WO2015198567A1 - Matériau de retrait de soufre, et colonne de purification et procédé de prétraitement d'analyse de matières organiques utilisant ledit matériau de retrait de soufre - Google Patents

Matériau de retrait de soufre, et colonne de purification et procédé de prétraitement d'analyse de matières organiques utilisant ledit matériau de retrait de soufre Download PDF

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Publication number
WO2015198567A1
WO2015198567A1 PCT/JP2015/003060 JP2015003060W WO2015198567A1 WO 2015198567 A1 WO2015198567 A1 WO 2015198567A1 JP 2015003060 W JP2015003060 W JP 2015003060W WO 2015198567 A1 WO2015198567 A1 WO 2015198567A1
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WIPO (PCT)
Prior art keywords
sulfur
removing material
inorganic particles
silica gel
material according
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PCT/JP2015/003060
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English (en)
Japanese (ja)
Inventor
恒彦 寺田
勉 村尾
雄真 高野
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タツタ電線株式会社
株式会社タツタ環境分析センター
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Application filed by タツタ電線株式会社, 株式会社タツタ環境分析センター filed Critical タツタ電線株式会社
Priority to JP2016529059A priority Critical patent/JP6063095B2/ja
Priority to CN201580022459.4A priority patent/CN106461620B/zh
Publication of WO2015198567A1 publication Critical patent/WO2015198567A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86

Definitions

  • the present invention relates to a sulfur removing material that can be suitably used for pretreatment of organic substance analysis such as residual organic pollutants, a purification column using the same, and a pretreatment method of organic substance analysis.
  • POPs Persistent Organic Pollutants
  • PCB polychlorinated biphenyl
  • the sample is extracted with toluene, hexane or the like, and the extract is purified using, for example, a multilayer silica gel column.
  • a column filler for removing sulfur in the sample JIS K0311 ( Silver nitrate silica gel described in (Measurement method of dioxins in exhaust gas) is generally used (for example, Patent Documents 1 and 2).
  • Silver nitrate silica gel is effective in removing sulfur by forming a complex with sulfur, but has a problem that it is troublesome to manufacture and is expensive. On the other hand, there is a demand for a sulfur removal material that is cheaper and has a high sulfur removal effect, but the present situation is that a sulfur removal material that satisfies these requirements has not yet been obtained.
  • US Pat. No. 6,057,049 uses chromatographic columns such as silica, organic polymers, siliceous polymers, graphite, etc., for selective absorption of specific components of the sample mixture in chromatographic separation and preliminary stages of analysis.
  • the separation medium described in Patent Document 3 is mainly intended to improve the separation efficiency by increasing the thermal conductivity of the separation medium in chromatographic separation performed at a very high pressure.
  • unrelated to sulfur removal as a pretreatment for analysis unrelated to sulfur removal as a pretreatment for analysis.
  • the selection range of the first and second substances constituting each of the above particles is extremely wide, and the blending amount of the second particles is small.
  • the total amount of both is preferably 1 to 25%, and most preferably about 10%. ing.
  • the present invention has been made in view of the above, and an object thereof is to provide a sulfur removing material that is cheaper than silver nitrate silica gel and has a high sulfur removing effect. It is another object of the present invention to provide a purification column using the sulfur removing material and a pretreatment method for organic substance analysis.
  • the sulfur removing material of the present invention is a sulfur removing material for removing sulfur in a liquid, and is composed of a mixture of inorganic particles having a metal having reactivity with sulfur on at least a part of the surface and an inorganic filler. Shall.
  • one or more selected from copper, silver and iron can be used as the metal having reactivity with sulfur.
  • inorganic particles copper particles having at least a part of the surface coated with silver can be used.
  • the specific surface area of the inorganic particles is preferably 0.2 m 2 / g or more.
  • the inorganic particles are preferably in a dendritic shape or a lump having irregularities on the surface.
  • the size of the inorganic particles is preferably an average particle size of 1 to 200 ⁇ m.
  • the inorganic filler one or more selected from silica gel, alumina, sea sand, and glass beads can be used.
  • the size of the inorganic filler is preferably an average particle size of 60 to 200 ⁇ m.
  • 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 includes the sulfur removing material of the present invention.
  • the pretreatment method for organic substance analysis of the present invention is a method for removing sulfur using the sulfur removing material of the present invention.
  • the sulfur removing material of the present invention can be manufactured at a lower cost than silver nitrate silica gel and has a high sulfur removing ability. Therefore, by using this, it is possible to further improve the accuracy and efficiency of analysis while reducing the cost of pretreatment for the analysis of organic substances such as residual organic pollutants.
  • the sulfur removing material of the present invention has the ability to remove not only sulfur but also analysis interfering components such as polycyclic aromatic hydrocarbons (PAHs) and unsaturated hydrocarbons to the same level or more as silver nitrate silica gel.
  • PAHs polycyclic aromatic hydrocarbons
  • unsaturated hydrocarbons to the same level or more as silver nitrate silica gel.
  • the sulfur removing material of the present invention and the sulfur removing method using the same, the analysis of residual organic pollutants such as dioxins and PCBs contained in waste water, exhaust gas, soil, etc. is cheaper and more expensive than before. It becomes possible to carry out with accuracy.
  • the sulfur removing material of the present invention comprises a mixture of inorganic particles having a metal reactive with sulfur on at least a part of the surface and an inorganic filler.
  • the inorganic particles are not particularly limited as long as they have a metal having reactivity with sulfur in at least a part of the surface. Therefore, for example, metal particles consisting of only one kind of metal having reactivity with sulfur can be used as a whole, or a metal having reactivity with sulfur or other inorganic substance forms a nucleus, and the surface of the nucleus Inorganic particles partially or wholly covered with a metal having reactivity with sulfur can also be used.
  • the type of metal having reactivity with sulfur is not particularly limited, but examples include copper, silver, iron, lead, zinc, magnesium, sodium, potassium, and the like. From the viewpoint of balance, copper and silver are particularly preferable.
  • the method for coating a part or all of the surface of the inorganic substance as a core with a metal having reactivity with sulfur is not particularly limited, and examples thereof include a method by electroless plating, a method by electroplating, vacuum deposition, ion Examples of the method include plating, ion sputtering, and mechanochemical method. From the viewpoint of ease of manufacturing the metal coating, a method using electroless plating is preferable.
  • the shape of the inorganic particles is not particularly limited, but a shape having a larger surface area is desirable for improving the sulfur removal ability. Therefore, a dendrid shape, a lump shape having irregularities on the surface generally called a “potato shape”, and a scale shape are preferable to a spherical shape close to a true sphere.
  • the inorganic particles include silver-coated copper particles in which copper particles form a nucleus and at least a part of the surface thereof is coated with silver. Particularly preferred. By covering with silver, the oxidation resistance of the copper particles can be improved.
  • the coating amount with silver is not particularly limited, but may be, for example, 1 to 20% by mass.
  • the above inorganic particles can be used alone or in a mixture of two or more.
  • the size of the inorganic particles is not limited, the average particle size is preferably 1 to 200 ⁇ m and more preferably 2 to 30 ⁇ m in view of sulfur removal ability and ease of handling.
  • the specific surface area of the inorganic particles is not limited, it is preferably 0.2 m 2 / g or more, and more preferably 0.3 m 2 / g or more in consideration of sulfur removal ability and the like.
  • the inorganic filler used in the present invention is a particle that plays a role of holding the inorganic particles at an appropriate interval inside a space such as a column, and itself does not need to have a sulfur removing ability.
  • the inorganic filler when the inorganic filler is mixed with the inorganic particles and packed in a column or the like under atmospheric pressure, the mixed state with the inorganic particles is stably maintained, and an organic solvent such as hexane is appropriately used. It is preferable that the particles can be transmitted at a high speed.
  • the type of inorganic filler is not particularly limited, and examples include silica gel, alumina, sea sand, glass beads and the like.
  • One of these inorganic fillers can be used alone, or a mixture of two or more can be used.
  • the size of the inorganic filler is preferably an average particle size of 5 to 600 ⁇ m, more preferably 60 to 200 ⁇ m from the viewpoint of sulfur removal ability and ease of handling.
  • the sulfur removing material of the present invention can be obtained by mixing the inorganic particles and the inorganic filler.
  • the mixing means is not particularly limited, and known stirring means can be appropriately used.
  • the mixing ratio of the inorganic particles is preferably in the range of 0.1 to 50% by mass from the viewpoint of excellent sulfur removal capability, and in the range of 5 to 10% by mass. It is more preferable that
  • the purification column of the present invention is a column containing the sulfur removing material of the present invention.
  • the specific configuration is not particularly limited, for example, as will be described later, in a multilayer silica gel column that has conventionally been composed of a silica gel layer and a silver nitrate silica gel layer, a layer filled with the sulfur removing material of the present invention instead of the silver nitrate silica gel layer As a use, it can be used as a pretreatment column for organic substance analysis such as dioxin.
  • the pretreatment method for organic substance analysis of the present invention is a method for removing sulfur using the sulfur removing material of the present invention.
  • the specific method is not limited, for example, using a multilayer silica gel column packed with the sulfur removing material of the present invention instead of silver nitrate silica gel as described above, in order to improve the analysis accuracy of organic substance analysis such as dioxin, toluene
  • a purification method for removing sulfur from a sample extracted with an organic solvent such as
  • FIG. 1 is a schematic diagram showing an example of a multilayer silica gel column used for pretreatment of organic substance analysis.
  • the multilayer silica gel column is formed by laminating silica gel and other fillers.
  • reference numeral 1 is copper powder or copper chip
  • reference numeral 2 is sodium sulfate
  • reference numerals 4, 7, and 9 are silica gel
  • Reference numeral 5 denotes 22% sulfuric acid silica gel
  • reference numeral 6 denotes 44% sulfuric acid silica gel
  • reference numeral 8 denotes 2% potassium hydroxide silica gel
  • reference numeral 10 denotes sodium sulfate
  • reference numeral 11 denotes a layer filled with quartz wool.
  • the layer denoted by reference numeral 3 is filled with the sulfur-removing material of the present invention instead of the conventionally used silver nitrate silica gel, and the sample solution is passed through this column in the same manner as before (atmospheric pressure and room temperature). By doing so, sulfur can be removed.
  • the amount of the sulfur removing material of the present invention is not particularly limited, but in order to obtain a sufficient sulfur removing effect, for example, when flowing down at a flow rate of about 2.5 ml / min using a column having an inner diameter of 10 to 15 mm,
  • the thickness of the sulfur-removing material layer of the invention is preferably 20 mm or more, and more preferably 20 to 30 mm in view of processing capability, cost, and the like.
  • silica gel 60N (Cat. No. 37565-79) manufactured by Kanto Chemical Co., Ltd. and 1.4 g of various inorganic particles (silver-coated copper powder) shown in Table 1 were mixed with an AUTOMATIC MIXER manufactured by Taitec. S-100) was used for vibration mixing. Moreover, the silver nitrate silica gel (silver content 6.5 mass%) was used as a comparative example.
  • the average particle size and specific surface area of the silver-coated copper powder were measured using a laser diffraction / scattering particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., MT3300EXII).
  • the sulfur removal materials of Examples 1 to 4 exhibited a higher sulfur treatment capacity than the silver nitrate silica gel of the comparative example.
  • the cleanup spike recovery rate of dioxins sufficiently satisfies 50 to 120% defined in JIS K0311, while the sulfur removal material of the present invention is relatively inexpensive. It can be seen that the sulfur removal effect is equivalent to or better than that of silver nitrate silica gel.
  • GC-MS ⁇ Gas chromatograph mass spectrometry (GC-MS) apparatus> GC: 7890A manufactured by Agilent Technologies MS: JMS-Q1050GC made by JEOL ⁇ GC measurement conditions> Carrier gas: He Inlet condition: Splitless mode Inlet temperature condition: 280 ° C Oven temperature condition: Initially held at 150 ° C. for 1 minute, then heated at a rate of temperature increase of 20 ° C./min and held at 320 ° C. for 10 minutes. The maximum temperature was 320 ° C. and the stabilization time was 0.1 minute. ⁇ MS measurement conditions> Ionization method: EI method Ionization current: 70 ⁇ A Ionization energy: 70 eV Detector voltage: -1000V Ion source temperature: 280 ° C GCITF temperature: 280 ° C
  • the column (inner diameter: 13 mm) was filled with the sulfur removal material of Example 1 or the silver nitrate silica gel of Comparative Example (packing height: 3 cm), and the crude extract sample of the exhaust gas sample was allowed to flow down for purification treatment. Later, GC-MS analysis was performed under the same conditions as described above.
  • the result of the treatment with the sulfur removing material of Example 1 is shown in FIG. 2 (3), and the result of the treatment with the silver nitrate silica gel of the comparative example is shown in (2).
  • the sulfur removing material of the present invention is equivalent to or better than silver nitrate silica gel in the ability to remove analysis interfering components such as polycyclic aromatic hydrocarbons and monocyclic aromatic hydrocarbons.
  • Multilayer silica gel column 1 Copper powder or copper chip 2 ; Sodium sulfate 3 — Sulfur removal material 4,7,9 ; Silica gel 5 ?? 22% sulfuric acid silica gel 6 ?? 44% sulfuric acid silica gel 8 ?? 2% potassium hydroxide silica gel 10 ... Sodium sulfate 11 ... Quartz wool a ... Peak due to polycyclic aromatic hydrocarbon b ... Peak due to unsaturated hydrocarbon

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
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  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

L'invention porte sur un mélange d'une charge minérale et de particules minérales qui ont un métal qui réagit avec le soufre sur au moins des parties des surfaces de ces dernières, lequel mélange est utilisé comme matériau de retrait de soufre, qui est moins coûteux qu'un gel de silice au nitrate d'argent, et qui présente une efficacité élevée de retrait du soufre. L'invention porte également sur un prétraitement pour une analyse de matières organiques, lequel prétraitement est effectué dans une colonne de purification utilisant ledit matériau de retrait de soufre.
PCT/JP2015/003060 2014-06-25 2015-06-18 Matériau de retrait de soufre, et colonne de purification et procédé de prétraitement d'analyse de matières organiques utilisant ledit matériau de retrait de soufre WO2015198567A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2016529059A JP6063095B2 (ja) 2014-06-25 2015-06-18 硫黄除去材料、並びにこれを用いた精製カラム及び有機物質分析の前処理方法
CN201580022459.4A CN106461620B (zh) 2014-06-25 2015-06-18 硫去除材料、以及使用其的纯化柱及有机物质分析的前处理方法

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JP2014-130504 2014-06-25
JP2014130504 2014-06-25

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
EP3730202A1 (fr) 2019-04-26 2020-10-28 Covestro Deutschland AG Procédé de nettoyage de gaz de processus corrosifs contenant du soufre

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CN110221002A (zh) * 2019-07-15 2019-09-10 山东拜尔检测股份有限公司 一种水产品中多氯联苯的测定方法
CN112730651B (zh) * 2020-12-15 2022-08-05 湖北微谱技术有限公司 一种二噁英样品快速前处理方法

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Publication number Priority date Publication date Assignee Title
EP3730202A1 (fr) 2019-04-26 2020-10-28 Covestro Deutschland AG Procédé de nettoyage de gaz de processus corrosifs contenant du soufre
WO2020216837A1 (fr) 2019-04-26 2020-10-29 Covestro Intellectual Property Gmbh & Co. Kg Procédé de nettoyage de gaz de traitement corrosifs contenant du soufre

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TW201615257A (zh) 2016-05-01
CN106461620A (zh) 2017-02-22
TWI648087B (zh) 2019-01-21
JPWO2015198567A1 (ja) 2017-04-20
JP6063095B2 (ja) 2017-01-18
CN106461620B (zh) 2020-02-18

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