JPH09221305A - Production of high purity hydrogen peroxide solution - Google Patents
Production of high purity hydrogen peroxide solutionInfo
- Publication number
- JPH09221305A JPH09221305A JP2656796A JP2656796A JPH09221305A JP H09221305 A JPH09221305 A JP H09221305A JP 2656796 A JP2656796 A JP 2656796A JP 2656796 A JP2656796 A JP 2656796A JP H09221305 A JPH09221305 A JP H09221305A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen peroxide
- resin
- exchange resin
- ultrafiltration membrane
- peroxide solution
- 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.)
- Granted
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
Description
【０００１】[0001]
【発明が属する技術分野】本発明は不純物、特にケイ素
化合物やアルミニウム化合物、ならびに過酸化水素水の
安定剤として添加されたスズ化合物などを含有する過酸
化水素水を安全に精製し、極めて高純度な過酸化水素水
を安定に製造する方法に関する。本発明による高純度過
酸化水素水は、特に半導体製造分野、医療分野での使用
に最適である。TECHNICAL FIELD The present invention safely purifies hydrogen peroxide water containing impurities, particularly silicon compounds and aluminum compounds, and tin compounds added as stabilizers of hydrogen peroxide water, to obtain an extremely high purity. The present invention relates to a method for stably producing a stable hydrogen peroxide solution. The high-purity hydrogen peroxide solution according to the present invention is particularly suitable for use in the semiconductor manufacturing field and medical field.
【０００２】[0002]
【従来の技術】現在、過酸化水素は主に自動酸化法によ
り製造されているが、この方法によって製造された過酸
化水素水中には各種の無機不純物が混入しており、実質
的な使用濃度の５〜７０重量％の過酸化水素水中には通
常数百μｇ／ｌの無機不純物が含まれている。また、過
酸化水素水には過酸化水素の分解を抑制するためにリン
酸等の酸やスズ酸ナトリウムなどの安定剤を添加する場
合もある。一方で、半導体製造分野で使用される過酸化
水素水は、無機不純物の残存濃度が数ｐｐｂ以下という
高純度なものが要求される。2. Description of the Related Art At present, hydrogen peroxide is mainly produced by the autoxidation method. However, various inorganic impurities are mixed in the hydrogen peroxide water produced by this method, and the actual use concentration The hydrogen peroxide water of 5 to 70% by weight usually contains several hundreds μg / l of inorganic impurities. In addition, an acid such as phosphoric acid or a stabilizer such as sodium stannate may be added to the hydrogen peroxide solution in order to suppress decomposition of hydrogen peroxide. On the other hand, the hydrogen peroxide solution used in the field of semiconductor manufacturing is required to have a high purity such that the residual concentration of inorganic impurities is several ppb or less.
【０００３】従来、過酸化水素水中に含まれる無機不純
物を除去、精製する方法として、イオン交換樹脂に過酸
化水素水を接触させる方法が種々提案されている。たと
えば、特公昭３５−１６６７７号公報には、重炭酸型ア
ニオン交換樹脂を使用する方法が示されており、ドイツ
特許公開第４２１４０７５号には、過酸化水素水の凝固
点から０℃の間の温度でカチオン交換樹脂、アニオン交
換樹脂および吸着樹脂で処理することが開示されてお
り、またフランス特許第２６７７０１１号には、過酸化
水素水の凝固点から０℃の間の温度でアニオン交換樹脂
で精製することが示されている。特開平５−１７１０５
号公報には過酸化水素の分解を抑制しながら重炭酸型ア
ニオン交換樹脂で処理すること開示されている。ドイツ
特許公開第４２２２１０９号にはカチオン交換樹脂、ア
ニオン交換樹脂が埋め込まれた膜による処理が示されて
いる。また、特開平７−１７２８０５号公報には炭酸ア
ンモニウムまたは重炭酸アンモニウムで炭酸型、重炭酸
型に再生したアニオン交換樹脂による精製法が開示され
ている。Conventionally, as a method for removing and purifying inorganic impurities contained in hydrogen peroxide water, various methods have been proposed in which hydrogen peroxide water is brought into contact with an ion exchange resin. For example, Japanese Patent Publication No. 35-16677 discloses a method of using a bicarbonate type anion exchange resin, and German Patent Publication No. 4214075 discloses a temperature between the freezing point of hydrogen peroxide solution and 0 ° C. Discloses treatment with a cation exchange resin, an anion exchange resin and an adsorption resin, and French Patent 2677011 purifies with an anion exchange resin at a temperature between 0 ° C. and the freezing point of hydrogen peroxide solution. Is shown. JP-A-5-17105
The publication discloses that the treatment with a bicarbonate type anion exchange resin is carried out while suppressing the decomposition of hydrogen peroxide. German Patent Publication No. 4222109 discloses treatment with a membrane in which a cation exchange resin and an anion exchange resin are embedded. Further, Japanese Patent Application Laid-Open No. 7-172805 discloses a purification method using an anion exchange resin regenerated into a carbonate type or a bicarbonate type with ammonium carbonate or ammonium bicarbonate.
【０００４】しかしながら、このようなイオン交換樹脂
による精製では、特にケイ素化合物はほとんど除去され
ない。また、アルミニウム化合物およびスズ化合物は、
イオン交換樹脂による精製で大部分除去されるが、一部
除去されないアルミニウム化合物およびスズ化合物ある
いは遊離イオンの状態のものが残存し、高純度な過酸化
水素水を製造することが困難である。However, the purification with such an ion-exchange resin hardly removes silicon compounds. Further, the aluminum compound and the tin compound are
Although most of the aluminum compound and tin compounds are not removed by purification with an ion exchange resin, some of the aluminum compounds and tin compounds or those in the state of free ions remain, and it is difficult to produce highly pure hydrogen peroxide solution.
【０００５】また、過酸化水素水中に存在する有機およ
び無機不純物成分を除去する方法として、逆浸透膜など
で処理する方法が知られており、たとえば、米国特許第
４，８７９，０４３号に逆浸透膜で金属イオン、アニオ
ン種、炭素成分を除去することが開示されており、特開
平７−３３４０８号公報に有機炭素を逆浸透膜で除去す
ること、また特開平７−１０９１０９号公報には逆浸透
膜、カチオン交換樹脂およびアニオン交換樹脂を組み合
わせて精製する方法が開示されている。Further, as a method for removing organic and inorganic impurity components existing in hydrogen peroxide water, a method of treating with a reverse osmosis membrane is known, and for example, it is described in US Pat. No. 4,879,043. It is disclosed that metal ions, anion species, and carbon components are removed by an osmosis membrane. JP-A-7-33408 discloses that organic carbon is removed by a reverse osmosis membrane, and JP-A-7-109109 discloses. A method of purifying by combining a reverse osmosis membrane, a cation exchange resin and an anion exchange resin is disclosed.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、過酸
化水素水を精製して、不純物、特にケイ素化合物、アル
ミニウム化合物およびスズ化合物が極めて低濃度にまで
除去された高純度の過酸化水素水を製造する方法を提供
することである。SUMMARY OF THE INVENTION An object of the present invention is to purify hydrogen peroxide water to remove impurities, particularly silicon compounds, aluminum compounds and tin compounds, to a very low concentration, and to obtain high purity hydrogen peroxide. It is to provide a method for producing water.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、前記の課
題を解決すべく鋭意検討した結果、過酸化水素水の精製
処理につき種々の点から検討し本発明を完成させた。す
なわち、本発明は不純物、特にケイ素化合物、アルミニ
ウム化合物およびスズ化合物を含有する過酸化水素水
を、イオン交換樹脂および限外濾過膜で精製処理するこ
とによる高純度過酸化水素水の製造方法である。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have completed various aspects of the hydrogen peroxide solution purification treatment and completed the present invention. That is, the present invention is a method for producing high-purity hydrogen peroxide water by purifying hydrogen peroxide water containing impurities, particularly silicon compounds, aluminum compounds and tin compounds, with an ion exchange resin and an ultrafiltration membrane. .
【０００８】[0008]
【発明の実施の形態】本発明の方法において採用される
限外濾過膜は、平均孔径が０．１５μｍ以下のものが使
用される。平均孔径が０．１５μｍ以下の限外濾過膜を
使用することによりケイ素化合物、アルミ化合物および
スズ化合物は殆ど除去されるが、膜の孔径が小さいほど
除去効果は高い。特にケイ素化合物は、平均孔径が０．
０５μｍ以下の限外濾過膜を使用する場合除去が効果的
に行われる。平均孔径が０．１５μｍを超える大きさの
場合は顕著な除去効果が得られず好ましくない。BEST MODE FOR CARRYING OUT THE INVENTION The ultrafiltration membrane employed in the method of the present invention has an average pore size of 0.15 μm or less. Most of silicon compounds, aluminum compounds and tin compounds are removed by using an ultrafiltration membrane having an average pore diameter of 0.15 μm or less, but the smaller the pore diameter of the membrane, the higher the removal effect. In particular, the silicon compound has an average pore size of 0.
When using an ultrafiltration membrane with a thickness of 05 μm or less, the removal is effectively performed. If the average pore size exceeds 0.15 μm, a remarkable removing effect cannot be obtained, which is not preferable.
【０００９】本発明において限外濾過膜の孔径を規定す
るにあたっては、例としてポリスチレンラテックス標準
粒子による方法が挙げられる。ポリスチレンラテックス
標準粒子としては、例えば、ダウケミカル（株）や日本
合成ゴム（株）製のものが使用される。この方法は、平
均直径の異なるポリスチレンラテックス標準粒子を分散
した超純水を限外濾過膜にそれぞれ通過させ、その通過
前後の超純水についてＵＶ光による濁度測定を行い、通
過を阻止される粒子の割合を求める。通過試験は複数の
異なる平均直径を有する標準粒子を通過させたとき、通
過阻止率が初めて７０％を超えた時点の平均直径をその
限外濾過膜の平均孔径とする。In defining the pore size of the ultrafiltration membrane in the present invention, a method using polystyrene latex standard particles can be mentioned as an example. As the polystyrene latex standard particles, for example, those manufactured by Dow Chemical Co., Ltd. or Nippon Synthetic Rubber Co., Ltd. are used. In this method, ultrapure water in which polystyrene latex standard particles having different average diameters are dispersed is passed through an ultrafiltration membrane, and turbidity of the ultrapure water before and after the passage is measured by UV light to prevent passage. Find the proportion of particles. In the passage test, when a plurality of standard particles having different average diameters are passed, the average diameter at the time when the passage inhibition rate exceeds 70% for the first time is taken as the average pore diameter of the ultrafiltration membrane.
【００１０】本発明で使用される限外濾過膜の材質は、
過酸化水素水と接触して精製するのに必要な時間安定な
もので、かつその材質からの不純物の溶出が少ないもの
が好ましい。このため、材質は、フッ素樹脂、ポリオレ
フィン樹脂、ポリアクリロニトリル樹脂、ポリスルホン
樹脂、ポリエーテルスルホン樹脂、ポリアミド樹脂、ポ
リイミド樹脂、ポリカーボネート樹脂の群から選択され
る。The material of the ultrafiltration membrane used in the present invention is
Those that are stable for the time required for purification by contact with hydrogen peroxide water and that elute less impurities from the material are preferable. Therefore, the material is selected from the group of fluororesin, polyolefin resin, polyacrylonitrile resin, polysulfone resin, polyethersulfone resin, polyamide resin, polyimide resin, and polycarbonate resin.
【００１１】また本発明を実施するに際して、限外濾過
膜の形状には特に制限はなく、平膜型でも良いし、管
型、スパイラル型、中空糸型、あるいは支持材と組み合
わせた膜を織り込み有効濾過面積を増加させたプリーツ
型でも良い。In carrying out the present invention, the shape of the ultrafiltration membrane is not particularly limited and may be a flat membrane type, a tubular type, a spiral type, a hollow fiber type, or a membrane in combination with a support material is woven. A pleated type with an increased effective filtration area may be used.
【００１２】本発明の方法を実施するに当たり、使用さ
れる過酸化水素水の濃度には制限はないが、一般に実用
的な５〜７０重量％の過酸化水素濃度のものが用いられ
る。また、酸などの安定剤が添加されている場合、その
過酸化水素水のｐＨは低い値を示すが、そのままこの過
酸化水素水を平均孔径０．１５μｍ以下の限外濾過膜で
処理し、引き続いてイオン交換樹脂による処理を行う
と、ケイ素化合物、アルミニウム化合物およびスズ化合
物の除去率に向上が見られる。さらに、過酸化水素水を
予めアルカリ水溶液、例えばアンモニア水でｐＨ３〜５
とした後に、限外濾過膜処理およびイオン交換樹脂処理
を行うと、特にアルミニウム化合物の除去性が向上す
る。しかし、ｐＨが５よりも大きくなると、これらの化
合物の除去性は低下する。In carrying out the method of the present invention, the concentration of hydrogen peroxide solution used is not limited, but a hydrogen peroxide concentration of 5 to 70% by weight, which is practical, is generally used. Further, when a stabilizer such as an acid is added, the pH of the hydrogen peroxide solution shows a low value, but this hydrogen peroxide solution is directly treated with an ultrafiltration membrane having an average pore size of 0.15 μm or less, Subsequent treatment with an ion exchange resin improves the removal rate of silicon compounds, aluminum compounds and tin compounds. Further, the hydrogen peroxide solution is previously adjusted to pH 3 to 5 with an alkaline aqueous solution, for example, ammonia water.
Then, if the ultrafiltration membrane treatment and the ion exchange resin treatment are performed, the removability of the aluminum compound is particularly improved. However, when the pH is higher than 5, the removability of these compounds decreases.
【００１３】一方、限外濾過膜で処理させる過酸化水素
水の温度も特別に制限はないが、過酸化水素水の分解に
より気泡が発生し濾過速度の低下を引き起こしたり、過
酸化水素水との接触により膜が劣化するなどの悪影響を
考慮すると、温度はできるだけ低温で行うことが好まし
い。一般的には使用されるその過酸化水素水の凝固点〜
３０℃である。On the other hand, the temperature of the hydrogen peroxide solution to be treated with the ultrafiltration membrane is not particularly limited, but bubbles are generated due to the decomposition of the hydrogen peroxide solution to cause a decrease in the filtration rate, and Considering adverse effects such as the deterioration of the film due to the contact, the temperature is preferably as low as possible. Generally used freezing point of hydrogen peroxide
30 ° C.
【００１４】本発明の方法は、過酸化水素水をイオン交
換樹脂および限外濾過膜により処理する方法であるが、
これらの順序は特に限定されず、限外濾過膜による処理
に引き続きイオン交換樹脂による処理を行ってもよく、
またその逆の順序でも差し支えない。いずれを選択する
かは過酸化水素水中の不純物成分の種類、あるいは濃度
などにより適宜決められる。The method of the present invention is a method of treating hydrogen peroxide water with an ion exchange resin and an ultrafiltration membrane.
The order of these is not particularly limited, and the treatment with the ion exchange resin may be performed subsequently to the treatment with the ultrafiltration membrane,
The reverse order is also acceptable. Which one is selected is appropriately determined depending on the type or concentration of the impurity component in the hydrogen peroxide solution.
【００１５】ここでいうイオン交換樹脂は、強酸性カチ
オン交換樹脂、強塩基性アニオン交換樹脂、任意の割合
からなる強酸性カチオン交換樹脂と塩基性アニオン交換
樹脂との樹脂混合物が使用される。この場合、イオン交
換樹脂による精製の他に、吸着樹脂、キレート樹脂等に
通液する精製を併用しても良い。The ion exchange resin used herein is a strongly acidic cation exchange resin, a strongly basic anion exchange resin, or a resin mixture of a strongly acidic cation exchange resin and a basic anion exchange resin in any proportion. In this case, in addition to the purification with the ion exchange resin, the purification with passing through an adsorption resin, a chelate resin or the like may be used together.
【００１６】[0016]
【実施例】以下に実施例を挙げて本発明を説明するが、
本発明はこれらの実施例により何ら制限されるものでは
ない。なお、ケイ素の分析は原子吸光法、アルミニウム
およびスズの分析はＩＣＰ−ＭＳ（Inductive Coupling
- Mass Spectrometry）法によった。なお、以下の実施
例、比較例において、過酸化水素水中のケイ素化合物、
アルミニウム化合物、スズ化合物またはこれらの遊離イ
オン、および処理後の分析値はイオン濃度で表示した。The present invention will be described below with reference to examples.
The present invention is not limited by these examples. Atomic absorption method is used for analysis of silicon, and ICP-MS (Inductive Coupling) is used for analysis of aluminum and tin.
-Mass Spectrometry) method. In the following Examples and Comparative Examples, silicon compounds in hydrogen peroxide water,
The aluminum compound, the tin compound or their free ions, and the analytical value after the treatment were expressed as the ion concentration.
【００１７】実施例１ ケイ素濃度１０重量ｐｐｂ、アルミニウム濃度１５０重
量ｐｐｂ、スズ濃度５００重量ｐｐｂであり、リン酸を
含みｐＨが２．２であり、ケイ素化合物、アルミニウム
化合物、スズ化合物またはこれらの遊離イオンを含有す
る３０重量％の過酸化水素水を、平均孔径０．１４μｍ
のポリテトラフルオロエチレン製の平膜型限外濾過膜
（ジャパンゴアテックス（株）製）に１０℃で通過さ
せ、次いで強酸性カチオン交換樹脂（オルガノ（株）製
商品名アンバーライト２０１Ｂ、Ｈ型）、強塩基性ア
ニオン交換樹脂（オルガノ（株）製 商品名アンバーラ
イトＩＲＡ−９００、ＨＣＯ3 型）の順で各樹脂層にそ
れぞれ空間速度（ＳＶ）５００ｈｒ-1で通液し、精製し
た。精製後のケイ素、アルミニウムおよびスズ濃度を表
−１に示す。Example 1 A silicon concentration of 10 ppb, an aluminum concentration of 150 ppb, a tin concentration of 500 ppb, a phosphoric acid-containing pH of 2.2, a silicon compound, an aluminum compound, a tin compound, or a release thereof. 30% by weight of hydrogen peroxide solution containing ions, average pore diameter of 0.14 μm
Polytetrafluoroethylene flat membrane ultrafiltration membrane (Japan Gore-Tex Co., Ltd.) at 10 ° C., followed by strong acid cation exchange resin (Organo Co., Ltd., trade name Amberlite 201B, H type) ), And a strongly basic anion exchange resin (trade name: Amberlite IRA-900 manufactured by Organo Corporation, HCO 3 type) in this order at a space velocity (SV) of 500 hr −1 to purify the resin layers. Table 1 shows the concentrations of silicon, aluminum and tin after purification.
【００１８】実施例２ 濾過前に過酸化水素水のｐＨを、アンモニア水を添加す
ることにより３に調整したこと以外は実施例１と同様に
処理し、精製した。精製後のケイ素、アルミニウムおよ
びスズ濃度を表−１に示す。Example 2 The same treatment and purification as in Example 1 were carried out except that the pH of the hydrogen peroxide solution was adjusted to 3 by adding ammonia water before filtration. Table 1 shows the concentrations of silicon, aluminum and tin after purification.
【００１９】実施例３ 濾過前に過酸化水素水のｐＨを、アンモニア水を添加す
ることにより５に調整したこと以外は実施例１と同様に
処理し、精製した。精製後のケイ素、アルミニウムおよ
びスズ濃度を表−１に示す。Example 3 The same treatment and purification as in Example 1 were carried out except that the pH of the hydrogen peroxide solution was adjusted to 5 by adding aqueous ammonia before filtration. Table 1 shows the concentrations of silicon, aluminum and tin after purification.
【００２０】実施例４ 平均孔径０．０４μｍのポリオレフィン製の平膜型限外
濾過膜（三菱化学（株）製）を使用した以外は実施例１
と同様に処理し、精製した。精製後のケイ素、アルミニ
ウムおよびスズ濃度を表−１に示す。Example 4 Example 1 was repeated except that a polyolefin flat membrane ultrafiltration membrane (manufactured by Mitsubishi Chemical Co., Ltd.) having an average pore diameter of 0.04 μm was used.
Was treated and purified in the same manner as in. Table 1 shows the concentrations of silicon, aluminum and tin after purification.
【００２１】実施例５ 濾過前に過酸化水素水にアンモニアを添加してｐＨを３
に調整した以外は実施例４と同様に処理し、精製した。
精製後のケイ素、アルミニウムおよびスズの濃度を表−
１に示す。Example 5 Ammonia was added to hydrogen peroxide to adjust the pH to 3 before filtration.
The same treatment and purification as in Example 4 were carried out except that the above was adjusted.
Shows the concentration of silicon, aluminum and tin after purification.
It is shown in FIG.
【００２２】実施例６ ケイ素濃度１０重量ｐｐｂ、アルミニウム濃度１５０重
量ｐｐｂであり、スズ化合物を含まないｐＨが３．９で
あり、ケイ素化合物、アルミニウム化合物またはこれら
の遊離イオンを含有する３０重量％の過酸化水素水を用
いた以外は、実施例１と同様に処理し、精製した。精製
後のケイ素およびアルミニウム濃度を表−１に示す。Example 6 A silicon concentration of 10 ppb, an aluminum concentration of 150 ppb, a tin compound-free pH of 3.9, and a silicon compound, an aluminum compound or 30 wt% of these free ions are contained. The same treatment and purification as in Example 1 were carried out except that hydrogen peroxide solution was used. Table 1 shows the silicon and aluminum concentrations after purification.
【００２３】実施例７ 実施例６に使用した過酸化水素水を、実施例４と同様に
平均孔径０．０４μｍの限外濾過膜を使用し実施例４と
同様に処理し、精製した。精製後のケイ素およびアルミ
ニウム濃度を表−１に示す。Example 7 The hydrogen peroxide solution used in Example 6 was treated and purified in the same manner as in Example 4 using an ultrafiltration membrane having an average pore diameter of 0.04 μm as in Example 4. Table 1 shows the silicon and aluminum concentrations after purification.
【００２４】実施例８ ケイ素濃度１０重量ｐｐｂ、アルミニウム濃度１５０重
量ｐｐｂ、スズ濃度５００重量ｐｐｂであり、リン酸を
含みｐＨが２．２であり、ケイ素化合物、アルミニウム
化合物、スズ化合物またはこれらの遊離イオンを含有す
る３０重量％の過酸化水素水を、アンモニア水を添加し
てｐＨ３に調整し、まず強酸性カチオン交換樹脂（オル
ガノ（株）製、商品名アンバーライト２０１Ｂ、Ｈ
型）、強塩基性アニオン交換樹脂（オルガノ（株）製、
商品名アンバーライトＩＲＡ−９００、ＨＣＯ3 型）の
順で各樹脂層にそれぞれ空間速度（ＳＶ）５００ｈｒ-1
で通過した。ついで、得られた過酸化水素水を平均孔径
０．１４μｍのポリテトラフルオロエチレン製平膜型限
外濾過膜（ジャパンゴアテックス（株）製）に１０℃で
通過し、精製した。精製後のケイ素、アルミニウムおよ
びスズ濃度を表−１に示す。Example 8 A silicon concentration of 10 ppb, an aluminum concentration of 150 ppb, a tin concentration of 500 ppb, a phosphoric acid-containing pH of 2.2, a silicon compound, an aluminum compound, a tin compound or a release thereof. Aqueous 30% by weight hydrogen peroxide containing ions was adjusted to pH 3 by adding ammonia water. First, a strong acid cation exchange resin (Organo Corporation, trade name Amberlite 201B, H) was used.
Type), a strongly basic anion exchange resin (manufactured by Organo Corporation,
Space velocity (SV) 500 hr -1 in each resin layer in the order of brand name Amberlite IRA-900, HCO 3 type)
I passed by. Then, the obtained hydrogen peroxide solution was passed through a flat membrane type ultrafiltration membrane (manufactured by Japan GORE-TEX Co., Ltd.) made of polytetrafluoroethylene having an average pore diameter of 0.14 μm at 10 ° C. for purification. Table 1 shows the concentrations of silicon, aluminum and tin after purification.
【００２５】実施例９ 過酸化水素水の濾過を、平均孔径０．０４μｍのポリオ
レフィン製の平膜型限外濾過膜（三菱化学（株）製）で
行った以外は実施例８と同様に処理し、精製した。精製
後のケイ素、アルミニウムおよびスズ濃度を表−１に示
す。Example 9 The same treatment as in Example 8 was carried out except that the hydrogen peroxide solution was filtered using a flat membrane ultrafiltration membrane (manufactured by Mitsubishi Chemical Corporation) made of polyolefin having an average pore size of 0.04 μm. And purified. Table 1 shows the concentrations of silicon, aluminum and tin after purification.
【００２６】比較例１ ケイ素濃度１０重量ｐｐｂ、アルミニウム濃度１５０重
量ｐｐｂ、スズ濃度５００重量ｐｐｂであり、リン酸を
含みｐＨが２．２であり、ケイ素化合物、アルミニウム
化合物、スズ化合物またはこれらの遊離イオンを含有す
る３０重量％の過酸化水素水を、強酸性カチオン交換樹
脂（オルガノ（株）製 商品名アンバーライト２０１
Ｂ、Ｈ型）、強塩基性アニオン交換樹脂（オルガノ
（株）製 商品名アンバーライトＩＲＡ−９００、ＨＣ
Ｏ3 型）の順で各樹脂層にそれぞれ空間速度（ＳＶ）５
００ｈｒ-1で通液し、精製した。精製後のケイ素、アル
ミニウムおよびスズ濃度を表−１に示す。Comparative Example 1 A silicon concentration of 10 ppb, an aluminum concentration of 150 ppb, a tin concentration of 500 ppb, a phosphoric acid-containing pH of 2.2, a silicon compound, an aluminum compound, a tin compound or a release thereof. Aqueous 30% by weight hydrogen peroxide solution containing ions was used as a strong acid cation exchange resin (Amberlite 201 manufactured by Organo Corporation)
B, H type), strongly basic anion exchange resin (manufactured by Organo Corporation, trade name: Amberlite IRA-900, HC)
Space velocity (SV) 5 for each resin layer in the order of O 3 type)
The solution was passed through at 00 hr -1 for purification. Table 1 shows the concentrations of silicon, aluminum and tin after purification.
【００２７】比較例２ イオン交換樹脂による処理の前に、過酸化水素水のｐＨ
をアンモニア水で３に調整した以外は比較例１と同様に
処理し、精製した。精製後のケイ素、アルミニウムおよ
びスズ濃度を表−１に示す。Comparative Example 2 Before treatment with an ion exchange resin, the pH of hydrogen peroxide solution was adjusted.
Was treated and purified in the same manner as in Comparative Example 1 except that was adjusted to 3 with aqueous ammonia. Table 1 shows the concentrations of silicon, aluminum and tin after purification.
【００２８】比較例３ 平均孔径０．２１μｍのポリテトラフルオロエチレン製
の平膜型限外濾過膜（ジャパンゴアテックス（株）製）
で行った以外は実施例１と同様に処理し、精製した。精
製後のケイ素、アルミニウムおよびスズ濃度を表−１に
示す。Comparative Example 3 Flat membrane ultrafiltration membrane made of polytetrafluoroethylene having an average pore diameter of 0.21 μm (manufactured by Japan Gore-Tex Co., Ltd.)
Was treated and purified in the same manner as in Example 1 except that the above procedure was performed. Table 1 shows the concentrations of silicon, aluminum and tin after purification.
【００２９】比較例４ 過酸化水素水のｐＨを、アンモニア水を添加することに
より７．５に調整した以外は実施例４と同様に処理し、
精製した。精製後のケイ素、アルミニウムおよびスズ濃
度を表−１に示す。Comparative Example 4 Treatment was carried out in the same manner as in Example 4 except that the pH of the hydrogen peroxide solution was adjusted to 7.5 by adding ammonia water,
Purified. Table 1 shows the concentrations of silicon, aluminum and tin after purification.
【００３０】比較例５ ケイ素濃度１０重量ｐｐｂ、アルミニウム濃度１５０重
量ｐｐｂであり、スズ化合物を含まないｐＨが３．９で
あり、ケイ素化合物、アルミニウム化合物またはこれら
の遊離イオンを含有する３０重量％の過酸化水素水を用
いた以外は、比較例３と同様に処理し、精製した。精製
後のケイ素およびアルミニウム濃度を表−１に示す。Comparative Example 5 A silicon concentration of 10 ppb, an aluminum concentration of 150 ppb, a tin compound-free pH of 3.9, and a silicon compound, an aluminum compound or 30 wt% of these free ions are contained. The same treatment and purification as in Comparative Example 3 were carried out except that hydrogen peroxide solution was used. Table 1 shows the silicon and aluminum concentrations after purification.
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【発明の効果】本発明によれば、従来の精製方法ではほ
とんど除去できないケイ素化合物を除去することができ
ると共に、従来のイオン交換樹脂による精製方法では一
部除去しきれなかったアルミニウム化合物やスズ化合物
をも極めて低濃度にまで除去することができ、極めて高
純度な過酸化水素水を製造することができる。本発明に
よる高純度過酸化水素水は、特に半導体製造分野、医療
分野での使用に最適である。EFFECTS OF THE INVENTION According to the present invention, a silicon compound which can hardly be removed by a conventional purification method can be removed, and an aluminum compound or a tin compound which cannot be partially removed by a conventional purification method using an ion exchange resin. Can also be removed to an extremely low concentration, and an extremely high-purity hydrogen peroxide solution can be produced. The high-purity hydrogen peroxide solution according to the present invention is particularly suitable for use in the semiconductor manufacturing field and medical field.
Claims (5)
過酸化水素水を処理することを特徴とする高純度過酸化
水素水の製造方法。1. A method for producing high-purity hydrogen peroxide water, which comprises treating the hydrogen peroxide water with an ion exchange resin and an ultrafiltration membrane.
下のものである請求項１記載の方法。2. The method according to claim 1, wherein the ultrafiltration membrane has an average pore diameter of 0.15 μm or less.
ン樹脂、ポリアクリロニトリル樹脂、ポリスルホン樹
脂、ポリエーテルスルホン樹脂、ポリアミド樹脂、ポリ
イミド樹脂、ポリカーボネート樹脂の群から選択される
請求項１および２記載の方法。3. The method according to claim 1, wherein the ultrafiltration membrane is selected from the group consisting of fluororesin, polyolefin resin, polyacrylonitrile resin, polysulfone resin, polyethersulfone resin, polyamide resin, polyimide resin and polycarbonate resin. .
Ｈを３〜５に調整される請求項１記載の方法。4. The hydrogen peroxide solution to be treated is previously p
The method of claim 1, wherein H is adjusted to 3-5.
脂、強塩基性アニオン交換樹脂、および強酸性カチオン
交換樹脂と強塩基性アニオン交換樹脂の混合物の単独ま
たは組み合わせによる請求項１〜４に記載の方法。5. The method according to claim 1, wherein the ion exchange resin is a strongly acidic cation exchange resin, a strongly basic anion exchange resin, or a mixture of a strongly acidic cation exchange resin and a strongly basic anion exchange resin, alone or in combination. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02656796A JP3849724B2 (en) | 1996-02-14 | 1996-02-14 | Production method of high purity hydrogen peroxide water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02656796A JP3849724B2 (en) | 1996-02-14 | 1996-02-14 | Production method of high purity hydrogen peroxide water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09221305A true JPH09221305A (en) | 1997-08-26 |
| JP3849724B2 JP3849724B2 (en) | 2006-11-22 |
Family
ID=12197128
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02656796A Expired - Fee Related JP3849724B2 (en) | 1996-02-14 | 1996-02-14 | Production method of high purity hydrogen peroxide water |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6649139B2 (en) | 2000-06-21 | 2003-11-18 | Santoku Chemical Industries Co., Ltd. | Process for producing a purified aqueous hydrogen peroxide solution |
| WO2005113115A1 (en) * | 2004-05-11 | 2005-12-01 | National Aeronautics And Space Administration | Emission control system |
| JP2008127231A (en) * | 2006-11-17 | 2008-06-05 | Santoku Kagaku Kogyo Kk | Method and apparatus for purifying hydrogen peroxide solution |
| CN112723316A (en) * | 2021-01-04 | 2021-04-30 | 联仕(昆山)化学材料有限公司 | Purification method for removing TOC in hydrogen peroxide at low temperature |
| CN113942979A (en) * | 2021-11-11 | 2022-01-18 | 河南慧泽生物工程有限公司 | Preparation method of ultra-pure hydrogen peroxide |
| FR3129148A1 (en) * | 2021-11-17 | 2023-05-19 | Arkema France | Hydrogen peroxide purification on membrane |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107265409A (en) | 2011-09-30 | 2017-10-20 | 三菱瓦斯化学株式会社 | The manufacture method of aqueous hydrogen peroxide solution |
-
1996
- 1996-02-14 JP JP02656796A patent/JP3849724B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6649139B2 (en) | 2000-06-21 | 2003-11-18 | Santoku Chemical Industries Co., Ltd. | Process for producing a purified aqueous hydrogen peroxide solution |
| WO2005113115A1 (en) * | 2004-05-11 | 2005-12-01 | National Aeronautics And Space Administration | Emission control system |
| JP2008127231A (en) * | 2006-11-17 | 2008-06-05 | Santoku Kagaku Kogyo Kk | Method and apparatus for purifying hydrogen peroxide solution |
| CN112723316A (en) * | 2021-01-04 | 2021-04-30 | 联仕(昆山)化学材料有限公司 | Purification method for removing TOC in hydrogen peroxide at low temperature |
| CN113942979A (en) * | 2021-11-11 | 2022-01-18 | 河南慧泽生物工程有限公司 | Preparation method of ultra-pure hydrogen peroxide |
| FR3129148A1 (en) * | 2021-11-17 | 2023-05-19 | Arkema France | Hydrogen peroxide purification on membrane |
| WO2023089251A1 (en) * | 2021-11-17 | 2023-05-25 | Arkema France | Membrane purification of hydrogen peroxide |
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| Publication number | Publication date |
|---|---|
| JP3849724B2 (en) | 2006-11-22 |
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