JP5782628B2 - Wastewater treatment method - Google Patents
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- JP5782628B2 JP5782628B2 JP2010258700A JP2010258700A JP5782628B2 JP 5782628 B2 JP5782628 B2 JP 5782628B2 JP 2010258700 A JP2010258700 A JP 2010258700A JP 2010258700 A JP2010258700 A JP 2010258700A JP 5782628 B2 JP5782628 B2 JP 5782628B2
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- 238000004065 wastewater treatment Methods 0.000 title claims description 37
- 239000002351 wastewater Substances 0.000 claims description 43
- 239000007787 solid Substances 0.000 claims description 26
- 239000002244 precipitate Substances 0.000 claims description 16
- 239000005416 organic matter Substances 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 12
- 238000004080 punching Methods 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000701 coagulant Substances 0.000 claims description 4
- 239000005446 dissolved organic matter Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000000638 stimulation Effects 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 239000000126 substance Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- 244000005700 microbiome Species 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000002306 biochemical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000011197 physicochemical method Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005011 time of flight secondary ion mass spectroscopy Methods 0.000 description 1
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- Treatment Of Water By Oxidation Or Reduction (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Physical Water Treatments (AREA)
Description
本発明は、マイクロバブルの圧壊を利用した排水処理において、無機系添加剤を添加することで排水中の溶解有機物を固体（有機物系固体析出物）として析出させる排水処理方法に関するものである。 The present invention relates to a wastewater treatment method for depositing dissolved organic matter in wastewater as a solid (organic matter solid precipitate) by adding an inorganic additive in wastewater treatment utilizing the collapse of microbubbles.
有機物系排水に対する排水処理の主たる目的は、排水中に存在している炭素分（有機物）の除去である。除去手段としては、大きく２つに分けることができる。１つは二酸化炭素などの気体として排水から除去する物理化学的な方法である。一般的には、有機物を徹底的に酸化させて二酸化炭素として除去する方法である。 The main purpose of wastewater treatment for organic wastewater is to remove carbon (organic matter) present in the wastewater. The removing means can be roughly divided into two. One is a physicochemical method for removing carbon dioxide and other gases from waste water. In general, organic substances are thoroughly oxidized and removed as carbon dioxide.
しかしながら、上記物理化学的な方法では、有機物を酸化させる為に、大量の酸化剤を必要とし、処理コストや排水における環境負荷がかかってしまうということが問題点であった。 However, the physicochemical method has a problem in that a large amount of an oxidant is required to oxidize an organic substance, resulting in a processing cost and an environmental load in wastewater.
もう１つは、炭素分を固体として除去する生物化学的な方法であり、一般的には好気的な微生物を利用する方法が相当する。排水中において、曝気をおこない微生物を繁殖させることにより、排水中に溶解している有機物を微生物体内に摂取させる。取り込まれた有機物は微生物の体躯となり、これを排水中から分離除去することで排水の環境負荷を低減することができる。 The other is a biochemical method for removing carbon as a solid, and generally corresponds to a method using an aerobic microorganism. In the wastewater, the microorganisms are aerated and the microorganisms are propagated, so that organic matter dissolved in the wastewater is ingested into the microorganisms. The taken-in organic matter becomes the body of the microorganism, and the environmental load of the waste water can be reduced by separating and removing it from the waste water.
しかしながら、上記生物化学的な方法では、非生分解性有機物に対しては効果を示さず、該有機物によっては、微生物が死滅してしまう問題点がある。 However, the biochemical method does not show an effect on non-biodegradable organic substances, and there is a problem that microorganisms are killed depending on the organic substances.
そこで、近年では、例えば本件出願人らによる特許第４３７８５４３号公報（特許文献１）に開示されているマイクロバブル（直径がμｍオーダーの気泡のことを言う。）を用いた技術が注目されている。 Therefore, in recent years, for example, a technique using microbubbles (referred to as bubbles having a diameter of μm order) disclosed in Japanese Patent No. 4378543 (Patent Document 1) by the present applicants has attracted attention. .
特許文献１には、オゾンなどの気体を含んだ直径が１０〜５０μｍ程度のマイクロバブルを水中で消滅させることにより発生する大量のフリーラジカル（主に水酸基ラジカル）を発生させて、該フリーラジカルにより有機物を酸化させ、最終的に二酸化炭素として取り除く方法が開示されている。この方法は汎用性が高いため難分解性化学物質にも対処できるまた、中間生成物が生分解性に優れたものである場合には上記に示したような好気的な微生物を利用した方法との併用も可能などの多くの利点を有している。 In Patent Document 1, a large amount of free radicals (mainly hydroxyl radicals) generated by erasing microbubbles having a diameter of about 10 to 50 μm containing a gas such as ozone in water are generated. A method of oxidizing organic matter and finally removing it as carbon dioxide is disclosed. Since this method is highly versatile, it can handle difficult-to-decompose chemical substances. In addition, when the intermediate product is excellent in biodegradability, it uses aerobic microorganisms as shown above. It has many advantages that can be used in combination.
この様なマイクロバブルによる圧壊処理に関しての技術開発を進める過程で、圧壊時に非常に奇妙な現象が起こることを発見した。それは有機系成分が固体として析出する現象である。そのメカニズムは気液界面の効果に関与していると考えている。すなわち気液界面にはイオンと溶解有機物が集まりやすい傾向がある。イオンは気液界面が帯電していることに関与している。気液界面近傍における水は、バルクとは異なった水素結合ネットワークを形成している。バルク水中では水分子の周囲に他の水分子が存在しており全方位的にネットワークを形成することができる。これに対して気液界面に存在する水分子にとっては気体側に手を繋ぐべき相手の水分子が存在していない。このため、ネットワークの構造そのものが、気液界面はバルクと異なってしまう。この構造的な違いが要因となり、水分子が電離して生じたＯＨ−やＨ＋が気液界面に高い密度で存在していると考えられる。特に通常のｐＨ条件下ではＯＨ−が優勢に界面に存在しているため、気液界面は負に帯電している。水溶液中には様々な電解質イオンが存在しているため、静電気的な引力を受けて界面近傍には陽イオンが引き寄せられている。気液界面にはこの様なイオン類の局在化に加えて水中に溶解した有機物も集積してくる傾向にある。溶解有機物は水溶液中に一様にとけ込んでいるわけではなく、特に分子量が多い有機物ほど疎水的な特性を持つため、気液界面に集まりやすい傾向を持つ。この様に気液界面には電解質イオンと溶解有機物が集まった状態であり、なおかつマイクロバブルが水中で縮小する状況下では、面積に反比例してこれらの電解質イオンや有機物濃度は急激に上昇する。さらに気泡消滅時には水酸基ラジカルなどのエネルギー種が形成される。これらが反応場を形成することにより溶解有機物や電解質イオン類が素材となって固体析出物が発生する。 In the process of advancing technological development related to such microbubble crushing treatment, we discovered that a very strange phenomenon occurred during crushing. It is a phenomenon in which organic components are deposited as solids. The mechanism is considered to be related to the effect of the gas-liquid interface. That is, ions and dissolved organic substances tend to collect at the gas-liquid interface. Ions are involved in the gas-liquid interface being charged. The water in the vicinity of the gas-liquid interface forms a hydrogen bond network different from the bulk. In the bulk water, other water molecules exist around the water molecules, and a network can be formed in all directions. On the other hand, for water molecules present at the gas-liquid interface, there is no water molecule as a partner to be connected to the gas side. For this reason, the network structure itself is different from the bulk at the gas-liquid interface. Due to this structural difference, it is considered that OH − and H + generated by ionization of water molecules are present at a high density at the gas-liquid interface. In particular, under normal pH conditions, OH − is predominantly present at the interface, so the gas-liquid interface is negatively charged. Since various electrolyte ions exist in the aqueous solution, positive ions are attracted to the vicinity of the interface due to electrostatic attraction. In addition to the localization of such ions, organic substances dissolved in water tend to accumulate at the gas-liquid interface. Dissolved organic substances are not uniformly dissolved in an aqueous solution, and organic substances having a higher molecular weight have a hydrophobic property and tend to collect at the gas-liquid interface. In this way, electrolyte ions and dissolved organic substances are collected at the gas-liquid interface, and the concentration of these electrolyte ions and organic substances increases rapidly in inverse proportion to the area under the condition that microbubbles shrink in water. Further, when the bubbles disappear, energy species such as hydroxyl radicals are formed. When these form a reaction field, dissolved organic substances and electrolyte ions are used as raw materials to generate solid precipitates.
しかしながら、特許文献１に記載の方法を用いて排水処理をした場合、溶解有機物や電解質イオンなどの素材が揃っていても、マイクロバブル圧壊時に固体（有機物系固体析出物）が析出することは非常に希であり、また排水処理過程でどのような条件を満足した場合に現象が再現されるかも不明であった。 However, when wastewater treatment is performed using the method described in Patent Document 1, even if materials such as dissolved organic matter and electrolyte ions are prepared, solids (organic solid precipitates) are very likely to precipitate when the microbubbles are collapsed. It was also unclear, and it was also unclear what conditions would be reproduced when the wastewater treatment process was satisfied.
本発明は上述したような実情に鑑みてなされたものであり、マイクロバブル圧壊技術と無機系凝集剤を使用することにより、排水中に溶解した有機物を固体、即ち有機物系固体析出物として析出させ、これを分離除去することで効果的に排水中の有機物量を低減させる排水処理方法を提供することを目的とする。 The present invention has been made in view of the above-described circumstances, and by using a microbubble crushing technique and an inorganic flocculant, an organic substance dissolved in waste water is precipitated as a solid, that is, an organic solid precipitate. An object of the present invention is to provide a wastewater treatment method that effectively reduces the amount of organic matter in wastewater by separating and removing this.
本発明の上記目的は、有機物を含む排水に対して、前記排水中で、気体が内在した直径が１０〜５０μｍのマイクロバブルを発生させる工程と、物理的刺激を与えて前記排水中の前記マイクロバブルを圧壊させる工程と、前記排水に無機系凝集剤を添加する工程と、前記無機系凝集剤によって析出した有機物系固体析出物を分離除去する工程とを具備する無機系凝集剤を利用した排水処理方法であって、前記排水は、ＣＯＤが１０００ｍｇ／Ｌ以上であり、及び前記マイクロバブルを発生させる工程前に、予め前処理により有機物系固体粒子が取り除かれており、前記無機系凝集剤は、前記排水に対し、０．１〜３％となるように、且つ前記圧壊工程の前若しくはその最中に添加され、前記圧壊工程にて圧壊された前記マイクロバブルの表面において、前記排水中の溶解有機物並びに前記排水中及び前記無機系凝集剤により供給された電解質イオンが高濃度に濃縮されると共に、前記圧壊により生じたフリーラジカルの作用を受けて化学反応を起こすことにより、前記排水に含まれる有機物を前記有機物系固体析出物として析出させ、並びに前記有機物系固体析出物を分離除去することにより、処理された前記排水のＣＯＤが、排水処理前のＣＯＤの１／８になることを特徴とすることにより効果的に達成される。
The object of the present invention is to generate a microbubble having a diameter of 10 to 50 μm in which a gas is contained in the wastewater containing organic matter, and to give a physical stimulus to the micro in the wastewater. a step of crushing the bubble, using a step of adding a free machine flocculant to said waste water, the inorganic coagulant to the inorganic organic based solid precipitates precipitated by aggregating agent and a step of separating and removing A wastewater treatment method, wherein the wastewater has a COD of 1000 mg / L or more, and the organic solid particles are removed in advance by pretreatment before the step of generating the microbubbles. is relative to the waste water, so that 0.1% to 3%, is and added before or during the said crushing step, crushing been the microbubble surface in said crushing step In addition, dissolved organic matter in the waste water and electrolyte ions supplied in the waste water and by the inorganic flocculant are concentrated to a high concentration, and a chemical reaction is caused by the action of free radicals generated by the crushing. by, organic matter contained in the wastewater is precipitated as the organic-based solid deposits, as well as by separating off the organic-based solid precipitates, treated the wastewater COD is before wastewater treatment COD 1 effectively achieved by said Rukoto such to / 8.
また本発明は、前記気体がオゾンであることにより、或いは前記物理的刺激は、循環流量１０〜１００Ｌ／分で前記マイクロバブルを含む排水を循環させながら、前記マイクロバブルを含む排水をパンチング板に通すことであることにより、或いは前記物理的刺激が、発振周波数が２０〜１０００ｋＨｚの超音波を照射することであることにより、或いは前記物理的刺激が、電圧が２０００〜３０００Ｖの放電を使用することであることにより、或いは前記無機系凝集剤がアルミニウム塩又は鉄塩のいずれかであることにより、或いは前記フリーラジカルがヒドロキシルラジカルであることにより、より効果的に達成される。
The present invention, by pre SL gas is ozone, or the physical stimulation, while circulating waste water containing the microbubbles in the circulation flow rate of 10 to 100 L / min, punched plate drainage containing the microbubbles Or the physical stimulus is by irradiating an ultrasonic wave having an oscillation frequency of 20 to 1000 kHz, or the physical stimulus uses a discharge having a voltage of 2000 to 3000V. by that is, walk by said inorganic coagulant is either an aluminum salt or iron salt, or by the free radicals is a hydroxyl radical, are more effectively achieved.
本発明の排水処理方法によれば、マイクロバブルの圧壊時の反応場で溶解有機物と化学反応を起こし、その結果として溶解有機物を固体として析出させることができ、析出した固体は、凝集剤自体の本来の作用を受けて凝集沈殿するため、これを処理水から分離除去することで排水の環境負荷を大幅に低減することが可能となった。また、ありとあらゆる有機物に対して適応が可能である。 According to the wastewater treatment method of the present invention, a chemical reaction is caused with a dissolved organic substance in a reaction field at the time of crushing microbubbles, and as a result, the dissolved organic substance can be precipitated as a solid. Since it coagulates and settles under the original action, it is possible to significantly reduce the environmental load of the wastewater by separating and removing it from the treated water. It can also be applied to all kinds of organic matter.
以下、本発明に係る排水処理方法の実施形態を説明する。なお、本発明は以下の実施形態に限定されるものではない。 Hereinafter, embodiments of the wastewater treatment method according to the present invention will be described. In addition, this invention is not limited to the following embodiment.
先ず、本発明に係る排水処理方法にて使用する排水処理装置の概要を説明する。 First, the outline | summary of the waste water treatment apparatus used with the waste water treatment method which concerns on this invention is demonstrated.
図１は、前記排水処理装置の概略図である。図１に示すように、排水処理装置１は、処理槽２内部にマイクロバブル発生装置３が設置され、処理槽２の側面に、循環ポンプ４及びパンチング板（多孔板）５が備え付けられている循環パイプ６が設置されて成る。 FIG. 1 is a schematic view of the waste water treatment apparatus. As shown in FIG. 1, the waste water treatment apparatus 1 is provided with a microbubble generator 3 inside a treatment tank 2, and a circulation pump 4 and a punching plate (porous plate) 5 are provided on the side of the treatment tank 2. A circulation pipe 6 is installed.
ここで、マイクロバブル発生装置３のタイプは限定されないが、シャフトタイプのものが望ましい。ちなみにマイクロバブル発生装置３の設置台数は特に制限はない。 Here, the type of the microbubble generator 3 is not limited, but a shaft type is preferable. Incidentally, the number of installed microbubble generators 3 is not particularly limited.
また、図１では処理槽２の側面に、循環ポンプ４及びパンチング板５が備え付けられている循環パイプ６が設置されているが、これらは無くても構わない（理由は後述）。
In FIG. 1, the circulation pipe 6 provided with the circulation pump 4 and the
そして、凝集剤添加装置７については、排水処理装置１に内蔵しても、パイプ等で該装置１に外付けで設置しても、また、無くても構わない。
The flocculant adding
次に、本発明に係る排水処理方法を図１の排水処理装置及び図２のフローチャートを基に説明する。 Next, the waste water treatment method according to the present invention will be described based on the waste water treatment apparatus of FIG. 1 and the flowchart of FIG.
先ず、処理槽２に処理する原水（排水）を導入する（スタート）。なお、本発明に係る排水処理方法で使用する該原水は、特に限定はないが、ＣＯＤ（化学的酸素要求量）が１０００ｍｇ／Ｌ以上のものに対して好適である。また、該原水は、予め有機物系固体微粒子（浮遊物）を取り除くための前処理がされていることが好ましい。ここで言う、有機物系固体微粒子（浮遊物）とは、本発明に係る排水処理方法を行う前の時点で、排水中に浮遊している微粒子のことを指し、本発明の方法によって析出する有機物系固体析出物とは異なるものである。 First, raw water (drainage) to be treated is introduced into the treatment tank 2 (start). The raw water used in the wastewater treatment method according to the present invention is not particularly limited, but is suitable for those having a COD (chemical oxygen demand) of 1000 mg / L or more. The raw water is preferably pretreated in advance to remove organic solid fine particles (floating matter). The organic solid fine particles (floating matter) as used herein refers to fine particles floating in the wastewater before the wastewater treatment method according to the present invention, and the organic matter deposited by the method of the present invention. It is different from the system solid precipitate.
次に、該原水を処理槽２に導入した後、マイクロバブル発生装置３にてマイクロバブルを発生させる（ステップＳ１）。この段階で発生するマイクロバブルの直径（粒径）は、数〜数百μｍオーダーである。この時点でマイクロバブルの直径分布（範囲）が大きいが、マイクロバブル発生装置３そのものや、パンチング板５（後述）を通過させる等によって最終的には直径が１０〜５０μｍに揃う。なお、該マイクロバブル内部に介在させる気体、即ちマイクロバブル発生装置３に吸入させる気体は、オゾンが好ましいが、酸素、窒素、希ガス類及び空気等といった気体でも構わない。 Next, after introducing the raw water into the treatment tank 2, microbubbles are generated by the microbubble generator 3 (step S1). The diameter (particle size) of the microbubbles generated at this stage is on the order of several to several hundred μm. At this point, the diameter distribution (range) of the microbubbles is large, but the diameter finally becomes 10 to 50 μm by passing the microbubble generator 3 itself or a punching plate 5 (described later). The gas interposed inside the microbubbles, that is, the gas sucked into the microbubble generator 3 is preferably ozone, but may be gases such as oxygen, nitrogen, rare gases, air, and the like.
次に、循環ポンプ４を使用して、マイクロバブルを含んだ原水（以下、マイクロバブル含有原水と記す。）を循環パイプ７内に循環させ（循環経路は、図１に示す矢印を参照）、前記マイクロバブル含有原水を処理槽２に戻す手前でパンチング板５に通過させる（ステップＳ２）。なお、マイクロバブル含有原水を循環パイプ６内にて循環させる際の循環量は、１０〜１００Ｌ／分が望ましい。また、循環ポンプ６の押し出し圧力は０．１〜０．３ＭＰａが望ましい。ちなみに前記循環量及び前記押し出し圧力について、これらの範囲以下であると圧壊が十分にされず、範囲以上としても効率はさほど上がらない。
Next, using the circulation pump 4, raw water containing microbubbles (hereinafter referred to as microbubble-containing raw water) is circulated in the circulation pipe 7 (see the arrows shown in FIG. 1 for the circulation path), The microbubble-containing raw water is passed through the punching
ちなみに、上記排水処理装置には循環ポンプ４及びパンチング板５が備え付けられている循環パイプ６が設置されなくても良いと上述したが、そもそも、パンチング板５に通過させる理由は、直径が１０〜５０μｍのマイクロバブルを圧壊（消滅）させるための物理的刺激として使用するためのものであり、この物理的刺激は、超音波照射、放電でも可能である。なお、超音波照射を物理的刺激として使用する場合は、発振周波数が２０〜１０００ｋ（１Ｍ）Ｈｚのものが使用可能であり、放電を使用する場合は２０００〜３０００Ｖのものが使用可能である。
Incidentally, although it has been described above that the circulation pipe 6 provided with the circulation pump 4 and the
また、マイクロバブル含有原水を循環パイプ７内で循環させるのと並行又は循環させる前に、凝集剤添加装置７を使用して、凝集剤を添加する（ステップＳ３）。凝集剤の量は、原水（排水）に対し、０．１〜３％となるように添加するのが望ましい。０．１％以下であると凝集が十分に進行せず、３％以上であると、余剰の凝集剤が排水中に残存してしまう。凝集剤には、アルミニウム塩、鉄塩などの無機系凝集剤が使用可能である。なお、凝集剤添加装置８を使用した場合、排水の連続供給量の０．１〜３％を連続的に添加するのが望ましい。
Further, before the microbubble-containing raw water is circulated in the
凝集剤を添加してマイクロバブル含有原水を処理した後、原水を静置し、凝集剤によって析出した有機物系固体析出物を適宜分離除去する（ステップＳ４）。該析出物を分離除去する方法は、特に限定は無い。また、該析出物を分離した後に残った液体部分は、再度本発明の排水処理方法或いは活性汚泥方法などの別法で処理して構わない。
After the microbubble-containing raw water is treated by adding a flocculant, the raw water is allowed to stand, and organic solid precipitates precipitated by the flocculant are appropriately separated and removed (step S4) . The method for separating and removing the precipitate is not particularly limited. Moreover, you may process the liquid part which remained after isolate | separating this deposit by another methods, such as the waste water treatment method of this invention, or an activated sludge method again.
以下、本発明に係る排水処理方法について実施例を説明する。なお、本実施例にて使用した排水処理装置については、図１及び上記実施形態を参照されたい。 Examples of the wastewater treatment method according to the present invention will be described below. For the wastewater treatment apparatus used in this example, see FIG. 1 and the above embodiment.
［実施例］
ＣＯＤ（化学的酸素要求量）が約４万ｍｇ／Ｌである排水を約０．１ｍ３／時の流量で処理槽に導入した。処理原水に対しては予め有機物系固体微粒子（浮遊物）を取り除くための前処理を実施しており、処理原水中の有機物系固体微粒子の量は有機物量として１％以下であった。処理槽は約０．５ｍ３であり、処理槽内部にはシャフトタイプのマイクロバブル発生装置（５０Ｗタイプ）を２台設置した。マイクロバブルの発生量は、パーティクルカウンタで測定したところ、５０μｍ以下の気泡として約２，０００個／ｍＬであった。また、発生装置の吸入気体としてオゾンを利用しており、吸入量は４Ｌ／分であった。
[Example]
Wastewater having a COD (chemical oxygen demand) of about 40,000 mg / L was introduced into the treatment tank at a flow rate of about 0.1 m 3 / hour. For processing raw water has implemented pretreated to remove beforehand organic-based solid fine particles (suspended solids), the amount of the organic-based solid material fine particles treated raw water was less than 1% organic matter . The treatment tank is about 0.5 m 3 , and two shaft type microbubble generators (50 W type) are installed inside the treatment tank. The amount of microbubbles generated was about 2,000 / mL as bubbles of 50 μm or less as measured with a particle counter. Further, ozone was used as the suction gas of the generator, and the suction amount was 4 L / min.
次に、処理槽内のマイクロバブルを含んだ排水（以下マイクロバブル含有排水）を、循環ポンプを利用して循環パイプ内を循環させ、処理槽に戻す前に、前記排水をパンチング板に通過させた。ポンプの循環量は約５０Ｌ／分であり、押し出し側の圧力は約０．２ＭＰａであった。次に、無機系凝集剤添加装置を利用してポリ塩化アルミニウム（ＰＡＣ）を約１５ｍＬ／分の割合で槽内に添加した。 Next, wastewater containing microbubbles in the treatment tank (hereinafter referred to as microbubble-containing wastewater) is circulated through the circulation pipe using a circulation pump, and the wastewater is passed through a punching plate before returning to the treatment tank. It was. The circulation rate of the pump was about 50 L / min, and the pressure on the extrusion side was about 0.2 MPa. Next, polyaluminum chloride (PAC) was added into the tank at a rate of about 15 mL / min using an inorganic flocculant addition apparatus.
上記の条件で処理を実施し、系が安定した段階で処理された排水について調べたところ大量の沈殿物（有機物系固体析出物）の発生を認めた。沈殿物には金属キレートなどの錯体も含まれており、ＴＯＦ−ＳＩＭＳにより分析したところＡｌ、ＮａやＫ、ＣａおよびＣ−Ｈ系が強く検知された。Ａｌは主にＰＡＣ由来であると思われるが、その他の元素も排水中に含まれていたものと考えられる。このことは有機物系固体析出物の析出に関して無機系凝集剤自体の無機成分のみでなく、排水自体に元来含まれていたイオン類も大きく関与していることを示している。 When the treatment was carried out under the above conditions and the wastewater treated at a stage where the system was stabilized was examined, generation of a large amount of precipitates (organic solid precipitates) was observed. The precipitate contained a complex such as a metal chelate, and when analyzed by TOF-SIMS, Al, Na, K, Ca, and C—H systems were strongly detected. Al is thought to be mainly derived from PAC, but other elements are also considered to be contained in the waste water. This indicates that not only the inorganic components of the inorganic flocculant itself but also the ions originally contained in the wastewater itself are involved in the precipitation of the organic solid precipitate.
処理水のＣＯＤは約５，０００ｍｇ／Ｌであった。比較例として、無機系凝集剤の添加を行わずに同様の処理を行った場合には沈殿物の生成はほとんど認められず、またＣＯＤは約３万ｍｇ／Ｌであった。 The COD of the treated water was about 5,000 mg / L. As a comparative example, when the same treatment was performed without adding the inorganic flocculant, almost no precipitate was observed, and the COD was about 30,000 mg / L.
なお、実施例は、あくまで一例である。 In addition, an Example is an example to the last.
１ 排水処理装置
２ 処理槽
３ マイクロバブル発生装置
４ 循環ポンプ
５ パンチング板
６ 循環パイプ
７ 凝集剤添加装置
DESCRIPTION OF SYMBOLS 1 Waste water treatment equipment 2 Processing tank 3 Micro bubble generator 4
Claims (7)
前記排水は、ＣＯＤが１０００ｍｇ／Ｌ以上であり、及び前記マイクロバブルを発生させる工程前に、予め前処理により有機物系固体粒子が取り除かれており、
前記無機系凝集剤は、前記排水に対し、０．１〜３％となるように、且つ前記圧壊工程の前若しくはその最中に添加され、
前記圧壊工程にて圧壊された前記マイクロバブルの表面において、前記排水中の溶解有機物並びに前記排水中及び前記無機系凝集剤により供給された電解質イオンが高濃度に濃縮されると共に、前記圧壊により生じたフリーラジカルの作用を受けて化学反応を起こすことにより、前記排水に含まれる有機物を前記有機物系固体析出物として析出させ、並びに前記有機物系固体析出物を分離除去することにより、処理された前記排水のＣＯＤが、排水処理前のＣＯＤの１／８になることを特徴とする排水処理方法。 For the wastewater containing organic matter, in the wastewater, a step of generating microbubbles having a diameter of 10 to 50 μm in which gas is contained, a step of giving a physical stimulus and crushing the microbubbles in the wastewater, wherein the step of adding a free machine flocculant to the wastewater, a wastewater treatment method using an inorganic flocculant and a step of separating and removing organic-based solid precipitates precipitated by the inorganic coagulant,
The waste water has a COD of 1000 mg / L or more, and before the step of generating the microbubbles, organic solid particles have been removed by pretreatment in advance,
The inorganic flocculant is added to the drainage so as to be 0.1 to 3% and before or during the crushing step ,
On the surface of the microbubbles crushed in the crushing step, the dissolved organic matter in the waste water and the electrolyte ions supplied by the inorganic flocculant in the waste water are concentrated to a high concentration and are generated by the crushing. under the action of free radicals by causing chemical reaction, the organic matter contained in the wastewater is precipitated as the organic-based solid deposits, as well as by separating off the organic-based solid precipitates, it treated the waste water treatment method COD of waste water, characterized in Rukoto such to 1/8 of COD before wastewater treatment.
The waste water treatment method according to any one of claims 1 to 6 , wherein the free radical is a hydroxyl radical.
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