JP2012012274A - Method for producing purified hydrogen peroxide aqueous solution - Google Patents
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本発明は過酸化水素水溶液中に含有する有機不純物を除去して精製過酸化水素水溶液を製造する方法に関するものである。 The present invention relates to a method for producing a purified aqueous hydrogen peroxide solution by removing organic impurities contained in the aqueous hydrogen peroxide solution.
過酸化水素は、現在ほとんどがアントラキノン法により製造されている。その工程は一般に以下の通りである。アントラキノン誘導体として、例えば、２−アルキルアントラキノンを水不溶性の溶媒中で水素化触媒の存在下水素化して対応するアントラヒドロキノンとし、触媒をろ別した後、空気により酸化することによって元の２−アルキルアントラキノンを再生するとともに、過酸化水素を得、これを水で抽出することによって過酸化水素含有水溶液を得る方法である。水抽出後の過酸化水素含有水溶液は、アントラキノン類や溶媒およびそれらの劣化物からなる有機不純物を混入しており、実用的な使用濃度の５〜７０ｗｔ％の過酸化水素水溶液中には全有機炭素量として２０〜数１００ｍｇ／ｌの有機不純物が含まれているのが普通である。これらの過酸化水素水溶液は、品質要求に応じた精製操作が行われる。 Most of hydrogen peroxide is currently produced by the anthraquinone method. The process is generally as follows. As an anthraquinone derivative, for example, 2-alkylanthraquinone is hydrogenated in a water-insoluble solvent in the presence of a hydrogenation catalyst to give the corresponding anthrahydroquinone, and after filtering the catalyst, the original 2-alkyl is oxidized by air. In this method, anthraquinone is regenerated, hydrogen peroxide is obtained, and this is extracted with water to obtain a hydrogen peroxide-containing aqueous solution. The aqueous hydrogen peroxide-containing solution after water extraction contains organic impurities consisting of anthraquinones, solvents and their degradation products, and all organics are contained in a hydrogen peroxide aqueous solution with a practical use concentration of 5 to 70 wt%. Usually, an organic impurity of 20 to several 100 mg / l in carbon content is contained. These hydrogen peroxide aqueous solutions are subjected to a purification operation according to quality requirements.
過酸化水素水溶液の用途は、これまでは主として紙、パルプの漂白、化学研磨液等の分野で広く利用されていたが、近年、シリコンウエハの洗浄剤や半導体工程の洗浄剤などの電子工業分野に於ける利用が増大し、デバイスの高集積化に伴う高純度化の要求は、これまでの有機不純物、Ａｌ、Ｆｅ、Ｃｒなどの金属成分を含めた全ての不純物を極力低減した高純度な品質が要求されるようになっている。 Up to now, hydrogen peroxide aqueous solution has been widely used mainly in the fields of paper, pulp bleaching, chemical polishing liquids, etc., but in recent years it has been used in the electronics industry such as silicon wafer cleaning agents and semiconductor process cleaning agents. The demand for high purity along with the high integration of devices has increased the use in semiconductors, and the high purity of all impurities including metal components such as organic impurities, Al, Fe, Cr, etc. has been reduced as much as possible. Quality is required.
過酸化水素水溶液中に含まれるこれらの有機不純物を除去する方法としてスチレンを重合し、ジビニルベンゼンで架橋させて得た網目状分子構造を持ち且つイオン交換基を持たない樹脂で、有機不純物を含む過酸化水素を４０℃以下で処理する方法が知られている。（特許文献１、２参照）。また、ハロゲン含有多孔性樹脂を使用して過酸化水素水溶液中の有機不純物を除去する方法が知られている（特許文献３参照）。 As a method for removing these organic impurities contained in hydrogen peroxide aqueous solution, a resin having a network molecular structure obtained by polymerizing styrene and crosslinking with divinylbenzene and having no ion exchange group, and containing organic impurities. A method of treating hydrogen peroxide at 40 ° C. or lower is known. (See Patent Documents 1 and 2). Further, a method for removing organic impurities in an aqueous hydrogen peroxide solution using a halogen-containing porous resin is known (see Patent Document 3).
しかしながら、これら従来使用されている吸着樹脂により過酸化水素水溶液中の有機不純物を除去使用とする場合、種々の問題が発生する。まず、従来のスチレン−ジビニルベンゼンで架橋させた分子吸着樹脂及びハロゲン含有多孔性樹脂の粒子表面は疎水性の状態になっているため、これに直接水あるいは過酸化水素水溶液を接触させることは分離、浮遊の問題が発生する。そのためこれらの溶液となじみやすくするためにアルコール又はアセトン等の極性溶媒による処理が必要であった。又、あらかじめアルコール又はアセトン等の処理を行った従来樹脂に過酸化水素水を通液させた場合、樹脂の一部が水溶液となじまなくなることが起こり、有機不純物の除去効率が大幅に低下する問題があった。
一方、イオン交換基を持たない親水性の多孔性樹脂としてアクリルエステル重合体があるが、この構造の場合、比表面積が前述の吸着樹脂と比べて格段に小さく過酸化水素水中の有機不純物を除去するには多量の樹脂が必要となる欠点があった。
However, various problems occur when these conventional adsorption resins are used to remove organic impurities in an aqueous hydrogen peroxide solution. First, since the particle surfaces of conventional molecular adsorption resin and halogen-containing porous resin crosslinked with styrene-divinylbenzene are in a hydrophobic state, contact with water or an aqueous hydrogen peroxide solution is a separation. , Floating problems occur. For this reason, treatment with a polar solvent such as alcohol or acetone is necessary in order to make it easy to become familiar with these solutions. In addition, when hydrogen peroxide solution is passed through a conventional resin that has been treated with alcohol or acetone in advance, a part of the resin may become incompatible with the aqueous solution, resulting in a significant reduction in organic impurity removal efficiency. was there.
On the other hand, there is an acrylic ester polymer as a hydrophilic porous resin that does not have an ion exchange group. In this structure, the specific surface area is much smaller than that of the aforementioned adsorption resin, and organic impurities in hydrogen peroxide water are removed. In this case, a large amount of resin is required.
本発明の目的は、従来技術における課題を解決し、過酸化水素水溶液中の有機不純物を高い除去効率で且つ簡便に除去する方法を提供することにある。 An object of the present invention is to solve the problems in the prior art and provide a method for easily removing organic impurities in an aqueous hydrogen peroxide solution with high removal efficiency.
本発明者らは、過酸化水素水溶液中の有機不純物を除去し、高純度化した精製過酸化水素水溶液を製造する方法について、鋭意、研究を重ねた結果、有機不純物を含む過酸化水素水溶液を三級アミン基と特定の比表面積を有する親水性の多孔性樹脂に接触させることにより、効率的に有機不純物を除去することができることを見いだし本発明に到達した。
すなわち、本発明は有機不純物を含む過酸化水素水溶液と、イオン交換容量０．６〜１．６ｍｅｑ／ｇの三級アミン基を含有し且つ比表面積が少なくとも８００ｍ2 ／ｇである親水性の多孔性樹脂とを接触させて、過酸化水素水溶液の有機不純物を除去することを特徴とする精製過酸化水素水溶液の製造方法に関するものである。
As a result of earnest and research on the method of producing a purified hydrogen peroxide solution with high purity by removing organic impurities in the hydrogen peroxide solution, the present inventors have obtained a hydrogen peroxide solution containing organic impurities. It has been found that organic impurities can be efficiently removed by contacting a tertiary amine group with a hydrophilic porous resin having a specific surface area.
That is, the present invention provides a hydrophilic porous solution containing an aqueous hydrogen peroxide solution containing organic impurities, a tertiary amine group having an ion exchange capacity of 0.6 to 1.6 meq / g, and a specific surface area of at least 800 m 2 / g. The present invention relates to a method for producing a purified aqueous solution of hydrogen peroxide, wherein the organic impurities in the aqueous solution of hydrogen peroxide are removed by contacting with a functional resin.
本発明によれば、有機不純物を含む過酸化水素水溶液を三級アミン基と特定の比表面積を有する親水性の多孔性樹脂に接触させることによって、有機不純物を効率的に除去でき、高純度に精製された過酸化水素水溶液を得ることができる。 According to the present invention, by bringing a hydrogen peroxide aqueous solution containing organic impurities into contact with a hydrophilic resin having a tertiary amine group and a specific specific surface area, the organic impurities can be efficiently removed, and the purity can be increased. A purified aqueous hydrogen peroxide solution can be obtained.
本発明で用いられる親水性の多孔性樹脂は、イオン交換容量が０．６〜１．６ｍｅｑ／ｇの三級アミン基を含有し且つ比表面積が少なくとも８００ｍ２／ｇである。ここで、多孔性樹脂の比表面積はＢＥＴ法（Ｎ2 ）により測定した比表面積に相当する。また、本発明の多孔性樹脂は連続した多孔を有するものであることが好ましい。また、本発明における親水性の多孔性樹脂は２〜１０ｎｍ（２０〜１００オングストローム）の最頻度細孔径を有する多孔性樹脂であることが好ましい。ここで、多孔性樹脂の最頻度細孔径は、窒素吸着法もしくは水銀圧入法により測定することができる。本発明における親水性の多孔性樹脂は平均粒子径が０．２〜１．２ｍｍの粒子の形状であることが好ましい。ここで、平均粒子径とは樹脂全体の１０％を通し９０％を網目上に残す網目の大きさを言うものとする。 The hydrophilic porous resin used in the present invention contains a tertiary amine group having an ion exchange capacity of 0.6 to 1.6 meq / g and a specific surface area of at least 800 m 2 / g. Here, the specific surface area of the porous resin corresponds to the specific surface area measured by the BET method (N 2 ). Moreover, it is preferable that the porous resin of the present invention has continuous porosity. Further, the hydrophilic porous resin in the present invention is preferably a porous resin having a most frequent pore diameter of 2 to 10 nm (20 to 100 angstrom). Here, the most frequent pore diameter of the porous resin can be measured by a nitrogen adsorption method or a mercury intrusion method. The hydrophilic porous resin in the present invention is preferably in the form of particles having an average particle diameter of 0.2 to 1.2 mm. Here, the average particle diameter refers to the size of a mesh that passes through 10% of the entire resin and leaves 90% on the mesh.
親水性の多孔性樹脂としては、例えば芳香族モノビニルモノマーと芳香族ポリビニルモノマーとの架橋重合体に水酸基、クロルアルキル基、水酸化アルキル基あるいはアミン基を導入したものが好適に用いられる。芳香族モノビニルモノマーとしては例えばスチレン、ビニルトルエン等が好適に使用される。又、芳香族ポリビニルモノマーとしては例えばジビニルベンゼン、トリビニルベンゼン等が好適に使用される。 As the hydrophilic porous resin, for example, a polymer obtained by introducing a hydroxyl group, a chloroalkyl group, an alkyl hydroxide group or an amine group into a crosslinked polymer of an aromatic monovinyl monomer and an aromatic polyvinyl monomer is preferably used. As the aromatic monovinyl monomer, for example, styrene, vinyl toluene and the like are preferably used. As the aromatic polyvinyl monomer, for example, divinylbenzene, trivinylbenzene and the like are preferably used.
本発明方法において、親水性の多孔性樹脂としては、スチレン−ジビニルベンゼン共重合体、スチレン−トリビニルベンゼン共重合体又はビニルトルエン−ジビニルベンゼン共重合体に三級アミン基を導入したものが好ましく、スチレン−ジビニルベンゼン共重合体の三級アミン化物が特に好適に使用される。これらの樹脂は市販品として入手しうることも可能である。例えば商品名「Optipore L-493」（ダウ・ケミカル社製）は親水性を持ったスチレン−ジビニルベンゼンの共重合体であり、比表面積が８００ｍ2 ／ｇである。 In the method of the present invention, the hydrophilic porous resin is preferably a styrene-divinylbenzene copolymer, styrene-trivinylbenzene copolymer or vinyltoluene-divinylbenzene copolymer into which a tertiary amine group is introduced. A tertiary amination product of a styrene-divinylbenzene copolymer is particularly preferably used. These resins can also be obtained as commercial products. For example, the trade name “Optipore L-493” (manufactured by Dow Chemical Co.) is a hydrophilic styrene-divinylbenzene copolymer having a specific surface area of 800 m 2 / g.
本発明で対象となる有機不純物を含む過酸化水素水溶液は、アントラキノン法、水素と酸素を直接反応させる直接合成法など、いかなる製造法によるものでも良い。しかし、前記の如く、現在ほとんどの過酸化水素がアントラキノン法によって製造されており、この方法により得られた過酸化水素水は、各種要求に応じ精製操作を行っているが、有機物、金属などの不純物を含んでおり、さらに精製操作が必要である。本発明の有機不純物を含む過酸化水素水溶液としては、好ましくは５〜７０重量％の過酸化水素濃度を有し、全有機炭素量として多くとも５００ｍｇ／ｌの有機不純物を含有する過酸化水素水溶液である。 The aqueous hydrogen peroxide solution containing the organic impurities targeted by the present invention may be produced by any production method such as an anthraquinone method or a direct synthesis method in which hydrogen and oxygen are directly reacted. However, as described above, most hydrogen peroxide is currently produced by the anthraquinone method, and the hydrogen peroxide solution obtained by this method is subjected to purification operations according to various requirements. It contains impurities and requires further purification operations. The aqueous hydrogen peroxide solution containing organic impurities of the present invention preferably has a hydrogen peroxide concentration of 5 to 70% by weight and contains an organic impurity of at most 500 mg / l as the total organic carbon content. It is.
本発明において、有機不純物を含む過酸化水素水溶液に親水性の多孔性樹脂に接触させる方法は連続通液方式又はバッチ方式のいずれでも実施することができる。例えば、連続通液方式は、カラムに充填した親水性の多孔性樹脂に有機不純物を含む過酸化水素水溶液を連続的に供給することにより実施される。又、バッチ方式では、親水性の多孔性樹脂と有機不純物を含む過酸化水素水溶液を所定時間撹拌混合した後、樹脂を分離した後、精製過酸化水素を抜き出す方法が考えられる。工業的には、カラムに充填した連続通液方式が精製度の高い過酸化水素が効率的に得られるため実用性が高く好ましい。 In the present invention, the method of bringing the aqueous solution of hydrogen peroxide containing organic impurities into contact with the hydrophilic porous resin can be carried out by either a continuous liquid feeding method or a batch method. For example, the continuous liquid flow method is performed by continuously supplying a hydrogen peroxide aqueous solution containing organic impurities to a hydrophilic porous resin packed in a column. In the batch method, a method in which a hydrophilic porous resin and an aqueous hydrogen peroxide solution containing organic impurities are stirred and mixed for a predetermined time, the resin is separated, and then purified hydrogen peroxide is extracted. Industrially, a continuous liquid flow system packed in a column is preferable because it is highly practical because hydrogen peroxide with a high degree of purification can be obtained efficiently.
次に実施例によって本発明を具体的に説明するが、その実施は以下の例に限定されるものではない。本発明において、過酸化水素水溶液中の全有機炭素量の測定は、全有機炭素計（島津 ＴＯＣ−５０００）を用いて測定した。 EXAMPLES Next, although an Example demonstrates this invention concretely, the implementation is not limited to the following examples. In the present invention, the total amount of organic carbon in the aqueous hydrogen peroxide solution was measured using a total organic carbon meter (Shimadzu TOC-5000).
実施例１
比表面積８００ｍ2 ／ｇ、三級アミン基のイオン交換容量０．８ｍｅｑ／ｇの親水性を有するOptipore L-493（親水性多孔性吸着樹脂、スチレン−ジビニルベンゼン架橋共重合体、ダウ・ケミカル社製）５ｍｌをＰＴＦＥ製カラムに充填し、５９重量％の粗精製過酸化水素水溶液（有機不純物を全有機炭素量として５２ｍｇ／ｌ含有）をＳＶ＝１８Ｈｒ-1で２．５時間通液した。カラムは水浴中に置き、１０℃に温度を保った。通液開始２時間後から２．５時間までサンプリングを行い、通液過酸化水素水溶液中に含まれる全有機炭素量を分析した。過酸化水素水溶液中の全有機炭素量は２．７ｍｇ／ｌに低減された。
Example 1
Optipore L-493 (hydrophilic porous adsorption resin, styrene-divinylbenzene cross-linked copolymer, Dow Chemical Company) having a specific surface area of 800 m 2 / g and tertiary amine group ion exchange capacity of 0.8 meq / g 5 ml) was packed in a PTFE column, and 59 wt% of a crude purified hydrogen peroxide aqueous solution (containing 52 mg / l of organic impurities as the total organic carbon content) was passed for 2.5 hours at SV = 18 Hr −1 . The column was placed in a water bath and the temperature was maintained at 10 ° C. Sampling was performed from 2 hours after the start of liquid flow to 2.5 hours, and the total amount of organic carbon contained in the liquid hydrogen peroxide solution was analyzed. The total amount of organic carbon in the aqueous hydrogen peroxide solution was reduced to 2.7 mg / l.
比較例１
実施例１の親水性多孔性吸着樹脂の代わりに、疎水性の多孔性吸着樹脂ＳＰ−７０（三菱化学社製）を使用し、前処理としてメタノールを多孔性吸着樹脂ＳＰ−７０の１０倍容量混合して水溶液になじむようにした後、多孔性樹脂に残留したメタノールを水洗により十分に除去した後にＰＴＦＥ製カラムに充填した以外は実施例１と同様にして処理を行った。
通液開始２時間後から２．５時間までサンプリングを行い、通液過酸化水素溶液中に含まれる全有機炭素量を分析した。過酸化水素水溶液中の全有機炭素量は６．０ｍｇ／ｌであった。
Comparative Example 1
Instead of the hydrophilic porous adsorption resin of Example 1, a hydrophobic porous adsorption resin SP-70 (manufactured by Mitsubishi Chemical Corporation) was used, and methanol was 10 times the volume of the porous adsorption resin SP-70 as a pretreatment. After mixing and adjusting to the aqueous solution, the treatment was performed in the same manner as in Example 1 except that the methanol remaining in the porous resin was sufficiently removed by washing with water and then packed into a PTFE column.
Sampling was performed from 2 hours after the start of liquid passage to 2.5 hours, and the total amount of organic carbon contained in the liquid hydrogen peroxide solution was analyzed. The total amount of organic carbon in the aqueous hydrogen peroxide solution was 6.0 mg / l.
Claims (5)
The manufacturing method as described in any one of Claims 1-4 in which the hydrogen peroxide aqueous solution containing an organic impurity has a hydrogen peroxide concentration of 5-70 weight%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058406A (en) * | 2013-01-11 | 2013-04-24 | 上海安赐机械设备有限公司 | Device and technology employed to hydrogen peroxide purification |
| US10301197B2 (en) | 2015-09-15 | 2019-05-28 | Dow Global Technologies Llc | Method of purifying water |
| US10610859B2 (en) | 2015-09-15 | 2020-04-07 | Dow Global Technologies Llc | Method of purifying water |
| US10610860B2 (en) | 2015-09-15 | 2020-04-07 | DDP Specialty Electronic Materials US, Inc. | Method of purifying water |
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2010
- 2010-07-05 JP JP2010152848A patent/JP2012012274A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058406A (en) * | 2013-01-11 | 2013-04-24 | 上海安赐机械设备有限公司 | Device and technology employed to hydrogen peroxide purification |
| US10301197B2 (en) | 2015-09-15 | 2019-05-28 | Dow Global Technologies Llc | Method of purifying water |
| US10610859B2 (en) | 2015-09-15 | 2020-04-07 | Dow Global Technologies Llc | Method of purifying water |
| US10610860B2 (en) | 2015-09-15 | 2020-04-07 | DDP Specialty Electronic Materials US, Inc. | Method of purifying water |
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