JPH085622A - Column for supercritical liquid chromatography - Google Patents
Column for supercritical liquid chromatographyInfo
- Publication number
- JPH085622A JPH085622A JP6135265A JP13526594A JPH085622A JP H085622 A JPH085622 A JP H085622A JP 6135265 A JP6135265 A JP 6135265A JP 13526594 A JP13526594 A JP 13526594A JP H085622 A JPH085622 A JP H085622A
- Authority
- JP
- Japan
- Prior art keywords
- column
- silica
- silver nitrate
- impregnated
- range
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は超臨界流体クロマトグラ
フィー用カラムに係り、特に、超臨界流体クロマトグラ
フィーを利用して灯油または軽油のタイプ分析を行うう
えで好適な超臨界流体クロマトグラフィー用カラムに関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a column for supercritical fluid chromatography, and more particularly to a column for supercritical fluid chromatography suitable for performing type analysis of kerosene or light oil using supercritical fluid chromatography. Regarding
【０００２】[0002]
【従来の技術】灯油や軽油のタイプ分析値は、精製工程
における反応解析や貯蔵安定性を評価するうえでの重要
なパラメータの一つである。また将来的には、ディーゼ
ル燃料としての性能評価や環境問題に関連して、灯油や
軽油に含まれている芳香族分量の定量が必要となる可能
性が高い。灯油や軽油のタイプ分析値を得る方法として
は、超臨界流体クロマトグラフィー（Supercritical Fl
uid Chromatography；以下、ＳＦＣと略記する）を用い
たＡＳＴＭ−Ｄ５１８６法がある。この方法では溶離液
として超臨界状態の二酸化炭素を用い、検出器として炭
化水素タイプ間の質量感度差が小さく定量性に優れた水
素炎イオン化検出器（ＦＩＤ）を用いている。また、カ
ラムとしてはシリカカラムが用いられている。このＡＳ
ＴＭ−Ｄ５１８６法によれば、灯油や軽油に含まれてい
る非芳香族分と芳香族分とを分離定量することができ
る。2. Description of the Related Art The type analysis value of kerosene or light oil is one of the important parameters for the reaction analysis in the refining process and the evaluation of storage stability. Further, in the future, there is a high possibility that it will be necessary to quantify the amount of aromatics contained in kerosene and light oil in relation to performance evaluation as diesel fuel and environmental problems. Supercritical fluid chromatography (Supercritical Fluid Chromatography) is a method of obtaining type analysis values for kerosene and gas oil.
UID Chromatography; hereinafter abbreviated as SFC). In this method, carbon dioxide in a supercritical state is used as an eluent, and a hydrogen flame ionization detector (FID) having a small mass sensitivity difference between hydrocarbon types and excellent in quantification is used as a detector. A silica column is used as the column. This AS
According to the TM-D5186 method, non-aromatic components and aromatic components contained in kerosene and light oil can be separated and quantified.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上記の
非芳香族分中には飽和分とオレフィン分とが混在してい
る。すなわち、上記のＡＳＴＭ−Ｄ５１８６法では灯油
や軽油に含まれている飽和分とオレフィン分とを分離定
量することができない。これらを分離定量することがで
きれば、より有効な情報が得られる。特にオレフィン分
は、灯油や軽油の安定性を評価するうえでの重要なパラ
メータの一つである。本発明の目的は、ＳＦＣによって
灯油や軽油を飽和分、オレフィン分および芳香族分に容
易に溶出分離することができるＳＦＣ用カラムを提供す
ることにある。However, in the above non-aromatic component, a saturated component and an olefin component are mixed. That is, the above-mentioned ASTM-D5186 method cannot separate and quantify the saturated component and the olefin component contained in kerosene or light oil. If these can be separated and quantified, more effective information can be obtained. In particular, the olefin content is one of the important parameters for evaluating the stability of kerosene and light oil. An object of the present invention is to provide an SFC column capable of easily eluting and separating kerosene or gas oil into a saturated component, an olefin component and an aromatic component by SFC.
【０００４】[0004]
【課題を解決するための手段】上記の目的を達成する本
発明のＳＦＣ用カラムは、硝酸銀含浸シリカをカラム用
容器に充填してなる硝酸銀含浸シリカカラムと、平均細
孔径が１０オングストローム以上６０オングストローム
未満の範囲内である微細孔シリカをカラム用容器に充填
してなる微細孔シリカカラムとを備え、前記硝酸銀含浸
シリカカラムと前記微細孔シリカカラムとが直列に連結
されていることを特徴とするものである（以下、このＳ
ＦＣ用カラムをＳＦＣ用カラムＩという）。A column for SFC of the present invention which achieves the above object is a silver nitrate-impregnated silica column obtained by filling a column container with silver nitrate-impregnated silica, and an average pore diameter of 10 angstroms or more and 60 angstroms. A fine pore silica column obtained by filling a column container with fine pore silica in the range of less than, wherein the silver nitrate-impregnated silica column and the fine pore silica column are connected in series. It is one (hereinafter, this S
The FC column is called SFC column I).
【０００５】また、上記の目的を達成する本発明の他の
ＳＦＣ用カラムは、平均細孔径が１０オングストローム
以上６０オングストローム未満の範囲内である微細孔シ
リカに硝酸銀を含浸させてなる硝酸銀含浸微細孔シリカ
をカラム用容器に充填してなることを特徴とするもので
ある（以下、このＳＦＣ用カラムをＳＦＣ用カラムIIと
いう）。Further, another SFC column of the present invention which achieves the above object is a silver nitrate-impregnated fine pore obtained by impregnating silver nitrate with fine pore silica having an average pore diameter of 10 angstroms or more and less than 60 angstroms. It is characterized in that silica is packed in a column container (hereinafter, this SFC column is referred to as SFC column II).
【０００６】以下、本発明を詳細に説明する。まず、本
発明のＳＦＣ用カラムＩにつて説明すると、上述したよ
うに、このＳＦＣ用カラムＩでは、硝酸銀含浸シリカを
カラム用容器に充填してなる硝酸銀含浸シリカカラム
と、平均細孔径が１０オングストローム以上６０オング
ストローム未満の範囲内である微細孔シリカをカラム用
容器に充填してなる微細孔シリカカラムとが直列に連結
されている。The present invention will be described in detail below. First, the SFC column I of the present invention will be described. As described above, in this SFC column I, a silver nitrate-impregnated silica column obtained by filling a column container with silver nitrate-impregnated silica and an average pore diameter of 10 angstroms are used. The above is connected in series with a microporous silica column obtained by filling a column container with microporous silica in the range of less than 60 Å.
【０００７】上記の硝酸銀含浸シリカカラム用に用いる
硝酸銀含浸シリカとは、シリカに硝酸銀を含浸させたも
のである。このような硝酸銀含浸シリカ自体は高速液体
クロマトグラフィー用充填剤等として公知のものである
が、本発明のＳＦＣ用カラムＩで使用する硝酸銀含浸シ
リカは下記（ａ）および／または（ｂ） （ａ）平均細孔径が１０オングストローム以上６０オン
グストローム未満の範囲内であるシリカ（以下、微細孔
シリカという）に硝酸銀を含浸させてなる硝酸銀含浸シ
リカ（以下、硝酸銀含浸微細孔シリカという）で、硝酸
銀含浸前の前記微細孔シリカが球状（球形を含む）また
は破砕形状を呈するとともに当該微細孔シリカの平均粒
子径（破砕形状のシリカについては平均最長寸法を意味
する。以下、他のシリカにおいても同じ。）が３〜２０
０μｍの範囲内であるもの、（ｂ）平均細孔径が６０〜
３００オングストロームの範囲内であるメソ細孔シリカ
に硝酸銀を含浸させてなる硝酸銀含浸メソ細孔シリカ
で、硝酸銀含浸前の前記メソ細孔シリカが球状（球形を
含む）または破砕形状を呈するとともに当該メソ細孔シ
リカの平均粒子径が３〜２００μｍの範囲内であるも
の、であることが好ましい。The silver nitrate-impregnated silica used for the above-mentioned silver nitrate-impregnated silica column is silica impregnated with silver nitrate. Such silver nitrate-impregnated silica itself is known as a packing material for high performance liquid chromatography, and the silver nitrate-impregnated silica used in the column I for SFC of the present invention is the following (a) and / or (b) (a) ) A silver nitrate-impregnated silica (hereinafter referred to as silver nitrate-impregnated micropore silica) obtained by impregnating silica having an average pore diameter of 10 angstroms or more and less than 60 angstroms (hereinafter referred to as micropore silica) with silver nitrate, before impregnation with silver nitrate. The fine pore silica of (1) has a spherical shape (including a spherical shape) or a crushed shape, and the average particle diameter of the fine pore silica (the average longest dimension of the crushed shape of the silica. The same applies to other silicas hereinafter). Is 3 to 20
Those having a diameter of 0 μm, (b) an average pore diameter of 60 to
A silver nitrate-impregnated mesopore silica obtained by impregnating mesopore silica in the range of 300 Å with silver nitrate, wherein the mesopore silica before impregnation with silver nitrate has a spherical shape (including a spherical shape) or a crushed shape. It is preferable that the average particle diameter of the fine pore silica is within the range of 3 to 200 μm.
【０００８】本発明のＳＦＣ用カラムＩで使用する硝酸
銀含浸シリカカラムは、上記（ａ）の硝酸銀含浸微細孔
シリカのみを充填剤として用いてもよいし、上記（ｂ）
の硝酸銀含浸メソ細孔シリカのみを充填剤として用いて
もよいし、上記（ａ）の硝酸銀含浸微細孔シリカと上記
（ｂ）の硝酸銀含浸メソ細孔シリカとの混合物を充填剤
として用いてもよい。The silver nitrate-impregnated silica column used in the column I for SFC of the present invention may use only the silver nitrate-impregnated microporous silica of the above (a) as a filler, or the above (b).
Only the silver nitrate-impregnated mesopore silica of (a) may be used as the filler, or the mixture of the silver nitrate-impregnated mesopore silica of (a) and the silver nitrate-impregnated mesopore silica of (b) may be used as the filler. Good.
【０００９】上記（ａ）の硝酸銀含浸微細孔シリカのみ
を充填剤として用いる場合、当該硝酸銀含浸微細孔シリ
カの材料として使用する微細孔シリカの平均細孔径は１
０オングストローム以上６０オングストローム未満の範
囲内であることが好ましく、２０〜４０オングストロー
ムの範囲内であることがより好ましい。また、このとき
の微細孔シリカの平均粒子径は３〜２００μｍの範囲内
であることが好ましく、３〜１０μｍの範囲内であるこ
とがより好ましい。When only the silver nitrate-impregnated microporous silica of (a) above is used as a filler, the average pore diameter of the microporous silica used as the material of the silver nitrate-impregnated microporous silica is 1
It is preferably in the range of 0 angstrom or more and less than 60 angstrom, and more preferably in the range of 20 to 40 angstrom. The average particle size of the microporous silica at this time is preferably in the range of 3 to 200 μm, more preferably in the range of 3 to 10 μm.
【００１０】上記（ｂ）の硝酸銀含浸メソ細孔シリカの
みを充填剤として用いる場合、当該硝酸銀含浸メソ細孔
シリカの材料として使用するメソ細孔シリカの平均細孔
径は６０〜３００オングストロームの範囲内であること
が好ましく、６０〜１５０オングストロームの範囲内で
あることがより好ましい。また、このときのメソ細孔シ
リカの平均粒子径は３〜２００μｍの範囲内であること
が好ましく、３〜１０μｍの範囲内であることがより好
ましい。なお、本明細書でいう平均細孔径とは平均細孔
直径を意味する。When only the silver nitrate-impregnated mesoporous silica of (b) above is used as a filler, the average pore diameter of the mesoporous silica used as the material of the silver nitrate-impregnated mesoporous silica is within the range of 60 to 300 angstroms. Is more preferable, and it is more preferable that it is in the range of 60 to 150 angstroms. The average particle size of the mesoporous silica at this time is preferably in the range of 3 to 200 μm, more preferably in the range of 3 to 10 μm. The average pore diameter as used herein means the average pore diameter.
【００１１】本発明のＳＦＣ用カラムＩを構成する硝酸
銀含浸シリカカラムにおいては、カラム用容器に充填さ
れている硝酸銀含浸シリカ（前記（ａ）の硝酸銀含浸微
細孔シリカおよび／または前記（ｂ）の硝酸銀含浸メソ
細孔シリカ）の硝酸銀含浸量が、０．１〜５．０wt％の
範囲内であることが好ましい。硝酸銀含浸量が０．１wt
％未満では飽和分とオレフィン分が分離しない可能性が
高い。一方、硝酸銀含浸量が５．０wt％を超えるとオレ
フィン分の保持力が強すぎて溶出しなくなる可能性が高
い。硝酸銀含浸量のより好ましい値は０．１〜１．０wt
％の範囲内である。なお、硝酸銀含浸シリカカラムに充
填されている硝酸銀含浸シリカ（前記（ａ）の硝酸銀含
浸微細孔シリカおよび／または前記（ｂ）の硝酸銀含浸
メソ細孔シリカ）の硝酸銀含浸量とは、カラム用容器に
充填されている当該硝酸銀含浸シリカの全量を対象に硝
酸銀含浸量を１回の操作で測定したときの値であって、
同一条件で別途作製した硝酸銀含浸シリカカラムからの
推測値を意味する。In the silver nitrate-impregnated silica column constituting the SFC column I of the present invention, the silver nitrate-impregnated silica (silver nitrate-impregnated microporous silica of the above (a) and / or (b)) packed in the column container is used. The silver nitrate impregnated amount of (silver nitrate-impregnated mesoporous silica) is preferably in the range of 0.1 to 5.0 wt%. Silver nitrate impregnation amount is 0.1wt
If it is less than%, it is likely that the saturated component and the olefin component are not separated. On the other hand, if the silver nitrate impregnation amount exceeds 5.0 wt%, the holding power of the olefin component is too strong and there is a high possibility that elution will not occur. The more preferable amount of silver nitrate impregnation is 0.1 to 1.0 wt.
It is within the range of%. The silver nitrate impregnated amount of the silver nitrate-impregnated silica (silver nitrate-impregnated microporous silica of (a) and / or silver nitrate-impregnated mesoporous silica of (b)) packed in the silver nitrate-impregnated silica column is the column container. The value when the silver nitrate impregnated amount is measured in one operation with respect to the total amount of the silver nitrate-impregnated silica filled in
It means an estimated value from a silver nitrate-impregnated silica column separately prepared under the same conditions.
【００１２】また、カラム用容器に充填されている硝酸
銀含浸シリカ（前記（ａ）の硝酸銀含浸微細孔シリカお
よび／または前記（ｂ）の硝酸銀含浸メソ細孔シリカ）
においては、硝酸銀が実質的に均一に含浸されているこ
とが望ましい。ここで、硝酸銀が実質的に均一に含浸さ
れているとは、含浸させたい硝酸銀の目標値と含浸され
た硝酸銀の実測値（２回以上測定したときの値）との差
が、目標値の１０％以内であることを意味する。Further, the silver nitrate-impregnated silica packed in the column container (silver nitrate-impregnated microporous silica of the above (a) and / or silver nitrate-impregnated mesoporous silica of the above (b)).
In, it is desirable that the silver nitrate is substantially uniformly impregnated. Here, the term “substantially uniformly impregnated with silver nitrate” means that the difference between the target value of the silver nitrate to be impregnated and the actually measured value of the impregnated silver nitrate (value when measured twice or more) It means within 10%.
【００１３】カラム用容器に充填する以前の段階での硝
酸銀含浸量が所望値で、かつ、硝酸銀が実質的に均一に
含浸されている硝酸銀含浸シリカ（前記（ａ）の硝酸銀
含浸微細孔シリカおよび／または前記（ｂ）の硝酸銀含
浸メソ細孔シリカ）は、例えば特開平４−３１９６６４
号公報に開示されている方法により得ることができる。
前記公報に開示されている方法は、所望量のシリカと当
該シリカの吸着水分量と実質的に同容量の溶媒（水、メ
タノール、エタノール、アセトニトリル、あるいはこれ
らの混合液）に所定量の硝酸銀を溶解させた溶液とを、
これらに超音波振動（周波数１０〜１００ｋＨｚ、高周
波出力３０〜１０００Ｗ）を与えつつ接触させて前記溶
液を前記シリカに含浸させた後、前記の溶媒を真空乾燥
等によって留去することにより硝酸銀含浸シリカを得る
ものである。A silver nitrate-impregnated silica (silver nitrate-impregnated microporous silica of the above (a) and a silver nitrate-impregnated silica which is impregnated with silver nitrate substantially uniformly at a desired value prior to filling into a column container) And / or (b) the silver nitrate-impregnated mesoporous silica) described in JP-A-4-319664.
It can be obtained by the method disclosed in the publication.
In the method disclosed in the above publication, a desired amount of silica and a solvent (water, methanol, ethanol, acetonitrile, or a mixture thereof) having substantially the same volume as the amount of adsorbed water of the silica are mixed with a predetermined amount of silver nitrate. The dissolved solution,
After contacting these with ultrasonic vibration (frequency 10 to 100 kHz, high frequency output 30 to 1000 W) to impregnate the silica with the solution, the solvent is removed by vacuum drying or the like to distill the silver nitrate impregnated silica. Is what you get.
【００１４】なお、硝酸銀含浸シリカ（前記（ａ）の硝
酸銀含浸微細孔シリカおよび／または前記（ｂ）の硝酸
銀含浸メソ細孔シリカ）をカラム用容器に充填する際の
溶媒としてクロロホルム（安定剤としてエタノールを含
有するもの）を使用すると、当該クロロホルムによって
前記硝酸銀含浸シリカから硝酸銀が溶出してしまう結
果、カラム用容器に充填した後での硝酸銀含浸量が目標
値より低下したり、硝酸銀が実質的に均一に含浸されて
いない状態になる。このような問題が生じることを防止
するうえから、上述した硝酸銀含浸シリカ（前記（ａ）
の硝酸銀含浸微細孔シリカおよび／または前記（ｂ）の
硝酸銀含浸メソ細孔シリカ）をカラム用容器に充填する
にあたっては、四塩化炭素を溶媒として用いることが好
ましい。Chloroform (as a stabilizer) was used as a solvent when the silver nitrate-impregnated silica (silver nitrate-impregnated microporous silica (a) and / or silver nitrate-impregnated mesopore silica (b)) was packed into the column container. (Containing ethanol), the silver nitrate is eluted from the silver nitrate-impregnated silica by the chloroform, so that the amount of silver nitrate impregnated after filling the column container drops below the target value, or the silver nitrate is substantially eliminated. Is not evenly impregnated. In order to prevent such problems from occurring, the above-mentioned silver nitrate-impregnated silica ((a) above) is used.
When filling the column container with the silver nitrate-impregnated microporous silica of (4) and / or the silver nitrate-impregnated mesoporous silica of (b)), carbon tetrachloride is preferably used as a solvent.
【００１５】本発明のＳＦＣ用カラムＩで使用する硝酸
銀含浸シリカカラムを得る際のカラム用容器としては、
目的に応じて種々の大きさのものを用いることができる
が、灯油や軽油のタイプ分析を行う場合は内径が１．０
〜２０．０ｍｍの範囲内、長さ（内寸）が１０．０〜５
０．０ｃｍの範囲のカラム用容器で実用上十分である。
硝酸銀含浸シリカ（前記（ａ）の硝酸銀含浸微細孔シリ
カおよび／または前記（ｂ）の硝酸銀含浸メソ細孔シリ
カ）をカラム用容器に充填するにあたっては、当該硝酸
銀含浸シリカの充填密度が０．３〜０．８の範囲内とな
るように適宜条件設定することが好ましい。硝酸銀含浸
シリカのより好ましい充填密度は０．４〜０．７５の範
囲内である。As a column container for obtaining the silver nitrate-impregnated silica column used in the SFC column I of the present invention,
Various sizes can be used according to the purpose, but the inner diameter is 1.0 when performing type analysis of kerosene or light oil.
Within the range of up to 20.0 mm, the length (inside dimension) is 10.0 to 5
A column container in the range of 0.0 cm is practically sufficient.
When the silver nitrate-impregnated silica (silver nitrate-impregnated microporous silica (a) and / or silver nitrate-impregnated mesoporous silica (b)) is packed in a column container, the packing density of the silver nitrate-impregnated silica is 0.3. It is preferable to appropriately set the conditions so that it falls within the range of 0.8. The more preferable packing density of the silver nitrate-impregnated silica is in the range of 0.4 to 0.75.
【００１６】本発明のＳＦＣ用カラムＩは、上述した硝
酸銀含浸シリカカラムに、平均細孔径が１０オングスト
ローム以上６０オングストローム未満の範囲内である微
細孔シリカをカラム用容器に充填してなる微細孔シリカ
カラムが直列に連結されているものである。ここで、微
細孔シリカカラムを構成する前記微細孔シリカの平均細
孔径を前述の範囲に限定する理由は、非芳香族分と芳香
族分との分離を良くするためである。微細孔シリカの好
ましい平均細孔径は、前述のように１０オングストロー
ム以上６０オングストローム未満の範囲内であることが
好ましく、２０〜４０オングストロームの範囲内である
ことがより好ましい。この微細孔シリカの形状は球状
（球形を含む）または破砕形状であることが好ましく、
その平均粒子径は３〜２００μｍの範囲内であることが
好ましい。微細孔シリカのより好ましい平均粒子径は３
〜１０μｍの範囲内である。The column I for SFC of the present invention is the above-mentioned silver nitrate-impregnated silica column filled with fine-pore silica having an average pore diameter in the range of 10 Å to less than 60 Å in a column container. The columns are connected in series. Here, the reason for limiting the average pore diameter of the fine pore silica constituting the fine pore silica column to the above range is to improve the separation of the non-aromatic component and the aromatic component. As described above, the preferable average pore diameter of the microporous silica is preferably in the range of 10 angstroms or more and less than 60 angstroms, and more preferably in the range of 20 to 40 angstroms. The shape of the microporous silica is preferably spherical (including spherical) or crushed,
The average particle diameter is preferably within the range of 3 to 200 μm. The more preferable average particle size of the microporous silica is 3
It is within the range of 10 μm.
【００１７】上記の微細孔シリカが充填されるカラム用
容器としては目的に応じて種々の大きさのものを用いる
ことができるが、灯油や軽油のタイプ分析を行う場合
は、内径が１．０〜２０．０ｍｍの範囲内、長さ（内
寸）が１０．０〜５０．０ｃｍの範囲のカラム用容器で
実用上十分である。このカラム用容器の形状と前述した
硝酸銀含浸シリカカラムのカラム用容器の形状とは同じ
であっても異なっていてもよい。上述した微細孔シリカ
カラムを前述した硝酸銀含浸シリカカラムと直列に連結
することで本発明のＳＦＣ用カラムＩが得られる。この
とき、微細孔シリカカラムと硝酸銀含浸シリカカラムと
は溶離液の流下方向に対してどちらを上流側に配置して
もよい。As the column container packed with the above-mentioned fine-pore silica, various sizes can be used according to the purpose, but when kerosene or light oil type analysis is carried out, the inner diameter is 1.0. A column container having a length (inside dimension) of 10.0 to 50.0 cm within a range of ˜20.0 mm is practically sufficient. The shape of this column container and the column container of the above-mentioned silver nitrate-impregnated silica column may be the same or different. The SFC column I of the present invention is obtained by connecting the above-mentioned fine-pore silica column in series with the above-mentioned silver nitrate-impregnated silica column. At this time, either the fine-pore silica column or the silver nitrate-impregnated silica column may be arranged on the upstream side with respect to the flow direction of the eluent.
【００１８】以上説明した本発明のＳＦＣ用カラムＩ
は、溶離液として超臨界状態の二酸化炭素を用いたＳＦ
Ｃにより灯油や軽油を飽和分、オレフィン分および芳香
族分に溶出分離するためのカラムとして好適である。The SFC column I of the present invention described above
Is an SF using supercritical carbon dioxide as an eluent.
It is suitable as a column for eluting and separating kerosene or light oil into saturated component, olefin component and aromatic component by C.
【００１９】次に、本発明のＳＦＣ用カラムの他の１つ
であるＳＦＣ用カラムIIについて説明する。このＳＦＣ
用カラムIIは、前述したように、平均細孔径が１０オン
グストローム以上６０オングストローム未満の範囲内で
ある微細孔シリカに硝酸銀を含浸させてなる硝酸銀含浸
微細孔シリカをカラム用容器に充填してなることを特徴
とするものである。ここで、前記の微細孔シリカは、球
状（球形を含む）または破砕形状を呈するとともにその
平均粒子径が３〜２００μｍの範囲内であるものが好ま
しい。このような微細孔シリカに硝酸銀を含浸させてな
る硝酸銀含浸微細孔シリカは、既に説明した本発明のＳ
ＦＣ用カラムＩの１構成材料である硝酸銀含浸微細孔シ
リカと実質的に同一のものである。Next, an SFC column II which is another one of the SFC columns of the present invention will be described. This SFC
As described above, the column II for use has a column container filled with silver nitrate-impregnated fine pore silica obtained by impregnating fine pore silica having an average pore diameter of 10 angstroms or more and less than 60 angstroms with silver nitrate. It is characterized by. Here, it is preferable that the microporous silica has a spherical shape (including a spherical shape) or a crushed shape and has an average particle diameter within a range of 3 to 200 μm. The silver nitrate-impregnated fine-pore silica obtained by impregnating such fine-pore silica with silver nitrate is the S of the present invention described above.
It is substantially the same as the silver nitrate-impregnated microporous silica which is one constituent material of the FC column I.
【００２０】ＳＦＣ用カラムIIの材料である微細孔シリ
カの平均細孔径を１０オングストローム以上６０オング
ストローム未満の範囲内に限定する理由は、既に説明し
た本発明のＳＦＣ用カラムＩの中で述べた理由と同じで
ある。微細孔シリカのより好ましい平均細孔径は２０〜
４０オングストロームの範囲内である。また、微細孔シ
リカの平均粒子径は前述のように３〜２００μｍの範囲
内であることが好ましく、３〜１０μｍの範囲内である
ことがより好ましい。The reason for limiting the average pore size of the microporous silica, which is the material for the SFC column II, to the range of 10 angstroms or more and less than 60 angstroms is the reason described above in the SFC column I of the present invention. Is the same as. The more preferable average pore diameter of the microporous silica is 20 to
It is in the range of 40 Å. The average particle size of the microporous silica is preferably in the range of 3 to 200 μm, and more preferably in the range of 3 to 10 μm as described above.
【００２１】ＳＦＣ用カラムIIにおいても、既に説明し
た本発明のＳＦＣ用カラムＩでの理由と同じ理由から、
カラム用容器に充填されている硝酸銀含浸微細孔シリカ
の硝酸銀含浸量は０．１〜５．０wt％の範囲内であるこ
とが好ましく、また、硝酸銀は実質的に均一に含浸され
ていることが好ましい。より好ましい硝酸銀含浸量は
０．１〜２．０wt％の範囲内がある。In the SFC column II as well, for the same reason as that of the SFC column I of the present invention described above,
The silver nitrate impregnated amount of the silver nitrate-impregnated microporous silica packed in the column container is preferably in the range of 0.1 to 5.0 wt%, and the silver nitrate is impregnated substantially uniformly. preferable. A more preferable silver nitrate impregnation amount is in the range of 0.1 to 2.0 wt%.
【００２２】ＳＦＣ用カラムIIを得る際のカラム用容器
としては目的に応じて種々の大きさのものを用いること
ができるが、灯油や軽油のタイプ分析を行う場合は内径
が１．０〜２０．０ｍｍの範囲内、長さ（内寸）が１
０．０〜５０．０ｃｍの範囲のカラム用容器で実用上十
分である。また、ＳＦＣ用カラムIIにおける硝酸銀含浸
微細孔シリカの充填密度は、既に説明した本発明のＳＦ
Ｃ用カラムＩでの理由と同じ理由から、０．３〜０．８
の範囲内であることが好ましい。より好ましい充填密度
は０．４〜０．７５の範囲内である。ＳＦＣ用カラムII
は、既に説明した本発明のＳＦＣ用カラムＩで使用する
硝酸銀含浸シリカカラムの製法に準じて製造することが
できる。As the column container for obtaining the SFC column II, various sizes can be used according to the purpose, but when kerosene or light oil type analysis is performed, the inner diameter is 1.0 to 20. Within the range of 0.0 mm, the length (inner dimension) is 1
A column container in the range of 0.0 to 50.0 cm is practically sufficient. In addition, the packing density of the silver nitrate-impregnated microporous silica in the SFC column II is the same as the SF of the present invention described above.
For the same reason as for the column I for C, 0.3 to 0.8
It is preferably within the range. A more preferable packing density is within the range of 0.4 to 0.75. SFC column II
Can be produced according to the method for producing the silver nitrate-impregnated silica column used in the SFC column I of the present invention described above.
【００２３】以上説明した本発明のＳＦＣ用カラムII
も、溶離液として超臨界状態の二酸化炭素を用いたＳＦ
Ｃにより灯油や軽油を飽和分、オレフィン分および芳香
族分に溶出分離するためのカラムとして好適である。The SFC column II of the present invention described above
SF using supercritical carbon dioxide as the eluent
It is suitable as a column for eluting and separating kerosene or light oil into saturated component, olefin component and aromatic component by C.
【００２４】本発明のＳＦＣ用カラムＩまたはＳＦＣ用
カラムIIを用いたＳＦＣにより灯油や軽油の成分分析を
行う場合、バックフラッシュを行わなくても目的とする
成分分析が可能であるので、バックフラッシュに必要な
機器（切替えバルブ等）は設けなくてもよい。また、カ
ラム温度は３０〜１１０℃の範囲内で適宜選択され、溶
離液（超臨界状態の二酸化炭素）の流量は５０〜４００
０μｌ／分の範囲内で適宜選択され、溶離液の圧力は１
００〜５００ｋｇ／ｃｍ2 の範囲内で適宜選択される。
カラムとして本発明のＳＦＣ用カラムを用い、溶離液と
して超臨界状態の二酸化炭素を用いたＳＦＣによれば、
灯油や軽油に含まれている飽和分、オレフィン分および
芳香族分をこの順に容易に溶出分離することができる。When the composition of kerosene or light oil is analyzed by SFC using the column I for SFC or the column II for SFC of the present invention, the target composition can be analyzed without backflushing. It is not necessary to provide the equipment (switching valve etc.) necessary for the above. The column temperature is appropriately selected within the range of 30 to 110 ° C., and the flow rate of the eluent (carbon dioxide in the supercritical state) is 50 to 400.
The pressure of the eluent is appropriately selected within the range of 0 μl / min.
It is appropriately selected within the range of 00 to 500 kg / cm 2 .
According to SFC using the column for SFC of the present invention as a column and carbon dioxide in a supercritical state as an eluent,
The saturated component, olefin component and aromatic component contained in kerosene or light oil can be easily eluted and separated in this order.
【００２５】[0025]
【実施例】以下、本発明の実施例について説明する。 実施例１ （１）ＳＦＣ用カラムＩの作製 まず、平均細孔径が１２０オングストロームである球形
（平均粒子径５μｍ）のメソ細孔シリカに硝酸銀を含浸
させてなる硝酸銀含浸メソ細孔シリカ１ｇ（硝酸銀含浸
量は０．２５wt％）と、内径２．１ｍｍ、長さ（内寸）
２０ｃｍのカラム用容器をそれぞれ用意した。次に、上
記の硝酸銀含浸メソ細孔シリカ１ｇに対して四塩化炭素
を１０ｍｌの割合で加え、これに超音波振動を付与して
スラリーとした。この後、前記のスラリーをカラムパッ
カーに入れ、溶媒（四塩化炭素）流量７ｍｌ／分、充填
開始から２０分後までの充填圧力３００ｋｇ／ｃｍ2 、
２０分経過後から３５分後までの充填圧力３２０ｋｇ／
ｃｍ2 の条件で前記のカラム用容器に注入して、硝酸銀
含浸メソ細孔シリカカラムを得た。このようにして得ら
れた硝酸銀含浸メソ細孔シリカカラムでは、カラム用容
器に充填されている硝酸銀含浸メソ細孔シリカの硝酸銀
含浸量は０．２５wt％であり、硝酸銀が実質的に均一に
含浸されていることが確認された。なお、硝酸銀含浸量
と、硝酸銀が実質的に均一に含浸されていることとは、
同一条件で別途作製した硝酸銀含浸メソ細孔シリカカラ
ムを用いて測定ないし確認した。Embodiments of the present invention will be described below. Example 1 (1) Preparation of SFC Column I First, 1 g of silver nitrate-impregnated mesopore silica (silver nitrate) obtained by impregnating spherical (average particle diameter 5 μm) mesopore silica having an average pore diameter of 120 Å with silver nitrate. Impregnation amount is 0.25wt%), inner diameter 2.1mm, length (inner dimension)
20 cm column containers were prepared. Next, carbon tetrachloride was added at a ratio of 10 ml to 1 g of the above-mentioned silver nitrate-impregnated mesoporous silica, and ultrasonic vibration was applied thereto to obtain a slurry. Then, the above slurry was put into a column packer, the solvent (carbon tetrachloride) flow rate was 7 ml / min, and the filling pressure was 300 kg / cm 2 from the beginning of filling to 20 minutes later.
Filling pressure from 20 minutes to 35 minutes 320kg /
It was injected into the column container under the condition of cm 2 to obtain a silver nitrate-impregnated mesoporous silica column. In the silver nitrate-impregnated mesoporous silica column thus obtained, the silver nitrate-impregnated amount of the silver nitrate-impregnated mesoporous silica packed in the column container was 0.25 wt%, and the silver nitrate was substantially uniformly impregnated. It was confirmed that it was done. The amount of silver nitrate impregnated and the fact that silver nitrate is impregnated substantially uniformly means
The measurement or confirmation was performed using a silver nitrate-impregnated mesoporous silica column separately prepared under the same conditions.
【００２６】また、微細孔シリカカラムとして、平均細
孔径が３０オングストロームである球形（平均粒子径５
μｍ）の微細孔シリカを内径２．０ｍｍ、長さ（内寸）
２５ｃｍのカラム用容器に充填した市販品（野村化学
（株）製のＤＥＶＥＬＯＳＩＬ３０−５）を用意した。
この後、前記の硝酸銀含浸メソ細孔シリカカラムと上記
の微細孔シリカカラムとを直列に連結して、目的とする
ＳＦＣ用カラムＩを得た。このＳＦＣ用カラムＩは、溶
離液の流下方向に対して硝酸銀含浸シリカカラムが上流
側、微細孔シリカカラムが下流側に位置するようにし
て、下記（２）で使用した。Further, as a fine-pore silica column, spherical particles having an average pore diameter of 30 Å (average particle diameter 5
(μm) microporous silica with an inner diameter of 2.0 mm and length (inner dimension)
A commercially available product (DEVELOSIL30-5 manufactured by Nomura Chemical Co., Ltd.) filled in a 25 cm column container was prepared.
Then, the silver nitrate-impregnated mesoporous silica column and the microporous silica column were connected in series to obtain a desired SFC column I. This SFC column I was used in the following (2) with the silver nitrate-impregnated silica column positioned upstream and the microporous silica column downstream with respect to the eluent flow direction.
【００２７】（２）ＳＦＣによる分解軽油の成分分析 カラムとして上記（１）のＳＦＣ用カラムＩを、溶離液
として超臨界状態の二酸化炭素を、検出器として水素炎
イオン化検出器（ＦＩＤ）をそれぞれ用いたＳＦＣによ
り、カラム温度３０℃、溶離液の流量３００μｌ／分、
溶離液の圧力２５０ｋｇ／ｃｍ2 の条件で分解軽油の成
分分析を行った。このときのＳＦＣの装置構成の概略を
図１に示す。(2) Component analysis of cracked gas oil by SFC The column I for SFC of the above (1) is used as a column, carbon dioxide in a supercritical state is used as an eluent, and a flame ionization detector (FID) is used as a detector. Depending on the SFC used, the column temperature was 30 ° C., the eluent flow rate was 300 μl / min,
The components of the cracked gas oil were analyzed under the condition that the pressure of the eluent was 250 kg / cm 2 . An outline of the SFC device configuration at this time is shown in FIG.
【００２８】同図に示した構成のＳＦＣでは、液化二酸
化炭素をガス精製器１で精製した後にポンプ２に導入
し、このポンプ２で圧縮して超臨界状態の二酸化炭素を
得る。ポンプ２で生成した超臨界状態の二酸化炭素は、
逆流防止弁３を介してインジェクター４に導入される。
超臨界状態の二酸化炭素の圧力状態は、ポンプ２と逆流
防止弁３とを結ぶ流路の途中に配設された圧力計５によ
り監視される。インジェクター４に導入された超臨界状
態の二酸化炭素は、ここで、当該インジェクター４に別
途導入された試料６と接触する。このとき、試料６は超
臨界状態の二酸化炭素中に溶解する。試料６が溶解した
超臨界状態の二酸化炭素はインジェクター４からＳＦＣ
用カラム７に所定流量および所定圧力の下に注入され、
ＳＦＣ用カラム７で分離されて、飽和分、オレフィン
分、および芳香族分の順で溶出する。溶出液のうちの一
部はＦＩＤ８に導入され、ここで成分の定量が行われ
る。なお、ＳＦＣ用カラム７とＦＩＤ８とは共にカラム
恒温槽９内に設けられており、ＳＦＣ用カラム７の温度
は所定温度に維持される。また、ＦＩＤ８はキャピラリ
ーになっており、このＦＩＤ８に導入された溶出液中の
超臨界状態の二酸化炭素は当該ＦＩＤ８を経由してカラ
ム恒温槽９の外部へ出た後、大気中に解放される。ＦＩ
Ｄ８に導入されない分の溶出液はカラム恒温槽９を出、
ＵＶ検出器１０を経て圧力制御器１１へ導入される。こ
の圧力制御器１１に設けられてるバルブ（図示せず）に
より、ＳＦＣ系内の圧力が制御されている。In the SFC having the configuration shown in the figure, liquefied carbon dioxide is purified by the gas purifier 1, then introduced into the pump 2, and compressed by the pump 2 to obtain carbon dioxide in a supercritical state. The carbon dioxide in the supercritical state generated by the pump 2 is
It is introduced into the injector 4 via the check valve 3.
The pressure state of carbon dioxide in the supercritical state is monitored by a pressure gauge 5 arranged in the middle of the flow path connecting the pump 2 and the check valve 3. The carbon dioxide in the supercritical state introduced into the injector 4 here comes into contact with the sample 6 separately introduced into the injector 4. At this time, the sample 6 is dissolved in carbon dioxide in the supercritical state. The carbon dioxide in the supercritical state in which the sample 6 is dissolved is discharged from the injector 4 into the SFC.
Is injected into the column 7 for a predetermined flow rate and a predetermined pressure,
It is separated in the SFC column 7 and is eluted in the order of saturated content, olefin content, and aromatic content. A part of the eluate is introduced into FID8, where the components are quantified. Both the SFC column 7 and the FID 8 are provided in the column constant temperature bath 9, and the temperature of the SFC column 7 is maintained at a predetermined temperature. Further, the FID 8 is a capillary, and the carbon dioxide in the eluate introduced into the FID 8 in the supercritical state is released to the atmosphere after flowing out of the column constant temperature bath 9 via the FID 8. . FI
The eluate that was not introduced into D8 exits the column thermostat 9,
It is introduced into the pressure controller 11 via the UV detector 10. The pressure in the SFC system is controlled by a valve (not shown) provided in the pressure controller 11.
【００２９】上記のＳＦＣによる成分分析の結果、分解
軽油中の飽和分は２１．３質量％、オレフィン分は３．
４質量％、芳香族分は７５．３質量％であり、三者が明
確に分離された。このときのクロマトグラムを図２に示
す。As a result of the above component analysis by SFC, the saturated content in the cracked gas oil was 21.3% by mass and the olefin content was 3.
4% by mass and aromatic content was 75.3% by mass, and the three were clearly separated. The chromatogram at this time is shown in FIG.
【００３０】実施例２ （１）ＳＦＣ用カラムＩの作製 まず、平均細孔径が３０オングストロームである球形
（平均粒子径５μｍ）の微細孔シリカに硝酸銀を含浸さ
せてなる硝酸銀含浸微細孔シリカ１ｇ（硝酸銀の含浸量
は０．１９wt％）と、内径２．１ｍｍ、長さ（内寸）２
０ｃｍのカラム用容器をそれぞれ用意した。次に、上記
の硝酸銀含浸微細孔シリカ１ｇに対して四塩化炭素を１
０ｍｌの割合で加え、これに超音波振動を付与してスラ
リーとした。この後、前記のスラリーをカラムパッカー
に入れ、溶媒（四塩化炭素）流量７ｍｌ／分、充填開始
から２０分後までの充填圧力３００ｋｇ／ｃｍ2 、２０
分経過後から３５分後までの充填圧力３２０ｋｇ／ｃｍ
2 の条件で前記のカラム用容器に注入して、硝酸銀含浸
微細孔シリカカラムを得た。このようにして得られた硝
酸銀含浸微細孔シリカカラムでは、カラム用容器に充填
されている硝酸銀含浸微細孔シリカの硝酸銀含浸量は
０．１９wt％であり、硝酸銀が実質的に均一に含浸され
ていることが確認された。なお、硝酸銀含浸量と、硝酸
銀が実質的に均一に含浸されていることとは、同一条件
で別途作製した硝酸銀含浸微細孔シリカカラムを用いて
測定ないし確認した。Example 2 (1) Preparation of Column I for SFC First, 1 g of silver nitrate-impregnated microporous silica obtained by impregnating spherical nitrate (average particle diameter 5 μm) fine pore silica with an average pore diameter of 30 Å with silver nitrate. Impregnation amount of silver nitrate is 0.19wt%), inner diameter 2.1mm, length (inner dimension) 2
A 0 cm column container was prepared. Next, 1 g of carbon tetrachloride was added to 1 g of the above-mentioned silver nitrate-impregnated microporous silica.
It was added at a rate of 0 ml, and ultrasonic vibration was applied to this to obtain a slurry. Then, the above slurry was put into a column packer, the solvent (carbon tetrachloride) flow rate was 7 ml / min, and the filling pressure from the start of filling to 20 minutes later was 300 kg / cm 2 , 20
320kg / cm filling pressure from 35 minutes to 35 minutes
It was injected into the column container under the condition of 2 to obtain a silver nitrate-impregnated microporous silica column. In the thus obtained silver nitrate-impregnated microporous silica column, the silver nitrate-impregnated amount of the silver nitrate-impregnated microporous silica packed in the column container was 0.19 wt%, and the silver nitrate was impregnated substantially uniformly. Was confirmed. The amount of silver nitrate impregnation and the fact that silver nitrate was substantially uniformly impregnated were measured or confirmed by using a separately prepared silver nitrate-impregnated microporous silica column.
【００３１】また、微細孔シリカカラムとして、平均細
孔径が３０オングストロームである球形（平均粒子径５
μｍ）の微細孔シリカを内径２．０ｍｍ、長さ（内寸）
２５ｃｍのカラム用容器に充填した市販品（野村化学
（株）製のＤＥＶＥＬＯＳＩＬ３０−５）を用意した。
この後、前記の硝酸銀含浸微細孔シリカカラムと上記の
微細孔シリカカラムとを直列に連結して、目的とするＳ
ＦＣ用カラムＩを得た。このＳＦＣ用カラムＩは、溶離
液の流下方向に対して硝酸銀含浸微細孔シリカカラムが
上流側、微細孔シリカカラムが下流側に位置するように
して、下記（２）で使用した。Further, as a fine pore silica column, a spherical shape having an average pore diameter of 30 Å (average particle diameter 5
(μm) microporous silica with an inner diameter of 2.0 mm and length (inner dimension)
A commercially available product (DEVELOSIL30-5 manufactured by Nomura Chemical Co., Ltd.) filled in a 25 cm column container was prepared.
After that, the silver nitrate-impregnated microporous silica column and the microporous silica column are connected in series to obtain the desired S
FC column I was obtained. This SFC column I was used in the following (2) with the silver nitrate-impregnated microporous silica column positioned upstream and the microporous silica column downstream with respect to the eluent flow direction.
【００３２】（２）ＳＦＣによる軽油の成分分析 カラムとして上記（１）のＳＦＣ用カラムＩを、溶離液
として超臨界状態の二酸化炭素を、検出器としてＦＩＤ
をそれぞれ用いたＳＦＣにより、カラム温度４０℃、溶
離液の流量３００μｌ／分、溶離液の圧力２５０ｋｇ／
ｃｍ2 の条件で分解軽油の成分分析を行った。このと
き、分解軽油は実施例１で用いたものと同質のものを用
い、ＳＦＣの装置構成はカラムを除いて実施例１でのＳ
ＦＣと同一とした。上記の成分分析の結果、分解軽油中
の飽和分は２１．１質量％、オレフィン分は３．１質量
％、芳香族分は７５．８質量％であり、三者が明確に分
離された。このときのクロマトグラムを図３に示す。(2) Component analysis of gas oil by SFC The column I for SFC of (1) above is used as a column, carbon dioxide in a supercritical state is used as an eluent, and FID is used as a detector.
Column temperature of 40 ° C., eluent flow rate 300 μl / min, eluent pressure 250 kg /
The components of cracked gas oil were analyzed under the condition of cm 2 . At this time, the same cracked gas oil as that used in Example 1 was used, and the SFC apparatus configuration was the same as that in Example 1 except for the column.
Same as FC. As a result of the above component analysis, the saturated content in the cracked gas oil was 21.1 mass%, the olefin content was 3.1 mass%, and the aromatic content was 75.8 mass%, and the three were clearly separated. The chromatogram at this time is shown in FIG.
【００３３】実施例３ （１）ＳＦＣ用カラムIIの作製 まず、平均細孔径が３０オングストロームである球形
（平均粒子径５μｍ）の微細孔シリカに硝酸銀を含浸さ
せてなる硝酸銀含浸微細孔シリカ２ｇ（硝酸銀の含浸量
は０．１０wt％）と、内径２．１ｍｍ、長さ（内寸）４
０ｃｍのカラム用容器をそれぞれれ用意した。次に、上
記の硝酸銀含浸微細孔シリカ１ｇに対して四塩化炭素を
１０ｍｌの割合で加え、これに超音波振動を付与してス
ラリーとした後、このスラリーをカラムパッカーに入
れ、溶媒（四塩化炭素）流量７ｍｌ／分、充填開始から
２０分後までの充填圧力３００ｋｇ／ｃｍ2 、２０分経
過後から３５分後までの充填圧力３２０ｋｇ／ｃｍ2 の
条件で前記のカラム用容器に注入して、目的とするＳＦ
Ｃ用カラムIIを得た。このようにして得られたＳＦＣ用
カラムIIでは、カラム用容器に充填されている硝酸銀含
浸微細孔シリカの硝酸銀含浸量は０．１０wt％であり、
硝酸銀が実質的に均一に含浸されていることが確認され
た。なお、硝酸銀含浸量と、硝酸銀が実質的に均一に含
浸されていることとは、同一条件で別途作製したＳＦＣ
用カラムIIを用いて測定ないし確認した。Example 3 (1) Preparation of SFC Column II First, 2 g of silver nitrate-impregnated fine-pore silica obtained by impregnating spherical nitrate (average particle diameter 5 μm) fine-pore silica having an average pore diameter of 30 Å with silver nitrate ( Impregnation amount of silver nitrate is 0.10wt%), inner diameter 2.1mm, length (inner dimension) 4
Each 0 cm column container was prepared. Next, carbon tetrachloride was added at a ratio of 10 ml to 1 g of the above-described fine pore silica impregnated with silver nitrate, and ultrasonic vibration was applied to this to make a slurry, and this slurry was put in a column packer and a solvent (tetrachloride Carbon) flow rate of 7 ml / min, filling pressure of 300 kg / cm 2 from 20 minutes after the start of filling, and 320 kg / cm 2 of filling pressure from 20 minutes to 35 minutes after injection into the column container. , The target SF
A column II for C was obtained. In the SFC column II thus obtained, the silver nitrate impregnation amount of the silver nitrate-impregnated microporous silica packed in the column container was 0.10 wt%,
It was confirmed that the silver nitrate was substantially uniformly impregnated. In addition, the amount of silver nitrate impregnated and the fact that silver nitrate is substantially uniformly impregnated means that the SFC prepared separately under the same conditions.
The column II was used for measurement or confirmation.
【００３４】（２）ＳＦＣによる軽油の成分分析 カラムとして上記（１）のＳＦＣ用カラムIIを、溶離液
として超臨界状態の二酸化炭素を、検出器としてＦＩＤ
をそれぞれ用いたＳＦＣにより、カラム温度４０℃、溶
離液の流量３００μｌ／分、溶離液の圧力２５０ｋｇ／
ｃｍ2 の条件で分解軽油の成分分析を行った。このと
き、分解軽油は実施例１で用いたものと同質のものを用
い、ＳＦＣの装置構成はカラムを除いて実施例１でのＳ
ＦＣと同一とした。上記の成分分析の結果、分解軽油中
のパラフィン炭化水素分は２０．９質量％、オレフィン
炭化水素分は３．２質量％、芳香族分は７５．９質量％
であり、三者が明確に分離されていた。このときのクロ
マトグラムを図４に示す。(2) Component analysis of gas oil by SFC The column II for SFC of the above (1) is used as a column, carbon dioxide in a supercritical state as an eluent, and FID as a detector.
Column temperature of 40 ° C., eluent flow rate 300 μl / min, eluent pressure 250 kg /
The components of cracked gas oil were analyzed under the condition of cm 2 . At this time, the same cracked gas oil as that used in Example 1 was used, and the SFC apparatus configuration was the same as that in Example 1 except for the column.
Same as FC. As a result of the above component analysis, the paraffin hydrocarbon content in the cracked gas oil was 20.9 mass%, the olefin hydrocarbon content was 3.2 mass%, and the aromatic content was 75.9 mass%.
And the three were clearly separated. The chromatogram at this time is shown in FIG.
【００３５】比較例１ まず、平均細孔径が９０オングストロームである球形
（平均粒子径５μｍ）のメソ細孔シリカを内径１．７ｍ
ｍ、長さ（内寸）２５ｃｍのカラム用容器に充填した市
販品のシリカカラム（日本電子モーレ（株）製のＳＦＰ
ＡＫ−ＳＩ０５−Ｓ２５）を用意した。次に、カラムと
して上記のシリカカラムを、溶離液として超臨界状態の
二酸化炭素を、検出器としてＦＩＤをそれぞれ用いたＳ
ＦＣにより、カラム温度３０℃、溶離液の流量３００μ
ｌ／分、溶離液の圧力２５０ｋｇ／ｃｍ2 の条件で分解
軽油の成分分析を行った。このとき、分解軽油は実施例
１で用いたものと同質のものを用い、ＳＦＣの装置構成
はカラムを除いて実施例１でのＳＦＣと同一とした。上
記のＳＦＣでは分解軽油中の飽和分とオレフィン分とを
分離することができず、分解軽油中の非芳香族分が２
４．５質量％、芳香族分が７５．５質量％という結果が
得られた。非芳香族分は飽和分とオレフィン分に分離さ
れなかった。このときのクロマトグラムを図５に示す。Comparative Example 1 First, a spherical (average particle diameter of 5 μm) mesopore silica having an average pore diameter of 90 angstrom was used to measure 1.7 m in inner diameter.
A commercially available silica column packed in a column container having a length of 25 m (inside dimension) (SFP manufactured by JEOL Ltd.)
AK-SI05-S25) was prepared. Next, S using the above silica column as a column, carbon dioxide in a supercritical state as an eluent, and FID as a detector, respectively.
By FC, column temperature 30 ℃, eluent flow rate 300μ
The components of the cracked gas oil were analyzed under the conditions of 1 / min and the eluent pressure of 250 kg / cm 2 . At this time, the same cracked gas oil as that used in Example 1 was used, and the apparatus configuration of SFC was the same as that of Example 1 except for the column. In the above SFC, the saturated component and the olefin component in the cracked gas oil cannot be separated, and the non-aromatic component in the cracked gas oil is 2%.
The result was 4.5 mass% and aromatic content was 75.5 mass%. The non-aromatic component was not separated into a saturated component and an olefin component. The chromatogram at this time is shown in FIG.
【００３６】[0036]
【発明の効果】以上説明したように、本発明の超臨界流
体クロマトグラフィー用カラムを用いれば、灯油や軽油
に含まれているパラフィン炭化水素分、オレフィン炭化
水素分および芳香族分を超臨界流体クロマトグラフィー
によって容易に溶出分離することができる。したがっ
て、本発明によれば灯油や軽油についてのより正確なタ
イプ分析値を得ることが可能になる。As described above, when the column for supercritical fluid chromatography of the present invention is used, the paraffin hydrocarbon content, olefin hydrocarbon content and aromatic content contained in kerosene and light oil are supercritical fluids. It can be easily eluted and separated by chromatography. Therefore, according to the present invention, it becomes possible to obtain a more accurate type analysis value for kerosene or light oil.
【図１】実施例で利用したＳＦＣの装置構成の概略図で
ある。FIG. 1 is a schematic diagram of a device configuration of an SFC used in an example.
【図２】実施例１で行ったＳＦＣのクロマトグラムであ
る。FIG. 2 is a chromatogram of SFC performed in Example 1.
【図３】実施例２で行ったＳＦＣのクロマトグラムであ
る。FIG. 3 is a chromatogram of SFC performed in Example 2.
【図４】実施例３で行ったＳＦＣのクロマトグラムであ
る。FIG. 4 is a chromatogram of SFC performed in Example 3.
【図５】比較例１で行ったＳＦＣのクロマトグラムであ
る。5 is a chromatogram of SFC performed in Comparative Example 1. FIG.
４…インジェクター、 ６…試料、 ７…超臨界クロマ
トグラフィー用カラム、８…水素炎イオン化検出器、
９…カラム恒温槽。4 ... Injector, 6 ... Sample, 7 ... Supercritical chromatography column, 8 ... Hydrogen flame ionization detector,
9 ... Column constant temperature bath.
Claims (10)
してなる硝酸銀含浸シリカカラムと、平均細孔径が１０
オングストローム以上６０オングストローム未満の範囲
内である微細孔シリカをカラム用容器に充填してなる微
細孔シリカカラムとを備え、前記硝酸銀含浸シリカカラ
ムと前記微細孔シリカカラムとが直列に連結されている
ことを特徴とする超臨界流体クロマトグラフィー用カラ
ム。1. A silver nitrate-impregnated silica column obtained by filling a column container with silver nitrate-impregnated silica, and an average pore diameter of 10
A fine pore silica column in which a column container is filled with fine pore silica having a range of angstrom or more and less than 60 angstrom, and the silver nitrate-impregnated silica column and the micropore silica column are connected in series. A column for supercritical fluid chromatography characterized by:
オングストローム以上６０オングストローム未満の範囲
内である微細孔シリカに硝酸銀を含浸させてなる硝酸銀
含浸微細孔シリカであり、かつ、硝酸銀含浸前の前記微
細孔シリカが球状または破砕形状を呈するとともに該微
細孔シリカの平均粒子径が３〜２００μｍの範囲内であ
る、請求項１に記載の超臨界流体クロマトグラフィー用
カラム。2. The silver nitrate-impregnated silica has an average pore diameter of 10
A silver nitrate-impregnated fine-pore silica obtained by impregnating fine-pore silica in the range of angstrom or more and less than 60 angstrom with silver nitrate, wherein the fine-pore silica before impregnation with silver nitrate has a spherical or crushed shape. The column for supercritical fluid chromatography according to claim 1, wherein the average particle size of is in the range of 3 to 200 μm.
〜３００オングストロームの範囲内であるメソ細孔シリ
カに硝酸銀を含浸させてなる硝酸銀含浸メソ細孔シリカ
であり、かつ、硝酸銀含浸前の前記メソ細孔シリカが球
状または破砕形状を呈するとともに該メソ細孔シリカの
平均粒子径が３〜２００μｍの範囲内である、請求項１
に記載の超臨界流体クロマトグラフィー用カラム。3. The silver nitrate-impregnated silica has an average pore diameter of 60.
To 300 angstroms, the silver nitrate-impregnated mesopore silica obtained by impregnating the mesopore silica with silver nitrate, wherein the mesopore silica before impregnation with silver nitrate has a spherical or crushed shape and The average particle diameter of the porous silica is within the range of 3 to 200 μm.
The column for supercritical fluid chromatography according to item 1.
る硝酸銀含浸シリカの硝酸銀含浸量が０．１〜５．０wt
％の範囲内である、請求項１〜請求項３のいずれか一項
に記載の超臨界流体クロマトグラフィー用カラム。4. The silver nitrate impregnated amount of the silver nitrate impregnated silica packed in the silver nitrate impregnated silica column is 0.1 to 5.0 wt.
The column for supercritical fluid chromatography according to any one of claims 1 to 3, which is in the range of%.
細孔シリカが球状または破砕形状を呈し、かつ、該微細
孔シリカの平均粒子径が３〜２００μｍの範囲内であ
る、請求項１〜請求項４のいずれか一項に記載の超臨界
流体クロマトグラフィー用カラム。5. The microporous silica packed in the microporous silica column has a spherical or crushed shape, and the average particle size of the microporous silica is in the range of 3 to 200 μm. Item 5. The column for supercritical fluid chromatography according to any one of items 4.
６０オングストローム未満の範囲内である微細孔シリカ
に硝酸銀を含浸させてなる硝酸銀含浸微細孔シリカをカ
ラム用容器に充填してなることを特徴とする超臨界流体
クロマトグラフィー用カラム。6. A column container is filled with silver nitrate-impregnated fine pore silica obtained by impregnating fine pore silica having an average pore diameter of 10 angstroms or more and less than 60 angstroms with silver nitrate. Columns for critical fluid chromatography.
し、かつ、該微細孔シリカの平均粒子径が３〜２００μ
ｍの範囲内である、請求項６に記載の超臨界流体クロマ
トグラフィー用カラム。7. The microporous silica has a spherical or crushed shape, and the average particle size of the microporous silica is 3 to 200 μm.
The column for supercritical fluid chromatography according to claim 6, which is in the range of m.
浸微細孔シリカの硝酸銀含浸量が０．１〜５．０wt％の
範囲内である、請求項６または請求項７に記載の超臨界
流体クロマトグラフィー用カラム。8. The supercritical fluid according to claim 6, wherein the silver nitrate-impregnated microporous silica packed in the column container has a silver nitrate impregnation amount in the range of 0.1 to 5.0 wt%. Chromatography column.
載の超臨界流体クロマトグラフィー用カラムを用いた超
臨界流体クロマトグラフィーにより、灯油または軽油に
含まれている芳香族分、飽和分およびオレフィン分を分
離定量することを特徴とする、灯油または軽油のタイプ
分析方法。9. A supercritical fluid chromatography using the column for supercritical fluid chromatography according to claim 1, wherein aromatic components contained in kerosene or gas oil are saturated. And kerosene or gas oil type analysis method, characterized by separating and quantifying water content and olefin content.
を用いる、請求項９に記載の方法。10. The method according to claim 9, wherein carbon dioxide in a supercritical state is used as an eluent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6135265A JPH085622A (en) | 1994-06-17 | 1994-06-17 | Column for supercritical liquid chromatography |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6135265A JPH085622A (en) | 1994-06-17 | 1994-06-17 | Column for supercritical liquid chromatography |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH085622A true JPH085622A (en) | 1996-01-12 |
Family
ID=15147666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6135265A Pending JPH085622A (en) | 1994-06-17 | 1994-06-17 | Column for supercritical liquid chromatography |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH085622A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5689058A (en) * | 1979-12-21 | 1981-07-20 | Toyo Soda Mfg Co Ltd | Method for analyzing hydrocarbon compound |
| JPH04319664A (en) * | 1991-04-18 | 1992-11-10 | Idemitsu Kosan Co Ltd | Preparation of metal component impregnated porous substance |
| JPH05223799A (en) * | 1990-03-02 | 1993-08-31 | Exxon Res & Eng Co | Quantitative analysis method of saturated compound, olefin and aromatic hydrocarbon component |
-
1994
- 1994-06-17 JP JP6135265A patent/JPH085622A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5689058A (en) * | 1979-12-21 | 1981-07-20 | Toyo Soda Mfg Co Ltd | Method for analyzing hydrocarbon compound |
| JPH05223799A (en) * | 1990-03-02 | 1993-08-31 | Exxon Res & Eng Co | Quantitative analysis method of saturated compound, olefin and aromatic hydrocarbon component |
| JPH04319664A (en) * | 1991-04-18 | 1992-11-10 | Idemitsu Kosan Co Ltd | Preparation of metal component impregnated porous substance |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Teo et al. | Adsorption of water from aqueous ethanol using 3-. ANG. molecular sieves | |
| Kirkland | High-performance liquid chromatography with porous silica microspheres | |
| Subra et al. | Breakthrough curves and adsorption isotherms of terpene mixtures in supercritical carbon dioxide | |
| Bruner et al. | Role of the liquid phase in gas-liquid-solid chromatography and its influence of column performance. Experimental approach | |
| Lundanes et al. | Group separation of oil residues by supercritical fluid chromatography | |
| Trones et al. | High temperature liquid chromatography on packed capillary columns with nonaqueous mobile phases | |
| Dewaele et al. | Influence of the particle size distribution of the packing material in reversed-phase high-performance liquid chromatography | |
| Perrut | Advances in supercritical fluid chromatographic processes | |
| Parcher et al. | High-pressure adsorption of carbon dioxide on super-critical-fluid chromatography adsorbents | |
| US4298472A (en) | Process for manufacturing impregnated silicas and the use of these silicas for analysis or purification of industrial products | |
| Reverchon | Supercritical desorption of limonene and linalool from silica gel: experiments and modelling | |
| JPH085622A (en) | Column for supercritical liquid chromatography | |
| Frederick et al. | The Use of Lightly Loaded Columns in Gas Chromatography. | |
| Strode III et al. | Evaporative light scattering detection for supercritical fluid chromatography | |
| Parcher et al. | Cooperative and competitive adsorption of propane and butane on graphitized carbon black | |
| Reverchon et al. | Supercritical desorption of bergamot peel oil from silica gel—Experiments and mathematical modelling | |
| Moskvin et al. | Analytical application of liquid-gas and liquid-gas-solid chromatography | |
| Schoenmakers et al. | Supercritical-fluid chromatography—prospects and problems | |
| Huddersman et al. | Separation of hexane isomers on zeolites mordenite and beta | |
| Schaeffer et al. | Modelling of the supercritical fluid extraction of monocrotaline from Crotalaria spectabilis | |
| Huber et al. | Solvent generated liquid-liquid chromatography with nonaqueous ternary systems | |
| Berezkin | Capillary gas-solid chromatography | |
| Janssen et al. | Packed columns in SFC: mobile and stationary phases and further requirements | |
| Subra et al. | Retention of some components in supercritical fluid chromatography and application to bergamot peel oil fractionation | |
| Yonker et al. | Sorption isotherms in supercritical fluid chromatography |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 19980203 |