JP5704979B2 - Method for producing purified hydrogen peroxide water - Google Patents
Method for producing purified hydrogen peroxide water Download PDFInfo
- Publication number
- JP5704979B2 JP5704979B2 JP2011053206A JP2011053206A JP5704979B2 JP 5704979 B2 JP5704979 B2 JP 5704979B2 JP 2011053206 A JP2011053206 A JP 2011053206A JP 2011053206 A JP2011053206 A JP 2011053206A JP 5704979 B2 JP5704979 B2 JP 5704979B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen peroxide
- exchange resin
- peroxide solution
- ion
- reverse osmosis
- 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.)
- Active
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- 238000004519 manufacturing process Methods 0.000 title claims description 23
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 title claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 163
- 239000012528 membrane Substances 0.000 claims description 94
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 87
- 238000001223 reverse osmosis Methods 0.000 claims description 66
- 239000003456 ion exchange resin Substances 0.000 claims description 56
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 56
- 239000003381 stabilizer Substances 0.000 claims description 53
- 239000012535 impurity Substances 0.000 claims description 34
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 19
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 17
- 150000001768 cations Chemical class 0.000 claims description 15
- 229920002647 polyamide Polymers 0.000 claims description 14
- 150000001450 anions Chemical class 0.000 claims description 13
- 238000000746 purification Methods 0.000 claims description 11
- 239000004952 Polyamide Substances 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- 239000002738 chelating agent Substances 0.000 claims description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- 235000011180 diphosphates Nutrition 0.000 claims description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 4
- 125000005402 stannate group Chemical group 0.000 claims description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229940071182 stannate Drugs 0.000 claims description 2
- 239000003957 anion exchange resin Substances 0.000 description 70
- 229910021642 ultra pure water Inorganic materials 0.000 description 42
- 239000012498 ultrapure water Substances 0.000 description 42
- 238000000034 method Methods 0.000 description 35
- 239000003729 cation exchange resin Substances 0.000 description 34
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 31
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 29
- 239000011347 resin Substances 0.000 description 29
- 229920005989 resin Polymers 0.000 description 29
- 239000012492 regenerant Substances 0.000 description 25
- 239000007864 aqueous solution Substances 0.000 description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000005342 ion exchange Methods 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 239000010410 layer Substances 0.000 description 12
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- 230000007935 neutral effect Effects 0.000 description 10
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- 239000002253 acid Substances 0.000 description 8
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- 238000004140 cleaning Methods 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 7
- -1 pulp bleaching Substances 0.000 description 7
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
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- 239000000178 monomer Substances 0.000 description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 description 6
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- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 3
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- 229910052804 chromium Inorganic materials 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
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- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
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- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- JSYBAZQQYCNZJE-UHFFFAOYSA-N benzene-1,2,4-triamine Chemical compound NC1=CC=C(N)C(N)=C1 JSYBAZQQYCNZJE-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
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- 150000004820 halides Chemical class 0.000 description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
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- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
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- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000003799 water insoluble solvent Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
Description
本発明は精製過酸化水素水の製造方法に関し、詳しくは、工業用過酸化水素水に含まれる安定剤を再現性よく除去することが可能な高純度過酸化水素水の製造方法、ならびにそのための精製過酸化水素水の製造装置に関する。 The present invention relates to a method for producing purified hydrogen peroxide solution, and more specifically, a method for producing high-purity hydrogen peroxide solution capable of reproducibly removing a stabilizer contained in industrial hydrogen peroxide solution, and for the same The present invention relates to an apparatus for producing purified hydrogen peroxide water.
過酸化水素水は、紙、パルプの漂白、化学研磨液等の多くの分野で広く利用されているが、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おける利用が増大し、これにともない、とりわけ、過酸化水素水中の種々の不純物を極力低減した高純度な品質が要求されている。 Hydrogen peroxide solution is widely used in many fields such as paper, pulp bleaching, chemical polishing liquid, etc., but in recent years, its use in the electronics industry such as silicon wafer cleaning agents and semiconductor process cleaning agents has increased. Along with this, in particular, there is a demand for high-purity quality in which various impurities in hydrogen peroxide water are reduced as much as possible.
過酸化水素水は、主にアントラキノン法により製造されており、その製造方法は、まず、２−アルキルアントラキノンなどのアントラキノン誘導体を、水不溶性の溶媒中で水素化触媒の存在下で水素化してアントラヒドロキノンとし、触媒を除去した後、空気により酸化することによって２−アルキルアントラキノンを再生するとともに、このとき生成する過酸化水素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。この方法をアントラキノン自動酸化法（AO法）という。 The hydrogen peroxide solution is mainly produced by the anthraquinone method. First, an anthraquinone derivative such as 2-alkylanthraquinone is hydrogenated in the presence of a hydrogenation catalyst in a water-insoluble solvent. In this method, hydroquinone is used to remove the catalyst, and then oxidize with air to regenerate 2-alkylanthraquinone and extract the hydrogen peroxide generated at this time with water to obtain a hydrogen peroxide-containing aqueous solution. This method is called anthraquinone auto-oxidation method (AO method).
この方法によって製造された過酸化水素水中には、装置材質などに起因するＡｌ、Ｆｅ、Ｃｒなどの金属不純物、無機イオン性不純物（塩）の他、製造方法などに起因する有機不純物が含まれている。 The hydrogen peroxide solution produced by this method contains metal impurities such as Al, Fe, Cr, and inorganic ionic impurities (salts) caused by equipment materials, and organic impurities caused by the production method. ing.
特に金属不純物は過酸化水素水の分解触媒となり得るため、存在していると、過酸化水素水の安定度が低い。また前記のような不純物が含まれていると、貯蔵、輸送、取扱などの過程においても過酸化水素水の分解起因となる汚染を受け、過酸化水素水の安定度を保つことは容易ではない。 In particular, since metal impurities can serve as a decomposition catalyst for hydrogen peroxide solution, if present, the stability of hydrogen peroxide solution is low. Also, if impurities such as those mentioned above are contained, it will be difficult to maintain the stability of the hydrogen peroxide solution due to contamination caused by the decomposition of the hydrogen peroxide solution in the process of storage, transportation, handling, etc. .
従って工業用の過酸化水素水には、安定剤が添加されており、主に使用される安定剤はリン酸塩、ピロリン酸塩、錫酸塩などの無機キレート剤や有機キレート剤ではエチレンジアミンテトラメチレンなどのホスホン酸系キレート剤や、エチレンジアミン４酢酸、ニトリロトリ酢酸等が列挙される安定剤がppmオーダーで添加されている。 Therefore, stabilizers are added to industrial hydrogen peroxide, and the stabilizers used mainly are inorganic diamines such as phosphates, pyrophosphates, and stannates, and ethylenediaminetetrachloride for organic chelators. Phosphonic acid-based chelating agents such as methylene, stabilizers such as ethylenediaminetetraacetic acid and nitrilotriacetic acid are added in the order of ppm.
一方で半導体ウェハや半導体デバイスの製造工程で使用される過酸化水素水は電子デバイスの特性上、非常に高い純度が要求され、その純度レベルはppb，pptさらにはppqに至っている。 On the other hand, hydrogen peroxide used in the manufacturing process of semiconductor wafers and semiconductor devices is required to have very high purity due to the characteristics of electronic devices, and the purity level has reached ppb, ppt, and ppq.
半導体向けの過酸化水素水は上記した不純物、さらに安定剤が含有された工業用過酸化水素水を精製することにより製造されている。過酸化水素水の精製は、吸着樹脂、イオン交換樹脂、キレート樹脂、逆浸透膜、限外ろ過などを用いて各々の目的に合わせて行われる。（特開平9-102480号公報：特許文献１、特開2003-1070号公報：特許文献２、特開2008-127231号公報：特許文献３、特開2000-272908号公報：特許文献４、特開平8-73205号公報：特許文献５など）
The hydrogen peroxide solution for semiconductors is manufactured by refining industrial hydrogen peroxide solution containing the impurities and stabilizers described above. Purification of the hydrogen peroxide solution is performed according to each purpose using an adsorption resin, an ion exchange resin, a chelate resin, a reverse osmosis membrane, an ultrafiltration and the like. (JP-A-9-102480: Patent Document 1, JP-A-2003-1070: Patent Document 2, JP-A-2008-127231:
このようなイオン交換樹脂による精製工程のライフは、精製する粗過酸化水素水に含まれる不純物や不純物と安定剤の含有量に依存する。特に安定剤の含有量は分解を防ぐために高濃度であり、安定剤が添加された工業用過酸化水素水を、イオン交換樹脂を用いて精製する方法において、イオン交換樹脂のライフは安定剤の添加量に依存する。 The life of the purification process using such an ion exchange resin depends on the impurities contained in the crude hydrogen peroxide solution to be purified and the contents of the impurities and the stabilizer. In particular, the content of the stabilizer is high in order to prevent decomposition, and in a method of purifying industrial hydrogen peroxide water to which the stabilizer is added using an ion exchange resin, the life of the ion exchange resin is that of the stabilizer. Depends on the amount added.
このため、イオン交換樹脂での処理に先立ち、安定剤を除去することが望まれている。
しかしながら、このような、安定剤を除去することに着目した技術なんら提案されていない。
For this reason, it is desired to remove the stabilizer prior to the treatment with the ion exchange resin.
However, no technology that focuses on removing such a stabilizer has been proposed.
このような状況の下、本発明者らは、鋭意検討を行なった結果、工業用過酸化水素水を、あらかじめ、膜表面に親水基が導入された逆浸透膜と、接触させて、安定剤を除去しておくことで、イオン交換樹脂のライフを長期に保つことが可能となり、長期にわたって、安定に精製過酸化水素水を調製できることを見出し、本発明を完成するに至った。 Under such circumstances, as a result of intensive studies, the present inventors have made industrial hydrogen peroxide water contact with a reverse osmosis membrane in which a hydrophilic group has been introduced on the membrane surface in advance, thereby stabilizing the stabilizer. It has been found that the life of the ion exchange resin can be maintained for a long time by removing the water, and it has been found that a purified hydrogen peroxide solution can be stably prepared over a long period of time, and the present invention has been completed.
本発明の構成は以下のとおりである。
[1]安定剤を含む工業用過酸化水素水を、
膜表面に親水基が導入された逆浸透膜と、接触させて、安定剤の７０重量％以上を除去したのち、
ついで、カチオンイオン交換樹脂および／またはアニオンイオン交換樹脂により、過酸化水素水に含まれる不純物を除去する精製過酸化水素水の製造方法。
[2]前記逆浸透膜が、ポリアミド系又はポリビニルアルコール系の複合膜からなる[1]の精製過酸化水素水の製造方法。
[3]安定剤がリン酸塩、ピロリン酸塩、錫酸塩、エチレンジアミンテトラメチレンのホスホン酸キレート剤や、エチレンジアミン４酢酸、ニトリロトリ酢酸から選ばれる少なくとも1種である[1]または[2]の精製過酸化水素水の製造方法。
[4]得られる精製過酸化水素水の安定度が９８％以上である前記[1]〜[3]の精製過酸化水素水の製造方法。
[5]安定剤を含む工業用過酸化水素水を、カチオンイオン交換樹脂および／またはアニオンイオン交換樹脂が充填された精製塔を使用して、過酸化水素水を精製する精製過酸化水素水の精製装置であって、
前処理手段として、親水基が導入され、ポリアミド系又はポリビニルアルコール系の複合膜から安定剤の７０重量％以上を除去しうる逆浸透膜が充填されてなるモジュールを備えてなることを特徴とする精製過酸化水素水の精製装置。
[6]得られる精製過酸化水素水の安定度が９８％以上であることを特徴とする[6]の製造装置。
The configuration of the present invention is as follows.
[1] Industrial hydrogen peroxide containing stabilizers
After contacting with a reverse osmosis membrane having a hydrophilic group introduced on the membrane surface to remove 70% by weight or more of the stabilizer,
Next, a method for producing purified hydrogen peroxide solution, wherein impurities contained in the hydrogen peroxide solution are removed by a cation ion exchange resin and / or an anion ion exchange resin.
[2] The method for producing purified hydrogen peroxide solution according to [1], wherein the reverse osmosis membrane is a polyamide-based or polyvinyl alcohol-based composite membrane.
[3] The stabilizer is at least one selected from phosphate, pyrophosphate, stannate, phosphonic acid chelating agent of ethylenediaminetetramethylene, ethylenediaminetetraacetic acid, nitrilotriacetic acid, [1] or [2] A method for producing purified hydrogen peroxide water.
[4] The method for producing purified hydrogen peroxide solution according to [1] to [3], wherein the stability of the purified hydrogen peroxide solution obtained is 98% or more.
[5] Purified hydrogen peroxide solution that purifies hydrogen peroxide solution using a purification tower filled with a cation ion exchange resin and / or anion ion exchange resin from industrial hydrogen peroxide solution containing a stabilizer A purification device,
As a pretreatment means, it is provided with a module in which a hydrophilic group is introduced and a reverse osmosis membrane capable of removing 70% by weight or more of a stabilizer from a polyamide-based or polyvinyl alcohol-based composite membrane is filled. Purification equipment for purified hydrogen peroxide.
[6] The production apparatus according to [6], wherein the stability of the obtained purified hydrogen peroxide solution is 98% or more.
なお、逆浸透膜を使用する精製過酸化水素水の製造方法は、いくつかの特許文献により提案されている。
たとえば、特開平11-139811号公報には、Fe，Cr含有量10ppb以下の過酸化水素水をさらに精製する方法として、0.2〜300μmol/Lの安定剤を添加後逆浸透膜で処理する。使用する逆浸透膜は芳香族架橋ポリアミドとポリスルホン系高分子及びポリエステル系高分子からなる複合膜で日東電工社製ES-10，ES-20が例示されている。また、特開平9-102480号公報には、Si 5ppb以下の過酸化水素水を得る方法として日東電工社製のNTR-759HRを使用することが開示され、かかる逆浸透膜は、Si成分阻止率が高い緻密な膜表面で膜表面にスキン層を有する。さらに、特開平8-151203号公報には、逆浸透膜を用いて過酸化水素水を精製する方法において逆浸透膜の濃縮水を粗過酸化水素水に戻す前にイオン交換樹脂／キレート樹脂の一種以上を使用し、遷移金属を80ppb以下とし、更に前記処理した過酸化水素水をアニオン交換樹脂とカチオン交換樹脂を用いて精製する方法が開示されている。
A method for producing purified hydrogen peroxide water using a reverse osmosis membrane has been proposed by several patent documents.
For example, in Japanese Patent Application Laid-Open No. 11-139811, as a method for further purifying hydrogen peroxide having an Fe and Cr content of 10 ppb or less, 0.2 to 300 μmol / L stabilizer is added and then treated with a reverse osmosis membrane. The reverse osmosis membrane used is a composite membrane composed of an aromatic crosslinked polyamide, a polysulfone polymer and a polyester polymer, and examples thereof include ES-10 and ES-20 manufactured by Nitto Denko Corporation. JP-A-9-102480 discloses that NTR-759HR manufactured by Nitto Denko Corporation is used as a method for obtaining hydrogen peroxide water of Si 5 ppb or less, and such reverse osmosis membrane has a Si component blocking rate. It has a skin layer on the film surface with a high and dense film surface. Further, JP-A-8-151203 discloses a method for purifying hydrogen peroxide solution using a reverse osmosis membrane before returning the concentrated water of the reverse osmosis membrane to the crude hydrogen peroxide solution. A method is disclosed in which at least one transition metal is used, the transition metal is 80 ppb or less, and the treated hydrogen peroxide solution is purified using an anion exchange resin and a cation exchange resin.
また、特許第2976776号公報には、工業用過酸化水素水をRO膜で処理するとTOCが10ppm以下になり、特開平7-33408号公報には、工業用過酸化水素水をポリアミド系RO膜で処理するとTOCが10ppm以下になることが開示されている。特開2000-302418号公報には、工業用過酸化水素水の製造工程で水添、酸化後の作動液から過酸化水素を水で抽出した時に混入する有機物を蒸留して除去しているが、この蒸留に替えて逆浸透膜処理すると熱による過酸化水素分解のロスを抑えることができることが開示されている。さらに、特開2003-1070号公報には、41〜75％の工業用過酸化水素水を逆浸透膜で処理し、さらにTOCを含まない超純水で希釈し、31％過酸化水素水を精製すればTOCが3ppm以下にできることが開示されている。また、特開平10-330102号公報には、工業用過酸化水素水をRO膜で処理するとTOCが10ppm以下になると記載されている。 Japanese Patent No. 2976776 discloses that industrial hydrogen peroxide is treated with an RO membrane, resulting in a TOC of 10 ppm or less, and Japanese Patent Application Laid-Open No. 7-33408 discloses industrial hydrogen peroxide with a polyamide RO membrane. It is disclosed that the TOC is 10 ppm or less when treated with. Japanese Patent Laid-Open No. 2000-302418 distills and removes organic substances mixed when hydrogen peroxide is extracted from water after hydrogenation and oxidation in the industrial hydrogen peroxide water production process. In addition, it is disclosed that a reverse osmosis membrane treatment instead of distillation can suppress a loss of hydrogen peroxide decomposition due to heat. Furthermore, Japanese Patent Laid-Open No. 2003-1070 discloses that 41-75% industrial hydrogen peroxide solution is treated with a reverse osmosis membrane, further diluted with ultrapure water containing no TOC, and 31% hydrogen peroxide solution is added. It is disclosed that TOC can be reduced to 3 ppm or less if purified. Japanese Patent Laid-Open No. 10-330102 describes that TOC is reduced to 10 ppm or less when industrial hydrogen peroxide is treated with an RO membrane.
このように、逆浸透膜を使用して過酸化水素水を精製することは知られていたが、本特許では安定剤が添加された工業用過酸化水素水を、イオン交換樹脂を用いて精製する方法において、イオン交換樹脂のライフ長期に保つため、前処理として逆浸透膜を使用し、イオン交換樹脂やキレート樹脂導入前の過酸化水素水中の安定剤を除去するという観点で逆浸透膜を使用することはなんら知られていなかった。 As described above, it was known to purify hydrogen peroxide using a reverse osmosis membrane, but in this patent, industrial hydrogen peroxide added with a stabilizer was purified using an ion exchange resin. In order to maintain the long life of the ion exchange resin, a reverse osmosis membrane is used as a pretreatment, and the reverse osmosis membrane is removed from the viewpoint of removing the stabilizer in the hydrogen peroxide solution before introducing the ion exchange resin or chelate resin. There was nothing known to use.
本発明によれば、あらかじめ工業用過酸化水素水に含まれる安定剤を70%以上除去するので、後段のイオン交換樹脂精製工程での処理ライフを長くすることができ、また安定剤を含まずに安定度98%以上の過酸化水素水を得ることができる。このように、逆浸透膜を使用することにより後段のイオン交換樹脂やキレート樹脂の性能を維持しつつ、逆浸透膜そのものの性能も長期に亘り維持することができる。 According to the present invention, since 70% or more of the stabilizer contained in the industrial hydrogen peroxide solution is removed in advance, the treatment life in the subsequent ion exchange resin purification step can be extended, and no stabilizer is contained. In addition, a hydrogen peroxide solution having a stability of 98% or more can be obtained. Thus, by using the reverse osmosis membrane, the performance of the reverse osmosis membrane itself can be maintained for a long time while maintaining the performance of the ion exchange resin or chelate resin in the subsequent stage.
従って過酸化水素水の精製工程全体の能力を低下させずに長時間運転することが可能であり、生産コストを抑制することが可能である。また、本発明で使用される逆浸透膜は低圧運転が可能であり、このことによって逆浸透膜工程のランニングコストも抑制できる。 Therefore, it is possible to operate for a long time without deteriorating the capacity of the entire hydrogen peroxide solution purification process, and it is possible to suppress the production cost. In addition, the reverse osmosis membrane used in the present invention can be operated at a low pressure, which can also reduce the running cost of the reverse osmosis membrane process.
以下、本発明に係る精製過酸化水素水の製造方法について具体的に説明する。なお、本明細書中において、ppm、ppb、pptおよびppqは、いずれも重量ppm、重量ppb、重量pptおよび重量ppqを示す。 Hereinafter, the method for producing purified hydrogen peroxide solution according to the present invention will be described in detail. In the present specification, ppm, ppb, ppt and ppq all indicate ppm by weight, ppb by weight, ppt by weight and ppq by weight.
［精製過酸化水素水の製造方法］
本発明では、まず、工業用過酸化水素水と、逆浸透膜と、接触させて、安定剤を除去する。
[Production method of purified hydrogen peroxide]
In the present invention, first, the stabilizer is removed by contacting with an industrial hydrogen peroxide solution and a reverse osmosis membrane.
工業用過酸化水素水
本発明で使用される工業用過酸化水素水としては、アントラキノン自動酸化法、水素と酸素を直接反応させる直接合成法など、公知の製造法によって製造された工業用過酸化水素水が使用される。通常、工業用過酸化水素水中の過酸化水素濃度は７０％以下であれば特に制限されない。
Industrial hydrogen peroxide solution The industrial hydrogen peroxide solution used in the present invention is an industrial peroxidation produced by a known production method such as an anthraquinone auto-oxidation method or a direct synthesis method in which hydrogen and oxygen are directly reacted. Hydrogen water is used. Usually, the hydrogen peroxide concentration in industrial hydrogen peroxide water is not particularly limited as long as it is 70% or less.
この方法によって製造された過酸化水素水中には、装置材質などに起因するＡｌ、Ｆｅ、Ｃｒなどの無機イオン・化合物不純物の他、製造方法などに起因する有機不純物が含まれている。特に金属不純物は過酸化水素水の分解触媒となり得るため、これら不純物の存在下においては過酸化水素水の安定度が低くなる。このため工業用の製品過酸化水素水となる過酸化水素水には、安定剤が添加されている。 The hydrogen peroxide water produced by this method contains organic impurities caused by the production method in addition to inorganic ions and compound impurities such as Al, Fe, and Cr caused by the material of the apparatus. In particular, since metal impurities can serve as a decomposition catalyst for hydrogen peroxide solution, the stability of the hydrogen peroxide solution is lowered in the presence of these impurities. For this reason, a stabilizer is added to the hydrogen peroxide solution, which is an industrial product hydrogen peroxide solution.
安定剤としては、リン酸塩、ピロリン酸塩、錫酸塩などの無機キレート剤や有機キレート剤ではエチレンジアミンテトラメチレンなどのホスホン酸系キレート剤や、エチレンジアミン４酢酸、ニトリロトリ酢酸等が列挙される。このような安定剤がppmオーダーで工業用過酸化水素水中に添加されている。具体的には、0.1〜100ppm程度の量で含まれている。なお安定剤量は、塩を構成する金属（アルカリ（土類）金属）、有機物量（TOC）、リン、窒素、錫量などから、求めることができる。 Examples of the stabilizer include inorganic chelating agents such as phosphates, pyrophosphates, and stannates, and organic chelating agents such as phosphonic acid-based chelating agents such as ethylenediaminetetramethylene, ethylenediaminetetraacetic acid, nitrilotriacetic acid, and the like. Such stabilizers are added to industrial hydrogen peroxide in the order of ppm. Specifically, it is contained in an amount of about 0.1 to 100 ppm. The amount of the stabilizer can be determined from the metal constituting the salt (alkali (earth) metal), the amount of organic matter (TOC), the amount of phosphorus, nitrogen, tin, and the like.
逆浸透膜
逆浸透膜としては、表面に親水基が導入された逆浸透膜が使用される。このような本発明で使用される逆浸透膜としては、ポリアミド系又はポリビニルアルコール系の複合膜からなる逆浸透膜であり、該逆浸透膜は電気的に中性の有機化合物を含有するか、および／または表面に電気的に中性の有機化合物を含有する保護層を有するものが使用される。このような逆浸透膜としては、特開平10-66846号公報、特開平11-28344号公報、特開平11-28466号公報、特開平10-337454号公報、国際公開WO97/34686号公報、特開平8-192033号などに開示されたものを使用できる。また特開2006-95476号公報、特開2006-95480号公報、特開2006-102624号公報、特開2006-130497号公報に開示されたものも使用することも可能である。
As the reverse osmosis membrane, a reverse osmosis membrane having a hydrophilic group introduced on the surface thereof is used. Such a reverse osmosis membrane used in the present invention is a reverse osmosis membrane composed of a polyamide-based or polyvinyl alcohol-based composite membrane, and the reverse osmosis membrane contains an electrically neutral organic compound, Those having a protective layer containing an electrically neutral organic compound on the surface are used. Examples of such reverse osmosis membranes include JP-A-10-66846, JP-A-11-28344, JP-A-11-28466, JP-A-10-337454, International Publication WO97 / 34686, Those disclosed in Kaihei 8-92033 can be used. In addition, those disclosed in JP-A-2006-95476, JP-A-2006-95480, JP-A-2006-102624, and JP-A-2006-130497 can also be used.
本発明で使用される逆浸透複合膜は、ポリアミド系、ポリビニルアルコール系等のスキン層が支持膜表面に界面重合法により製膜されたものがある。これらの膜は従来の公知の方法等によって、容易に得ることができる。 Some reverse osmosis composite membranes used in the present invention have polyamide or polyvinyl alcohol skin layers formed on the surface of a support membrane by an interfacial polymerization method. These films can be easily obtained by a conventionally known method or the like.
たとえば、多官能芳香族アミンと多官能酸ハロゲン化物を多孔性支持体表面で界面重合すれば、ポリアミド系スキン層を形成できる。具体的には、多孔性支持膜を用い、メタフェニレンジアミン、ピペラジン、ポリエチレンイミン、等の反応性アミノ基を有するモノマー、又はポリマーの水溶液を前記多孔性支持膜の少なくとも片面に塗布した後、トリメシン酸クロライド、イソフタル酸クロライド等の多官能酸クロライド、またはトリレンジイソシアネート等の多官能イソシアネート、又はこれら混合物のヘキサン等の溶媒と接触させ、多孔性支持膜上で界面重合を行なわせてポリアミド系被膜を形成する方法などが挙げられる。 For example, a polyamide skin layer can be formed by interfacial polymerization of a polyfunctional aromatic amine and a polyfunctional acid halide on the surface of the porous support. Specifically, using a porous support film, an aqueous solution of a monomer or polymer having a reactive amino group such as metaphenylenediamine, piperazine, polyethyleneimine, or the like is applied to at least one surface of the porous support film, and then trimesin. Polyamide-based coating by contacting with polyfunctional acid chloride such as acid chloride, isophthalic acid chloride, polyfunctional isocyanate such as tolylene diisocyanate, or a solvent such as hexane of these mixtures, and performing interfacial polymerization on the porous support film The method of forming is mentioned.
また、ポリビニルアルコール層のスキン層は、多孔性支持体にポリビニルアルコールを浸漬させると形成可能であるが、ポリビニルアルコールは、多価アルデヒドで架橋してもよく、また、ジルコニウムによって架橋されていてもよい。さらに、多孔質支持膜表面に形成された、ポリアミド薄膜のスキン層を形成したのち、表面に、ポリビニルアルコールのスキン層を設けてもよい。 The skin layer of the polyvinyl alcohol layer can be formed by immersing polyvinyl alcohol in a porous support. Polyvinyl alcohol may be cross-linked with a polyhydric aldehyde or cross-linked with zirconium. Good. Further, after a polyamide thin film skin layer formed on the surface of the porous support membrane is formed, a polyvinyl alcohol skin layer may be provided on the surface.
多孔性支持膜としては、化学的、機械的、及び熱的に安定である観点から、ポリスルホン、ポリエーテルスルホンのようなポリアリールエーテルスルホンなどの多孔性ポリスルホン支持膜が好ましく、かかる多孔性ポリスルホン支持膜は、通常使用される逆浸透膜の厚さに応じて、厚さは適宜選択されるが、通常約２５〜１２５μｍ、好ましくは約４０〜７５μｍの厚みを有するが、必ずしもこれらに限定されるものではない。多孔性ポリスルホン支持膜は織布、不織布等による裏打ちにて補強されていてもよい。 The porous support membrane is preferably a porous polysulfone support membrane such as polysulfone or polyarylethersulfone such as polyethersulfone from the viewpoint of being chemically, mechanically and thermally stable. The thickness of the membrane is appropriately selected according to the thickness of the reverse osmosis membrane that is usually used, but usually has a thickness of about 25 to 125 μm, preferably about 40 to 75 μm, but is not necessarily limited thereto. It is not a thing. The porous polysulfone support membrane may be reinforced by lining with a woven fabric, a nonwoven fabric or the like.
本発明で使用される逆浸透複合膜においては、スキン層を構成するポリアミドが、芳香族系ポリアミドであることが好ましい。ここで芳香族系ポリアミドとは、酸成分及びアミン成分から選ばれる少なくとも一つの成分が芳香族を含むものをいう。好ましい芳香族系ポリアミドは、酸成分及びアミン成分がともに芳香族を含む全芳香族系ポリアミドである。このような芳香族系ポリアミドは、高い透液性と高い塩阻止率を保持できるとともに、過酸化水素水の処理にも使用することができる。 In the reverse osmosis composite membrane used in the present invention, the polyamide constituting the skin layer is preferably an aromatic polyamide. Here, the aromatic polyamide means that at least one component selected from an acid component and an amine component contains an aromatic. A preferred aromatic polyamide is a wholly aromatic polyamide in which both the acid component and the amine component contain aromatics. Such an aromatic polyamide can maintain high liquid permeability and a high salt rejection, and can also be used for treatment of hydrogen peroxide.
またポリビニルアルコールはケン化度９０％以上のものが好ましい。この場合、分子鎖間水素結合により25℃では水不溶性になるが、80℃の水には可溶であることが好ましい。このようなポリビニルアルコールは膜汚染物質の吸着を抑制する作用が高く、過酸化水素水の処理にも使用することができる。 Polyvinyl alcohol preferably has a saponification degree of 90% or more. In this case, it becomes water-insoluble at 25 ° C. due to intermolecular hydrogen bonding, but it is preferably soluble in water at 80 ° C. Such polyvinyl alcohol has a high effect of suppressing the adsorption of membrane contaminants and can be used for the treatment of hydrogen peroxide.
このような有機化合物を含むか表面に保護層を有するものは、表面に親水基を有する。このため、安定剤が通過しにくくなり除去できる。
電気的に中性の有機化合物とは、非イオン系の親水性基を有する、ビニル系重合体、縮合系重合体または付加系重合体などの有機重合体である。非イオン系の親水性基としては、−ＯＨ、ピロリドン基、−ＣＯＮＨ−、−ＣＨ2ＣＨ2ＯＲ（Ｒは炭素数が１〜４のアルキル基）、−ＳＨなどが挙げられる。有機重合体は、上記に例示したような親水性基のうちの少なくとも１種を含んでいればよいが、水酸基を含んでいることが好ましい。また、有機重合体は、ポリビニルピロリドン、ポリアミド系重合体、ポリエチレングルコール等であってもよいが、ポリビニルアルコ−ル系重合体であることが好ましい。ここで、ポリビニルアルコール系重合体とは、ビニルアルコールを主な単量体とする重合体であり、ポリビニルアルコールおよびポリビニルアルコールと他のビニル単量体との共重合体を含むものである。ここにいうビニル単量体には、例えば、エチレン、ビニルピロリドン、アクリロニトリル、塩化ビニルが含まれる。ポリビニルアルコール系共重合体は、このようなビニル単量体を５０モル％未満含むものが好ましい。
Those containing such an organic compound or having a protective layer on the surface have a hydrophilic group on the surface. For this reason, a stabilizer becomes difficult to pass and can be removed.
The electrically neutral organic compound is an organic polymer having a nonionic hydrophilic group, such as a vinyl polymer, a condensation polymer, or an addition polymer. Examples of the nonionic hydrophilic group include —OH, pyrrolidone group, —CONH—, —CH 2 CH 2 OR (R is an alkyl group having 1 to 4 carbon atoms), —SH, and the like. The organic polymer only needs to contain at least one of the hydrophilic groups exemplified above, but preferably contains a hydroxyl group. The organic polymer may be polyvinyl pyrrolidone, polyamide polymer, polyethylene glycol or the like, but is preferably a polyvinyl alcohol polymer. Here, the polyvinyl alcohol polymer is a polymer having vinyl alcohol as a main monomer, and includes polyvinyl alcohol and copolymers of polyvinyl alcohol and other vinyl monomers. Examples of the vinyl monomer include ethylene, vinyl pyrrolidone, acrylonitrile, and vinyl chloride. The polyvinyl alcohol copolymer preferably contains less than 50 mol% of such a vinyl monomer.
また、電気的に中性の有機化合物としては、カチオン性官能基とアニオン性官能基とを双方有する有機重合体（すなわち電気的には中和されているもの）であってもよい。たとえば芳香族多官能アミン成分と多官能酸ハライド化合物成分との反応物であってもよく、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、ｏ−フェニレンジアミン、１，３，５−トリアミノベンゼン、１，２，４−トリアミノベンゼン、３，５−ジアミノ安息香酸、２，４−ジアミノトルエン、２，６−ジアミノトルエン、Ｎ，Ｎ'−ジメチル−ｍ−フェニレンジアミン、２，４−ジアミノアニソール、アミドール、及びキシリレンジアミン等の芳香族多官能アミンと、反応性カルボニル基を２個以上有する芳香族、脂肪族、又は脂環式の多官能酸ハライドとの反応物でもよい。 Further, the electrically neutral organic compound may be an organic polymer having both a cationic functional group and an anionic functional group (that is, an electrically neutralized one). For example, it may be a reaction product of an aromatic polyfunctional amine component and a polyfunctional acid halide compound component, such as m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3,5-triaminobenzene, 1 , 2,4-triaminobenzene, 3,5-diaminobenzoic acid, 2,4-diaminotoluene, 2,6-diaminotoluene, N, N′-dimethyl-m-phenylenediamine, 2,4-diaminoanisole, A reaction product of an aromatic polyfunctional amine such as amidole and xylylenediamine and an aromatic, aliphatic, or alicyclic polyfunctional acid halide having two or more reactive carbonyl groups may be used.
電気的に中性の有機化合物からなる表層を形成する場合には、逆浸透膜を電気的に中性の有機化合物を含む溶液に浸透させたり、塗布したりすればよい。表層の厚みは、０．００１μｍ〜１μｍ、さらには０．００５μｍ〜０．５μｍ程度とすることが好ましい。電気的に中性の有機化合物を、逆浸透膜に含ませる場合には、有機重合体を、前述のポリアミドの界面重合法において使用する、反応性アミノ基を有するモノマーおよび／またはポリマーの水溶液、あるいは多官能酸クロライド等を含む有機溶媒に混合して、逆浸透複合膜を製膜すればよい。 In the case of forming a surface layer made of an electrically neutral organic compound, the reverse osmosis membrane may be permeated or applied to a solution containing an electrically neutral organic compound. The thickness of the surface layer is preferably about 0.001 μm to 1 μm, more preferably about 0.005 μm to 0.5 μm. When an electrically neutral organic compound is contained in the reverse osmosis membrane, the organic polymer is used in the above-described polyamide interfacial polymerization method, and an aqueous solution of a monomer having a reactive amino group and / or a polymer, Alternatively, a reverse osmosis composite membrane may be formed by mixing with an organic solvent containing polyfunctional acid chloride or the like.
このような逆浸透膜として具体的には、低圧逆浸透膜が望ましく、このような膜としては東レ(株)製逆浸透膜SU-700シリーズ、SUL-Gシリーズが挙げられる。
浸透膜の形態としては、平膜、プリーツ膜、スパイラル膜、チューブ膜、ロッド膜ファインチューブ膜、スパゲティ膜または中空糸膜またはそれら複数の組合せが挙げられる。
Specifically, such a reverse osmosis membrane is desirably a low-pressure reverse osmosis membrane, and examples of such a membrane include Toray's reverse osmosis membranes SU-700 series and SUL-G series.
Examples of the form of the osmotic membrane include a flat membrane, a pleated membrane, a spiral membrane, a tube membrane, a rod membrane, a fine tube membrane, a spaghetti membrane, a hollow fiber membrane, or a combination thereof.
過酸化水素水を逆浸透膜で処理する装置は、逆浸透膜を固定支持する耐圧容器と加圧手段を有する逆浸透法により液体を精製する装置が用いられる。加圧圧力は低圧逆浸透膜の一般的な操作圧力は1.5MPa以下であり、0.5〜1.0MPaの範囲が好ましい。また、加圧時の温度は30℃を越えない範囲が好ましい。このため冷却手段を設けていてもよい。 As an apparatus for treating hydrogen peroxide water with a reverse osmosis membrane, an apparatus for purifying a liquid by a reverse osmosis method having a pressure vessel and a pressurizing means for fixing and supporting the reverse osmosis membrane is used. The general pressure of the low pressure reverse osmosis membrane is 1.5 MPa or less, preferably 0.5 to 1.0 MPa. Further, the temperature during pressurization is preferably within a range not exceeding 30 ° C. For this reason, a cooling means may be provided.
このような、逆浸透膜による処理によって、工業用過酸化水素水中の安定剤は、その添加量の70重量％以上、より好ましくは90重量％以上を除去する。これ以下の量であれば、後述イオン交換のライフを長期に保つことは難しく、また安定剤除去にイオン交換能力を多く消費するため、イオン価数が低く、交換順位の低い金属を効率良く除去することが出来ず、結果安定度の高い過酸化水素水を得ることが難しいことがある。 By such treatment with a reverse osmosis membrane, the stabilizer in the industrial hydrogen peroxide solution removes 70% by weight or more, more preferably 90% by weight or more of the amount added. If the amount is less than this, it is difficult to maintain the ion exchange life for a long period of time, and it consumes a lot of ion exchange capacity for removing the stabilizer, so that the metal with low ion valence and low exchange order is efficiently removed. It may not be possible to obtain hydrogen peroxide solution with high stability as a result.
このように前段の逆浸透膜処理によって安定剤を除去しても、後述のイオン交換処理によって、それ以外の不純物も効果的に除去されるため、非常に安定性が高い。また不純物も含まないために、半導体や基板洗浄に使用しても、結晶欠陥による酸化膜耐圧の劣化やリーク電流の増加やシリコン酸化膜の絶縁耐圧の劣化などを引き起こすこともない。 Thus, even if the stabilizer is removed by the reverse osmosis membrane treatment in the previous stage, since other impurities are also effectively removed by the ion exchange treatment described later, the stability is very high. Further, since it does not contain impurities, even if it is used for semiconductor or substrate cleaning, it does not cause deterioration of oxide film breakdown voltage due to crystal defects, increase of leakage current, deterioration of dielectric breakdown voltage of silicon oxide film, and the like.
本発明ではこのような逆浸透膜処理に続いてイオン交換樹脂による処理を行う。このような逆浸透膜処理と組み合わせることで、イオン交換能力を過剰消費する安定剤が除かれるとともに、イオン交換樹脂表面に付着しイオン交換を阻害する高分子有機物も除去されているので、イオン交換樹脂による過酸化水素水の精製を、高水準で長期間行うことができる。更にまたイオン交換樹脂の交換・洗浄間隔を従来に比べて長くすることが可能となり、運転効率を高めることができる。 In the present invention, treatment with an ion exchange resin is performed following such reverse osmosis membrane treatment. Combined with such reverse osmosis membrane treatment, stabilizers that excessively consume ion exchange capacity are removed, and polymer organic substances that adhere to the ion exchange resin surface and inhibit ion exchange are also removed. The purification of the hydrogen peroxide solution by the resin can be performed at a high level for a long time. Furthermore, the ion exchange resin replacement / cleaning interval can be made longer than before, and the operation efficiency can be improved.
イオン交換処理
次に、前記特定の逆浸透膜で処理した過酸化水素水を、さらにカチオンイオン交換樹脂および／またはアニオンイオン交換樹脂により、過酸化水素水に含まれる不純物を除去する。
Ion exchange treatment Next, impurities contained in the hydrogen peroxide solution are removed from the hydrogen peroxide solution treated with the specific reverse osmosis membrane with a cation ion exchange resin and / or an anion ion exchange resin.
イオン交換樹脂はアニオンイオン交換樹脂あるいはカチオンイオン交換樹脂あるいはこれらの混合でも良い。
カチオンイオン交換樹脂は、Ｈ+型カチオンイオン交換樹脂が使用される。カチオンイオン交換樹脂としては一般にはスチレンージビニルベンゼン架橋共重合体にスルホン酸基を導入した網目状分子構造からなる強酸性カチオンイオン交換が望ましい。例えばＰＫ２１６，ＳＫ１Ｂ，ＩＲ−１２０Ｂなどが挙げられる。これら樹脂は一般にＮａイオン型で上市されている。これらカチオンイオン交換樹脂を塩酸や硫酸などの無機酸で処理し使用する。
The ion exchange resin may be an anion ion exchange resin, a cation ion exchange resin, or a mixture thereof.
As the cation ion exchange resin, an H + type cation ion exchange resin is used. In general, the cation ion exchange resin is preferably a strongly acidic cation ion exchange having a network molecular structure in which a sulfonic acid group is introduced into a styrene-divinylbenzene crosslinked copolymer. Examples thereof include PK216, SK1B, and IR-120B. These resins are generally marketed in Na ion type. These cation ion exchange resins are used after being treated with an inorganic acid such as hydrochloric acid or sulfuric acid.
市販のカチオンイオン交換樹脂を５重量％の塩酸などで再生する。このときのＳＶは２０Hr-1以下であることが望ましい。次いで、水洗液が中性になるまで水で洗浄する。
アニオンイオン交換樹脂としては、一般にはスチレン-ジビニルベンゼン架橋共重合体をクロルメチル化後、アミノ化をトリメチルアミン、ジメチルエタノールアミンで行い４級化して得られる強塩基性樹脂（交換基は第４級アンモニウム基）、スチレン-ジビニルベンゼン架橋共重合体で第１ないし第３級アミンを交換基とする弱塩基性樹脂、アクリル酸系架橋重合体で第３級アミンを交換基とする樹脂、ピリジル基または置換ピリジル基を有するポリマーからなるピリジン系アニオン樹脂などが挙げられる。このうち第４級アンモニウム基を有する強塩基性アニオン交換樹脂が好ましい。第４級アンモニウム基のアニオン交換樹脂としては、多くのものが市販されている。例えば、ダイヤイオンのＰＡシリーズ（例えばＰＡ−３１６，ＰＡ−４１６）、ＳＡシリーズ（例えばＳＡ−１０Ａ、ＳＡ−２０Ａ）やアンバーライトのＩＲＡシリーズ（例えばＩＲＡ-４００、ＩＲＡ-４１０、ＩＲＡ-９００、ＩＲＡ-９０４）が代表例として挙げられる。これらの樹脂は一般に塩化物イオン型で上市されている。これらアニオンイオン交換樹脂を炭酸塩、炭酸水素塩で処理し使用する。
A commercially available cation ion exchange resin is regenerated with 5% by weight hydrochloric acid or the like. The SV at this time is preferably 20 Hr −1 or less. Then, it is washed with water until the washing solution becomes neutral.
The anion ion exchange resin is generally a strongly basic resin obtained by chlormethylating a styrene-divinylbenzene cross-linked copolymer, followed by amination with trimethylamine or dimethylethanolamine (the exchange group is quaternary ammonium). Group), a weakly basic resin having a styrene-divinylbenzene crosslinked copolymer with a primary to tertiary amine as an exchange group, a resin having a tertiary amine as an exchange group with an acrylic acid-based crosslinked polymer, a pyridyl group or Examples thereof include a pyridine anion resin made of a polymer having a substituted pyridyl group. Of these, strongly basic anion exchange resins having a quaternary ammonium group are preferred. Many quaternary ammonium group anion exchange resins are commercially available. For example, Diaion PA series (eg PA-316, PA-416), SA series (eg SA-10A, SA-20A) and Amberlite IRA series (eg IRA-400, IRA-410, IRA-900, IRA-904) is a typical example. These resins are generally marketed in the chloride ion type. These anion ion exchange resins are used after being treated with a carbonate or bicarbonate.
炭酸塩、炭酸水素塩で処理する際に、まず、市販のアニオンイオン交換樹脂を初めに５重量％水酸化ナトリウム水溶液で再生する。このときのＳＶは２０Hr-1以下であることが望ましい。次いで、水洗液が中性になるまで水で洗浄する。次に５〜１０重量％の炭酸塩、炭酸水素塩で再生する。このときのＳＶは２０Hr-1以下であることが望ましい。水洗液が中性になるまで水で洗浄する。 When treating with carbonate or bicarbonate, a commercially available anion exchange resin is first regenerated with a 5 wt% aqueous sodium hydroxide solution. The SV at this time is preferably 20 Hr −1 or less. Then, it is washed with water until the washing solution becomes neutral. Next, it is regenerated with 5 to 10% by weight of carbonate and bicarbonate. The SV at this time is preferably 20 Hr −1 or less. Wash with water until the water wash is neutral.
また、前記した塩化物イオン型などのアニオン交換樹脂を、フッ化物アニオン型に変換して使用してもよい。
上記で処理されたカチオンイオン交換樹脂あるいはアニオンイオン交換あるいはカチオンイオン交換樹脂／アニオンイオン交換樹脂の混床イオン交換樹脂に逆浸透膜を透過した過酸化水素水を通液する。ＳＶは小さいほど望ましい。このときの液温は過酸化水素水の分解抑制の安全面から５℃以下の低温が望ましい。
Further, the above-described anion exchange resin such as chloride ion type may be used after being converted to fluoride anion type.
Hydrogen peroxide solution permeated through the reverse osmosis membrane is passed through the cation ion exchange resin or anion ion exchange or cation ion exchange resin / anion ion exchange resin mixed bed ion exchange resin treated as described above. The smaller the SV, the better. The liquid temperature at this time is preferably a low temperature of 5 ° C. or less from the viewpoint of safety of suppressing the decomposition of the hydrogen peroxide solution.
また、イオン交換処理として、本願の出願人による特許第3895540号に記載のイオン交換樹脂を組み合わせても良い。
具体的には、上記逆浸透膜を使用して安定剤を除去したのち、以下の製造方法と組み合わせることが望ましい。
Further, as the ion exchange treatment, an ion exchange resin described in Japanese Patent No. 3895540 by the applicant of the present application may be combined.
Specifically, it is desirable to combine the following manufacturing method after removing the stabilizer using the reverse osmosis membrane.
安定剤が除去された過酸化水素水を、Ｈ+型カチオン交換樹脂と接触させた後、炭酸イオン(CO3 2-)型または炭酸水素イオン(HCO3 -)型アニオン交換樹脂と接触させ、次いで、Ｈ+型カチオン交換樹脂と接触させる。 The hydrogen peroxide solution from which the stabilizer has been removed is brought into contact with an H + type cation exchange resin, and then brought into contact with a carbonate ion (CO 3 2− ) type or hydrogen carbonate ion (HCO 3 − ) type anion exchange resin, It is then contacted with an H + type cation exchange resin.
または、安定剤が除去された過酸化水素水を、Ｈ+型カチオン交換樹脂と接触させた後、フッ化物イオン（Ｆ-）型アニオン交換樹脂と接触させ、次いで、炭酸イオン(CO3 2-)型または炭酸水素イオン(HCO3 -)型アニオン交換樹脂と接触させ、さらに、Ｈ+型カチオン交換樹脂と接触させる。 Alternatively, the hydrogen peroxide solution from which the stabilizer has been removed is brought into contact with the H + type cation exchange resin, then brought into contact with a fluoride ion (F − ) type anion exchange resin, and then carbonate ions (CO 3 2− ) Type or bicarbonate ion (HCO 3 − ) type anion exchange resin, and further contact with H + type cation exchange resin.
このように逆浸透膜を使用して安定剤を除去したのち、２段階または４段階のイオン交換樹脂で処理することによって、金属イオン不純物が極力除去された高純度な過酸化水素水を製造することができる。 After removing the stabilizer using the reverse osmosis membrane in this way, a high-purity hydrogen peroxide solution from which metal ion impurities are removed as much as possible is produced by treating with a two-stage or four-stage ion exchange resin. be able to.
Ｈ + 型カチオン交換樹脂処理（１段目）
たとえば、逆浸透膜を透過した過酸化水素水をＨ+型カチオン交換樹脂と接触させる。使用されるＨ+型カチオン交換樹脂は、強酸性カチオン交換樹脂として公知のものが使用される。強酸性カチオン交換樹脂の種類としては、一般にはスチレン−ジビニルベンゼン架橋共重合体にスルホン酸基を導入した網目状分子構造からなる強酸性カチオン交換樹脂が好ましい。このようなカチオン交換樹脂の架橋度は、通常６〜１０、好ましくは７〜９の範囲にあることが望ましい。
H + type cation exchange resin treatment (first stage)
For example, hydrogen peroxide solution that has permeated the reverse osmosis membrane is brought into contact with the H + type cation exchange resin. As the H + -type cation exchange resin used, those known as strong acid cation exchange resins are used. As a kind of strong acid cation exchange resin, generally a strong acid cation exchange resin having a network molecular structure in which a sulfonic acid group is introduced into a styrene-divinylbenzene crosslinked copolymer is preferable. The degree of crosslinking of such a cation exchange resin is usually in the range of 6 to 10, preferably 7 to 9.
Ｈ+型強酸性カチオン交換樹脂として具体的には、たとえばＰＫ２１６、ＳＫ１Ｂ、ＩＲ−１２０Ｂなどが使用される。Ｈ+型カチオン交換樹脂は、カチオン交換樹脂を下降流の無機酸水溶液（再生剤）で処理したのち、上昇流の超純水で洗浄する操作を一工程とし、その工程を２回以上、好ましくは２〜１２回繰り返すことによって再生されたものが好ましい。 Specifically, for example, PK216, SK1B, IR-120B and the like are used as the H + type strongly acidic cation exchange resin. The H + type cation exchange resin is an operation in which the cation exchange resin is treated with a downflow inorganic acid aqueous solution (regenerant) and then washed with an upflow ultrapure water, and the process is preferably performed twice or more. Is preferably regenerated by repeating 2 to 12 times.
通常、カチオン交換樹脂と再生剤水溶液との接触は、再生剤水溶液を通液したのち、押出し、超純水で水洗することによって行われるが、本発明では、特に２回以上、再生剤通液・超純水水洗のサイクルを繰り返すことが望ましい。このように無機酸水溶液-超純水通液を繰り返すことで、カチオン交換樹脂が収縮・膨潤するため、交換樹脂の内部まで洗浄できる。 Usually, the contact between the cation exchange resin and the regenerant aqueous solution is carried out by passing the regenerant aqueous solution and then extruding and washing with ultrapure water.・ It is desirable to repeat the cycle of ultrapure water washing. By repeating the aqueous solution of inorganic acid and ultrapure water in this way, the cation exchange resin contracts and swells, so that the inside of the exchange resin can be washed.
無機酸としては、硫酸、塩酸などの公知の無機酸が使用される。
再生剤水溶液中の無機酸濃度としては、５〜１５重量％好ましくは５〜１２重量％の範囲にあるものが好適に使用される。このような再生剤の使用量は、処理するカチオン交換樹脂の樹脂量（体積）の３倍以上、好ましくは４〜１２倍の範囲にあることが望ましい。
As the inorganic acid, known inorganic acids such as sulfuric acid and hydrochloric acid are used.
As the concentration of the inorganic acid in the aqueous regenerant solution, a concentration within the range of 5 to 15% by weight, preferably 5 to 12% by weight is suitably used. The amount of such a regenerant used is at least 3 times, preferably 4 to 12 times, the amount (volume) of the cation exchange resin to be treated.
このような再生剤の通液は、通常ＳＶ（空間速度）＝１〜５Hr-1、ＢＶ（Bed Volume イオン交換樹脂の体積の何倍量を処理したかを表す。単位はＬ／Ｌ-Ｒ）＝０．５〜１Ｌ／Ｌ-Ｒの下降流で行い、ＳＶ＝１０〜３０Hr-1、ＢＶ＝０．１〜０．５Ｌ／Ｌ-Ｒの超純水上昇流を通液して洗浄する。 The flow of such a regenerant usually represents SV (space velocity) = 1 to 5 Hr −1 , BV (Bed Volume) indicating how many times the volume of the ion exchange resin has been processed. The unit is L / LR. ) = 0.5 to 1 L / LR downflow, cleaning by passing an ultrapure water upflow with SV = 10 to 30 Hr -1 and BV = 0.1 to 0.5 L / LR To do.
また、再生剤および超純水通液後、さらに超純水の下降流および超純水の上昇流の通液を一工程とする超純水洗浄を、４回〜９回繰り返し行い、再生後のイオン交換樹脂をさらに洗浄する。超純水の上昇流通液は、ＳＶ＝１０〜３０Hr-1、ＢＶ＝３〜５Ｌ／Ｌ-Ｒで行い、下降流通液は、ＳＶ＝１０〜３０Hr-1、ＢＶ＝３〜５Ｌ／Ｌ-Ｒで行うことが望ましく、樹脂量に対し、３０〜６０倍の体積の超純水で洗浄することが望ましい。 In addition, after passing the regenerant and ultrapure water, cleaning with ultrapure water is performed 4 to 9 times with the flow of ultrapure water downward and ultrapure water upward flowing as one step. The ion exchange resin is further washed. The ascending flow of ultrapure water is performed at SV = 10 to 30 Hr −1 and BV = 3 to 5 L / L−R, and the descending flow is SV = 10 to 30 Hr −1 and BV = 3 to 5 L / L−. It is desirable to carry out with R, and it is desirable to wash with 30 to 60 times the volume of ultrapure water relative to the amount of resin.
本発明において、不純物を含む原料過酸化水素水をＨ+型カチオン交換樹脂と接触させる方法は、通常、連続通液方式が採用され、過酸化水素水のカチオン交換樹脂層を通液は、空間速度（ＳＶ）が、５〜４０Ｈｒ-1、好ましくは１０〜３０Ｈｒ-1の範囲で行うことが望ましい。
こうしてＨ+型カチオン交換樹脂で処理することによって、過酸化水素水中のカチオン性の金属イオン不純物が除去される。
In the present invention, the method of bringing the raw material hydrogen peroxide solution containing impurities into contact with the H + type cation exchange resin usually adopts a continuous liquid passing method, and the cation exchange resin layer passing through the hydrogen peroxide solution passes through the space. The speed (SV) is 5 to 40 Hr −1 , preferably 10 to 30 Hr −1 .
By treating with the H + type cation exchange resin in this way, cationic metal ion impurities in the hydrogen peroxide solution are removed.
アニオン交換樹脂処理
(i)炭酸イオン(CO3 2-)型または炭酸水素イオン(HCO3 -)型アニオン交換樹脂
次に、過酸化水素水をアニオン交換樹脂と接触させる。
Anion exchange resin treatment
(i) Carbonate ion (CO 3 2- ) type or hydrogen carbonate ion (HCO 3 − ) type anion exchange resin Next, hydrogen peroxide solution is brought into contact with the anion exchange resin.
アニオン交換樹脂としては、炭酸イオン(CO3 2-)型または炭酸水素イオン(HCO3 -)型アニオン交換樹脂が使用される。
炭酸イオン(CO3 2-)型または炭酸水素イオン(HCO3 -)型アニオン交換樹脂は、公知のアニオン交換樹脂を、炭酸イオン(CO3 2-)型または炭酸水素イオン(HCO3 -)型アニオン交換樹脂に再生したものである。
As the anion exchange resin, a carbonate ion (CO 3 2− ) type or a hydrogen carbonate ion (HCO 3 − ) type anion exchange resin is used.
Carbonate ion (CO 3 2- ) type or hydrogen carbonate ion (HCO 3 − ) type anion exchange resin is a known anion exchange resin, carbonate ion (CO 3 2− ) type or hydrogen carbonate ion (HCO 3 − ) type. Regenerated to anion exchange resin.
公知のアニオン交換樹脂としては、一般にはスチレン−ジビニルベンゼン架橋共重合体をクロロメチル化後、アミノ化をトリメチルアミン、ジメチルエタノールアミンで行い４級化して得られる強塩基性樹脂（交換基は第４級アンモニウム基）、スチレン−ジビニルベンゼン架橋共重合体で第１ないし第３級アミンを交換基とする弱塩基性樹脂、アクリル酸系架橋重合体で第３級アミンを交換基とする樹脂、ピリジル基または置換ピリジル基を有するポリマーからなるピリジン系アニオン交換樹脂などが知られている。このうち、本発明では交換基として第４級アンモニウム基を有する強塩基性アニオン交換樹脂が好ましく使用される。 Known anion exchange resins are generally strongly basic resins obtained by chloromethylation of a styrene-divinylbenzene crosslinked copolymer, followed by amination with trimethylamine and dimethylethanolamine (the exchange group is a fourth group). A quaternary ammonium group), a weakly basic resin having a styrene-divinylbenzene cross-linked copolymer with a primary to tertiary amine as an exchange group, a resin having an acrylic acid cross-linked polymer with a tertiary amine as an exchange group, pyridyl A pyridine anion exchange resin made of a polymer having a group or a substituted pyridyl group is known. Among these, in the present invention, a strongly basic anion exchange resin having a quaternary ammonium group as an exchange group is preferably used.
このような第４級アンモニウム基を交換基として有するアニオン交換樹脂としては、多くの種類のものが市販されている。たとえばダイヤイオンのＰＡシリーズ（たとえばＰＡ３１６、ＰＡ４１６）、ＳＡシリーズ（たとえばＳＡ１０Ａ、ＳＡ２０Ａ）、アンバーライトのＩＲＡシリーズ（たとえばＩＲＡ−４００、ＩＲＡ−４１０、ＩＲＡ−９００、ＩＲＡ−９０４）が代表例として挙げられる。これらの樹脂は一般に塩化物イオン型で上市されている。 Many types of anion exchange resins having such a quaternary ammonium group as an exchange group are commercially available. For example, Diaion PA series (eg PA316, PA416), SA series (eg SA10A, SA20A), Amberlite IRA series (eg IRA-400, IRA-410, IRA-900, IRA-904) are given as typical examples. It is done. These resins are generally marketed in the chloride ion type.
本発明で使用される炭酸イオン(CO3 2-)型または炭酸水素イオン(HCO3 -)型アニオン交換樹脂は、前記した塩化物イオン型などのアニオン交換樹脂を、炭酸イオン(CO3 2-)型または炭酸水素イオン(HCO3 -)型に変換して使用する。なお、炭酸イオン(CO3 2-)型または炭酸水素イオン(HCO3 -)型に変換する前のアニオン交換樹脂は、塩化物イオン型に限らず、水酸化物イオン型、フッ化物イオン型等であってもよい。 The carbonate ion (CO 3 2- ) type or hydrogen carbonate ion (HCO 3 − ) type anion exchange resin used in the present invention is an anion exchange resin such as the above-mentioned chloride ion type, which is converted to carbonate ion (CO 3 2−). ) Type or bicarbonate ion (HCO 3 − ) type for use. Incidentally, carbonate ions (CO 3 2-) type or bicarbonate ion (HCO 3 -) anion exchange resin before converting the type is not limited to chloride ion type, hydroxide ion type, fluoride ion type, etc. It may be.
本発明で使用される炭酸イオン(CO3 2-)型または炭酸水素イオン(HCO3 -)型アニオン交換樹脂の再生は、塩化物イオン型のアニオン交換樹脂を、水酸化物イオン型にアニオン交換樹脂を変換したのち、炭酸イオン型または炭酸水素イオン型に変換することによって行われる。 Regeneration of carbonate ion (CO 3 2- ) type or hydrogen carbonate ion (HCO 3 − ) type anion exchange resin used in the present invention is achieved by converting anion exchange resin of chloride ion type into anion exchange type of hydroxide ion type. After converting the resin, it is carried out by converting to a carbonate ion type or a hydrogen carbonate ion type.
また、いったん使用した炭酸イオン(CO3 2-)型または炭酸水素イオン(HCO3 -)型アニオン交換樹脂の再生も、同様に水酸化物イオン型にアニオン交換樹脂を変換したのち、炭酸イオン型または炭酸水素イオン型に変換することによって行われる。 Also, once used the carbonate ion (CO 3 2-) type or bicarbonate ion (HCO 3 -) type reproducing anion exchange resins, after converting the anion-exchange resin similar to the hydroxide ion type, ionic carbonate Alternatively, it is carried out by converting to a bicarbonate ion type.
水酸化物イオン型アニオン交換樹脂への変換は、アニオン交換樹脂を下降流の強アルカリ水溶液（再生剤）で処理したのち、上昇流の超純水で処理する操作を一工程とし、その工程を２回以上繰り返すことによって再生されたものが好ましい。通常、アニオン交換樹脂と再生剤水溶液との接触は、再生剤水溶液を通液したのち、押し出し超純水で水洗することによって行われるが、本発明では特に２回以上、再生剤通液・超純水水洗のサイクルを繰り返すことが望ましい。このように強アルカリ水溶液-超純水通液を繰り返すことで、アニオン交換樹脂が収縮・膨潤するため、交換樹脂の内部まで洗浄できる。 Conversion to a hydroxide ion type anion exchange resin is a process in which the anion exchange resin is treated with a strong alkaline aqueous solution (regenerant) in the downward flow and then treated with ultrapure water in the upward flow. What was reproduced | regenerated by repeating twice or more is preferable. Usually, the contact between the anion exchange resin and the aqueous regenerant solution is carried out by passing the aqueous regenerant solution and then rinsing with extruded ultrapure water. It is desirable to repeat the cycle of pure water washing. By repeating the flow of strong alkaline aqueous solution and ultrapure water in this manner, the anion exchange resin contracts and swells, so that the inside of the exchange resin can be washed.
強アルカリとしては、水酸化ナトリウム、水酸化カリウムなどの公知のアルカリが使用される。
再生剤水溶液中の強アルカリ濃度としては、２〜１０重量％好ましくは２〜８重量％の範囲にあるものが好適である。このような再生剤の使用量は、処理するアニオン交換樹脂の樹脂量（体積）の３倍以上、好ましくは４〜１２倍の範囲にあることが望ましい。
As the strong alkali, a known alkali such as sodium hydroxide or potassium hydroxide is used.
The strong alkali concentration in the aqueous regenerant solution is preferably 2 to 10% by weight, preferably 2 to 8% by weight. The amount of such a regenerant used is desirably 3 times or more, preferably 4 to 12 times the resin amount (volume) of the anion exchange resin to be treated.
このような再生剤の通液は、通常ＳＶ（空間速度）＝１〜５Hr-1、ＢＶ（Bed Volume イオン交換樹脂の体積の何倍量を処理したかを表す。単位はＬ／Ｌ-Ｒ）＝０．５〜１Ｌ／Ｌ-Ｒの下降流で行い、ＳＶ＝１０〜３０Hr-1、ＢＶ＝０．１〜０．５Ｌ／Ｌ-Ｒの超純水上昇流を通液して洗浄する。 The flow of such a regenerant usually represents SV (space velocity) = 1 to 5 Hr −1 , BV (Bed Volume) indicating how many times the volume of the ion exchange resin has been processed. The unit is L / LR. ) = 0.5 to 1 L / LR downflow, cleaning by passing an ultrapure water upflow with SV = 10 to 30 Hr -1 and BV = 0.1 to 0.5 L / LR To do.
また、再生剤および超純水通液後、さらに超純水の下降流および超純水の上昇流の通液を１工程とする超純水洗浄を、４回〜９回繰り返し行い、再生後のイオン交換樹脂をさらに洗浄してもよい。超純水の上昇流通液は、ＳＶ＝１０〜３０Hr-1、ＢＶ＝３〜５Ｌ／Ｌ-Ｒで行い、下降流通液は、ＳＶ＝１０〜３０Hr-1、ＢＶ＝３〜５Ｌ／Ｌ-Ｒで行うことが望ましく、樹脂量に対し、３０〜６０倍の体積の超純水で洗浄することが望ましい。 In addition, after the regeneration agent and the ultrapure water flow, the ultrapure water washing in which the flow of the ultrapure water downward flow and the ultrapure water upward flow is performed in one step is repeated 4 to 9 times. The ion exchange resin may be further washed. The ascending flow of ultrapure water is performed at SV = 10 to 30 Hr −1 and BV = 3 to 5 L / L−R, and the descending flow is SV = 10 to 30 Hr −1 and BV = 3 to 5 L / L−. It is desirable to carry out with R, and it is desirable to wash with 30 to 60 times the volume of ultrapure water relative to the amount of resin.
次に、こうして水酸化物イオン型にしたアニオン交換樹脂を炭酸塩または炭酸水素塩水溶液（再生剤）で処理して炭酸イオン型または炭酸水素イオン型アニオン交換樹脂に変換（再生）する。 Next, the hydroxide ion type anion exchange resin is treated with a carbonate or hydrogen carbonate aqueous solution (regeneration agent) to convert (regenerate) into a carbonate ion type or hydrogen carbonate ion type anion exchange resin.
本発明で使用される炭酸イオン型または炭酸水素イオン型アニオン交換樹脂は、上記で処理した水酸化物イオン型アニオン交換樹脂を下降流の炭酸塩または炭酸水素塩水溶液（再生剤）で処理したのち、上昇流の超純水で処理する操作を一工程とし、この工程を２回以上繰り返すことによって再生されたものが好ましい。 The carbonate ion type or bicarbonate ion type anion exchange resin used in the present invention is obtained by treating the hydroxide ion type anion exchange resin treated as described above with a downstream carbonate or bicarbonate aqueous solution (regenerant). It is preferable that the operation is carried out by treating with an ultrapure water in an upward flow as one step and this step is repeated twice or more.
炭酸塩および炭酸水素塩としては、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、炭酸水素カリウムなどの公知の炭酸塩または炭酸水素塩が使用される。このように炭酸塩または炭酸水素塩水溶液-超純水通液を繰り返すことで、前記したようにアニオン交換樹脂が収縮・膨潤するため、交換樹脂の内部まで洗浄できる。 As the carbonate and bicarbonate, known carbonates or bicarbonates such as sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate are used. As described above, by repeating the carbonate or hydrogen carbonate aqueous solution-ultra pure water flow, the anion exchange resin contracts and swells as described above, so that the inside of the exchange resin can be washed.
再生剤水溶液中の炭酸塩または炭酸水素イオン濃度としては、５〜１５重量％好ましくは５〜１２重量％の範囲にあるものが好適に使用される。このような再生剤の使用量は、処理するアニオン交換樹脂の樹脂量（体積）の３倍以上、好ましくは４〜１２倍の範囲にあることが望ましい。 As the carbonate or hydrogen carbonate ion concentration in the aqueous regenerant solution, those in the range of 5 to 15% by weight, preferably 5 to 12% by weight, are preferably used. The amount of such a regenerant used is desirably 3 times or more, preferably 4 to 12 times the resin amount (volume) of the anion exchange resin to be treated.
このような再生剤の通液は、通常ＳＶ（空間速度）＝１〜５Hr-1、ＢＶ（Bed Volume イオン交換樹脂の体積の何倍量を処理したかを表す。単位はＬ／Ｌ-Ｒ）＝０．５〜１Ｌ／Ｌ-Ｒの下降流で行い、ＳＶ＝１０〜３０Hr-1、ＢＶ＝０．１〜０．５Ｌ／Ｌ-Ｒの超純水上昇流を通液して洗浄する。 The flow of such a regenerant usually represents SV (space velocity) = 1 to 5 Hr −1 , BV (Bed Volume) indicating how many times the volume of the ion exchange resin has been processed. The unit is L / LR. ) = 0.5 to 1 L / LR downflow, cleaning by passing an ultrapure water upflow with SV = 10 to 30 Hr -1 and BV = 0.1 to 0.5 L / LR To do.
また、再生剤および超純水通液後、さらに超純水の下降流および超純水の上昇流の通液を１工程とする超純水洗浄を、４回〜９回繰り返し行い、再生後のイオン交換樹脂をさらに洗浄する。超純水の上昇流通液は、ＳＶ＝１０〜３０Hr-1、ＢＶ＝３〜５Ｌ／Ｌ-Ｒで行い、下降流通液は、ＳＶ＝１０〜３０Hr-1、ＢＶ＝３〜５Ｌ／Ｌ-Ｒで行うことが望ましく、樹脂量に対し、３０〜６０倍の体積の超純水で洗浄することが望ましい。 In addition, after the regeneration agent and the ultrapure water flow, the ultrapure water washing in which the flow of the ultrapure water downward flow and the ultrapure water upward flow is performed in one step is repeated 4 to 9 times. The ion exchange resin is further washed. The ascending flow of ultrapure water is performed at SV = 10 to 30 Hr −1 and BV = 3 to 5 L / L−R, and the descending flow is SV = 10 to 30 Hr −1 and BV = 3 to 5 L / L−. It is desirable to carry out with R, and it is desirable to wash with 30 to 60 times the volume of ultrapure water relative to the amount of resin.
本発明において、過酸化水素水を炭酸イオン型または炭酸水素イオン型アニオン交換樹脂と接触させる方法は、通常、連続通液方式が採用され、アニオン交換樹脂層を通過させる過酸化水素水の通液は、空間速度（ＳＶ）が、５〜４０Ｈｒ-1、好ましくは１０〜３０Ｈｒ-1の範囲で行うことが望ましい。 In the present invention, the method of bringing the hydrogen peroxide solution into contact with the carbonate ion type or the bicarbonate ion type anion exchange resin usually adopts a continuous liquid passing method, and the hydrogen peroxide water passing through the anion exchange resin layer is passed. The space velocity (SV) is preferably 5 to 40 Hr −1 , preferably 10 to 30 Hr −1 .
このようなアニオン交換樹脂と過酸化水素水との接触は、樹脂の酸化劣化防止、接触時の分解ガスの発生防止および分解発熱などの安全上の面から、低温で行うことが好ましい。特に、Ｈ+型カチオン交換樹脂で処理された過酸化水素水中には、過酸化水素の解離によって生じる以上のＨ+が含まれていることがあり、このＨ+とアニオン交換基のCO3 2-またはHCO3 -とが中和反応して、発熱することがある。また、炭酸イオン型または炭酸水素イオン型アニオン交換樹脂と過酸化水素水とを接触させる場合、過酸化水素水の分解によって分解ガスが発生し、さらには分解発熱することもある。このため、アニオン交換樹脂で過酸化水素水を処理する場合には、過酸化水素水を５℃以下の低温に冷却しておくことが望ましい。 Such anion exchange resin and hydrogen peroxide solution are preferably contacted at a low temperature from the viewpoint of safety such as prevention of oxidative degradation of the resin, generation of decomposition gas at the time of contact, and decomposition heat generation. In particular, H + in the treated aqueous hydrogen peroxide solution type cation exchange resin, may contain more than H + produced by the dissociation of hydrogen peroxide, CO 3 2 of the H + and an anion-exchange group - or HCO 3 - and is neutralized reactions may be exothermic. Further, when the carbonate ion type or hydrogen carbonate ion type anion exchange resin is brought into contact with the hydrogen peroxide solution, decomposition gas is generated due to decomposition of the hydrogen peroxide solution, and further decomposition heat may be generated. For this reason, when the hydrogen peroxide solution is treated with an anion exchange resin, it is desirable to cool the hydrogen peroxide solution to a low temperature of 5 ° C. or lower.
(ii)フッ化物イオン(Ｆ-)型アニオン交換樹脂
過酸化水素水を、Ｈ+型カチオン交換樹脂と接触させた後、上記炭酸イオン(CO3 2-)型または炭酸水素イオン(HCO3 -)型アニオン交換樹脂を接触させる前に、フッ化物イオン型アニオン交換樹脂と接触させてもよい。フッ化物イオン型にしたアニオン交換樹脂と過酸化水素水とを接触させることにより、過酸化水素水中に溶解している溶解性シリカが、アニオン交換樹脂に捕捉され、除去される。
(ii) Fluoride ion (F − ) type anion exchange resin After contacting hydrogen peroxide with H + type cation exchange resin, the carbonate ion (CO 3 2− ) type or hydrogen carbonate ion (HCO 3 − ) Type anion exchange resin may be brought into contact with the fluoride ion type anion exchange resin. By bringing the fluoride ion type anion exchange resin into contact with the hydrogen peroxide solution, the soluble silica dissolved in the hydrogen peroxide solution is captured and removed by the anion exchange resin.
フッ化物イオン(Ｆ-)型アニオン交換樹脂は、公知のアニオン交換樹脂を、フッ化物イオン型に再生したものである。公知のアニオン交換樹脂としては、前記したものと同様のものが挙げられる。 The fluoride ion (F − ) type anion exchange resin is obtained by regenerating a known anion exchange resin into a fluoride ion type. Known anion exchange resins include those similar to those described above.
本発明で使用されるフッ化物イオン型アニオン交換樹脂は、塩化物イオン型のアニオン交換樹脂、水酸化物イオン型、炭酸イオン型、炭酸水素イオン型等のいずれかを、フッ化物イオン型に変換することによって行われる。 The fluoride ion type anion exchange resin used in the present invention is converted from a chloride ion type, a hydroxide ion type, a carbonate ion type, a bicarbonate ion type, etc. to a fluoride ion type. Is done by doing.
フッ化物イオン型アニオン交換樹脂に変換するために使用される再生剤としては、フッ化ナトリウム、フッ化カリウムおよびフッ化アンモニウムからなる群から選ばれる少なくとも一種のフッ素化合物が挙げられる。 Examples of the regenerant used for conversion to the fluoride ion type anion exchange resin include at least one fluorine compound selected from the group consisting of sodium fluoride, potassium fluoride, and ammonium fluoride.
アニオン交換樹脂のフッ化物イオン型への変換は、アニオン交換樹脂に前記した再生剤を含む水溶液と接触させることにより行うことができる。アニオン交換樹脂と再生剤水溶液との接触方法は、連続通液方式でカラムにアニオン交換樹脂を充填し再生剤を含む水溶液を通液した後、超純水を通水して、アニオン交換樹脂を充分に水洗する方法が効果的である。再生剤濃度は通常１〜４重量％、望ましくは２〜４量％であり、通液させる再生剤水溶液量は、樹脂量（体積）の３倍以上、好ましくは４〜１２倍の範囲にあることが望ましい。 The conversion of the anion exchange resin to the fluoride ion type can be performed by bringing the anion exchange resin into contact with an aqueous solution containing the above-mentioned regenerant. The contact method between the anion exchange resin and the aqueous regenerant solution is as follows: the column is filled with the anion exchange resin in a continuous liquid flow method, and after passing through the aqueous solution containing the regenerant, ultrapure water is passed through the anion exchange resin A method of sufficiently washing with water is effective. The concentration of the regenerant is usually 1 to 4% by weight, desirably 2 to 4% by weight, and the amount of the regenerant aqueous solution to be passed is 3 times or more, preferably 4 to 12 times the resin amount (volume). It is desirable.
本発明では、アニオン交換樹脂をフッ化物イオン型に変換する際に、このような再生剤水溶液の通液と超純水の通液を２回以上繰り返すことが望ましく、具体的には、再生剤水溶液の下降流通液と超純水の上昇流通液を２回以上繰り返すことが望ましい。 In the present invention, when the anion exchange resin is converted into the fluoride ion type, it is desirable to repeat the flow of the regenerant aqueous solution and the ultrapure water two or more times. It is desirable to repeat the descending flowing liquid of the aqueous solution and the rising flowing liquid of ultrapure water twice or more.
このようにフッ素化合物水溶液-超純水通液を繰り返すことで、アニオン交換樹脂が収縮・膨潤するため、交換樹脂の内部まで洗浄できる。
このような再生剤の通液は、通常ＳＶ（空間速度）＝１〜５Hr-1、ＢＶ（Bed Volume イオン交換樹脂の体積の何倍量を処理したかを表す。単位はＬ／Ｌ-Ｒ）＝０．５〜１Ｌ／Ｌ-Ｒの下降流で行い、ＳＶ＝１０〜３０Hr-1、ＢＶ＝０．１〜０．５Ｌ／Ｌ-Ｒの超純水上昇流を通液して洗浄する。
Thus, by repeating the fluorine compound aqueous solution-ultra pure water flow, the anion exchange resin contracts and swells, so that the inside of the exchange resin can be washed.
The flow of such a regenerant usually represents SV (space velocity) = 1 to 5 Hr −1 , BV (Bed Volume) indicating how many times the volume of the ion exchange resin has been processed. The unit is L / LR. ) = 0.5 to 1 L / LR downflow, cleaning by passing an ultrapure water upflow with SV = 10 to 30 Hr -1 and BV = 0.1 to 0.5 L / LR To do.
また、再生剤および超純水通液後、さらに超純水の下降流および超純水の上昇流の通液を１工程とする超純水洗浄を、４回〜９回繰り返し行い、再生後のイオン交換樹脂をさらに洗浄する。超純水の上昇流通液は、ＳＶ＝１０〜３０Hr-1、ＢＶ＝３〜５Ｌ／Ｌ-Ｒで行い、下降流通液は、ＳＶ＝１０〜３０Hr-1、ＢＶ＝３〜５Ｌ／Ｌ-Ｒで行うことが望ましく、樹脂量に対し、３０〜６０倍の体積の超純水で洗浄することが望ましい。 In addition, after the regeneration agent and the ultrapure water flow, the ultrapure water washing in which the flow of the ultrapure water downward flow and the ultrapure water upward flow is performed in one step is repeated 4 to 9 times. The ion exchange resin is further washed. The ascending flow of ultrapure water is performed at SV = 10 to 30 Hr −1 and BV = 3 to 5 L / L−R, and the descending flow is SV = 10 to 30 Hr −1 and BV = 3 to 5 L / L−. It is desirable to carry out with R, and it is desirable to wash with 30 to 60 times the volume of ultrapure water relative to the amount of resin.
なお、フッ化物イオン型のアニオン交換樹脂で処理する場合、過酸化水素水は分解しないため、炭酸塩型または重炭酸塩型アニオン交換樹脂のように、過酸化水素水と接触させる際に、冷却する必要はない。 When treating with a fluoride ion type anion exchange resin, the hydrogen peroxide solution is not decomposed. Therefore, as with carbonate type or bicarbonate type anion exchange resin, cooling is required when contacting with hydrogen peroxide solution. do not have to.
本発明において、過酸化水素水をフッ化物イオン型アニオン交換樹脂と接触させる方法は、通常、連続通液方式が採用され、アニオン交換樹脂層を通過させる過酸化水素水の通液は、空間速度（ＳＶ）が、５〜４０Ｈｒ-1、好ましくは１０〜３０Ｈｒ-1の範囲で行うことが望ましい。 In the present invention, the method of bringing the hydrogen peroxide solution into contact with the fluoride ion-type anion exchange resin usually employs a continuous liquid passing method, and the hydrogen peroxide solution passing through the anion exchange resin layer has a space velocity. (SV) is 5-40Hr < -1 >, It is desirable to carry out in the range of 10-30Hr < -1 > preferably.
フッ化物イオン型アニオン交換樹脂で処理された精製過酸化水素水中には、イオン交換によって生じたフッ化物イオンが含まれているが、このフッ化物イオンは、前記炭酸塩または重炭酸塩型などのアニオン交換樹脂と接触させることによって除去することができる。 The purified hydrogen peroxide solution treated with the fluoride ion type anion exchange resin contains fluoride ions generated by ion exchange, and this fluoride ion is the one of the carbonate type or bicarbonate type. It can be removed by contacting with an anion exchange resin.
以上のように、アニオン交換樹脂と過酸化水素水とを接触させることによって、溶解性シリカおよびアニオン性の金属錯体不純物や他のアニオン類および使用したＨ+型カチオン交換樹脂に起因する硫酸イオンなどが除去される。 As described above, by bringing the anion exchange resin into contact with hydrogen peroxide solution, soluble silica and anionic metal complex impurities, other anions, and sulfate ions caused by the H + type cation exchange resin used, etc. Is removed.
Ｈ + 型カチオン交換樹脂処理（２段目）
こうしてアニオン交換樹脂と過酸化水素水とを接触させたのち、再度、Ｈ+型カチオン交換樹脂と過酸化水素水とを接触させてもよい。Ｈ+型カチオン交換樹脂としては、前記したものと同様のものが使用される。過酸化水素水をカチオン交換樹脂と接触させる方法は、前記したように連続通液方式で行われ、Ｈ+型カチオン交換樹脂層を通過させる過酸化水素水は、空間速度（ＳＶ）が、５〜４０、好ましくは１０〜３０Ｈｒ-1の範囲で行うことが望ましい。本発明では、アニオン交換樹脂で処理した過酸化水素水をさらにＨ+型カチオン交換樹脂で処理している。このように、再度Ｈ+型カチオン交換樹脂で処理することによって、アニオン交換樹脂中に不純物として含まれる微量のＮａ+、Ｋ+、Ａｌ3+などが除去できるので、極めて高レベル（pptないしサブpptオーダー）まで金属イオン不純物を除去できる。なお、除去されるべきＮａ+、Ｋ+、Ａｌ3+などのカウンターイオンは炭酸イオンまたは炭酸水素イオンであり、これらはカチオン交換後に二酸化炭素となって揮散し、過酸化水素水中には残存しない。なお、２段目のＨ+型カチオン交換樹脂で過酸化水素水の処理を行わないと、不純物として含まれる微量の金属イオンを除去できないことがある。
H + type cation exchange resin treatment (2nd stage)
After contacting the anion exchange resin and the hydrogen peroxide solution in this manner, the H + -type cation exchange resin and the hydrogen peroxide solution may be contacted again. As the H + type cation exchange resin, the same ones as described above are used. The method of bringing the hydrogen peroxide solution into contact with the cation exchange resin is carried out by the continuous liquid passing method as described above. The hydrogen peroxide solution passing through the H + type cation exchange resin layer has a space velocity (SV) of 5 It is desirable to carry out in the range of ˜40, preferably 10 to 30 Hr −1 . In the present invention, the hydrogen peroxide solution treated with the anion exchange resin is further treated with the H + type cation exchange resin. In this way, by treating with the H + type cation exchange resin again, trace amounts of Na + , K + , Al 3+ and the like contained as impurities in the anion exchange resin can be removed, so that the level is extremely high (ppt or sub). Metal ion impurities can be removed up to ppt order). The counter ions such as Na + , K + , and Al 3+ to be removed are carbonate ions or hydrogen carbonate ions, which are volatilized as carbon dioxide after cation exchange and do not remain in hydrogen peroxide water. . Note that a trace amount of metal ions contained as impurities may not be removed unless the hydrogen peroxide solution is treated with the second-stage H + -type cation exchange resin.
以上のような操作によって、安定剤、金属イオン不純物が極めて少ない高純度精製過酸化水素水を製造することができる。
図１は、本発明の処理装置における一態様を示し、濃縮タンク１、高圧ポンプ２、逆浸透膜モジュール３、循環ライン４を備えてなる。逆浸透膜モジュールには、圧力バルブおよび精製された過酸化水素水の排出口が適宜設けられている。
By the operation as described above, a high purity purified hydrogen peroxide solution with very little stabilizer and metal ion impurities can be produced.
FIG. 1 shows an embodiment of the processing apparatus of the present invention, which includes a concentration tank 1, a high-pressure pump 2, a reverse
原料の工業用過酸化水素水は濃縮タンク１からポンプ２によって逆浸透膜モジュール３に送られる。過酸化水素水は循環するものと透過するものに分かれる。一部の過酸化水素水は逆浸透膜を透過して、次工程であるイオン交換樹脂処理５に送液される。同時に、安定剤と残りの過酸化水素は循環ラインを通り、濃縮液として濃縮タンク１に戻され、原料の工業用過酸化水素水と混合され、また再度逆浸透膜モジュール３へ供給される。逆浸透膜で分離された濃縮過酸化水素水の割合は、逆浸透膜へ供給された過酸化水素水量の１〜６０％であることが好ましい。特に４０〜６０％であれば安定剤の除去効率が高い。また、安定剤が濃縮された過酸化水素水は装置の外に分離し、蒸留等などの処理を行い、再生するのが一般的であるが、ここでは濃縮タンク１へ戻し、濃縮タンク量の20倍量ぐらいの透過過酸化水素水が得られる毎に、逆浸透膜処理を停止し、濃縮タンク１内の安定剤が大量に濃縮された濃縮過酸化水素水を定期的に抜き出すことにしてもよい。このようにすると濃縮タンク１から定期的に抜き取られた再処理（蒸留やイオン交換樹脂処理）する必要のある濃縮過酸化水素水の量はかなり少ないので、再処理時間も短縮できる。
The raw industrial hydrogen peroxide solution is sent from the concentration tank 1 to the reverse
逆浸透膜を透過して、次工程であるイオン交換樹脂処理に、ライン４をとおり、送液される。過酸化水素水はイオン交換処理としては特に制限されないが、通常イオン交換筒５を通液して精製過酸化水素水が得られる。 The liquid passes through the reverse osmosis membrane and is fed through the line 4 to the ion exchange resin treatment as the next step. The hydrogen peroxide solution is not particularly limited as the ion exchange treatment, but a purified hydrogen peroxide solution is usually obtained by passing the ion exchange tube 5 through.
イオン交換筒５はカラムあるいはボンベでも良く、材質はテフロンコーティングしたステンレスあるいはテフロンライニングしたステンレスあるいはＰＦＡやＰＴＦＥなどのテフロン材が望ましい。イオン交換樹脂は合理的な処理法に従って再生し再利用することができる。 The ion exchange cylinder 5 may be a column or a cylinder, and the material is preferably Teflon-coated stainless steel, Teflon-lined stainless steel, or a Teflon material such as PFA or PTFE. The ion exchange resin can be regenerated and reused according to reasonable processing methods.
本発明に係る過酸化水素水の精製装置としては、安定剤を含む原料過酸化水素水を、カチオンイオン交換樹脂および／またはアニオンイオン交換樹脂が充填された精製塔を使用して、過酸化水素水を精製する過酸化水素水の精製装置であって、工業用過酸化水素水中に含まれる安定剤の70重量％以上を除去するための、逆浸透膜が充填されてなるモジュールと、イオン交換処理用の交換塔およびこれらを連結・送液するためのラインおよび圧縮ポンプを備えてなる。 The apparatus for purifying hydrogen peroxide solution according to the present invention uses a purification tower filled with a cation ion exchange resin and / or an anion ion exchange resin as a raw material hydrogen peroxide solution containing a stabilizer. A hydrogen peroxide purifier for purifying water, a module filled with a reverse osmosis membrane to remove 70% by weight or more of the stabilizer contained in industrial hydrogen peroxide water, and ion exchange It comprises an exchange tower for processing, a line for connecting and feeding them, and a compression pump.
このような装置の概略は前記図１に示される。
以上のような本発明の精製過酸化水素水の製造方法および製造装置によれば安定度が９８％以上、さらには９９％以上、特に９９．５％以上の精製過酸化水素水が得られる。
An outline of such an apparatus is shown in FIG.
According to the method and apparatus for producing purified hydrogen peroxide solution of the present invention as described above, purified hydrogen peroxide solution having a stability of 98% or more, further 99% or more, particularly 99.5% or more can be obtained.
[実施例]
以下、本発明を実施例により説明するが、本発明はかかる実施例に何ら限定されるものではない。
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this Example at all.
なお、実施例・比較例の安定度は、特開2002-122586号公報に記載された測定方法に基づいて行った。具体的にはＪＩＳ Ｋ １４６３に準拠した試験方法で行った。すなわち、３１．５１重量％の過酸化水素水を、合成石英ガラス製メスフラスコ５０ml容量に、標線まで入れたのち、上記冷却管の嵌合部を合成石英ガラス製メスフラスコ開口部に嵌合し、沸騰水浴内で、標線が水面化に没するように保持しながら５時間加熱した。加熱後、合成石英ガラス製メスフラスコに連通した冷却管を取り外し、合成石英ガラス製メスフラスコを氷水で冷却したのち、取り出して室温２０±３℃に１時間放置し、次いで、合成石英ガラス製メスフラスコ内に充填された安定度試験後の過酸化水素水を約１ml採取し、0.1mgのオーダーまで精秤したのち、２５０mlの硬質ガラス製メスフラスコに移し、標線まで、イオン交換水を加え、均一に混合した。硬質ガラス製メスフラスコ内の試料過酸化水素水から２０mlを、２００ml容量のコニカルビーカーに分取し、硫酸（１＋１５）を２０ml加え、０．０２ｍｏｌ／Ｌの過マンガン酸カリウム水溶液で滴定し、終点近くになってから約７０℃に加熱し、３０秒間微紅色を保持するまで０．０２ｍｏｌ／Ｌの過マンガン酸カリウム水溶液で滴定して、安定度試験後の過酸化水素の濃度を求めた。 The stability of the examples and comparative examples was performed based on the measurement method described in JP-A-2002-122586. Specifically, the test was performed according to JIS K 1463. That is, after placing 31.51% by weight of hydrogen peroxide water in a 50 ml synthetic quartz glass volumetric flask up to the marked line, the fitting part of the cooling tube is fitted into the synthetic flask glass flask opening. And it heated for 5 hours, hold | maintaining so that a marked line might be immersed in water surface formation in a boiling water bath. After heating, remove the cooling pipe connected to the synthetic quartz glass measuring flask, cool the synthetic quartz glass measuring flask with ice water, take it out and leave it at room temperature 20 ± 3 ° C. for 1 hour, and then use the synthetic quartz glass measuring flask. About 1 ml of the hydrogen peroxide solution after the stability test filled in the flask is collected, weighed precisely to the order of 0.1 mg, transferred to a 250 ml hard glass volumetric flask, and added with ion-exchanged water up to the marked line. And mixed uniformly. Twenty ml of sample hydrogen peroxide solution in a hard glass volumetric flask is taken into a 200 ml conical beaker, 20 ml of sulfuric acid (1 + 15) is added, and titrated with 0.02 mol / L potassium permanganate aqueous solution. Then, the solution was heated to about 70 ° C., and titrated with a 0.02 mol / L potassium permanganate aqueous solution until a slight red color was maintained for 30 seconds to determine the concentration of hydrogen peroxide after the stability test.
［実施例１］
安定剤が添加されている３５％工業用過酸化水素水中の金属不純物分析を行った。各金属不純物の濃度はAl 900ppb,Cr 1ppb以下,Cu 1ppb以下, Fe 4ppb以下,Na 8ppm,Mg 6ppb,P 10ppmであり、Na，Pは安定剤由来である。
[Example 1]
Metal impurity analysis was performed in 35% industrial hydrogen peroxide water with added stabilizer. The concentration of each metal impurity is Al 900 ppb, Cr 1 ppb or less, Cu 1 ppb or less, Fe 4 ppb or less, Na 8 ppm,
この工業用過酸化水素水を逆浸透膜で圧力1.3MPa、温度25〜29℃で処理し、透過液として得た過酸化水素水を強酸性カチオン交換樹脂に通液し、ついで強塩基性アニオン交換樹脂に通液した。このイオン交換樹脂の出口から任意の処理量でサンプリングを行い金属不純物の濃度を測定した。逆浸透膜には東レ社製のSU-710を使用した。結果、100時間通液しても全ての金属不純物が1ppb以下であった。 This industrial hydrogen peroxide solution was treated with a reverse osmosis membrane at a pressure of 1.3 MPa and a temperature of 25 to 29 ° C., and the hydrogen peroxide solution obtained as a permeate was passed through a strongly acidic cation exchange resin, followed by a strong basic anion. The exchange resin was passed through. Sampling was performed at an arbitrary amount from the outlet of the ion exchange resin, and the concentration of metal impurities was measured. SU-710 made by Toray Industries, Inc. was used for the reverse osmosis membrane. As a result, all metal impurities were 1 ppb or less even after 100 hours of liquid flow.
更にこの過酸化水素水を95℃で5時間加熱し、加熱前後の濃度減少率を評価して安定度を求めた。結果、安定剤由来のNaやPが1ppb以下と安定剤が除去された状態にも関わらず99.9%の安定度であった。 Furthermore, this hydrogen peroxide solution was heated at 95 ° C. for 5 hours, and the concentration reduction rate before and after the heating was evaluated to obtain the stability. As a result, Na or P derived from the stabilizer was 1 ppb or less, and the stability was 99.9% despite the state where the stabilizer was removed.
［実施例２］
実施例1と同じ工業用過酸化水素水を用いて、逆浸透膜に東レ社製のSUL-G10を使用した以外は全て同一の条件として、強酸性カチオン交換樹脂の出口の金属不純物濃度及び安定度を評価した。その結果、100時間通液しても全ての金属不純物が1ppb以下であり、また安定度は99.8%であった。
[Example 2]
Using the same industrial hydrogen peroxide solution as in Example 1, except that SUL-G10 manufactured by Toray Industries, Inc. was used for the reverse osmosis membrane, the metal impurity concentration and stability at the outlet of the strongly acidic cation exchange resin were all the same conditions. The degree was evaluated. As a result, even when the solution was passed for 100 hours, all metal impurities were 1 ppb or less, and the stability was 99.8%.
［比較例１］
実施例1と同じ工業用過酸化水素水を用いて、逆浸透膜処理を行わず0.05μmのテフロンフィルターでろ過した過酸化水素水を実施例1と同一の条件でイオン交換樹脂に通液し、出口から任意の処理量でサンプリングを行い金属不純物の濃度を測定した。結果、30時間目までは全ての金属不純物が1ppb以下であったが、その後は徐々にNa濃度が上昇し、70時間目には1ppmとなり、P濃度は82時間目で600ppbであった。その他の元素については90時間通液しても1ppb以下であった。82時間目の過酸化水素水は安定剤成分がリークしたことにより98.0%の安定度であった。
[Comparative Example 1]
Using the same industrial hydrogen peroxide solution as in Example 1, the hydrogen peroxide solution filtered through a 0.05 μm Teflon filter without the reverse osmosis membrane treatment was passed through the ion exchange resin under the same conditions as in Example 1. Sampling was performed at an arbitrary processing amount from the outlet, and the concentration of metal impurities was measured. As a result, all metal impurities were 1 ppb or less until the 30th hour, but thereafter the Na concentration gradually increased to 1 ppm at the 70th hour, and the P concentration was 600 ppb at the 82th hour. The other elements were 1 ppb or less even after 90 hours. The hydrogen peroxide solution at 82 hours had a stability of 98.0% due to leakage of stabilizer components.
Claims (6)
膜表面に、ポリビニルアルコールのスキン層が設けられ、親水基が導入された、逆浸透膜と、接触させて、安定剤の７０重量％以上を除去したのち、
ついで、カチオンイオン交換樹脂および／またはアニオンイオン交換樹脂により、過酸化水素水に含まれる不純物を除去することを特徴とする精製過酸化水素水の製造方法。 Industrial hydrogen peroxide containing stabilizers
After the surface of the membrane is contacted with a reverse osmosis membrane in which a polyvinyl alcohol skin layer is provided and a hydrophilic group is introduced, 70% by weight or more of the stabilizer is removed .
Next, a method for producing purified hydrogen peroxide solution, wherein impurities contained in the hydrogen peroxide solution are removed with a cation ion exchange resin and / or an anion ion exchange resin.
前処理手段として、ポリビニルアルコールのスキン層が設けられ、親水基が導入され、ポリアミド系又はポリビニルアルコール系の複合膜により安定剤の７０重量％以上を除去しうる逆浸透膜が充填されてなるモジュールを備えてなることを特徴とする精製過酸化水素水の精製装置。 A purified hydrogen peroxide solution purifying apparatus for purifying hydrogen peroxide solution using a purification tower filled with cation ion exchange resin and / or anion ion exchange resin. There,
A module in which a polyvinyl alcohol skin layer is provided as a pretreatment means , a hydrophilic group is introduced, and a reverse osmosis membrane capable of removing 70% by weight or more of the stabilizer by a polyamide or polyvinyl alcohol composite membrane is filled. An apparatus for purifying purified hydrogen peroxide water, comprising:
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| KR20160022642A (en) | 2014-08-20 | 2016-03-02 | 동우 화인켐 주식회사 | The purification process of the hydrogen peroxide |
| KR20160022643A (en) | 2014-08-20 | 2016-03-02 | 동우 화인켐 주식회사 | The purification process of the hydrogen peroxide |
| KR20160023051A (en) | 2014-08-21 | 2016-03-03 | 동우 화인켐 주식회사 | The purification process of the hydrogen peroxide |
| KR20160023261A (en) | 2014-08-22 | 2016-03-03 | 동우 화인켐 주식회사 | The purification process of the hydrogen peroxide |
| JP6365623B2 (en) | 2016-10-20 | 2018-08-01 | 栗田工業株式会社 | Method and apparatus for purifying hydrogen peroxide aqueous solution |
| JP6365624B2 (en) * | 2016-10-20 | 2018-08-01 | 栗田工業株式会社 | Method and apparatus for purifying hydrogen peroxide aqueous solution |
| CN109761201A (en) * | 2019-03-08 | 2019-05-17 | 住化电子材料科技(西安)有限公司 | A kind of preparation facilities and preparation method of ultrapure hydrogen peroxide aqueous solution |
| CN113443606A (en) * | 2021-08-02 | 2021-09-28 | 苏州晶瑞化学股份有限公司 | Process for preparing ultra-pure hydrogen peroxide |
| EP4163252A1 (en) * | 2021-10-06 | 2023-04-12 | Solvay SA | Method for purifying an aqueous hydrogen peroxide solution |
| FR3129148A1 (en) * | 2021-11-17 | 2023-05-19 | Arkema France | Hydrogen peroxide purification on membrane |
| KR102639039B1 (en) * | 2022-12-29 | 2024-02-22 | 오씨아이 주식회사 | Method for purifying hydrogen peroxide |
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| JP3265929B2 (en) * | 1994-09-26 | 2002-03-18 | 住友化学工業株式会社 | Hydrogen peroxide water purification apparatus and hydrogen peroxide water purification method |
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| JP2002122586A (en) * | 2000-10-12 | 2002-04-26 | Santoku Kagaku Kogyo Kk | Apparatus for testing stability of hydrogen peroxide, and method for testing stability of hydrogen peroxide |
| JP4102980B2 (en) * | 2002-09-04 | 2008-06-18 | 三菱瓦斯化学株式会社 | Reverse osmosis membrane treatment method |
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