JP2020001984A - Method for producing hydrogen peroxide - Google Patents

Method for producing hydrogen peroxide Download PDF

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JP2020001984A
JP2020001984A JP2018125252A JP2018125252A JP2020001984A JP 2020001984 A JP2020001984 A JP 2020001984A JP 2018125252 A JP2018125252 A JP 2018125252A JP 2018125252 A JP2018125252 A JP 2018125252A JP 2020001984 A JP2020001984 A JP 2020001984A
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hydrogen peroxide
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purified
aqueous solution
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JP7187839B2 (en
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倫太朗 松本
Rintaro Matsumoto
倫太朗 松本
耕平 茂田
Kohei Shigeta
耕平 茂田
賢 田崎
Masaru Tazaki
賢 田崎
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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Priority to JP2018125252A priority Critical patent/JP7187839B2/en
Priority to TW108121429A priority patent/TW202005907A/en
Priority to CN201920971063.XU priority patent/CN210163126U/en
Priority to KR1020190076221A priority patent/KR20200002639A/en
Priority to CN201910559819.4A priority patent/CN110655039A/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
    • C01B15/01—Hydrogen peroxide
    • C01B15/013—Separation; Purification; Concentration

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
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Abstract

To provide a method for improving the quality of a crude hydrogen peroxide aqueous solution (hyperconcentrated water) in which impurities generated by reverse osmosis membrane (RO membrane) purification of a hydrogen peroxide aqueous solution are concentrated.SOLUTION: There is provided a method for producing a purified hydrogen peroxide aqueous solution comprising a step of bringing a crude hydrogen peroxide aqueous solution into contact with a reverse osmosis membrane, which comprises the following step (1a) and/or (1b). Step (1a): a step of washing a crude hydrogen peroxide aqueous solution before contacting with a reverse osmosis membrane module 102 with a solvent in a washing tank A101a. Step (1b): a step of washing a concentrated hydrogen peroxide aqueous solution after contacting with the reverse osmosis membrane module 102 with a solvent in a washing tank B101b.SELECTED DRAWING: Figure 1

Description

本発明は、アントラキノン類を用いた過酸化水素の製造方法、特に逆浸透膜（ＲＯ膜）による過酸化水素水溶液の精製工程と、溶剤による過酸化水素水溶液の洗浄工程とを含む過酸化水素の製造方法に関する。   The present invention relates to a method for producing hydrogen peroxide using anthraquinones, in particular, a method for purifying hydrogen peroxide including a step of purifying an aqueous solution of hydrogen peroxide by a reverse osmosis membrane (RO membrane) and a step of washing the aqueous solution of hydrogen peroxide by a solvent. It relates to a manufacturing method.

過酸化水素は、酸化力を有し強力な漂白・殺菌作用を持つことから、紙、パルプ、繊維等の漂白剤、殺菌剤、食品添加剤等として使用される。さらに半導体基板等の表面の洗浄、銅、スズ及び他の銅合金表面の化学的研磨、電子回路の蝕刻等の電子工業においても過酸化水素の使用量が増大している。電子工業用や食品添加物用の過酸化水素には高い純度が求められており、高純度過酸化水素への需要は増加傾向にある。過酸化水素の製造方法としてはアントラキノン法が一般的だが、このような有機溶媒を用いる方法によって製造される過酸化水素水溶液は、使用する有機溶媒に由来する有機物や、装置材料に由来する金属などの不純物を含んでいる。このため、高純度の過酸化水素水溶液を得るために、アントラキノン法で得られた過酸化水素水溶液を精製することが行われている。一般的な過酸化水素水溶液の精製方法として、蒸留、サイクロン、吸着樹脂、イオン交換樹脂、逆浸透膜などを用いる方法がある（特許文献１）。   Hydrogen peroxide is used as a bleaching agent for paper, pulp, fiber, etc., a bactericide, a food additive and the like because it has an oxidizing power and a strong bleaching / bactericidal action. The use of hydrogen peroxide is also increasing in the electronics industry, such as for cleaning the surface of semiconductor substrates and the like, for chemically polishing copper, tin and other copper alloy surfaces, and for etching electronic circuits. High purity is required for hydrogen peroxide for the electronics industry and food additives, and the demand for high-purity hydrogen peroxide is increasing. As a method for producing hydrogen peroxide, the anthraquinone method is generally used.However, an aqueous solution of hydrogen peroxide produced by a method using such an organic solvent includes an organic substance derived from the organic solvent used, a metal derived from equipment materials, and the like. Contains impurities. For this reason, in order to obtain a high-purity aqueous hydrogen peroxide solution, an aqueous hydrogen peroxide solution obtained by the anthraquinone method has been purified. As a general method for purifying an aqueous hydrogen peroxide solution, there is a method using distillation, a cyclone, an adsorption resin, an ion exchange resin, a reverse osmosis membrane, or the like (Patent Document 1).

特開2000-302418JP 2000-302418

過酸化水素水溶液の精製方法として、ＲＯ膜精製は設置コストが安く、かつ設置が容易などの利点がある一方、分離精製技術であるため、ＲＯ膜を透過し、不純物が低減された過酸化水素水溶液（透過過水）だけではなく、ＲＯ膜を透過せずに、不純物が濃縮された過酸化水素水溶液（濃縮過水）が生じる。濃縮過水は、透過過水に本来含まれていた不純物を追加で含んでいるため、ＲＯ膜精製前の過酸化水素水溶液よりも品質が悪くなり、スペックアウトとなる可能性がある。スペックアウトとなった濃縮過水は、再度ＲＯ膜精製に供するか、廃棄することとなり、収率の低下をもたらすが、逆に考えると、濃縮過水の品質を改善し、スペックアウトとなる状況を回避することができれば、収率は改善することとなる。したがって、本発明の１つの目的は、過酸化水素水溶液のＲＯ膜精製によって生じる濃縮過水の品質を改善する方法を提供することにある。   As a method for purifying an aqueous hydrogen peroxide solution, RO membrane purification has advantages such as low installation cost and easy installation. On the other hand, since it is a separation and purification technique, hydrogen peroxide that has passed through the RO membrane and has reduced impurities is used. In addition to the aqueous solution (permeated hydrogen peroxide), an aqueous solution of hydrogen peroxide (concentrated hydrogen peroxide) in which impurities are concentrated without passing through the RO membrane is generated. Since the concentrated hydrogen peroxide additionally contains impurities originally contained in the permeated hydrogen peroxide, the quality thereof is lower than that of the aqueous hydrogen peroxide solution before the RO membrane purification, and there is a possibility of a spec-out. Condensed permeate that has become a spec-out will either be subjected to RO membrane purification again or be discarded, resulting in a decrease in yield. Can be avoided, the yield will be improved. Accordingly, it is an object of the present invention to provide a method for improving the quality of concentrated hydrogen peroxide produced by RO membrane purification of an aqueous hydrogen peroxide solution.

本発明者は、上記課題を解決すべく鋭意検討した結果、ＲＯ膜精製に接触させる前の粗過酸化水素水溶液（粗過水）及び／又はＲＯ膜精製後の濃縮過水を溶剤洗浄に供することよって、濃縮過水の品質を改善できることを見出した。また、洗浄に使用した溶剤を繰り返し使用する場合、適宜蒸留精製することで良好な品質改善効果が継続して得られることも見出した。   As a result of intensive studies to solve the above-mentioned problems, the present inventors provide a crude hydrogen peroxide aqueous solution (coarse peroxide) before contact with RO membrane purification and / or a concentrated peroxide after RO membrane purification for solvent cleaning. As a result, it has been found that the quality of the concentrated water can be improved. It has also been found that, when the solvent used for washing is repeatedly used, a good quality improvement effect can be continuously obtained by appropriately purifying by distillation.

本発明の一側面は、以下のとおりである。
［１］ 粗過酸化水素水溶液を逆浸透膜に接触させる工程を含む、精製過酸化水素水溶液の製造方法であって、
以下の工程（１ａ）及び／又は（１ｂ）を含む、製造方法。
工程（１ａ）：逆浸透膜接触前の粗過酸化水素水溶液を溶剤により洗浄する工程。
工程（１ｂ）：逆浸透膜接触後の濃縮過酸化水素水溶液を溶剤により洗浄する工程。
［２］ 下記工程（２ａ）及び／又は（２ｂ）を含む、［１］に記載の製造方法。
工程（２ａ）：前記工程（１ａ）から得られる使用済み溶剤の少なくとも一部を、前記工程（１ａ）及び／又は（１ｂ）へ導入する工程。
工程（２ｂ）：前記工程（１ｂ）から得られる使用済み溶剤の少なくとも一部を、前記工程（１ａ）及び／又は（１ｂ）へ導入する工程。
［３］ 下記工程（３ａ）及び／又は（３ｂ）を含む、［２］に記載の製造方法。
工程（３ａ）：前記工程（１ａ）から得られる使用済み溶剤の少なくとも一部を精製し、精製後の溶剤を前記工程（２ａ）へ、工程（１ａ）から得られる使用済み溶剤の少なくとも一部の代わりに導入する工程。
工程（３ｂ）：前記工程（１ｂ）から得られる使用済み溶剤の少なくとも一部を精製し、精製後の溶剤を前記工程（２ｂ）へ、工程（１ｂ）から得られる使用済み溶剤の少なくとも一部の代わりに導入する工程。 One aspect of the present invention is as follows.
[1] A method for producing a purified aqueous hydrogen peroxide solution, comprising a step of bringing a crude aqueous hydrogen peroxide solution into contact with a reverse osmosis membrane,
A manufacturing method comprising the following steps (1a) and / or (1b).
Step (1a): a step of washing the crude aqueous hydrogen peroxide solution before contact with the reverse osmosis membrane with a solvent.
Step (1b): a step of washing the concentrated aqueous hydrogen peroxide solution after contact with the reverse osmosis membrane with a solvent.
[2] The production method according to [1], comprising the following steps (2a) and / or (2b).
Step (2a): a step of introducing at least a part of the used solvent obtained from the step (1a) to the step (1a) and / or (1b).
Step (2b): a step of introducing at least a part of the used solvent obtained from the step (1b) to the step (1a) and / or (1b).
[3] The production method according to [2], comprising the following steps (3a) and / or (3b).
Step (3a): At least a part of the used solvent obtained from the step (1a) is purified, and the purified solvent is transferred to the step (2a), and at least a part of the used solvent obtained from the step (1a) is purified. Step to introduce instead of.
Step (3b): At least a part of the used solvent obtained from the step (1b) is purified, and the purified solvent is transferred to the step (2b), and at least a part of the used solvent obtained from the step (1b) is purified. Step to introduce instead of.

［４］ 工程（１ａ）及び（１ｂ）の両方を含み、下記工程（Ｉ）を含む、［１］に記載の製造方法。
工程（Ｉ）：工程（１ａ）及び（１ｂ）から得られる使用済み溶剤を混合する工程。
［５］ 下記工程（ＩＩ）を含む、［４］に記載の製造方法。
工程（ＩＩ）：前記工程（Ｉ）から得られる混合後の溶剤の少なくとも一部を、前記工程（１ａ）及び／又は（１ｂ）へ導入する工程。
［６］ 下記工程（ＩＩＩ）を含む、［５］に記載の製造方法。
工程（ＩＩＩ）：前記工程（Ｉ）から得られる混合後の溶剤の少なくとも一部を精製し、精製後の溶剤を、工程（Ｉ）から得られる混合後の溶剤の少なくとも一部の代わりに、前記工程（ＩＩ）へ導入する工程
［７］ 下記工程（ＩＶ）を含む、［４］〜［６］のいずれかに記載の製造方法。
工程（ＩＶ）：工程（１ａ）及び（１ｂ）から得られる使用済み溶剤を精製し、精製後の溶剤を、工程（１ａ）及び（１ｂ）から得られる使用済み溶剤の代わりに、前記工程（Ｉ）へ導入する工程。
［８］ 前記精製が、蒸留により行われる、［３］、［６］又は［７］に記載の製造方法。 [4] The production method according to [1], which includes both the steps (1a) and (1b) and includes the following step (I).
Step (I): a step of mixing the used solvent obtained from steps (1a) and (1b).
[5] The production method according to [4], including the following step (II).
Step (II): a step of introducing at least a part of the mixed solvent obtained from the step (I) to the step (1a) and / or (1b).
[6] The production method according to [5], including the following step (III).
Step (III): At least a part of the mixed solvent obtained from the step (I) is purified, and the purified solvent is replaced with at least a part of the mixed solvent obtained from the step (I), Step (7) of introducing into the step (II) The production method according to any of [4] to [6], including the following step (IV).
Step (IV): The used solvent obtained from the steps (1a) and (1b) is purified, and the solvent after purification is replaced with the above-mentioned step (1) instead of the used solvent obtained from the steps (1a) and (1b). Step of introducing into I).
[8] The production method according to [3], [6] or [7], wherein the purification is performed by distillation.

［９］ 洗浄装置Ａ及び洗浄装置Ｂの少なくとも１つと、逆浸透膜モジュールとを備えた精製過酸化水素水溶液製造システムであって、洗浄装置Ａは、未洗浄粗過酸化水素水溶液輸送ラインと、溶剤供給ラインＡと、溶剤排出ラインＡとを備え、洗浄装置Ｂは、洗浄濃縮過酸化水素水溶液輸送ラインと、溶剤供給ラインＢと、溶剤排出ラインＢとを備え、逆浸透膜モジュールは、透過過酸化水素水溶液輸送ラインを備え、洗浄装置Ａと逆浸透膜モジュールとは洗浄粗過酸化水素水溶液輸送ラインにより連通し、洗浄装置Ｂと逆浸透膜モジュールとは濃縮過酸化水素水溶液輸送ラインにより連通し、洗浄装置Ａが存在しない場合、溶剤供給ラインＡ、溶剤排出ラインＡ及び洗浄粗過酸化水素水溶液輸送ラインも存在せず、未洗浄粗過酸化水素水溶液輸送ラインは逆浸透膜モジュールに接続し、洗浄装置Ｂが存在しない場合、溶剤供給ラインＢ、溶剤排出ラインＢ及び洗浄濃縮過酸化水素水溶液輸送ラインも存在しない、システム。
［１０］ 溶剤再利用ラインＡ及び／又は溶剤再利用ラインＢをさらに備え、溶剤供給ラインＡと溶剤排出ラインＡとが溶剤再利用ラインＡにより連通し、及び／又は、溶剤供給ラインＢと溶剤排出ラインＢとが溶剤再利用ラインＢにより連通している、［９］に記載のシステム。
［１１］ 溶剤精製装置をさらに備え、溶剤精製装置と溶剤排出ラインＡとは溶剤再利用ラインＡにより連通し、溶剤精製装置と溶剤供給ラインＡ又は洗浄装置Ａとは精製溶剤輸送ラインＡにより連通し、及び／又は、溶剤精製装置と溶剤排出ラインＢとは溶剤再利用ラインＢにより連通し、溶剤精製装置と溶剤供給ラインＢ又は洗浄装置Ｂとは精製溶剤輸送ラインＢにより連通している、［１０］に記載のシステム。
［１２］ 精製装置が蒸留塔を含む、［１１］に記載のシステム。 [9] A purified hydrogen peroxide aqueous solution production system including at least one of the cleaning device A and the cleaning device B and a reverse osmosis membrane module, wherein the cleaning device A includes an uncleaned crude hydrogen peroxide aqueous solution transport line, The cleaning device B includes a solvent supply line A and a solvent discharge line A. The cleaning device B includes a cleaning concentrated hydrogen peroxide aqueous solution transport line, a solvent supply line B, and a solvent discharge line B. A hydrogen peroxide aqueous solution transport line is provided, and the cleaning device A and the reverse osmosis membrane module are connected by a cleaning coarse hydrogen peroxide aqueous solution transport line, and the cleaning device B and the reverse osmosis membrane module are connected by a concentrated hydrogen peroxide aqueous solution transport line. However, when the cleaning device A does not exist, the solvent supply line A, the solvent discharge line A, and the cleaning crude hydrogen peroxide aqueous solution transport line do not exist, and the uncleaned crude hydrogen peroxide aqueous solution does not exist. A system in which the liquid transport line is connected to the reverse osmosis membrane module, and when the cleaning device B is not present, the solvent supply line B, the solvent discharge line B, and the transport line for cleaning concentrated hydrogen peroxide solution are not present.
[10] A solvent recycling line A and / or a solvent recycling line B are further provided, and the solvent supply line A and the solvent discharge line A communicate with each other through the solvent recycling line A, and / or the solvent supply line B and the solvent The system according to [9], wherein the discharge line B is communicated with the solvent reuse line B.
[11] A solvent refining device is further provided, and the solvent refining device and the solvent discharge line A are connected by a solvent reusing line A, and the solvent refining device is connected to the solvent supply line A or the cleaning device A by a purified solvent transport line A. And / or the solvent refining device and the solvent discharge line B communicate with each other through a solvent reuse line B, and the solvent refining device communicates with the solvent supply line B or the cleaning device B through a purified solvent transport line B. The system according to [10].
[12] The system according to [11], wherein the purification device includes a distillation column.

本発明は、以下の１以上の効果を奏する。
（１）濃縮過水の品質を改善することができる。
（２）濃縮過水の全有機炭素（ＴＯＣ）を低減することができる。
（３）濃縮過水のハーゼン色数（ＡＰＨＡ）を低減することができる。
（４）過酸化水素製造の収率を高めることができる。
（５）廃棄される濃縮過水を低減し、資源の有効活用が可能となる。
（６）廃棄される溶剤を低減し、資源の有効活用が可能となる。 The present invention has one or more of the following effects.
(1) The quality of the concentrated water can be improved.
(2) Total organic carbon (TOC) of the concentrated water can be reduced.
(3) It is possible to reduce the Hazen color number (APHA) of the concentrated superoxide.
(4) The yield of hydrogen peroxide production can be increased.
(5) The concentrated excess water to be discarded is reduced, and the resources can be effectively used.
(6) The amount of solvent to be discarded is reduced, and resources can be effectively used.

図１は、前洗浄工程と後洗浄工程の両方を行うことができる、本発明の精製過酸化水素水溶液製造システムの一態様の概略図である。FIG. 1 is a schematic view of one embodiment of the purified hydrogen peroxide aqueous solution production system of the present invention, in which both a pre-cleaning step and a post-cleaning step can be performed. 図２は、前洗浄工程を行うことができる、本発明の精製過酸化水素水溶液製造システムの一態様の概略図である。FIG. 2 is a schematic view of one embodiment of the purified hydrogen peroxide aqueous solution production system of the present invention, in which a pre-cleaning step can be performed. 図３は、後洗浄工程を行うことができる、本発明の精製過酸化水素水溶液製造システムの一態様の概略図である。FIG. 3 is a schematic view of one embodiment of the purified hydrogen peroxide aqueous solution production system of the present invention, in which a post-cleaning step can be performed. 図４は、溶剤再利用ラインを備えた、本発明の精製過酸化水素水溶液製造システムの一態様の概略図である。FIG. 4 is a schematic view of one embodiment of the purified hydrogen peroxide aqueous solution production system of the present invention, which includes a solvent recycling line. 図５は、溶剤精製装置を備えた、本発明の精製過酸化水素水溶液製造システムの一態様の概略図である。FIG. 5 is a schematic diagram of one embodiment of the purified hydrogen peroxide aqueous solution production system of the present invention, which includes a solvent purification device.

本発明の一態様は、粗過酸化水素水溶液を逆浸透膜に接触させる工程を含む、精製過酸化水素水溶液の製造方法であって、
工程（１ａ）：逆浸透膜接触前の粗過酸化水素水溶液を溶剤により洗浄する工程、及び／又は、
工程（１ｂ）：逆浸透膜接触後の濃縮過酸化水素水溶液を溶剤により洗浄する工程、
を有する方法（以下、本発明の製造方法と称することがある）に関する。 One aspect of the present invention is a method for producing a purified aqueous hydrogen peroxide solution, comprising the step of contacting a crude aqueous hydrogen peroxide solution with a reverse osmosis membrane,
Step (1a): a step of washing the crude hydrogen peroxide aqueous solution before contact with the reverse osmosis membrane with a solvent, and / or
Step (1b): washing the concentrated aqueous hydrogen peroxide solution after contact with the reverse osmosis membrane with a solvent,
(Hereinafter sometimes referred to as the production method of the present invention).

本方法に使用する逆浸透膜は、粗過酸化水素水溶液に含まれる不純物を除去する能力があれば特に限定されない。逆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、スパゲティ膜又は中空糸膜又はそれら複数の組合せが挙げられる。逆浸透膜の素材としては、ポリエチレンイミン縮合体、酢酸セルロース、変性ポリアクリロニトリル、ポリベンツイミダピロン、ポリエーテルアミド、三酢酸セルロース、ポリアミドカルボン酸、架橋ポリエーテル、架橋ポリアミド、ポリイミド、ポリベンツイミダゾール、スルホン化フェニレンオキシド、ポリピペラジンアミド、ポリエチレンイミントール、エンジイソシアネート、ポリエチレンイシン酸クロリド、スルホン化ポリフルフリルアルコール、スルホン化ポリスルホン、ポリエーテル尿素、ポリビニルアルコール、ポリスルホン、ポリアミドポリビニルアルコール、スルホン化ポリエーテルスルホン又はポリアミドなどが例示される。逆浸透膜は非対称膜でも複合膜でもよい。逆浸透膜はポリアミドから成る複合膜が好ましい。   The reverse osmosis membrane used in the present method is not particularly limited as long as it has an ability to remove impurities contained in the crude hydrogen peroxide aqueous solution. Examples of the form of the reverse osmosis 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. As materials for the reverse osmosis membrane, polyethyleneimine condensate, cellulose acetate, modified polyacrylonitrile, polybenzimidapiron, polyetheramide, cellulose triacetate, polyamide carboxylic acid, cross-linked polyether, cross-linked polyamide, polyimide, polybenzimidazole , Sulfonated phenylene oxide, polypiperazine amide, polyethyleneimitol, enedisocyanate, polyethyleneisinic chloride, sulfonated polyfurfuryl alcohol, sulfonated polysulfone, polyether urea, polyvinyl alcohol, polysulfone, polyamide polyvinyl alcohol, sulfonated polyether sulfone Or polyamide. The reverse osmosis membrane may be an asymmetric membrane or a composite membrane. The reverse osmosis membrane is preferably a composite membrane made of polyamide.

粗過酸化水素水溶液を逆浸透膜に接触させるときに逆浸透膜に適用する処理圧力は、逆浸透膜が許容する範囲内であればよく、典型的には５ＭＰａ以下であり、好ましくは０．３〜１．５ＭＰａの範囲である。処理時の温度は、過酸化水素の過度の分解が生じないものが望ましく、好ましくは−２０〜４０℃、より好ましくは５〜２５℃の範囲である。逆浸透膜は、逆浸透膜モジュールに組み込んで使用することができる。逆浸透膜モジュールは、逆浸透膜と、逆浸透膜を固定支持する耐圧容器とを備えていてもよく、粗過酸化水素水溶液を逆浸透膜に接触させるための加圧手段をさらに備えていてもよい。   The treatment pressure applied to the reverse osmosis membrane when bringing the crude hydrogen peroxide aqueous solution into contact with the reverse osmosis membrane may be within the range permitted by the reverse osmosis membrane, and is typically 5 MPa or less, and preferably 0.1 MPa or less. The range is 3 to 1.5 MPa. The temperature during the treatment is preferably such that excessive decomposition of hydrogen peroxide does not occur, and is preferably in the range of -20 to 40C, more preferably 5 to 25C. The reverse osmosis membrane can be used by being incorporated into a reverse osmosis membrane module. The reverse osmosis membrane module may include a reverse osmosis membrane and a pressure-resistant container fixedly supporting the reverse osmosis membrane, and further includes a pressurizing unit for bringing the crude hydrogen peroxide aqueous solution into contact with the reverse osmosis membrane. Is also good.

粗過酸化水素水溶液は、ＲＯ膜精製されていない過酸化水素水溶液を意味する。過酸化水素水溶液は任意の手法によって製造されたものであってよく、アントラキノン法、アルコール酸化法、酸化還元法、直接法（直接酸化法）、電解法などにより製造されたものを含む。粗過酸化水素水溶液は、有機不純物及び無機不純物のいずれか一方又は両方を含んでいてもよい。粗過酸化水素水溶液に含まれる過酸化水素の濃度は特に限定されず、例えば、２０〜９０重量％、３０〜８０重量％、３５〜７０重量％、４０〜６０重量％等であってよい。   The crude aqueous hydrogen peroxide solution means an aqueous hydrogen peroxide solution that has not been RO membrane purified. The aqueous hydrogen peroxide solution may be produced by any method, and includes those produced by an anthraquinone method, an alcohol oxidation method, an oxidation-reduction method, a direct method (direct oxidation method), an electrolytic method, or the like. The crude hydrogen peroxide aqueous solution may contain one or both of organic impurities and inorganic impurities. The concentration of hydrogen peroxide contained in the crude aqueous hydrogen peroxide solution is not particularly limited, and may be, for example, 20 to 90% by weight, 30 to 80% by weight, 35 to 70% by weight, 40 to 60% by weight, or the like.

有機不純物としては、例えば、アントラキノン法では、作動溶液組成物とその劣化物等が挙げられる。劣化物としては、非極性溶剤劣化物（例えば、ベンズアルデヒド類、安息香酸類、フェノール類、ベンジルアルコール類等）、極性溶剤劣化物（例えば、２−エチルヘキサノール、２−エチルヘキサナール等）、アントラキノン劣化物（例えば、アントロン、オキシアントロン、テトラヒドロオキシアントロン、アントラキノンエポキシド、テトラヒドロアントラキノンエポキシド等）などが挙げられる。無機不純物としては、例えば、銅、亜鉛、クロム、パラジウム、ロジウム、ルテニウム、白金、鉄、ニッケル、アルミニウム、ナトリウム、カリウム、カルシウム、塩素、硫黄、シリカ、ホウ素などが挙げられる。   Examples of the organic impurities include, in the anthraquinone method, a working solution composition and its degraded products. As the degraded products, non-polar solvent degraded products (eg, benzaldehydes, benzoic acids, phenols, benzyl alcohols, etc.), polar solvent degraded products (eg, 2-ethylhexanol, 2-ethylhexanal, etc.), anthraquinone degraded products (For example, anthrone, oxyanthrone, tetrahydrooxyanthrone, anthraquinone epoxide, tetrahydroanthraquinone epoxide, etc.). Examples of the inorganic impurities include copper, zinc, chromium, palladium, rhodium, ruthenium, platinum, iron, nickel, aluminum, sodium, potassium, calcium, chlorine, sulfur, silica, and boron.

粗過酸化水素水溶液は、工程（１ａ）の溶剤洗浄を受けた洗浄粗過酸化水素水溶液と、前記溶剤洗浄を受けていない未洗浄粗過酸化水素水溶液とを含む。未洗浄粗過酸化水素水溶液の全有機炭素は特に限定されず、例えば、２０〜５００ｍｇ／Ｌ、５０〜５００ｍｇ／Ｌ、５０〜２００ｍｇ／Ｌ、８０〜２００ｍｇ／Ｌ等であってよい。未洗浄粗過酸化水素水溶液のハーゼン色数は特に限定されず、例えば、１〜５０、３〜３５、５〜３０、５〜２０等であってよい。洗浄粗過酸化水素水溶液の全有機炭素は特に限定されず、例えば、１８〜４５０ｍｇ／Ｌ、４５〜４５０ｍｇ／Ｌ、４５〜１８０ｍｇ／Ｌ、７０〜１８０ｍｇ／Ｌ等であってよい。また、洗浄粗過酸化水素水溶液の全有機炭素は、未洗浄粗過酸化水素水溶液の全有機炭素より、例えば、６％以上、好ましくは８％以上、より好ましくは１０％以上、特に１１％以上低くてもよい。洗浄粗過酸化水素水溶液のハーゼン色数は特に限定されず、例えば、０〜３０、０〜２０、０〜１０等であってよい。また、洗浄粗過酸化水素水溶液のハーゼン色数は、最小値を０として、未洗浄粗過酸化水素水溶液のハーゼン色数より、例えば、２以上、好ましくは３以上、より好ましくは４以上、特に５以上低くてもよい。   The crude hydrogen peroxide aqueous solution includes the washed crude hydrogen peroxide aqueous solution that has been subjected to the solvent cleaning in step (1a), and the uncleaned crude hydrogen peroxide aqueous solution that has not been subjected to the solvent cleaning. The total organic carbon of the unwashed crude hydrogen peroxide aqueous solution is not particularly limited, and may be, for example, 20 to 500 mg / L, 50 to 500 mg / L, 50 to 200 mg / L, 80 to 200 mg / L, or the like. The Hazen color number of the unwashed crude hydrogen peroxide aqueous solution is not particularly limited, and may be, for example, 1 to 50, 3 to 35, 5 to 30, 5 to 20, or the like. The total organic carbon of the washed crude hydrogen peroxide aqueous solution is not particularly limited, and may be, for example, 18 to 450 mg / L, 45 to 450 mg / L, 45 to 180 mg / L, 70 to 180 mg / L, and the like. Further, the total organic carbon of the washed crude hydrogen peroxide aqueous solution is, for example, 6% or more, preferably 8% or more, more preferably 10% or more, and especially 11% or more than the total organic carbon of the uncleaned crude hydrogen peroxide aqueous solution. May be lower. The Hazen color number of the washed crude hydrogen peroxide aqueous solution is not particularly limited, and may be, for example, 0 to 30, 0 to 20, 0 to 10, or the like. Further, the Hazen color number of the washed crude hydrogen peroxide aqueous solution is set to a minimum value of 0, and is, for example, 2 or more, preferably 3 or more, more preferably 4 or more, and especially more than the Hazen color number of the unwashed crude hydrogen peroxide aqueous solution. It may be lower by 5 or more.

精製過酸化水素水溶液は、ＲＯ膜精製により得られた透過過水（未洗浄粗過酸化水素水溶液のＲＯ膜精製により得られた未洗浄透過過水と、洗浄粗過酸化水素水溶液のＲＯ膜精製により得られた前洗浄透過過水を含む）、洗浄粗過酸化水素水溶液のＲＯ膜精製により得られた前洗浄濃縮過水、未洗浄粗過酸化水素水溶液のＲＯ膜精製により得られた未洗浄濃縮過水を溶剤洗浄した後洗浄濃縮過水、及び、前洗浄濃縮過水を溶剤洗浄した前後洗浄濃縮過水を包含する。本明細書において、「前洗浄濃縮過水」、「後洗浄濃縮過水」及び「前後洗浄濃縮過水」を「洗浄濃縮過水」と総称する場合もある。また、本明細書において、「未洗浄濃縮過水」、「前洗浄濃縮過水」、「後洗浄濃縮過水」及び「前後洗浄濃縮過水」を「濃縮過水」と総称する場合もある。精製過酸化水素水溶液のハーゼン色数は特に限定されず、例えば、０〜５０、０〜３０、０〜１５等であってよい。精製過酸化水素水溶液の全有機炭素は特に限定されず、例えば、１〜９００ｍｇ／Ｌ、１〜６００ｍｇ／Ｌ、１〜２６０ｍｇ／Ｌ等であってよい。透過過水のハーゼン色数は特に限定されず、例えば、０〜１０、０〜７、０〜４等であってよい。透過過水の全有機炭素は特に限定されず、例えば、１〜５０ｍｇ／Ｌ、１〜３０ｍｇ／Ｌ、１〜２０ｍｇ／Ｌ等であってよい。洗浄濃縮過水のハーゼン色数は特に限定されず、例えば、０〜５０、０〜３０、０〜１５等であってよい。また、洗浄濃縮過水のハーゼン色数は、最小値を０として、未洗浄濃縮過水（すなわち、その生成プロセス中、溶剤洗浄を１回も行わずに生成された濃縮過水）のハーゼン色数より、例えば、１０以上、好ましくは１１以上、より好ましくは１２以上、特に１４以上低くてもよい。洗浄濃縮過水の全有機炭素は特に限定されず、例えば、３２〜９００ｍｇ／Ｌ、３２〜４００ｍｇ／Ｌ、３２〜２６０ｍｇ／Ｌ等であってよい。また、洗浄濃縮過水の全有機炭素は、未洗浄濃縮過水の全有機炭素より、例えば、６％以上、好ましくは８％以上、より好ましくは１０％以上、特に１１％以上低くてもよい。透過過水及び洗浄濃縮過水のハーゼン色数及び全有機炭素は低いほど好ましい。   The purified aqueous hydrogen peroxide solution is a permeated hydrogen peroxide obtained by RO membrane purification (an unwashed permeated hydrogen peroxide obtained by RO membrane purification of an unwashed crude hydrogen peroxide aqueous solution, and a RO membrane purification of a washed crude hydrogen peroxide aqueous solution). The pre-cleaned concentrated hydrogen peroxide obtained by the RO membrane purification of the washed crude hydrogen peroxide aqueous solution, and the unwashed obtained by the RO membrane purification of the unwashed crude hydrogen peroxide aqueous solution It includes washing concentrated hydrogen peroxide after solvent washing of concentrated hydrogen peroxide, and pre- and post-wash concentrated hydrogen peroxide washing of pre-washing concentrated hydrogen peroxide. In this specification, the “pre-cleaning concentrated hydrogen peroxide”, the “post-cleaning concentrated hydrogen peroxide” and the “front and rear cleaning concentrated hydrogen peroxide” may be collectively referred to as “washing concentrated hydrogen peroxide”. Further, in the present specification, the “unwashed concentrated permeate”, the “pre-washed concentrated permeate”, the “post-washed concentrated permeate”, and the “front and back concentrated washout” may be collectively referred to as “concentrated permeate”. . The Hazen color number of the purified aqueous hydrogen peroxide solution is not particularly limited, and may be, for example, 0 to 50, 0 to 30, 0 to 15, and the like. The total organic carbon of the purified aqueous hydrogen peroxide solution is not particularly limited, and may be, for example, 1 to 900 mg / L, 1 to 600 mg / L, 1 to 260 mg / L, and the like. The number of Hazen colors of the permeated water is not particularly limited, and may be, for example, 0 to 10, 0 to 7, 0 to 4, or the like. The total organic carbon permeate is not particularly limited, and may be, for example, 1 to 50 mg / L, 1 to 30 mg / L, 1 to 20 mg / L, and the like. The Hazen color number of the washing concentrated water is not particularly limited, and may be, for example, 0 to 50, 0 to 30, 0 to 15, and the like. Also, the Hazen color number of the washing concentrated water is set to a minimum value of 0, and the Hazen color number of the unwashed concentrated water (that is, the concentrated water generated without performing any solvent washing during the generation process) is set. It may be lower than the number, for example, 10 or more, preferably 11 or more, more preferably 12 or more, especially 14 or more. The total organic carbon of the washing concentrated water is not particularly limited, and may be, for example, 32 to 900 mg / L, 32 to 400 mg / L, or 32 to 260 mg / L. Further, the total organic carbon of the washed concentrated permeate may be, for example, 6% or more, preferably 8% or more, more preferably 10% or more, particularly 11% or more lower than the total organic carbon of the unwashed concentrated permeate. . The lower the Hazen color number and the total organic carbon of the permeated water and the washed concentrated water, the better.

溶剤洗浄に用いる溶剤は、洗浄により濃縮過水の品質を改善できるものであれば特に限定されない。かかる溶剤としては、濃縮過水に含まれる不純物、特に有機不純物に対する分配係数が高いものが好ましい。また、溶剤洗浄後の過酸化水素水溶液には若干の洗浄溶剤が含まれるため、溶剤洗浄後の過酸化水素水溶液を蒸留により濃縮するなど、高温での処理を行う場合は、引火点の高い洗浄溶剤（例えば、引火点が４０℃以上の溶剤）を用いることが安全上の観点から好ましい。
例えば、過酸化水素が有機溶媒を使用する方法（例えば、アントラキノン法）で製造されている場合、前記方法で使用される非極性有機溶媒を溶剤洗浄の溶剤として使用することが好ましい。溶剤洗浄に用いる溶剤の非限定例としては、芳香族炭化水素（例えば、Ｃ９〜Ｃ１２芳香族炭化水素等、特にＣ９〜Ｃ１１芳香族炭化水素）、脂肪族炭化水素、脂環族炭化水素等の炭化水素等が挙げられる。芳香族炭化水素としては、例えば、ベンゼン、トルエン、少なくとも１個のアルキル基で置換された芳香族炭化水素、特に炭素原子を８、９、１０、１１又は１２個含むアルキルベンゼン（例えば、１，２，４−トリメチルベンゼン（プソイドクメン）などの、炭素原子を９個含むトリメチルベンゼン、クメンなど）又はその混合物などが挙げられ、脂肪族炭化水素としては、例えば、ｎ−ヘキサン、シクロヘキサン、石油ベンジン又はその混合物などが挙げられる。 The solvent used for the solvent cleaning is not particularly limited as long as the quality of the concentrated hydrogen peroxide can be improved by the cleaning. As such a solvent, those having a high partition coefficient with respect to impurities contained in the concentrated hydrogen peroxide, particularly organic impurities are preferable. Also, since the aqueous solution of hydrogen peroxide after solvent cleaning contains a small amount of cleaning solvent, when performing high-temperature treatment, such as concentrating the aqueous solution of hydrogen peroxide after solvent cleaning by distillation, cleaning with a high flash point is required. It is preferable to use a solvent (for example, a solvent having a flash point of 40 ° C. or higher) from the viewpoint of safety.
For example, when hydrogen peroxide is produced by a method using an organic solvent (for example, an anthraquinone method), it is preferable to use the non-polar organic solvent used in the method as a solvent for solvent washing. Non-limiting examples of solvents used for solvent cleaning include aromatic hydrocarbons (e.g., C9-C12 aromatic hydrocarbons, particularly C9-C11 aromatic hydrocarbons), aliphatic hydrocarbons, alicyclic hydrocarbons, and the like. Hydrocarbons and the like. As the aromatic hydrocarbon, for example, benzene, toluene, an aromatic hydrocarbon substituted with at least one alkyl group, particularly an alkylbenzene containing 8, 9, 10, 11 or 12 carbon atoms (for example, 1, 2, or 3) , 4-trimethylbenzene (pseudocumene) and the like, trimethylbenzene containing 9 carbon atoms, cumene and the like) or a mixture thereof. Examples of the aliphatic hydrocarbon include n-hexane, cyclohexane, petroleum benzene and the like. And mixtures thereof.

溶剤洗浄は、未洗浄粗過酸化水素水溶液又は未洗浄濃縮過水に含まれる不純物を低減し得る任意の手法で行うことができる。溶剤洗浄の非限定例としては、例えば、洗浄の対象となる溶液（未洗浄粗過酸化水素水溶液、未洗浄濃縮過水又は前洗浄濃縮過水）と溶剤とを混合し、所定時間静置した後に分離する方法、多孔板抽出塔を用いて、洗浄対象溶液と溶剤とを向流接触させ、洗浄する方法、スプレー塔や遠心抽出器を用いる方法などが挙げられる。洗浄対象溶液と溶剤との混合比は、洗浄対象溶液の不純物を低減し得るものであれば特に限定されないが、例えば、洗浄対象溶液：溶剤の体積比で０．５：１〜２０：１、１：１〜１５：１、２：１〜１０：１、３：１〜８：１等であってよい。洗浄時の温度は、過酸化水素の抽出効率や、過酸化水素の安定性などの観点から、１０〜８０℃、２０〜７０℃、３０〜６０℃等であってよい。特定の態様において、溶剤洗浄は、例えば、洗浄対象溶液と溶剤をラインミキサーで混合し、コアレッサーフィルターに通液した後、セトラーで静置分離する方法で行うことができる。静置分離を含む洗浄方法において、溶剤混合後の静置時間は、溶剤が分離することができれば特に限定されないが、例えば、５分〜３６時間、５分〜２４時間、１０分〜１８時間、１０分〜１２時間等であってよい。使用済みの溶剤は、後述のように再度溶剤洗浄に用いるために一部又は全部を再利用してもよいし、一部又は全部を廃棄してもよい。   The solvent washing can be performed by any method that can reduce impurities contained in the unwashed crude hydrogen peroxide aqueous solution or the unwashed concentrated hydrogen peroxide. As a non-limiting example of the solvent washing, for example, a solution to be washed (unwashed crude hydrogen peroxide aqueous solution, unwashed concentrated hydrogen peroxide or pre-washed concentrated hydrogen peroxide) and a solvent are mixed and allowed to stand for a predetermined time. Examples of the method include a method of separating the solution, a method of washing the solution to be washed and the solvent in countercurrent contact with each other using a perforated plate extraction tower, and a method of using a spray tower or a centrifugal extractor. The mixing ratio between the solution to be cleaned and the solvent is not particularly limited as long as impurities in the solution to be cleaned can be reduced, and for example, the volume ratio of the solution to be cleaned: solvent is 0.5: 1 to 20: 1. 1: 1 to 15: 1, 2: 1 to 10: 1, 3: 1 to 8: 1, and the like. The temperature at the time of washing may be 10 to 80 ° C., 20 to 70 ° C., 30 to 60 ° C., etc., from the viewpoint of the extraction efficiency of hydrogen peroxide and the stability of hydrogen peroxide. In a specific embodiment, the solvent washing can be performed, for example, by a method in which a solution to be washed and a solvent are mixed by a line mixer, passed through a coalescer filter, and then separated by standing in a settler. In the washing method including the stationary separation, the stationary time after mixing the solvent is not particularly limited as long as the solvent can be separated, for example, 5 minutes to 36 hours, 5 minutes to 24 hours, 10 minutes to 18 hours, It may be from 10 minutes to 12 hours. A part or all of the used solvent may be reused to be used again for solvent cleaning as described later, or a part or all of the used solvent may be discarded.

本発明の製造方法は、工程（１ａ）の洗浄工程（以下、「前洗浄工程」と称することがある）と工程（１ｂ）の洗浄工程（以下、「後洗浄工程」と称することがある）の一方又は両方を含む。前洗浄工程と後洗浄工程の両方を含む態様において、洗浄工程は共通の洗浄装置で行ってもよいし、前洗浄工程と後洗浄工程をそれぞれ別の洗浄装置（例えば、前洗浄用洗浄装置と後洗浄用洗浄装置）で行ってもよい。洗浄装置は、洗浄対象溶液と溶剤の混合及び分離が可能な洗浄槽で構成されても、混合機と分離機の組合せで構成されてもよい。また、洗浄用の溶剤は、共通のタンクから供給されてもよいし、前洗浄工程と後洗浄工程とでそれぞれ別のタンク（例えば、前洗浄用溶剤タンクと後洗浄用溶剤タンク）から供給してもよい。前洗浄工程と後洗浄工程は、同じ条件で行っても、異なる条件で行ってもよい。一般に後洗浄工程の方が洗浄対象溶液中の不純物が多いため、後洗浄工程で使用する洗浄対象溶液に対する溶剤の量を、前洗浄工程のものより多くしてもよい。   In the manufacturing method of the present invention, the cleaning step (1a) (hereinafter sometimes referred to as “pre-cleaning step”) and the cleaning step of step (1b) (hereinafter sometimes referred to as “post-cleaning step”). One or both. In the embodiment including both the pre-cleaning step and the post-cleaning step, the cleaning step may be performed by a common cleaning apparatus, or the pre-cleaning step and the post-cleaning step may be performed by separate cleaning apparatuses (for example, a pre-cleaning cleaning apparatus and a pre-cleaning cleaning apparatus). Cleaning device for post-cleaning). The washing device may be constituted by a washing tank capable of mixing and separating a solution to be washed and a solvent, or may be constituted by a combination of a mixer and a separator. Further, the cleaning solvent may be supplied from a common tank, or may be supplied from separate tanks (for example, a pre-cleaning solvent tank and a post-cleaning solvent tank) in the pre-cleaning step and the post-cleaning step. You may. The pre-cleaning step and the post-cleaning step may be performed under the same conditions or different conditions. In general, since the post-cleaning step has more impurities in the cleaning target solution, the amount of the solvent for the cleaning target solution used in the post-cleaning step may be larger than that in the pre-cleaning step.

一部の態様において、本発明の製造方法は、
工程（２ａ）：前記工程（１ａ）から得られる使用済み溶剤の少なくとも一部を、前記工程（１ａ）及び／又は（１ｂ）へ導入する工程、及び／又は
工程（２ｂ）：前記工程（１ｂ）から得られる使用済み溶剤の少なくとも一部を、前記工程（１ａ）及び／又は（１ｂ）へ導入する工程
をさらに含む。
上記工程を含むことにより、使用済み溶剤が再利用され、新たに使用する溶剤の量を低減することができる。工程（１ａ）及び／又は（１ｂ）へ導入される使用済み溶剤の割合は、洗浄効率に顕著な悪影響を与えるものでなければ特に限定されないが、例えば、５０％以下、好ましくは４０％以下、より好ましくは３０％以下である。この態様において、工程（１ａ）及び／又は（１ｂ）で使用する溶剤は、そのすべてが使用済み溶剤であってもよいし、一部が使用済み溶剤、残りが新たな溶剤（すなわち、未使用の溶剤）であってもよい。後者の場合、使用済み溶剤と新たな溶剤の割合は、例えば、使用済み溶剤：新たな溶剤の体積比で５０：５０、好ましくは４０：６０、より好ましくは３０：７０である。また、工程（１ａ）及び／又は（１ｂ）で使用済み溶剤と新たな溶剤の両方を使用する場合、洗浄装置へのこれらの溶剤の導入は、例えば、使用済み溶剤と新たな溶剤とを混合後、単一の配管で導入してもよいし、使用済み溶剤と新たな溶剤とを別々の配管で供給してもよい。 In some embodiments, the method of the present invention comprises:
Step (2a): a step of introducing at least a part of the used solvent obtained from the step (1a) to the step (1a) and / or (1b), and / or Step (2b): the step (1b) )), Further comprising the step of introducing at least a part of the used solvent obtained in the above step (1a) and / or (1b).
By including the above steps, the used solvent can be reused, and the amount of newly used solvent can be reduced. The ratio of the used solvent introduced into the step (1a) and / or (1b) is not particularly limited as long as it does not significantly affect the cleaning efficiency, and is, for example, 50% or less, preferably 40% or less. It is more preferably at most 30%. In this embodiment, the solvent used in the step (1a) and / or (1b) may be entirely a used solvent, a part of the solvent is used, and the remaining is a new solvent (that is, unused solvent). Solvent). In the latter case, the ratio between the used solvent and the new solvent is, for example, 50:50, preferably 40:60, and more preferably 30:70 by volume ratio of used solvent: new solvent. When both the used solvent and the new solvent are used in the step (1a) and / or (1b), the introduction of these solvents into the cleaning device may be performed, for example, by mixing the used solvent and the new solvent. Thereafter, the solvent may be introduced through a single pipe, or the used solvent and the new solvent may be supplied through separate pipes.

本発明の製造方法が工程（１ａ）を含む場合、本態様の製造方法は工程（２ａ）を含み、本発明の製造方法が工程（１ｂ）を含む場合、本態様の製造方法は工程（２ｂ）を含み、本発明の製造方法が工程（１ａ）と（１ｂ）の両方を含む場合、本態様の製造方法は工程（２ａ）及び（２ｂ）の一方又は両方を含む。例えば、本発明の製造方法が工程（１ａ）と（１ｂ）の両方を含む場合、洗浄対象溶液中の不純物がより少ない工程（１ａ）に係る工程（２ａ）のみ行い、工程（１ｂ）では常に新たな溶剤を用いることなどが可能である。工程（２ａ）と（２ｂ）の両方を含む態様において、使用済み溶剤の回収及び工程（１ａ）又は（１ｂ）への導入は、共通のポンプを使用してもよいし、別々のポンプを使用してもよい。工程（１ａ）及び（１ｂ）で回収した使用済み溶剤は、そのまま混合することなく、それぞれ工程（１ａ）及び／又は（１ｂ）に導入してもよい。例えば、比較的不純物の少ない工程（１ａ）で回収した使用済み溶剤を、洗浄対象溶液中の不純物が比較的高い工程（１ｂ）に導入することなどが可能である。また、工程（１ａ）及び（１ｂ）で回収した使用済み溶剤は、後述のように混合してから工程（１ａ）及び／又は（１ｂ）に導入してもよい。   When the production method of the present invention includes the step (1a), the production method of the present embodiment includes the step (2a). When the production method of the present invention includes the step (1b), the production method of the present embodiment includes the step (2b). ), And when the production method of the present invention includes both steps (1a) and (1b), the production method of this embodiment includes one or both of steps (2a) and (2b). For example, when the manufacturing method of the present invention includes both the steps (1a) and (1b), only the step (2a) relating to the step (1a) containing less impurities in the solution to be cleaned is performed, and the step (1b) is always performed. It is possible to use a new solvent. In the embodiment including both the steps (2a) and (2b), the recovery of the used solvent and the introduction to the step (1a) or (1b) may use a common pump or use a separate pump. May be. The used solvents recovered in the steps (1a) and (1b) may be introduced into the steps (1a) and / or (1b), respectively, without being mixed. For example, it is possible to introduce the used solvent recovered in the step (1a) containing relatively few impurities into the step (1b) containing relatively high impurities in the solution to be cleaned. Further, the used solvents recovered in the steps (1a) and (1b) may be mixed as described later and then introduced into the step (1a) and / or (1b).

上記態様において、本発明の製造方法は、
工程（３ａ）：前記工程（１ａ）から得られる使用済み溶剤の少なくとも一部を精製し、精製後の溶剤を前記工程（２ａ）へ、工程（１ａ）から得られる使用済み溶剤の少なくとも一部の代わりに導入する工程、及び／又は
工程（３ｂ）：前記工程（１ｂ）から得られる使用済み溶剤の少なくとも一部を精製し、精製後の溶剤を前記工程（２ｂ）へ、工程（１ｂ）から得られる使用済み溶剤の少なくとも一部の代わりに導入する工程
をさらに含んでもよい。 In the above aspect, the production method of the present invention comprises:
Step (3a): At least a part of the used solvent obtained from the step (1a) is purified, and the purified solvent is transferred to the step (2a), and at least a part of the used solvent obtained from the step (1a) is purified. And / or Step (3b): refining at least a part of the used solvent obtained from the step (1b), and purifying the purified solvent to the step (2b) and the step (1b) May be introduced instead of at least a part of the used solvent obtained from the above.

この態様において、使用済み溶剤の精製は、使用済み溶剤に含まれる不純物を低減し得るあらゆる処理を含む。精製の非限定例としては、例えば、蒸留、吸着、水による洗浄、アルカリ水溶液による洗浄などが挙げられる。蒸留法としては、水蒸気蒸留法、単蒸留法、精密蒸留法などが使用できる。蒸留の条件は、使用する溶媒に応じて適宜設定することができる。吸着には、活性炭、アルミナ、イオン交換樹脂などの、不純物の吸着に適した吸着材を利用できる。水による洗浄に用いる水は、蒸留水、イオン交換水、逆浸透法などで精製された水が好ましいが、上記以外の方法で精製された水も好ましく用いられる。特に洗浄に用いられる水として純水が好ましい。アルカリ水溶液による洗浄に用いるアルカリ水溶液に含まれるアルカリとしてはアルカリ金属、例えば、リチウム、ナトリウム、カリウム、カルシウムなどが好ましい。
この態様において、本発明の製造方法は、工程（３ａ）と（３ｂ）の一方又は両方を含んでもよい。工程（３ａ）と（３ｂ）の両方を含む場合、工程（１ａ）から得られる使用済み溶剤と、工程（１ｂ）から得られる使用済み溶剤とを別々に精製してもよいし、後述のように、両使用済み溶剤を混合してから一緒に精製してもよい。 In this embodiment, the purification of the used solvent includes any treatment that can reduce impurities contained in the used solvent. Non-limiting examples of purification include, for example, distillation, adsorption, washing with water, washing with an aqueous alkaline solution, and the like. As the distillation method, a steam distillation method, a simple distillation method, a precision distillation method, or the like can be used. Distillation conditions can be appropriately set according to the solvent used. For the adsorption, an adsorbent suitable for adsorbing impurities, such as activated carbon, alumina, and ion exchange resin, can be used. The water used for washing with water is preferably distilled water, ion-exchanged water, or water purified by a reverse osmosis method, but water purified by a method other than the above is also preferably used. Particularly, pure water is preferable as water used for washing. The alkali contained in the aqueous alkali solution used for washing with the aqueous alkali solution is preferably an alkali metal, for example, lithium, sodium, potassium, calcium and the like.
In this embodiment, the production method of the present invention may include one or both of the steps (3a) and (3b). When both the steps (3a) and (3b) are included, the used solvent obtained from the step (1a) and the used solvent obtained from the step (1b) may be separately purified, or as described below. Alternatively, both used solvents may be mixed and then purified together.

精製される使用済み溶剤の割合は、全使用済み溶剤のうち例えば、５０％以上、好ましくは８０％以上、より好ましくは９０％以上、特に好ましくは１００％である。この態様において、工程（１ａ）及び／又は（１ｂ）で使用する溶剤は、そのすべてが精製溶剤であってもよいし、一部が精製溶剤、残りが新たな溶剤（すなわち、未使用の溶剤）であってもよい。後者の場合、精製溶剤と新たな溶剤の割合は、例えば、精製溶剤：新たな溶剤の体積比で５０：５０、好ましくは８０：２０、より好ましくは９０：１０、特に好ましくは１００：０である。また、工程（１ａ）及び／又は（１ｂ）で精製溶剤と新たな溶剤の両方を使用する場合、洗浄装置へのこれらの溶剤の導入は、例えば、精製溶剤と新たな溶剤とを混合後、単一の配管で導入してもよいし、精製溶剤と新たな溶剤とを別々の配管で供給してもよい。   The ratio of the used solvent to be purified is, for example, 50% or more, preferably 80% or more, more preferably 90% or more, and particularly preferably 100% of all the used solvents. In this embodiment, the solvent used in the step (1a) and / or (1b) may be entirely a purified solvent, a part of the solvent may be a purified solvent, and the remainder may be a new solvent (ie, an unused solvent). ). In the latter case, the ratio of the purified solvent to the new solvent is, for example, 50:50, preferably 80:20, more preferably 90:10, particularly preferably 100: 0, by volume ratio of the purified solvent: new solvent. is there. When both the purified solvent and the new solvent are used in the step (1a) and / or (1b), the introduction of these solvents into the cleaning device is performed, for example, after mixing the purified solvent with the new solvent. A single pipe may be introduced, or a purified solvent and a new solvent may be supplied through separate pipes.

一部の態様において、本発明の製造方法は、工程（１ａ）と（１ｂ）の両方を含み、かつ、
工程（Ｉ）：工程（１ａ）及び（１ｂ）から得られる使用済み溶剤を混合する工程
を含む。
混合は液体と液体を混合し得る任意の手法、例えば、機械攪拌方式、ラインミキサー方式などで行うことができる。混合後の使用済み溶剤は、使用するまでタンクなどの容器に貯蔵してもよいし、直接再利用や精製に供してもよい。両方の使用済み溶剤を混合することにより、貯蔵容器の数を減らすことや、再利用、精製などの後続の処理を同一の経路で同時に行うこと、使用済み溶剤の品質を平均化することなどが可能となる。 In some embodiments, the production method of the present invention includes both steps (1a) and (1b);
Step (I): Includes a step of mixing the used solvent obtained from Steps (1a) and (1b).
Mixing can be performed by any method capable of mixing the liquid and the liquid, for example, a mechanical stirring method, a line mixer method, or the like. The used solvent after mixing may be stored in a container such as a tank until use, or may be directly reused or purified. By mixing both used solvents, it is possible to reduce the number of storage containers, to carry out subsequent processes such as recycling and refining simultaneously on the same route, and to average the quality of used solvents. It becomes possible.

上記態様において、本発明の製造方法は、
工程（ＩＩ）：前記工程（Ｉ）から得られる混合後の溶剤の少なくとも一部を、前記工程（１ａ）及び／又は（１ｂ）へ導入する工程
を含んでもよい。
混合後の溶剤の少なくとも一部は、工程（１ａ）と（１ｂ）の一方又は両方に導入することができる。この態様では、混合後の溶剤の輸送を単一の配管で行うことができるため、システムの構造やプロセスの制御を簡素化することが可能となる。
工程（１ａ）及び／又は（１ｂ）へ導入される使用済み溶剤の割合は、洗浄効率に顕著な悪影響を与えるものでなければ特に限定されないが、例えば、５０％以下、好ましくは４０％以下、より好ましくは３０％以下である。この態様において、工程（１ａ）及び／又は（１ｂ）で使用する溶剤は、そのすべてが使用済み溶剤であってもよいし、一部が使用済み溶剤、残りが新たな溶剤（すなわち、未使用の溶剤）であってもよい。後者の場合、使用済み溶剤と新たな溶剤の割合は、例えば、使用済み溶剤：新たな溶剤の体積比で５０：５０、好ましくは４０：６０、より好ましくは３０：７０である。また、工程（１ａ）及び／又は（１ｂ）で使用済み溶剤と新たな溶剤の両方を使用する場合、洗浄装置へのこれらの溶剤の導入は、例えば、使用済み溶剤と新たな溶剤とを混合後、単一の配管で導入してもよいし、使用済み溶剤と新たな溶剤とを別々の配管で供給してもよい。 In the above aspect, the production method of the present invention comprises:
Step (II): The method may include a step of introducing at least a part of the mixed solvent obtained from the step (I) to the step (1a) and / or (1b).
At least a portion of the mixed solvent can be introduced into one or both of the steps (1a) and (1b). In this embodiment, the transport of the mixed solvent can be performed with a single pipe, so that the control of the system structure and the process can be simplified.
The ratio of the used solvent introduced into the step (1a) and / or (1b) is not particularly limited as long as it does not significantly affect the cleaning efficiency, and is, for example, 50% or less, preferably 40% or less. It is more preferably at most 30%. In this embodiment, the solvent used in the step (1a) and / or (1b) may be entirely a used solvent, a part of the solvent is used, and the remaining is a new solvent (that is, unused solvent). Solvent). In the latter case, the ratio between the used solvent and the new solvent is, for example, 50:50, preferably 40:60, and more preferably 30:70 by volume ratio of used solvent: new solvent. When both the used solvent and the new solvent are used in the step (1a) and / or (1b), the introduction of these solvents into the cleaning device may be performed, for example, by mixing the used solvent and the new solvent. Thereafter, the solvent may be introduced through a single pipe, or the used solvent and the new solvent may be supplied through separate pipes.

上記態様において、本発明の製造方法は、
工程（ＩＩＩ）：前記工程（Ｉ）から得られる混合後の溶剤の少なくとも一部を精製し、精製後の溶剤を、工程（Ｉ）から得られる混合後の溶剤の少なくとも一部の代わりに、前記工程（ＩＩ）へ導入する工程
をさらに含んでもよい。
この態様では、工程（１ａ）及び（１ｂ）からの使用済み溶剤を一緒に精製することができるため、システムの構造やプロセスの制御を簡素化することや、エネルギー効率の向上などが可能となる。この態様における精製などの特徴については、工程（３ａ）／（３ｂ）について上記したとおりである。 In the above aspect, the production method of the present invention comprises:
Step (III): At least a part of the mixed solvent obtained from the step (I) is purified, and the purified solvent is replaced with at least a part of the mixed solvent obtained from the step (I), The method may further include a step of introducing the step (II).
In this aspect, the spent solvent from steps (1a) and (1b) can be purified together, which simplifies system structure and process control, improves energy efficiency, etc. . The features such as purification in this embodiment are as described above for step (3a) / (3b).

精製される使用済み溶剤の割合は、全使用済み溶剤のうち例えば、５０％以上、好ましくは８０％以上、より好ましくは９０％以上、特に好ましくは１００％である。この態様において、工程（１ａ）及び／又は（１ｂ）で使用する溶剤は、そのすべてが精製溶剤であってもよいし、一部が精製溶剤、残りが新たな溶剤（すなわち、未使用の溶剤）であってもよい。後者の場合、精製溶剤と新たな溶剤の割合は、例えば、精製溶剤：新たな溶剤の体積比で５０：５０、好ましくは８０：２０、より好ましくは９０：１０、特に好ましくは１００：０である。また、工程（１ａ）及び／又は（１ｂ）で精製溶剤と新たな溶剤の両方を使用する場合、洗浄装置へのこれらの溶剤の導入は、例えば、精製溶剤と新たな溶剤とを混合後、単一の配管で導入してもよいし、精製溶剤と新たな溶剤とを別々の配管で供給してもよい。   The ratio of the used solvent to be purified is, for example, 50% or more, preferably 80% or more, more preferably 90% or more, and particularly preferably 100% of all the used solvents. In this embodiment, the solvent used in the step (1a) and / or (1b) may be entirely a purified solvent, a part of the solvent may be a purified solvent, and the remainder may be a new solvent (ie, an unused solvent). ). In the latter case, the ratio of the purified solvent to the new solvent is, for example, 50:50, preferably 80:20, more preferably 90:10, particularly preferably 100: 0, by volume ratio of the purified solvent: new solvent. is there. When both the purified solvent and the new solvent are used in the step (1a) and / or (1b), the introduction of these solvents into the cleaning device is performed, for example, after mixing the purified solvent with the new solvent. A single pipe may be introduced, or a purified solvent and a new solvent may be supplied through separate pipes.

工程（Ｉ）を含む態様において、本発明の製造方法は、
工程（ＩＶ）：工程（１ａ）及び（１ｂ）から得られる使用済み溶剤を精製し、精製後の溶剤を、工程（１ａ）及び（１ｂ）から得られる使用済み溶剤の代わりに、前記工程（Ｉ）へ導入する工程
を含んでもよい。
この態様では、工程（１ａ）及び（１ｂ）から得られる使用済み溶剤を別々に精製し、精製後の各溶剤を混合する。混合は液体と液体を混合し得る任意の手法、例えば、機械攪拌方式、ラインミキサー方式などで行うことができる。混合後の使用済み溶剤は、使用するまでタンクなどの容器に貯蔵してもよいし、直接再利用等に供してもよい。両方の精製済み溶剤を混合することにより、貯蔵容器の数を減らすことや、再利用、輸送などの後続の処理を同一の経路で同時に行うこと、精製済み溶剤の品質を平均化することなどが可能となる。 In an embodiment including the step (I), the production method of the present invention comprises:
Step (IV): The used solvent obtained from the steps (1a) and (1b) is purified, and the solvent after purification is replaced with the above-mentioned step (1) instead of the used solvent obtained from the steps (1a) and (1b). A step of introducing into I) may be included.
In this embodiment, the used solvents obtained from the steps (1a) and (1b) are separately purified, and the purified solvents are mixed. Mixing can be performed by any method capable of mixing the liquid and the liquid, for example, a mechanical stirring method, a line mixer method, or the like. The used solvent after mixing may be stored in a container such as a tank until it is used, or may be directly reused. By mixing both purified solvents, it is possible to reduce the number of storage containers, perform subsequent processing such as reuse and transportation at the same time on the same route, and average the quality of purified solvents. It becomes possible.

本発明の別の側面は、洗浄装置Ａ及び洗浄装置Ｂの少なくとも１つと、逆浸透膜モジュールとを備えた精製過酸化水素水溶液製造システムであって、洗浄装置Ａは、粗過酸化水素水溶液輸送ラインと、溶剤供給ラインＡと、溶剤排出ラインＡとを備え、洗浄装置Ｂは、洗浄濃縮過酸化水素水溶液輸送ラインと、溶剤供給ラインＢと、溶剤排出ラインＢとを備え、逆浸透膜モジュールは、透過過酸化水素水溶液輸送ラインを備え、洗浄装置Ａと逆浸透膜モジュールとは洗浄粗過酸化水素水溶液輸送ラインにより連通し、洗浄装置Ｂと逆浸透膜モジュールとは濃縮過酸化水素水溶液輸送ラインにより連通し、洗浄装置Ａが存在しない場合、逆浸透膜モジュールは粗過酸化水素水溶液輸送ラインをさらに備え、洗浄装置Ｂが存在しない場合、逆浸透膜モジュールは濃縮過酸化水素水溶液輸送ラインをさらに備える、システムに関する（以下、「本発明の精製過酸化水素水溶液製造システム」又は「本発明の過酸化水素製造システム」と称する場合がある）。本発明の過酸化水素製造システムは、上記のほか、溶剤タンクをさらに備えていてもよい。洗浄装置Ａ及び／又は洗浄装置Ｂは、洗浄対象液と溶剤の混合及び分離が可能な洗浄槽であっても、混合機と分離機の組合せであってもよい。本発明の過酸化水素製造システムの一態様を、以下に図面を参照して説明する。   Another aspect of the present invention is a purified hydrogen peroxide aqueous solution production system including at least one of a cleaning device A and a cleaning device B and a reverse osmosis membrane module, wherein the cleaning device A is configured to transport a crude hydrogen peroxide aqueous solution. The cleaning apparatus B includes a line, a solvent supply line A, and a solvent discharge line A. The cleaning device B includes a cleaning concentrated hydrogen peroxide aqueous solution transport line, a solvent supply line B, and a solvent discharge line B. Has a permeated hydrogen peroxide solution transport line, the cleaning device A and the reverse osmosis membrane module communicate with each other through a washed coarse hydrogen peroxide solution transport line, and the cleaning device B and the reverse osmosis membrane module transport a concentrated hydrogen peroxide solution. When the cleaning device A does not exist, the reverse osmosis membrane module further includes a crude hydrogen peroxide aqueous solution transport line, and when the cleaning device B does not exist, the reverse osmosis Module further comprises a concentrated aqueous hydrogen peroxide solution transport line, the system relates (hereinafter, sometimes referred to as "purified aqueous hydrogen peroxide solution production system of the present invention" or "hydrogen peroxide production system of the present invention"). In addition to the above, the hydrogen peroxide production system of the present invention may further include a solvent tank. The cleaning device A and / or the cleaning device B may be a cleaning tank capable of mixing and separating a liquid to be cleaned and a solvent, or a combination of a mixer and a separator. One embodiment of the hydrogen peroxide production system of the present invention will be described below with reference to the drawings.

図１には、洗浄槽Ａ１０１ａ、洗浄槽Ｂ１０１ｂ、逆浸透膜（ＲＯ膜）モジュール１０２及び溶剤タンク１０３を備えた本発明の精製過酸化水素水溶液製造システムＡ１が記載されている。洗浄槽Ａ１０１ａは、未洗浄粗過酸化水素水溶液（粗過水）輸送ライン１０４と、溶剤排出ラインＡ１０６ａとを備え、洗浄槽Ｂ１０１ｂは、洗浄濃縮過酸化水素水溶液（洗浄濃縮過水）輸送ライン１０７と、溶剤排出ラインＢ１０６ｂとを備え、逆浸透膜モジュール１０２は、透過過酸化水素水溶液（透過過水）輸送ライン１０８を備え、溶剤タンク１０３は溶剤供給ライン１０５と、未使用溶剤供給ライン１１５とを備え、洗浄槽Ａ１０１ａと逆浸透膜モジュール１０２とは洗浄粗過酸化水素水溶液（洗浄粗過水）輸送ライン１０９により連通し、洗浄槽Ｂ１０１ｂと逆浸透膜モジュール１０２とは濃縮過酸化水素水溶液（濃縮過水）輸送ライン１１０により連通し、洗浄槽Ａ１０１ａと溶剤供給ライン１０５は溶剤供給ラインＡ１０５ａにより連通し、洗浄槽Ａ１０１ａと溶剤供給ライン１０５は溶剤供給ラインＢ１０５ｂにより連通している。洗浄槽Ａ１０１ａ及び洗浄槽Ｂ１０１ｂは、洗浄対象溶液（粗過水又は濃縮過水）と溶剤との混合、静置、分離が可能である。逆浸透膜モジュール１０２は、逆浸透膜と、逆浸透膜を固定支持する耐圧容器と、粗過酸化水素水溶液を逆浸透膜に接触させるための加圧手段とを備えている。また、各ラインには、バルブＶが備えられている。なお、簡潔のため、図１〜５において、バルブの符号「Ｖ」は、濃縮過水輸送ライン１１０に備えられたものにのみ付してある。   FIG. 1 illustrates a purified hydrogen peroxide aqueous solution production system A1 of the present invention including a cleaning tank A101a, a cleaning tank B101b, a reverse osmosis membrane (RO membrane) module 102, and a solvent tank 103. The cleaning tank A101a includes an uncleaned crude hydrogen peroxide aqueous solution (coarse peroxide) transport line 104 and a solvent discharge line A106a. The cleaning tank B101b includes a cleaning concentrated hydrogen peroxide aqueous solution (cleaned concentrated peroxide) transport line 107. The reverse osmosis membrane module 102 includes a permeated hydrogen peroxide aqueous solution (permeated permeate) transport line 108, and the solvent tank 103 includes a solvent supply line 105, an unused solvent supply line 115, The cleaning tank A101a and the reverse osmosis membrane module 102 communicate with each other through a cleaning coarse hydrogen peroxide aqueous solution (clean coarse hydrogen peroxide) transport line 109, and the cleaning tank B101b and the reverse osmosis membrane module 102 communicate with the concentrated hydrogen peroxide aqueous solution ( Condensed water) is communicated by a transport line 110, and a washing tank A101a and a solvent supply line 105 are connected to a solvent supply line A105. Communicating, the cleaning tank A101a and a solvent supply line 105 communicates with the solvent supply line B 105b. In the cleaning tank A101a and the cleaning tank B101b, a solution to be cleaned (coarse water or concentrated water) and a solvent can be mixed, allowed to stand, and separated. The reverse osmosis membrane module 102 includes a reverse osmosis membrane, a pressure-resistant container fixedly supporting the reverse osmosis membrane, and pressurizing means for bringing the crude hydrogen peroxide aqueous solution into contact with the reverse osmosis membrane. Each line is provided with a valve V. In addition, for simplicity, in FIGS. 1 to 5, the reference numeral “V” of the valve is attached only to the one provided in the concentrated-superheater transport line 110.

未洗浄粗過水１１１は、未洗浄粗過水輸送ライン１０４を通り、洗浄槽Ａ１０１ａに入る。洗浄槽Ａ１０１ａでは、溶剤が、溶剤タンク１０３から溶剤供給ライン１０５及び溶剤供給ラインＡ１０５ａを介して供給され、未洗浄粗過水１１１と混合、分離され、未洗浄粗過水１１１中の不純物の少なくとも一部を取り込んだ使用済み溶剤Ａ１１２ａは溶剤排出ラインＡ１０６ａから排出される。溶剤タンク１０３には、未使用溶剤供給ライン１１５から未使用溶剤１１６が適宜供給される。洗浄槽Ａ１０１ａでの溶剤洗浄（前洗浄工程）を終えた洗浄粗過水は洗浄粗過水輸送ライン１０９を通ってＲＯ膜モジュール１０２に入り、透過過水１１３と濃縮過水に分離される。透過過水１１３は透過過水輸送ライン１０８で輸送され、濃縮過水は濃縮過水輸送ライン１１０を通って洗浄槽Ｂ１０１ｂに入る。洗浄槽Ｂ１０１ｂでは、洗浄槽Ａ１０１ａと同様に、溶剤が溶剤タンク１０３から溶剤供給ライン１０５及び溶剤供給ラインＢ１０５ｂを介して供給され、濃縮過水と混合、分離され、濃縮過水中の不純物の少なくとも一部を取り込んだ使用済み溶剤Ｂ１１２ｂは溶剤排出ラインＢ１０６ｂから排出される。洗浄槽Ｂ１０１ｂでの溶剤洗浄（後洗浄工程）を終えた洗浄濃縮過水１１４は洗浄濃縮過水輸送ライン１０７で輸送される。   The unwashed coarse water 111 passes through the unwashed coarse water transport line 104 and enters the cleaning tank A101a. In the cleaning tank A101a, a solvent is supplied from the solvent tank 103 through the solvent supply line 105 and the solvent supply line A105a, mixed with and separated from the unwashed coarse water 111, and at least impurities contained in the uncleaned coarse water 111. The used solvent A112a partially taken in is discharged from the solvent discharge line A106a. An unused solvent 116 is appropriately supplied to the solvent tank 103 from an unused solvent supply line 115. After washing with the solvent (pre-washing step) in the washing tank A101a, the washed coarse permeate enters the RO membrane module 102 through the clean coarse permeate transport line 109 and is separated into permeated permeate 113 and concentrated permeate. The permeated permeate 113 is transported by the permeated permeate transport line 108, and the concentrated permeate enters the washing tank B101b through the concentrated permeate transport line 110. In the cleaning tank B101b, similarly to the cleaning tank A101a, the solvent is supplied from the solvent tank 103 via the solvent supply line 105 and the solvent supply line B105b, mixed with and separated from the concentrated permeate, and at least one of the impurities in the concentrated permeate is supplied. The used solvent B112b into which the portion has been taken is discharged from the solvent discharge line B106b. After washing the solvent in the washing tank B 101 b (post-washing step), the concentrated washing water 114 is transported through the washing concentrated water transport line 107.

図２には、洗浄槽Ａ１０１ａ、ＲＯ膜モジュール１０２及び溶剤タンク１０３を備えた本発明の精製過酸化水素水溶液製造システムＡ’１’が記載されている。本発明の精製過酸化水素水溶液製造システムＡ’１’は、本発明の精製過酸化水素水溶液製造システムＡ１が備えている洗浄槽Ｂ１０１ｂとそれに関連する構成要素（溶剤供給ラインＢ１０５ｂ、洗浄濃縮過水輸送ライン１０７、溶剤排出ラインＢ１０６ｂ）を備えていない。本発明の精製過酸化水素水溶液製造システムＡ’１’において、前洗浄工程は本発明の精製過酸化水素水溶液製造システムＡ１と同様に行われるが、ＲＯ膜モジュール１０２で分離された濃縮過水（前洗浄濃縮過水１１７）は、溶剤洗浄（後洗浄工程）を受けずに、濃縮過水輸送ライン１１０を通って輸送される。   FIG. 2 illustrates a purified hydrogen peroxide aqueous solution production system A'1 'of the present invention including a cleaning tank A101a, an RO membrane module 102, and a solvent tank 103. The purified hydrogen peroxide aqueous solution production system A'1 'of the present invention comprises a cleaning tank B101b provided in the purified hydrogen peroxide aqueous solution production system A1 of the present invention and its related components (solvent supply line B105b, cleaning concentrated peroxide). It does not have the transport line 107 and the solvent discharge line B106b). In the purified aqueous hydrogen peroxide solution production system A′1 ′ of the present invention, the pre-cleaning step is performed in the same manner as in the purified hydrogen peroxide aqueous solution production system A1 of the present invention, but the concentrated peroxide separated by the RO membrane module 102 ( The pre-cleaning concentrated hydrogen peroxide 117) is transported through the concentrated hydrogen peroxide transport line 110 without undergoing solvent cleaning (post-cleaning step).

図３には、洗浄槽Ａ１０１ｂ、ＲＯ膜モジュール１０２及び溶剤タンク１０３を備えた本発明の精製過酸化水素水溶液製造システムＡ”１”が記載されている。本発明の精製過酸化水素水溶液製造システムＡ”１”は、本発明の精製過酸化水素水溶液製造システムＡ１が備えている洗浄槽Ａ１０１ａとそれに関連する構成要素（溶剤供給ラインＡ１０５ａ、洗浄粗過水輸送ライン１０９、溶剤排出ラインＡ１０６ａ）を備えておらず、ＲＯ膜モジュール１０２には、洗浄粗過水輸送ライン１０９に代えて、未洗浄粗過水輸送ライン１０４が接続している。本発明の精製過酸化水素水溶液製造システムＡ”１”において、後洗浄工程は本発明の精製過酸化水素水溶液製造システムＡ１と同様に行われるが、未洗浄粗過水１１１は、未洗浄粗過水輸送ラインを通り、溶剤洗浄（前洗浄工程）を受けずに、ＲＯ膜モジュール１０２に供給される。   FIG. 3 illustrates a purified hydrogen peroxide aqueous solution production system A "1" of the present invention including a cleaning tank A101b, an RO membrane module 102, and a solvent tank 103. The purified hydrogen peroxide aqueous solution production system A "1" of the present invention comprises a cleaning tank A101a provided in the purified hydrogen peroxide aqueous solution production system A1 of the present invention and its related components (solvent supply line A105a, cleaning coarse peroxide solution). The transport line 109 and the solvent discharge line A 106 a) are not provided, and the RO membrane module 102 is connected to the uncleaned coarse water transport line 104 instead of the washed coarse water transport line 109. In the purified hydrogen peroxide aqueous solution production system A "1" of the present invention, the post-cleaning step is performed in the same manner as in the purified hydrogen peroxide aqueous solution production system A1 of the present invention. It is supplied to the RO membrane module 102 through the water transport line without undergoing solvent cleaning (pre-cleaning step).

本発明の過酸化水素製造システムは、溶剤再利用ラインＡ及び／又は溶剤再利用ラインＢをさらに備え、溶剤供給ラインＡと溶剤排出ラインＡとが溶剤再利用ラインＡにより連通し、及び／又は、溶剤供給ラインＢと溶剤排出ラインＢとが溶剤再利用ラインＢにより連通したものであってもよい。溶剤再利用ラインＡ及び溶剤再利用ラインＢを備えた本発明の過酸化水素製造システムの概要を、図４を参照して説明する。なお、図４において、図１に示した精製過酸化水素水溶液製造システムＡと同じ構成要素については同じ符号を付し、その説明は省略する。   The hydrogen peroxide production system of the present invention further includes a solvent recycling line A and / or a solvent recycling line B, and the solvent supply line A and the solvent discharge line A communicate with each other through the solvent recycling line A, and / or Alternatively, the solvent supply line B and the solvent discharge line B may be connected by a solvent reuse line B. The outline of the hydrogen peroxide production system of the present invention including the solvent recycling line A and the solvent recycling line B will be described with reference to FIG. In FIG. 4, the same components as those of the purified hydrogen peroxide aqueous solution production system A shown in FIG. 1 are denoted by the same reference numerals, and the description thereof will be omitted.

図４に示す精製過酸化水素水溶液製造システムＢ２は、図１に示す精製過酸化水素水溶液製造システムＡ１が有する構成要素に加え、溶剤再利用ラインＡ２０１ａと溶剤再利用ラインＢ２０１ｂとをさらに備え、溶剤供給ラインＡ１０５ａと溶剤排出ラインＡ１０６ａは、溶剤再利用ラインＡ２０１ａにより連通し、溶剤供給ラインＢ１０５ｂと溶剤排出ラインＢ１０６ｂは、溶剤再利用ラインＢ２０１ｂにより連通している。
洗浄槽Ａ１０１ａから排出される使用済み溶剤Ａ１１２ａの少なくとも一部は、溶剤再利用ラインＡ２０１ａ、次いで溶剤供給ラインＡ１０５ａを通り、洗浄槽Ａ１０１ａに供給され、再利用される。同様に、洗浄槽Ｂ１０１ｂから排出される使用済み溶剤Ｂ１１２ｂの少なくとも一部は、溶剤再利用ラインＢ２０１ｂ、次いで溶剤供給ラインＢ１０５ｂを通り、洗浄槽Ｂ１０１ｂに供給され、再利用される。再利用されない使用済み溶剤Ａ１１２ａ／使用済み溶剤Ｂ１１２ｂは、溶剤排出ラインＡ１０６ａ／溶剤排出ラインＢ１０６ｂから排出される。溶剤を再利用することにより、新たな溶剤の使用量を低減することができる。 The purified hydrogen peroxide aqueous solution production system B2 shown in FIG. 4 further includes a solvent reuse line A201a and a solvent reuse line B201b in addition to the components of the purified hydrogen peroxide aqueous solution production system A1 shown in FIG. The supply line A105a and the solvent discharge line A106a communicate with each other via a solvent reuse line A201a, and the solvent supply line B105b and the solvent discharge line B106b communicate with each other via a solvent reuse line B201b.
At least a part of the used solvent A112a discharged from the cleaning tank A101a is supplied to the cleaning tank A101a through a solvent reuse line A201a and then a solvent supply line A105a, and is reused. Similarly, at least a part of the used solvent B112b discharged from the cleaning tank B101b is supplied to the cleaning tank B101b through a solvent reuse line B201b and then a solvent supply line B105b, and is reused. The used solvent A112a / used solvent B112b that is not reused is discharged from the solvent discharge line A106a / solvent discharge line B106b. By reusing the solvent, the amount of new solvent used can be reduced.

本発明の過酸化水素製造システムは、溶剤精製装置をさらに備え、溶剤精製装置と溶剤排出ラインＡとは使用済み溶剤供給ラインＡにより連通し、溶剤精製装置と溶剤供給ラインＡ又は洗浄装置Ａとは精製溶剤輸送ラインＡにより連通し、及び／又は、溶剤精製装置と溶剤排出ラインＢとは使用済み溶剤供給ラインＢにより連通し、溶剤精製装置と溶剤供給ラインＢ又は洗浄装置Ｂとは精製溶剤輸送ラインＢにより連通していてもよい。溶剤精製装置は、有機不純物を除去するための蒸留塔や、水溶性不純物を除去するための水洗浄装置などを含んでいてもよい。精製溶剤輸送ラインＡと精製溶剤輸送ラインＢは、別々であっても、一緒になって精製溶剤輸送ラインを構成してもよい。また、溶剤精製装置と溶剤供給ラインＡ／Ｂ又は洗浄装置Ａ／Ｂとの連通は、直接的であっても間接的であってもよい。例えば、溶剤精製装置に接続する精製溶剤輸送ラインが溶剤タンクに接続し、溶剤タンクが溶剤供給ラインＡ／Ｂにより洗浄装置Ａ／Ｂと連通することで、溶剤精製装置と洗浄装置Ａ／Ｂとの連通が達成されてもよい。溶剤精製装置を備えた本発明の過酸化水素製造システムの概要を、図５を参照して説明する。なお、図５において、図１〜４に示した精製過酸化水素水溶液製造システムと同じ構成要素については同じ符号を付し、その説明は省略する。   The hydrogen peroxide production system of the present invention further includes a solvent refining device, the solvent refining device and the solvent discharge line A communicate with each other through a used solvent supply line A, and the solvent refining device and the solvent supply line A or the cleaning device A Communicates with a purified solvent transport line A, and / or communicates a solvent refining device with a solvent discharge line B via a used solvent supply line B, and a solvent refining device communicates with a solvent supply line B or a cleaning device B with a purified solvent. The communication may be performed by the transport line B. The solvent refining device may include a distillation column for removing organic impurities, a water washing device for removing water-soluble impurities, and the like. The purified solvent transport line A and the purified solvent transport line B may be separate or may together constitute a purified solvent transport line. Communication between the solvent refining device and the solvent supply line A / B or the cleaning device A / B may be direct or indirect. For example, a solvent transport line connected to a solvent refining device is connected to a solvent tank, and the solvent tank is connected to a cleaning device A / B by a solvent supply line A / B. Communication may be achieved. The outline of the hydrogen peroxide production system of the present invention equipped with a solvent refining device will be described with reference to FIG. In FIG. 5, the same components as those in the purified aqueous hydrogen peroxide solution manufacturing system shown in FIGS. 1 to 4 are denoted by the same reference numerals, and description thereof will be omitted.

図５に示す精製過酸化水素水溶液製造システムＣ３は、図４に示す精製過酸化水素水溶液製造システムＢ２が有する構成要素に加え、溶剤精製装置（蒸留塔３０１）及び精製溶剤輸送ライン３０２をさらに備え、蒸留塔３０１は釜残排出ライン３０３を備え、洗浄槽Ａ１０１ａと蒸留塔３０１は使用済み溶剤供給ラインＡ３０４ａにより連通し、洗浄槽Ｂ１０１ｂと蒸留塔３０１は使用済み溶剤供給ラインＢ３０４ｂにより連通し、蒸留塔３０１と溶剤タンク１０３は精製溶剤輸送ライン３０２により連通している。使用済み溶剤供給ラインＡ３０４ａと使用済み溶剤供給ラインＢ３０４ｂは、途中で合流し、使用済み溶剤供給ライン３０４を形成している。
洗浄槽Ａ１０１ａから排出される使用済み溶剤Ａ１１２ａの少なくとも一部は、使用済み溶剤供給ラインＡ３０４ａ、次いで使用済み溶剤供給ライン３０４を通り、蒸留塔３０１に入る。同様に、洗浄槽Ｂ１０１ｂから排出される使用済み溶剤Ｂ１１２ｂの少なくとも一部は、使用済み溶剤供給ラインＢ３０４ｂ、次いで使用済み溶剤供給ライン３０４を通り、蒸留塔３０１に入る。蒸留塔３０１に入った使用済み溶剤は蒸留により精製され、蒸留塔３０１からの精製溶剤は、精製溶剤輸送ライン３０２を通って溶剤タンク１０３に収容される。精製溶剤は、必要に応じて、未使用溶剤供給ライン１１５からの未使用溶剤１１６と溶剤タンク１０３内で混合される。蒸留塔３０１で生成された釜残３０５は釜残排出ライン３０３から排出される。 The purified hydrogen peroxide solution production system C3 shown in FIG. 5 further includes a solvent refining device (distillation column 301) and a purified solvent transport line 302 in addition to the components of the purified hydrogen peroxide solution production system B2 shown in FIG. The distillation column 301 is provided with a bottom discharge line 303, the cleaning tank A101a and the distillation column 301 are connected by a used solvent supply line A304a, and the cleaning tank B101b and the distillation column 301 are connected by a used solvent supply line B304b. The tower 301 and the solvent tank 103 are connected by a purified solvent transport line 302. The used solvent supply line A 304a and the used solvent supply line B 304b join on the way to form a used solvent supply line 304.
At least a part of the used solvent A112a discharged from the washing tank A101a enters the distillation column 301 through the used solvent supply line A304a and then through the used solvent supply line 304. Similarly, at least a part of the used solvent B112b discharged from the cleaning tank B101b enters the distillation column 301 through the used solvent supply line B304b and then the used solvent supply line 304. The used solvent that has entered the distillation column 301 is purified by distillation, and the purified solvent from the distillation column 301 is stored in the solvent tank 103 through the purified solvent transport line 302. The purified solvent is mixed with the unused solvent 116 from the unused solvent supply line 115 in the solvent tank 103 as needed. The bottom 305 generated in the distillation column 301 is discharged from the bottom discharge line 303.

本発明の過酸化水素製造システムは、上記に説明した態様に限定されず、本発明の趣旨の範囲内で種々の改変が可能である。例えば、図４及び５に示した精製過酸化水素水溶液製造システムＢ及びＣにおいて、洗浄槽を、洗浄槽Ａ及び洗浄槽Ｂのいずれか一方のみとすること、図１〜５に示した精製過酸化水素水溶液製造システムＡ〜Ｃにおいて、洗浄槽Ａ及び／又は洗浄槽Ｂを、粗過水又は濃縮過水と溶剤とを混合する混合器と、前記混合器の下流に接続された、粗過水又は濃縮過水溶剤との混合液を、洗浄粗過水又は洗浄濃縮過水と使用済み溶剤とに分離する分離機とを備えた洗浄装置とすること、図４に示した精製過酸化水素水溶液製造システムＢにおいて、溶剤排出ラインＡ１０６ａと溶剤供給ラインＢ１０５ｂとを、溶剤再利用ラインＡ２０１ａ、又は、これとは別に設けた溶剤再利用ラインＡ’などのラインにより連通し、洗浄槽Ａ１０１ａから排出される比較的不純物の少ない使用済み溶剤Ａ１１２ａを、洗浄対象溶液中の不純物が比較的高い洗浄槽Ｂ１０１ｂに供給すること、図５に示した精製過酸化水素水溶液製造システムＣにおいて、使用済み溶剤供給ラインＡ３０４ａ及び／又は使用済み溶剤供給ラインＢ３０４ｂの途中に、純水洗浄装置（例えば、使用済み溶剤供給ラインＡ３０４ａ及び／又は使用済み溶剤供給ラインＢ３０４ｂに接続され、前記ラインに純水を供給する純水供給ラインと、前記純水供給ラインとの接続部の下流で前記使用済み溶剤供給ラインに接続された、使用済み溶剤と純水とを混合する混合器と、前記混合器の下流に接続された、純水洗浄された溶剤と廃水とを分離する分離機とを備えたもの）を設けること、蒸留塔３０１からの排出物を輸送する精製溶剤輸送ライン３０２及び／又は釜剤排出ライン３０３に熱交換器を設けること、さらに前記熱交換器を、蒸留塔３０１へ蒸留対象物を輸送する使用済み溶剤供給ラインＡ３０４ａ及び／又は使用済み溶剤供給ラインＢ３０４ｂと接触するように配置し、蒸留塔３０１からの排出物から蒸留対象物に熱を伝達できるようにすること、精製溶剤輸送ライン３０２にポンプを設けること、ポンプを設けた精製溶剤輸送ライン３０２にレシーバーを設け、ポンプへのガスの混入を防止すること、蒸留塔３０１に釜残を供給するラインを設けること、などが可能である。
また、精製過酸化水素水溶液製造システムＡ〜Ｃのいずれにおいても、必要に応じてラインの少なくとも１つにポンプや追加のバルブ、分岐ライン、タンク等を設けることや、ラインからバルブを取り除くことが可能である。 The hydrogen peroxide production system of the present invention is not limited to the embodiment described above, and various modifications can be made within the scope of the present invention. For example, in the purified hydrogen peroxide aqueous solution production systems B and C shown in FIGS. 4 and 5, the cleaning tank is only one of the cleaning tank A and the cleaning tank B, and the purification tank shown in FIGS. In the hydrogen oxide aqueous solution production systems A to C, the washing tank A and / or the washing tank B is provided with a mixer for mixing a crude permeate or a concentrated permeate with a solvent, and a coarse condenser connected downstream of the mixer. 4. A cleaning device comprising a separator for separating a mixed solution of water or a concentrated permeate solvent into a coarse wash or a concentrated permeate wash and a used solvent, the purified hydrogen peroxide shown in FIG. In the aqueous solution production system B, the solvent discharge line A106a and the solvent supply line B105b are communicated with each other by a line such as a solvent reuse line A201a or a solvent reuse line A ′ separately provided, and discharged from the cleaning tank A101a. Is Supplying the used solvent A112a having a relatively small amount of impurities to the cleaning tank B101b having a relatively high amount of impurities in the solution to be cleaned. In the purified hydrogen peroxide aqueous solution production system C shown in FIG. A 304 a and / or a used solvent supply line B 304 b, a pure water washing device (for example, pure water connected to the used solvent supply line A 304 a and / or used solvent supply line B 304 b and supplying pure water to the line) Supply line, connected to the used solvent supply line downstream of the connection with the pure water supply line, a mixer for mixing the used solvent and pure water, connected to the downstream of the mixer And a separator for separating the purified water-washed solvent and the wastewater), and a purified solvent for transporting the effluent from the distillation column 301. A heat exchanger is provided in the feed line 302 and / or the kettle agent discharge line 303, and the heat exchanger is used as a used solvent supply line A304a and / or used solvent supply line for transporting the distillation target to the distillation column 301. B304b so as to be able to transfer heat from the effluent from the distillation column 301 to the distillation target, providing a pump in the purified solvent transport line 302, and providing a purified solvent transport line 302 provided with a pump. It is possible to provide a receiver to prevent mixing of gas into the pump, and to provide a line for supplying the bottom to the distillation column 301.
Further, in any of the purified hydrogen peroxide aqueous solution production systems A to C, it is possible to provide a pump, an additional valve, a branch line, a tank, and the like in at least one of the lines as necessary, and to remove a valve from the line. It is possible.

以下、本発明を実施例により具体的に説明するが、本発明はこれに限定されるものではない。   Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

<分析方法>
分析には、以下の装置を用いた。
・ＴＯＣ濃度測定：島津製作所製全有機体炭素計（ＴＯＣ−Ｌ）
・ハーゼン色数（ＡＰＨＡ）：エックス電子設計製ハーゼンメーター（ＨＭ−Ｖ）
＜ＲＯ膜精製＞
ＲＯ膜精製は以下の条件で行った。
・ＲＯ膜：スパイラル膜（２．５インチ、日東電工製）
・採取比：透過過水：濃縮過水＝６：４
・供給液流量：１Ｌ／分
・供給液温度：１６℃
・処理圧力：１．６ＭＰａ（Ｇ） <Analysis method>
The following apparatus was used for the analysis.
・ TOC concentration measurement: Total organic carbon meter (TOC-L) manufactured by Shimadzu Corporation
・ Hazen color number (APHA): Hazen meter (HM-V) manufactured by X Electronic Design
<RO membrane purification>
The RO membrane purification was performed under the following conditions.
・ RO film: Spiral film (2.5 inch, manufactured by Nitto Denko)
-Collection ratio: permeate permeate: concentrated permeate = 6: 4
・ Supply liquid flow rate: 1 L / min ・ Supply liquid temperature: 16 ° C
-Processing pressure: 1.6 MPa (G)

比較例１：
アントラキノン法により調製した４５％過酸化水素水（未洗浄粗過水）をＲＯ膜精製した。未洗浄粗過水及びＲＯ膜精製で得られた透過過水、濃縮過水（未洗浄濃縮過水）のＴＯＣ濃度、ハーゼン色数（ＡＰＨＡ）を測定した。結果を表１に示す。なお、未洗浄粗過水、透過過水、未洗浄濃縮過水とも溶剤洗浄には供していない。
Comparative Example 1:
An RO membrane was purified from 45% aqueous hydrogen peroxide (unwashed crude hydrogen peroxide) prepared by the anthraquinone method. The TOC concentration and the Hazen color number (APHA) of the unwashed crude permeate and the permeated permeate and the concentrated permeate (unwashed concentrated permeate) obtained by RO membrane purification were measured. Table 1 shows the results. Note that none of the unwashed crude permeate, permeate permeate and unwashed concentrated permeate were not used for solvent washing.

実施例１：
比較例１と同じ４５％過酸化水素水（未洗浄粗過水）を溶剤洗浄に供した。即ち、粗過水１２００ｍＬとプソイドクメン２００ｍＬを混合し、１２時間静置することで水層と有機層を分離し、水層を洗浄粗過水とした。溶剤洗浄した粗過水（洗浄粗過水）を、比較例１と同様にＲＯ膜精製し、透過過水（前洗浄透過過水）と濃縮過水（前洗浄濃縮過水）を得た。未洗浄粗過水、洗浄粗過水、前洗浄透過過水及び濃縮過水のＴＯＣ濃度、ハーゼン色数（ＡＰＨＡ）を測定した。結果を表２に示す。

未洗浄粗過水を溶剤洗浄することで、濃縮過水のＴＯＣ濃度とハーゼン色数を低減することができた。 Example 1
The same 45% aqueous hydrogen peroxide (unwashed crude hydrogen peroxide) as in Comparative Example 1 was subjected to solvent washing. That is, 1200 mL of crude permeate and 200 mL of pseudocumene were mixed, and allowed to stand for 12 hours to separate an aqueous layer and an organic layer, and the aqueous layer was washed as coarse permeate. The solvent-washed crude permeate (washed coarse permeate) was subjected to RO membrane purification in the same manner as in Comparative Example 1 to obtain a permeated permeate (pre-washed permeate) and a concentrated permeate (pre-washed concentrated permeate). The TOC concentration and the Hazen color number (APHA) of the unwashed crude permeate, the washed coarse permeate, the pre-clean permeate and the concentrated permeate were measured. Table 2 shows the results.

The TOC concentration of concentrated concentrated water and the number of Hazen colors could be reduced by washing the unwashed crude water with the solvent.

実施例２：
比較例１で得られた未洗浄濃縮過水を溶剤洗浄に供した。即ち、未洗浄濃縮過水１００ｍＬとプソイドクメン１７ｍＬを混合し、１２時間静置することで水層と有機層を分離し、水層を後洗浄濃縮過水とした。後洗浄濃縮過水のＴＯＣ濃度、ハーゼン色数（ＡＰＨＡ）を測定した。結果を表３に示す。

未洗浄濃縮過水を溶剤洗浄することで、ＴＯＣ濃度とハーゼン色数を低減することができた。 Example 2:
The unwashed concentrated peroxide obtained in Comparative Example 1 was subjected to solvent washing. That is, 100 mL of unwashed concentrated hydrogen peroxide and 17 mL of pseudocumene were mixed and allowed to stand for 12 hours to separate an aqueous layer and an organic layer, and the aqueous layer was subjected to post-washing concentrated hydrogen peroxide. The TOC concentration and the Hazen color number (APHA) of the post-wash concentrated water were measured. Table 3 shows the results.

The TOC concentration and the number of Hazen colors could be reduced by washing the unwashed concentrated peroxide with a solvent.

実施例３：
比較例１と同様にして得た未洗浄濃縮過水を第１の溶剤洗浄に供した。即ち、未洗浄濃縮過水１００ｍＬとプソイドクメン１７ｍＬを混合し、１２時間静置することで水層と有機層を分離し、水層を後洗浄濃縮過水とし、有機層を使用済みプソイドクメンとした。
比較例１と同様にして得た未洗浄濃縮過水を、上記の溶剤洗浄で分離した使用済みプソイドクメン１７ｍＬによる第２の溶剤洗浄に供した（再利用１回目）。同様に、第２の溶剤洗浄で分離した使用済みプソイドクメン１７ｍＬにより、第３の溶剤洗浄を行なった（再利用２回目）。表４の結果が示す通り、再利用した溶剤を用いた場合（再利用１回目及び２回目）であっても、洗浄前の濃縮過水に比べＴＯＣ濃度とハーゼン色数が低減したことから、洗浄溶剤の再利用が可能であることが明らかとなった。
上記の第３の溶剤洗浄より得られた、溶剤洗浄後の使用済みプソイドクメン（再利用２回目）を水洗し、過酸化水素を除去した後、圧力１０ｍｍＨｇ、温度６５℃の条件で蒸留した。プソイドクメンの回収率は９８％であった。蒸留後のプソイドクメンを用い、比較例１と同様にして得た未洗浄濃縮過水の溶剤洗浄を行った。その結果、ＴＯＣ濃度及びハーゼン色数の低減率が、再利用前のプソイドクメンを用いて溶剤洗浄を行った場合と同等程度となった。このことから、洗浄に使用した溶剤を繰り返し使用する場合、適宜蒸留精製することで良好な品質改善効果が継続して得られることが明らかとなった。 Example 3
The unwashed concentrated peroxide obtained in the same manner as in Comparative Example 1 was subjected to a first solvent washing. That is, 100 mL of unwashed concentrated hydrogen peroxide and 17 mL of pseudocumene were mixed and allowed to stand for 12 hours to separate an aqueous layer and an organic layer. The aqueous layer was subjected to post-washing concentrated hydrogen peroxide, and the organic layer was used pseudocumene.
The unwashed concentrated peroxide obtained in the same manner as in Comparative Example 1 was subjected to a second solvent washing with 17 mL of used pseudocumene separated by the solvent washing (first reuse). Similarly, a third solvent washing was performed with 17 mL of used pseudocumene separated by the second solvent washing (second reuse). As shown in the results of Table 4, even when the reused solvent was used (the first and second reuses), the TOC concentration and the number of Hazen colors were reduced as compared with the concentrated water before washing. It has become clear that the cleaning solvent can be reused.
The used pseudocumene (the second reuse) after the solvent washing, obtained from the third solvent washing, was washed with water to remove hydrogen peroxide, and then distilled under the conditions of a pressure of 10 mmHg and a temperature of 65 ° C. The recovery of pseudocumene was 98%. Using the pseudocumene after the distillation, solvent washing of the unwashed concentrated peroxide obtained in the same manner as in Comparative Example 1 was performed. As a result, the reduction rates of the TOC concentration and the number of Hazen colors were almost the same as in the case where solvent washing was performed using pseudocumene before reuse. From this, it has been clarified that, when the solvent used for washing is repeatedly used, a good quality improvement effect can be continuously obtained by appropriately distilling and purifying.

１： 精製過酸化水素水溶液製造システムＡ
１’： 精製過酸化水素水溶液製造システムＡ’
１”： 精製過酸化水素水溶液製造システムＡ”
１０１ａ：洗浄槽Ａ
１０１ｂ：洗浄槽Ｂ
１０２： 逆浸透膜モジュール
１０３： 溶剤タンク
１０４： 未洗浄粗過酸化水素水溶液（粗過水）輸送ライン
１０５： 溶剤供給ライン
１０５ａ：溶剤供給ラインＡ
１０５ｂ：溶剤供給ラインＢ
１０６ａ：溶剤排出ラインＡ
１０６ｂ：溶剤排出ラインＢ
１０７： 洗浄濃縮過酸化水素水溶液（洗浄濃縮過水）輸送ライン
１０８： 透過過酸化水素水溶液（透過過水）輸送ライン
１０９： 洗浄粗過酸化水素水溶液（洗浄粗過水）輸送ライン
１１０： 濃縮過酸化水素水溶液（濃縮過水）輸送ライン
１１１： 未洗浄粗過水
１１２ａ：使用済み溶剤Ａ
１１２ｂ：使用済み溶剤Ｂ
１１３： 透過過水
１１４： 前後洗浄濃縮過水
１１５： 未使用溶剤供給ライン
１１６： 未使用溶剤
１１７： 前洗浄濃縮過水輸送ライン
１１８： 前洗浄濃縮過水
１１９： 後洗浄濃縮過水
２： 精製過酸化水素水溶液製造システムＢ
２０１ａ：溶剤再利用ラインＡ
２０１ｂ：溶剤再利用ラインＢ
３： 精製過酸化水素水溶液製造システムＣ
３０１： 蒸留塔
３０２： 精製溶剤輸送ライン
３０３： 釜残排出ライン
３０４： 使用済み溶剤供給ライン
３０４ａ：使用済み溶剤供給ラインＡ
３０４ｂ：使用済み溶剤供給ラインＢ
３０５： 釜残
1: Purified hydrogen peroxide aqueous solution production system A
1 ': Purified aqueous hydrogen peroxide production system A'
1 ″: Purified hydrogen peroxide aqueous solution production system A ″
101a: Cleaning tank A
101b: Cleaning tank B
102: reverse osmosis membrane module 103: solvent tank 104: uncleaned crude hydrogen peroxide aqueous solution (coarse peroxide) transport line 105: solvent supply line 105a: solvent supply line A
105b: solvent supply line B
106a: Solvent discharge line A
106b: Solvent discharge line B
107: Washing concentrated hydrogen peroxide aqueous solution (washing concentrated hydrogen peroxide) transport line 108: Permeated hydrogen peroxide aqueous solution (permeable hydrogen peroxide) transporting line 109: Washing crude hydrogen peroxide aqueous solution (washing coarse peroxide) transporting line 110: Concentration Hydrogen oxide aqueous solution (concentrated hydrogen peroxide) transport line 111: unwashed crude hydrogen peroxide 112a: used solvent A
112b: Used solvent B
113: Permeate permeate 114: Pre- and post-cleaning concentrated permeate 115: Unused solvent supply line 116: Unused solvent 117: Pre-cleaned concentrated permeate transport line 118: Pre-cleaned concentrated permeate 119: Post-cleaned concentrated permeate 2: Purification Hydrogen peroxide aqueous solution production system B
201a: solvent reuse line A
201b: solvent reuse line B
3: Purified hydrogen peroxide aqueous solution production system C
301: distillation column 302: purified solvent transport line 303: bottom discharge line 304: used solvent supply line 304a: used solvent supply line A
304b: Used solvent supply line B
305: Pot remaining

Claims (12)

粗過酸化水素水溶液を逆浸透膜に接触させる工程を含む、精製過酸化水素水溶液の製造方法であって、
以下の工程（１ａ）及び／又は（１ｂ）を含む、製造方法。
工程（１ａ）：逆浸透膜接触前の粗過酸化水素水溶液を溶剤により洗浄する工程。
工程（１ｂ）：逆浸透膜接触後の濃縮過酸化水素水溶液を溶剤により洗浄する工程。 A method for producing a purified aqueous hydrogen peroxide solution, comprising the step of contacting a crude aqueous hydrogen peroxide solution with a reverse osmosis membrane,
A manufacturing method comprising the following steps (1a) and / or (1b).
Step (1a): a step of washing the crude aqueous hydrogen peroxide solution before contact with the reverse osmosis membrane with a solvent.
Step (1b): a step of washing the concentrated aqueous hydrogen peroxide solution after contact with the reverse osmosis membrane with a solvent. 下記工程（２ａ）及び／又は（２ｂ）を含む、請求項１に記載の製造方法。
工程（２ａ）：前記工程（１ａ）から得られる使用済み溶剤の少なくとも一部を、前記工程（１ａ）及び／又は（１ｂ）へ導入する工程。
工程（２ｂ）：前記工程（１ｂ）から得られる使用済み溶剤の少なくとも一部を、前記工程（１ａ）及び／又は（１ｂ）へ導入する工程。 The production method according to claim 1, comprising the following steps (2a) and / or (2b).
Step (2a): a step of introducing at least a part of the used solvent obtained from the step (1a) to the step (1a) and / or (1b).
Step (2b): a step of introducing at least a part of the used solvent obtained from the step (1b) to the step (1a) and / or (1b). 下記工程（３ａ）及び／又は（３ｂ）を含む、請求項２に記載の製造方法。
工程（３ａ）：前記工程（１ａ）から得られる使用済み溶剤の少なくとも一部を精製し、精製後の溶剤を前記工程（２ａ）へ、工程（１ａ）から得られる使用済み溶剤の少なくとも一部の代わりに導入する工程。
工程（３ｂ）：前記工程（１ｂ）から得られる使用済み溶剤の少なくとも一部を精製し、精製後の溶剤を前記工程（２ｂ）へ、工程（１ｂ）から得られる使用済み溶剤の少なくとも一部の代わりに導入する工程。 The production method according to claim 2, comprising the following steps (3a) and / or (3b).
Step (3a): At least a part of the used solvent obtained from the step (1a) is purified, and the purified solvent is transferred to the step (2a), and at least a part of the used solvent obtained from the step (1a) is purified. Step to introduce instead of.
Step (3b): At least a part of the used solvent obtained from the step (1b) is purified, and the purified solvent is transferred to the step (2b), and at least a part of the used solvent obtained from the step (1b) is purified. Step to introduce instead of. 工程（１ａ）及び（１ｂ）の両方を含み、下記工程（Ｉ）を含む、請求項１に記載の製造方法。
工程（Ｉ）：工程（１ａ）及び（１ｂ）から得られる使用済み溶剤を混合する工程。 The production method according to claim 1, comprising both steps (1a) and (1b), and comprising the following step (I).
Step (I): a step of mixing the used solvent obtained from steps (1a) and (1b). 下記工程（ＩＩ）を含む、請求項４に記載の製造方法。
工程（ＩＩ）：前記工程（Ｉ）から得られる混合後の溶剤の少なくとも一部を、前記工程（１ａ）及び／又は（１ｂ）へ導入する工程。 The production method according to claim 4, comprising the following step (II).
Step (II): a step of introducing at least a part of the mixed solvent obtained from the step (I) to the step (1a) and / or (1b). 下記工程（ＩＩＩ）を含む、請求項５に記載の製造方法。
工程（ＩＩＩ）：前記工程（Ｉ）から得られる混合後の溶剤の少なくとも一部を精製し、精製後の溶剤を、工程（Ｉ）から得られる混合後の溶剤の少なくとも一部の代わりに、前記工程（ＩＩ）へ導入する工程 The production method according to claim 5, comprising the following step (III).
Step (III): At least a part of the mixed solvent obtained from the step (I) is purified, and the purified solvent is replaced with at least a part of the mixed solvent obtained from the step (I), Step of introducing to the step (II) 下記工程（ＩＶ）を含む、請求項４〜６のいずれかに記載の製造方法。
工程（ＩＶ）：工程（１ａ）及び（１ｂ）から得られる使用済み溶剤を精製し、精製後の溶剤を、工程（１ａ）及び（１ｂ）から得られる使用済み溶剤の代わりに、前記工程（Ｉ）へ導入する工程。 The production method according to any one of claims 4 to 6, comprising the following step (IV).
Step (IV): The used solvent obtained from the steps (1a) and (1b) is purified, and the solvent after purification is replaced with the above-mentioned step (1) instead of the used solvent obtained from the steps (1a) and (1b). Step of introducing into I). 前記精製が、蒸留により行われる、請求項３、６又は７に記載の製造方法。   The production method according to claim 3, 6 or 7, wherein the purification is performed by distillation. 洗浄装置Ａ及び洗浄装置Ｂの少なくとも１つと、逆浸透膜モジュールとを備えた精製過酸化水素水溶液製造システムであって、洗浄装置Ａは、未洗浄粗過酸化水素水溶液輸送ラインと、溶剤供給ラインＡと、溶剤排出ラインＡとを備え、洗浄装置Ｂは、洗浄濃縮過酸化水素水溶液輸送ラインと、溶剤供給ラインＢと、溶剤排出ラインＢとを備え、逆浸透膜モジュールは、透過過酸化水素水溶液輸送ラインを備え、洗浄装置Ａと逆浸透膜モジュールとは洗浄粗過酸化水素水溶液輸送ラインにより連通し、洗浄装置Ｂと逆浸透膜モジュールとは濃縮過酸化水素水溶液輸送ラインにより連通し、洗浄装置Ａが存在しない場合、溶剤供給ラインＡ、溶剤排出ラインＡ及び洗浄粗過酸化水素水溶液輸送ラインも存在せず、未洗浄粗過酸化水素水溶液輸送ラインは逆浸透膜モジュールに接続し、洗浄装置Ｂが存在しない場合、溶剤供給ラインＢ、溶剤排出ラインＢ及び洗浄濃縮過酸化水素水溶液輸送ラインも存在しない、システム。   A purified hydrogen peroxide aqueous solution production system including at least one of a cleaning device A and a cleaning device B and a reverse osmosis membrane module, wherein the cleaning device A includes a non-cleaned crude hydrogen peroxide aqueous solution transport line, a solvent supply line A, and a solvent discharge line A, the cleaning device B includes a cleaning concentrated hydrogen peroxide aqueous solution transport line, a solvent supply line B, and a solvent discharge line B, and the reverse osmosis membrane module includes a permeated hydrogen peroxide. An aqueous solution transport line is provided, and the cleaning device A and the reverse osmosis membrane module communicate with each other through a cleaning coarse hydrogen peroxide aqueous solution transport line, and the cleaning device B and the reverse osmosis membrane module communicate with each other via a concentrated hydrogen peroxide aqueous solution transport line. When the apparatus A does not exist, the solvent supply line A, the solvent discharge line A, and the transport line for transporting the washed crude hydrogen peroxide solution are not present, and the transport of the uncleaned crude hydrogen peroxide aqueous solution is not performed. Inn is connected to the reverse osmosis membrane module, if the cleaning device B is not present, the solvent supply line B, also a solvent discharge line B and washing concentrated aqueous hydrogen peroxide solution transporting line does not exist, the system. 溶剤再利用ラインＡ及び／又は溶剤再利用ラインＢをさらに備え、溶剤供給ラインＡと溶剤排出ラインＡとが溶剤再利用ラインＡにより連通し、及び／又は、溶剤供給ラインＢと溶剤排出ラインＢとが溶剤再利用ラインＢにより連通している、請求項９に記載のシステム。   It further includes a solvent recycling line A and / or a solvent recycling line B, and the solvent supply line A and the solvent discharge line A communicate with each other through the solvent reuse line A, and / or a solvent supply line B and a solvent discharge line B And the system is in communication with the solvent recycling line B. 溶剤精製装置をさらに備え、溶剤精製装置と溶剤排出ラインＡとは溶剤再利用ラインＡにより連通し、溶剤精製装置と溶剤供給ラインＡ又は洗浄装置Ａとは精製溶剤輸送ラインＡにより連通し、及び／又は、溶剤精製装置と溶剤排出ラインＢとは溶剤再利用ラインＢにより連通し、溶剤精製装置と溶剤供給ラインＢ又は洗浄装置Ｂとは精製溶剤輸送ラインＢにより連通している、請求項１０に記載のシステム。   Further comprising a solvent refining device, the solvent refining device and the solvent discharge line A communicate with a solvent reusing line A, the solvent refining device communicates with the solvent supply line A or the cleaning device A with a purified solvent transport line A, and And / or the solvent refining device and the solvent discharge line B communicate with each other through a solvent reuse line B, and the solvent refining device communicates with the solvent supply line B or the cleaning device B through a purified solvent transport line B. System. 精製装置が蒸留塔を含む、請求項１１に記載のシステム。

The system according to claim 11, wherein the purifier comprises a distillation column.

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