JPH09253669A - Treatment of dye-containing waste water - Google Patents
Treatment of dye-containing waste waterInfo
- Publication number
- JPH09253669A JPH09253669A JP6813896A JP6813896A JPH09253669A JP H09253669 A JPH09253669 A JP H09253669A JP 6813896 A JP6813896 A JP 6813896A JP 6813896 A JP6813896 A JP 6813896A JP H09253669 A JPH09253669 A JP H09253669A
- Authority
- JP
- Japan
- Prior art keywords
- dye
- waste water
- oxygen
- containing gas
- solid catalyst
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は染料含有廃水の処理
方法に関する。更に詳しくは固体触媒存在下で染料含有
廃水を湿式酸化処理する方法に関するものである。TECHNICAL FIELD The present invention relates to a method for treating dye-containing wastewater. More specifically, it relates to a method for performing wet oxidation treatment of dye-containing wastewater in the presence of a solid catalyst.
【０００２】[0002]
【従来の技術とその解決すべき課題】従来から行われて
いる染料含有廃水の処理方法としてオゾン酸化処理法、
活性炭吸着法及び凝集沈殿法が知られている。2. Description of the Related Art As a conventional treatment method for dye-containing wastewater, ozone oxidation treatment method,
Activated carbon adsorption method and coagulation sedimentation method are known.
【０００３】オゾン酸化処理法は空気を原料した場合、
消費電力が大きく経済性に問題がある。また、オゾン酸
化によって処理された廃水は、切断された着色成分の共
役二重結合が再結合反応を起こして色戻り現象を生ず
る。In the ozone oxidation treatment method, when air is used as a raw material,
Power consumption is large and there is a problem in economy. In the wastewater treated by ozone oxidation, the conjugated double bond of the cleaved coloring component causes a recombination reaction to cause a color returning phenomenon.
【０００４】活性炭吸着処理は廃水に対して多量の活性
炭が必要であり、活性炭の交換・再生が必要なため、維
持費が高い。また、大きな設置面積が必要であり、建設
費も高くなる。The activated carbon adsorption treatment requires a large amount of activated carbon with respect to waste water, and requires replacement / regeneration of activated carbon, resulting in high maintenance costs. In addition, a large installation area is required, and construction costs are high.
【０００５】凝集沈殿処理は、凝集沈殿剤で染料を沈殿
処理により発生する汚泥の処理が必要であり、処理コス
トが膨らむ。The coagulation-sedimentation treatment requires treatment of sludge generated by precipitating a dye with a coagulation-sedimentation agent, which increases the treatment cost.
【０００６】[0006]
【課題を解決するための手段】そこで、本発明者らは染
料含有廃水の処理方法について鋭意検討を重ねた結果、
固体触媒存在下で、染料含有廃水に酸素含有ガスを導入
することにより、廃水の脱色及びＣＯＤ成分の除去が可
能であることを見い出し、本発明に至ったものである。Therefore, as a result of intensive investigations by the present inventors regarding the method for treating dye-containing wastewater,
The present invention has been completed by discovering that it is possible to decolorize wastewater and remove COD components by introducing an oxygen-containing gas into the dye-containing wastewater in the presence of a solid catalyst.
【０００７】[0007]
【作用】本発明は主にパルプ工場、製紙工場、染料工
場、染料製造工場から排出される廃水に適用できる。The present invention is mainly applicable to waste water discharged from pulp mills, paper mills, dye mills and dye mills.
【０００８】本発明で処理できる染料は酸性染料、分散
染料、直接染料、カチオン染料、建染染料、硫化染料が
挙げられる。The dyes which can be treated in the present invention include acid dyes, disperse dyes, direct dyes, cationic dyes, vat dyes and sulfur dyes.
【０００９】酸性染料は例えば、acid red 6、acid bla
ck 60、acid blue 112、acid yellow11、acid red 87、
acid violet 7、acid violet 15、acid blue 9、acid g
reen19、acid black 1、acid black 2、acid black 48
が挙げられる。Acid dyes include, for example, acid red 6 and acid bla.
ck 60, acid blue 112, acid yellow 11, acid red 87,
acid violet 7, acid violet 15, acid blue 9, acid g
reen19, acid black 1, acid black 2, acid black 48
Is mentioned.
【００１０】分散染料は例えば、disperse blue 56、di
sperse blue 165、 disperse red 356、 disperse yell
ow 3、 disperse orange 3、 disperse red 1、 disper
se red11、 disperse red 15、 disperse violet 1、 d
isperse blue 1、 disperse blue 3、 disperse blue 1
4、 disperse green 1、 disperse black 1が挙げられ
る。Disperse dyes are, for example, disperse blue 56, di
sperse blue 165, disperse red 356, disperse yell
ow 3, disperse orange 3, disperse red 1, disper
se red11, disperse red 15, disperse violet 1, d
isperse blue 1, disperse blue 3, disperse blue 1
4, disperse green 1 and disperse black 1 are listed.
【００１１】直接染料は例えば、direct red 79、direc
t black 19、direct yellow 4、direct yellow 8、dire
ct red 2、direct red 81、direct violet 9、direct b
lue 8、direct blue 86、direct green 24が挙げられ
る。Direct dyes are, for example, direct red 79, direc
t black 19, direct yellow 4, direct yellow 8, dire
ct red 2, direct red 81, direct violet 9, direct b
Examples include lue 8, direct blue 86, and direct green 24.
【００１２】カチオン染料は例えば、basic red 29、ba
sic blue 47、basic yellow 1、basicyellow 2、basic
orange 2、basic red 1、basic violet 1、basic viole
t 3、basic violet 10、basic blue 1、basic blue 9、
basic green 4が挙げられる。Cationic dyes are, for example, basic red 29, ba
sic blue 47, basic yellow 1, basicyellow 2, basic
orange 2, basic red 1, basic violet 1, basic viole
t 3, basic violet 10, basic blue 1, basic blue 9,
basic green 4 is mentioned.
【００１３】硫化染料は例えば、sulphur red 6、sulph
ur blue 7、sulphur black 6、sulphur blue 12、sulph
ur green 2、sulphur green 3、sulphur green 6、sulp
hur black 1、sulphur brown 63、sulphur red 3、sulp
hur red 4、sulphur brown 12、sulphur blue 1、sulph
ur blue 7が挙げられる。Sulfur dyes are, for example, sulphur red 6, sulph
ur blue 7, sulphur black 6, sulphur blue 12, sulph
ur green 2, sulphur green 3, sulphur green 6, sulp
hur black 1, sulphur brown 63, sulphur red 3, sulp
hur red 4, sulphur brown 12, sulphur blue 1, sulph
ur blue 7 is mentioned.
【００１４】本方法では建染染料などのアルカリを含有
する染料廃水を分解するのは困難である。従って、本発
明で処理する廃水は建染染料を含有しない廃水が望まし
い。With this method, it is difficult to decompose dye wastewater containing an alkali such as vat dye. Therefore, the wastewater treated in the present invention is preferably wastewater containing no vat dye.
【００１５】染料濃度は特に限定されるものではない
が、廃水に対して0.01〜5重量％が望ましい。The dye concentration is not particularly limited, but is preferably 0.01 to 5% by weight with respect to the wastewater.
【００１６】触媒は通常、金属担持型のものが用いら
れ、具体的にはルテニウム、パラジウム、ロジウム及び
白金よりなる群から選ばれる少なくとも１種の金属を無
機酸化物あるいは活性炭に担持した固体触媒が用いられ
る。貴金属の担持量は触媒量全体に対して1〜5重量％が
望ましい。As the catalyst, a metal-supported catalyst is usually used. Specifically, a solid catalyst in which at least one metal selected from the group consisting of ruthenium, palladium, rhodium and platinum is supported on an inorganic oxide or activated carbon is used. Used. The amount of the noble metal supported is preferably 1 to 5% by weight with respect to the total amount of the catalyst.
【００１７】触媒の形状としては粉末型、粒型、ペレッ
ト型が用いることができ、特に形状は限定されない。The shape of the catalyst may be powder type, grain type or pellet type, and the shape is not particularly limited.
【００１８】反応温度は150〜250℃が望ましい。150℃
以下の低温では触媒活性は十分発揮されず、脱色は不十
分となる。殆どの染料の場合は250℃以下の温度で脱
色、ＣＯＤ除去がほぼ完全に行われるため、250℃以上
の反応温度が必要になることは少ない。The reaction temperature is preferably 150 to 250 ° C. 150 ℃
At low temperatures below, the catalytic activity is not sufficiently exhibited and decolorization becomes insufficient. In the case of most dyes, decolorization and COD removal are performed almost completely at a temperature of 250 ° C. or lower, so that a reaction temperature of 250 ° C. or higher is rarely necessary.
【００１９】反応圧力は10〜90ｋｇ／ｃｍ2Ｇ、特に15
〜70ｋｇ／ｃｍ2Ｇが望ましい。廃水は液相を保持する
必要があり、反応温度が決まれば圧力の下限は決定され
る。15ｋｇ／ｃｍ2Ｇ以下では染料の酸化分解に要する
酸素分圧が不足するため、脱色及びＣＯＤ除去が十分に
行われない。The reaction pressure is 10 to 90 kg / cm 2 G, especially 15
~ 70 kg / cm 2 G is desirable. It is necessary to maintain the liquid phase of the wastewater, and the lower limit of the pressure is determined when the reaction temperature is determined. If it is 15 kg / cm 2 G or less, the oxygen partial pressure required for oxidative decomposition of the dye is insufficient, so that decolorization and COD removal are not sufficiently performed.
【００２０】湿式分解で使用する酸素含有ガスは空気、
純酸素、酸素富化空気のいずれを用いることもできる
が、経済性を考慮すれば、空気を用いるのが望ましい。
オゾン酸化で使用される高価なオゾンを使用する必要は
無い。The oxygen-containing gas used in the wet decomposition is air,
Either pure oxygen or oxygen-enriched air can be used, but it is preferable to use air in view of economy.
It is not necessary to use the expensive ozone used in ozone oxidation.
【００２１】酸素含有ガスの使用量は廃水濃度によって
適宜選択する必要がある。この場合、使用量は染料を完
全に水、炭酸ガス、窒素ガスに分解するのに必要な酸素
量の0.5〜5倍、より好ましくは1〜2倍である。0.5倍以
下では必要酸素量に対して不足であり、5倍以上では未
使用酸素が過剰に残留する結果となる。The amount of oxygen-containing gas used must be appropriately selected depending on the concentration of wastewater. In this case, the amount used is 0.5 to 5 times, more preferably 1 to 2 times the amount of oxygen required to completely decompose the dye into water, carbon dioxide gas and nitrogen gas. If it is 0.5 times or less, the amount of oxygen is insufficient, and if it is 5 times or more, unused oxygen remains excessively.
【００２２】本発明は回分式、連続式のいずれの方式を
用いることもできる。The present invention may use either a batch system or a continuous system.
【００２３】[0023]
【実施例】次に実施例を掲げて本発明を具体的に説明す
る。Next, the present invention will be described specifically with reference to examples.
【００２４】［実施例１］攪拌機を備えた内容積500ｍ
Ｌのチタン・ライニング製オートクレーブに、disperse
blue 56 2000ｐｐｍを含有するＴＯＣ23,240ｐｐｍの
廃水100ｇ、及び外径１ｍｍのチタニア球上に２重量％
のルテニウムを担持させた触媒12.5ｇを封入して200℃
に昇温した。このとき、オートクレーブ内圧は15ｋｇ／
ｃｍ2Ｇとなった。続いて、オートクレーブ内圧が41ｋ
ｇ／ｃｍ2Ｇに到達するまで空気を導入して攪拌速度100
0ｒｐｍで攪拌しながら200℃で１時間反応を行った。反
応終了後、反応液を室温まで冷却したのち、処理水を取
り出し、ＴＯＣ分析、吸光度分析により染料分解率を定
量した。吸光度は染料含有廃水の最大吸光度を測定し、
処理前後における減少率を染料分解率とした。結果は表
１に記載した通りであった。[Example 1] Internal volume of 500 m equipped with a stirrer
L titanium lining autoclave, disperse
blue 56 TOC23 containing 2000ppm, 240g wastewater 100g, and 2% by weight on a titania ball with an outer diameter of 1mm
Encapsulate 12.5g of catalyst supporting ruthenium of 200 ℃
The temperature rose. At this time, the internal pressure of the autoclave is 15 kg /
It became cm 2 G. Then, the internal pressure of the autoclave is 41k.
Introduce air until reaching g / cm 2 G and stir speed 100
The reaction was carried out at 200 ° C. for 1 hour while stirring at 0 rpm. After completion of the reaction, the reaction solution was cooled to room temperature, treated water was taken out, and the dye decomposition rate was quantified by TOC analysis and absorbance analysis. Absorbance measures the maximum absorbance of dye-containing wastewater,
The reduction rate before and after the treatment was defined as the dye decomposition rate. The results were as described in Table 1.
【００２５】［実施例２〜１１］実施例１において染料
の種類を変更し、反応温度を170℃、反応圧力を33ｋｇ
／ｃｍ2Ｇとした以外は実施例１と同じ方法で染料含有
廃水の処理テストを行った。結果は表１に記載した通り
であった。[Examples 2 to 11] In Example 1, the type of dye was changed, the reaction temperature was 170 ° C, and the reaction pressure was 33 kg.
/ Cm 2 except that the G has been processed test dye-containing waste water in the same manner as in Example 1. The results were as described in Table 1.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【発明の効果】以上で述べた本発明の方法によれば、染
料含有廃水を効率的に脱色、ＣＯＤ成分の除去を行うこ
とができる。According to the method of the present invention described above, the dye-containing wastewater can be efficiently decolorized and the COD component can be removed.
Claims (3)
相を保持する圧力下で酸素含有ガスにより酸化分解処理
する染料含有廃水の処理方法。1. A method for treating a dye-containing wastewater by oxidatively decomposing a dye-containing wastewater in the presence of a solid catalyst with an oxygen-containing gas under a pressure at which the wastewater maintains a liquid phase.
ジウム及び白金からなる群から選ばれる少なくとも１種
の金属を無機酸化物または活性炭に担持した触媒である
請求項１に記載の染料含有廃水の処理方法。2. The method for treating dye-containing wastewater according to claim 1, wherein the solid catalyst is a catalyst in which at least one metal selected from the group consisting of ruthenium, palladium, rhodium and platinum is supported on an inorganic oxide or activated carbon. .
料、硫化染料及び分散染料からなる群から選ばれる少な
くとも１種の染料である請求項１に記載の染料含有廃水
の処理方法。3. The method for treating dye-containing wastewater according to claim 1, wherein the dye is at least one dye selected from the group consisting of acid dyes, cationic dyes, direct dyes, sulfur dyes and disperse dyes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6813896A JPH09253669A (en) | 1996-03-25 | 1996-03-25 | Treatment of dye-containing waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6813896A JPH09253669A (en) | 1996-03-25 | 1996-03-25 | Treatment of dye-containing waste water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09253669A true JPH09253669A (en) | 1997-09-30 |
Family
ID=13365093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6813896A Pending JPH09253669A (en) | 1996-03-25 | 1996-03-25 | Treatment of dye-containing waste water |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09253669A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6797184B2 (en) | 2000-01-05 | 2004-09-28 | Nippon Shokubai Co., Ltd. | Catalyst for treating waste water, method for preparing the same and process for treating waste water |
| CN105800757A (en) * | 2016-05-26 | 2016-07-27 | 徐伟鹏 | Treatment agent for dye wastewater |
| CN105800710B (en) * | 2016-05-26 | 2018-10-09 | 嘉兴市七洲漂染有限公司 | A kind of anionic dye waste water inorganic agent |
-
1996
- 1996-03-25 JP JP6813896A patent/JPH09253669A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6797184B2 (en) | 2000-01-05 | 2004-09-28 | Nippon Shokubai Co., Ltd. | Catalyst for treating waste water, method for preparing the same and process for treating waste water |
| KR100451646B1 (en) * | 2000-01-05 | 2004-10-08 | 니폰 쇼쿠바이 컴파니 리미티드 | Catalyst for treating waste water, method for producing the catalyst and method for treating waste water |
| CN105800757A (en) * | 2016-05-26 | 2016-07-27 | 徐伟鹏 | Treatment agent for dye wastewater |
| CN105800710B (en) * | 2016-05-26 | 2018-10-09 | 嘉兴市七洲漂染有限公司 | A kind of anionic dye waste water inorganic agent |
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