TW201615257A - Sulfur-removing material, and purification column and organic-matter-analysis pretreatment method using said sulfur-removing material - Google Patents

Abstract

A mixture of an inorganic filler and inorganic particles that have a metal that reacts with sulfur on at least parts of the surfaces thereof is used as a sulfur-removing material that is less expensive than silver-nitrate silica gel and exhibits high sulfur-removal effectiveness. A pretreatment for organic-matter analysis is performed in a purification column using said sulfur-removing material.

Description

Sulfur removal material, and purification column and organic matter analysis method using the same Field of invention

The present invention relates to a sulfur-removing material which can be applied to the treatment of an organic substance such as a residual organic pollutant or the like, and a purification column and an organic substance-preparing treatment method using the same.

Background of the invention

In the qualitative and quantitative analysis of residual organic pollutants (Persistent Organic Pollutants, POPs) such as dioxin or polychlorinated biphenyls (PCBs) contained in drainage, exhaust, and soil, the pre-removal of the sample is usually performed. Analyze the composition of the work as a treatment to improve the accuracy of the analysis.

Specifically, the sample is extracted with toluene, hexane, or the like, and the extract is purified, for example, using a multilayer rubber column or the like. In the column packing for removing sulfur in the sample, generally, for example, JIS is used. K0311 (manufacturing method of dioxin in exhaust gas), silver nitrate gel (for example, Patent Documents 1 and 2).

Silver nitrate gel can effectively achieve sulfur removal by forming a complex with sulfur, which is a problem that is time-consuming and expensive to manufacture. Relatively cheaper, In addition, there is a demand for desulfurization materials with high sulfur removal effect, but the current situation is that the sulfur removal materials satisfying the requirements are still not obtained.

Patent Document 3 related thereto discloses that a first particle composed of a first substance and a second substance are used in order to selectively absorb a specific component of a sample mixture in a preliminary stage of separation or analysis of a chromatography method. The mixture of the second particles is used as a separation medium, and the first substance is cerium oxide, an organic polymer, an enamel polymer, graphite, or the like, which has been conventionally used in a chromatography column; the second substance is The first substance also has a high thermal conductivity of silver, copper, aluminum, and other metals, carbon allotropes such as diamonds, ceramics such as alumina, and the like.

However, in the separation medium described in Patent Document 3, the chromatographic separation method or the like performed under a very high pressure, the main purpose is to increase the separation efficiency by increasing the thermal conductivity of the separation medium, and before the analysis. The treatment of sulfur removal does not matter. The range of selection of the first and second substances constituting each of the above particles is extremely wide, and the amount of the second particles to be blended is preferably at least 1 to 25%, and preferably about 10%.

Advanced technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open Publication No. 2002-40007

Patent Document 2: Japanese Patent Laid-Open Publication No. 2002-122577

Patent Document 3: Japanese Patent Special Publication No. 2010-527003

Summary of invention

The present invention has been made in view of the above, and aims to provide a sulfur-removing material which is cheaper than silver nitrate rubber and has a high sulfur removal effect. Further, it is intended to provide a purification column using the sulfur-removing material and a treatment method prior to analysis of the organic substance.

The sulfur-removing material of the present invention is for removing sulfur in a liquid and is composed of a mixture of inorganic particles and an inorganic filler, and the inorganic particles have a metal reactive with sulfur at least in part on the surface.

Among the above-mentioned sulfur-removing materials, one or two or more selected from the group consisting of copper, silver, and iron can be used as the metal reactive with sulfur.

As the inorganic particles, copper particles in which at least a part of the surface is coated with silver can be used.

The specific surface area of the inorganic particles is preferably 0.2 m ² /g or more.

Further, the inorganic particles are preferably dendritic or have a block shape having irregularities on the surface.

The size of the inorganic particles is preferably from 1 to 200 μm .

The inorganic filler may be one or more selected from the group consisting of silicone rubber, alumina, sea sand, and glass beads.

The inorganic filler should preferably have an average particle size of 60 to 200 μm .

In the mixture of the inorganic particles and the inorganic filler, the blending ratio of the inorganic particles is preferably in the range of 0.1 to 50% by mass.

The purification column of the present invention is set to contain the above-described sulfur-removing material of the present invention.

The pretreatment method for organic substance analysis of the present invention is a method for desulfurization using the above-described sulfur-removing material of the present invention.

The sulfur-removing material of the present invention is cheaper to manufacture than silver nitrate rubber and has a high sulfur removal ability. Therefore, by using the sulfur-removing material of the present invention, the cost of analyzing the organic substance such as residual organic pollutants can be reduced, and the accuracy or efficiency of the analysis can be further improved.

Further, the sulfur-removing material of the present invention not only removes sulfur, but also has the ability to remove analytical components such as polycyclic aromatic hydrocarbons (PAHs) or unsaturated hydrocarbons to the same extent as silver nitrate rubber.

Therefore, by using the sulfur-removing material of the present invention and the sulfur-removing method using the same, it is possible to carry out drainage, exhaust gas, and soil residual organic pollutants such as dioxin or PCB which are cheaper and more precise than ever before. Analysis.

A‧‧‧Multilayer rubber hose column

1‧‧‧copper or copper

2‧‧‧ sodium sulfate

3‧‧‧Desulfurization materials

4,7,9‧‧‧矽

5‧‧22% sulfuric acid gel

6‧‧44% sulphate

8‧‧‧%% Potassium Hydroxide

10‧‧‧ sodium sulfate

11‧‧‧Quartz cotton

a‧‧‧The peak from polycyclic aromatic hydrocarbons

b‧‧‧The peak from unsaturated hydrocarbons

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing the outline of a multilayer rubber hose column.

2 is a chromatogram showing the results of gas chromatography mass spectrometry (GC-MS) of each of the following samples: (1) a crude extract of an exhaust sample (before purification treatment); (2) using an implementation The treatment liquid obtained by purifying the crude extract of the exhaust sample of the sulfur-removing material of Example 1; (3) the treatment liquid obtained by purifying the crude extract of the exhaust sample with silver nitrate gel.

Form for implementing the invention

Hereinafter, embodiments of the present invention will be described more specifically.

The sulfur-removing material of the present invention is composed of a mixture of inorganic particles and an inorganic filler as described above, and the inorganic particles have a metal reactive with sulfur at least in part on the surface.

First, the inorganic particles are not particularly limited as long as they have at least a part of the surface which is reactive with sulfur. Therefore, for example, it is possible to use, as a whole, metal particles composed of only one metal having reactivity with sulfur, or inorganic particles having a property reactive with sulfur or an inorganic substance other than sulfur. The core, and some or all of the surface of the core is coated with a metal having reactivity with sulfur.

The type of the metal having reactivity with sulfur is not particularly limited, and examples thereof include copper, silver, iron, lead, zinc, magnesium, sodium, potassium, and the like, and from the viewpoint of balance with reactivity with sulfur and cost. Look, especially suitable for copper and silver.

The method of coating a part or all of the surface of the inorganic substance of the core with a metal having reactivity with sulfur is not particularly limited, and examples thereof include a method using electroless plating, a method using electroplating, vacuum evaporation, and ion. A method such as plating, ion sputtering, or mechanochemical method is preferably a method using electroless plating from the viewpoint of easiness of metal coating.

The shape of the inorganic particles is not particularly limited, but in order to enhance the sulfur removal ability, it is preferred that the surface area be a large surface. Therefore, it is preferably a dendritic shape, or a block shape having a concave or convex surface, or a scale shape, which is generally referred to as a "potato shape" as compared with a spherical ball close to a spherical shape.

If it is easy to make a shape or a cost with a large surface area as described above, the inorganic particles are made of copper particles as a core, and Silver-coated copper-coated particles having at least a portion of the surface are particularly preferred. By coating with silver, the oxidation resistance of the copper particles can be improved. The amount of silver to be coated is not particularly limited, and may be, for example, 1 to 20% by mass.

The inorganic particles may be used singly or in combination of two or more.

The size of the inorganic particles is not limited. However, in consideration of the sulfur removal ability or the ease of handling, it is preferred that the average particle diameter is from 1 to 200 μm , and preferably from 2 to 30 μm .

The specific surface area of the inorganic particles is not limited, however in consideration of desulfurization capability and the like, appropriate for the 0.2m ² / g or more, and to 0.3m ² / g or more is preferable.

Next, the inorganic filler used in the present invention is a particle which plays a role of maintaining the inorganic particles in an appropriate space in the internal space of a column or the like, and does not require a sulfur-removing ability. In order to achieve the above object, when the inorganic filler is mixed with the inorganic particles and filled in a column or the like under atmospheric pressure, the inorganic filler is preferably stably maintained in a mixed state with the inorganic particles, and an organic solvent such as hexane can be used. Particles that pass through at an appropriate rate.

The type of the inorganic filler is not particularly limited, and examples thereof include silicone, alumina, sea sand, and glass beads. The inorganic filler may be used alone or in combination of two or more.

The inorganic filler is preferably of an average particle diameter of 5 to 600 μm and preferably 60 to 200 μm from the viewpoints of sulfur removal ability and ease of handling.

The sulfur-removing material of the present invention can be obtained by mixing the above inorganic particles with an inorganic filler. The means for mixing is not particularly limited, and a well-known stirring means can be suitably used.

In the mixture of the inorganic particles and the inorganic filler, the mixing ratio of the inorganic particles is preferably in the range of 0.1 to 50% by mass, and preferably in the range of 5 to 10% by mass.

The purification column of the present invention is a column containing the above-described sulfur-removing material of the present invention. The specific configuration is not particularly limited, and may be, for example, a multi-layer rubber tube column which is conventionally composed of a silicone layer and a silver nitrate layer or the like, and has a layer filled with the sulfur-removing material of the present invention in place of the silver nitrate rubber. The column of the layer; in terms of use, for example, the column for the treatment before the analysis can be used as an organic substance such as dioxin.

The pretreatment method for analyzing an organic substance of the present invention is a method for desulfurizing using the above-described sulfur-removing material of the present invention. The specific method is not limited, and a multilayer rubber hose column in which, for example, the above-described sulfur-removing material of the present invention is substituted for silver nitrate tantalum rubber can be used, and in order to improve the analysis precision of organic substances such as dioxin, organic matter such as toluene is used. Solvent extraction of the sample to remove the sulfur purification method.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing an example of a multilayer rubber hose column used for treatment prior to analysis of an organic substance. As shown in the figure, the multi-layer rubber hose column has laminated silicone and other filler materials. In this example, the layers are filled with the following: symbol 1 is copper powder or copper chip, and symbol 2 is sodium sulfate. Symbols 4, 7, and 9 are silicone, symbol 5 is 22% barium sulfate, symbol 6 is 44% barium sulfate, symbol 8 is 2% potassium hydroxide, and symbol 10 is sulfur. Sodium, symbol 11 is quartz wool. The layer indicated by the symbol 3 is obtained by filling the sulfur-removing material of the present invention in place of the silver nitrate gel used in the prior art, and passing the sample liquid through the column by the same method as in the prior art (at atmospheric pressure, room temperature), whereby sulfur can be removed.

The amount of the sulfur-removing material to be used in the present invention is not particularly limited, but in order to obtain a sufficient sulfur removal effect, the present invention is used in the case of using, for example, a column having an inner diameter of 10 to 15 mm and flowing at a flow rate of about 2.5 ml/min. The thickness of the layer of the sulfur material is preferably 20 mm or more, and 20 to 30 mm is preferable in consideration of handling ability, cost, and the like.

Example

The embodiments of the present invention are shown below, but the present invention is not limited to the following examples. In addition, the following blending ratio and the like are based on mass unless otherwise specified.

1. Manufacturing of sulfur removal materials

In the examples, 20 g of Kannon Chemical Silicone 60N (Cat. No. 37565-79) and 1.4 g of various inorganic particles (silver-coated copper powder) shown in Table 1 were vibrated using a mixer (AUMATIC MIXER S-100 manufactured by TIETECH). mixing. Further, in the comparative example, silver nitrate gelatin (silver content: 6.5% by mass) was used.

In addition, the average particle diameter and specific surface area of the silver-coated copper powder were measured using a laser diffraction/diffuse particle size distribution measuring apparatus (manufactured by Nikkiso Co., Ltd., MT3300EXII).

2. Evaluation of sulfur removal capacity in hexane solution

0.8 g of the mixture of the examples and 0.8 g of the silver nitrate gel of the comparative example were mixed with 20 ml of a hexane solution of 3 mg/ml of sulfur, respectively, and stirred for 15 minutes. It Thereafter, the unreacted sulfur in the hexane solution was quantified by a fluorescent X-ray analysis (Fundamental parameter method), and the treatment ability of the sulfur of the silver nitrate tantalum gel per 1 g of the mixture of the examples and the comparative example was calculated (mg/g). ). The results are shown in Table 1.

3. Evaluation of the maximum recovery rate of dioxin

Using the sulfur-removing material of Example 1, the maximum recovery rate of the dioxin-like substance was evaluated by JIS K0311 ("calculation of the maximum recovery rate of 7.6.1 removal"). The results are shown in Table 2.

As shown in Table 1, the sulfur-removing materials of Examples 1 to 4 showed higher sulfur treatment ability than the silver nitrate rubber of the comparative example. It can also be seen that, as shown in Table 2, in the maximum recovery rate of the dioxin-eliminating agent, the sulphur-removing material of the present invention is relatively inexpensive and has a sulfur removal effect equivalent to or higher than that of the silver nitrate-based rubber.

4. Removal of polycyclic aromatic hydrocarbons and unsaturated hydrocarbons in exhaust gas evaluation of

The sample of the exhaust gas 15 from the incinerator is taken and extracted according to JIS K0311, and is randomly fractionated from the taken and mixed, and used as a crude extract sample of the exhaust sample, and then subjected to the following apparatus and conditions for gas phase Chromatographic mass analysis (GC-MS). The obtained chromatogram is shown in (1) of Fig. 2. The horizontal axis of the chromatogram shows the retention time (RT, min), the peak of the part shown in (a) is from the polycyclic aromatic hydrocarbon, and the peak of the part shown in (b) is from the unsaturated hydrocarbon.

<Gas Chromatography Mass Analysis (GC-MS) Device>

GC: 7890A by Agilent Technologies

MS: JEOL JMS-Q1050GC

<GC measurement conditions>

Carrier gas: He

Note entry conditions: Splitless mode

Injection inlet temperature condition: 280 ° C

Oven temperature conditions: After initializing at 150 ° C for 1 minute, the temperature was raised at a temperature increase rate of 20 ° C / min, and maintained at 320 ° C for 10 minutes. The maximum temperature is 0.1 minutes at 320 °C.

<MS measurement conditions>

Ionization method: EI method

Free current: 70μA

Free energy: 70eV

Detector voltage: -1000V

Ion source temperature: 280 ° C

GCITF temperature: 280 ° C

The column (internal diameter: 13 mm) was filled with the sulfur-removing material of the above-mentioned Example 1 or the silver nitrate-based rubber of the comparative example (filling height: 3 cm), and the crude extract liquid sample of the above-mentioned exhaust sample was subjected to purification treatment, after the treatment. GC-MS analysis was carried out under the same conditions as above. The results of the treatment using the sulfur-removing material of Example 1 are shown in (2) of Fig. 2, and the results of the treatment using the silver nitrate gel of the comparative example are shown in (3).

From the comparison of these chromatograms, the sulfur-removing material of the present invention is equivalent to or higher than the silver nitrate rubber even in the ability to remove the analysis component such as polycyclic aromatic hydrocarbon or monocyclic aromatic hydrocarbon.

Claims (11)

A sulfur removal material for removing sulfur in a liquid, which is characterized in that it is composed of a mixture of inorganic particles and an inorganic filler, and the inorganic particles have a metal reactive with sulfur at least in part on the surface. The sulfur-removing material of claim 1, wherein the metal reactive with sulfur is one or more selected from the group consisting of copper, silver, and iron. The sulfur removal material of claim 1, wherein the inorganic particles are copper particles having at least a portion of the surface covered with silver. The sulfur-removing material of claim 1, wherein the inorganic particles have a specific surface area of 0.2 m ² /g or more. The sulfur-removing material according to any one of claims 1 to 4, wherein the inorganic particles are dendritic or have a block shape having irregularities on the surface. The sulfur-removing material according to any one of claims 1 to 4, wherein the inorganic particles have an average particle diameter of from 1 to 200 μm. The sulfur-removing material according to any one of claims 1 to 4, wherein the inorganic filler is one or more selected from the group consisting of silicone rubber, alumina, sea sand, and glass beads. The sulfur-removing material according to any one of claims 1 to 4, wherein the inorganic filler has an average particle diameter of 60 to 200 μm. The sulfur-removing material according to any one of claims 1 to 4, wherein a blending ratio of the inorganic particles in the mixture of the inorganic particles and the inorganic filler is in the range of 0.1 to 50% by mass. A purification column comprising the sulfur removal material of any one of claims 1 to 4 material. A method of treating an organic matter prior to analysis, characterized in that the sulfur removal material is used for sulfur removal according to any one of claims 1 to 4.