JPH0680594A - Method for removing heavy metal - Google Patents
Method for removing heavy metalInfo
- Publication number
- JPH0680594A JPH0680594A JP23568492A JP23568492A JPH0680594A JP H0680594 A JPH0680594 A JP H0680594A JP 23568492 A JP23568492 A JP 23568492A JP 23568492 A JP23568492 A JP 23568492A JP H0680594 A JPH0680594 A JP H0680594A
- Authority
- JP
- Japan
- Prior art keywords
- silica gel
- alcohol
- modified silica
- heavy metals
- group
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、製薬用，消毒用，電子
工学用アルコールに含まれる重金属の吸着除去方法、特
に基板等の電子工学部品洗浄用としてのイソプロピルア
ルコールに含まれる鉄，銅等の重金属吸着除去方法に関
する。FIELD OF THE INVENTION The present invention relates to a method for adsorbing and removing heavy metals contained in alcohol for pharmaceuticals, disinfection, and electronics, especially iron and copper contained in isopropyl alcohol for cleaning electronic parts such as substrates. The present invention relates to a method for removing and adsorbing heavy metals.
【０００２】[0002]
【従来の技術】従来、有機溶媒に含まれる重金属の除去
には、重金属用キレート樹脂、若しくはイオン交換樹脂
を用いる方法や蒸留法が知られている。しかしながら、
上記重金属除去用のキレート樹脂、又はイオン交換樹脂
は有機高分子であるため、アルコールに対して膨潤が激
しく、またリサイクルを行うための再生に手間と時間を
要する。また蒸留法を用いる場合は熱エネルギーコスト
の面で経済的に問題であり、また蒸留中のミスト等で電
子工学用のレベルまで重金属を除去するのは困難であ
る。2. Description of the Related Art Conventionally, for removing heavy metals contained in organic solvents, a method using a chelating resin for heavy metals or an ion exchange resin and a distillation method are known. However,
Since the chelate resin for removing heavy metals or the ion exchange resin is an organic polymer, it swells sharply in alcohol, and it takes time and time to regenerate it for recycling. Further, when the distillation method is used, it is economically problematic in terms of heat energy cost, and it is difficult to remove heavy metals to a level for electronics by a mist during distillation.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、上記
のような問題点が無く容易にしかも効率良く重金属濃度
の低いアルコールを得る方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for obtaining an alcohol having a low heavy metal concentration easily and efficiently without the above-mentioned problems.
【０００４】[0004]
【課題を解決するための手段】本発明はすなわち、重金
属を含むアルコールに、化学修飾を施したシリカゲルよ
りなる吸着剤を接触させることを特徴とするアルコール
中の重金属除去方法である。SUMMARY OF THE INVENTION The present invention is a method for removing heavy metals in alcohol, which comprises contacting an alcohol containing heavy metals with an adsorbent composed of chemically modified silica gel.
【０００５】本発明に用いられる吸着剤は、工学用ある
いは試薬用のアルコールと接触させることにより、アル
コール中の鉄，銅等の重金属を吸着することが可能な物
質であって、具体的にはオクタデシル基修飾型シリカゲ
ル，オクチル基修飾型シリカゲル，アミノプロピル基修
飾型シリカゲル，モルフォリノプロピル基修飾型シリカ
ゲル，ピペラジノプロピル基修飾型シリカゲル，ピペリ
ジノ基修飾型シリカゲル等が好ましい。The adsorbent used in the present invention is a substance capable of adsorbing heavy metals such as iron and copper in alcohol by contacting with alcohol for engineering or reagents. Octadecyl group-modified silica gel, octyl group-modified silica gel, aminopropyl group-modified silica gel, morpholinopropyl group-modified silica gel, piperazinopropyl group-modified silica gel, piperidino group-modified silica gel and the like are preferable.
【０００６】上記の吸着剤は、それぞれ公知の方法によ
って（例えば特開昭５５−１１６２５２号公報，特開昭
５５−１１６２５３号公報，特開平３−９９２５９号公
報参照）調整することができる。例えば細孔径６〜３０
μｍ，細孔容積０．８〜１．２ｍｌ／ｇのシリカゲル担
体表面のシラノール基を、トルエン溶液中でシランカッ
プリング剤を用い、ピリジン存在下脱塩酸反応もしくは
無触媒での脱アルコール反応によってオクタデシル基，
オクチル基，アミノプロピル基，モルフォリノプロピル
基，ピペラジノプロピル基，ピペリジノ基等で置換す
る。The above adsorbents can be prepared by known methods (see, for example, JP-A-55-116252, JP-A-55-116253, and JP-A-3-99259). For example, pore size 6 to 30
The silanol groups on the surface of a silica gel carrier having a pore size of 0.8 μm / g and a pore volume of 0.8-1.2 ml / g were octadecyl-dehydrochlorinated in the presence of pyridine using a silane coupling agent in the presence of pyridine or without a catalyst. Basis,
Substitute with an octyl group, aminopropyl group, morpholinopropyl group, piperazinopropyl group, piperidino group, etc.
【０００７】上記シランカップリング剤としては、オク
タデシルジメチルクロルシラン，オクタデシルジメチル
メトキシシラン，オクタデシルジクロルメチルシラン，
オクタデシルジメトキシメチルシラン，オクタデシルト
リクロルシラン，オクタデシルトリメトキシシラン，ジ
メチルオクチルクロルシラン，オクチルメチルジクロロ
シラン，３−アミノプロピルジメチルエトキシシラン，
３−アミノプロピルメチルジエトキシシラン，３−アミ
ノプロピルトリエトキシシラン，３−モルフォリノプロ
ピルトリメトキシシラン，３−モルフォリノプロピルト
リエトキシシラン，３−ピペラジノプロピルトリメトキ
シシラン，３−ピペラジノプロピルトリエトキシシラ
ン，３−ピペリジノプロピルトリメトキシシラン，３−
ピペリジノプロピルトリエトキシシラン等が好ましく用
いられる。Examples of the silane coupling agent include octadecyldimethylchlorosilane, octadecyldimethylmethoxysilane, octadecyldichloromethylsilane,
Octadecyldimethoxymethylsilane, octadecyltrichlorosilane, octadecyltrimethoxysilane, dimethyloctylchlorosilane, octylmethyldichlorosilane, 3-aminopropyldimethylethoxysilane,
3-aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, 3-morpholinopropyltrimethoxysilane, 3-morpholinopropyltriethoxysilane, 3-piperazinopropyltrimethoxysilane, 3-piperazino Propyltriethoxysilane, 3-piperidinopropyltrimethoxysilane, 3-
Piperidinopropyltriethoxysilane and the like are preferably used.
【０００８】これら修飾基の修飾率は、上記シランカッ
プリング剤の使用量により行うことができる。本発明に
用いられる吸着剤として、より有効な修飾率は０．１〜
２．５μｍｏｌ／ｍ2 であり、さらに好ましくは１．０
〜２．５μｍｏｌ／ｍ2 である。本発明で用いる修飾率
は次式により定義される。 修飾率（μｍｏｌ／ｍ2 ）＝Ｃ×１０6 ／Ｍ×Ｓ×１０
2 （但し、Ｃは修飾シリカ担体中の炭素含有率（重量
％），Ｍはシランカップリング剤１モル中の炭素含有量
（１モル中の炭素数×１２），Ｓはシリカ担体の窒素吸
着法による表面積（ｍ2 ／ｇ）を示す）。The modification ratio of these modifying groups can be determined by the amount of the silane coupling agent used. A more effective modification rate of the adsorbent used in the present invention is 0.1 to 0.1%.
2.5 μmol / m 2 , more preferably 1.0
˜2.5 μmol / m 2 . The modification rate used in the present invention is defined by the following equation. Modification rate (μmol / m 2 ) = C × 10 6 / M × S × 10
2 (However, C is the carbon content in the modified silica carrier (% by weight), M is the carbon content in 1 mol of the silane coupling agent (the number of carbons in 1 mol x 12), and S is the nitrogen adsorption of the silica carrier. Surface area (m 2 / g) according to the method).
【０００９】これら吸着剤の基材となるシリカゲルの形
状は球型，破砕型いずれでもよく、また多孔質なものが
好ましい。The silica gel serving as the base material for these adsorbents may be spherical or crushed, and is preferably porous.
【００１０】吸着されるアルコール中の重金属は鉄，
銅，クロム，ニッケル，チタン，カドミウム，マンガン
等のいずれでもよいが、特に鉄，銅に有効である。アル
コールとしては脂肪族アルコール，脂環式アルコール，
芳香族アルコールいずれでもよいが炭素数１〜６の低級
脂肪族アルコールに好適に用いられ、特にイソプロピル
アルコールに有効である。The heavy metal in the adsorbed alcohol is iron,
Any of copper, chromium, nickel, titanium, cadmium, manganese, etc. may be used, but it is particularly effective for iron and copper. As alcohol, aliphatic alcohol, alicyclic alcohol,
Although any aromatic alcohol may be used, it is preferably used for a lower aliphatic alcohol having 1 to 6 carbon atoms, and is particularly effective for isopropyl alcohol.
【００１１】本発明において、アルコールを吸着剤に接
触させる方法としては、アルコールと吸着剤とを容器に
投入し混合するバッチ式、吸着剤をカラムに充填し、こ
れにアルコールを通液するカラム式等が可能であるが、
操作，汚染等の面からカラム式が好ましい。In the present invention, the method of bringing the alcohol into contact with the adsorbent includes a batch method in which the alcohol and the adsorbent are put into a container and mixed, and a column method in which the adsorbent is packed in a column and alcohol is passed through the column. Etc. are possible,
The column type is preferable in terms of operation and contamination.
【００１２】[0012]
【実施例】以下、本発明を実施例により、さらに具体的
に説明するが、本発明はこれらに限定されるものではな
い。EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited thereto.
【００１３】実施例１ 孔径２μｍのステンレス製フィルターを装着した内径
４．６ｍｍ，長さ１５ｍｍのカラムにオクタデシル基修
飾型球状シリカゲル（平均細孔径１２０オングストロー
ム，平均粒子径５μｍ，修飾率２．１μｍｏｌ／ｍ2 ，
商品名ダイソーゲルＳＰ−１２０−５−ＯＤＳ）を約
０．３ｇ充填した後、Ｆｅ０．５ｐｐｍ，Ｃｕ０．５ｐ
ｐｍを含むイソプロピルアルコールを調整し、流量１．
０ｍｌ／ｍｉｎで２００ｍｌ通液した。流出液中のＦｅ
は０．０５ｐｐｍ以下、Ｃｕは０．０５ｐｐｍ以下であ
った。Example 1 Octadecyl group-modified spherical silica gel (average pore size 120 angstrom, average particle size 5 μm, modification rate 2.1 μmol / into a column having an inner diameter of 4.6 mm and a length of 15 mm equipped with a stainless steel filter having a pore size of 2 μm. m 2 ,
About 0.3 g of trade name Daiso gel SP-120-5-ODS) was filled, and then Fe0.5 ppm, Cu0.5 p
isopropyl alcohol containing pm was adjusted, and the flow rate was 1.
200 ml was passed through at 0 ml / min. Fe in the effluent
Was 0.05 ppm or less and Cu was 0.05 ppm or less.
【００１４】実施例２ 実施例１と同様のカラムにモルフォリノプロピル基修飾
型球状シリカゲル（平均細孔径１２０オングストロー
ム，平均粒子径１５μｍ，修飾率１．６μｍｏｌ／
ｍ2 ，商品名ダイソーゲルＳＰ−１２０−１５ＩＭＰ）
を約０．３ｇ充填した後、Ｆｅ１．０ｐｐｍ，Ｃｕ１．
０ｐｐｍを含むイソプロピルアルコールを調整し、流量
１．０ｍｌ／ｍｉｎで１００ｍｌ通液した。流出液中の
Ｆｅは０．０１ｐｐｍ以下、Ｃｕは０．０１ｐｐｍ以下
であった。Example 2 A morpholinopropyl group-modified spherical silica gel (average pore size 120 Å, average particle size 15 μm, modification rate 1.6 μmol / was applied to the same column as in Example 1).
m 2 , product name Daiso gel SP-120-15IMP)
Of about 0.3 g, Fe1.0 ppm, Cu1.
Isopropyl alcohol containing 0 ppm was prepared, and 100 ml of the solution was passed at a flow rate of 1.0 ml / min. Fe in the effluent was 0.01 ppm or less and Cu was 0.01 ppm or less.
【００１５】[0015]
【発明の効果】本発明によれば、アルコール中に含まれ
る重金属を簡単な操作で効率良く非常に低い濃度まで除
去することができる。本発明に用いられる化学修飾型シ
リカゲルは基体が無機物質であるため有機高分子物質の
ようにアルコールにより膨張を起すことがない。この方
法は特に電子工業部品洗浄用のイソプロピルアルコール
中の重金属除去に有用である。According to the present invention, heavy metals contained in alcohol can be efficiently removed to a very low concentration by a simple operation. The chemically modified silica gel used in the present invention does not cause swelling by alcohol unlike organic polymer substances because the substrate is an inorganic substance. This method is especially useful for removing heavy metals in isopropyl alcohol for cleaning electronic parts.
Claims (4)
施したシリカゲルよりなる吸着剤を接触させることを特
徴とするアルコール中の重金属除去方法。1. A method for removing heavy metals in alcohol, which comprises bringing an adsorbent made of chemically modified silica gel into contact with an alcohol containing heavy metals.
シル基修飾型シリカゲル，オクチル基修飾型シリカゲ
ル，アミノプロピル基修飾型シリカゲル，モルフォリノ
プロピル基修飾型シリカゲル，ピペラジノプロピル基修
飾型シリカゲル，ピペリジノ基修飾型シリカゲルである
請求項１記載の重金属除去方法。2. The chemically modified silica gel is octadecyl group-modified silica gel, octyl group-modified silica gel, aminopropyl group-modified silica gel, morpholinopropyl group-modified silica gel, piperazinopropyl group-modified silica gel, piperidino group. The method for removing heavy metals according to claim 1, which is a modified silica gel.
る請求項１又は２に記載の重金属除去方法。3. The method for removing heavy metals according to claim 1, wherein the alcohol is a lower aliphatic alcohol.
ルコールである請求項３に記載の重金属除去方法。4. The method for removing heavy metals according to claim 3, wherein the lower aliphatic alcohol is isopropyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23568492A JPH0680594A (en) | 1992-09-03 | 1992-09-03 | Method for removing heavy metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23568492A JPH0680594A (en) | 1992-09-03 | 1992-09-03 | Method for removing heavy metal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0680594A true JPH0680594A (en) | 1994-03-22 |
Family
ID=16989682
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23568492A Pending JPH0680594A (en) | 1992-09-03 | 1992-09-03 | Method for removing heavy metal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0680594A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001036067A1 (en) * | 1999-11-12 | 2001-05-25 | Aventis Cropscience S.A. | Multiple sorbent cartridges for solid phase extraction |
| JP2003535836A (en) * | 2000-06-02 | 2003-12-02 | エクソンモービル・ケミカル・パテンツ・インク | Method for producing ultra-high purity isopropanol |
| DE102009015413A1 (en) | 2009-03-27 | 2010-09-30 | B.P.S. Engineering Gesellschaft für Umwelt und Automatisierungstechnik mbH | Adsorbent to remove heavy metals from contaminated water, comprises mesoporous material with homogeneous distribution containing metal oxides and high-molecular cationic polymers, which contain quaternary ammonium and/or phosphonium groups |
| DE102011009223A1 (en) | 2011-01-13 | 2012-07-19 | Gesellschaft zur Förderung von Medizin-, Bio- und Umwelttechnologien e.V. | Multifunctional composite material, useful e.g. as an adsorbent for removing heavy metal ions from contaminated waste water comprises a solid magnesium ammonium phosphate and homogeneously dispersed titania nanoparticle |
| JP2013023439A (en) * | 2011-07-15 | 2013-02-04 | Japan Organo Co Ltd | Method and apparatus for purifying alcohol |
| JP2013023440A (en) * | 2011-07-15 | 2013-02-04 | Japan Organo Co Ltd | Method and apparatus for purifying alcohol |
| JP2013023441A (en) * | 2011-07-15 | 2013-02-04 | Japan Organo Co Ltd | Method and apparatus for purifying alcohol |
| JP2016007601A (en) * | 2014-06-26 | 2016-01-18 | 国立大学法人九州大学 | Ion exchange resin and method of adsorption separation of metal |
-
1992
- 1992-09-03 JP JP23568492A patent/JPH0680594A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001036067A1 (en) * | 1999-11-12 | 2001-05-25 | Aventis Cropscience S.A. | Multiple sorbent cartridges for solid phase extraction |
| JP2003535836A (en) * | 2000-06-02 | 2003-12-02 | エクソンモービル・ケミカル・パテンツ・インク | Method for producing ultra-high purity isopropanol |
| JP4801870B2 (en) * | 2000-06-02 | 2011-10-26 | エクソンモービル・ケミカル・パテンツ・インク | Method for producing ultra-high purity isopropanol |
| DE102009015413A1 (en) | 2009-03-27 | 2010-09-30 | B.P.S. Engineering Gesellschaft für Umwelt und Automatisierungstechnik mbH | Adsorbent to remove heavy metals from contaminated water, comprises mesoporous material with homogeneous distribution containing metal oxides and high-molecular cationic polymers, which contain quaternary ammonium and/or phosphonium groups |
| DE102011009223A1 (en) | 2011-01-13 | 2012-07-19 | Gesellschaft zur Förderung von Medizin-, Bio- und Umwelttechnologien e.V. | Multifunctional composite material, useful e.g. as an adsorbent for removing heavy metal ions from contaminated waste water comprises a solid magnesium ammonium phosphate and homogeneously dispersed titania nanoparticle |
| JP2013023439A (en) * | 2011-07-15 | 2013-02-04 | Japan Organo Co Ltd | Method and apparatus for purifying alcohol |
| JP2013023440A (en) * | 2011-07-15 | 2013-02-04 | Japan Organo Co Ltd | Method and apparatus for purifying alcohol |
| JP2013023441A (en) * | 2011-07-15 | 2013-02-04 | Japan Organo Co Ltd | Method and apparatus for purifying alcohol |
| JP2016007601A (en) * | 2014-06-26 | 2016-01-18 | 国立大学法人九州大学 | Ion exchange resin and method of adsorption separation of metal |
| US9863018B2 (en) | 2014-06-26 | 2018-01-09 | Kyushu University, National University Corporation | Ion exchange resin and method for adsorbing and separating metal |
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