JP4503523B2 - A method and apparatus for treating wastewater containing a crystallization target component. - Google Patents

A method and apparatus for treating wastewater containing a crystallization target component. Download PDF

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JP4503523B2
JP4503523B2 JP2005312944A JP2005312944A JP4503523B2 JP 4503523 B2 JP4503523 B2 JP 4503523B2 JP 2005312944 A JP2005312944 A JP 2005312944A JP 2005312944 A JP2005312944 A JP 2005312944A JP 4503523 B2 JP4503523 B2 JP 4503523B2
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crystallization
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紀夫 山田
康彦 鈴木
厚史 小林
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荏原エンジニアリングサービス株式会社
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Description

本発明は、晶析対象成分を含む排水、例えば下水、し尿、浄化槽汚泥、一般廃棄物処分場浸出水もしくはその他の工場排水またはこれらを生物処理等の処理がなされた排水の処理に関し、特に、カルシウムとリン酸イオン、又はフッ素イオン、硫酸イオンを含む排水の蒸留濃縮処理と、晶析処理をする方法及び装置に関する。   The present invention relates to the treatment of wastewater containing components to be crystallized, such as sewage, human waste, septic tank sludge, general waste disposal site leachate or other industrial wastewater, or wastewater that has been subjected to biological treatment or the like. The present invention relates to a method and an apparatus for subjecting a waste water containing calcium and phosphate ions, or fluorine ions and sulfate ions to distillation concentration treatment and crystallization treatment.

従来、カルシウムとリン酸イオン、又はフッ素イオン、硫酸イオンを含む排水などの晶析対象成分を含む排水を蒸留により凝縮水と濃縮排水に分離する方法において、蒸留単独では蒸発後の凝縮水は清澄なものが得られても、排水の濃縮により濃縮排水の晶析対象成分濃度が高くなり、晶析によりスケールが析出し蒸留装置内の蒸発面に付着するため、濃縮倍率を高くとることができなかった。その結果、廃棄物となる濃縮排水の発生量が低減できないという問題があった。   Conventionally, in a method of separating wastewater containing components to be crystallized such as wastewater containing calcium and phosphate ions, or fluorine ions and sulfate ions into condensed water and concentrated wastewater by distillation, the distilled water alone is clarified by distillation alone. However, the concentration of the crystallization target component of the concentrated wastewater becomes high due to the concentration of the wastewater, and the scale is deposited by the crystallization and adheres to the evaporation surface in the distillation apparatus. There wasn't. As a result, there has been a problem that the amount of concentrated wastewater that becomes waste cannot be reduced.

従って、本発明の目的は、蒸留濃縮処理と晶析処理を組合せることで、蒸留濃縮装置に流入する排水の晶析対象成分濃度を低減し、また、蒸留濃縮処理により晶析対象成分を高くし、晶析処理を行うことを可能にする排水の処理方法及びその処理装置を提供することである。   Therefore, the object of the present invention is to reduce the concentration of the crystallization target component of the wastewater flowing into the distillation concentration apparatus by combining the distillation concentration process and the crystallization process, and to increase the crystallization target component by the distillation concentration process. It is another object of the present invention to provide a wastewater treatment method and a treatment apparatus for enabling crystallization treatment.

本発明は、下記の手段により課題を解決することができた。
（１）晶析対象成分を含む排水を後の晶析工程からの晶析対象成分濃度が低減された濃縮排水と混合したものを蒸留濃縮工程に導入して蒸留濃縮し、蒸留により生じた蒸気は凝縮水として取り出し、蒸留濃縮により得られた濃縮排水は、一部を系外に取り出し、残りは晶析工程に導入して晶析させ、晶析物を取り出し、晶析工程からの晶析対象成分濃度が低減された濃縮排水を前記晶析対象成分を含む排水と混合するために循環することを特徴とする晶析対象成分を含む排水の処理方法。
（２）前記晶析対象成分を含む排水と前記晶析対象成分濃度が低減された濃縮排水との混合水のｐＨを調整することにより前記蒸留濃縮工程における液のｐＨを４〜７とし、晶析工程に入る濃縮排水の残りのｐＨを調整することにより前記晶析工程における液のｐＨを６〜９とすることを特徴とする前記（１）記載の晶析対象成分を含む排水の処理方法。 The present invention has solved the problems by the following means.
(1) Vapor produced by distillation by introducing a mixture of waste water containing the crystallization target component with concentrated waste water having a reduced concentration of the crystallization target component from the subsequent crystallization step into the distillation concentration step. Is taken out as condensed water, and part of the concentrated wastewater obtained by distillation and concentration is taken out of the system, the rest is introduced into the crystallization process to crystallize, the crystallized product is taken out, and the crystallization from the crystallization process A method for treating wastewater containing a crystallization target component, wherein the concentrated wastewater having a reduced concentration of the target component is circulated in order to mix with the wastewater containing the crystallization target component.
(2) The pH of the liquid in the distillation concentration step is adjusted to 4 to 7 by adjusting the pH of the mixed water of the waste water containing the crystallization target component and the concentrated waste water in which the concentration of the crystallization target component is reduced. The method for treating wastewater containing a crystallization target component according to (1), wherein the pH of the liquid in the crystallization step is adjusted to 6 to 9 by adjusting the remaining pH of the concentrated wastewater entering the crystallization step .

（３）前記晶析工程に入る濃縮排水に晶析用薬品を添加することを特徴とする前記（１）又は（２）記載の晶析対象成分を含む排水の処理方法。
（４）前記晶析工程においては、晶析装置の水位を一定に維持し、晶析装置内の晶析物貯留量をロードセルで管理することを特徴とする前記（１）〜（３）のいずれか１項記載の晶析対象成分を含む排水の処理方法。
（５）晶析物が、リン酸カルシウム、リン酸水素カルシウム、リン酸アパタイト、フッ化カルシウム、硫酸カルシウムの少なくとも１種であることを特徴とする前記（１）〜（４）のいずれか１項記載の晶析対象成分を含む排水の処理方法。 (3) The method for treating wastewater containing a crystallization target component according to (1) or (2), wherein a crystallization chemical is added to the concentrated wastewater entering the crystallization step.
(4) In the crystallization step, the water level of the crystallization apparatus is maintained constant, and the amount of crystallized matter stored in the crystallization apparatus is managed by a load cell. The processing method of the waste_water | drain containing the crystallization object component of any one.
(5) The crystallized product is at least one of calcium phosphate, calcium hydrogen phosphate, phosphate phosphate, calcium fluoride, and calcium sulfate, wherein any one of the above (1) to (4) is described. A method for treating wastewater containing the components to be crystallized.

（６）晶析対象成分を含む排水を後の晶析装置からの晶析対象成分濃度が低減された濃縮排水と混合した混合水を導入し、蒸留濃縮する、蒸留により生じた蒸気を凝縮水として取り出す蒸留濃縮装置と、該蒸留濃縮装置からの濃縮排水を、一部は系外に排出する配管から排出し、残りは配管から晶析装置に導入し晶析させ、晶析物の取出し管を有する晶析装置と、前記晶析装置の晶析対象成分濃度が低減された濃縮排水を前記晶析対象成分を含む排水の導入管に循環する配管とを有することを特徴とする晶析対象成分を含む排水の処理装置。
（７）前記蒸留濃縮装置は熱可塑性合成樹脂薄膜を蒸発面とするものであることを特徴とする前記（６）記載の晶析対象成分を含む排水の処理装置。
（８）前記晶析装置は、装置内に攪拌機が設けられ、種晶が流動する状態に維持されていることを特徴とする前記（６）又は（７）記載の晶析対象成分を含む排水の処理装置。 (6) Introducing mixed water obtained by mixing waste water containing the crystallization target component with concentrated effluent from a subsequent crystallization apparatus with reduced concentration of the crystallization target component, concentrating by distillation, and condensing water generated by distillation As a distillation concentrating device to be taken out, a part of the concentrated drainage from the distillation concentrating device is discharged from a pipe for discharging out of the system, and the rest is introduced into the crystallizer from the pipe to be crystallized, and a crystallized substance takeout pipe And a pipe for circulating the concentrated waste water in which the concentration of the crystallization target component of the crystallization device is reduced to the introduction pipe of the waste water containing the crystallization target component. Wastewater treatment equipment containing ingredients.
(7) The apparatus for treating wastewater containing a crystallization target component as described in (6) above, wherein the distillation concentration apparatus has a thermoplastic synthetic resin thin film as an evaporation surface.
(8) The waste water containing the crystallization target component according to (6) or (7), wherein the crystallizer is provided with a stirrer in the apparatus and is maintained in a state in which the seed crystal flows. Processing equipment.

通常の晶析処理では、晶析反応に必要な晶析対象成分のうち、不足している成分がある場合にはその不足する成分を、晶析用薬剤として添加するが、本発明では、晶析対象成分濃度が低くても濃縮に伴い、晶析対象成分濃度を晶析反応に必要な濃度とすることができる。又、晶析物を晶析装置で分離除去し、晶析対象成分濃度が低くなった排水を蒸留濃縮装置に返送するため、蒸留濃縮装置内でのスケール付着を抑制しながら濃縮倍率を高めることができるので、濃縮液発生量が小さくなり濃縮液産廃処分費を大幅に低減させることができる。   In a normal crystallization treatment, if there are insufficient components among the components to be crystallized necessary for the crystallization reaction, the insufficient components are added as a crystallization agent. Even if the concentration of the crystallization target component is low, the concentration of the crystallization target component can be set to a concentration necessary for the crystallization reaction with the concentration. In addition, the crystallization product is separated and removed by the crystallizer, and the wastewater with a low concentration of the crystallization target is returned to the distillation concentrator. As a result, the amount of concentrated liquid generated is reduced and the concentrated liquid production waste disposal cost can be greatly reduced.

本発明の実施形態の一例を、図面を参照して更に詳細に説明する。なお、実施の形態および実施例を説明する全図において、同一機能を有する構成要素は同一の符号を付けて説明する。   An example of an embodiment of the present invention will be described in more detail 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 and examples.

本発明の実施の形態を図１のフロー図で示す。
図１に示す処理装置は、蒸留濃縮装置１、晶析装置２で構成され、晶析対象成分を含む排水１１は、蒸留濃縮装置１で蒸発後に熱回収した凝縮水１２（処理水、場内再利用）と濃縮排水１３に分かれる。濃縮排水１３の一部１３Ａは系外に引き抜かれ、残る部分は晶析装置２で晶析され、晶析対象成分を含む排水１１とともに蒸留濃縮装置１に循環される。なお、図示していないが、各装置の前後には、適宜、配管、ポンプ等が設けられ、各排水が流入又は流出する。 An embodiment of the present invention is shown in the flowchart of FIG.
The treatment apparatus shown in FIG. 1 is composed of a distillation concentrating apparatus 1 and a crystallization apparatus 2, and waste water 11 containing a crystallization target component is condensed water 12 (treated water, in-site recycle) recovered by heat after evaporation in the distillation concentrating apparatus 1. Use) and concentrated drainage 13. A part 13A of the concentrated waste water 13 is drawn out of the system, and the remaining part is crystallized by the crystallizer 2 and circulated to the distillation concentrator 1 together with the waste water 11 containing the components to be crystallized. In addition, although not shown in figure, piping, a pump, etc. are suitably provided before and behind each apparatus, and each waste_water | drain flows in or out.

ここで、蒸留により晶析対象成分濃度が高くなった濃縮排水１３の一部は、晶析装置２に送られる。晶析槽２では種晶が流動している形式のものであって、そこでは濃縮排水１３の晶析対象成分が反応し、晶析物が析出する。
濃縮排水１３の晶析対象成分濃度が、蒸留濃縮されるにつれて高くなるため、晶析用薬品を添加することなく晶析反応は継続される。この反応の際に種晶があると、新たに晶析する晶析物は種晶表面に析出する。この特質により晶析物は次第に成長するため、沈降性の良い粒状となり、晶析槽内で、晶析物と濃縮排水の固液分離が可能となる。この後、晶析対象成分の低減された濃縮排水１４は蒸留濃縮装置１に循環される。晶析反応においては、晶析物の溶解度が小さいために、晶析物の回収率が高く、晶析槽から出る濃縮排水１４における晶析対象成分濃度は前記排水１１の晶析対象成分濃度よりも低くなる。 Here, a part of the concentrated waste water 13 whose concentration to be crystallized is increased by distillation is sent to the crystallizer 2. In the crystallization tank 2, seed crystals are flowing, in which the components to be crystallized in the concentrated waste water 13 react and precipitates.
Since the concentration of the component to be crystallized in the concentrated waste water 13 becomes higher as it is concentrated by distillation, the crystallization reaction is continued without adding crystallization chemicals. If there is a seed crystal in this reaction, a newly crystallized product is deposited on the surface of the seed crystal. Due to this characteristic, the crystallized product gradually grows, so that it becomes granular with good sedimentation properties, and it is possible to separate the crystallized product from the concentrated waste water in the crystallization tank. Thereafter, the concentrated drainage 14 in which the crystallization target component is reduced is circulated to the distillation concentration apparatus 1. In the crystallization reaction, since the solubility of the crystallized product is small, the recovery rate of the crystallized product is high, and the concentration of the crystallization target component in the concentrated drainage 14 coming out of the crystallization tank is higher than the concentration of the crystallization target component in the drainage 11. Also lower.

この濃縮排水１４は、スケール発生原因となる晶析対象成分濃度が低減されているので、蒸留濃縮装置１内の蒸発面等でのスケールの発生付着を抑制させ、濃縮排水１３の濃縮倍率をさらに高めることが可能となる。
また、上記晶析処理は、従来のように晶析用薬品を添加しなくとも達成でき、蒸留濃縮前の炭酸ソーダなどのカルシウム軟化剤も不要となる。 Since the concentration of the crystallization target component that causes the scale generation is reduced in the concentrated waste water 14, the generation of scale on the evaporation surface or the like in the distillation concentration apparatus 1 is suppressed, and the concentration rate of the concentrated waste water 13 is further increased. It becomes possible to raise.
In addition, the crystallization treatment can be achieved without adding a crystallization chemical as in the prior art, and a calcium softening agent such as sodium carbonate before distillation concentration is not required.

また、図２は、本発明の別の実施の形態を示すフロー図を示すものであって、蒸留濃縮装置１に入る晶析対象成分を含む排水にｐＨ調整剤、例えば酸を添加することにより、蒸留濃縮装置１内の液のｐＨを４〜７に調整し、また晶析装置２に入る濃縮排水１３にｐＨ調整剤、例えばアルカリを添加することにより、ｐＨを６〜９に調整する態様を示す。
図３は、晶析装置２に入る濃縮排水１３が、晶析反応を十分に進行させるには晶析対象成分の一部が不足している場合に、前記濃縮排水１３に晶析用成分（晶析用薬品）１０を添加する態様を示すものである。
なお、図２〜３では、図１と共通する番号はその装置等の構成が同一のものであることを意味している。 Moreover, FIG. 2 shows the flowchart which shows another embodiment of this invention, Comprising: By adding a pH adjuster, for example, an acid, to the waste_water | drain containing the crystallization target component which enters into the distillation concentration apparatus 1. FIG. The pH of the liquid in the distillation concentration apparatus 1 is adjusted to 4 to 7, and the pH is adjusted to 6 to 9 by adding a pH adjusting agent such as an alkali to the concentrated waste water 13 entering the crystallizer 2. Indicates.
FIG. 3 shows that when the concentrated drainage 13 entering the crystallization apparatus 2 has a part of the crystallization target component insufficient to cause the crystallization reaction to sufficiently proceed, the crystallization component ( The aspect which adds the chemical | medical agent for crystallization) 10 is shown.
In FIGS. 2 to 3, the numbers common to those in FIG. 1 mean that the configuration of the device or the like is the same.

蒸留装置の蒸発部は水平管型、垂直管型、コイル型、撹拌膜型、遠心式薄膜型、プレート型などいずれの形式でもよいが、スケール付着を抑制できるものが望ましい。特に蒸発面が金属面の場合、スケールが蒸発面に一度付着すると、付着したスケールの上にさらに新しいスケールが成長し続け、薬品による溶解、または、高圧力スプレー等の外力による剥離でしか、スケールを蒸発面から除去する方法がないという難点がある。このような問題を解決できるものとして以下の形態の蒸留濃縮装置による蒸留濃縮方法がある。   The evaporation unit of the distillation apparatus may be any type such as a horizontal tube type, a vertical tube type, a coil type, a stirring film type, a centrifugal thin film type, and a plate type, but it is desirable to be able to suppress scale adhesion. Especially when the evaporation surface is a metal surface, once the scale adheres to the evaporation surface, a new scale will continue to grow on the adhered scale, and the scale can only be dissolved by chemicals or peeled off by external force such as high pressure spray. There is a difficulty in that there is no method for removing from the evaporation surface. As a solution to such a problem, there is a distillation concentration method using a distillation concentration apparatus of the following form.

図５に、本発明の蒸留濃縮装置１の概略構成図を示す。蒸留濃縮装置１は、装置内部に蒸発面として１つ又は２つ以上の袋状の熱可塑性合成樹脂薄膜袋１６（例えばポリエチレン、又はポリプロピレンが利用される）が装着された蒸留濃縮装置本体１７、蒸留濃縮装置１本体に受け入れた濃縮対象排水を蒸発面に供給する循環ポンプ１８、蒸留によって蒸発した蒸気を圧縮するとともに昇温する自己蒸気再圧縮ファン又は外部蒸気加熱器２０、蒸発面を減圧する（負圧にする）真空ポンプ又はエジェクタ２１で構成される。晶析対象成分を含む排水１１は、蒸留濃縮装置１本体に流入する。ここで、流入した排水は本体を循環している濃縮排水と混合され、濃縮排水循環ポンプ１８により装置１本体上部に送水され、各熱可塑性合成樹脂薄膜袋１６に均等分配（流入水均等分配器１９）され、熱可塑性合成樹脂薄膜袋１６外面を流下し、蒸発濃縮される。蒸発蒸気は、自己蒸気再圧縮ファン又は外部蒸気加熱器２０により圧縮され、圧縮により１〜５℃ほど昇温され、熱可塑性合成樹脂薄膜袋１６内面に流入される。ここで圧縮蒸気は、薄膜１６面を流れる濃縮排水を蒸発させるべく熱可塑性合成樹脂薄膜袋１６内面から外面に熱を放出し、熱可塑性合成樹脂薄膜袋１６内で清澄な凝縮水となる。この凝縮水は、熱可塑性合成樹脂薄膜袋１６底部ノズル（図示せず）から排出され、場内で再利用等がなされる。装置の減圧方式には、真空ポンプ式又はエジェクタ式がある。また、蒸留濃縮装置１内圧は、１２０〜２００ｈＰａで運転する。   In FIG. 5, the schematic block diagram of the distillation concentration apparatus 1 of this invention is shown. The distillation concentrating apparatus 1 includes a distillation concentrating apparatus main body 17 in which one or two or more bag-like thermoplastic synthetic resin thin film bags 16 (for example, polyethylene or polypropylene are used) are attached as evaporation surfaces inside the apparatus. A circulation pump 18 that supplies the waste water to be concentrated received in the main body of the distillation concentrator 1 to the evaporation surface, a self-vapor recompression fan or external steam heater 20 that compresses and evaporates the vapor evaporated by distillation, and depressurizes the evaporation surface. It is composed of a vacuum pump or ejector 21 (to make negative pressure). The waste water 11 containing the crystallization target component flows into the distillation concentration apparatus 1 main body. Here, the influent wastewater is mixed with the concentrated wastewater circulating in the main body, and is sent to the upper part of the main body of the apparatus 1 by the concentrated wastewater circulation pump 18, and is evenly distributed to each thermoplastic synthetic resin thin film bag 16 (inflow water equalizing distributor). 19) and flows down the outer surface of the thermoplastic synthetic resin thin film bag 16 and is concentrated by evaporation. The evaporated steam is compressed by a self-vapor recompression fan or an external steam heater 20, heated to about 1 to 5 ° C. by compression, and flows into the inner surface of the thermoplastic synthetic resin thin film bag 16. Here, the compressed steam releases heat from the inner surface of the thermoplastic synthetic resin thin film bag 16 to evaporate the concentrated waste water flowing on the surface of the thin film 16, and becomes clear condensed water in the thermoplastic synthetic resin thin film bag 16. This condensed water is discharged from the bottom nozzle (not shown) of the thermoplastic synthetic resin thin film bag 16 and reused in the field. There are a vacuum pump type and an ejector type in the pressure reducing system of the apparatus. Moreover, the distillation concentration apparatus 1 is operated at an internal pressure of 120 to 200 hPa.

蒸留時の濃縮排水ｐＨを調整することでスケール発生がより抑制されることになる。スケール発生をより抑制するために、ｐＨを４〜７、望ましくは５〜６に調整する。ｐＨを７から下げるほどスケールが生成しにくい安全領域になるが、ｐＨ調整のための薬品コスト、排水の水質変動の影響などを考慮すると上記の範囲にすることが妥当である。また、ｐＨを７より高くするとスケールが生成しやすい方向となる。このｐＨ調整は蒸留濃縮装置１内に流入する排水、又は、蒸留濃縮装置１内を循環する濃縮排水のｐＨを計測し、ｐＨを下げる場合は塩酸等を、ｐＨを上げる場合は苛性ソーダなどを装置内または装置入口付近で注入し行う。   Scale generation is further suppressed by adjusting the concentrated drainage pH during distillation. In order to further suppress the generation of scale, the pH is adjusted to 4 to 7, preferably 5 to 6. As the pH is lowered from 7, it becomes a safe region where scales are less likely to be generated. However, considering the chemical cost for pH adjustment, the influence of fluctuations in the water quality of the drainage, etc., it is appropriate to make the above range. On the other hand, when the pH is higher than 7, the scale is likely to be generated. This pH adjustment measures the pH of the wastewater flowing into the distillation concentrator 1 or the concentrated wastewater circulating in the distillation concentrator 1, and equipment such as hydrochloric acid is used to lower the pH and caustic soda is used to raise the pH. Inject in or near the device inlet.

合成樹脂薄膜袋１６は、合成樹脂のためスケールが付着しにくく、また薄膜膜厚が１０〜１００μｍ、望ましくは４０〜６０μｍと非常に薄く、常に薄膜面が変形するためにスケール払い落し機能も持つ。これらの理由により、一般的な金属面の蒸発装置に比べ、スケールが付着しにくいという特徴を持つ。   Since the synthetic resin thin film bag 16 is a synthetic resin, the scale does not easily adhere to the thin film bag, and the thin film thickness is 10 to 100 μm, preferably 40 to 60 μm, and the thin film surface is always deformed. . For these reasons, the scale is less likely to adhere as compared with a general metal surface evaporation apparatus.

図６に、本発明の晶析装置の概略構成図を示す。晶析装置は、種晶が充填された晶析槽２２、撹拌機２３、ｐＨ計２４で構成される。晶析対象成分を含む排水１１は、晶析槽２２の上面と下面のない円筒形のバッフル板２５内側に流入され、撹拌機２３により流動している種晶表面に、新たな晶析物が析出し、晶析物１５が成長する。晶析反応により晶析対象成分が低減された濃縮排水１４は、バッフル板外側を上昇し、オーバーフロー口より排出される。また、晶析物１５は、槽内晶析物濃度が一定になるように定期的に引き抜かれる。さらに、槽内ｐＨは、晶析物の析出反応が起こりやすいｐＨ範囲に、ｐＨ計と苛性ソーダなどのアルカリ剤で調整される。
晶析対象成分により異なるが、晶析槽２２の滞留時間は概ね３０〜１８０分間、槽内ｐＨは６〜９、望ましくは７〜８、槽内晶析物濃度は２００００〜４００００ｍｇ／Ｌ（リットル）である。ｐＨが６を下回ると晶析物が析出しにくくなり、ｐＨが９を超えると晶析物が微細になり、ｐＨ調整のための薬品コストが高くなる。 In FIG. 6, the schematic block diagram of the crystallizer of this invention is shown. The crystallizer comprises a crystallizer 22 filled with seed crystals, a stirrer 23, and a pH meter 24. The waste water 11 containing the crystallization target component is introduced into the inside of the cylindrical baffle plate 25 having no upper and lower surfaces of the crystallization tank 22, and new crystallized substances are formed on the seed crystal surface flowing by the stirrer 23. Precipitates and crystallized product 15 grows. The concentrated drainage 14 in which the crystallization target component has been reduced by the crystallization reaction rises outside the baffle plate and is discharged from the overflow port. Further, the crystallized product 15 is periodically pulled out so that the crystallized product concentration in the tank becomes constant. Furthermore, the pH in the tank is adjusted with a pH meter and an alkaline agent such as caustic soda to a pH range in which the precipitation reaction of the crystallized product easily occurs.
The residence time of the crystallization tank 22 is generally 30 to 180 minutes, the pH in the tank is 6 to 9, preferably 7 to 8, and the crystallized substance concentration in the tank is 20000 to 40000 mg / L (liter), although it varies depending on the crystallization target component. ). When the pH is less than 6, the crystallized product is difficult to precipitate, and when the pH exceeds 9, the crystallized product becomes fine, and the chemical cost for pH adjustment increases.

撹拌機２３による種晶流動は、従来の上向流の水流による種晶流動に比べ、成長した粒径の大きな種晶も確実に流動させることができ、種晶が固着し流動性を失うことを防ぐことができる。また、種晶濃度を高く維持できるため、装置を小さくでき、さらに、安定した晶析処理が可能となる。撹拌機２３は、モータ２６、シャフト２７、羽根２８で構成されており、羽根２８の形状は、パドル、プロペラ、タービン等、種晶を流動させることができるものならば、どのような形状でも良い。
本発明において、晶析対象成分を含む排水としては、例示したカルシウムとリン酸を含有する排水の他に、カルシウムと硫酸を含有する排水、カルシウムとフッ素を含有する排水などが挙げられ、いずれも両方の成分が難溶性塩を生成する成分を含有する場合に好適である。 The seed crystal flow by the stirrer 23 can surely flow a seed crystal having a large particle size as compared with the conventional seed crystal flow by an upward water flow, and the seed crystal is fixed and loses fluidity. Can be prevented. In addition, since the seed crystal concentration can be maintained high, the apparatus can be made small, and stable crystallization treatment can be performed. The stirrer 23 includes a motor 26, a shaft 27, and blades 28. The blades 28 may have any shape as long as seed crystals can flow, such as paddles, propellers, and turbines. .
In the present invention, the waste water containing the crystallization target component includes waste water containing calcium and sulfuric acid, waste water containing calcium and fluorine, and the like, in addition to the exemplified waste water containing calcium and phosphoric acid. It is suitable when both components contain a component that forms a sparingly soluble salt.

以下において、本発明を実施例によりさらに詳細に説明するが、本発明の範囲はこれらの実施例により制限されるものではない。   EXAMPLES In the following, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited by these examples.

実施例１
図４に示す処理フローを備えた設備を用い実験を行った。この実験の晶析対象成分は、カルシウムとリンで、晶析物は、リン酸ヒドロキシアパタイト（以下「ＨＡＰ」とする）である。この晶析反応における反応式は、下記（１）で示される。
１０Ｃａ２＋＋６ＰＯ４ ３−＋２ＯＨ− → Ｃａ１０（ＰＯ４）６（ＯＨ）２・・・（１）
図４に示す処理フローは、図１に示す処理フローと同じであるが、処理する排水３がカルシウムとリン酸を含む排水であり、その関係で、図１とは異なって、晶析物はＨＡＰ７であり、凝縮水４、濃縮排水５、カルシウムが低減された濃縮排水６と示されている。
濃縮排水５のカルシウムイオンとリン酸イオン濃度が、蒸留濃縮されるにつれて高くなるため、カルシウム系薬品を添加することなくＨＡＰ晶析反応は継続される。この反応の際にＨＡＰ種晶があると、新たに晶析するＨＡＰは種晶表面に析出する。この特質によりＨＡＰ晶析物は次第に成長するため、沈降性の良い粒状となり、ＨＡＰ晶析槽内で、晶析物と濃縮排水の固液分離が可能となる。この後、カルシウムイオンの低減された濃縮排水６は蒸留濃縮装置１に循環される。ＨＡＰ晶析反応においては、ＨＡＰの溶解度が小さいために、ＨＡＰ晶析槽から出る濃縮排水６におけるカルシウム濃度は前記排水３のカルシウム濃度よりも低くなる。 Example 1
Experiments were performed using equipment equipped with the processing flow shown in FIG. The components to be crystallized in this experiment are calcium and phosphorus, and the crystallized product is hydroxyapatite phosphate (hereinafter referred to as “HAP”). The reaction formula in this crystallization reaction is shown by the following (1).
10Ca 2+ + 6PO 4 3- + 2OH − → Ca 10 (PO 4 ) 6 (OH) 2 (1)
The processing flow shown in FIG. 4 is the same as the processing flow shown in FIG. 1, but the waste water 3 to be treated is waste water containing calcium and phosphoric acid. HAP7 is shown as condensed water 4, concentrated drainage 5, and concentrated drainage 6 with reduced calcium.
Since the concentration of calcium ions and phosphate ions in the concentrated wastewater 5 increases as the concentration is increased by distillation, the HAP crystallization reaction is continued without adding calcium-based chemicals. If there is a HAP seed crystal during this reaction, newly crystallized HAP is deposited on the surface of the seed crystal. Due to this characteristic, the HAP crystallized product gradually grows, so that it becomes granular with good sedimentation, and the solid-liquid separation of the crystallized product and the concentrated waste water becomes possible in the HAP crystallizer. Thereafter, the concentrated drainage 6 with reduced calcium ions is circulated to the distillation concentrating device 1. In the HAP crystallization reaction, since the solubility of HAP is small, the calcium concentration in the concentrated drainage 6 coming out of the HAP crystallization tank is lower than the calcium concentration in the drainage 3.

第２表に示す水質の、し尿と浄化槽汚泥の混合排水の生物処理水を、第３表に示す条件で蒸留濃縮する連続試験を行った。濃縮排水濃縮倍率が所定の倍率になるように、濃縮排水引抜量を調整した。濃縮排水の一部をＨＡＰ晶析装置に流入させ、ＨＡＰを析出させ、ＨＡＰ晶析物を沈降分離した後、カルシウムが低減された濃縮排水を蒸留濃縮装置に循環させた。試験後、蒸留濃縮装置内のスケール付着状況を確認した。この試験により、第１表に示す結果を得た。濃縮排水のカルシウムイオンをＨＡＰ晶析により分離低減することにより、蒸留濃縮装置内にスケールを付着させることなく濃縮排水を７倍まで濃縮させることができた。一方、比較例（従来例）では、濃縮排水をＨＡＰ処理なしで循環したところ、濃縮排水は３倍まで濃縮した時点で、蒸留濃縮装置内にスケールが多く付着する結果となった。試験結果は第１表に示す。
また、第２表に実施例１（本発明）で行った蒸留濃縮の水質結果を示す。 A continuous test was conducted in which the biologically treated water of the mixed wastewater of human waste and septic tank sludge shown in Table 2 was distilled and concentrated under the conditions shown in Table 3. The amount of concentrated drainage withdrawn was adjusted so that the concentrated wastewater concentration ratio would be a predetermined ratio. A part of the concentrated wastewater was allowed to flow into the HAP crystallizer, HAP was precipitated, and the HAP crystallized product was settled and separated, and then the concentrated wastewater with reduced calcium was circulated through the distillation concentrator. After the test, the state of scale adhesion in the distillation concentration apparatus was confirmed. By this test, the results shown in Table 1 were obtained. By separating and reducing calcium ions in the concentrated wastewater by HAP crystallization, the concentrated wastewater could be concentrated up to 7 times without depositing scale in the distillation concentration apparatus. On the other hand, in the comparative example (conventional example), when the concentrated wastewater was circulated without HAP treatment, when the concentrated wastewater was concentrated up to 3 times, a large amount of scale adhered to the distillation concentrator. The test results are shown in Table 1.
Table 2 shows the water quality results of the distillation and concentration performed in Example 1 (the present invention).

Figure 0004503523
Figure 0004503523

Figure 0004503523
Figure 0004503523

Figure 0004503523
Figure 0004503523

本発明によれば、蒸留濃縮装置内でのカルシウム系スケール発生付着を抑制しながら濃縮倍率を高めることができる。そのため、濃縮排水引抜き量を従来の１／３程度にすることができ、廃棄物処分費を大きく削減させることができる。
また、本発明の蒸留処理による凝縮水（処理水）の水質は、ＢＯＤ、ＣＯＤ、ＳＳ、色度、蒸発残留物が、全くない清澄なものになり、場内の工業用水としての再利用が可能になる。 ADVANTAGE OF THE INVENTION According to this invention, a concentration magnification can be raised, suppressing the calcium system scale generation | occurrence | production adhesion | attachment in a distillation concentration apparatus. Therefore, the amount of concentrated drainage can be reduced to about 1/3 of the conventional amount, and the waste disposal cost can be greatly reduced.
In addition, the water quality of the condensed water (treated water) by the distillation treatment of the present invention is clear with no BOD, COD, SS, chromaticity, and evaporation residue, and can be reused as industrial water in the field. become.

また、特にＨＡＰ晶析処理では、ＨＡＰ晶析反応に必要なカルシウムを、カルシウム系薬品として添加している。ところが、本発明では、濃縮にともないカルシウムイオン濃度が高くなることを利用しＨＡＰ晶析反応を継続するため、カルシウム系薬品の添加が不要となる。
さらに、ＨＡＰ晶析反応により発生したＨＡＰはリン酸肥料つまり有価物として再利用可能で、従来のカルシウム軟化処理により発生する炭酸カルシウム汚泥の、廃棄物処分費を無くすことができる。 Particularly in the HAP crystallization treatment, calcium necessary for the HAP crystallization reaction is added as a calcium-based chemical. However, in the present invention, since the HAP crystallization reaction is continued by utilizing the fact that the calcium ion concentration increases with concentration, it is not necessary to add calcium-based chemicals.
Furthermore, the HAP generated by the HAP crystallization reaction can be reused as a phosphate fertilizer, that is, a valuable material, and the waste disposal cost of the calcium carbonate sludge generated by the conventional calcium softening treatment can be eliminated.

本発明は、下水、し尿、産業排水などの晶析対象成分を含有する排水を、カルシウム軟化薬品や晶析用添加薬品を添加せず処理することができるので、下水処理場や各種排水処理施設等における利用が期待される。   The present invention can treat wastewater containing crystallization target components such as sewage, human waste, and industrial wastewater without adding calcium softening chemicals or additive chemicals for crystallization. The use in etc. is expected.

本発明の処理フローを示す図である。It is a figure which shows the processing flow of this invention. ｐＨ調整手段を用いる本発明の処理フローを示す図である。It is a figure which shows the processing flow of this invention using a pH adjustment means. 晶析用薬品を添加する本発明の処理フローを示す図である。It is a figure which shows the processing flow of this invention which adds the chemical | medical agent for crystallization. 本発明の実施例における処理フローを示す図である。It is a figure which shows the processing flow in the Example of this invention. 本発明の処理装置において、蒸留濃縮装置の概略構成を示す図である。In the processing apparatus of this invention, it is a figure which shows schematic structure of the distillation concentration apparatus. 本発明の処理装置において、晶析装置の概略構成を示す図である。In the processing apparatus of this invention, it is a figure which shows schematic structure of a crystallization apparatus.

符号の説明Explanation of symbols

１ 蒸留濃縮装置
２ 晶析装置
３ カルシウムとリン酸を含む排水
４ 凝縮水
５ 濃縮排水
６ カルシウムが低減された濃縮排水
７ ＨＡＰ晶析物
８ 酸
９ アルカリ
１０ 晶析用薬品
１１ 晶析対象成分を含む排水
１２ 凝縮水（処理水、場内再利用）
１３ 濃縮排水
１３Ａ 濃縮排水（系外へ）
１４ 晶析対象成分が低減された濃縮排水
１５ 晶析物（系外へ）
１６ 熱可塑性合成樹脂薄膜袋
１７ 蒸留濃縮装置本体
１８ 濃縮排水循環ポンプ
１９ 流入水均等分配器
２０ 自己蒸気再圧縮ファン（又は外部蒸気加熱器）
２１ 真空ポンプ（又はエジェクタ）
２２ 晶析槽
２３ 攪拌機
２４ ｐＨ計
２５ バッフル板
２６ モータ
２７ 攪拌シャフト
２８ 攪拌羽根
２９ アルカリ DESCRIPTION OF SYMBOLS 1 Distillation concentration apparatus 2 Crystallization apparatus 3 Waste water containing calcium and phosphoric acid 4 Condensed water 5 Concentrated waste water 6 Concentrated waste water with reduced calcium 7 HAP crystallization product 8 Acid 9 Alkali 10 Crystallizing chemical 11 Including waste water 12 Condensed water (treated water, reuse in the field)
13 Concentrated wastewater 13A Concentrated wastewater (outside the system)
14 Concentrated wastewater with reduced crystallization target components 15 Crystallized product (outside system)
16 Thermoplastic Synthetic Resin Thin Film Bag 17 Distillation Concentrator Main Body 18 Concentrated Drain Circulation Pump 19 Inflow Water Equal Distributor 20 Self Steam Recompression Fan (or External Steam Heater)
21 Vacuum pump (or ejector)
22 Crystallization tank 23 Stirrer 24 pH meter 25 Baffle plate 26 Motor 27 Stirrer shaft 28 Stirrer blade 29 Alkali

Claims (8)

晶析対象成分を含む排水を後の晶析工程からの晶析対象成分濃度が低減された濃縮排水と混合したものを蒸留濃縮工程に導入して蒸留濃縮し、蒸留により生じた蒸気は凝縮水として取り出し、蒸留濃縮により得られた濃縮排水は、一部を系外に取り出し、残りは晶析工程に導入して晶析させ、晶析物を取り出し、晶析工程からの晶析対象成分濃度が低減された濃縮排水を前記晶析対象成分を含む排水と混合するために循環することを特徴とする晶析対象成分を含む排水の処理方法。   The waste water containing the crystallization target component mixed with the concentrated effluent from which the concentration of the crystallization target component from the subsequent crystallization step is reduced is introduced into the distillation concentration step and concentrated by distillation. The vapor generated by the distillation is condensed water. Concentrated wastewater obtained by distillation and concentration is partially taken out of the system, the rest is introduced into the crystallization step for crystallization, the crystallization product is taken out, and the concentration of crystallization target components from the crystallization step A method for treating wastewater containing a crystallization target component, characterized in that the concentrated wastewater reduced in water is circulated to mix with the wastewater containing the crystallization target component. 前記晶析対象成分を含む排水と前記晶析対象成分濃度が低減された濃縮排水との混合水のｐＨを調整することにより前記蒸留濃縮工程における液のｐＨを４〜７とし、晶析工程に入る濃縮排水の残りのｐＨを調整することにより前記晶析工程における液のｐＨを６〜９とすることを特徴とする請求項１記載の晶析対象成分を含む排水の処理方法。   By adjusting the pH of the mixed water of the waste water containing the crystallization target component and the concentrated waste water having a reduced concentration of the crystallization target component, the pH of the liquid in the distillation concentration step is set to 4 to 7, and the crystallization step The method for treating wastewater containing a crystallization target component according to claim 1, wherein the pH of the liquid in the crystallization step is adjusted to 6 to 9 by adjusting the remaining pH of the concentrated wastewater that enters. 前記晶析工程に入る濃縮排水に晶析用薬品を添加することを特徴とする請求項１又は請求項２記載の晶析対象成分を含む排水の処理方法。   The method for treating wastewater containing a crystallization target component according to claim 1 or 2, wherein a crystallization chemical is added to the concentrated wastewater entering the crystallization step. 前記晶析工程においては、晶析装置の水位を一定に維持し、晶析装置内の晶析物貯留量をロードセルで管理することを特徴とする請求項１〜３のいずれか１項記載の晶析対象成分を含む排水の処理方法。   In the said crystallization process, the water level of a crystallizer is maintained constant, and the crystallized material storage amount in a crystallizer is managed with a load cell, The any one of Claims 1-3 characterized by the above-mentioned. A method for treating wastewater containing components to be crystallized. 晶析物が、リン酸カルシウム、リン酸水素カルシウム、リン酸アパタイト、フッ化カルシウム、硫酸カルシウムの少なくとも１種であることを特徴とする請求項１〜４のいずれか１項記載の晶析対象成分を含む排水の処理方法。   The crystallization target component according to any one of claims 1 to 4, wherein the crystallized product is at least one of calcium phosphate, calcium hydrogen phosphate, phosphate apatite, calcium fluoride, and calcium sulfate. Wastewater treatment method including. 晶析対象成分を含む排水を後の晶析装置からの晶析対象成分濃度が低減された濃縮排水と混合した混合水を導入し、蒸留濃縮する、蒸留により生じた蒸気を凝縮水として取り出す蒸留濃縮装置と、該蒸留濃縮装置からの濃縮排水を、一部は系外に排出する配管から排出し、残りは配管から晶析装置に導入し晶析させ、晶析物の取出し管を有する晶析装置と、前記晶析装置の晶析対象成分濃度が低減された濃縮排水を前記晶析対象成分を含む排水の導入管に循環する配管とを有することを特徴とする晶析対象成分を含む排水の処理装置。   Distillation that removes the vapor generated by distillation as condensed water by introducing mixed water mixed with wastewater containing the target component for crystallization and concentrated wastewater from the subsequent crystallizer with reduced concentration of target component for crystallization. Concentrated wastewater from the concentrating device and the distillation concentrating device, partly discharged from the piping for discharging out of the system, the rest is introduced into the crystallization device from the piping to be crystallized, and has a crystallized material extraction tube. A crystallization target component comprising: a crystallization apparatus; and a pipe that circulates a concentrated waste water in which the concentration of the crystallization target component of the crystallization apparatus is reduced to an introduction pipe of the waste water containing the crystallization target component. Wastewater treatment equipment. 前記蒸留濃縮装置は熱可塑性合成樹脂薄膜を蒸発面とするものであることを特徴とする請求項６記載の晶析対象成分を含む排水の処理装置。   7. The apparatus for treating wastewater containing a crystallization target component according to claim 6, wherein the distillation concentrating apparatus has a thermoplastic synthetic resin thin film as an evaporation surface. 前記晶析装置は、装置内に攪拌機が設けられ、種晶が流動する状態に維持されていることを特徴とする請求項６又は請求項７記載の晶析対象成分を含む排水の処理装置。   The apparatus for treating wastewater containing a crystallization target component according to claim 6 or 7, wherein the crystallization apparatus is provided with a stirrer in the apparatus and maintained in a state in which seed crystals flow.
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