JP6051560B2 - Treatment of formaldehyde-containing wastewater - Google Patents
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- JP6051560B2 JP6051560B2 JP2012077255A JP2012077255A JP6051560B2 JP 6051560 B2 JP6051560 B2 JP 6051560B2 JP 2012077255 A JP2012077255 A JP 2012077255A JP 2012077255 A JP2012077255 A JP 2012077255A JP 6051560 B2 JP6051560 B2 JP 6051560B2
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims description 166
- 239000002351 wastewater Substances 0.000 title claims description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 22
- 230000003647 oxidation Effects 0.000 claims description 20
- 238000007254 oxidation reaction Methods 0.000 claims description 20
- 239000012528 membrane Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 238000001223 reverse osmosis Methods 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 238000006114 decarboxylation reaction Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000005446 dissolved organic matter Substances 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
Description
本発明は、食品工場等で生じるホルムアルデヒド含有排水を逆浸透膜処理及び化学酸化処理により処理する方法に関する。 The present invention relates to a method for treating formaldehyde-containing wastewater generated in a food factory or the like by reverse osmosis membrane treatment and chemical oxidation treatment.
食品製造工場の容器洗浄排水や高圧殺菌窯（レトルト）からの冷却排水にホルムアルデヒドが含まれることがある（特許文献１）。 Formaldehyde may be contained in the cooling waste water from the container washing waste water and the high-pressure sterilization kiln (retort) in the food manufacturing factory (Patent Document 1).
特許文献１には、ホルムアルデヒド含有排水に過酸化水素を添加した後、活性炭と接触させ、ホルムアルデヒドを分解して除去することが記載されている。特許文献１の００２５段落には、過酸化水素が活性炭と接触すると、ヒドロキシラジカルが発生し、これによってホルムアルデヒドが分解、除去されると記載されている。 Patent Document 1 describes that after adding hydrogen peroxide to formaldehyde-containing wastewater, it is brought into contact with activated carbon to decompose and remove formaldehyde. In paragraph 0025 of Patent Document 1, it is described that when hydrogen peroxide comes into contact with activated carbon, hydroxy radicals are generated, thereby decomposing and removing formaldehyde.
特許文献２，３には、ホルムアルデヒド含有排水にアンモニアを添加してヘキサメチレンテトラミンを生成させた後、逆浸透膜分離処理してヘキサメチレンテトラミンを濃縮側に分離する方法が記載されている。 Patent Documents 2 and 3 describe a method in which ammonia is added to formaldehyde-containing wastewater to produce hexamethylenetetramine, and then a reverse osmosis membrane separation treatment is performed to separate hexamethylenetetramine to the concentration side.
上記特許文献１の方法では、ホルムアルデヒドが十分には除去されない。例えば特許文献１の実施例１，２ではホルムアルデヒド分解能は２０％又は４５％に止まる。 In the method of Patent Document 1, formaldehyde is not sufficiently removed. For example, in Examples 1 and 2 of Patent Document 1, the formaldehyde resolution is 20% or 45%.
特許文献２，３では、アンモニアを用いることが必要である。 In Patent Documents 2 and 3, it is necessary to use ammonia.
本発明は、上記従来の問題点を解決し、アンモニアを用いることなくホルムアルデヒドを十分に分解除去することができるホルムアルデヒド含有排水の処理法を提供することを目的とする。 An object of the present invention is to solve the above-described conventional problems and to provide a method for treating formaldehyde-containing wastewater that can sufficiently decompose and remove formaldehyde without using ammonia.
本発明のホルムアルデヒド含有排水の処理法は、食品工場の容器洗浄排水又はレトルト冷却排水であるホルムアルデヒド含有排水をｐＨ５．５以下の酸性下で脱炭酸処理した後、逆浸透膜分離処理する膜分離工程と、該膜分離工程からの、ホルムアルデヒド濃度０．５〜５ｍｇ／Ｌの分離処理水に、ｐＨ６〜７で、該分離処理水中のホルムアルデヒド１ｍｇ／Ｌ当り５〜１５ｍｇ／Ｌの過酸化水素を添加して１〜５ｋＷｋ／ｍ ３ のＵＶ照射量で紫外線を照射することによりホルムアルデヒドを酸化処理して、ホルムアルデヒド濃度０．００８ｍｇ／Ｌ未満の化学酸化処理水を得る化学酸化工程とを有する。 The treatment method of formaldehyde-containing wastewater of the present invention is a membrane separation step in which a formaldehyde-containing wastewater that is a container washing wastewater or a retort cooling wastewater in a food factory is decarboxylated under an acidity of pH 5.5 or less and then subjected to reverse osmosis membrane separation treatment. And 5 to 15 mg / L of hydrogen peroxide per 1 mg / L of formaldehyde in the separation-treated water at pH 6 to 7 to the separation-treated water having a formaldehyde concentration of 0.5 to 5 mg / L from the membrane separation step. by oxidizing the formaldehyde by irradiation with ultraviolet rays UV dose of 1~5kWk / m 3 and has a resulting Ru chemical oxidation step the chemical oxidation process water of less than formaldehyde concentrations 0.008 mg / L.
本発明では、ホルムアルデヒド含有排水を逆浸透膜処理した後、逆浸透膜を透過したホルムアルデヒドを化学酸化処理することにより、ホルムアルデヒドを十分に分解処理することができる。即ち、ホルムアルデヒド含有排水を逆浸透膜（ＲＯ）処理することにより、分子量の大きな溶存有機物が除去されるので、化学酸化工程で化学酸化剤がホルムアルデヒドの酸化に有効に利用され、ホルムアルデヒドが十分に化学酸化分解される。 In the present invention, after formaldehyde-containing wastewater is treated with a reverse osmosis membrane, the formaldehyde that has permeated through the reverse osmosis membrane is subjected to a chemical oxidation treatment, whereby the formaldehyde can be sufficiently decomposed. That is, formaldehyde-containing wastewater is treated with a reverse osmosis membrane (RO) to remove dissolved organic matter with a large molecular weight. Therefore, chemical oxidants are effectively used for the oxidation of formaldehyde in the chemical oxidation process, and formaldehyde is sufficiently chemically It is oxidatively decomposed.
また、ＲＯ処理によりＣｌ−、ＨＣＯ３ −などのＯＨラジカルのスカベンチャーイオンが除去されるので、化学酸化工程におけるホルムアルデヒドの分解効率が向上する。ホルムアルデヒド含有排水を脱炭酸した後、逆浸透膜処理することにより、逆浸透膜の被処理水中のＨＣＯ３ −イオン濃度が低下し、逆浸透膜処理の負荷が低下する。 Moreover, since scavenger ions of OH radicals such as Cl − and HCO 3 — are removed by the RO treatment, the decomposition efficiency of formaldehyde in the chemical oxidation process is improved. By performing the reverse osmosis membrane treatment after decarboxylation of the formaldehyde-containing wastewater, the HCO 3 − ion concentration in the water to be treated of the reverse osmosis membrane is reduced, and the load of the reverse osmosis membrane treatment is reduced.
化学酸化工程において、逆浸透膜処理水に過酸化水素を添加した後、紫外線（以下、ＵＶということがある。）を照射すると、ホルムアルデヒドが分解される。このホルムアルデヒド分解反応は、酸性下で効率よく進行する。上記の脱炭酸のために被処理水のｐＨを酸性としておくと、ＲＯ透過水も酸性となり、化学酸化工程においてホルムアルデヒドが過酸化水素及びＵＶにより効率よく分解される。 In the chemical oxidation step, after adding hydrogen peroxide to the reverse osmosis membrane treated water and irradiating with ultraviolet rays (hereinafter sometimes referred to as UV), formaldehyde is decomposed. This formaldehyde decomposition reaction proceeds efficiently under acidic conditions. If the pH of the water to be treated is made acidic for the above decarboxylation, the RO permeate becomes acidic and formaldehyde is efficiently decomposed by hydrogen peroxide and UV in the chemical oxidation step.
本発明において処理対象とするホルムアルデヒド含有排水としては、食品工場の容器洗浄排水や、レトルト冷却排水などが例示される。 Examples of the formaldehyde-containing wastewater to be treated in the present invention include container washing wastewater in a food factory, retort cooling wastewater, and the like.
本発明では、必要に応じ脱炭酸処理した後、ＲＯ処理する。 In the present invention, RO treatment is performed after decarboxylation treatment as necessary.
脱炭酸を行う場合、ホルムアルデヒド含有排水を塩酸を添加すること等によってｐＨ５．５以下例えば５〜５．５とし、膜脱気装置、脱炭酸塔、真空脱気装置などによって脱炭酸する。脱炭酸により被処理水のｐＨは約０．５〜１程度高くなるが、酸性である。 When decarboxylation is performed, the formaldehyde-containing wastewater is adjusted to pH 5.5 or less, for example, 5 to 5.5 by adding hydrochloric acid or the like, and decarboxylated using a membrane degassing apparatus, a decarboxylation tower, a vacuum degassing apparatus, or the like. Decarboxylation increases the pH of the water to be treated by about 0.5 to 1, but it is acidic.
ホルムアルデヒド含有排水をそのまま又は上記脱炭酸処理した後、ＲＯ装置（逆浸透膜分離装置）に通水してＲＯ処理し、各種イオンのほか、分子量の大きい溶解性有機物質を除去する。ホルムアルデヒドや、尿素、メタノール、エタノール等の低分子量有機物はＲＯ膜を透過する。 After the formaldehyde-containing wastewater is treated as it is or after decarboxylation, it is passed through an RO device (reverse osmosis membrane separation device) and subjected to RO treatment to remove various ions and soluble organic substances having a large molecular weight. Low molecular weight organic substances such as formaldehyde, urea, methanol, and ethanol permeate the RO membrane.
そこで、このＲＯ処理水を化学酸化処理してホルムアルデヒドや残存有機物を酸化処理する。化学酸化処理方法としては、オゾン及び過酸化水素を添加する方法、過酸化水素を添加してＵＶ照射する方法、又はこれらを併用する方法が好適である。 Therefore, this RO-treated water is chemically oxidized to oxidize formaldehyde and residual organic matter. As the chemical oxidation treatment method, a method in which ozone and hydrogen peroxide are added, a method in which hydrogen peroxide is added and UV irradiation is performed, or a method in which these are used in combination is suitable.
過酸化水素及びオゾンによる化学酸化処理を行う場合、ＲＯ処理水中のホルムアルデヒド濃度は０．５ｍｇ／Ｌ以上、特に２ｍｇ／Ｌ以上例えば２〜５ｍｇ／Ｌ程度であることが好ましい。 When performing the chemical oxidation treatment with hydrogen peroxide and ozone, the formaldehyde concentration in the RO-treated water is preferably 0.5 mg / L or more, particularly 2 mg / L or more, for example, about 2 to 5 mg / L.
オゾンの吹込量はＲＯ処理水中のホルムアルデヒド濃度１ｍｇ／Ｌ当り１０〜２０ｍｇ／Ｌ特に１０〜１５ｍｇ／Ｌ程度が好ましい。過酸化水素の添加量は、［オゾン吹込量（ｍｇ／Ｌ）］／［過酸化水素添加量（ｍｇ／Ｌ）］が１〜１５特に２〜１０とりわけ５〜８程度となる量が好ましい。 The amount of ozone blown is preferably about 10 to 20 mg / L, especially about 10 to 15 mg / L per 1 mg / L of formaldehyde concentration in the RO-treated water. The amount of hydrogen peroxide added is preferably such that [ozone blowing amount (mg / L)] / [hydrogen peroxide added amount (mg / L)] is 1 to 15, particularly 2 to 10, especially about 5 to 8.
このオゾン及び過酸化水素によるホルムアルデヒド分解時のｐＨは８〜１１特に９〜１０程度であることが好ましく、このｐＨ範囲とすることによりホルムアルデヒドの分解が効率よく進行する。ｐＨ調整のために必要に応じＮａＯＨ及び／又はＫＯＨを添加することが好ましい。 The pH at the time of decomposition of formaldehyde with ozone and hydrogen peroxide is preferably about 8 to 11, particularly about 9 to 10. By setting the pH within this range, decomposition of formaldehyde proceeds efficiently. It is preferable to add NaOH and / or KOH as needed for pH adjustment.
化学酸化処理を過酸化水素添加およびＵＶ照射により行う場合、過酸化水素添加量は、ホルムアルデヒド１ｍｇ／Ｌ当り５〜１５ｍｇ／Ｌ特に６〜１０ｍｇ／Ｌ程度とすることが好ましい。ＵＶ照射量は１ｋＷｈ／ｍ３以上例えば１〜５ｋＷｈ／ｍ３特に２〜３ｋＷｈ／ｍ３程度が好ましい。 When the chemical oxidation treatment is performed by addition of hydrogen peroxide and UV irradiation, the amount of hydrogen peroxide added is preferably about 5 to 15 mg / L, especially about 6 to 10 mg / L per 1 mg / L of formaldehyde. UV irradiation dose is 1 kWh / m 3 or more for example 1~5kWh / m 3, especially 2~3kWh / m about 3 are preferred.
このときのｐＨは７以下例えば４〜７特に６〜７であることが好ましい。上述の通り、酸性下で脱炭酸された脱炭酸処理水は、ＲＯ処理後でも酸性となっているので、この過酸化水素ＵＶ処理に供するのに好適である。 The pH at this time is preferably 7 or less, for example, 4 to 7, particularly 6 to 7. As described above, the decarboxylated water decarboxylated under acidity is acidic even after the RO treatment, and is suitable for use in this hydrogen peroxide UV treatment.
本発明では、ＲＯ処理水を上記オゾン及び過酸化水素による第１化学酸化工程により、ホルムアルデヒド濃度が０．５ｍｇ／Ｌ以下特に０．４ｍｇ／Ｌ以下となるまでホルムアルデヒドを分解した後、過酸化水素添加ＵＶ照射による第２化学酸化工程を行ってもよい。 In the present invention, after the formaldehyde is decomposed in the RO-treated water in the first chemical oxidation step using ozone and hydrogen peroxide until the formaldehyde concentration is 0.5 mg / L or less, particularly 0.4 mg / L or less, You may perform the 2nd chemical oxidation process by addition UV irradiation.
本発明では、ＲＯ処理により溶存有機物濃度が低くなっていると共に、ＯＨラジカルスカベンジャーであるＣｌ−，ＨＣＯ３ −等が除去されたＲＯ処理水を化学酸化工程に供給するので、化学酸化工程においてホルムアルデヒドが効率よく酸化分解される。 In the present invention, the dissolved organic matter concentration is lowered by the RO treatment, and the RO treated water from which Cl − , HCO 3 —, etc., which are OH radical scavengers are removed, is supplied to the chemical oxidation step. Is efficiently oxidized and decomposed.
［参考例１（ＲＯ＋Ｏ３／Ｈ２Ｏ２処理）］
水道水にホルムアルデヒドを１ｍｇ／Ｌ ａｓ ＨＣＨＯとなるように添加し、ｐＨ６のホルムアルデヒド含有模擬排水を調製した。
[ Reference Example 1 (RO + O 3 / H 2 O 2 treatment)]
Formaldehyde was added to tap water to 1 mg / L as HCHO to prepare a pH 6 formaldehyde-containing simulated waste water.
この模擬排水を前段のＲＯ装置（日東電工製ＥＳ−２０−Ｄ２）と後段のＯ３／Ｈ２Ｏ２化学酸化処理装置として連続通水する試験を行った。まずＲＯ装置に７５Ｌ／ｈで通水し、回収率８０％にて透過水を得た。このＲＯ処理水のホルムアルデヒド濃度は０．８２ｍｇ／Ｌであった。 A test was conducted in which this simulated waste water was continuously passed as an upstream RO device (ES-20-D2 manufactured by Nitto Denko) and an O 3 / H 2 O 2 chemical oxidation treatment device at the subsequent stage. First, water was passed through the RO device at 75 L / h, and permeated water was obtained at a recovery rate of 80%. The formaldehyde concentration of this RO-treated water was 0.82 mg / L.
このＲＯ処理水に過酸化水素を２ｍｇ／Ｌとなるよう添加し、さらにＮａＯＨを添加してｐＨ９に調整した後、化学酸化処理装置に供給し、室温（約２０℃）でオゾンを０．７５ｇ／ｈの吹込量で吹き込み、処理後のホルムアルデヒド濃度を測定したところ、０．０１ｍｇ／Ｌであり、ホルムアルデヒド濃度が大幅に低下したことが認められた。 Hydrogen peroxide is added to this RO-treated water to 2 mg / L, and NaOH is further added to adjust the pH to 9, then supplied to a chemical oxidation treatment apparatus and 0.75 g of ozone at room temperature (about 20 ° C.). When the formaldehyde concentration after measurement was measured by blowing with a blowing amount of / h, it was found to be 0.01 mg / L, indicating that the formaldehyde concentration was greatly reduced.
［比較例１］
参考例１において、模擬排水をＲＯ処理なしに化学酸化処理したところ、化学酸化処理水中のホルムアルデヒド濃度は０．１ｍｇ／Ｌと参考例１よりも著しく高い値であった。
[Comparative Example 1]
In Reference Example 1, when the simulated waste water was chemically oxidized without RO treatment, the formaldehyde concentration in the chemically oxidized water was 0.1 mg / L, which was significantly higher than Reference Example 1.
［比較例２］
比較例１において、過酸化水素添加量を７．５ｇ／Ｌ、オゾン吹込量を２．８ｇ／ｈと多くしたが、化学酸化処理水中のホルムアルデヒド濃度は０．０８ｍｇ／Ｌと高い値であった。
[Comparative Example 2]
In Comparative Example 1, the hydrogen peroxide addition amount was increased to 7.5 g / L and the ozone blowing amount was increased to 2.8 g / h, but the formaldehyde concentration in the chemically oxidized water was as high as 0.08 mg / L. .
［実施例２（ＲＯ＋Ｈ２Ｏ２／ＵＶ）］
実施例１において、化学酸化処理を過酸化水素８ｍｇ／Ｌ添加、ＵＶ照射処理１ｋＷｈで通水としたこと以外は同様とした。その結果、化学酸化処理水中のホルムアルデヒド濃度は０．０１５ｍｇ／Ｌであった。
[Example 2 (RO + H 2 O 2 / UV)]
In Example 1, the chemical oxidation treatment was the same except that 8 mg / L of hydrogen peroxide was added and water was passed by 1 kWh of UV irradiation treatment. As a result, the formaldehyde concentration in the chemically oxidized water was 0.015 mg / L.
［実施例３（脱炭酸＋ＲＯ＋Ｈ２Ｏ２／ＵＶ）］
実施例２において、ホルムアルデヒド含有模擬排水を塩酸によりｐＨ５．５とし、脱炭酸塔に通水して脱炭酸処理した。この脱炭酸処理水（ｐＨ＝６）をＲＯ装置に給水したこと以外は同様とした。その結果、化学酸化処理水中のホルムアルデヒド濃度は０．００８ｍｇ／Ｌ未満と著しく低い値であった。
[Example 3 (decarboxylation + RO + H 2 O 2 / UV)]
In Example 2, the formaldehyde-containing simulated waste water was adjusted to pH 5.5 with hydrochloric acid and passed through a decarbonation tower for decarboxylation treatment. It was the same except that this decarboxylated water (pH = 6) was supplied to the RO device. As a result, the formaldehyde concentration in the chemically oxidized treated water was a remarkably low value of less than 0.008 mg / L.
Claims (1)
該膜分離工程からの、ホルムアルデヒド濃度０．５〜５ｍｇ／Ｌの分離処理水に、ｐＨ６〜７で、該分離処理水中のホルムアルデヒド１ｍｇ／Ｌ当り５〜１５ｍｇ／Ｌの過酸化水素を添加して１〜５ｋＷｋ／ｍ ３ のＵＶ照射量で紫外線を照射することによりホルムアルデヒドを酸化処理して、ホルムアルデヒド濃度０．００８ｍｇ／Ｌ未満の化学酸化処理水を得る化学酸化工程と
を有するホルムアルデヒド含有排水の処理法。 A membrane separation step of performing reverse osmosis membrane separation treatment after decarboxylation treatment of formaldehyde-containing wastewater which is container washing wastewater or retort cooling wastewater at pH 5.5 or lower,
From the membrane separation step, 5 to 15 mg / L hydrogen peroxide per 1 mg / L of formaldehyde in the separation-treated water was added at pH 6 to 7 to the separation-treated water having a formaldehyde concentration of 0.5 to 5 mg / L. by oxidizing the formaldehyde by irradiation with ultraviolet rays UV dose of 1~5kWk / m 3, formaldehyde-containing waste water and a resulting Ru chemical oxidation step the chemical oxidation process water of less than formaldehyde concentrations 0.008 mg / L Processing method.
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