JP2004074088A - Treatment method for waste liquid containing chemical polishing liquid - Google Patents
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Abstract
【課題】化学研磨液の廃液に含まれる過酸化水素及び／又は水質汚濁性有機物質を分解除去する効果的な方法を提供する。
【解決手段】廃液処理系に、活性炭単独、あるいは活性炭と過酸化水素及び／又は鉄塩を合わせて加え、ｐＨ５以下の条件下で反応させることによって、化学研磨廃液中に含まれる過酸化水素のみならず水質汚濁性有機物質を一つの工程で効率よく分解除去できる。
【選択図】なしThe present invention provides an effective method for decomposing and removing hydrogen peroxide and / or water-polluting organic substances contained in a waste liquid of a chemical polishing liquid.
SOLUTION: Activated carbon alone or a mixture of activated carbon and hydrogen peroxide and / or iron salt is added to a waste liquid treatment system and reacted under a condition of pH 5 or less, whereby only hydrogen peroxide contained in chemical polishing waste liquid is contained. In addition, water polluting organic substances can be efficiently decomposed and removed in one step.
[Selection diagram] None
Description
【０００１】
【産業上の利用分野】
本発明は、過酸化水素及び／又は水質汚濁性有機物質を含有する化学研磨液含有廃液の処理方法に関する。
【０００２】
【従来の技術】過酸化水素を含有する化学研磨液は、鉄または銅を溶解研磨する薬剤として広く使用されているが、長時間使用していると溶解した金属や水質汚濁性の有機物質などの不純物が蓄積し化学研磨液としての機能が損なわれるため、定期的に更新される。廃液中の金属は、通常、中和処理（凝集沈殿処理）を行って溶解していた金属を沈降させ分離除去する。しかし、中和処理の際に、化学研磨液に含まれていた過酸化水素が廃液中に少量でも残存していると、過酸化水素の分解により酸素ガスが発生し、沈降すべき金属が浮遊して十分な金属分離が出来ない問題が生じる。従って、中和処理工程に入る前に廃液中に含まれている過酸化水素を完全に分解する必要がある。また、化学研磨液の廃液処理を専門の業者へ依頼する場合においても、運送途中で過酸化水素が分解し発泡したりすることがないように、廃液中の過酸化水素を分解して置く必要がある。
【０００３】
従来、過酸化水素の分解法としては、還元剤による分解方法、酵素による分解方法、金属触媒による分解方法、活性炭による分解方法などが用いられてきた。還元剤による分解方法は、原理的に過酸化水素と同当量の還元剤を必要とするため、還元剤の使用量が多くコストアップになるなどの問題がある。また、反応時に発熱や臭気などを伴なうと言った問題もある。
【０００４】
酵素による分解方法は、通常、化学研磨液の廃液が強酸性であるため、酵素活性が阻害されないように、廃液ｐＨを多量のアルカリで中和して置く必要がある。また、酵素による分解方法は廃液に含まれている金属や水質汚濁性有機物質の影響を受け易いため、安定した分解活性を得にくいという問題がある。
【０００５】
金属触媒による分解方法としては、過酸化水素分解能を有する白金、パラジウム等の金属及び鉄、マンガン、銅、銀等の金属酸化物を使用する方法が挙げられる。しかしながら、研磨液には研磨性能を維持するために、ある程度金属が溶解しても過酸化水素が分解しないように、キレート剤などの安定化剤が配合されているため、その影響を受け十分な効果が得られない問題がある。
【０００６】
また、活性炭による分解法では、化学研磨液廃液が強酸性で且つ金属が１Ｌ当り数１０ｇも溶解しているため、十分な分解活性が得らず、大量の活性炭を要するという問題がある。
【０００７】
一方、化学研磨液含有廃液中の水質汚濁性有機物質については、前記した各種の方法で過酸化水素を除去した後、中和処理により廃液中に含まれる鉄イオンや銅イオンなどの金属イオンを除去し、さらに活性炭による吸着法、活性汚泥に代表される生物学的処理法により除去するという、複雑かつ長い処理工程を要する方法で処理されている実状にある。
【０００８】
【発明が解決しようとする課題】
本発明は、従来技術における上記したような課題を解決し、化学研磨液の廃液に含まれる過酸化水素及び／又は水質汚濁性有機物質を分解除去する効果的な方法を提供するものである。
【０００９】
【課題を解決するための手段】
本発明者等は、上記の問題を解決すべく鋭意検討を重ねた結果、過酸化水素及び／又は水質汚濁性有機物質を含む化学研磨液の廃液に、活性炭単独、あるいは活性炭と過酸化水素及び／又は鉄塩を合わせて加え、ｐＨ５以下の条件下で反応させることにより、廃液中に含まれる過酸化水素のみならず水質汚濁性有機物質を一つの工程で効率良く分解除去できることを見出した。
【００１０】
即ち、本発明は、化学研磨液の廃液中に、活性炭単独、あるいは活性炭と過酸化水素及び／又は鉄塩を合わせて加え、ｐＨ５以下の条件下で反応させることを特徴とする、（１）から（４）に示す化学研磨液廃液中に含まれる過酸化水素及び／又は水質汚濁性有機物質の分解除去方法である。
（１）化学研磨液含有廃液に、活性炭単独、あるいは活性炭と鉄塩及び／又は過酸化水素を加え、ｐＨ５以下の条件下で反応させることを特徴とする、化学研磨液含有廃液の処理方法。
（２）活性炭が、温度２７℃、過酸化水素濃度０．５％の水溶液において、当該活性炭を０．５％添加したときの６０分後の過酸化水素の分解率が５％以上となる活性炭を使用する、（１）記載の化学研磨液含有廃液の処理方法。
（３）活性炭が、１０００μｍ以下の平均粒子径を有する微粉末である、（１）又は（２）記載の化学研磨液含有廃液の処理方法。
（４）活性炭が、１０００μｍ以下の平均粒子径を有する微粉末の懸濁液である、（３）記載の化学研磨液含有廃液の処理方法。
【００１１】
【発明の実施の形態】
本発明で示す活性炭の過酸化水素分解能力は、温度２７℃、過酸化水素濃度０．５％の水溶液において、活性炭を０．５％添加し、６０分間放置後、残存過酸化水素濃度を測定し、下式で算出される。
（０．５−残存過酸化水素濃度（％））／０．５ × １００
【００１２】
本発明においては、上記過酸化水素分解率が５％以上、好ましくは２０％以上となる活性炭を用いることが望ましい。活性炭の過酸化水素分解活性が高いほど、廃液中の過酸化水素及び／又は水質汚濁性有機物質の分解が効率的に進み、活性炭使用量を少なく、処理時間を短くでき有利である。またこのとき、活性炭の平均粒子径が１０００μｍ以下のもの、好ましくは１００μｍから５０μｍの微粉末化された活性炭を用いることが望ましい。この場合、活性炭の平均粒子径が小さいほど、廃液中の過酸化水素及び／又は水質汚濁性有機物質の分解が効率的に進み、活性炭使用量を少なく、処理時間を短くでき有利である。なお、平均粒子径の下限は特にないが、微粉末化する際に要する動力コスト、使用した活性炭の回収等の問題より、平均粒子径が１μｍ以上のものを用いることが好ましい。
【００１３】
本発明で使用する活性炭の由来は特に限定されないが、通常、木材、セルロース、のこくず、木炭、ヤシガラ炭、パーム核炭、素灰などの植物質を原料としたもの、泥炭、亜炭、褐炭、瀝青炭、無煙炭などの石炭系鉱物質を原料としたもの、石油残渣、硫酸スラッジ、オイルカーボンなどの石油系鉱物質を原料としたもの。蛋白質を原料としたもの、蛋白質を含有する汚泥もしくは廃棄物を出発原料としたもの、発酵生産の廃菌体を原料としたもの、ポリアクリロニトリル（ＰＡＮ）を原料としたものなどが使用され、特に発酵生産の廃菌体を原料とした活性炭が好適に用いられる。また、これら活性炭に処理を加えることにより、過酸化水素分解能力を向上させて使用することもできる。
【００１４】
活性炭は通常水分吸着などによりその吸着能力を減ずるが、本発明においては、活性炭を水などの分散媒中に懸濁して使用することができる。廃液への活性炭の供給方法には特に制限は無く、粉末状の活性炭をそのまま供給してもよいが、予め懸濁液となしポンプなどで供給しても良い。工業的には、粉塵発生抑制、操作性の点で懸濁液として供給する方法が有利であり、懸濁液の流動性、操作性の点からは、平均粒子径が１０００μｍ以下、好ましくは３００μｍ以下の粉末懸濁液として供給する方法が望ましい。
【００１５】
本発明では活性炭と同時に、必要に応じて鉄塩及び／又は過酸化水素を合わせて用いることにより、廃液中の過酸化水素のみならず水質汚濁性有機物質を効率的に分解除去することができる。鉄塩は、通常の廃液処理に用いられるものであれば良く、特に制限はない。例えば硫酸第一鉄、塩化第一鉄などが挙げられるが、価格、汎用性の点から硫酸第一鉄が好ましい。一方、過酸化水素に、酸化剤として、過酢酸、過酢酸塩、過炭酸、過炭酸塩、過硫酸、過硫酸塩、過ホウ酸、過ホウ酸塩、次亜塩素酸、次亜塩素酸塩、オゾン、酸素、塩素、空気などを併用することも可能であるが、使用後の環境負荷が少ない点で過酸化水素の単独使用が最も好ましい。
【００１６】
その際の鉄塩、過酸化水素の使用量には特に制限はなく、必要とされる廃液の処理レベルにより適宜選択されるが、一般的には、鉄塩として硫酸第一鉄を用いた場合、処理廃液に対して０．０１％から１０％、過酸化水素は処理廃液に対して０．１％から１０％が適当である。本発明による廃液処理においてはｐＨ５以下の条件下で反応を行う。廃液ｐＨがこれより高い場合は本発明の効果が著しく損なわれるので、その際は、硫酸、塩酸などの酸を別途滴下しｐＨ調節を行えば良い。しかしながら、化学研磨液は一般的に強酸性であるため、廃液ｐＨを敢えて調整する必要がないのが通常である。
【００１７】
【実施例】
以下実施例にて本発明を詳細に説明する。なお、本発明は下記実施例に限定されるものではない。また、実施例中の「活性炭の過酸化水素分解力」とは、温度２７℃、過酸化水素濃度０．５％の水溶液において、該活性炭を０．５％添加し、６０分間放置後、残存過酸化水素濃度を測定し、式「（０．５−残存過酸化水素濃度（％））／０．５ × １００」により算出した過酸化水素分解率である。
【００１８】
実施例１
化学研磨液（商品名ＣＰＬ−２００：三菱瓦斯化学（株）製）原液１０Ｌを純水で５倍希釈した液で、４２アロイ材のＩＣリードフレームをエッチング処理した後の廃液（過酸化水素濃度１．５％、溶解鉄濃度１５ｇ／Ｌ、ＴＯＣ値（全有機炭素）４０００ｐｐｍ）１Ｌに対して、撹拌下、水酸化ナトリウムを加えｐＨを２．７に調整した後、表１に示した量の活性炭と硫酸第一鉄７水塩を加え２４時間放置した。処理温度は２０℃とした。反応終了後、過マンガン酸カリウム溶液滴定法により残存過酸化水素濃度測定を行い、さらに水酸化カルシウムでｐＨを中性とした後、一部を濾別し、ろ過液についてＴＯＣ値を測定した。結果を表１に示す。なお、表中の各成分の濃度及び分解率は、分解処理前の初発の試験廃液に対する値である。
【表１】
実施例２
化学研磨液（商品名ＣＰＥ−７００：三菱瓦斯化学（株）製）原液１０Ｌを純水で５倍希釈した液で、銅プリント基板をエッチング処理した後の廃液（過酸化水素濃度２．５％、溶解銅濃度２５ｇ／Ｌ、ＴＯＣ値４０００ｐｐｍ）１Ｌに対して、撹拌下、水酸化ナトリウムを加えｐＨを２．７に調整した後、表２に示した量の活性炭と硫酸第一鉄７水塩を加え、さらに３５％過酸化水素溶液１７０ｇを２４時間かけて滴下した。処理温度は２０℃とした。反応終了後、過マンガン酸カリウム溶液滴定法により残存過酸化水素濃度測定を行い、ついで水酸化カルシウムでｐＨを中性とした後、一部を濾別し、ろ過液についてＴＯＣ値を測定した。結果を表２に示す。なお、表中の各成分の濃度及び分解率のうち、過酸化水素の分解率については分解処理前の初発の試験廃液中の量と添加した３５％過酸化水素溶液中の量の和に対する値、その他については分解処理前の初発の試験廃液に対する値である。
【表２】
比較例１
活性炭を用いなかった以外は、実施例１と同様に実験を行った。結果を表３に示す。
【表３】
比較例２
活性炭を用いなかった以外は、実施例２と同様に実験を行った。結果を表４に示す。
【表４】
実施例３
活性炭として廃菌体系活性炭の２０％水スラリー液の３０００ｐｐｍを用いた以外は、実施例２と同様に実験を行った。結果を表５に示す。
【表５】
実施例４
化学研磨液（商品名ＣＰＥ−７００：三菱瓦斯化学（株）製）原液１０Ｌを純水で５倍希釈した液で、銅プリント基板をエッチング処理した後の廃液（過酸化水素濃度２．５％、溶解銅濃度２５ｇ／Ｌ、ＴＯＣ値４０００ｐｐｍ）１Ｌに対して、撹拌下、水酸化ナトリウムを加えｐＨを２．７に調整した後、表６に示した硫酸第一鉄７水塩、廃菌体系活性炭の２０％水スラリー液を加え放置した。処理温度は２０℃とした。経時的に反応処理液のサンプリングを行い、過マンガン酸カリウム溶液滴定法により残存過酸化水素濃度を測定し、過酸化水素分解率が９９．９％以上となるまでの時間を求めた。また併せて、水酸化カルシウムでｐＨを中性とした後、一部を濾別し、ろ過液についてＴＯＣ値を測定した。結果を表６に示す。なお、表中の各成分の濃度及び分解率は、分解処理前の初発の試験廃液に対する値である。
【表６】
【発明の効果】
本発明の方法によれば、従来処理の難しかった化学研磨液含有廃液中の残存過酸化水素に加えて、水質汚濁性有機物質をも一つの工程で簡便に分解除去することができるので、産業上極めて有用な方法である。[0001]
[Industrial applications]
The present invention relates to a method for treating a chemical polishing liquid-containing waste liquid containing hydrogen peroxide and / or a water polluting organic substance.
[0002]
2. Description of the Related Art Chemical polishing liquids containing hydrogen peroxide are widely used as chemicals for dissolving and polishing iron or copper. However, when used for a long time, dissolved metals and water-polluting organic substances are used. Are periodically updated because impurities accumulate and the function as a chemical polishing liquid is impaired. The metal in the waste liquid is usually subjected to a neutralization treatment (coagulation sedimentation treatment) to sediment the dissolved metal and separate and remove it. However, if a small amount of hydrogen peroxide contained in the chemical polishing solution remains in the waste liquid during the neutralization treatment, decomposition of the hydrogen peroxide generates oxygen gas, and the metal to be settled is suspended. Therefore, there is a problem that sufficient metal separation cannot be performed. Therefore, it is necessary to completely decompose the hydrogen peroxide contained in the waste liquid before entering the neutralization treatment step. Also, when requesting the disposal of a chemical polishing solution to a specialized company, it is necessary to decompose the hydrogen peroxide in the waste solution to prevent hydrogen peroxide from decomposing and foaming during transportation. There is.
[0003]
Conventionally, as a decomposition method of hydrogen peroxide, a decomposition method using a reducing agent, a decomposition method using an enzyme, a decomposition method using a metal catalyst, a decomposition method using activated carbon, and the like have been used. Since the decomposition method using a reducing agent basically requires the same amount of reducing agent as hydrogen peroxide, there is a problem that the amount of the reducing agent used is large and the cost is increased. There is also a problem that the reaction is accompanied by heat generation and odor.
[0004]
In the decomposition method using an enzyme, since the waste liquid of the chemical polishing liquid is usually strongly acidic, it is necessary to neutralize the pH of the waste liquid with a large amount of alkali so as not to inhibit the enzyme activity. In addition, the decomposition method using an enzyme has a problem that it is difficult to obtain a stable decomposition activity because it is easily affected by metals and water-polluting organic substances contained in the waste liquid.
[0005]
Examples of the decomposition method using a metal catalyst include a method using a metal such as platinum and palladium having a hydrogen peroxide decomposability and a metal oxide such as iron, manganese, copper, and silver. However, in order to maintain the polishing performance, the polishing liquid contains a stabilizer such as a chelating agent so that the hydrogen peroxide does not decompose even if the metal is dissolved to some extent. There is a problem that the effect cannot be obtained.
[0006]
In addition, in the decomposition method using activated carbon, there is a problem in that the chemical polishing liquid waste liquid is strongly acidic and several tens of g of metal are dissolved per liter, so that sufficient decomposition activity is not obtained and a large amount of activated carbon is required.
[0007]
On the other hand, with respect to the water-polluting organic substances in the chemical polishing liquid-containing waste liquid, after removing hydrogen peroxide by the above-described various methods, metal ions such as iron ions and copper ions contained in the waste liquid are subjected to neutralization treatment. It is actually being treated by a method that requires a complicated and long treatment step, such as removal by an activated carbon adsorption method and a biological treatment method represented by activated sludge.
[0008]
[Problems to be solved by the invention]
The present invention solves the above-mentioned problems in the prior art, and provides an effective method for decomposing and removing hydrogen peroxide and / or water-polluting organic substances contained in a waste liquid of a chemical polishing liquid.
[0009]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above problems, and as a result, activated carbon alone or activated carbon and hydrogen peroxide were added to the waste liquid of the chemical polishing solution containing hydrogen peroxide and / or water polluting organic substances. By adding and / or adding an iron salt and reacting under conditions of pH 5 or less, it has been found that not only hydrogen peroxide contained in the waste liquid but also water-polluting organic substances can be efficiently decomposed and removed in one step.
[0010]
That is, the present invention is characterized in that activated carbon alone or a combination of activated carbon and hydrogen peroxide and / or iron salt is added to a waste liquid of a chemical polishing solution and reacted under a condition of pH 5 or less, (1) To (4) are methods for decomposing and removing hydrogen peroxide and / or water polluting organic substances contained in the chemical polishing liquid waste liquid.
(1) A method for treating a chemical polishing liquid-containing waste liquid, wherein activated carbon alone or activated carbon and an iron salt and / or hydrogen peroxide are added to the chemical polishing liquid-containing waste liquid and reacted under conditions of pH 5 or less.
(2) Activated carbon whose decomposition rate of hydrogen peroxide is 5% or more 60 minutes after adding 0.5% of the activated carbon in an aqueous solution having a temperature of 27 ° C. and a hydrogen peroxide concentration of 0.5%. (1) The method for treating a waste liquid containing a chemical polishing liquid according to (1).
(3) The method for treating a waste liquid containing a chemical polishing liquid according to (1) or (2), wherein the activated carbon is a fine powder having an average particle diameter of 1000 μm or less.
(4) The method for treating a waste liquid containing a chemical polishing liquid according to (3), wherein the activated carbon is a suspension of fine powder having an average particle diameter of 1000 µm or less.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
The hydrogen peroxide decomposing ability of the activated carbon shown in the present invention is determined by measuring the residual hydrogen peroxide concentration after adding 0.5% of activated carbon to an aqueous solution having a temperature of 27 ° C. and a hydrogen peroxide concentration of 0.5%, allowing the mixture to stand for 60 minutes. And is calculated by the following equation.
(0.5-concentration of residual hydrogen peroxide (%)) / 0.5 × 100
[0012]
In the present invention, it is desirable to use activated carbon having a hydrogen peroxide decomposition rate of 5% or more, preferably 20% or more. The higher the activated carbon decomposition activity of activated carbon, the more advantageously the decomposition of hydrogen peroxide and / or water polluting organic substances in the waste liquid proceeds, the less the amount of activated carbon used, and the shorter the processing time, which is advantageous. Also, at this time, it is desirable to use activated carbon having an average particle diameter of 1000 μm or less, preferably 100 μm to 50 μm. In this case, as the average particle size of the activated carbon is smaller, the decomposition of the hydrogen peroxide and / or the water polluting organic substance in the waste liquid proceeds more efficiently, the amount of the activated carbon used is reduced, and the treatment time is advantageously reduced. Although there is no particular lower limit on the average particle diameter, it is preferable to use one having an average particle diameter of 1 μm or more in view of the power cost required for pulverization and recovery of the used activated carbon.
[0013]
Although the origin of the activated carbon used in the present invention is not particularly limited, it is usually wood, cellulose, sawdust, charcoal, coconut shell charcoal, palm kernel charcoal, lignite, peat, lignite, lignite , Coal-based minerals such as bituminous coal and anthracite, and petroleum-based minerals such as petroleum residue, sulfuric acid sludge, and oil carbon. Protein-based raw materials, protein-containing sludge or waste as starting materials, waste bacterial cells of fermentation production, polyacrylonitrile (PAN) as raw materials, and the like are used. Activated carbon made from waste cells of fermentation production is preferably used. Further, by treating these activated carbons, the hydrogen peroxide decomposing ability can be improved and used.
[0014]
Activated carbon usually reduces its adsorption capacity by adsorbing moisture or the like, but in the present invention, activated carbon can be used by suspending it in a dispersion medium such as water. The method of supplying the activated carbon to the waste liquid is not particularly limited, and powdered activated carbon may be supplied as it is, or may be supplied in advance by a suspension or a non-pump. Industrially, a method of supplying as a suspension is advantageous in terms of suppressing dust generation and operability. From the viewpoint of fluidity and operability of the suspension, the average particle diameter is 1000 μm or less, preferably 300 μm. The following method of supplying as a powder suspension is desirable.
[0015]
In the present invention, not only hydrogen peroxide in the waste liquid but also water-polluting organic substances can be efficiently decomposed and removed by using iron salt and / or hydrogen peroxide, if necessary, together with activated carbon. . The iron salt is not particularly limited as long as it is used for ordinary waste liquid treatment. For example, ferrous sulfate, ferrous chloride and the like can be mentioned, but ferrous sulfate is preferred from the viewpoint of price and versatility. On the other hand, hydrogen peroxide is used as an oxidizing agent as peracetic acid, peracetate, percarbonate, percarbonate, persulfate, persulfate, perboric acid, perborate, hypochlorous acid, hypochlorous acid. Although salt, ozone, oxygen, chlorine, air and the like can be used in combination, it is most preferable to use hydrogen peroxide alone because it has a low environmental load after use.
[0016]
The amount of the iron salt and hydrogen peroxide used at that time is not particularly limited, and is appropriately selected depending on the required waste liquid treatment level.In general, when ferrous sulfate is used as the iron salt, The suitable amount of the waste liquid is 0.01% to 10%, and the concentration of the hydrogen peroxide is 0.1% to 10% based on the waste liquid. In the waste liquid treatment according to the present invention, the reaction is performed under the condition of pH 5 or less. If the pH of the waste liquid is higher than this, the effect of the present invention is significantly impaired. In this case, the pH may be adjusted by separately dropping an acid such as sulfuric acid or hydrochloric acid. However, since the chemical polishing liquid is generally strongly acidic, it is usually unnecessary to adjust the pH of the waste liquid.
[0017]
【Example】
Hereinafter, the present invention will be described in detail with reference to Examples. In addition, this invention is not limited to a following example. The term “hydrogen peroxide decomposing ability of activated carbon” in Examples refers to an aqueous solution having a temperature of 27 ° C. and a hydrogen peroxide concentration of 0.5%. The hydrogen peroxide concentration was measured, and the hydrogen peroxide decomposition rate was calculated by the formula “(0.5−concentration of residual hydrogen peroxide (%)) / 0.5 × 100”.
[0018]
Example 1
A waste liquid (hydrogen peroxide concentration) obtained by etching a 42 alloy IC lead frame with a chemical polishing liquid (trade name: CPL-200: manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 L of a stock solution diluted 5 times with pure water. To 1.5 L, a dissolved iron concentration of 15 g / L, and a TOC value (total organic carbon) of 1 L, sodium hydroxide was added to the mixture under stirring to adjust the pH to 2.7, and then the amount shown in Table 1 was added. Of activated carbon and ferrous sulfate heptahydrate were added and left for 24 hours. The processing temperature was 20 ° C. After the completion of the reaction, the concentration of residual hydrogen peroxide was measured by potassium permanganate solution titration, and the pH was neutralized with calcium hydroxide. Then, a part of the solution was filtered off, and the TOC value of the filtrate was measured. Table 1 shows the results. In addition, the concentration and decomposition rate of each component in the table are values for the first test waste liquid before the decomposition treatment.
[Table 1]
Example 2
A waste liquid (2.5% hydrogen peroxide concentration) obtained by etching a copper printed circuit board with a 10 L stock solution of a chemical polishing solution (trade name: CPE-700: manufactured by Mitsubishi Gas Chemical Co., Ltd.) diluted 5 times with pure water. , Dissolved copper concentration of 25 g / L, TOC value of 4000 ppm), 1 L of sodium carbonate was added thereto with stirring to adjust the pH to 2.7, and then the amounts of activated carbon and ferrous sulfate in water shown in Table 2 were adjusted. The salt was added, and 170 g of a 35% hydrogen peroxide solution was further added dropwise over 24 hours. The processing temperature was 20 ° C. After completion of the reaction, the concentration of residual hydrogen peroxide was measured by potassium permanganate solution titration, and then the pH was neutralized with calcium hydroxide. Then, a part was filtered off, and the TOC value of the filtrate was measured. Table 2 shows the results. Among the concentrations and decomposition rates of each component in the table, the decomposition rate of hydrogen peroxide is the value based on the sum of the amount in the initial test waste liquid before the decomposition treatment and the amount in the added 35% hydrogen peroxide solution. , Others are the values for the first test waste liquid before the decomposition treatment.
[Table 2]
Comparative Example 1
The experiment was performed in the same manner as in Example 1 except that no activated carbon was used. Table 3 shows the results.
[Table 3]
Comparative Example 2
The experiment was performed in the same manner as in Example 2 except that activated carbon was not used. Table 4 shows the results.
[Table 4]
Example 3
The experiment was carried out in the same manner as in Example 2, except that 3000 ppm of a 20% aqueous slurry of waste bacteria-based activated carbon was used as the activated carbon. Table 5 shows the results.
[Table 5]
Example 4
A waste liquid (2.5% hydrogen peroxide concentration) obtained by etching a copper printed circuit board with a 10 L stock solution of a chemical polishing solution (trade name: CPE-700: manufactured by Mitsubishi Gas Chemical Co., Ltd.) diluted 5 times with pure water. , Dissolved copper concentration of 25 g / L, TOC value of 4000 ppm), 1 L of sodium hydroxide was added with stirring to adjust the pH to 2.7, and then ferrous sulfate heptahydrate shown in Table 6 and waste bacteria A 20% aqueous slurry of systemic activated carbon was added and allowed to stand. The processing temperature was 20 ° C. The reaction treatment solution was sampled with time, and the concentration of residual hydrogen peroxide was measured by a potassium permanganate solution titration method, and the time required until the hydrogen peroxide decomposition rate became 99.9% or more was determined. At the same time, after the pH was neutralized with calcium hydroxide, a part was filtered off, and the TOC value of the filtrate was measured. Table 6 shows the results. In addition, the concentration and decomposition rate of each component in the table are values for the first test waste liquid before the decomposition treatment.
[Table 6]
【The invention's effect】
According to the method of the present invention, in addition to the residual hydrogen peroxide in the chemical polishing liquid-containing waste liquid, which has been difficult to treat conventionally, water-polluting organic substances can also be easily decomposed and removed in a single step. This is a very useful method.
Claims (4)
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