JP4131837B2 - Aroma component adsorbent - Google Patents

Description

【００２６】
比較例４ （吸着材Ｃを使用したスタティック法による香気分析）
吸着材Ｂに代えて吸着材Ｃを使用した以外は実施例４と同様に操作してガスクロマトグラフにより分析した。
【００２７】
（香気成分の分析結果）
標準調合香料を直接ガスクロマトグラフで分析した結果を対照例として、実施例４及び比較例４で分析した結果を図５に示す。実施例４で分析した調合香料の香気成分は、比較例４の分析結果に比して、各種の官能基を有する化合物についてバランス良く分析できていた。
【００２８】
【発明の効果】
本発明によれば、従来の吸着材に比し香気成分の吸着特性に優れ、香気成分をバランス良く採集できる吸着材が提供される。さらに本発明によれば、ヘッドスペース中の気相成分を、バランスを崩すことなく採集分析できる香気成分の分析方法が提供される。
【図面の簡単な説明】
【図１】本発明で使用される気相成分吸着を示す説明図である。
【図２】吸着材吸着成分の吸脱着機構を示す説明図である。
【図３】脱着成分のガスクロマトグラフ送入機構を示す説明図である。
【図４】実施例２、比較例２、３のガスクロマトグラムを示す図面である。
【図５】実施例４、比較例４のガスクロマトグラムを示す図面である。
【図６】ダイナミック法による気相成分の吸着機構を示す説明図である。
【符号の説明】
１ 容器
１１ 吸着材
１２ 吸着剤層
１３ 支持管
１４ 開閉部材
１５ Ｕ字管
１６ 加熱手段
１７ ハンドル
１８ 不活性ガス注入口
１９ ガスクロマトグラフ連結口
２０ 冷媒槽[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an adsorbent suitable for analyzing an aroma component present in a minute amount, a method for producing the adsorbent, and a method for analyzing an aroma component using the adsorbent. More specifically, the present invention relates to an adsorbent capable of efficiently collecting components in the headspace of the container while maintaining a balance, a method for producing the adsorbent, and a method for analyzing an aroma component using the adsorbent.
[0002]
[Prior art]
Conventionally, as a method for analyzing a gas phase component in a container into which a sample is injected, for example, a perfume and its aroma component, so-called dynamic method and static method are known. As shown in FIG. 6, the apparatus used for the dynamic method is usually configured as follows. The container 1 into which the sample has been injected is placed in a water bath 2 having a predetermined temperature, and a stirring bar 3 is provided in the sample or at the bottom of the water bath 2 so that the sample can be stirred as necessary. In the figure, symbol 9 is a stirrer. A column 5 filled with an adsorbent is installed at the top of the container 1 through a water-cooled tube 4. The container 1 is provided with an inert gas inlet 6 such as nitrogen gas. An inert gas is blown into the container, and the gas phase component together with the inert gas is passed through a cooling pipe to the column filled with the adsorbent, and the gas phase component is collected in the column, and the collected gas phase component is analyzed. Is the method. Because the gas phase component is forced to move to the column side by blowing in inert gas, it tends to detect more low-boiling components in the sample than the gas phase component originally present in the headspace. This method has the following disadvantages.
[0003]
In the static method, for example, a headspace gas phase is directly sampled with a gas tight syringe and injected into a gas chromatograph to analyze a headspace gas phase component, for example, a fiber in which an adsorbent is coated in the headspace gas phase. A solid phase micro-extraction method (SPME method; Patent Document 1) in which a gas phase component is adsorbed by an adsorbent and injected into a gas chromatograph to analyze the gas phase component is well known. The apparatus used for the SPME method is usually configured as follows. A fiber coated with an adsorbent is inserted into the head space of a container into which a sample placed in a water bath is injected to adsorb gas phase components. This fiber is accommodated in the hollow needle of the syringe. After adsorption, the fiber is housed in a needle and the needle is connected to a gas chromatograph to analyze the adsorbed components. In this method, it is possible to measure the gas phase component while maintaining the balance as it is. However, since the fiber can be stored in the needle, the fiber must be thin. For this reason, the amount of adsorption is small, and therefore the amount is often insufficient for analysis of various types of aroma components. Even in the method of analyzing fragrance components using a gas tight syringe, the amount of sampling of each fragrance component is insufficient and there are many cases where sufficiently satisfactory analysis results cannot be obtained.
[0004]
In order to solve the above problems, the present inventors have proposed a method and an apparatus for analyzing a gas phase component in a head space in a container into which a sample has been injected without losing the balance (Patent Document 2). As a result of continuing investigations on this method, the present inventors have found that the adsorbents coated with adsorbents that have been proposed in the past may not have sufficient adsorbed amounts of each aroma component in the head space. It was.
[0005]
[Patent Document 1]
JP 5-506715A [Patent Document 2]
Japanese Patent Laid-Open No. 2001-221785 [0006]
[Problems to be solved by the invention]
An object of the present invention is to provide an adsorbent having a volume substantially equal to that of a conventional adsorbent and capable of increasing its adsorption amount, a method for producing the adsorbent, and a method for analyzing aroma components using the adsorbent.
[0007]
[Means for Solving the Problems]
The present invention provides an adsorbent for aroma components, characterized in that a bar is coated with a carbon-based adsorbent, and then the coating is coated with a second adsorbent composed of 2,6-diphenyl-P-phenylene oxide. provide. The present invention forms a first coating layer and dried was dipped bars to a suspension of water carbonaceous adsorbent and / or a hydrophilic organic solvent, and then contains the second adsorbent There is provided a method for producing an adsorbent for aroma components, comprising first and second coating layers that are dipped in a solution to be dried and then dried.
[0008]
The present invention further relates to a method for analyzing a headspace component comprising the following steps a to d, wherein the adsorbent comprises a bar material coated with a carbon-based adsorbent, and then the coating is made from 2,6-diphenyl-P-phenylene oxide. provides a method of analyzing aroma components, characterized in that comprising a adsorbent aroma components, characterized by coating with a second adsorbent.
[0009]
a. charging the adsorbent with adsorbent into the headspace of the sealed container into which the sample has been injected;
b. A step of taking out the adsorbent adsorbing the components in the head space from the sealed container and inserting it into the U-shaped tube from one end of the U-shaped tube provided with heating means on at least the upper side,
c. After immersing at least the lower part of the U-tube with the adsorbent in the refrigerant, the U-tube is heated to desorb the components adsorbed on the adsorbent, and the desorbed components are placed on the bottom of the U-tube. The process of accumulating,
d. The step of connecting the other end of the U-shaped tube taken out from the refrigerant to the sample inlet of the gas chromatograph and analyzing the components desorbed by the introduction of the inert gas.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The adsorbent of the present invention is obtained by coating a rod with a carbon-based adsorbent and then coating the coating with a second adsorbent made of 2,6-diphenyl-P-phenylene oxide . As the rod material, not only a metal rod such as a glass rod and a stainless steel rod but also a bundle of fibers may be used. For example, it is formed from a fused silica fiber, a graphite fiber, a fiber made from a solid polymer material, a fiber made from a metal material, or the like. Appropriate dimensions are adopted for the length and diameter of the bar depending on the purpose of use. The surface shape of the bar may be smooth, but is preferably a spiral groove or a surface provided with appropriate irregularities. This is because, while the length and diameter of the bar are limited depending on the purpose of use, the coverage of the adsorbent can be increased by increasing the surface area, or the adhesion strength of the adsorbent to the bar can be increased.
[0011]
A carbon-based adsorbent is used as the adsorbent used in the first adsorbent layer. Examples of the carbon-based adsorbent include soot, graphite carbon, activated carbon and the like. Two or more of these may be mixed and used at an appropriate ratio. The most preferable adsorbent is an adsorbent having a mixing weight ratio of about 9: 1 between graphite carbon and activated carbon. Depending on the method of use, those having an average particle size of 0.5 to 10 μm, preferably an average particle size of 1 to 2 μm are used. The adsorbent used for the second adsorbent layer coated on the first adsorbent layer is 2,6-diphenyl-p-phenylene oxide (trade name Tenax, manufactured by GL Sciences Inc.) . The reason why the aromatic component adsorption characteristics are improved by providing the second adsorbent layer on the carbon-based adsorbent layer is not always clear. It is presumed that there is a minute through hole in the second adsorbent layer, and the carbon-based adsorbent layer and the second adsorbent layer are combined through the through hole to improve the adsorption characteristics.
[0012]
Next, a method for manufacturing the adsorbent will be described. In the carbon-based adsorbent layer, the rod is immersed in a suspension of carbon-based adsorbent having a solute concentration of 5 to 50% by weight, preferably 10 to 40% by weight. The immersion time may be several seconds to several minutes and is dried after immersion. As a solvent for the carbon-based adsorbent, water and / or a hydrophilic organic solvent is used. Examples of the hydrophilic organic solvent include methanol, ethanol, propanol, acetone and the like, and two or more of these may be used in combination. The most preferable blending weight ratio of water to the hydrophilic organic solvent is water / ethanol / acetone = 15/70/15 or water / propanol / acetone = 15/70/15. Tenax is most preferably used as the second adsorbent layer. Tenax preferably has a particle size of 60 to 80 mesh. This Tenax is made into a solution having a solute concentration of 0.5 to 30% by weight, preferably 1 to 10% by weight, and a rod provided with a carbon-based adsorbent layer in this solution is usually immersed for several seconds to several minutes and then dried. To manufacture. Examples of Tenax solvents include chlorinated solvents such as dichloromethane, chloroform, and trichloroethylene.
[0013]
The most preferable method for analyzing aroma components using the adsorbent of the present invention will be described below. FIG. 1 shows an example of an apparatus for adsorbing a gas phase component on the adsorbent of the present invention. The adsorbent 11 is inserted into the head space of the container 1 placed in the water bath 2 into which the sample is injected, and the gas phase component is adsorbed on the adsorbent layer. The sample may be agitated as necessary by the agitator 3. The adsorbent 11 having adsorbed the gas phase component is charged into the U-shaped tube.
[0014]
The analyzer of the present invention including a U-shaped tube is shown in FIGS. The U-shaped tube 15 is provided with heating means 16 for desorbing the adsorbed gas phase component. The heating means 16 may be a nichrome wire wound around a U-shaped tube at an appropriate interval. At the end of the U-tube adsorbent 11 on the charging side, a support tube 13 for the adsorbent 11 is provided via an opening / closing member 14 that blocks the inside of the U-tube from outside air and allows the adsorbent to be slidable. Is installed. A so-called ball valve is preferably used as the opening / closing member 14. With the ball valve 14 open, the adsorbent 11 is loaded into the support tube 13 and the U-shaped tube 15. A handle 17 is preferably provided on the top of the adsorbent 11 so that the inside of the support tube 13 can be blocked from the outside air when the adsorbent 11 is completely charged. An inert gas inlet 18 is provided near the opening / closing member 14 of the U-shaped tube 15. A gas chromatograph connecting member 19 communicating with the inside of the U-shaped tube 15 is provided on the other end side of the U-shaped tube 15.
[0015]
The lower part of the U-shaped tube 15 charged with the adsorbent 11 is installed in the refrigerant tank 20. As the refrigerant, an appropriate refrigerant is selected and used in accordance with a gas phase component such as liquid nitrogen or liquid oxygen. After installing in the refrigerant tank 20, it heats with the heating means 16, and desorb | desorbs a gaseous phase component from an adsorbent tank. The desorbed vapor phase component is cooled by the refrigerant and accumulates at the bottom of the U-shaped tube. An inert gas may be injected from the inert gas inlet 18 in order to promote desorption from the adsorbent tank and promote movement toward the bottom of the U-shaped tube. As the inert gas, an appropriate gas such as argon gas, helium gas or nitrogen gas is selectively used.
[0016]
After desorption of the gas phase component, as shown in FIG. 3, the adsorbent 11 is lifted above the opening / closing member 14, the opening / closing member, for example, the ball valve is closed, and then removed from the refrigerant tank 20. A gas chromatograph connecting member 19 provided at the other end of the U-shaped tube 15 is connected to the gas chromatograph, an inert gas is injected from an inert gas inlet 18, a gas phase component is fed into the gas chromatograph, and a gas phase Analyze ingredients.
[0017]
【Example】
(Creation of adsorbent)
Example 1 (graphite carbon + activated carbon / Tenax: two-layer coating)
Adsorbent (metal rod, diameter 12mm, diameter: 22.5g) and activated carbon 0.225g in a glass bottle containing a suspension of 15.0g of water, 70.0g of ethanol and 15.0g of acetone. 90 mm long) was immersed for 20 seconds and then dried to prepare an adsorbent provided with an adsorbent layer (inner layer). This adsorbent was dipped in a solution of 0.6 g of Tenax in 18.0 ml of dichloromethane for 20 seconds, and then dried to prepare an adsorbent coated with two layers (adsorbent A).
[0018]
Example 2 (Agate / Tenax: Two-layer coating)
Adsorbent (metal bar, diameter 1.2 mm, length 90 mm) in a glass bottle containing a suspension of 2.5 g of candy in a mixed solvent of 2.0 g of water, 6.0 g of ethanol and 2.0 g of acetone Was soaked for 20 seconds and dried to prepare an adsorbent provided with an adsorbent layer. This adsorbent was immersed in a solution of 0.6 g of Tenax dissolved in 18.0 ml of dichloromethane for 20 seconds and then dried to prepare an adsorbent coated with two layers (adsorbent B).
[0019]
Comparative Example 1
An adsorbent (metal rod, diameter 1.2 mm, length 90 mm) was immersed in a solution prepared by dissolving 0.6 g of Tenax in 18.0 ml of dichloromethane for 20 seconds and then dried to prepare an adsorbent coated with one layer. (Adsorbent C).
[0020]
Example 3 (Aroma analysis by static method using adsorbent A)
For the crushed roasted coffee beans (trade name: Colombia L-24), the apparatus shown in FIG. 1 is used to collect the gas phase component (fragrance) in the head space using the adsorbent A, The adsorbed components were desorbed with the apparatus shown in FIG. 2 and FIG. 3, and then the adsorbed components were analyzed using a gas chromatograph. Analysis conditions are shown below
Gas phase component collection conditions Sample amount: 10.0 g
Sample temperature: 30 ° C
Collection time: 30 minutes Adsorbent: Graphite carbon + activated carbon (inner layer) / Tenax (outer layer)
Adsorption / desorption method The adsorbent 11 is mounted on a U-shaped tube as shown in FIG. 2, and the support tube 13 side and the U-shaped tube side are blocked by the ball valve 14 and then the inert gas inlet 18 is used. The heater was heated to 220 ° C. while feeding helium gas, and the gas phase component adsorbed by the adsorbent was accumulated at the bottom of the U-shaped tube cooled in the refrigerant tank 20. Thereafter, the adsorbent 11 is moved to the position shown in FIG. 3, and the support tube side and the U-shaped tube side are similarly shut off by the ball valve 14. Then, the refrigerant tank 20 is removed, and then helium gas is sent to remove the gas phase component. Injection into a gas chromatograph.
Gas chromatograph conditions <br/> Gas chromatograph: Shimadzu GC-14A (manufactured by Shimadzu Corporation)
Column: TC-WAX 025MMI.D. × 60m
Column temperature: 70 ° C to 220 ° C (3 ° C / min increase)
Detector: FID.
[0021]
Comparative Example 2 (Aroma analysis by dynamic method)
For the crushed roasted coffee beans (trade name: Colombia L-24), the gas phase component (fragrance) in the headspace is collected by the dynamic method using the apparatus shown in FIG. Were analyzed using a graph. Water was not passed through the catching water condenser. The analysis conditions are shown below.
Gas phase component collection conditions Sample amount: 1.0 g
Sample temperature: 30 ° C
Nitrogen gas flow rate: 50 ml / min.
Collection time: 1 minute Adsorbent: Tenax
Gas chromatographic conditions The same as in Example 3.
[0022]
Comparative Example 3 (Aroma analysis by solvent extraction method)
The crushed roasted coffee beans (trade name: Colombia L-24) were extracted with dichloromethane. Dichloromethane was distilled off from the obtained extract under normal pressure to prepare an aroma concentrate, which was analyzed using a gas chromatograph. The analysis conditions of the gas chromatograph are the same as in Example 3.
[0023]
(Aroma component analysis results)
The results of gas chromatographs analyzed in Example 3, Comparative Example 2 and Comparative Example 3 are shown in FIG. Compared with the methods of Comparative Example 2 and Comparative Example 3, the aromatic component of roasted coffee beans analyzed by the method using the adsorbent of the present invention was able to analyze even the middle and high boiling components.
[0024]
Example 4 (Aroma analysis by static method using adsorbent B)
Using the standard blended fragrance shown below (mixing each component in the same amount), using the adsorbent B, collecting the gas phase component (fragrance) in the headspace by the method shown in FIG. The adsorbed components were desorbed using the apparatus shown in FIGS. 2 and 3 and then analyzed by gas chromatography. The analysis conditions are shown below.
Gas phase component collection conditions Sample amount: 10.0 g
Sample temperature: 30 ° C
Collection time: 30 minutes Adsorbent: cocoon (inner layer) / Tenax (outer layer)
Adsorption / desorption method Same as Example 3
Gas chromatographic conditions The same as in Example 3.
[0025]
Standard preparation sample

[0026]
Comparative Example 4 (Aroma analysis by static method using adsorbent C)
The gas chromatograph was analyzed in the same manner as in Example 4 except that the adsorbent C was used instead of the adsorbent B.
[0027]
(Aroma component analysis results)
FIG. 5 shows the results of analysis in Example 4 and Comparative Example 4 with the result of direct gas chromatograph analysis of the standard blended fragrance as a control example. Compared with the analysis result of the comparative example 4, the aromatic component of the blended fragrance | flavor analyzed in Example 4 was able to be analyzed with sufficient balance about the compound which has various functional groups.
[0028]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the adsorption material which is excellent in the adsorption | suction characteristic of an aromatic component compared with the conventional adsorption material, and can collect an aromatic component with sufficient balance is provided. Furthermore, according to the present invention, there is provided an aroma component analysis method capable of collecting and analyzing gas phase components in the head space without breaking the balance.
[Brief description of the drawings]
FIG. 1 is an explanatory view showing gas phase component adsorption used in the present invention.
FIG. 2 is an explanatory view showing an adsorption / desorption mechanism of an adsorbent adsorbing component.
FIG. 3 is an explanatory view showing a gas chromatograph feeding mechanism of a desorption component.
4 is a drawing showing gas chromatograms of Example 2 and Comparative Examples 2 and 3. FIG.
5 is a drawing showing gas chromatograms of Example 4 and Comparative Example 4. FIG.
FIG. 6 is an explanatory view showing an adsorption mechanism of a gas phase component by a dynamic method.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Container 11 Adsorbent 12 Adsorbent layer 13 Support pipe 14 Opening / closing member 15 U-shaped pipe 16 Heating means 17 Handle 18 Inert gas inlet 19 Gas chromatograph connection port 20 Refrigerant tank

Claims (7)

An adsorbent for aroma components, wherein a rod material is coated with a carbon-based adsorbent, and then the coating is coated with a second adsorbent composed of 2,6-diphenyl-P-phenylene oxide .   2. The aroma component adsorbent according to claim 1, wherein the bar is a metal bar or a fiber focusing bar.   3. The aroma component adsorbent according to claim 2, wherein the fiber focusing rod is formed of a fiber of a metal material, an inorganic material, or an organic material.   2. The adsorbent for aroma components according to claim 1, wherein the bar has a spiral groove on its side surface.   The adsorbent for aroma components according to claim 1, wherein the carbon-based adsorbent is at least one selected from the group consisting of graphite carbon, activated carbon, and soot. A rod is immersed in a suspension of carbon-based adsorbent in water and / or a hydrophilic organic solvent and dried to form a first coating layer, and then a second coating composed of 2,6-diphenyl-P-phenylene oxide . A method for producing an adsorbent for aroma components, comprising: first and second coating layers that are dipped in a solution containing the adsorbent of 2 and then dried. In the method for analyzing a head space component comprising the following steps a to d, the adsorbent is a second adsorbent comprising a rod-like material coated with a carbon-based adsorbent and then the coating comprising 2,6-diphenyl-P-phenylene oxide. A method for analyzing aroma components, characterized by being coated with an agent,
a. loading the adsorbent with the adsorbent into the headspace of the sealed container into which the sample has been injected;
b. A step of taking out the adsorbent adsorbing the components in the head space from the sealed container and inserting it into the U-shaped tube from one end of the U-shaped tube provided with heating means on at least the upper side,
c. After immersing at least the lower part of the U-tube with the adsorbent in the refrigerant, the U-tube is heated to desorb the components adsorbed on the adsorbent, and the desorbed components are placed on the bottom of the U-tube. The process of accumulating,
d. The step of connecting the other end of the U-shaped tube taken out from the refrigerant to the sample inlet of the gas chromatograph and analyzing the components desorbed by the introduction of the inert gas.

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