JPH11197674A - Treatment of peroxide-containing waste water - Google Patents
Treatment of peroxide-containing waste waterInfo
- Publication number
- JPH11197674A JPH11197674A JP10310557A JP31055798A JPH11197674A JP H11197674 A JPH11197674 A JP H11197674A JP 10310557 A JP10310557 A JP 10310557A JP 31055798 A JP31055798 A JP 31055798A JP H11197674 A JPH11197674 A JP H11197674A
- Authority
- JP
- Japan
- Prior art keywords
- peroxide
- wastewater
- waste water
- packed bed
- treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、過酸化物含有排水
を無害化処理する方法に関し、特に半導体工業における
シリコンウェハーの研磨やエッチング処理で発生する過
酸化物含有排水、食品工業等における設備等の殺菌洗浄
で発生する過酸化物含有排水、或いは薬品工業等におい
て発生する過酸化物含有排水などを、環境に放出しても
安全なまでに無害化処理するための排水処理方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for detoxifying a wastewater containing peroxide, and more particularly to a wastewater containing peroxide generated by polishing and etching silicon wafers in the semiconductor industry, facilities in the food industry, and the like. The present invention relates to a wastewater treatment method for detoxifying a wastewater containing peroxide generated by sterilizing washing or a wastewater containing peroxide generated in a chemical industry or the like so that it can be safely discharged to the environment.
【０００２】[0002]
【従来の技術】水中に溶解している過酸化水素を分解し
て除去するための技術として、カタラーゼを用いて酸素
と水とに分解する方法、亜硫酸塩などの還元剤を添加し
て還元分解する方法がある。しかし酵素による分解方法
は、過酸化水素を完全に分解することが困難であるう
え、処理後の排水のＣＯＤが高くなるという問題があ
る。また還元剤による分解方法は、薬剤の添加量を精密
に制御することが必要であるが、かかる制御は容易でな
い。しかもこれらの方法は、何れも薬剤を使用するた
め、ランニングコストが嵩むという欠点がある。2. Description of the Related Art As a technique for decomposing and removing hydrogen peroxide dissolved in water, a method of decomposing into hydrogen and oxygen using catalase, a reductive decomposition by adding a reducing agent such as a sulfite, and the like. There is a way to do that. However, the enzymatic decomposition method has a problem that it is difficult to completely decompose hydrogen peroxide, and the COD of the treated wastewater is increased. Further, the decomposition method using a reducing agent requires precise control of the amount of drug added, but such control is not easy. Moreover, all of these methods have a drawback that running cost is increased because a drug is used.
【０００３】また、活性炭や粉末状の二酸化マンガンを
水中に投入して、過酸化水素を分解させる方法がある
が、活性炭は分解速度が遅いため設備の効率が低く、粉
末状の二酸化マンガンは分解速度は速いものの、処理排
水から二酸化マンガンを分離回収するために、特別な後
処理装置が必要となる不利がある。[0003] There is also a method in which activated carbon or powdered manganese dioxide is put into water to decompose hydrogen peroxide. However, activated carbon has a low decomposition rate, so the efficiency of equipment is low, and powdered manganese dioxide is decomposed. Although the speed is high, there is a disadvantage that a special after-treatment device is required to separate and recover manganese dioxide from the treated wastewater.
【０００４】近時に至り、皮革のクロムなめし工程で発
生した、クロムイオンと過酸化水素とを含有する排水
を、粒状酸化マンガン充填塔に通して過酸化水素を１０
０mg／L 以下の濃度まで分解し、その後イオン交換樹脂
塔に通してクロムイオンを回収する方法（特開平８−２
４８９７号）が提案されている。しかし、この粒状酸化
マンガンを用いる方法は過酸化水素の除去が十分に進ま
ず、排水を無害化することも困難である。Recently, wastewater containing chromium ions and hydrogen peroxide generated in a leather tanning step of leather is passed through a granular manganese oxide packed tower to reduce the amount of hydrogen peroxide to 10%.
A method of decomposing to a concentration of 0 mg / L or less, and then recovering chromium ions by passing through an ion exchange resin tower (Japanese Patent Laid-Open No.
No. 4897) has been proposed. However, in the method using this granular manganese oxide, the removal of hydrogen peroxide does not proceed sufficiently, and it is also difficult to make the wastewater harmless.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記のよう
な従来技術では、排水中の過酸化水素を経済的に完全除
去することができないことに鑑み、排水中の過酸化水素
等の過酸化物を効率的に分解除去すると共に、処理後の
排水中の汚染物質を増加させることがない、経済的な過
酸化物含有排水の処理方法を提供することを目的とし
た。SUMMARY OF THE INVENTION The present invention has been made in view of the fact that hydrogen peroxide in wastewater cannot be completely removed economically with the above-mentioned prior art, and therefore, the present invention is not limited to such a technique. An object of the present invention is to provide an economical method for treating peroxide-containing wastewater, which efficiently decomposes and removes oxides and does not increase pollutants in treated wastewater.
【０００６】[0006]
【課題を解決するための手段】本発明の目的は、真比重
３〜５であって微粉末を実質的に含まない酸化マンガン
粒子からなる充填層に排水を接触通過させて、排水中に
含まれる過酸化物を分解除去することを特徴とする過酸
化物含有排水の処理方法によって達成することができ
る。DISCLOSURE OF THE INVENTION An object of the present invention is to contact and pass waste water through a packed bed of manganese oxide particles having a true specific gravity of 3 to 5 and containing substantially no fine powder, to contain the waste water in the waste water. It can be achieved by a method for treating peroxide-containing wastewater, which comprises decomposing and removing the peroxide.
【０００７】[0007]
【発明の実施の形態】本発明の過酸化物含有排水の処理
方法に使用される酸化マンガン粒子は、過酸化水素の分
解触媒として作用するものであるが、真比重が３〜５の
範囲内にあることが必要である。かかる酸化マンガン粒
子としては、必ずしも化学組成の一定な純物質である必
要はなく、真比重３〜５の酸化マンガン部分の他に、本
発明の効果を阻害しない程度の不純物等を含有していて
もよく、担持体上に支持されているもの、或いは複合酸
化物等であってもよい。その中でも二酸化マンガンの結
晶構造を有するものが好ましく、中でも真比重が４．５
〜５の範囲内にあるものが特に好ましい。DETAILED DESCRIPTION OF THE INVENTION The manganese oxide particles used in the method for treating peroxide-containing wastewater of the present invention act as a catalyst for decomposing hydrogen peroxide, but have a true specific gravity in the range of 3 to 5. It is necessary to be in. Such manganese oxide particles do not necessarily need to be pure substances having a constant chemical composition, and contain impurities and the like that do not impair the effects of the present invention, in addition to the manganese oxide portion having a true specific gravity of 3 to 5. Or a composite oxide or the like supported on a carrier. Among them, those having a manganese dioxide crystal structure are preferable, and among them, the true specific gravity is 4.5.
Those in the range of from 5 to 5 are particularly preferred.
【０００８】かかる酸化マンガン粒子の径は、０．２mm
乃至３mm程度であることが望ましいが、特に微粉末を実
質的に含まないことが必要である。粒径が０．２mmより
小さい粒子、特に微粉末が存在すると、処理水中に流出
するマンガンの量が増加するから、予め水洗などによっ
て微粉末を除去しておくことが望ましい。一方、粒径の
上限は３mm以下であることは必ずしも必要ではないが、
３mmを超えて大き過ぎるときは過酸化物の分解により発
生したガスが抜け難く、また排水との接触効率が低下す
るので好ましくない。本発明において特に好ましいの
は、径が０．４〜１．０mmの範囲内にある二酸化マンガ
ン粒子である。The diameter of the manganese oxide particles is 0.2 mm
Although it is desirable that the thickness is about 3 to 3 mm, it is particularly necessary that the fine powder is not substantially contained. If particles having a particle size smaller than 0.2 mm, particularly fine powder, are present, the amount of manganese flowing out into the treated water increases. Therefore, it is desirable to remove the fine powder in advance by washing with water or the like. On the other hand, the upper limit of the particle size is not necessarily required to be 3 mm or less,
If it exceeds 3 mm, it is not preferable because the gas generated by decomposition of the peroxide is difficult to escape and the contact efficiency with the waste water is reduced. Particularly preferred in the present invention are manganese dioxide particles having a diameter in the range of 0.4 to 1.0 mm.
【０００９】本発明における酸化マンガン粒子は、例え
ば下部に目皿を設けた円筒形状の反応器中に層状に充填
されることが好ましい。過酸化物含有排水はこのような
反応器の底部から導入され、充填層に対して下から上向
きに通過しながら、充填層を構成する酸化マンガン粒子
と接触して過酸化物が分解し、発生ガスと共に反応器の
上部から流出する。この際の充填層に対する排水の通過
線速度は、排水中の過酸化物濃度をＸ（mg／L の単位で
表した値）としたときに、次式（１）で表されるＹ（ｍ
／ｈ）以下とするのが良い。The manganese oxide particles in the present invention are preferably packed in a layered manner in a cylindrical reactor having, for example, a perforated plate at the bottom. Peroxide-containing wastewater is introduced from the bottom of such a reactor, and while passing upward from the bottom to the packed bed, comes into contact with the manganese oxide particles constituting the packed bed, and the peroxide is decomposed and generated. It flows out of the top of the reactor with the gas. At this time, the passing linear velocity of the wastewater with respect to the packed bed is represented by Y (m) represented by the following equation (1), where the peroxide concentration in the wastewater is X (a value expressed in units of mg / L).
/ H).
【数２】Ｙ＝ａＸ-b （１） 但し、ａ＝２５００ｍ／ｈ、ｂ＝０．７３４である。こ
のような過酸化物濃度に応じた処理速度で過酸化物含有
排水を処理すれば、排水中の過酸化物は、処理前の濃度
の高低にかかわらず処理後は１mg／L 以下までに低下さ
せることができ、また処理水の汚染物質となるマンガン
濃度を、５mg／L を超えないように抑制することができ
る。Y = aX- b (1) where a = 2500 m / h and b = 0.834. If peroxide-containing wastewater is treated at a treatment speed corresponding to such peroxide concentration, the peroxide in the wastewater will be reduced to 1 mg / L or less after treatment regardless of the concentration before and after treatment. And the concentration of manganese, which is a pollutant of the treated water, can be suppressed so as not to exceed 5 mg / L.
【００１０】更に本発明においては、上記のように酸化
マンガン粒子からなる充填層を通して処理した排水は、
同様な酸化マンガン粒子からなる第２の充填層を設けた
濾過器の上部から導入し、第２の充填層を通過して下部
から排出ようにしてもよい。この第２の充填層による処
理をすれば、排水中に残留している過酸化物を更に完全
に分解すると共に、反応器の充填層から流出するマンガ
ンを捕捉することができる。Further, in the present invention, the wastewater treated through the packed bed composed of manganese oxide particles as described above,
The gas may be introduced from the upper part of the filter provided with the second packed bed made of similar manganese oxide particles, and may pass through the second packed bed and be discharged from the lower part. By performing the treatment using the second packed bed, peroxide remaining in the wastewater can be further completely decomposed, and manganese flowing out from the packed bed of the reactor can be captured.
【００１１】このような本発明の処理方法を適用するこ
とができる排水は、例えば過酸化水素のほか、過硼酸
塩、過硫酸塩、過酢酸塩など、水溶性の過酸化物を含有
するものであれば特に制限を受けることなく、処理可能
である。また排水中の過酸化物の含有量は、１００００
mg／L 以下であれば何等の問題もなく、処理可能であ
る。The wastewater to which the treatment method of the present invention can be applied includes, for example, hydrogen peroxide and water-soluble peroxides such as perborate, persulfate and peracetate. If it is, processing can be performed without any particular limitation. The peroxide content in the wastewater is 10,000
If it is less than mg / L, it can be processed without any problems.
【００１２】[0012]
【実施例】（第１実施例）内径３２mm、長さ５０cmのガ
ラスカラムに、真比重が４．８で、粒径が０．４〜０．
６mmの二酸化マンガン粒子からなる分解処理剤Ｍの１５
０mLを、充填して得た縦型の反応器１と、反応器の上方
に設けた気液分離器２とを備えた、図１に示す装置を準
備した。EXAMPLE (First Example) A glass column having an inner diameter of 32 mm and a length of 50 cm was provided with a true specific gravity of 4.8 and a particle size of 0.4 to 0.4 mm.
Decomposition agent M consisting of 6 mm manganese dioxide particles
An apparatus shown in FIG. 1 was provided, which was provided with a vertical reactor 1 obtained by filling 0 mL and a gas-liquid separator 2 provided above the reactor.
【００１３】この装置では、試験液は反応器１の底部か
ら導入されて頂部から気液分離器２に入り、気液分離器
２から流出した処理液を回収するものであるが、更に気
液分離器２の後に上記の反応器１と同様な構造の濾過器
３を付加し、前記の処理液を濾過器３の上部に供給して
底部から排出することにより、２次処理することもでき
る。In this apparatus, the test liquid is introduced from the bottom of the reactor 1, enters the gas-liquid separator 2 from the top, and collects the processing liquid flowing out of the gas-liquid separator 2. After the separator 2, a filter 3 having the same structure as that of the reactor 1 described above is added, and the treatment liquid is supplied to the upper part of the filter 3 and discharged from the bottom to perform the secondary treatment. .
【００１４】水道水に過酸化水素を５０００mg／L の濃
度となるよう添加した、ｐＨ６．９の試験液Ａを、前記
の装置の反応器１に１．６ L／ｈの速度で供給した。こ
のときの反応器１の充填層に対する線速度ＬＶは２ｍ／
ｈであった。そして、稼働時間が２００時間に達するま
での間に、順次に反応器出口から回収した処理液中の過
酸化水素（ＨＰＯ）の残存濃度を分析して、処理能力の
経時変化を調べたところ、表１に示すような結果が得ら
れた。A test solution A having a pH of 6.9 in which hydrogen peroxide was added to a concentration of 5000 mg / L to tap water was supplied to the reactor 1 of the above apparatus at a rate of 1.6 L / h. At this time, the linear velocity LV with respect to the packed bed of the reactor 1 is 2 m /
h. Until the operating time reached 200 hours, the residual concentration of hydrogen peroxide (HPO) in the processing liquid collected from the reactor outlet was sequentially analyzed, and the time-dependent change in the processing capacity was examined. The results as shown in Table 1 were obtained.
【００１５】また、上記の分解処理剤Ｍに代えて、アル
ミノケイ酸セラミックス粒子（径０．６〜０．７mm）の
表面に、厚さ０．０５〜０．１mmの酸化マンガン層を焼
結させてなる市販の分解処理剤Ｎ（真比重：２．５）、
又は径０．５〜０．６mmに粉砕された酸化マンガン粒子
からなる市販の分解処理剤Ｏ（真比重：２．６）を、反
応器に上記と同様に充填した他は全く同様に構成した装
置を用い、上記と全く同様の試験条件（通液量：１．６
L／ｈ）で試験液Ａを処理したときの過酸化水素（ＨＰ
Ｏ）残存量を分析し、表１に併せて示した。In place of the decomposition agent M, a manganese oxide layer having a thickness of 0.05 to 0.1 mm is sintered on the surfaces of the aluminosilicate ceramic particles (diameter: 0.6 to 0.7 mm). Commercially available decomposition treating agent N (true specific gravity: 2.5),
Alternatively, the reactor was filled with a commercially available decomposition treatment agent O (true specific gravity: 2.6) composed of manganese oxide particles pulverized to a diameter of 0.5 to 0.6 mm in the same manner as described above, except that the reactor was charged. Using the apparatus, the test conditions were exactly the same as those described above (flow rate: 1.6).
L / h) when the test solution A was treated with hydrogen peroxide (HP
O) The residual amount was analyzed and is shown in Table 1.
【００１６】[0016]
【表１】 [Table 1]
【００１７】表１の結果をみると、比較例において用い
た分解処理剤Ｎ、及びＯは、いずれも稼働時間が長くな
ると共に劣化が進むのに対して、本発明における分解処
理剤Ｍは極めて安定で、劣化し難いことがわかる。According to the results shown in Table 1, the decomposition treatment agents N and O used in the comparative examples both deteriorated with increasing operation time, whereas the decomposition treatment agent M in the present invention was extremely deteriorated. It turns out that it is stable and hard to deteriorate.
【００１８】（第２実施例）第１実施例の粒径が０．４
〜０．６mmの分解処理剤Ｍを充填した装置と、分解処理
剤Ｍに代えて、真比重がいずれも４．８ではあるが、粒
径がそれぞれ０．１〜０．２mmの二酸化マンガン粒子か
らなる分解処理剤Ｍ′、及び３．０〜３．６mmの二酸化
マンガン粒子からなる分解処理剤Ｍ″を、それぞれ第１
実施例と同様に充填した他は全く同様に構成した装置と
を用意し、第１実施例と同様な過酸化水素５０００mg／
L を含む試験液Ａを、１５ L／ｈの速度（反応器１の充
填層に対する線速度ＬＶ：１８．５ｍ／ｈ）で供給し
て、稼働中の反応器充填層の状況を観察したところ、以
下の表２のような結果が得られ、粒径が０．２mm以下の
ものや３mmを超えるものは、いずれも好ましくないこと
が分かった。(Second Embodiment) The particle diameter of the first embodiment is 0.4.
Manganese dioxide particles each having a true specific gravity of 4.8 but a particle size of 0.1 to 0.2 mm, respectively, in place of an apparatus filled with a decomposition treatment agent M of ~ 0.6 mm and a decomposition treatment agent M. A decomposition treatment agent M 'consisting of 3.0 to 3.6 mm of manganese dioxide particles, respectively.
A device was prepared in exactly the same manner as in the first embodiment except that it was charged in the same manner as in the first embodiment.
The test solution A containing L was supplied at a speed of 15 L / h (linear velocity LV with respect to the packed bed of the reactor 1: 18.5 m / h), and the state of the packed bed in operation was observed. The results shown in Table 2 below were obtained, and it was found that any of those having a particle size of 0.2 mm or less and those having a particle size of more than 3 mm were not preferable.
【００１９】[0019]
【表２】 [Table 2]
【００２０】（第３実施例）第１実施例におけると同様
な分解処理剤Ｍを充填した装置を用い、第１実施例と同
様な試験液Ａ（過酸化水素濃度５０００mg／L ）を、種
々の通液速度で処理した。そして、反応器出口液中の過
酸化水素（ＨＰＯ）残存量、全マンガン（ＴＭｎ）含有
量及び溶解マンガン（ＳＭｎ）含有量を分析し、その結
果を表３に示した。この表３の結果から、反応器に対す
る線速度ＬＶは５ｍ／ｈ以下が好ましいことが分かっ
た。(Third Embodiment) Using a device filled with the same decomposition treatment agent M as in the first embodiment, a test solution A (hydrogen peroxide concentration 5000 mg / L) similar to that of the first embodiment was prepared. At a liquid passing speed of Then, the residual amount of hydrogen peroxide (HPO), the total manganese (TMn) content, and the dissolved manganese (SMn) content in the reactor outlet liquid were analyzed, and the results are shown in Table 3. From the results in Table 3, it was found that the linear velocity LV with respect to the reactor was preferably 5 m / h or less.
【００２１】[0021]
【表３】 [Table 3]
【００２２】（第４実施例）内径３２mm、長さ１００cm
のガラスカラムに、第１実施例で用いたのと同じ分解処
理剤Ｍを５６０mL充填した反応器１を組み合わせた装置
を用い、水道水に過酸化水素を１００mg／L の濃度とな
るよう添加したｐＨ６．９の試験液ａを、種々の通液速
度で供給して処理した。そして、反応器出口液中の過酸
化水素（ＨＰＯ）残存量、全マンガン（ＴＭｎ）含有量
及び溶解マンガン（ＳＭｎ）含有量を分析し、その結果
を表４に示した。この表４の結果から、反応器に対する
線速度ＬＶは７０ｍ／ｈ以下が好ましいことが分かっ
た。(Fourth embodiment) Inner diameter 32 mm, length 100 cm
Hydrogen peroxide was added to tap water at a concentration of 100 mg / L using a combination of a reactor 1 filled with 560 mL of the same decomposition treatment agent M as used in the first example. The test solution a having a pH of 6.9 was supplied and processed at various flow rates. Then, the residual amount of hydrogen peroxide (HPO), the total manganese (TMn) content, and the dissolved manganese (SMn) content in the reactor outlet liquid were analyzed, and the results are shown in Table 4. From the results in Table 4, it was found that the linear velocity LV with respect to the reactor was preferably 70 m / h or less.
【００２３】[0023]
【表４】 [Table 4]
【００２４】更に、これと同様にして過酸化水素濃度を
１００mg／L から１００００mg／Lの範囲で変化させた
試験液を用意し、種々の通液速度で装置に供給して処理
し、反応器出口液中の過酸化物濃度が１mg／L 以下で、
且つ全マンガン濃度（ＴＭｎ）が５mg／L 以下となるよ
うな、過酸化水素濃度と線速度の限界値との関係を求
め、この結果を図２に示した。Further, in the same manner, test liquids in which the concentration of hydrogen peroxide is changed in the range of 100 mg / L to 10,000 mg / L are prepared, supplied to the apparatus at various flow rates, and treated. When the concentration of peroxide in the outlet liquid is 1 mg / L or less,
In addition, the relationship between the concentration of hydrogen peroxide and the limit value of the linear velocity was determined so that the total manganese concentration (TMn) was 5 mg / L or less. The results are shown in FIG.
【００２５】図２から、この限界値以下の線速度（Ｌ
Ｖ：ｍ／ｈ）で過酸化物含有排水を通液すれば、反応器
出口液中の過酸化物濃度と全マンガン濃度の双方が、共
に前記の限界濃度以下となり、これを更に濾過器で処理
することにより、一層無害化された安全な処理液が得ら
れることが分かる。From FIG. 2, it can be seen that the linear velocity (L
V: m / h), when the peroxide-containing wastewater is passed, both the peroxide concentration and the total manganese concentration in the outlet liquid of the reactor are both below the limit concentration, and this is further filtered by a filter. It can be seen that the treatment makes it possible to obtain a more harmless and safe processing solution.
【００２６】そこで、図２に示した過酸化水素濃度Ｘ
（mg／L の単位で表した値）と線速度（ｍ／ｈ）の限界
値Ｙとの関係を調べたところ、線速度の限界値Ｙは、次
式（１）のようなＸの関数として整理できることが分か
った。Therefore, the hydrogen peroxide concentration X shown in FIG.
The relationship between the linear velocity (m / h) limit value Y and the linear velocity (m / h) limit value Y was determined by the following equation (1). It turns out that it can be organized as.
【数３】 Ｙ＝ａＸ-b （１） 但し、ａ＝２５００ｍ／ｈ、ｂ＝０．７３４である。(Equation 3) Y = aX −b (1) where a = 2500 m / h and b = 0.834.
【００２７】（第５実施例）第１実施例におけると同じ
く分解処理剤Ｍを充填した装置を用い、水道水に対して
過酸化水素（ＨＰＯ）を５０００mg／L となるよう添加
したうえ、塩酸と水酸化ナトリウムによりｐＨを３〜１
０の範囲でそれぞれ調整した試験液を用意した。そし
て、これらの各試験液を第１実施例と同じ処理条件で処
理して、反応器出口液中の過酸化水素（ＨＰＯ）残存
量、及び全マンガン（ＴＭｎ）含有量を分析し、その結
果を表５に示した。(Fifth Embodiment) In the same manner as in the first embodiment, hydrogen peroxide (HPO) was added to tap water at a concentration of 5000 mg / L using a device filled with a decomposition agent M, and hydrochloric acid was added. PH with sodium hydroxide
Test solutions adjusted in the range of 0 were prepared. Then, each of these test liquids was processed under the same processing conditions as in the first example, and the residual amount of hydrogen peroxide (HPO) and the total manganese (TMn) content in the liquid at the outlet of the reactor were analyzed. Are shown in Table 5.
【００２８】[0028]
【表５】 [Table 5]
【００２９】表５の結果を見ると、過酸化物の分解効率
は試験液の値にかかわらず良好であるが、試験液のｐＨ
が４以上、特に６〜９の範囲内にあれば、マンガンの流
出が少ないことが分かる。According to the results in Table 5, the decomposition efficiency of the peroxide is good irrespective of the value of the test solution, but the pH of the test solution is high.
It can be seen that when the value is in the range of 4 or more, particularly in the range of 6 to 9, the outflow of manganese is small.
【００３０】（第６実施例）第１実施例におけると同じ
く分解処理剤Ｍを充填した装置を用い、第１実施例にお
けると同様な過酸化水素５０００mg／L を含む試験液Ａ
と、水道水に対して過酢酸８０mg／L 、又は過硫酸カリ
ウム５０００mg／L を含有するように調製した試験液Ｂ
及びＣをそれぞれ用意した。そして、いずれも第１実施
例と同様な処理条件で処理し、反応器出口液と濾過器出
口液とについて、それぞれ過酸化水素（ＨＰＯ）、過酢
酸（ＰＡＡ）、過硫酸カリウム（ＫＰＳ）、全マンガン
（ＴＭｎ）、溶解マンガン（ＳＭｎ）の含有量を分析し
たところ、表６に示すような結果が得られた。この結果
から、分解処理剤Ｍを用いた本発明の過酸化物含有排水
の処理方法によれば、水溶性の過酸化物をいずれも有効
に分解処理できることがわかる。(Sixth Embodiment) A test solution A containing 5000 mg / L of hydrogen peroxide as in the first embodiment using an apparatus filled with the decomposition agent M as in the first embodiment.
And a test solution B prepared to contain 80 mg / L of peracetic acid or 5000 mg / L of potassium persulfate in tap water.
And C were prepared. Then, all were treated under the same treatment conditions as in the first embodiment, and the hydrogen peroxide (HPO), peracetic acid (PAA), potassium persulfate (KPS), When the contents of total manganese (TMn) and dissolved manganese (SMn) were analyzed, the results shown in Table 6 were obtained. From these results, it can be seen that according to the method for treating peroxide-containing wastewater of the present invention using the decomposition treating agent M, any water-soluble peroxide can be effectively decomposed.
【００３１】[0031]
【表６】 [Table 6]
【００３２】[0032]
【発明の効果】本発明の過酸化物含有排水の処理方法に
よれば、特定の性状を有する酸化マンガン粒子からなる
分解処理剤を充填した層に、水溶性の過酸化物を含有す
る排水を流通し接触させることにより、水溶性の過酸化
物を極めて効率よく分解処理できるうえ、分解活性の劣
化が少なく、排水を経済的に且つ信頼性高く無害化処理
することができる利点がある。According to the method for treating a peroxide-containing wastewater of the present invention, a wastewater containing a water-soluble peroxide is added to a layer filled with a decomposition treatment agent composed of manganese oxide particles having specific properties. By flowing and contacting, there is an advantage that the water-soluble peroxide can be extremely efficiently decomposed, the degradation activity of the peroxide is small, and the wastewater can be economically and reliably detoxified.
【図１】本発明の過酸化物含有排水の処理方法に使用す
る処理装置の例の構成を示す説明図である。FIG. 1 is an explanatory diagram showing a configuration of an example of a treatment apparatus used in a method for treating a peroxide-containing wastewater of the present invention.
【図２】本発明の過酸化物含有排水の処理方法におい
て、過酸化物及びマンガンの濃度が処理基準を満たした
処理液を得るための排水処理条件を表すグラフである。FIG. 2 is a graph showing wastewater treatment conditions for obtaining a treatment solution in which the concentrations of peroxide and manganese satisfy treatment standards in the method for treating peroxide-containing wastewater of the present invention.
１ 反応器 ２ 気液分離器 ３ 濾過器 Reference Signs List 1 reactor 2 gas-liquid separator 3 filter
───────────────────────────────────────────────────── フロントページの続き (72)発明者 池谷 正雄 茨城県つくば市緑ケ原４−４ アクアス株 式会社つくば総合研究所内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masao Ikeya 4-4 Midorigahara, Tsukuba, Ibaraki Pref.
Claims (7)
含まない酸化マンガン粒子からなる充填層に排水を接触
通過させて、排水中に含まれる過酸化物を分解除去する
ことを特徴とする過酸化物含有排水の処理方法。1. A method for decomposing and removing peroxide contained in wastewater by passing wastewater through a packed bed composed of manganese oxide particles having a true specific gravity of 3 to 5 and containing substantially no fine powder. A method for treating peroxide-containing wastewater.
５〜５の範囲内にある、請求項１に記載の過酸化物含有
排水の処理方法。2. The true specific gravity of the manganese oxide particles is 4.
The method for treating peroxide-containing wastewater according to claim 1, which is within a range of 5 to 5.
る成分を実質的に含まないものである、請求項１又は２
に記載の過酸化物含有排水の処理方法。3. The manganese oxide particles according to claim 1, wherein the manganese oxide particles do not substantially contain a component having a diameter exceeding 3 mm.
The method for treating a peroxide-containing wastewater according to claim 1.
させる、請求項１乃至３のいずれかに記載の過酸化物含
有排水の処理方法。4. The method for treating peroxide-containing wastewater according to claim 1, wherein the wastewater is passed upward through the packed bed.
の単位で表した数値）としたとき、前記充填層に対する
排水の通過線速度を次式（１）で表されるＹ（ｍ／ｈ）
以下とする、請求項４に記載の過酸化物含有排水の処理
方法。 【数１】 Ｙ＝ａＸ-b （１） 但し、ａ＝２５００ｍ／ｈ、ｂ＝０．７３４である。5. The method according to claim 5, wherein the concentration of peroxide in the wastewater is X (mg / L).
, The linear velocity of the drainage passing through the packed bed is represented by Y (m / h) represented by the following equation (1).
The method for treating peroxide-containing wastewater according to claim 4, wherein the method is as follows. Y = aX− b (1) where a = 2500 m / h and b = 0.834.
求項１乃至５のいずれかに記載の過酸化物含有排水の処
理方法。6. The method for treating peroxide-containing wastewater according to claim 1, wherein the pH of the wastewater before treatment is 4 or more.
求項６に記載の過酸化物含有排水の処理方法。7. The method for treating peroxide-containing wastewater according to claim 6, wherein the pH of the wastewater before the treatment is 6 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10310557A JPH11197674A (en) | 1997-11-11 | 1998-10-30 | Treatment of peroxide-containing waste water |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30874297 | 1997-11-11 | ||
| JP9-308742 | 1997-11-11 | ||
| JP10310557A JPH11197674A (en) | 1997-11-11 | 1998-10-30 | Treatment of peroxide-containing waste water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11197674A true JPH11197674A (en) | 1999-07-27 |
Family
ID=26565677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10310557A Pending JPH11197674A (en) | 1997-11-11 | 1998-10-30 | Treatment of peroxide-containing waste water |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11197674A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003225677A (en) * | 2002-02-06 | 2003-08-12 | Japan Organo Co Ltd | Method for treating drainage containing fluorine and hydrogen peroxide |
| FR2912129A1 (en) * | 2007-02-05 | 2008-08-08 | Ingenierie Conception Expertis | Treating wash water to remove hydrogen peroxide comprises passing the water through a filter cartridge containing manganese dioxide |
| WO2010113918A1 (en) * | 2009-04-03 | 2010-10-07 | 栗田工業株式会社 | Device for treating water containing hydrogen peroxide |
| JP4860008B1 (en) * | 2011-06-02 | 2012-01-25 | 株式会社アサカ理研 | Hydrogen peroxide decomposition apparatus and hydrogen peroxide decomposition method |
-
1998
- 1998-10-30 JP JP10310557A patent/JPH11197674A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003225677A (en) * | 2002-02-06 | 2003-08-12 | Japan Organo Co Ltd | Method for treating drainage containing fluorine and hydrogen peroxide |
| FR2912129A1 (en) * | 2007-02-05 | 2008-08-08 | Ingenierie Conception Expertis | Treating wash water to remove hydrogen peroxide comprises passing the water through a filter cartridge containing manganese dioxide |
| WO2010113918A1 (en) * | 2009-04-03 | 2010-10-07 | 栗田工業株式会社 | Device for treating water containing hydrogen peroxide |
| JP2010240557A (en) * | 2009-04-03 | 2010-10-28 | Kurita Water Ind Ltd | Hydrogen peroxide solution treatment apparatus |
| CN102361824A (en) * | 2009-04-03 | 2012-02-22 | 栗田工业株式会社 | Device for treating water containing hydrogen peroxide |
| US20150136705A1 (en) * | 2009-04-03 | 2015-05-21 | Kurita Water Industries Ltd. | Method for treating hydrogen peroxide water |
| JP4860008B1 (en) * | 2011-06-02 | 2012-01-25 | 株式会社アサカ理研 | Hydrogen peroxide decomposition apparatus and hydrogen peroxide decomposition method |
| WO2012164948A1 (en) * | 2011-06-02 | 2012-12-06 | 株式会社アサカ理研 | Hydrogen peroxide decomposition device and decomposition method for hydrogen peroxide |
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