coated silica gel, or sulfuric acid-coated silica gel. . The transferred solution after passing may be concentrated by a method such as solvent distillation.

  After the pretreatment, the PCBs are analyzed by an immunoassay process using an antigen-antibody reaction between the PCBs and the antibody.

  The immunoassay process using the antigen-antibody reaction between the PCBs and the antibody is not particularly limited, and a known method can be adopted as appropriate. For example, (1) PCBs obtained in the pretreatment process are After adding the primary antibody against the PCBs in an excessive amount and mixing, the primary antibody is bound to the PCBs by an antigen-antibody reaction, and then (2) has an antigen-antibody reaction ability with the primary antibody. Then, an excess amount of a labeled secondary antibody labeled with a fluorescent substance is added and mixed, and the hapten antigen, which is a similar compound of PCBs, is brought into contact with an antigen-immobilized carrier immobilized on the carrier, thereby The excess primary antibody that did not bind to the PCBs was bound to the hapten antigen of the antigen-immobilized carrier, and the labeled secondary antibody was bound to the bound primary antibody, and (3) Primary Supported on antigen-immobilized carrier through the body may be obtained the supported amount of a labeled secondary antibody.

  According to this method, when the content of PCBs is large, the amount of the labeled secondary antibody supported on the antigen-immobilized carrier decreases, and when the content of PCBs is small, the labeled secondary antibody is present. Since the amount of antibody supported increases, the content of PCBs can be determined by determining the amount of labeled secondary antibody supported on the antigen-immobilized carrier. The amount of the labeled secondary antibody supported can be determined by a usual fluorescence analysis method in which the antigen-immobilized carrier after the support is irradiated with ultraviolet rays or the like to measure the fluorescence intensity.

  EXAMPLES Hereinafter, although an Example demonstrates this invention method in detail, this invention is not limited by these Examples.

In addition, the BET specific surface area of the silica gel used in the Examples was measured by a one-point method using a “flow type specific surface area automatic measuring device Flow Sorb 2300” manufactured by MICROMETRICS.
The pore volume was determined as a pore volume having a pore radius in the range of 0.001 μm to 100 μm using “Auto Porosimeter Autopore III 9420” manufactured by MICROMETRICS.

Example 1
[Preparation of fuming sulfuric acid impregnated silica gel]
Silica gel having a BET specific surface area of 252 m ² / g and a pore volume of 2.58 cm ² / g was dried at 150 ° C. for 12 hours. 10 g of this silica gel is weighed with an electronic balance into a vial with a capacity of 100 mL, and after adding 20 g of fuming sulfuric acid having a free SO ₃ concentration of 25% by mass (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade 1), it is quickly sealed. Shake for about 90 minutes to thoroughly mix the contents. The contents were in the form of a fluid powder that did not stick to each other.
2 g of fuming sulfuric acid-impregnated silica gel prepared as described above was put into a glass tube having an inner diameter of 5 mm and a length of 146 mm sealed at one end, and the opening was sealed to produce a fuming sulfuric acid-impregnated silica gel sealed ampule. .

[Measurement step of sulfuric acid (1)]
After adding 10 mL of pure water to a 100 mL volumetric flask and measuring the volume of the volumetric flask, one of the fuming sulfuric acid impregnated silica gel sealed ampule obtained above was cut and opened with an ampule cutter, and the total amount of fuming sulfuric acid impregnated silica gel was quickly removed. It was transferred to a 100 mL volumetric flask containing pure water and sealed. After sealing, measure the weight of the volumetric flask, gently shake by hand, disperse the fuming sulfuric acid impregnated silica gel in pure water, leave it at room temperature for 60 minutes, and then leave acetone to the mark of the volumetric flask (made by Wako Pure Chemical Industries, Agricultural chemical / PCB test concentrate 300] was added and shaken by hand to mix well. From the sulfuric acid eluate thus obtained, 10 mL of sulfuric acid eluate was placed in a 200 mL Erlenmeyer flask (previously charged with 190 mL of pure water), 3 drops of phenolphthalein solution (5 g / L) as an indicator, and as a titrant The sulfuric acid concentration was measured by a neutralization titration method using a 0.1 molar aqueous sodium hydroxide solution. The results are shown in Table 1.

[Measurement step of sulfuric acid (2)]
After putting 10 mL of dodecylbenzene (Cat. No. 10780-02, manufactured by Kanto Chemical Co., Ltd.) into a 100 mL volumetric flask and measuring the weight of the volumetric flask, one of the fuming sulfuric acid impregnated silica gel sealed ampules obtained above was measured with an ampule cutter. After cutting and opening, the entire amount of fuming sulfuric acid-impregnated silica gel was quickly transferred to a 100 mL volumetric flask containing dodecylbenzene and sealed tightly. After sealing, the weight of the measuring flask was measured, and then the fuming sulfuric acid-impregnated silica gel was gently dispersed in the dodecylbenzene in the shaking container by hand. Next, after reacting for 90 minutes with dodecylbenzene and fuming sulfuric acid in a volumetric flask at a temperature of 70 ° C. in a water bath with occasional gentle shaking, acetone (Wako Pure Chemical Industries, residual Agricultural chemical / PCB test concentrate 300] was added and shaken by hand to mix well. From the reaction solution thus obtained, 10 mL of the reaction solution is placed in a 200 mL Erlenmeyer flask (with 190 mL of pure water previously), 3 drops of a phenolphthalein solution (5 g / L) as an indicator, and 0 titrant as a titrant. The sulfuric acid concentration was measured by a neutralization titration method using a 1 molar aqueous sodium hydroxide solution. The results are shown in Table 1.

[Step of calculating sulfur trioxide amount (3)]
The amount of sulfuric acid obtained in step (2) was subtracted from the amount of sulfuric acid obtained in step (1), and the amount of sulfuric acid obtained was converted to SO3. The results are shown in Table 1.

Example 2
In the method of Example 1, the contact condition between the fuming sulfuric acid-impregnated silica gel in step (1) and water was changed to 2 hours under ice cooling, and propylbenzene (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the solvent in step (2). The amount of sulfuric acid and sulfur trioxide impregnated in fuming sulfuric acid-impregnated silica gel was measured using the same experimental equipment and experimental conditions as in Example 1 except that the reaction was performed at 50 ° C. for 1 hour. did. The results are shown in Table 1.

Reference example 1
In Example 1, instead of fuming sulfuric acid-impregnated silica gel as a sample, commercially available fuming sulfuric acid [manufactured by Wako Pure Chemical Industries, reagent grade, sulfur trioxide value by JIS K1321 1994 measurement method: 24.3%] The experiment was conducted.

[Measurement step of sulfuric acid (1)]
After adding 10 mL of pure water to a 100 mL volumetric flask and measuring the weight of the volumetric flask, 1.25 g of the commercially available fuming sulfuric acid was quickly transferred to the 100 mL volumetric flask containing pure water and sealed. After sealing, measure the weight of the volumetric flask, gently shake it by hand, leave it at room temperature for 6 hours, and then add acetone (made by Wako Pure Chemical Industries, Ltd., residual pesticide / PCB concentration 300) to a total volume of 100 mL. Add, shake by hand and mix well. From the reaction solution thus obtained, 10 mL of the reaction solution was placed in a 200 mL Erlenmeyer flask (100 mL of pure water in advance), 3 drops of a phenolphthalein solution (5 g / L) as an indicator, and 0 titrant as a titrant. The sulfuric acid concentration was measured by a neutralization titration method using a 1 molar aqueous sodium hydroxide solution. The results are shown in Table 1.

[Measurement step of sulfuric acid (2)]
10 mL of dodecylbenzene (Kanto Chemical Co., Ltd., Cat. No. 10780-02) was placed in a 100 mL volumetric flask, and after measuring the weight of the volumetric flask, 1.43 g of the above commercially available fuming sulfuric acid was charged with the above dodecylbenzene. It was quickly transferred to a 100 mL volumetric flask and sealed. After sealing, the weight of the volumetric flask was measured, and then gently shaken by hand to disperse fuming sulfuric acid in dodecylbenzene, reacted at a temperature of 70 ° C. in a water bath for 120 minutes with occasional gentle shaking, then acetone [ Wako Pure Chemical Industries, Ltd., residual pesticides / PCB test concentrate 300] was added to a total volume of 100 mL, and shaken by hand to mix well. From the reaction solution thus obtained, 10 mL of the reaction solution is placed in a 200 mL Erlenmeyer flask (with 100 mL of pure water added beforehand), 3 drops of phenolphthalein solution (5 g / L) as an indicator, and 0. The sulfuric acid concentration was measured by a neutralization titration method using a 1 molar aqueous caustic soda solution. The results are shown in Table 1.

[Step of calculating sulfur trioxide amount (3)]
The amount of sulfuric acid obtained in step (2) was subtracted from the amount of sulfuric acid obtained in step (1), and the amount of sulfuric acid obtained was converted to SO3. The results are shown in Table 1.

As is apparent from the results of Example 1, Example 2, and Reference Example 1, the analytical values obtained by the method of the present invention are the theoretical values of SO ₃ possessed by the samples used in Examples 1 and 2. Since it is in the vicinity of 5%, the results of the method of the present invention using a reagent that can be measured by the JIS method are close to the results of the analysis by the JIS method. It can be seen that the analysis method is useful as a means of knowing the amount of fuming sulfuric acid impregnated below.

Table 1

  According to the present invention, even in the presence of a carrier such as silica gel, the amount of sulfur trioxide and sulfuric acid impregnated on the carrier can be accurately and individually quantified, so that a gas chromatograph or In the method of quantifying polychlorinated biphenyls using an immunoassay, the performance evaluation of a fuming sulfuric acid impregnated carrier used as a pretreatment of a sample can be accurately performed, so that the applicability in industrial fields such as waste treatment is extremely large.

Claims (4)

A method for analyzing sulfuric acid and sulfur trioxide in a fuming sulfuric acid-impregnated carrier, characterized by analyzing by the following procedure.
(1) A step of immersing a fuming sulfuric acid-impregnated carrier in water and reacting sulfur trioxide in the carrier with water to obtain sulfuric acid, and measuring the total amount of sulfuric acid previously present in the carrier and sulfuric acid derived from sulfur trioxide ( 2) The fuming sulfuric acid impregnated carrier is immersed in a solvent that does not react with sulfuric acid but reacts only with sulfur trioxide to form a reaction product different from sulfuric acid, and the sulfur trioxide and the solvent are reacted with sulfuric acid in the solvent. Step of measuring content (3) Step of calculating the content of sulfuric acid and sulfur trioxide contained in the fuming sulfuric acid impregnated carrier from the amount of sulfuric acid obtained in (1) and the amount of sulfuric acid obtained in (2)   2. The sulfuric acid in the fuming sulfuric acid-impregnated carrier according to claim 1, wherein the solvent that does not react with sulfuric acid but reacts only with sulfur trioxide to form a reactant different from sulfuric acid is an aromatic hydrocarbon. Analysis method of sulfur oxide. 3. The sulfuric acid in the fuming sulfuric acid-impregnated carrier according to claim 1 or 2, wherein the solvent which does not react with sulfuric acid but reacts only with sulfur trioxide and forms a reactant different from sulfuric acid is dodecylbenzene. Analysis method of sulfur trioxide.   The amount of sulfur trioxide supported on the carrier is adjusted based on the analysis result of sulfuric acid and sulfur trioxide in the fuming sulfuric acid impregnated carrier obtained by the analysis method according to any one of claims 1 to 3. A method for producing a fuming sulfuric acid impregnated carrier.