JP5348297B1 - Method and apparatus for treating formaldehyde-containing wastewater - Google Patents
Method and apparatus for treating formaldehyde-containing wastewater Download PDFInfo
- Publication number
- JP5348297B1 JP5348297B1 JP2012187805A JP2012187805A JP5348297B1 JP 5348297 B1 JP5348297 B1 JP 5348297B1 JP 2012187805 A JP2012187805 A JP 2012187805A JP 2012187805 A JP2012187805 A JP 2012187805A JP 5348297 B1 JP5348297 B1 JP 5348297B1
- Authority
- JP
- Japan
- Prior art keywords
- formaldehyde
- sulfite
- water
- reverse osmosis
- wastewater
- 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.)
- Active
Links
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 328
- 239000002351 wastewater Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000011282 treatment Methods 0.000 claims abstract description 46
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000012528 membrane Substances 0.000 claims abstract description 29
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 26
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims abstract 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract 2
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 10
- 229910021529 ammonia Inorganic materials 0.000 abstract description 5
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 239000008399 tap water Substances 0.000 description 9
- 235000020679 tap water Nutrition 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- DETXZQGDWUJKMO-UHFFFAOYSA-N alpha-hydroxymethanesulfonic acid Natural products OCS(O)(=O)=O DETXZQGDWUJKMO-UHFFFAOYSA-N 0.000 description 3
- 235000013361 beverage Nutrition 0.000 description 3
- 239000004312 hexamethylene tetramine Substances 0.000 description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 3
- DETXZQGDWUJKMO-UHFFFAOYSA-M hydroxymethanesulfonate Chemical compound OCS([O-])(=O)=O DETXZQGDWUJKMO-UHFFFAOYSA-M 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 sulphite ion Chemical class 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Images
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
【課題】アンモニアを用いることなく、ホルムアルデヒドを高除去率にて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方法および処理装置を提供する。
【解決手段】ホルムアルデヒド含有排水に亜硫酸塩を添加して逆浸透膜処理する工程を複数回行うホルムアルデヒド含有排水の処理方法。亜硫酸塩を添加する添加装置と、該添加装置によって亜硫酸塩が添加された水を逆浸透膜処理する逆浸透膜装置とからなる処理手段が直列に複数段設置されているホルムアルデヒド含有排水の処理装置。亜硫酸塩としては亜硫酸ナトリウム及び／又は亜硫酸水素ナトリウムが好適である。
【選択図】図１Disclosed is a formaldehyde-containing wastewater treatment method and treatment apparatus capable of removing formaldehyde at a high removal rate without using ammonia.
A method for treating formaldehyde-containing wastewater, wherein a step of adding reverse osmosis membrane by adding sulfite to formaldehyde-containing wastewater is performed a plurality of times. An apparatus for treating formaldehyde-containing wastewater in which a plurality of treatment means are installed in series, each of which includes an addition device for adding sulfite and a reverse osmosis membrane device for treating water to which sulfite has been added by the addition device. . As the sulfite, sodium sulfite and / or sodium hydrogen sulfite is preferable.
[Selection] Figure 1
Description
本発明は、ホルムアルデヒド含有排水の処理方法及び処理装置に係り、特にホルムアルデヒド含有排水に亜硫酸塩を添加して逆浸透膜処理することにより、ホルムアルデヒドを除去する方法及び装置に関する。 The present invention relates to a method and apparatus for treating formaldehyde-containing wastewater, and more particularly, to a method and apparatus for removing formaldehyde by adding sulfite to formaldehyde-containing wastewater and treating it with a reverse osmosis membrane.
食品工場や飲料工場の容器洗浄工程、高圧殺菌（レトルト）工程、ホルムアルデヒドを原料とするフェノール樹脂等の樹脂や薬剤の製造工程等から、ホルムアルデヒド含有排水が排出されることがある。 Formaldehyde-containing wastewater may be discharged from a container washing process, a high-pressure sterilization (retort) process in a food factory or a beverage factory, a manufacturing process of a resin such as a phenol resin using formaldehyde as a raw material, or a drug.
ホルムアルデヒド含有排水の処理方法として、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、生じたヒドロキシラジカルによってホルムアルデヒドを分解除去する方法が記載されている。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分離する方法が記載されている。
As a method for treating formaldehyde-containing wastewater, Patent Document 1 describes a method in which hydrogen peroxide is added to formaldehyde-containing wastewater, and then contacted with activated carbon, and formaldehyde is decomposed and removed by generated hydroxyl radicals.
なお、熱水式のレトルト処理では、レトルト釜に水道水（１０〜２５℃）を供給して加圧下に１２０℃程度まで昇温して飲料缶などを高圧高温殺菌（レトルト処理）し、その後、徐々に冷却して５０〜８０℃程度（６０〜７０℃程度）まで温度が下がった後、レトルト釜から排水して、総合排水処理を行うなどした後に放流する。 In the hot water type retort treatment, tap water (10 to 25 ° C.) is supplied to the retort kettle, and the temperature is raised to about 120 ° C. under pressure to sterilize beverage cans and the like at high pressure and high temperature (retort treatment). After gradually cooling to a temperature of about 50 to 80 ° C. (about 60 to 70 ° C.), the water is drained from the retort kettle and discharged after being subjected to a comprehensive drainage treatment.
このレトルト排水は、高温であるため、水道水（通常は１０〜２５℃）を昇温するよりもレトルト排水（５０〜８０℃）を昇温する方がエネルギー効率が良いので、レトルト排水を回収し、再利用することが望まれている。 Since this retort drainage is hot, it is more energy efficient to raise the retort drainage (50 to 80 ° C) than to raise the tap water (usually 10 to 25 ° C). However, it is desired to be reused.
しかし、レトルト排水の回収再利用には以下の技術的課題がある。
（１）回収水を容器洗浄排水やレトルト排水に再利用するときは安全のため水道法の水質基準を満たす水質とする。レトルト排水を単に循環利用すると高温で水分蒸発量が多いことから微量不純物が徐々に濃縮されていく。また、ホルムアルデヒド（ＨＣＨＯ）は水への溶解性が高いため、空気中のＨＣＨＯがレトルト排水に取り込まれやすいと推測され、そのまま無処理で循環運転し続けると０．５〜３ｐｐｍ程度まで濃縮される恐れもあると考えられる。近年、水道法の水質基準が改定され、ホルムアルデヒドも監視項目に加えられて水道水の水質基準８０ｐｐｂ（８０μｇ／Ｌ）となったため、レトルト排水を回収したときは予めホルムアルデヒドを除去してから再利用することが望ましい。
（２）もともとレトルトには水道水を使用しているので水道水由来の緩衝性物質（炭酸ソーダなど）が含まれておりｐＨ調整が困難か又はｐＨ調整剤の必要量が多くなる恐れがある。
However, recovery and reuse of retort wastewater has the following technical problems.
(1) When the recovered water is reused for container washing drainage or retort drainage, it shall be water quality that meets the water quality standards of the Waterworks Act for safety. If the retort wastewater is simply recycled, trace impurities are gradually concentrated because the amount of water evaporation is high at high temperatures. In addition, since formaldehyde (HCHO) is highly soluble in water, it is presumed that HCHO in the air is likely to be taken into retort wastewater, and if it is continuously circulated without treatment, it is concentrated to about 0.5 to 3 ppm. There seems to be fear. In recent years, the water quality standards of the Water Supply Law have been revised, and formaldehyde has been added to the monitoring items to 80 ppb (80 μg / L), so when retort wastewater is collected, it is reused after removing formaldehyde in advance. It is desirable to do.
(2) Since tap water is originally used in retort, buffer substances (sodium carbonate, etc.) derived from tap water are included, and pH adjustment is difficult or the required amount of pH adjuster may increase. .
以上のことから、レトルト排水を回収して、なるべくｐＨ調整を行わずに、ＨＣＨＯを確実に水道水水質基準以下まで除去して、レトルト処理や工業用水への再利用を可能にすることが望まれている。 Based on the above, it is hoped that the retort wastewater will be collected and HCHO will be reliably removed to below the tap water quality standard without any pH adjustment so that it can be reused for retort treatment and industrial water. It is rare.
なお、ＨＣＨＯ除去として促進酸化が考えられるが、原水中のＨＣＨＯのすべてを促進酸化によって除去する場合、装置コストが高く実用的ではない。 Although accelerated oxidation can be considered as HCHO removal, when all of HCHO in raw water is removed by accelerated oxidation, the apparatus cost is high and impractical.
特許文献１では、ホルムアルデヒドが十分に除去されない。例えば、特許文献１の実施例１，２では、ホルムアルデヒド濃度２ｐｐｍのホルムアルデヒド含有排水に過酸化水素を１００ｐｐｍ注入し、活性炭充填カラムにＳＶ＝２０ｈ−１又は１０ｈ−１にて通水しているが、ホルムアルデヒドの分解能は２０％または４５％に止まる。
In Patent Document 1, formaldehyde is not sufficiently removed. For example, in Examples 1 and 2 of
特許文献２，３は、刺激臭を有し、劇物でもあるアンモニアを用いる事が必要である。
In
本発明は、アンモニアを用いることなく、ホルムアルデヒドを高除去率にて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方法および装置を提供することを目的とする。 An object of this invention is to provide the processing method and apparatus of formaldehyde containing waste water which can remove formaldehyde with a high removal rate, without using ammonia.
本発明のホルムアルデヒド含有排水の処理方法は、ホルムアルデヒド含有排水を処理する方法であって、該ホルムアルデヒド含有排水のホルムアルデヒド濃度が０．０８〜１０ｍｇ／Ｌであり、亜硫酸塩を添加して逆浸透膜処理する工程を複数回行い、第１回目の前記工程では、亜硫酸塩イオン濃度と当該工程の被処理水中のホルムアルデヒド濃度との重量比［ＳＯ ３ ］／［ＨＣＨＯ］が３〜１０となるように亜硫酸塩を添加し、第２回目以降の前記工程では、この比が４〜１０となるように亜硫酸塩を添加し、第１回目の前記重量比［ＳＯ ３ ］／［ＨＣＨＯ］が、第２回目の該比よりも小さいことを特徴とするものである。 The method for treating formaldehyde-containing wastewater according to the present invention is a method for treating formaldehyde-containing wastewater , wherein the formaldehyde-containing wastewater has a formaldehyde concentration of 0.08 to 10 mg / L, and sulfite is added to perform reverse osmosis membrane treatment. a have multiple rows steps, in the first round of the process, such that the weight ratio of the treated formaldehyde concentration in water of sulphite ion concentration and the step [sO 3] / [HCHO] is 3 to 10 Sulphite is added, and in the second and subsequent steps, sulfite is added so that this ratio is 4 to 10, and the weight ratio [SO 3 ] / [HCHO] is It is characterized by being smaller than the ratio of the second time .
本発明のホルムアルデヒド含有排水の処理装置は、ホルムアルデヒド含有排水を処理する装置であって、該ホルムアルデヒド含有排水のホルムアルデヒド濃度が０．０８〜１０ｍｇ／Ｌであり、亜硫酸塩を添加する添加装置と、該添加装置によって亜硫酸塩が添加された水を逆浸透膜処理する逆浸透膜装置とからなる処理手段が直列に複数段設置されており、第１段目の処理手段では、亜硫酸塩イオン濃度と当該処理手段の逆浸透膜装置の被処理水中のホルムアルデヒド濃度との重量比［ＳＯ ３ ］／［ＨＣＨＯ］が３〜１０となるように亜硫酸塩が添加され、第２段目以降の処理手段の逆浸透膜装置では、この比が４〜１０となるように亜硫酸塩が添加され、第１段目の前記重量比［ＳＯ ３ ］／［ＨＣＨＯ］が、第２段目の該比よりも小さいことを特徴とするものである。 The formaldehyde-containing wastewater treatment apparatus of the present invention is an apparatus for treating formaldehyde-containing wastewater , wherein the formaldehyde concentration of the formaldehyde-containing wastewater is 0.08 to 10 mg / L, and an addition device for adding sulfite, The treatment means comprising a reverse osmosis membrane device for treating the water added with sulfite by the addition device with a reverse osmosis membrane device is installed in a plurality of stages in series . In the first stage treatment means, the sulfite ion concentration and The sulfite is added so that the weight ratio [SO 3 ] / [HCHO] to the formaldehyde concentration in the treated water of the reverse osmosis membrane device of the treatment means is 3 to 10, and the reverse of the treatment means in the second and subsequent stages. In the osmotic membrane device, sulfite is added so that this ratio is 4 to 10, and the weight ratio [SO 3 ] / [HCHO] in the first stage is smaller than the ratio in the second stage. It is characterized in that the decoction.
ホルムアルデヒド含有排水に亜硫酸塩を添加すると、ヒドロキシメタンスルホン酸塩が生成する。このヒドロキシメタンスルホン酸塩は、ホルムアルデヒドに比べて分子量が４倍以上大きく、また、イオン半径も大きい為、逆浸透膜によって分離され易くなる。この逆浸透膜処理により、ホルムアルデヒドの大半が除去される。この亜硫酸塩添加及び逆浸透膜処理を複数回行うことにより、ホルムアルデヒドが十分に除去される。 When sulfite is added to formaldehyde-containing wastewater, hydroxymethanesulfonate is formed. This hydroxymethane sulfonate has a molecular weight that is four times or more larger than that of formaldehyde and has a large ionic radius, so that it is easily separated by a reverse osmosis membrane. This reverse osmosis membrane treatment removes most of the formaldehyde. By performing this sulfite addition and reverse osmosis membrane treatment a plurality of times, formaldehyde is sufficiently removed.
本発明では亜硫酸塩を使用するが、この亜硫酸塩はアンモニアに比べ取り扱いが極めて容易である。 In the present invention, sulfite is used, but this sulfite is very easy to handle compared to ammonia.
以下、本発明についてさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail.
本発明では、ホルムアルデヒド含有排水を、亜硫酸塩添加及び逆浸透膜処理よりなるホルムアルデヒド除去処理を複数回行う。このホルムアルデヒド除去処理の回数は、原水水質、目標とするホルムアルデヒド除去率（又は目標水質）等に応じて設定すればよいが、通常は２〜４特に２〜３が好適である。 In the present invention, the formaldehyde-containing wastewater is subjected to a formaldehyde removal treatment consisting of sulfite addition and reverse osmosis membrane treatment a plurality of times. The number of formaldehyde removal treatments may be set according to the quality of raw water, the target formaldehyde removal rate (or target water quality), etc., but usually 2 to 4, particularly 2 to 3, are suitable.
本発明で処理対象とするホルムアルデヒド含有排水としては、食品工場や飲料工場の容器洗浄工程や高圧殺菌（レトルト）工程からの排水のほか、ホルムアルデヒド製造工程排水、ホルムアルデヒドを原料とするフェノール樹脂、尿素樹脂、メラミン樹脂、ポリアセタール樹脂、ビニロン、ヘキサメチレンテトラミン、ペンタエリトリシド、パラホルムアルデヒド、界面活性剤、農薬、消毒剤、防腐剤等の製造工程からの排水が例示されるが、これらに限定されない。 Formaldehyde-containing wastewater to be treated in the present invention includes wastewater from the container washing process and high-pressure sterilization (retort) process of food factories and beverage factories, formaldehyde production process wastewater, phenolic resin made from formaldehyde, urea resin Examples include, but are not limited to, effluent from manufacturing processes such as melamine resin, polyacetal resin, vinylon, hexamethylenetetramine, pentaerythriside, paraformaldehyde, surfactant, agricultural chemical, disinfectant, and preservative.
第１回目のホルムアルデヒド除去処理の対象となるホルムアルデヒド含有排水中のホルムアルデヒド濃度は、０．０８〜１０ｍｇ／Ｌ、特に０．０８〜５ｍｇ／Ｌ程度である。 The formaldehyde concentration in the formaldehyde-containing wastewater subject to the first formaldehyde removal treatment is 0 . 08~10mg / L, Ru especially 0.08~5mg / L about Der.
第１回目及び第２回目以降のホルムアルデヒド除去処理工程において、逆浸透膜処理される水のｐＨは、特に限定されるものではないが、４〜８．６特に５〜８程度が望ましい。 In the first and second and subsequent formaldehyde removal treatment steps, the pH of the water subjected to the reverse osmosis membrane treatment is not particularly limited, but is preferably about 4 to 8.6, particularly about 5 to 8.
亜硫酸塩としては、Ｎａ２ＳＯ３及び／又はＮａＨＳＯ３などが好適である。 As the sulfite, Na 2 SO 3 and / or NaHSO 3 are suitable.
亜硫酸塩の添加量は、第１回目及び第２回目以降のホルムアルデヒド除去処理の対象となる被処理水中のホルムアルデヒド濃度以上となる量であることが好ましく、特に亜硫酸イオンとホルムアルデヒドとの重量濃度比（［ＳＯ３］／［ＨＣＨＯ］）が、第１回目のホルムアルデヒド除去処理では、３〜１０望ましくは５〜８となる。第２回目以降のホルムアルデヒド除去処理では、この比が４〜１０望ましくは５〜８となる。この比が上記範囲よりも小さいとヒドロキシメタンスルホン酸塩の生成が少なく、ホルムアルデヒドの除去効率が低くなるおそれがある。また、この比が上記範囲よりも大きいと、亜硫酸塩が過剰となり、コスト高となる。なお、第１回目のホルムアルデヒド除去処理はホルムアルデヒドを粗取りすればよいため、第２回目のホルムアルデヒド除去処理よりも上記比が小さい。 The amount of sulfite added is preferably an amount that is equal to or higher than the formaldehyde concentration in the water to be treated for the first and second and subsequent formaldehyde removal treatments, and in particular, the weight concentration ratio of sulfite ions to formaldehyde ( [SO 3] / [HCHO] ) is, in the first round of formaldehyde removal process, 3-10 preferably 5-8 and that Do. The formaldehyde removal process of the second and subsequent times, that Do this ratio is 4-10 preferably 5-8. When this ratio is smaller than the above range, the production of hydroxymethanesulfonate is small, and the removal efficiency of formaldehyde may be lowered. Moreover, when this ratio is larger than the said range, a sulfite will become excess and it will become high-cost. The first round of formaldehyde removal process since it is sufficient to take the crude formaldehyde, the ratio is less than the second formaldehyde removal process.
第１回目及び第２回目以降のホルムアルデヒド除去処理のいずれにおいても、被処理水に亜硫酸塩を添加した後、直ちに逆浸透膜（以下、ＲＯということがある。）処理してもよく、所定時間経過後、ＲＯ処理してもよい。 In any of the first and second and subsequent formaldehyde removal treatments, a reverse osmosis membrane (hereinafter sometimes referred to as RO) treatment may be performed immediately after adding sulfite to the water to be treated, for a predetermined time. You may perform RO process after progress.
ＲＯ装置のＲＯ膜としては、食塩排除率９９％以上のものが好ましい。また、被処理水の温度が５０〜８０℃の程度の高温になることがあるため、ＲＯ膜としては５０〜８０℃以上の耐熱性を有するものが好ましい。 The RO membrane of the RO device is preferably a salt rejection rate of 99% or more. Moreover, since the temperature of to-be-processed water may become a high temperature about 50-80 degreeC, what has heat resistance of 50-80 degreeC or more is preferable as RO membrane.
最終段のホルムアルデヒド除去処理水中の亜硫酸塩濃度は１ｍｇ／Ｌ以下特に０．５ｍｇ／Ｌ以下が望ましい。 The concentration of sulfite in the final-stage formaldehyde-removed water is preferably 1 mg / L or less, particularly 0.5 mg / L or less.
本発明では、ホルムアルデヒド除去処理を複数回行うことにより、ホルムアルデヒドを高除去率にて除去することができる。例えば、１回のホルムアルデヒド除去処理のホルムアルデヒド除去率が約９０％である場合、ホルムアルデヒド除去処理を２回行うことにより、原水中のホルムアルデヒドの約９９％を除去することができる。 In the present invention, formaldehyde can be removed at a high removal rate by performing the formaldehyde removal treatment a plurality of times. For example, when the formaldehyde removal rate of one formaldehyde removal treatment is about 90%, about 99% of formaldehyde in the raw water can be removed by performing the formaldehyde removal treatment twice.
本発明では、複数回のホルムアルデヒド除去処理後の処理水をさらに別の手段で浄化処理してもよい。例えば、複数回のホルムアルデヒド除去処理後の処理水を過酸化水素及び／又はオゾンによって処理したり、紫外線照射によって処理してもよい。また、複数回のホルムアルデヒド除去処理後の処理水を促進酸化処理してもよい。促進酸化処理としては、過酸化水素を添加し、次いで紫外線照射するか又はオゾンを添加するのが好ましい。これにより、ホルムアルデヒドがさらに高度に除去される。なお、これらの酸化処理により、処理水中の残留亜硫酸イオンが硫酸イオンに酸化される。 In the present invention, the treated water after a plurality of formaldehyde removal treatments may be purified by another means. For example, the treated water after a plurality of formaldehyde removal treatments may be treated with hydrogen peroxide and / or ozone, or may be treated by ultraviolet irradiation. In addition, the treated water after the multiple formaldehyde removal treatments may be subjected to accelerated oxidation treatment. As the accelerated oxidation treatment, it is preferable to add hydrogen peroxide and then irradiate with ultraviolet rays or add ozone. This further removes formaldehyde to a higher degree. By these oxidation treatments, residual sulfite ions in the treated water are oxidized to sulfate ions.
図１は、本発明のホルムアルデヒド含有排水処理装置の一例を示すフロー図である。 FIG. 1 is a flowchart showing an example of a formaldehyde-containing wastewater treatment apparatus of the present invention.
被処理原水（ホルムアルデヒド含有排水）は、ポンプ１を経て混合器２へ送られ、亜硫酸塩溶液と混合される。亜硫酸塩溶液は、タンク３からポンプ４を経て混合器２へ供給される。混合器２で亜硫酸塩溶液が添加及び混合された被処理水は、ＲＯ装置５でＲＯ処理され、透過水が貯槽６へ導入される。貯槽６内のＲＯ処理水は、ポンプ１’を経て混合器２’へ送られ、亜硫酸塩溶液と混合される。亜硫酸塩溶液は、タンク３’からポンプ４’を経て混合器２’へ供給される。混合器２’で亜硫酸塩溶液が添加及び混合された被処理水は、ＲＯ装置５’でＲＯ処理され、透過水が処理水として取り出される。
The raw water to be treated (formaldehyde-containing wastewater) is sent to the
図１では、亜硫酸塩溶液添加装置（タンク３，３’、ポンプ４，４’、混合器２，２’）とＲＯ装置５，５’とからなるホルムアルデヒド除去手段が２段設置されているが、３段以上設置されてもよい。ホルムアルデヒド除去手段をｋ段（ｋは３以上）設置した場合、ｋ段目のホルムアルデヒド除去手段では、（ｋ−１）段のホルムアルデヒド除去手段からの処理水を処理する。
In FIG. 1, two stages of formaldehyde removing means are installed, each comprising a sulfite solution addition device (
なお、図１のいずれにおいても、ＲＯ装置５の濃縮水は原水に戻すか、又は好気性生物処理又は嫌気性生物処理によって処理するのが好ましい。ＲＯ装置５’など、２段目以降のＲＯ装置の濃縮水は、１段目ＲＯ装置の原水に戻すか又は当該段の直ぐ上流側の貯槽６に戻すのが好ましい。
In any of FIGS. 1A and 1B, it is preferable that the concentrated water of the
［比較例１（１段処理）］
ホルムアルデヒド濃度３ｍｇ／ＬでｐＨ５．４のホルムアルデヒド含有排水を調製した。この排水に［ＳＯ３］／［ＨＣＨＯ］比（重量比）が０，３，５，又は１０となるようにＮａＨＳＯ３を添加した（「０」は無添加）。室温で十数秒撹拌した後、逆浸透膜装置（日東電工(株)製ＥＳ−２０）に１回のみ通水して、処理水を得た。この処理水中のホルムアルデヒド濃度を測定して、ホルムアルデヒドの除去率を求めた。結果を図２に示す。なお、［ＳＯ３］／［ＨＣＨＯ］比＝５の場合、処理水中のホルムアルデヒド濃度は０．４２ｍｇ／Ｌであった。
[Comparative Example 1 (one-stage processing)]
A formaldehyde-containing wastewater having a formaldehyde concentration of 3 mg / L and a pH of 5.4 was prepared. NaHSO 3 was added to this waste water so that the [SO 3 ] / [HCHO] ratio (weight ratio) was 0, 3 , 5, or 10 (“0” was not added). After stirring at room temperature for tens of seconds, water was passed only once through a reverse osmosis membrane apparatus (ES-20 manufactured by Nitto Denko Corporation) to obtain treated water. The formaldehyde concentration in this treated water was measured to determine the removal rate of formaldehyde. The results are shown in FIG. In addition, when the [SO 3 ] / [HCHO] ratio = 5, the formaldehyde concentration in the treated water was 0.42 mg / L.
図２の通り、排水に添加するＮａＨＳＯ３量を増やし、［ＳＯ３］／［ＨＣＨＯ］比を５程度まで高めると、ホルムアルデヒド除去率も急激に高くなるが、［ＳＯ３］／［ＨＣＨＯ］比が５を越えると、ホルムアルデヒド除去率の伸びは鈍化し、［ＳＯ３］／［ＨＣＨＯ］比１０で９０％と、ほぼ一定になる。この時の処理水のホルムアルデヒド濃度は、０．３ｍｇ／Ｌであり、水道水基準は満足しない。
As shown in FIG. 2, when the amount of NaHSO 3 added to the waste water is increased and the [SO 3 ] / [HCHO] ratio is increased to about 5, the formaldehyde removal rate increases rapidly, but the [SO 3 ] / [HCHO] ratio increases. When the ratio exceeds 5, the growth of the formaldehyde removal rate slows down, and the [SO 3 ] / [HCHO]
［参考例１（２段処理）］
上記の比較例１の［ＳＯ３］／［ＨＣＨＯ］比＝５のＲＯ処理水に［ＳＯ３］／［ＨＣＨＯ］比（重量比）が５となるようにＮａＨＳＯ３を添加した。室温で十数秒撹拌した後、逆浸透膜装置（日東電工(株)製ＥＳ−２０）に通水して処理水を得た。この処理水のホルムアルデヒド濃度を測定した結果、０．０６ｍｇ／Ｌであり、水道水基準を満足するものであった。
[ Reference Example 1 (2-stage treatment)]
NaHSO 3 was added to the RO-treated water having the [SO 3 ] / [HCHO] ratio = 5 in Comparative Example 1 so that the [SO 3 ] / [HCHO] ratio (weight ratio) was 5. After stirring at room temperature for tens of seconds, water was passed through a reverse osmosis membrane device (ES-20 manufactured by Nitto Denko Corporation) to obtain treated water. As a result of measuring the formaldehyde concentration of this treated water, it was 0.06 mg / L and satisfied the tap water standard.
［実施例２（２段処理）］
上記の比較例１の［ＳＯ３］／［ＨＣＨＯ］比＝５のＲＯ処理水に［ＳＯ３］／［ＨＣＨＯ］比（重量比）が６となるようにＮａＨＳＯ３を添加した。室温で十数秒撹拌した後、逆浸透膜装置（日東電工(株)製ＥＳ−２０）に通水して処理水を得た。この処理水のホルムアルデヒド濃度を測定した結果、０．０５ｍｇ／Ｌであり、水道水基準を満足するものであった。
[Example 2 (two-stage process)]
NaHSO 3 was added to the RO-treated water having the [SO 3 ] / [HCHO] ratio = 5 in Comparative Example 1 so that the [SO 3 ] / [HCHO] ratio (weight ratio) was 6. After stirring at room temperature for tens of seconds, water was passed through a reverse osmosis membrane device (ES-20 manufactured by Nitto Denko Corporation) to obtain treated water. As a result of measuring the formaldehyde concentration of this treated water, it was 0.05 mg / L and satisfied the tap water standard.
［実施例３（２段処理）］
上記の比較例１の［ＳＯ３］／［ＨＣＨＯ］比＝６のＲＯ処理水に［ＳＯ３］／［ＨＣＨＯ］比（重量比）が７となるようにＮａＨＳＯ３を添加した。室温で十数秒撹拌した後、逆浸透膜装置（日東電工(株)製ＥＳ−２０）に通水して処理水を得た。この処理水のホルムアルデヒド濃度を測定した結果、０．３８ｍｇ／Ｌであり、水道水基準を満足するものであった。
[Example 3 (two-stage process)]
Was added NaHSO 3 as described above in Comparative Example 1 to [SO 3] / [HCHO] ratio = 6 RO treated water [SO 3] / [HCHO] ratio (weight ratio) of 7. After stirring at room temperature for tens of seconds, water was passed through a reverse osmosis membrane device (ES-20 manufactured by Nitto Denko Corporation) to obtain treated water. As a result of measuring the formaldehyde concentration of this treated water, it was 0.38 mg / L, which satisfied the tap water standard.
２，２’ 混合器
５，５’ ＲＯ装置
2,2 '
Claims (6)
該ホルムアルデヒド含有排水のホルムアルデヒド濃度が０．０８〜１０ｍｇ／Ｌであり、
亜硫酸塩を添加して逆浸透膜処理する工程を複数回行い、
第１回目の前記工程では、亜硫酸塩イオン濃度と当該工程の被処理水中のホルムアルデヒド濃度との重量比［ＳＯ ３ ］／［ＨＣＨＯ］が３〜１０となるように亜硫酸塩を添加し、第２回目以降の前記工程では、この比が４〜１０となるように亜硫酸塩を添加し、第１回目の前記重量比［ＳＯ ３ ］／［ＨＣＨＯ］が、第２回目の該比よりも小さいことを特徴とするホルムアルデヒド含有排水の処理方法。 A method for treating formaldehyde-containing wastewater,
The formaldehyde concentration of the wastewater containing formaldehyde is 0.08 to 10 mg / L,
The process of reverse osmosis membrane treatment by adding sulfite have multiple rows,
In the first step, sulfite is added so that the weight ratio [SO 3 ] / [HCHO] of the sulfite ion concentration and the formaldehyde concentration in the water to be treated in the step is 3 to 10, In the subsequent steps, sulfite is added so that this ratio is 4 to 10, and the weight ratio [SO 3 ] / [HCHO] in the first round is smaller than the ratio in the second round. A method for treating wastewater containing formaldehyde.
該ホルムアルデヒド含有排水のホルムアルデヒド濃度が０．０８〜１０ｍｇ／Ｌであり、
亜硫酸塩を添加する添加装置と、
該添加装置によって亜硫酸塩が添加された水を逆浸透膜処理する逆浸透膜装置と
からなる処理手段が直列に複数段設置されており、
第１段目の処理手段では、亜硫酸塩イオン濃度と当該処理手段の逆浸透膜装置の被処理水中のホルムアルデヒド濃度との重量比［ＳＯ ３ ］／［ＨＣＨＯ］が３〜１０となるように亜硫酸塩が添加され、第２段目以降の処理手段の逆浸透膜装置では、この比が４〜１０となるように亜硫酸塩が添加され、第１段目の前記重量比［ＳＯ ３ ］／［ＨＣＨＯ］が、第２段目の該比よりも小さいことを特徴とするホルムアルデヒド含有排水の処理装置。 An apparatus for treating formaldehyde-containing wastewater,
The formaldehyde concentration of the wastewater containing formaldehyde is 0.08 to 10 mg / L,
An addition device for adding sulfite;
The treatment means comprising a reverse osmosis membrane device that performs reverse osmosis membrane treatment of water to which sulfite has been added by the addition device is installed in a plurality of stages in series .
In the first-stage treatment means, the sulfite is adjusted so that the weight ratio [SO 3 ] / [HCHO] between the sulfite ion concentration and the formaldehyde concentration in the treated water of the reverse osmosis membrane device of the treatment means is 3-10. In the reverse osmosis membrane apparatus of the processing means in the second and subsequent stages after adding salt, sulfite is added so that this ratio becomes 4 to 10, and the weight ratio [SO 3 ] / [in the first stage is added . HCHO] is smaller than the ratio in the second stage, and the apparatus for treating formaldehyde-containing wastewater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012187805A JP5348297B1 (en) | 2012-08-28 | 2012-08-28 | Method and apparatus for treating formaldehyde-containing wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012187805A JP5348297B1 (en) | 2012-08-28 | 2012-08-28 | Method and apparatus for treating formaldehyde-containing wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP5348297B1 true JP5348297B1 (en) | 2013-11-20 |
| JP2014042897A JP2014042897A (en) | 2014-03-13 |
Family
ID=49764911
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012187805A Active JP5348297B1 (en) | 2012-08-28 | 2012-08-28 | Method and apparatus for treating formaldehyde-containing wastewater |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5348297B1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016179457A (en) * | 2015-03-25 | 2016-10-13 | 三浦工業株式会社 | Water treatment method and system |
| JP2016203079A (en) * | 2015-04-21 | 2016-12-08 | 三浦工業株式会社 | Water treatment metho |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6036011B2 (en) * | 2012-08-28 | 2016-11-30 | 栗田工業株式会社 | Method and apparatus for treating wastewater containing formaldehyde |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4742579A (en) * | 1971-05-18 | 1972-12-16 | ||
| JPS51131806A (en) * | 1975-05-12 | 1976-11-16 | Kurita Water Ind Ltd | Method for concentrating organic acids |
| JPS5710305A (en) * | 1980-06-19 | 1982-01-19 | Nitto Electric Ind Co Ltd | Membrane separation for compound having aldehyde group |
| JPS60137403A (en) * | 1983-12-23 | 1985-07-22 | Sasakura Eng Co Ltd | Liquid sealing device using formaldehyde solution |
| JPH10314735A (en) * | 1997-05-14 | 1998-12-02 | Kurita Water Ind Ltd | Pure water preparation process |
| JP2007152265A (en) * | 2005-12-07 | 2007-06-21 | Toray Ind Inc | Method for operating freshwater production device and freshwater production device |
-
2012
- 2012-08-28 JP JP2012187805A patent/JP5348297B1/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4742579A (en) * | 1971-05-18 | 1972-12-16 | ||
| JPS51131806A (en) * | 1975-05-12 | 1976-11-16 | Kurita Water Ind Ltd | Method for concentrating organic acids |
| JPS5710305A (en) * | 1980-06-19 | 1982-01-19 | Nitto Electric Ind Co Ltd | Membrane separation for compound having aldehyde group |
| JPS60137403A (en) * | 1983-12-23 | 1985-07-22 | Sasakura Eng Co Ltd | Liquid sealing device using formaldehyde solution |
| JPH10314735A (en) * | 1997-05-14 | 1998-12-02 | Kurita Water Ind Ltd | Pure water preparation process |
| JP2007152265A (en) * | 2005-12-07 | 2007-06-21 | Toray Ind Inc | Method for operating freshwater production device and freshwater production device |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016179457A (en) * | 2015-03-25 | 2016-10-13 | 三浦工業株式会社 | Water treatment method and system |
| JP2016203079A (en) * | 2015-04-21 | 2016-12-08 | 三浦工業株式会社 | Water treatment metho |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014042897A (en) | 2014-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100976903B1 (en) | Method and apparatus for fluid treatment by reverse osmosis under acidic conditions | |
| US20110180485A1 (en) | Ultraviolet light activated oxidation process for the reduction of organic carbon in semiconductor process water | |
| JP2015037766A (en) | Method for treating drainage containing formaldehyde with membrane | |
| JP5782229B2 (en) | Wastewater treatment method | |
| KR102248156B1 (en) | Water treatment method and apparatus | |
| JP5348297B1 (en) | Method and apparatus for treating formaldehyde-containing wastewater | |
| JP5527473B2 (en) | Membrane treatment method for formaldehyde-containing wastewater | |
| JP2014083521A (en) | Treatment method of aldehyde-containing drainage water and treatment apparatus of aldehyde-containing drainage water | |
| JP6036011B2 (en) | Method and apparatus for treating wastewater containing formaldehyde | |
| TW201427910A (en) | Device for treating ammonia-containing wastewater, and method for treating ammonia-containing wastewater | |
| JP4974276B2 (en) | Separation membrane modification method and apparatus, separation membrane modified by the method, and separation membrane operation method and apparatus | |
| JP5093883B2 (en) | Separation membrane modification method and apparatus, separation membrane modified by the method, and separation membrane operation method and apparatus | |
| Sikdar et al. | Sustainability and how membrane technologies in water treatment can be a contributor | |
| US11814304B2 (en) | Ultraviolet treatment method and system | |
| JP2011131209A (en) | Method and apparatus for treating acidic solution | |
| JP4412474B2 (en) | Water treatment method and water treatment apparatus | |
| JP2009160500A (en) | Ultrapure water production method and apparatus | |
| JP2006223963A (en) | Method and device for modifying separation membrane, and separation membrane modified by the method | |
| JP6051560B2 (en) | Treatment of formaldehyde-containing wastewater | |
| KR101794672B1 (en) | Method of treating phenol-containing water | |
| JP2013103156A (en) | Biological sludge volume reduction method and apparatus | |
| JP2013220406A (en) | Apparatus for treating cleaning wastewater, and method for treating cleaning wastewater | |
| JP2007000790A (en) | Method and device for treating/preserving separation membrane | |
| Garrido et al. | Reconditioning of Wash Water for the Fresh-Cut Industry | |
| JP2006224048A (en) | Method and device for modifying separation membrane, and separation membrane modified by the method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| TRDD | Decision of grant or rejection written | ||
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5348297 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |