JP2003053350A - Method and device for highly removing cod component in water - Google Patents
Method and device for highly removing cod component in waterInfo
- Publication number
- JP2003053350A JP2003053350A JP2001246085A JP2001246085A JP2003053350A JP 2003053350 A JP2003053350 A JP 2003053350A JP 2001246085 A JP2001246085 A JP 2001246085A JP 2001246085 A JP2001246085 A JP 2001246085A JP 2003053350 A JP2003053350 A JP 2003053350A
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- tank
- cod
- acid
- liquid
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 140
- 239000007788 liquid Substances 0.000 claims abstract description 47
- 239000010802 sludge Substances 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 23
- 239000002351 wastewater Substances 0.000 claims abstract description 15
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 36
- 230000003647 oxidation Effects 0.000 claims description 30
- 238000007254 oxidation reaction Methods 0.000 claims description 30
- 238000000926 separation method Methods 0.000 claims description 28
- 238000005345 coagulation Methods 0.000 claims description 22
- 230000015271 coagulation Effects 0.000 claims description 22
- 239000000701 coagulant Substances 0.000 claims description 17
- 238000001179 sorption measurement Methods 0.000 claims description 17
- 238000010306 acid treatment Methods 0.000 claims description 10
- 238000005189 flocculation Methods 0.000 claims description 7
- 230000016615 flocculation Effects 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 5
- 230000001112 coagulating effect Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052742 iron Inorganic materials 0.000 abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 238000004062 sedimentation Methods 0.000 description 7
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- -1 iron ions Chemical class 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- VNWKTOKETHGBQD-AKLPVKDBSA-N carbane Chemical class [15CH4] VNWKTOKETHGBQD-AKLPVKDBSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 101100316860 Autographa californica nuclear polyhedrosis virus DA18 gene Proteins 0.000 description 1
- 102100033007 Carbonic anhydrase 14 Human genes 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000276457 Gadidae Species 0.000 description 1
- 101000867862 Homo sapiens Carbonic anhydrase 14 Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- ARYKTOJCZLAFIS-UHFFFAOYSA-N hydrogen peroxide;ozone Chemical compound OO.[O-][O+]=O ARYKTOJCZLAFIS-UHFFFAOYSA-N 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 239000003295 industrial effluent Substances 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Treatment Of Sludge (AREA)
- Separation Of Solids By Using Liquids Or Pneumatic Power (AREA)
- Water Treatment By Sorption (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、下水、下水処理
水、各種産業排水、湖沼水、河川水など、種々のＣＯＤ
含有排水（以下「原水」ともいう）が含有するＣＯＤ成
分を高度に除去する新規処理方法及び装置に関する。TECHNICAL FIELD The present invention relates to various CODs such as sewage, sewage treatment water, various industrial effluents, lake water and river water.
The present invention relates to a novel treatment method and apparatus for highly removing COD components contained in contained wastewater (hereinafter also referred to as "raw water").
【０００２】[0002]
【従来の技術】ＣＯＤを除去するための従来の最も代表
的な除去技術は、凝集沈殿法である。この技術は、原水
に硫酸アルミニウム、ＰＡＣ、塩化第２鉄、硫酸第２
鉄、ポリ硫酸第２鉄などの無機凝集剤を添加して攪拌
し、ＣＯＤを取り込んだフロックを形成させたのちフロ
ックを沈殿させ、浄化処理水を得る技術である。無機凝
集剤を添加して凝集フロックを形成させた後、フロック
を分離する凝集沈殿などの凝集分離法は、簡単な装置、
操作でＣＯＤが効果的に除去できることが特徴である。
しかし、大量の難脱水性凝集分離汚泥が発生し、その処
理処分が非常に面倒であるという重大な欠点がある。一
方、ＣＯＤを高度に除去する場合は、凝集沈殿処理水に
対し、活性炭吸着処理が行われるが、活性炭の再生が高
額かつ煩雑であり、下水処理への実規模での実施例はな
い。2. Description of the Prior Art The most typical conventional removal technique for removing COD is a coagulating sedimentation method. This technology uses aluminum sulfate, PAC, ferric chloride, and ferric sulfate in raw water.
This is a technique in which an inorganic coagulant such as iron or ferric polysulfate is added and stirred to form flocs incorporating COD, and then the flocs are precipitated to obtain purified treated water. After the inorganic flocculant is added to form floc, the flocculation and separation method such as flocculation and sedimentation for separating the flocs is performed with a simple device,
The feature is that COD can be effectively removed by operation.
However, there is a serious drawback in that a large amount of hardly dehydratable coagulation separation sludge is generated and the treatment and disposal thereof is very troublesome. On the other hand, in the case of highly removing COD, activated carbon adsorption treatment is carried out on the coagulation-sedimentation-treated water, but the regeneration of activated carbon is expensive and complicated, and there is no real-scale example of sewage treatment.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、従来の凝集
分離法の上記問題点を解決し、利用価値の無い難脱水性
凝集分離汚泥の発生を大幅に減少でき、かつ活性炭の再
生が容易に実施できる新技術を提供することを課題とす
る。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the conventional coagulation separation method, can significantly reduce the generation of hardly dehydratable coagulation separation sludge that is not useful, and facilitates the regeneration of activated carbon. The challenge is to provide new technologies that can be implemented in
【０００４】[0004]
【課題を解決するための手段】本発明者等は、上記の課
題を解決すべく研究した結果、ＣＯＤ含有水（原水）に
無機凝集剤を添加して攪拌する凝集沈殿法と、ＣＯＤを
高度に除去する活性炭吸着処理法を組合せ、更に鉱酸に
よる酸溶解処理とオゾン等による化学酸化処理を併用
し、活性炭共存酸性液を、前記ＣＯＤ含有排水（原水）
に返送すれば、ＣＯＤ成分が効率的に除去できるととも
に、処分が面倒な難脱水性凝集分離汚泥の発生、及び高
額かつ煩雑な活性炭の再生の問題も解決できることを見
出し、この知見に基づき、本発明を完成するに至った。Means for Solving the Problems As a result of researches aimed at solving the above-mentioned problems, the present inventors have found that the COD-containing water (raw water) is added with an inorganic coagulant and stirred, and the COD is highly advanced. Combined with the activated carbon adsorption treatment method for removal of the activated carbon, and the combined use of acid dissolution treatment with mineral acid and chemical oxidation treatment with ozone etc., the activated carbon coexisting acidic liquid is treated with the COD-containing wastewater (raw water).
It was found that the COD component can be efficiently removed, and the problems of difficult dehydration coagulation separation sludge that is troublesome to dispose of and the expensive and complicated regeneration of activated carbon can be solved by returning the COD component to The invention was completed.
【０００５】すなわち、本発明は次の構成からなるもの
である。
（１）ＣＯＤ含有排水に、鉄又はアルミニウム系無機凝
集剤と活性炭を添加して凝集分離するとともに、凝集分
離汚泥に酸を添加して凝集汚泥を溶解せしめ、該溶解液
を活性炭および金属イオン共存状態で化学酸化処理した
のち、該活性炭共存酸性液を、前記ＣＯＤ含有排水に添
加することを特徴とする水中のＣＯＤ成分の高度除去方
法。That is, the present invention has the following configuration. (1) An iron or aluminum-based inorganic coagulant and activated carbon are added to the COD-containing wastewater for coagulation separation, and an acid is added to the coagulation separation sludge to dissolve the coagulation sludge, and the dissolved liquid coexists with activated carbon and metal ions. A method for highly removing COD components in water, which comprises chemically oxidizing in a state and then adding the activated carbon coexisting acidic liquid to the COD-containing wastewater.
【０００６】（２）ＣＯＤ含有排水を無機凝集剤及び活
性炭によってＣＯＤを凝集・吸着する凝集・活性炭吸着
槽と、前記槽で生成したフロックを固液分離する固液分
離装置と、前記固液分離装置からの分離凝集汚泥に鉱酸
を添加する酸溶解槽と、前記酸溶解槽からの酸処理液の
化学酸化処理槽と、再生された活性炭が共存する化学酸
化酸性処理液のＣＯＤ含有排水への返送配管を具備する
ことを特徴とする水中のＣＯＤ成分の高度除去装置。
（３）前記分離凝集汚泥の酸溶解槽と酸処理液の化学酸
化処理槽との間に、更に酸不溶性物質と活性炭の分級す
るための分級装置、前記分級装置からの分離液から酸不
溶性物質を除去するための沈殿槽、前記沈殿槽からの分
離液及び前記分級装置で分級された活性炭を化学酸化処
理槽への供給するための配管をそれぞれ設けたことを特
徴とする前記（２）記載の水中のＣＯＤ成分の高度除去
装置。
（４）前記凝集・活性炭吸着槽に代えて、凝集槽及びそ
れに続く活性炭流動層式吸着槽を用い、前記凝集汚泥の
酸溶解槽と酸処理液の化学酸化処理槽との間に、更に酸
不溶性物質除去用の沈殿槽を設け、活性炭流動層式吸着
槽からの引き抜き活性炭を化学酸化処理槽へ供給する配
管を設けたことを特徴とする前記（２）記載の水中のＣ
ＯＤ成分の高度除去装置。(2) A coagulation / active carbon adsorption tank for coagulating / adsorbing COD from COD-containing wastewater with an inorganic coagulant and activated carbon, a solid-liquid separation device for separating the flocs produced in the tank into solid-liquid separation, and the solid-liquid separation To the COD-containing wastewater of the chemical oxidation acid treatment liquid in which the acid treatment liquid for adding the mineral acid to the separated coagulation sludge from the device, the chemical oxidation treatment tank for the acid treatment liquid from the acid dissolution tank, and the regenerated activated carbon coexist An advanced removal device for COD components in water, characterized in that it is provided with a return pipe. (3) A classifier for further classifying the acid-insoluble substance and the activated carbon between the acid-dissolving tank for the separated coagulation sludge and the chemical oxidation-treating tank for the acid-treating solution, and the acid-insoluble substance from the separation solution from the classifying apparatus. (2) characterized in that a pipe for supplying a settling tank for removing ash, a separated liquid from the settling tank, and activated carbon classified by the classifying device to the chemical oxidation treatment tank is provided, respectively. Advanced COD component removal device for water. (4) Instead of the coagulation / activated carbon adsorption tank, a coagulation tank and a subsequent activated carbon fluidized bed type adsorption tank are used, and an acid is further added between the coagulation sludge acid dissolution tank and the acid treatment liquid chemical oxidation treatment tank. A settling tank for removing insoluble substances is provided, and a pipe for supplying the activated carbon drawn from the activated carbon fluidized bed type adsorption tank to the chemical oxidation treatment tank is provided.
Advanced removal equipment for OD components.
【０００７】[0007]
【発明の実施の形態】以下に、本発明の実施の形態を図
面に基づいて詳細に説明する。なお、実施の形態を説明
するための全図において、同一機能を有するものは同一
符号を付けて説明する。図１に本発明のＣＯＤ成分の除
去装置の一構成例を示す。ＣＯＤ含有排水（以下「原
水」と呼ぶことがある。）１に、硫酸アルミニウム、Ｐ
ＡＣ、塩化第２鉄、ポリ硫酸鉄などの無機凝集剤２と活
性炭３（粉末状又は微細顆粒状）を添加して、凝集・活
性炭吸着槽４中で攪拌し、ＣＯＤを凝集除去するととも
に、活性炭にＣＯＤを吸着させる。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below with reference to the drawings. Note that components having the same function are denoted by the same reference symbols throughout the drawings for describing the embodiments. FIG. 1 shows an example of the configuration of the COD component removing device of the present invention. COD-containing wastewater (hereinafter sometimes referred to as “raw water”) 1, aluminum sulfate, P
Inorganic flocculant 2 such as AC, ferric chloride, and polyferric sulfate and activated carbon 3 (powdered or fine granular) are added and stirred in flocculation / activated carbon adsorption tank 4 to coagulate and remove COD, and COD is adsorbed on activated carbon.
【０００８】次いで、活性炭が取り込まれたフロックを
形成させ、フロックを沈殿、膜分離などの固液分離装置
５で固液分離し、ＣＯＤが高度に除去された清澄な処理
水６が得られる。次に、分離された凝集汚泥７に、硫酸
などの鉱酸８を添加し、酸溶解槽９中で水酸化アルミニ
ウム、又は水酸化鉄が溶解するｐＨ以下に調整して攪拌
し、Ａｌイオン又はＦｅイオンを生成させる。フロック
が溶解するに伴って、凝集フロックに取り込まれていた
ＣＯＤ成分が溶出する。Then, flocs containing activated carbon are formed, and the flocs are subjected to solid-liquid separation by a solid-liquid separation device 5 such as precipitation and membrane separation, whereby clear treated water 6 from which COD is highly removed is obtained. Next, a mineral acid 8 such as sulfuric acid is added to the separated coagulated sludge 7, the pH is adjusted to a pH at which aluminum hydroxide or iron hydroxide is dissolved in the acid dissolution tank 9, and the mixture is stirred to obtain Al ions or Generate Fe ions. As the floc dissolves, the COD component taken in by the floc elutes.
【０００９】更に、Ａｌイオン、Ｆｅイオンと活性炭が
共存する液（これを「酸処理液」又は「酸溶解液」と呼
ぶ）１０に対し、化学酸化処理槽１１中で、オゾン酸
化、過酸化水素酸化、オゾン過酸化水素併用酸化、光触
媒光化学酸化などの化学酸化、フェントン酸化などを行
う。活性炭３存在下でオゾン酸化すると、活性炭３が触
媒になり、オゾン１２からヒドロキシラジカルが生成
し、強力な酸化力が現れる。また、無機凝集剤２として
鉄系凝集剤を使用すると、酸処理液１０中に鉄イオンが
存在するので、鉄イオンがオゾン１２、過酸化水素など
の酸化触媒になり、酸化力が増加する。化学酸化処理の
結果、酸処理液１０の液中に含まれているＣＯＤ成分が
酸化分解を受け除去され、かつ活性炭３に吸着されてい
るＣＯＤ成分も化学酸化を受けて分解されて、活性炭３
が再生され、活性炭３のＣＯＤ吸着力が回復することが
認められた。Further, with respect to a liquid 10 in which Al ions, Fe ions and activated carbon coexist (referred to as "acid treatment liquid" or "acid solution"), ozone oxidation and peroxidation are carried out in a chemical oxidation treatment tank 11. Hydrogen oxidation, ozone hydrogen peroxide combined oxidation, photocatalytic photochemical oxidation and other chemical oxidation, and Fenton oxidation are performed. When ozone is oxidized in the presence of the activated carbon 3, the activated carbon 3 serves as a catalyst, a hydroxyl radical is generated from the ozone 12, and a strong oxidizing power appears. When an iron-based coagulant is used as the inorganic coagulant 2, since iron ions are present in the acid treatment liquid 10, the iron ions serve as an oxidation catalyst for ozone 12, hydrogen peroxide, etc., and the oxidizing power increases. As a result of the chemical oxidation treatment, the COD component contained in the liquid of the acid treatment liquid 10 is oxidatively decomposed and removed, and the COD component adsorbed on the activated carbon 3 is also chemically oxidized and decomposed, whereby the activated carbon 3
Was regenerated, and it was confirmed that the COD adsorption force of activated carbon 3 was recovered.
【００１０】次に、再生された活性炭３が共存する化学
酸化処理液１３を、返送管を経て原水１に返送・添加す
ると、化学酸化処理液１３中の鉄イオン又はアルミニウ
ムイオンが、無機凝集剤２として作用し、また活性炭３
がＣＯＤ吸着剤として機能し、原水１のＣＯＤが除去さ
れる。この結果、新鮮な無機凝集剤２の所要量が大幅
（１／１０以下）に減少できる。このため、系外に排出
して汚泥処分すべき量が大幅に減少する。Next, when the chemical oxidation treatment liquid 13 in which the regenerated activated carbon 3 coexists, is returned and added to the raw water 1 through the return pipe, the iron ions or aluminum ions in the chemical oxidation treatment liquid 13 become inorganic coagulants. Acts as 2 and also activated carbon 3
Functions as a COD adsorbent, and COD of the raw water 1 is removed. As a result, the required amount of fresh inorganic coagulant 2 can be greatly reduced (1/10 or less). For this reason, the amount of sludge to be discharged to the outside of the system and to be disposed of is greatly reduced.
【００１１】再生凝集剤（化学酸化処理液のこと）を添
加する際に、新鮮な無機凝集剤２の添加量をゼロにする
と、処理水６の水質が悪化する場合があるので、再生凝
集剤を原水１に添加する場合においても、少量の新鮮無
機凝集剤２を添加できるようにしておくことが好まし
い。また活性炭３が化学酸化分解によって少量減少する
こと及び系外に少量ロスすることを考慮して、新鮮な活
性炭３を補給できるようにしておく。When the amount of the fresh inorganic coagulant 2 added is made zero when the regenerated coagulant (chemical oxidation treatment liquid) is added, the quality of the treated water 6 may deteriorate. It is preferable that a small amount of fresh inorganic coagulant 2 can be added even when water is added to raw water 1. Further, in consideration of a small amount of activated carbon 3 being reduced by chemical oxidative decomposition and a small loss outside the system, fresh activated carbon 3 can be replenished.
【００１２】なお、原水１にＣＯＤ以外にＳＳが含まれ
ている場合は、図２又は図３のように装置を構成する。
すなわち図２において、活性炭３を粉末ではなく、粒径
１〜２ｍｍ程度の小顆粒状（ビーズ状活性炭が適切）を
使用し、酸溶解工程（酸溶解槽９）で酸に溶解しなかっ
た不溶性物質１８（原水１に含まれている粘土分、有機
性ＳＳ、プランクトン、藻類等）を含む液を顆粒状活性
炭１５と分級装置１４（サイクロンが好適）で分級した
後、分離液１６を沈殿槽１７で沈殿処理、分離液１９と
活性炭１５を混合し、化学酸化処理槽１１で化学酸化す
る。なぜなら、この固液分離工程を省略して長期間運転
すると、酸不溶性物質１８が凝集分離工程（凝集・活性
炭吸着槽４）に大量に蓄積し、処理水６へのＳＳ流出な
どのトラブルが起き、凝集分離処理を破綻させるからで
ある。なお、凝集分離汚泥７を酸に溶解させた液中の酸
不溶性物質１８の固液分離は、必ずしも常時行う必要は
なく、間欠的に行っても良い。すなわち、系内に酸不溶
性固体１８がある限度以上に蓄積した場合に、固液分離
工程（沈殿槽１７）を運転すれば良い。When the raw water 1 contains SS in addition to COD, the apparatus is constructed as shown in FIG. 2 or 3.
That is, in FIG. 2, the activated carbon 3 is not powder, but is used in the form of small granules having a particle size of about 1 to 2 mm (bead-shaped activated carbon is suitable) and is not dissolved in the acid in the acid dissolving step (acid dissolving tank 9). A liquid containing a substance 18 (a clay content contained in raw water 1, organic SS, plankton, algae, etc.) is classified by the granular activated carbon 15 and a classifier 14 (a cyclone is suitable), and then the separated liquid 16 is settling tank. At 17, the separated liquid 19 is mixed with the activated carbon 15 and the chemical oxidation is carried out in the chemical oxidation treatment tank 11. This is because if the solid-liquid separation step is omitted and the operation is continued for a long time, a large amount of the acid-insoluble substance 18 accumulates in the coagulation separation step (coagulation / activated carbon adsorption tank 4), and troubles such as SS outflow to the treated water 6 occur. This is because the aggregation and separation process is broken. The solid-liquid separation of the acid-insoluble substance 18 in the liquid obtained by dissolving the coagulation-separation sludge 7 in an acid is not always required and may be performed intermittently. That is, the solid-liquid separation step (precipitation tank 17) may be operated when the acid-insoluble solid 18 is accumulated in the system beyond a certain limit.
【００１３】更に、図３は、本発明のＣＯＤ除去装置に
粒状活性炭の流動層を採用する場合の一構成例を示すも
のである。図３において、ＣＯＤ含有排水１に無機凝集
剤２を添加して、凝集槽２０でフロックを形成しＣＯＤ
を凝集除去した後、活性炭流動層式吸着槽２１に上向流
で供給し、凝集除去されなかった残留ＣＯＤを吸着す
る。凝集フロックは、活性炭３よりも沈降速度が小さい
ので、活性炭流動層を通過し、後続する固液分離装置５
で除去される。Further, FIG. 3 shows an example of the constitution in which a fluidized bed of granular activated carbon is adopted in the COD removing apparatus of the present invention. In FIG. 3, inorganic flocculant 2 is added to COD-containing wastewater 1 to form flocs in the flocculation tank 20.
Is coagulated and removed, and then is supplied to the activated carbon fluidized bed type adsorption tank 21 in an upward flow to adsorb the residual COD that has not been coagulated and removed. Since the flocculation flocs have a lower sedimentation speed than the activated carbon 3, they pass through the activated carbon fluidized bed, and the subsequent solid-liquid separation device 5
Will be removed.
【００１４】活性炭流動層式吸着槽２１において、ＣＯ
Ｄを吸着した活性炭３は定期的に引き抜かれ、引き抜き
活性炭２２は、凝集汚泥７の酸溶解液１０を沈殿槽１７
で酸不溶性成分１８を除いた後の分離液１９に添加する
ことにより化学酸化槽１１に供給され、ここで化学酸化
を受け、活性炭３に吸着されたＣＯＤが分解され、活性
炭３が再生される。（凝集汚泥７の再生系統は、図２と
同じである）In the activated carbon fluidized bed type adsorption tank 21, CO
The activated carbon 3 having adsorbed D is regularly extracted, and the extracted activated carbon 22 extracts the acid solution 10 of the coagulated sludge 7 from the settling tank 17
The COD adsorbed on the activated carbon 3 is decomposed and supplied to the chemical oxidation tank 11 by adding it to the separated liquid 19 after removing the acid-insoluble component 18 in step 1, and the activated carbon 3 is regenerated. . (The regenerating system of the coagulated sludge 7 is the same as that of FIG. 2)
【００１５】[0015]
【実施例】以下に本発明の実施例の一例を示すが、本発
明はこの実施例により限定されるものではない。EXAMPLE An example of the present invention will be shown below, but the present invention is not limited to this example.
【００１６】実施例１
下水の標準活性汚泥法処理水を砂ろ過したろ過水（ＣＯ
ＤMn１５．２ｍｇ／リットル、ＳＳ２ｍｇ／リットル）
を対象に、図１に示す工程によって、本発明の試験を行
った。運転開始後１０日間は新鮮な無機凝集剤（硫酸ア
ルミニウム）と粉末活性炭を添加し、そのあとは、図１
の工程で生成されたアルミニウムイオン含有酸性液を、
無機凝集剤として再利用した。化学酸化は酸化剤として
過酸化水素を添加して行った。試験条件及び方法を第１
表に示す。Example 1 Sewage treated by standard activated sludge method was filtered with sand (CO
D Mn 15.2 mg / liter, SS 2 mg / liter)
The test of the present invention was carried out by using the process shown in FIG. Fresh inorganic coagulant (aluminum sulphate) and powdered activated carbon were added for 10 days after the start of operation, after which Figure 1
The aluminum ion-containing acidic liquid generated in the step of
It was reused as an inorganic coagulant. Chemical oxidation was performed by adding hydrogen peroxide as an oxidant. First test conditions and methods
Shown in the table.
【００１７】[0017]
【表１】 [Table 1]
【００１８】以上の条件で１ヶ月運転し、処理水のＣＯ
Ｄを分析した。運転開始後１０日間の新鮮な塩化第２鉄
を添加した場合には、処理水ＣＯＤ３．２ｍｇ／リット
ルであった。これに対し、新鮮な塩化第２鉄添加率をＦ
ｅとして１０ｍｇ／リットルに減少させ、本発明のＦｅ
イオン含有酸性液を凝集剤として再利用した場合には、
処理水ＣＯＤ５．２ｍｇ／リットルであった。凝集沈殿
汚泥の発生が、通常の凝集沈殿法の約１／１０に減少し
た。After operating for 1 month under the above conditions, CO
D was analyzed. When fresh ferric chloride was added for 10 days after the start of operation, the treated water COD was 3.2 mg / liter. On the other hand, the fresh ferric chloride addition rate is F
e of Fe of the present invention was reduced to 10 mg / liter.
When the ion-containing acidic liquid is reused as a flocculant,
The treated water had a COD of 5.2 mg / liter. The generation of coagulation sedimentation sludge was reduced to about 1/10 of that of the usual coagulation sedimentation method.
【００１９】[0019]
【発明の効果】本発明によれば、下記の効果が得られ
た。
（１）凝集沈殿汚泥がほとんど発生しない。特に、利用
価値の無い難脱水性凝集分離汚泥の発生を大幅に減少で
きる。
（２）汚泥処理が容易になる。
（３）活性炭の再生が、凝集剤の再生工程で同時に行え
るため、活性炭の再生が容易に実施でき、ＣＯＤ成分の
除去が容易である。
（４）活性炭の再生操作がシンプルである。活性炭の熱
的再生設備が不要である。
（５）凝集剤および活性炭をリサイクル使用しても、処
理水ＣＯＤが良好に維持される。According to the present invention, the following effects are obtained. (1) Almost no coagulation sedimentation sludge is generated. In particular, it is possible to greatly reduce the generation of hardly dehydratable coagulation separation sludge that has no utility value. (2) Sludge treatment becomes easy. (3) Since the activated carbon can be regenerated at the same time in the coagulant regeneration step, the activated carbon can be easily regenerated and the COD component can be easily removed. (4) Regeneration operation of activated carbon is simple. No thermal regeneration equipment for activated carbon is required. (5) Even if the flocculant and activated carbon are recycled and used, the treated water COD is maintained in good condition.
【図１】本発明のＣＯＤ成分の除去方法の一実施態様の
ブロック図である。FIG. 1 is a block diagram of an embodiment of a COD component removing method of the present invention.
【図２】本発明のＣＯＤ成分とＳＳの除去方法の一実施
態様のブロック図である。FIG. 2 is a block diagram of an embodiment of a method for removing COD components and SS according to the present invention.
【図３】本発明のＣＯＤ成分とＳＳの除去方法の別の実
施態様のブロック図である。FIG. 3 is a block diagram of another embodiment of the COD component and SS removal method of the present invention.
１ ＣＯＤ含有排水（原水） ２ 無機凝集剤 ３ 活性炭 ４ 凝集・活性炭吸着槽 ５ 固液分離装置 ６ 処理水 ７ 凝集汚泥 ８ 鉱酸 ９ 酸溶解槽 １０ 酸処理液（酸溶解液） １１ 化学酸化処理槽 １２ オゾン １３ 化学酸化処理液 １４ 酸不溶性物質（酸不溶解ＳＳ） １５ 顆粒活性炭 １６ 分級装置（サイクロン） １７ 分離液 １８ 沈殿槽 １９ 分離液 ２０ 凝集槽 ２１ 活性炭流動層式吸着槽 ２２ 引き抜き活性炭 1 COD-containing wastewater (raw water) 2 Inorganic coagulant 3 activated carbon 4 Coagulation / activated carbon adsorption tank 5 Solid-liquid separator 6 treated water 7 Coagulated sludge 8 Mineral acid 9 Acid dissolution tank 10 Acid treatment liquid (acid solution) 11 Chemical oxidation treatment tank 12 ozone 13 Chemical oxidation treatment liquid 14 Acid-insoluble substance (acid-insoluble SS) 15 Granular activated carbon 16 classifier (Cyclone) 17 Separation liquid 18 settling tank 19 Separation liquid 20 aggregation tank 21 Activated carbon fluidized bed type adsorption tank 22 Extracted activated carbon
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０２Ｆ 11/06 Ｃ０２Ｆ 11/06 Ａ (72)発明者 田中 俊博 東京都大田区羽田旭町11番１号 株式会社 荏原製作所内 Ｆターム(参考） 4D015 BA04 BA15 CA02 CA14 DA04 DA05 DA16 DA17 DC02 EA32 FA03 FA19 FA24 4D024 AA02 AA04 AA05 AB02 BA02 BB01 BC04 DA07 DA08 DB07 DB12 DB20 DB24 4D059 AA06 BC02 BH07 BK12 CA23 CA28 DA43 4D071 AA53 CA01 DA01 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C02F 11/06 C02F 11/06 A (72) Inventor Toshihiro Tanaka 11-1 Haneda Asahi-cho, Ota-ku, Tokyo F term in EBARA CORPORATION (reference) 4D015 BA04 BA15 CA02 CA14 DA04 DA05 DA16 DA17 DC02 EA32 FA03 FA19 FA24 4D024 AA02 AA04 AA05 AB02 BA02 BB01 BC04 DA07 DA08 DB07 DB12 DB20 DB24 4D059 AA06 BC02 BH07 A43 CA01 DA43 CA01 CA23 CA01
Claims (4)
系無機凝集剤と活性炭を添加して凝集分離するととも
に、凝集分離汚泥に酸を添加して凝集汚泥を溶解せし
め、該溶解液を活性炭および金属イオン共存状態で化学
酸化処理したのち、該活性炭共存酸性液を、前記ＣＯＤ
含有排水に添加することを特徴とする水中のＣＯＤ成分
の高度除去方法。1. A COD-containing wastewater is added with an iron- or aluminum-based inorganic coagulant and activated carbon to coagulate and separate, and an acid is added to the coagulation-separation sludge to dissolve the coagulation sludge. After the chemical oxidation treatment in the ion coexisting state, the activated carbon coexisting acidic liquid is subjected to the above-mentioned COD.
A method for highly removing COD components in water, which is characterized in that it is added to contained wastewater.
によってＣＯＤを凝集・吸着する凝集・活性炭吸着槽
と、前記槽で生成したフロックを固液分離する固液分離
装置と、前記固液分離装置からの分離凝集汚泥に鉱酸を
添加する酸溶解槽と、前記酸溶解槽からの酸処理液の化
学酸化処理槽と、再生された活性炭が共存する化学酸化
酸性処理液のＣＯＤ含有排水への返送配管を具備するこ
とを特徴とする水中のＣＯＤ成分の高度除去装置。2. A coagulation / active carbon adsorption tank for coagulating / adsorbing COD from COD-containing wastewater with an inorganic coagulant and activated carbon, a solid-liquid separation device for separating the flocs produced in the tank into solid-liquid, and the solid-liquid separation device. To the COD-containing wastewater of the chemical oxidation treatment solution in which regenerated activated carbon coexists, An advanced removal device for COD components in water, which is equipped with a return pipe.
の化学酸化処理槽との間に、更に酸不溶性物質と活性炭
の分級するための分級装置、前記分級装置からの分離液
から酸不溶性物質を除去するための沈殿槽、前記沈殿槽
からの分離液及び前記分級装置で分級された活性炭を化
学酸化処理槽への供給するための配管をそれぞれ設けた
ことを特徴とする請求項２記載の水中のＣＯＤ成分の高
度除去装置。3. A classifier for further classifying the acid-insoluble substance and activated carbon between the acid dissolving tank of the separated coagulated sludge and the chemical oxidation treatment tank of the acid treatment liquid, and the acid separated from the separation liquid from the classification device. 3. A precipitation tank for removing insoluble substances, a pipe for supplying the separated liquid from the precipitation tank and the activated carbon classified by the classifier to the chemical oxidation treatment tank are provided respectively. The advanced removal device for COD components in water as described.
槽及びそれに続く活性炭流動層式吸着槽を用い、前記凝
集汚泥の酸溶解槽と酸処理液の化学酸化処理槽との間
に、更に酸不溶性物質除去用の沈殿槽を設け、活性炭流
動層式吸着槽からの引き抜き活性炭を化学酸化処理槽へ
供給する配管を設けたことを特徴とする請求項２記載の
水中のＣＯＤ成分の高度除去装置。4. A flocculation tank and a subsequent activated carbon fluidized bed type adsorption tank are used in place of the flocculation / activated carbon adsorption tank, and between the acid dissolution tank of the flocculated sludge and the chemical oxidation treatment tank of the acid treatment liquid, The advanced COD component in water according to claim 2, further comprising a precipitation tank for removing an acid-insoluble substance, and a pipe for supplying the activated carbon drawn from the activated carbon fluidized bed type adsorption tank to the chemical oxidation treatment tank. Removal device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001246085A JP2003053350A (en) | 2001-08-14 | 2001-08-14 | Method and device for highly removing cod component in water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001246085A JP2003053350A (en) | 2001-08-14 | 2001-08-14 | Method and device for highly removing cod component in water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003053350A true JP2003053350A (en) | 2003-02-25 |
Family
ID=19075715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001246085A Pending JP2003053350A (en) | 2001-08-14 | 2001-08-14 | Method and device for highly removing cod component in water |
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| Country | Link |
|---|---|
| JP (1) | JP2003053350A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012516229A (en) * | 2009-01-29 | 2012-07-19 | ヴェオリア・ウォーター・ソリューションズ・アンド・テクノロジーズ・サポート | Process for treating water by ballast flocculation and sedimentation, including pre-contact of water and adsorbent |
| CN103086545A (en) * | 2013-02-28 | 2013-05-08 | 曾嵘斌 | Method and device for removing and recovering heavy metal in waste water through regenerated active carbon |
| CN105347537A (en) * | 2015-11-27 | 2016-02-24 | 湖北君集水处理有限公司 | System and method for deeply processing industrial wastewater |
| CN105621829A (en) * | 2016-02-27 | 2016-06-01 | 常州大学 | Heavy metal removing device for agricultural sludge |
| JP2017109162A (en) * | 2015-12-16 | 2017-06-22 | 株式会社オメガ | Water treatment method |
| CN114432785A (en) * | 2021-12-13 | 2022-05-06 | 北京万邦达环保技术股份有限公司 | Method for coordinately treating and recycling waste ionic liquid |
-
2001
- 2001-08-14 JP JP2001246085A patent/JP2003053350A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012516229A (en) * | 2009-01-29 | 2012-07-19 | ヴェオリア・ウォーター・ソリューションズ・アンド・テクノロジーズ・サポート | Process for treating water by ballast flocculation and sedimentation, including pre-contact of water and adsorbent |
| CN103086545A (en) * | 2013-02-28 | 2013-05-08 | 曾嵘斌 | Method and device for removing and recovering heavy metal in waste water through regenerated active carbon |
| CN105347537A (en) * | 2015-11-27 | 2016-02-24 | 湖北君集水处理有限公司 | System and method for deeply processing industrial wastewater |
| JP2017109162A (en) * | 2015-12-16 | 2017-06-22 | 株式会社オメガ | Water treatment method |
| CN105621829A (en) * | 2016-02-27 | 2016-06-01 | 常州大学 | Heavy metal removing device for agricultural sludge |
| CN114432785A (en) * | 2021-12-13 | 2022-05-06 | 北京万邦达环保技术股份有限公司 | Method for coordinately treating and recycling waste ionic liquid |
| CN114432785B (en) * | 2021-12-13 | 2023-04-14 | 北京万邦达环保技术股份有限公司 | Method for coordinately treating and recycling waste ionic liquid |
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