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JP2015178107A - Method of producing ultrapure water and ultrapure water production equipment - Google Patents

Method of producing ultrapure water and ultrapure water production equipment Download PDF

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JP2015178107A
JP2015178107A JP2015115518A JP2015115518A JP2015178107A JP 2015178107 A JP2015178107 A JP 2015178107A JP 2015115518 A JP2015115518 A JP 2015115518A JP 2015115518 A JP2015115518 A JP 2015115518A JP 2015178107 A JP2015178107 A JP 2015178107A
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water
hydrogen peroxide
pure water
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JP5854163B2 (en
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長雄 福井
Nagao Fukui
長雄 福井
洋一 宮▲崎▼
Yoichi Miyazaki
洋一 宮▲崎▼
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Kurita Water Industries Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide a method and an apparatus for producing pure water by bringing UV oxidation-treated water from a UV oxidation unit into contact with a platinum metal supported catalyst resin which prevent deterioration of the catalyst resin and decompose hydrogen peroxide stably over a long period.SOLUTION: In a method and an apparatus for producing pure water by subjecting to-be-treated water to a UV oxidation treatment in a UV oxidation unit 2 and performing a hydrogen peroxide removal treatment by a hydrogen peroxide removal unit 4 using a platinum-based catalyst, the TOC of feed water to the UV oxidation unit 2 is 5 ppb, and an anion exchange resin tower 3 is arranged in the subsequent stage of the UV oxidation unit 2.

Description

本発明は、純水製造方法及び装置に係り、特に紫外線酸化装置と過酸化水素除去装置とを用いた純水製造方法及び装置に関する。なお、本発明において、純水は超純水を包含する。   The present invention relates to a pure water production method and apparatus, and more particularly to a pure water production method and apparatus using an ultraviolet oxidation apparatus and a hydrogen peroxide removal apparatus. In the present invention, pure water includes ultrapure water.

半導体・電子材料洗浄用の超純水製造装置は、通常、前処理システム、一次純水システム、サブシステム等から構成されている。各システムはそれぞれ濁質、塩類、TOCなど様々な不純物を除去する装置で成り立っている。   An ultrapure water manufacturing apparatus for cleaning semiconductors and electronic materials is usually composed of a pretreatment system, a primary pure water system, a subsystem, and the like. Each system consists of devices that remove various impurities such as turbidity, salts, and TOC.

図4は超純水製造装置の一例を示すフロー図である。図示の通り、超純水は、前処理装置10、一次純水製造装置11、二次純水製造装置(サブシステム)12から構成される超純水製造設備で原水(工業用水、市水、井水等)を処理することにより製造される。   FIG. 4 is a flowchart showing an example of the ultrapure water production apparatus. As shown in the figure, ultrapure water is a raw water (industrial water, city water, Manufactured by treating wells).

凝集、加圧浮上(沈殿)、濾過(膜濾過)装置などよりなる前処理装置10は、原水中の懸濁物質やコロイド物質の除去を行う。また、この過程では高分子系有機物、疎水性有機物などの除去も可能である。   A pretreatment device 10 comprising agglomeration, pressurized flotation (precipitation), filtration (membrane filtration) device, etc. removes suspended substances and colloidal substances in raw water. In this process, it is also possible to remove high molecular organic substances, hydrophobic organic substances, and the like.

逆浸透膜分離装置、脱気装置及びイオン交換装置(混床式又は4床5塔式など)を備える一次純水製造装置11では、原水中のイオンや有機成分の除去を行う。なお、逆浸透膜分離装置では、塩類を除去すると共に、イオン性、コロイド性のTOCを除去する。イオン交換装置では、塩類を除去すると共にイオン交換樹脂によって吸着又はイオン交換されるTOC成分の除去を行う。脱気装置では無機系炭素(IC)、溶存酸素の除去を行う。   The primary pure water production apparatus 11 including a reverse osmosis membrane separation device, a deaeration device, and an ion exchange device (such as a mixed bed type or a 4-bed 5-tower type) removes ions and organic components from raw water. The reverse osmosis membrane separation apparatus removes salts and ionic and colloidal TOC. The ion exchange apparatus removes salts and removes the TOC component adsorbed or ion exchanged by the ion exchange resin. In the deaerator, inorganic carbon (IC) and dissolved oxygen are removed.

一次純水製造装置11からの一次純水は、サブシステム12において、タンク14からポンプ15により熱交換器16に通水され、次いで紫外線(UV)照射装置(図4では低圧UV酸化装置)17、イオン交換装置18及び限外濾過(UF)膜分離装置19で処理されて、超純水が製造される。低圧UV酸化装置17では、UVランプより照射される185nmのUVによりTOCを有機酸、さらにはCOまで分解する。分解により生成した有機物及びCOは後段のイオン交換装置(通常は混床式イオン交換装置)18で除去される。UF膜分離装置19では微粒子が除去され、イオン交換装置18から流出するイオン交換樹脂の破片等も除去される。 In the subsystem 12, the primary pure water from the primary pure water production apparatus 11 is passed from the tank 14 to the heat exchanger 16 by the pump 15, and then the ultraviolet (UV) irradiation apparatus (low-pressure UV oxidation apparatus in FIG. 4) 17 is used. Then, it is processed by the ion exchange device 18 and the ultrafiltration (UF) membrane separation device 19 to produce ultrapure water. In the low-pressure UV oxidizer 17, TOC is decomposed to an organic acid and further to CO 2 by 185 nm UV irradiated from a UV lamp. Organic substances and CO 2 produced by the decomposition are removed by an ion exchange device (usually a mixed bed type ion exchange device) 18 in the subsequent stage. Fine particles are removed in the UF membrane separation device 19, and ion exchange resin debris flowing out from the ion exchange device 18 is also removed.

このようにして得られた超純水は、配管20よりユースポイント21に送給され、余剰の超純水が配管22よりタンク14に戻される。   The ultrapure water obtained in this manner is supplied from the pipe 20 to the use point 21, and surplus ultrapure water is returned to the tank 14 through the pipe 22.

紫外線酸化装置17での紫外線照射による酸化処理により、水中の有機物(TOC成分)が分解して有機酸及び炭酸が生じる。この紫外線酸化装置におけるTOC成分の酸化分解機構は、水を酸化分解してOHラジカルを生成させ、このOHラジカルによりTOC成分を酸化分解するものであり、サブシステム12の紫外線酸化装置17においても、紫外線照射量は水中のTOCを十分に酸化分解できるような過剰照射とされている。   Oxidation treatment by ultraviolet irradiation in the ultraviolet oxidizer 17 decomposes organic substances (TOC component) in the water to produce organic acids and carbonic acid. The oxidative decomposition mechanism of the TOC component in this ultraviolet oxidation apparatus is to oxidize and decompose water to generate OH radicals, and oxidatively decompose the TOC component by this OH radicals. In the ultraviolet oxidation apparatus 17 of the subsystem 12, The amount of UV irradiation is excessive irradiation that can sufficiently oxidatively decompose TOC in water.

このように紫外線照射量が多い場合、水の分解で生成したOHラジカルが過剰となるため、余剰のOHラジカルが会合することにより過酸化水素が生成する。生成した過酸化水素は、後段の混床式イオン交換装置のイオン交換樹脂と接触すると分解されるが、その際、イオン交換樹脂を劣化させる。また、イオン交換樹脂の分解で新たにイオン交換樹脂由来のTOC成分が生成し、得られる超純水の水質が低下する。また、混床式イオン交換装置に通水後もなお残留する過酸化水素は、混床式イオン交換装置の後段の脱気装置やUF膜を劣化させる。   Thus, when there is much ultraviolet irradiation amount, since the OH radical produced | generated by decomposition | disassembly of water will become excess, hydrogen peroxide will be produced | generated when an excess OH radical associates. The produced hydrogen peroxide is decomposed when it comes into contact with the ion exchange resin of the subsequent mixed bed ion exchange apparatus, but at this time, the ion exchange resin is deteriorated. Moreover, the TOC component derived from an ion exchange resin newly produces | generates by decomposition | disassembly of an ion exchange resin, and the quality of the obtained ultrapure water falls. Further, the hydrogen peroxide still remaining after passing water through the mixed bed ion exchanger deteriorates the deaerator and UF membrane in the subsequent stage of the mixed bed ion exchanger.

特開2007−185587(特許5124946)には、超純水中の過酸化水素除去方法として、超純水製造装置の紫外線酸化処理装置から排出される過酸化水素を含む被処理水を、白金族の金属ナノコロイド粒子をアニオン交換樹脂担体に担持させた過酸化水素分解触媒と接触させて、被処理水中の過酸化水素を1ppb以下にまで分解する方法が記載されている。   JP 2007-185587 (Patent No. 5124946) discloses, as a method for removing hydrogen peroxide in ultrapure water, water to be treated containing hydrogen peroxide discharged from an ultraviolet oxidation treatment apparatus of an ultrapure water production apparatus. Is a method of decomposing hydrogen peroxide in water to be treated to 1 ppb or less by bringing the metal nanocolloid particles into contact with a hydrogen peroxide decomposition catalyst supported on an anion exchange resin carrier.

特開2007−185587JP2007-185587

本発明者が種々研究を重ねた結果、特許文献1に従って紫外線酸化装置からの過酸化水素含有水を白金系金属担持触媒と接触させて過酸化水素を除去する場合、過酸化水素含有水中の有機酸濃度が高いときには、該白金系金属担持触媒の過酸化水素分解能力が早期に低下し、処理水に過酸化水素が早期にリークすることが認められた。このように触媒の劣化が早いと、高純度な超純水を製造する場合には触媒の交換頻度が高くなり、超純水製造コストが増大する。   As a result of various studies by the inventor, when hydrogen peroxide is removed by bringing hydrogen peroxide-containing water from an ultraviolet oxidizer into contact with a platinum-based metal-supported catalyst according to Patent Document 1, organic matter in the hydrogen peroxide-containing water is removed. When the acid concentration was high, it was recognized that the hydrogen peroxide decomposition ability of the platinum-based metal-supported catalyst decreased early, and hydrogen peroxide leaked early into the treated water. Thus, when the deterioration of the catalyst is fast, the replacement frequency of the catalyst becomes high when high purity ultrapure water is produced, and the production cost of ultrapure water increases.

本発明は、上記従来の問題点を解決し、紫外線酸化装置からの紫外線酸化処理水を白金系触媒と接触させて純水を製造する方法及び装置において、触媒樹脂の劣化を防止(抑制を包含する。)し、長期にわたって安定して過酸化水素を分解処理することができる純水製造方法及び装置を提供することを目的とする。   The present invention solves the above-mentioned conventional problems, and prevents deterioration (including suppression) of catalyst resin in a method and apparatus for producing pure water by contacting ultraviolet oxidation water from an ultraviolet oxidation apparatus with a platinum-based catalyst. It is an object of the present invention to provide a pure water production method and apparatus capable of stably decomposing hydrogen peroxide over a long period of time.

本発明の純水の製造方法は、被処理水を紫外線酸化装置で紫外線酸化処理した後、白金系触媒を用いた過酸化水素除去装置により過酸化水素除去処理する純水の製造方法において、該紫外線酸化装置への給水のTOCを5ppb以下とすることを特徴とする。   The method for producing pure water according to the present invention is the method for producing pure water, wherein the water to be treated is subjected to an ultraviolet oxidation treatment with an ultraviolet oxidation device and then subjected to a hydrogen peroxide removal treatment with a hydrogen peroxide removal device using a platinum catalyst. The TOC of water supplied to the ultraviolet oxidation device is 5 ppb or less.

本発明の純水の製造方法では、前記紫外線酸化装置への給水の無機炭酸イオン濃度が1ppb未満であり、該紫外線酸化装置で処理された紫外線酸化処理水の無機炭酸イオン濃度が1ppb以上であることが好ましい。   In the method for producing pure water of the present invention, the inorganic carbonate ion concentration of water supplied to the ultraviolet oxidation apparatus is less than 1 ppb, and the inorganic carbonate ion concentration of ultraviolet oxidation treated water treated by the ultraviolet oxidation apparatus is 1 ppb or more. It is preferable.

本発明の純水の製造方法では、前記紫外線酸化装置からの紫外線酸化処理水をアニオン交換処理した後、前記過酸化水素除去装置により過酸化水素除去処理することが好ましい。   In the method for producing pure water according to the present invention, it is preferable that after the ultraviolet oxidation water from the ultraviolet oxidation device is subjected to anion exchange treatment, the hydrogen peroxide removal treatment is performed by the hydrogen peroxide removal device.

本発明の純水の製造装置は、紫外線酸化装置と、その後段に設けられた、白金系触媒を有する過酸化水素除去装置とを備えた純水の製造装置において、該紫外線酸化装置の給水のTOCを5ppb以下とする手段を備えたことを特徴とする。   An apparatus for producing pure water according to the present invention is an apparatus for producing pure water comprising an ultraviolet ray oxidizer and a hydrogen peroxide removing device having a platinum-based catalyst provided in a subsequent stage. A means for setting the TOC to 5 ppb or less is provided.

本発明の純水の製造装置は、前記紫外線酸化装置と過酸化水素除去装置との間にアニオン交換手段を備えることが好ましい。   The pure water production apparatus of the present invention preferably includes an anion exchange means between the ultraviolet oxidation apparatus and the hydrogen peroxide removal apparatus.

紫外線酸化装置での紫外線酸化処理により被処理水中のTOC成分が酸化分解され、有機酸及び炭酸が生成する。本発明では、紫外線酸化装置への給水中のTOC濃度を5ppb以下、好ましくは3ppb以下とすることにより、紫外線酸化装置の流出水中の有機酸濃度が低くなり、紫外線酸化装置の後段に設置された過酸化水素除去用白金系触媒の被毒(劣化)が防止され、この触媒の寿命を長く保つことができる。   The TOC component in the water to be treated is oxidatively decomposed by the ultraviolet oxidation treatment in the ultraviolet oxidation apparatus, and an organic acid and carbonic acid are generated. In the present invention, by setting the TOC concentration in the feed water to the ultraviolet oxidizer to 5 ppb or less, preferably 3 ppb or less, the organic acid concentration in the effluent water of the ultraviolet oxidizer is lowered and installed in the subsequent stage of the ultraviolet oxidizer. Poisoning (deterioration) of the platinum-based catalyst for removing hydrogen peroxide is prevented, and the life of this catalyst can be kept long.

本発明では、紫外線酸化装置からの流出水をアニオン交換処理して有機酸及び炭酸を除去することが好ましい。このように有機酸を除去することにより、後段に設置された白金系触媒の寿命をさらに長くすることができる。   In the present invention, it is preferable to remove the organic acid and carbonic acid by anion exchange treatment of the effluent from the ultraviolet oxidizer. By removing the organic acid in this way, the life of the platinum-based catalyst installed in the subsequent stage can be further extended.

本発明では、紫外線酸化装置への給水の無機炭酸イオン濃度が1ppb未満である場合、紫外線酸化装置の流出水中の無機炭酸イオン濃度が1ppb以上となるように紫外線酸化処理条件を設定することにより、COにまで分解される有機物の割合が多くなり、この結果過酸化水素の発生量が減少する。これにより白金系触媒の寿命を延長することができる。 In the present invention, when the inorganic carbonate ion concentration of the feed water to the ultraviolet oxidizer is less than 1 ppb, by setting the ultraviolet oxidation treatment conditions so that the inorganic carbonate ion concentration in the effluent of the ultraviolet oxidizer is 1 ppb or more, The proportion of organic matter that is decomposed to CO 2 increases, and as a result, the amount of hydrogen peroxide generated decreases. Thereby, the lifetime of a platinum-type catalyst can be extended.

実施の形態に係る純水製造方法及び装置を示すブロック図である。It is a block diagram which shows the pure water manufacturing method and apparatus which concern on embodiment. 実施例及び比較例の説明図である。It is explanatory drawing of an Example and a comparative example. 実施例及び比較例の説明図である。It is explanatory drawing of an Example and a comparative example. 超純水製造装置のブロック図である。It is a block diagram of an ultrapure water manufacturing apparatus.

以下、本発明について図1を参照してさらに詳細に説明する。図1の実施の形態では、被処理水を紫外線酸化装置2で処理した後、白金系触媒を有する過酸化水素除去装置4で過酸化水素除去処理する。この被処理水としては、一次純水製造装置からの一次純水が好適である。一次純水製造装置からの一次純水の水質は、通常
電気比抵抗;18MΩ・cm以上
(金属イオン濃度:5ng/L以下、残留イオン濃度:10ng/L以下)
微粒子数;1mL中に0.1μm以上の微粒子5個以下
である。
Hereinafter, the present invention will be described in more detail with reference to FIG. In the embodiment of FIG. 1, the water to be treated is treated by the ultraviolet oxidation device 2 and then the hydrogen peroxide removal treatment is performed by the hydrogen peroxide removal device 4 having a platinum catalyst. As this treated water, primary pure water from a primary pure water production apparatus is suitable. The quality of primary pure water from the primary pure water production equipment is usually
Electrical specific resistance: 18 MΩ · cm or more (metal ion concentration: 5 ng / L or less, residual ion concentration: 10 ng / L or less)
Number of fine particles: 5 or less fine particles of 0.1 μm or more in 1 mL
It is.

この一次純水などの被処理水中の無機炭酸イオン濃度は1ppb未満であることが好ましい。被処理水中の無機炭酸イオン濃度が1ppb以上の場合には、脱炭酸塔、アニオン交換装置、真空脱気装置、脱気膜装置などの脱炭酸装置を単独で、あるいは組合せることによって脱炭酸処理して無機炭酸濃度を1ppb未満とすることが好ましい。   The inorganic carbonate ion concentration in the water to be treated such as primary pure water is preferably less than 1 ppb. When the concentration of inorganic carbonate ions in the water to be treated is 1 ppb or more, decarbonation treatment is performed by using a decarboxylation device such as a decarboxylation tower, anion exchange device, vacuum degassing device, or degassing membrane device alone or in combination. Thus, the inorganic carbonic acid concentration is preferably less than 1 ppb.

一次純水などの被処理水中のTOC濃度が5ppb以下である場合には、被処理水をそのまま紫外線酸化装置2に供給する。被処理水中のTOC濃度が5ppb超の場合には、TOC低減手段1によってTOC濃度を5ppb以下好ましくは3ppb以下とする。TOC低減手段としてはUV酸化装置、イオン(主にアニオン)交換装置、活性炭等による有機物吸着装置、促進酸化処理装置(UV酸化+Hや過硫酸等の酸化促進剤)などを用いることができるが、中でもUV酸化装置、イオン交換装置が好適である。 When the TOC concentration in the water to be treated such as primary pure water is 5 ppb or less, the water to be treated is supplied to the ultraviolet oxidizer 2 as it is. When the TOC concentration in the water to be treated is more than 5 ppb, the TOC reducing means 1 sets the TOC concentration to 5 ppb or less, preferably 3 ppb or less. As the TOC reduction means, a UV oxidation apparatus, an ion (mainly anion) exchange apparatus, an organic substance adsorption apparatus using activated carbon, an accelerated oxidation treatment apparatus (an oxidation accelerator such as UV oxidation + H 2 O 2 or persulfuric acid), or the like is used. Among them, a UV oxidation device and an ion exchange device are preferable.

紫外線酸化装置2での紫外線酸化処理によりTOC成分は酸化分解され、有機酸及び炭酸が生成すると共に、過酸化水素が生じる。本発明では、紫外線酸化装置2への給水中のTOC濃度を5ppb以下、好ましくは3ppb以下とすることにより、紫外線酸化装置2の流出水中の有機酸濃度が低くなり、紫外線酸化装置2の後段に設置された過酸化水素除去用白金系触媒の被毒が防止され、この触媒の寿命を長く保つことができる。   The TOC component is oxidatively decomposed by the ultraviolet oxidation treatment in the ultraviolet oxidation apparatus 2 to produce an organic acid and carbonic acid, and hydrogen peroxide is produced. In the present invention, by setting the TOC concentration in the feed water to the ultraviolet oxidizer 2 to 5 ppb or less, preferably 3 ppb or less, the organic acid concentration in the effluent water of the ultraviolet oxidizer 2 is lowered, The installed platinum catalyst for removing hydrogen peroxide is prevented from being poisoned, and the life of the catalyst can be kept long.

本発明では、紫外線酸化装置2への給水の無機炭酸イオン濃度が1ppb未満である場合、紫外線酸化装置2の流出水中の無機炭酸イオン濃度が1ppb以上となるように紫外線酸化装置2の処理条件(例えば投入電力、通水速度など)を設定することが好ましい。これにより、COにまで分解される有機物の割合が多くなり、この結果有機酸の生成量が減少する。これにより白金系触媒の寿命を延長することができる。なお、紫外線酸化装置2への給水の無機炭酸イオン濃度を1ppb未満にするのは後段処理への負荷を減らすためである。 In the present invention, when the inorganic carbonate ion concentration of the feed water to the ultraviolet oxidizer 2 is less than 1 ppb, the treatment conditions of the ultraviolet oxidizer 2 so that the inorganic carbonate ion concentration in the effluent of the ultraviolet oxidizer 2 is 1 ppb or more ( For example, it is preferable to set input power, water flow rate, and the like. Thus, the proportion of organic material is increased to be decomposed into CO 2, the amount of this result the organic acid is reduced. Thereby, the lifetime of a platinum-type catalyst can be extended. Note that the inorganic carbonate ion concentration of water supplied to the ultraviolet oxidizer 2 is less than 1 ppb in order to reduce the load on the subsequent processing.

紫外線酸化装置2からの流出水中の有機酸が触媒を被毒させることを防止するために、紫外線酸化装置2からの流出水をアニオン交換手段3に通水して有機酸を除去するのが好ましい。アニオン交換手段としては、アニオン交換樹脂特に強酸性アニオン交換樹脂が好ましく、アニオン交換樹脂はカチオン交換樹脂と混合した状態で用いてもよい。なお、アニオン交換処理により有機酸と共に炭酸も除去される。アニオン交換樹脂への通水SVは10〜200h−1程度が好ましい。 In order to prevent the organic acid in the effluent from the ultraviolet oxidizer 2 from poisoning the catalyst, it is preferable to pass the effluent from the ultraviolet oxidizer 2 through the anion exchange means 3 to remove the organic acid. . The anion exchange means is preferably an anion exchange resin, particularly a strongly acidic anion exchange resin, and the anion exchange resin may be used in a state mixed with a cation exchange resin. Carbonic acid is removed together with the organic acid by the anion exchange treatment. The water flow SV to the anion exchange resin is preferably about 10 to 200 h −1 .

アニオン交換手段3からの流出水を過酸化水素除去装置4に通水して過酸化水素を除去する。この過酸化水素除去装置4としては、白金系触媒を用いたものを採用する。白金系触媒としては、白金系金属のコロイド粒子、特にナノコロイド粒子を担体に担持させたものが好ましい。   The effluent water from the anion exchange means 3 is passed through the hydrogen peroxide removing device 4 to remove hydrogen peroxide. As this hydrogen peroxide removing device 4, a device using a platinum catalyst is employed. The platinum-based catalyst is preferably a platinum-based metal colloidal particle, particularly a nano-colloidal particle supported on a carrier.

白金系金属としては、ルテニウム、ロジウム、パラジウム、オスミウム、イリジウム及び白金を挙げることができる。こられの白金族金属は、1種を単独で用いることができ、2種以上を組み合わせて用いることもでき、2種以上の合金として用いることもでき、あるいは、天然に産出される混合物の精製品を単体に分離することなく用いることもできる。これらの中で、白金、パラジウム、白金/パラジウム合金の単独又はこれらの2種以上の混合物は、触媒活性が強いので特に好適に用いることができる。   Examples of platinum-based metals include ruthenium, rhodium, palladium, osmium, iridium, and platinum. These platinum group metals can be used singly, in combination of two or more, can be used as two or more alloys, or can be a refinement of a naturally produced mixture. It is also possible to use the product without separating it into a single unit. Among these, platinum, palladium, a platinum / palladium alloy alone or a mixture of two or more of them is particularly suitable because of its strong catalytic activity.

白金系金属のナノコロイド粒子を製造する方法に特に制限はなく、例えば、金属塩還元反応法、燃焼法などを挙げることができる。これらの中で、金属塩還元反応法は、製造が容易であり、安定した品質の金属ナノコロイド粒子を得ることができるので好適に用いることができる。金属塩還元反応法によると、例えば、白金系金属の塩化物、硝酸塩、硫酸塩、金属錯化物などの0.1〜0.4mmol/L水溶液に、アルコール、クエン酸又はその塩、ギ酸、アセトン、アセトアルデヒドなどの還元剤を4〜20当量倍添加し、1〜3時間煮沸することにより、白金系金属ナノコロイド粒子を製造することができる。また、ポリビニルピロリドン水溶液に、ヘキサクロロ白金酸、ヘキサクロロ白金酸カリウムなどの白金系金属塩を1〜2mmol/L溶解し、エタノールなどの還元剤を加え、窒素雰囲気下で2〜3時間加熱還流することにより、白金系金属のナノコロイド粒子を製造することができる。   There is no particular limitation on the method for producing platinum-based metal colloidal particles, and examples thereof include a metal salt reduction reaction method and a combustion method. Among these, the metal salt reduction reaction method can be suitably used because it is easy to produce and stable metal nanocolloid particles can be obtained. According to the metal salt reduction reaction method, for example, 0.1 to 0.4 mmol / L aqueous solution of platinum-based metal chloride, nitrate, sulfate, metal complex, etc., alcohol, citric acid or a salt thereof, formic acid, acetone Platinum metal nanocolloid particles can be produced by adding a reducing agent such as acetaldehyde 4 to 20 equivalent times and boiling for 1 to 3 hours. Also, dissolve 1 to 2 mmol / L of a platinum metal salt such as hexachloroplatinic acid or potassium hexachloroplatinate in an aqueous polyvinylpyrrolidone solution, add a reducing agent such as ethanol, and heat to reflux for 2 to 3 hours in a nitrogen atmosphere. Thus, nano colloidal particles of platinum-based metal can be produced.

白金系金属のナノコロイド粒子の平均粒子径は好ましくは1〜50nmであり、より好ましくは1.2〜20nmであり、さらに好ましくは1.4〜5nmである。この粒径は電子顕微鏡撮像から得た値である。   The average particle diameter of the platinum-based metal nanocolloid particles is preferably 1 to 50 nm, more preferably 1.2 to 20 nm, and still more preferably 1.4 to 5 nm. This particle size is a value obtained from electron microscope imaging.

白金系金属ナノコロイド粒子を担持させる担体としては、例えば、マグネシア、チタニア、アルミナ、シリカ−アルミナ、ジルコニア、活性炭、ゼオライト、ケイソウ土、イオン交換樹脂などを挙げることができる。これらの中で、アニオン交換樹脂を特に好適に用いることができる。白金系金属ナノコロイド粒子は、電気二重層を有し、負に帯電しているので、アニオン交換樹脂に安定に担持されて剥離しにくいものとなる。アニオン交換樹脂に担持された白金系金属ナノコロイド粒子は、過酸化水素の分解除去に対して強い触媒活性を示す。アニオン交換樹脂の交換基は、OH形であることが好ましい。OH形アニオン交換樹脂は、樹脂表面がアルカリ性となり、過酸化水素の分解を促進する。   Examples of the carrier for supporting the platinum-based metal nanocolloid particles include magnesia, titania, alumina, silica-alumina, zirconia, activated carbon, zeolite, diatomaceous earth, and ion exchange resin. Among these, an anion exchange resin can be particularly preferably used. The platinum-based metal nanocolloid particles have an electric double layer and are negatively charged. Therefore, the platinum-based metal nanocolloid particles are stably supported on the anion exchange resin and are difficult to peel off. Platinum-based metal nanocolloid particles supported on an anion exchange resin exhibit a strong catalytic activity for the decomposition and removal of hydrogen peroxide. The exchange group of the anion exchange resin is preferably in the OH form. In the OH-type anion exchange resin, the resin surface becomes alkaline and promotes decomposition of hydrogen peroxide.

アニオン交換樹脂への白金系金属ナノコロイド粒子の担持量は、0.01〜0.2重量%であることが好ましく、0.04〜0.1重量%であることがより好ましい。   The amount of platinum-based metal nanocolloid particles supported on the anion exchange resin is preferably 0.01 to 0.2% by weight, and more preferably 0.04 to 0.1% by weight.

白金系金属ナノコロイド粒子を担体に担持させた過酸化水素分解触媒に対し過酸化水素含有水を接触させることにより、水中の過酸化水素は、2H22
2H2O+O2の反応により分解される。過酸化水素含有水を過酸化水素分解触媒との接触方法に特に制限はないが、過酸化水素分解触媒を充填した過酸化水素分解装置へ通水することが好ましい。通水方向は、上向流、下向流のいずれともすることができるが、触媒が流動しない下向流であることが好ましい。
By bringing hydrogen peroxide-containing water into contact with a hydrogen peroxide decomposition catalyst in which platinum-based metal nanocolloid particles are supported on a carrier, hydrogen peroxide in water is converted into 2H 2 O 2
Decomposed by 2H 2 O + O 2 reaction. The method for contacting the hydrogen peroxide-containing water with the hydrogen peroxide decomposition catalyst is not particularly limited, but it is preferable to pass the water through a hydrogen peroxide decomposition apparatus filled with the hydrogen peroxide decomposition catalyst. The water flow direction can be either an upward flow or a downward flow, but is preferably a downward flow in which the catalyst does not flow.

過酸化水素含有水の過酸化水素除去触媒への通水速度は、空間速度SV100〜2,000h-1であることが好ましく、500〜1,500h-1であることがより好ましい。白金系触媒は、過酸化水素の分解速度が非常に速いので、通水空間速度SVが100h-1以上であっても過酸化水素が十分に分解される。ただし、通水空間速度SVが2,000h-1を超えると、通水の圧力損失が過大になるとともに、過酸化水素の分解除去が不十分となるおそれがある。 The water flow rate of the hydrogen peroxide-containing water to the hydrogen peroxide removal catalyst is preferably a space velocity SV of 100 to 2,000 h −1 , more preferably 500 to 1,500 h −1 . Since the platinum-based catalyst has a very high decomposition rate of hydrogen peroxide, hydrogen peroxide is sufficiently decomposed even when the water passing space velocity SV is 100 h −1 or more. However, when the water passing space velocity SV exceeds 2,000 h −1 , the pressure loss of the water passing becomes excessive, and the decomposition and removal of hydrogen peroxide may be insufficient.

アニオン交換樹脂に担持された白金系金属ナノコロイド粒子は、比表面積が大きいので、過酸化水素分解の反応速度が非常に速く、通水空間速度を高くすることができる。触媒の量に比べて通水量が多いために、使用する過酸化水素分解触媒量が少なく済み、処理コストを低減することができる。また、白金系金属ナノコロイド粒子がアニオン交換樹脂に担持された触媒の場合であっても、過酸化水素は白金系金属ナノコロイド粒子と接触して速やかに分解するので、アニオン交換樹脂に作用することがない。そのため、アニオン交換樹脂が過酸化水素に侵されて有機体炭素(TOC)が溶出するおそれもない。   Since the platinum-based metal nanocolloid particles supported on the anion exchange resin have a large specific surface area, the reaction rate of hydrogen peroxide decomposition is very high, and the water passing space velocity can be increased. Since the amount of water passing is larger than the amount of the catalyst, the amount of the hydrogen peroxide decomposition catalyst to be used can be reduced, and the processing cost can be reduced. Even in the case of a catalyst in which platinum-based metal nanocolloid particles are supported on an anion exchange resin, hydrogen peroxide acts on the anion exchange resin because it decomposes rapidly upon contact with the platinum-based metal nanocolloid particles. There is nothing. Therefore, there is no possibility that the anion exchange resin is attacked by hydrogen peroxide and organic carbon (TOC) is eluted.

過酸化水素分解触媒と接触した処理水中に含まれる過酸化水素の濃度は5ppb(重量比)以下であることが好ましく、1ppb(重量比)以下であることがより好ましい。超純水に含まれる過酸化水素の濃度が5ppb(重量比)以下であれば、半導体、液晶などの部品に悪影響を与えることなく、超純水を用いて洗浄などの処理をすることができる。   The concentration of hydrogen peroxide contained in the treated water in contact with the hydrogen peroxide decomposition catalyst is preferably 5 ppb (weight ratio) or less, and more preferably 1 ppb (weight ratio) or less. If the concentration of hydrogen peroxide contained in ultrapure water is 5 ppb (weight ratio) or less, it is possible to perform treatments such as cleaning using ultrapure water without adversely affecting semiconductor and liquid crystal components. .

図4の超純水製造装置に本発明を適用する場合には、低圧UV酸化装置17と混床式イオン交換装置18との間にアニオン交換樹脂塔と、過酸化水素除去装置とをこの順に直列に設置するのが好ましい。   When the present invention is applied to the ultrapure water production apparatus of FIG. 4, an anion exchange resin tower and a hydrogen peroxide removal apparatus are arranged in this order between the low pressure UV oxidation apparatus 17 and the mixed bed ion exchange apparatus 18. It is preferable to install them in series.

[実験例1〜3]
超純水にIPA(イソプロピルアルコール)を添加した合成一次純水を図2のフローに従って処理した。
[Experimental Examples 1-3]
A synthetic primary pure water obtained by adding IPA (isopropyl alcohol) to ultrapure water was treated according to the flow of FIG.

即ち、超純水にIPAをタンク及びポンプよりなるIPA添加装置5によって定量ライン注入し、TOC濃度3,5又は10ppbのIPA含有合成一次純水を調製し、低圧紫外線酸化装置7(出力0.6kW、UV波長185nm)に10L/minにて通水した。紫外線酸化装置7の流出水を強酸性アニオン交換樹脂塔8にSV=100h−1にて通水し、さらにPt担持アニオン交換樹脂(日本板硝子(株)製。Ptナノコロイドの平均粒径10nm)を充填した触媒塔9にSV=1000h−1にて通水した。紫外線酸化装置7の流出水中の過酸化水素濃度の経時変化を表1に示し、Pt触媒塔9からの処理水中の過酸化水素濃度の経時変化を表2に示す。 That is, IPA is injected into ultrapure water by an IPA addition device 5 comprising a tank and a pump to prepare a quantitative primary IP water containing IPA containing a TOC concentration of 3, 5 or 10 ppb. 6 kW, UV wavelength 185 nm) at 10 L / min. The effluent from the ultraviolet oxidizer 7 was passed through the strongly acidic anion exchange resin tower 8 at SV = 100 h −1 , and further Pt-supported anion exchange resin (manufactured by Nippon Sheet Glass Co., Ltd., average particle diameter of Pt nanocolloid 10 nm) Water was passed through the catalyst tower 9 packed with NO at SV = 1000 h −1 . Table 1 shows the change over time in the hydrogen peroxide concentration in the effluent water of the ultraviolet oxidizer 7, and Table 2 shows the change over time in the hydrogen peroxide concentration in the treated water from the Pt catalyst tower 9.

[実験例4〜6]
図3の通り、アニオン交換樹脂塔8を省略し、紫外線酸化装置7からの流出水をそのままPt触媒塔9に通水するようにしたこと以外は実験例1〜3と全く同様にして処理を行った。Pt触媒塔9からの処理水中の過酸化水素濃度の経時変化を表3に示す。
[Experimental Examples 4 to 6]
As shown in FIG. 3, the anion exchange resin tower 8 was omitted, and the treatment was performed in exactly the same manner as in Experimental Examples 1 to 3, except that the effluent water from the ultraviolet oxidizer 7 was directly passed through the Pt catalyst tower 9. went. Table 3 shows changes with time in the hydrogen peroxide concentration in the treated water from the Pt catalyst tower 9.

Figure 2015178107
Figure 2015178107

Figure 2015178107
Figure 2015178107

Figure 2015178107
Figure 2015178107

表1の通り、紫外線酸化装置7への給水中のTOC濃度が3,5,10ppbのいずれの場合も、紫外線酸化装置7流出水中の過酸化水素濃度は同一であった。   As shown in Table 1, the hydrogen peroxide concentration in the effluent of the ultraviolet oxidizer 7 was the same regardless of whether the TOC concentration in the feed water to the ultraviolet oxidizer 7 was 3, 5, or 10 ppb.

表2の通り、紫外線酸化装置流出水をアニオン交換樹脂と接触させた後、Pt触媒塔9に通水するようにした図2のフローでは、紫外線酸化装置入口TOC=10ppbでも過酸化水素分解能は長期にわたって高く維持される。   As shown in Table 2, in the flow of FIG. 2 in which the ultraviolet oxidizer effluent was brought into contact with the anion exchange resin and then passed through the Pt catalyst tower 9, the hydrogen peroxide resolution was not reduced even at the ultraviolet oxidizer inlet TOC = 10 ppb. Maintained high over time.

表3の通り、紫外線酸化装置流出水をそのままPt触媒塔9に通水する図3のフローでは、紫外線酸化装置入口TOC=10ppbの場合、通水15日後にはすでに過酸化水素分解能が低下している。この結果から、処理水過酸化水素濃度<1ppbが必要な場合、実機で使用するSVが1/10であることを考えても、2〜3カ月に1度過酸化水素分解触媒を交換することが必要になってくる。TOC≦5ppbの超純水を製造する場合であれば、過酸化水素分解触媒を交換することなく、実機で1年以上の性能確保ができる。   As shown in Table 3, in the flow of FIG. 3 in which the effluent from the ultraviolet oxidizer is passed through the Pt catalyst tower 9 as it is, when the ultraviolet oxidizer inlet TOC = 10 ppb, the hydrogen peroxide resolution has already decreased 15 days after the passage. ing. From this result, if the treated water hydrogen peroxide concentration <1 ppb is required, the hydrogen peroxide decomposition catalyst should be replaced once every 2 to 3 months, even considering that the SV used in the actual machine is 1/10. Will be needed. In the case of producing ultrapure water with TOC ≦ 5 ppb, it is possible to ensure performance for one year or more with an actual machine without replacing the hydrogen peroxide decomposition catalyst.

これらの結果から、紫外線酸化装置によるTOC分解物が白金系触媒の過酸化水素分解能を低下させるが、紫外線酸化装置の給水のTOCを5ppb以下とし、また好ましくは過酸化水素分解触媒装置の前段でアニオン交換樹脂によりTOC分解物を除去することにより、白金系過酸化水素分解触媒の交換頻度が著しく減少することが認められた。   From these results, the TOC decomposition product by the ultraviolet oxidation device reduces the hydrogen peroxide resolution of the platinum-based catalyst, but the TOC of the water supply of the ultraviolet oxidation device is set to 5 ppb or less, and preferably at the front stage of the hydrogen peroxide decomposition catalyst device. It was recognized that the frequency of replacement of the platinum-based hydrogen peroxide decomposition catalyst was significantly reduced by removing the TOC decomposition product with an anion exchange resin.

[実験例7〜10]
実験例5及び6において、紫外線酸化装置7の流出水(UV処理水)の無機炭酸イオン濃度が表4のようになるよう、紫外線酸化装置7の紫外線照射量を変化させて処理した場合の結果を、実験例5及び6の結果とともにあわせて示す。
[Experimental Examples 7 to 10]
In Experimental Examples 5 and 6, the result when the ultraviolet ray irradiation amount of the ultraviolet oxidation device 7 is changed so that the inorganic carbonate ion concentration of the effluent water (UV treated water) of the ultraviolet oxidation device 7 becomes as shown in Table 4 Is shown together with the results of Experimental Examples 5 and 6.

Figure 2015178107
Figure 2015178107

表4の通り、紫外線酸化装置7の流出水(UV処理水)中の無機炭酸イオン濃度が高いほど、過酸化水素分解触媒の寿命が長くなり、1ppb以上、特に2ppb以上であれば、通水45日経過した後も過酸化水素は検出されないことがわかる。   As shown in Table 4, the higher the concentration of inorganic carbonate ions in the effluent water (UV treated water) of the ultraviolet oxidizer 7, the longer the life of the hydrogen peroxide decomposition catalyst, and the water flow is 1 ppb or more, particularly 2 ppb or more. It can be seen that hydrogen peroxide is not detected after 45 days.

1 TOC低減手段
2 紫外線酸化装置
3 アニオン交換手段
4 過酸化水素除去手段
7 低圧紫外線酸化装置
DESCRIPTION OF SYMBOLS 1 TOC reduction means 2 Ultraviolet oxidizer 3 Anion exchange means 4 Hydrogen peroxide removal means 7 Low pressure ultraviolet oxidizer

本発明の純水の製造方法は、一次純水製造装置及び二次純水製造装置を備え、該二次純水製造装置で得られた超純水がユースポイントに送給され、該ユースポイントから戻された余剰の超純水と該一次純水製造装置からの一次純水との混合水が被処理水として、該二次純水製造装置で処理される超純水製造設備における超純水製造方法であって、該二次純水製造装置において、該被処理水を紫外線酸化装置で紫外線酸化処理した後、白金系触媒を用いた過酸化水素除去装置により過酸化水素除去処理する純水の製造方法において、該紫外線酸化装置への給水のTOCを5ppb以下とすることを特徴とする。 Method for manufacturing ultra-pure water of the present invention includes a primary pure water production system and the secondary pure water producing device, the ultrapure water obtained in the secondary pure water production system is fed to a use point, the use The ultrapure water in the ultrapure water production facility treated with the secondary pure water production equipment is treated with the mixed water of the extra pure water returned from the point and the primary pure water from the primary pure water production equipment. a pure water production method, in the secondary pure water producing device, after the treatment water to ultraviolet oxidation treatment with ultraviolet oxidation device, hydrogen peroxide removal process by the hydrogen peroxide removal apparatus using a platinum catalyst In the method for producing ultrapure water, the TOC of water supplied to the ultraviolet oxidizer is 5 ppb or less.

本発明の純水の製造方法では、前記紫外線酸化装置への給水の無機炭酸イオン濃度が1ppb未満であり、該紫外線酸化装置で処理された紫外線酸化処理水の無機炭酸イオン濃度が1ppb以上であることが好ましい。 In the ultra-pure water manufacturing method of the present invention, the inorganic carbonate ion concentration of the water supply to the ultraviolet oxidation device is less than 1ppb, inorganic carbonate ion concentration of ultraviolet oxidation treatment water treated by the ultraviolet oxidation device than 1ppb Preferably there is.

本発明の純水の製造方法では、前記紫外線酸化装置からの紫外線酸化処理水をアニオン交換処理した後、前記過酸化水素除去装置により過酸化水素除去処理することが好ましい。 In the method for producing ultrapure water present invention, after the anion exchange treatment to ultraviolet oxidation treatment water from the ultraviolet oxidation device, it is preferable to hydrogen peroxide removal process by the hydrogen peroxide removal equipment.

本発明の水製設備は、一次純水製造装置及び二次純水製造装置を備え、該二次純水製造装置で得られた超純水がユースポイントに送給され、該ユースポイントから戻された余剰の超純水と該一次純水製造装置からの一次純水との混合水が被処理水として、該二次純水製造装置で処理される超純水製造設備であって、該二次純水製造装置は、紫外線酸化装置と、その後段に設けられた、白金系触媒を有する過酸化水素除去装置と、該紫外線酸化装置の給水のTOCを5ppb以下とする手段を備えたことを特徴とする。 Ultrapure water Manufacturing equipment of the present invention includes a primary pure water production system and the secondary pure water producing device, the ultrapure water obtained in the secondary pure water production system is fed to a use point, the use This is an ultrapure water production facility where the mixed water of excess ultrapure water returned from the point and primary pure water from the primary pure water production device is treated as secondary water, and is treated in the secondary pure water production device. Te, the secondary pure water producing device includes an ultraviolet oxidation device, provided in a subsequent stage, and hydrogen peroxide removal apparatus having a platinum-based catalyst, means for less 5ppb water supply TOC of the ultraviolet oxidation device It is provided with.

本発明の水製設備は、前記紫外線酸化装置と過酸化水素除去装置との間にアニオン交換手段を備えることが好ましい。 Ultrapure water Manufacturing equipment of the present invention preferably includes an anion exchange means between the ultraviolet oxidation device and hydrogen peroxide removal equipment.

Claims (6)

被処理水を紫外線酸化装置で紫外線酸化処理した後、白金系触媒を用いた過酸化水素除去装置により過酸化水素除去処理する純水の製造方法において、該紫外線酸化装置への給水のTOCを5ppb以下とすることを特徴とする純水の製造方法。   In a pure water production method in which water to be treated is subjected to ultraviolet oxidation treatment with an ultraviolet oxidation apparatus and then subjected to hydrogen peroxide removal treatment using a hydrogen peroxide removal apparatus using a platinum catalyst, the TOC of water supplied to the ultraviolet oxidation apparatus is 5 ppb. The manufacturing method of the pure water characterized by the following. 請求項1に記載の純水の製造方法において、前記紫外線酸化装置への給水の無機炭酸イオン濃度が1ppb未満であり、該紫外線酸化装置で処理された紫外線酸化処理水の無機炭酸イオン濃度が1ppb以上であることを特徴とする純水の製造方法。   2. The method for producing pure water according to claim 1, wherein an inorganic carbonate ion concentration of water supplied to the ultraviolet oxidation apparatus is less than 1 ppb, and an inorganic carbonate ion concentration of ultraviolet oxidation treated water treated by the ultraviolet oxidation apparatus is 1 ppb. A method for producing pure water, which is as described above. 請求項1又は2に記載の純水の製造方法において、前記紫外線酸化装置からの紫外線酸化処理水をアニオン交換処理した後、前記過酸化水素除去装置により過酸化水素除去処理することを特徴とする純水の製造方法。   3. The method for producing pure water according to claim 1, wherein the ultraviolet oxidation water from the ultraviolet oxidation device is subjected to anion exchange treatment, and then the hydrogen peroxide removal treatment is performed by the hydrogen peroxide removal device. A method for producing pure water. 請求項1ないし3のいずれか1項に記載の純水の製造方法において、前記白金系触媒は、白金系金属のコロイド粒子をアニオン交換樹脂に担持させたものであることを特徴とする純水の製造方法。   4. The method for producing pure water according to claim 1, wherein the platinum-based catalyst is obtained by supporting a colloidal particle of platinum-based metal on an anion exchange resin. Manufacturing method. 紫外線酸化装置と、その後段に設けられた、白金系触媒を有する過酸化水素除去装置とを備えた純水の製造装置において、該紫外線酸化装置の給水のTOCを5ppb以下とする手段を備えたことを特徴とする純水の製造装置。   An apparatus for producing pure water comprising an ultraviolet oxidation apparatus and a hydrogen peroxide removal apparatus having a platinum-based catalyst provided in a subsequent stage, comprising means for reducing the TOC of water supplied to the ultraviolet oxidation apparatus to 5 ppb or less. An apparatus for producing pure water characterized by the above. 請求項5に記載の純水の製造装置であって、前記紫外線酸化装置と過酸化水素除去装置との間にアニオン交換手段を設けたことを特徴とする純水の製造装置。   6. The apparatus for producing pure water according to claim 5, wherein an anion exchange means is provided between the ultraviolet oxidizer and the hydrogen peroxide remover.
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