JPS6211634B2 - - Google Patents
Info
- Publication number
- JPS6211634B2 JPS6211634B2 JP9284480A JP9284480A JPS6211634B2 JP S6211634 B2 JPS6211634 B2 JP S6211634B2 JP 9284480 A JP9284480 A JP 9284480A JP 9284480 A JP9284480 A JP 9284480A JP S6211634 B2 JPS6211634 B2 JP S6211634B2
- Authority
- JP
- Japan
- Prior art keywords
- ozone
- added
- treatment method
- cod
- oxidation
- 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.)
- Expired
Links
- 230000003647 oxidation Effects 0.000 claims description 42
- 238000007254 oxidation reaction Methods 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 38
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000010802 sludge Substances 0.000 claims description 9
- 239000002351 wastewater Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims 1
- -1 oxides Chemical class 0.000 claims 1
- 238000006385 ozonation reaction Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000002505 iron Chemical class 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 229910018626 Al(OH) Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000010800 human waste Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
Description
本発明は、し尿などの有機性廃水の生物処理水
に残留する難性物分解性COD成分、色度成分
や、産業廃水中の難生物分解性COD成分、色度
成分の化学酸化法に関するものである。
一般にオゾン酸化法は周知の如く、色度は効果
的に除去できる反面、COD成分を効果的に除去
できない。
一方、最近オゾン酸化法の代替手段として、過
酸化水素（H2O2）と鉄塩をPH３〜４の酸性条件下
で作用せしめる方法、いわゆるフエントン酸化法
が検討されている。このように従来COD含有廃
水をオゾン酸化後、活性炭吸着したり、フエント
ン酸化後活性炭吸着を行なう方法は良く知られて
いたが、フエントン法がオゾン酸化法の代替手
段、対立的手段として考えられていたため、フエ
ントン法がオゾン酸化法よりはCOD除去に効果
的ではあるが、やはりCOD成分を充分除去でき
ずかなりのCOD成分がフエントン酸化後も残留
し、まだ十分満足するものには至らないという問
題点があつた。
本発明は、このような従来の化学酸化法の
COD除去の限界を打破することが可能な、効果
的な処理方法を提供することを目的とするもので
ある。
本発明は、COD含有廃水をオゾン処理したの
ちオゾン処理水に少なくとも金属イオン物質又は
金属イオンを水溶液中で解離しうる物質と過酸化
水素を添加して撹拌したのち、アルカリ剤を添加
し、固液分離するとともに、固液分離されたスラ
ツジを、前記オゾン処理工程に添加することを特
徴とするCOD含有廃水の処理方法で、オゾン酸
化法でフエントン酸化法を合理的に結合させ、フ
エントン酸化後生成するFe（OH）3などの金属水
酸化物をオゾン酸化工程の触媒として再利用する
ものである。
即ち、本発明はオゾン酸化後のCOD成分がフ
エントン酸化を受けやすいこと、およびフエント
ン酸化後生成するFe（OH）3、Al（OH）3、Cu
（OH）3などの金属水酸化物がオゾン酸化の触媒効
果を有することを知見して完成されたものであ
る。
本発明の一実施態様を第１図を参照しながら説
明すれば、COD含有廃水１は、オゾン酸化塔２
に流入し、オゾン含有ガス３と接触したのち管４
から撹拌槽５に流入させる。この撹拌槽５におい
ては硫酸第１鉄FeSO4などの鉄塩６と過酸化水素
（H2O2）７が添加され、PH２〜４の酸性条件下で
所定時間（通常数時間）撹拌されたのち、中和槽
８にて、アルカリ剤９が添加され中和されたの
ち、高分子凝集剤１０によつてフロツク形成さ
れ、沈澱池１１にてSSが分離され処理水１２と
沈殿スラツジ１３となる。
しかして、この沈澱スラツジ１３（Fe（OH）3
が主体である）の一部は返送管１４を経由してオ
ゾン酸化塔２にリサイクルされ、オゾン酸化の触
媒として再利用される。
また、前記管４からのオゾン処理水に硫酸、塩
酸、硝酸などの鉱酸１６を添加して水酸化鉄を溶
解したのちH2O2を添加する方法を採用すれば、
新品の鉄塩の添加を不要にできるか、大幅に添加
量を節減できることが認められた。尚オゾン酸化
のPH条件を２〜４の範囲で行う場合は鉱酸１６は
必要ない。また第２図のように、前記沈澱スラツ
ジ１３に酸１５を撹拌槽１８で添加するようにし
て返送管１４′で前記オゾン酸化塔２にリサイク
ルしてもよい。
またオゾン酸化塔２の排ガス１７中にはオゾン
が含有しているので、これをH2O2が添加された
撹拌槽５に導入するとオゾンとH2O2の併有処理
ができるので極めて好ましい。
なお、本発明ではフエントン法として知られる
鉄塩とH2O2のほかにも公知のアルミ、Cu、Mn、
Co、Ni、ＶとH2O2の併用法も採用できることは
当然であるが、実用的にはコストの安い鉄塩と
H2O2とが採用される。また金属イオンを水溶液
中で解離し得る物質としては鉄、銅、アルミ、マ
ンガン、コバルト、ニツケル、バナジウムの塩、
水酸化物、酸化物、単体金属を単独又は複数くみ
あわせて使用できる。要するに添加する物質の種
類には関係なく、水溶液中でこれらのイオンを解
離し得るものであればよく、場合によつては金属
イオン物質の形態でもその目的を達することがで
きる。
さらに前記中和槽８に添加するアルカリ剤９と
しては、カ性ソーダ（NaOH）消石灰（Ca
（OH）2）よりも水酸化マグネシウム（Mg
（OH）2）、酸化マグネシウム（MgO）のようにマ
グネシウム系アルカリ剤又は炭酸カルシウムのほ
うが、はるかに、濃縮性のよい緻密な沈殿スラツ
ジ１３が得られることが認められた。
以上述べたように、本発明はオゾン酸化法とフ
エントン酸化法を合理的に結合し、フエントン酸
化後生成するFe（OH）3やAl（OH）3やCu（OH）3
をオゾン酸化の触媒に再利用するので、従来のオ
ゾン酸化法やフエントン酸化法よりもCODが効
果的に除去できると共に、COD除去に要する薬
品の添加を大巾に削減でき著しい省資源化が可能
となり、難生物分解性COD成分、色度成分の化
学酸化の高級処理工程を設ける場合でも、COD
負荷色度負荷が低くなり、高級処理工程の建設
費、維持費が低減される利益がある。
次に本発明の実施例を述べる。
比較例 １
（従来法：オゾン酸化法）
し尿を無希釈で生物学的硝化脱窒素処理を行つ
た生物処理水に、塩化第２鉄を1500mg／添加
し、最適PH5.5の条件で、凝集沈殿処理を行つて
得た処理水の水質は下表のとおりであつた。
The present invention relates to a chemical oxidation method for refractory COD components and chromaticity components remaining in biologically treated organic wastewater such as human waste, and refractory COD components and chromaticity components in industrial wastewater. It is. As is generally known, the ozone oxidation method can effectively remove chromaticity, but cannot effectively remove COD components. On the other hand, recently, as an alternative to the ozone oxidation method, the so-called Fuenton oxidation method, which is a method in which hydrogen peroxide (H 2 O 2 ) and iron salt are allowed to act under acidic conditions of pH 3 to 4, has been studied. In this way, conventional methods such as ozone oxidation of COD-containing wastewater followed by activated carbon adsorption, and Fuenton oxidation followed by activated carbon adsorption are well known, but the Fuenton method has not been considered as an alternative or an alternative method to the ozone oxidation method. Therefore, although the Fuenton method is more effective in removing COD than the ozone oxidation method, it still cannot remove COD components sufficiently and a considerable amount of COD components remain even after Fuenton oxidation, so the problem is that it is still not fully satisfactory. The dot was hot. The present invention overcomes such conventional chemical oxidation methods.
The purpose is to provide an effective treatment method that can overcome the limitations of COD removal. The present invention involves ozonating COD-containing wastewater, adding at least a metal ion substance or a substance capable of dissociating metal ions in an aqueous solution, and hydrogen peroxide to the ozonated water, stirring the mixture, and then adding an alkaline agent to solidify the ozone-treated water. A method for treating COD-containing wastewater, which is characterized by liquid separation and adding the solid-liquid separated sludge to the ozone treatment step, which rationally combines the ozone oxidation method with the Fenton oxidation method, The generated metal hydroxides such as Fe(OH) 3 are reused as catalysts in the ozone oxidation process. That is, the present invention focuses on the fact that COD components after ozone oxidation are susceptible to Fenton oxidation, and that Fe(OH) 3 , Al(OH) 3 , and Cu produced after Fenton oxidation are
It was completed after discovering that metal hydroxides such as (OH) 3 have a catalytic effect on ozone oxidation. One embodiment of the present invention will be described with reference to FIG.
After coming into contact with the ozone-containing gas 3, the pipe 4
from there into the stirring tank 5. In this stirring tank 5, an iron salt 6 such as ferrous sulfate FeSO 4 and hydrogen peroxide (H 2 O 2 ) 7 were added and stirred for a predetermined period of time (usually several hours) under acidic conditions of pH 2 to 4. After that, in the neutralization tank 8, an alkaline agent 9 is added and neutralized, and then a floc is formed by the polymer flocculant 10, and the SS is separated in the settling tank 11 to form treated water 12 and settled sludge 13. Become. However, this precipitated sludge 13 (Fe(OH) 3
A part of the ozone oxidation tower 2 is recycled via the return pipe 14 to the ozone oxidation tower 2, where it is reused as a catalyst for ozone oxidation. Alternatively, if a method is adopted in which a mineral acid 16 such as sulfuric acid, hydrochloric acid, or nitric acid is added to the ozonated water from the pipe 4 to dissolve iron hydroxide, then H 2 O 2 is added.
It was confirmed that the addition of new iron salt could be made unnecessary or the amount added could be significantly reduced. Note that mineral acid 16 is not required when ozone oxidation is carried out under pH conditions in the range of 2 to 4. Alternatively, as shown in FIG. 2, acid 15 may be added to the precipitated sludge 13 in a stirring tank 18 and then recycled to the ozone oxidation tower 2 via a return pipe 14'. Furthermore, since ozone is contained in the exhaust gas 17 of the ozone oxidation tower 2, it is extremely preferable to introduce this into the stirring tank 5 to which H 2 O 2 has been added, since it is possible to simultaneously process ozone and H 2 O 2 . . In addition, in the present invention, in addition to iron salt and H 2 O 2 known as the Fuenton method, known aluminum, Cu, Mn,
It is natural that a combination of Co, Ni, V and H 2 O 2 can be used, but in practical terms it is better to use iron salts, which are cheaper.
H 2 O 2 is used. Substances that can dissociate metal ions in aqueous solutions include salts of iron, copper, aluminum, manganese, cobalt, nickel, and vanadium;
Hydroxides, oxides, and single metals can be used alone or in combination. In short, it does not matter what kind of substance is added, as long as it can dissociate these ions in an aqueous solution, and in some cases, the purpose can be achieved even in the form of a metal ion substance. Further, as the alkaline agent 9 added to the neutralization tank 8, caustic soda (NaOH), slaked lime (Ca
(OH) 2 ) than magnesium hydroxide (Mg
(OH) 2 ), a magnesium-based alkaline agent such as magnesium oxide (MgO), or calcium carbonate was found to yield a dense precipitated sludge 13 with much better concentration. As described above, the present invention rationally combines the ozone oxidation method and the Fuenton oxidation method, and eliminates the Fe(OH) 3 , Al(OH) 3 , and Cu(OH) 3 produced after the Fuenton oxidation.
Since it is reused as a catalyst for ozone oxidation, COD can be removed more effectively than the conventional ozone oxidation method or Fuenton oxidation method, and the addition of chemicals required for COD removal can be greatly reduced, resulting in significant resource savings. Therefore, even if an advanced treatment process for chemical oxidation of difficult-to-biodegradable COD components and chromaticity components is provided, COD
There is an advantage that the load chromaticity load is lowered, and the construction cost and maintenance cost of high-grade processing steps are reduced. Next, examples of the present invention will be described. Comparative Example 1 (Conventional method: ozone oxidation method) Ferric chloride was added at 1500 mg/day to biologically treated water that had been subjected to biological nitrification and denitrification treatment without diluting human waste, and flocculated under conditions of optimal pH 5.5. The quality of the treated water obtained through the precipitation treatment was as shown in the table below.
【表】
この凝集沈澱処理水を原水として、気泡塔内で
回分式のオゾン曝気処理を行つた結果、オゾン添
加量（mgO3／）とオゾン酸化処理水のCODは
第３図曲線ａであり、色度は完全に除去された
が、CODを74mg／以下にすることはできなか
つた。
比較例 ２
（従来法：フエントン法）
比較例１の原水と同一の原水（水質は前記表の
とおり）を対象として、フエントン酸化を行つ
た。鉄塩としては硫酸第１鉄（FeSO4）を採用
し、添加量は1000mg／（Fe2+として）一定と
し、過酸化水素（H2O2）の添加量を200〜1000
mg／の範囲で変化させCOD除去効果を調べ
た。またアルカリ剤としてはMg（OH）2を使用し
た。なお反応時のPHは最適PH3.5、反応時間は24
時間として、反応時間が不足しないようにした。
この結果を第３図曲線ｂを示す。
第３図からフエントン酸化法では、オゾン酸化
法よりはCODがよく除去されているが、41mg／
以下にすることはできないことがわかる。
なお、曲線ｂは残留H2O2でCODを補正した有
機物に起因するCODを示しているものである。
実施例
（本発明方法）
比較例１、２と同一の原水を対象として、ま
ず、オゾン酸化を後続するフエントン酸化後生成
した水酸化第２鉄（Fe（OH）3）を主体とするス
ラツジ約2000〜3000ppmの共有下でオゾン添加
量500mg／で行つたのち、フエントン酸化をオ
ゾン処理水に対して行つた。フエントン酸化は次
の条件で行つた。
Fe2+注入率 1000mg／
H2O2注入率 300mg／および500mg／
PH 3.5
反応時間 24時間
この結果を第４図に示す。
第４図と第３図ａの比較からFe（OH）3の触媒
効果が認められ、第３図ｂとの比較から、オゾン
処理を行つたのち、フエントン酸化すると、処理
水CODMoが10mg／にまで低下することが認め
られた。[Table] As a result of performing batch ozone aeration treatment in a bubble column using this coagulation-sedimentation treated water as raw water, the amount of ozone added (mgO 3 /) and the COD of the ozone oxidation treated water are shown in curve a in Figure 3. Although the chromaticity was completely removed, it was not possible to reduce the COD below 74 mg/. Comparative Example 2 (Conventional method: Fuenton method) The same raw water as the raw water in Comparative Example 1 (water quality is as shown in the table above) was subjected to Fuenton oxidation. Ferrous sulfate (FeSO 4 ) was used as the iron salt, the amount added was constant at 1000 mg/(as Fe 2+ ), and the amount of hydrogen peroxide (H 2 O 2 ) added was varied from 200 to 1000 mg/(as Fe 2+ ).
The COD removal effect was investigated by changing the amount in mg/. Moreover, Mg(OH) 2 was used as an alkali agent. The optimum pH during the reaction is 3.5, and the reaction time is 24
In terms of time, we made sure that reaction time would not be insufficient.
This result is shown as curve b in Figure 3. Figure 3 shows that the Fuenton oxidation method removes COD better than the ozone oxidation method, but only 41mg/
It turns out that you can't do the following. Note that the curve b shows the COD caused by organic matter, which is corrected using residual H 2 O 2 . Example (method of the present invention) Using the same raw water as in Comparative Examples 1 and 2, first, a sludge mainly consisting of ferric hydroxide (Fe(OH) 3 ) produced after Fenton oxidation followed by ozone oxidation was prepared. Fuenton oxidation was carried out on the ozonated water after the addition of 500 mg of ozone with a co-existence of 2000 to 3000 ppm. Fenton oxidation was performed under the following conditions. Fe 2+ injection rate 1000 mg/H 2 O 2 injection rate 300 mg/and 500 mg/PH 3.5 Reaction time 24 hours The results are shown in FIG. Comparison of Fig. 4 and Fig. 3a shows the catalytic effect of Fe(OH) 3 , and comparison with Fig. 3b shows that when Fuenton oxidation is performed after ozone treatment, the COD Mo of the treated water is 10mg/ It was observed that the temperature decreased to .
第１図は本発明方法の実施態様の系統説明図、
第２図は他の実施態様の系統説明図、第３図及び
第４図は処理水COD量と薬剤添加量の関係線図
で、第３図は従来法第４図は本発明法のものであ
る。
１……廃水、２……オゾン酸化塔、３……オゾ
ン含有ガス、４……管、５……撹拌槽、６……鉄
塩、７……過酸化水素、８……中和槽、９……ア
ルカリ剤、１０……高分子凝集剤、１１……沈澱
池、１２……処理水、１３……沈殿スラツジ、１
４，１４′……返送管、１５……酸、１６……鉱
酸、１７……排ガス、１８……撹拌槽。
FIG. 1 is a system explanatory diagram of an embodiment of the method of the present invention,
Figure 2 is a system explanatory diagram of another embodiment, Figures 3 and 4 are relationship diagrams between the amount of COD in treated water and the amount of chemical added, Figure 3 is for the conventional method, and Figure 4 is for the method of the present invention. It is. 1... Waste water, 2... Ozone oxidation tower, 3... Ozone-containing gas, 4... Pipe, 5... Stirring tank, 6... Iron salt, 7... Hydrogen peroxide, 8... Neutralization tank, 9... Alkaline agent, 10... Polymer flocculant, 11... Sedimentation tank, 12... Treated water, 13... Sedimentation sludge, 1
4, 14'... Return pipe, 15... Acid, 16... Mineral acid, 17... Exhaust gas, 18... Stirring tank.
Claims (1)
たのち、該オゾン処理水に金属イオンを水溶液中
で解離し得る物質と過酸化水素を添加撹拌したの
ち、アルカリ剤を添加し固液分離工程にて分離
し、該分離されたスラツジを前記オゾン処理工程
に添加して処理することを特徴とするCOD含有
廃水の処理方法。 ２ 前記オゾン処理水に鉱酸を添加したのち前記
過酸化水素を添加して処理する特許請求の範囲第
１項記載の処理方法。 ３ 前記オゾン処理工程における排オゾンを前記
過酸化水素とともに添加して処理する特許請求の
範囲第１項又は第２項記載の処理方法。 ４ 前記水溶液中で金属イオンを解離し得る物質
として鉄、アルミニウム、銅、ニツケル、マンガ
ン又はコバルトの塩、酸化物、水酸化物、単体金
属のうち少なくとも一つを使用する特許請求の範
囲第１項、第２項又は第３項記載の処理方法。 ５ 前記中和工程がアルカリ剤としてマグネシウ
ム系アルカリ剤又は炭酸カルシウムを使用するも
のである特許請求の範囲第１項、第２項、第３項
又は第４項記載の処理方法。 ６ 前記オゾン処理水の酸化工程がPH２〜４の酸
性条件下で行われるものである特許請求の範囲第
２項、第３項、第４項又は第５項記載の処理方
法。[Claims] 1. After treating COD-containing wastewater in an ozonation process, a substance capable of dissociating metal ions in an aqueous solution and hydrogen peroxide are added to the ozonated water and stirred, and then an alkali agent is added. A method for treating COD-containing wastewater, which comprises separating the sludge in a solid-liquid separation step and adding the separated sludge to the ozone treatment step. 2. The treatment method according to claim 1, wherein the ozonated water is treated by adding a mineral acid and then adding the hydrogen peroxide. 3. The treatment method according to claim 1 or 2, wherein exhaust ozone in the ozone treatment step is added together with the hydrogen peroxide. 4. Claim 1 in which at least one of iron, aluminum, copper, nickel, manganese, or cobalt salts, oxides, hydroxides, and elemental metals is used as the substance capable of dissociating metal ions in the aqueous solution. The treatment method described in Section 2, Section 2, or Section 3. 5. The treatment method according to claim 1, 2, 3, or 4, wherein the neutralization step uses a magnesium-based alkali agent or calcium carbonate as the alkali agent. 6. The treatment method according to claim 2, 3, 4, or 5, wherein the oxidation step of the ozonated water is performed under acidic conditions of pH 2 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9284480A JPS5719088A (en) | 1980-07-08 | 1980-07-08 | Disposal of cod-contng. waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9284480A JPS5719088A (en) | 1980-07-08 | 1980-07-08 | Disposal of cod-contng. waste water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5719088A JPS5719088A (en) | 1982-02-01 |
| JPS6211634B2 true JPS6211634B2 (en) | 1987-03-13 |
Family
ID=14065736
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9284480A Granted JPS5719088A (en) | 1980-07-08 | 1980-07-08 | Disposal of cod-contng. waste water |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5719088A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496077A (en) * | 2014-12-22 | 2015-04-08 | 同济大学 | Deep scrap iron catalytic ozonation wastewater treatment method |
| CN110156144A (en) * | 2018-03-30 | 2019-08-23 | 铜仁学院 | A method of strengthening ozone oxidation using ferrate and removes organic pollutants |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2699914B1 (en) * | 1992-12-28 | 1995-05-12 | Degremont | Reactor for optimized ozonation of water intended for human consumption. |
| BR9307833A (en) * | 1993-04-01 | 1996-02-06 | Solvay Interox Gmbh | Oxidative chemical process for purification of overloaded wastewater |
| DE19618074A1 (en) * | 1996-03-04 | 1997-09-11 | Ind Tech Res Inst | Waste liquor treatment to reduce chemical oxygen demand |
| CN102070263B (en) * | 2010-11-25 | 2012-07-04 | 杭州诚洁环保有限公司 | Coking phenol cyanogen sewage treating method |
| CN103979735B (en) * | 2014-05-21 | 2015-07-22 | 青岛中通臭氧科技有限公司 | Process and device for treating refractory industrial wastewater |
| CN105396590A (en) * | 2015-11-03 | 2016-03-16 | 同济大学 | Method for preparing ozonation catalyst by scrap iron surface modifying, and application of ozonation catalyst |
| CN106348560B (en) * | 2016-08-19 | 2019-03-15 | 陕西鼎益源投资有限公司 | A kind of ozone-hydroxyl radical free radical joint catalysis oxidation sludge conditioning method |
-
1980
- 1980-07-08 JP JP9284480A patent/JPS5719088A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496077A (en) * | 2014-12-22 | 2015-04-08 | 同济大学 | Deep scrap iron catalytic ozonation wastewater treatment method |
| CN110156144A (en) * | 2018-03-30 | 2019-08-23 | 铜仁学院 | A method of strengthening ozone oxidation using ferrate and removes organic pollutants |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5719088A (en) | 1982-02-01 |
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