JPH11147088A - Dephosphorization of waste water - Google Patents
Dephosphorization of waste waterInfo
- Publication number
- JPH11147088A JPH11147088A JP25052198A JP25052198A JPH11147088A JP H11147088 A JPH11147088 A JP H11147088A JP 25052198 A JP25052198 A JP 25052198A JP 25052198 A JP25052198 A JP 25052198A JP H11147088 A JPH11147088 A JP H11147088A
- Authority
- JP
- Japan
- Prior art keywords
- phosphorus
- membrane separation
- water
- adsorbent
- adsorption tower
- 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.)
- Granted
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Removal Of Specific Substances (AREA)
- Water Treatment By Sorption (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、化学工業、食品工
業、医薬工業、肥料工業等の各種工場から出る排水や、
下水処理場、し尿処理場等の処理施設から出る排水の処
理に関し、より詳しくは、排水中にオルトリン酸イオ
ン、ポリリン酸イオン、有機リン酸イオン等の形態で含
まれているリンの除去方法に関するものである。TECHNICAL FIELD The present invention relates to wastewater from various factories such as the chemical, food, pharmaceutical, and fertilizer industries,
The present invention relates to treatment of wastewater from treatment facilities such as sewage treatment plants and human waste treatment plants, and more particularly to a method for removing phosphorus contained in wastewater in the form of orthophosphate ions, polyphosphate ions, organic phosphate ions, and the like. Things.
【0002】[0002]
【従来の技術】従来、排水中のリンを除去するには、凝
集剤として硫酸アルミニウム(硫酸バンド)、ポリ塩化
アルミニウム(PAC)等のアルミニウム塩や、硫酸第
1鉄、塩化第2鉄等の鉄塩を用い、リンを凝集沈殿させ
る方法が一般的であった。2. Description of the Related Art Conventionally, to remove phosphorus from wastewater, aluminum salts such as aluminum sulfate (sulfuric acid band) and polyaluminum chloride (PAC) as a coagulant, and ferrous sulfate and ferric chloride such as ferric chloride are used. A method of coagulating and precipitating phosphorus using an iron salt was generally used.
【0003】[0003]
【発明が解決しようとする課題】しかし、上記従来の方
法では多量の凝集剤を連続して使用するため、処理コス
トが高く付き、また凝集剤から大量の沈殿物が汚泥とし
て発生し、汚泥の処理ないし管理に苦慮するという問題
があり、汚泥の再資源化も困難であった。However, in the above-mentioned conventional method, a large amount of coagulant is used continuously, so that the treatment cost is high, and a large amount of sediment is generated from the coagulant as sludge, and There was a problem of difficulty in treatment or management, and it was difficult to recycle sludge.
【0004】本発明は、このような点に鑑み、処理コス
トが少なくてすみ、厄介な凝集沈殿物の発生がなく、ま
た吸着したリンを再資源化することができる、排水の脱
リン方法を提供することを目的とする。[0004] In view of the above, the present invention provides a method for removing phosphorus from wastewater, which can reduce the processing cost, does not generate troublesome coagulated precipitates, and can recycle adsorbed phosphorus. The purpose is to provide.
【0005】[0005]
【課題を解決するための手段】本発明による第1の脱リ
ン方法は、排水を膜分離処理し、ついでジルコニウムフ
ェライト水和物を構成材料とするリン吸着剤でリン吸着
処理することを特徴とする方法である。A first method for removing phosphorus according to the present invention is characterized in that waste water is subjected to membrane separation treatment, and then to phosphorus absorption treatment with a phosphorus adsorbent containing zirconium ferrite hydrate as a constituent material. How to
【0006】膜分離処理水のpHは好ましくは5.8〜
8.6、より好ましくは6.5〜7.5の範囲とし、リ
ン吸着剤の性能を向上させる。[0006] The pH of the membrane separation treatment water is preferably 5.8 to
8.6, more preferably in the range of 6.5 to 7.5, to improve the performance of the phosphorus adsorbent.
【0007】また、膜分離処理水のpHを1.0〜6.
5に調整し、リン吸着処理水のpHを5.8〜8.6に
調整することも好ましい。この場合、ジルコニウムフェ
ライト水和物のリン吸着容量が大幅に増える。pH調整
剤としては硫酸、塩酸等の一般的な酸性水溶液や、苛性
ソーダ、苛性カリ等の一般的なアルカリ性水溶液が用い
られる。Further, the pH of the membrane separation treatment water is adjusted to 1.0 to 6.
It is also preferable to adjust the pH to 5 and adjust the pH of the phosphorus adsorption treatment water to 5.8 to 8.6. In this case, the phosphorus adsorption capacity of zirconium ferrite hydrate greatly increases. As the pH adjusting agent, a general acidic aqueous solution such as sulfuric acid or hydrochloric acid, or a general alkaline aqueous solution such as caustic soda or caustic potash is used.
【0008】リン吸着塔内の通水条件は、線速度(L
V)で好ましくは50〜500(cm/h)、より好ま
しくは100〜250(cm/h)、空間速度(SV)
で1〜10(1/h)、より好ましくは2〜5(1/
h)の範囲である。[0008] The water flow conditions in the phosphorus adsorption tower are linear velocity (L
V), preferably 50 to 500 (cm / h), more preferably 100 to 250 (cm / h), space velocity (SV)
1 to 10 (1 / h), more preferably 2 to 5 (1 / h).
h).
【0009】膜分離処理水を吸着塔より高い位置にある
受け槽に一旦受けることが好ましい。これによって、膜
分離装置の間欠運転時にも受け槽から吸着塔へ水を連続
供給することができる。It is preferable that the membrane separation treatment water is once received in a receiving tank located at a position higher than the adsorption tower. Thus, water can be continuously supplied from the receiving tank to the adsorption tower even during the intermittent operation of the membrane separation device.
【0010】受け槽からリン吸着塔への流量を、流量調
整バルブ、または、水中ポンプと三角堰を備えた計量器
との組合せによって調整することが好ましい。流量調整
バルブとしては流量自動調整バルブが、水中ポンプとし
ては空転防止機能付きのものが好ましい。上記計量器は
三角堰の働きにより水を一定流量ずつ吸着塔に供給する
ものであり、三角堰の堰板は上下にスライド自在であ
り、これにより供給量を変えることができる。It is preferable that the flow rate from the receiving tank to the phosphorus adsorption tower be adjusted by a flow rate control valve or a combination of a submersible pump and a measuring device having a triangular weir. It is preferable that the flow control valve be an automatic flow control valve, and that the submersible pump be one with an anti-spin function. The above-mentioned measuring device supplies water to the adsorption tower at a constant flow rate by the function of the triangular weir, and the weir plate of the triangular weir is slidable up and down, so that the supply amount can be changed.
【0011】膜分離処理水をリン吸着塔へ供給するに当
たり、吸着塔の頂部に塔直径の好ましくは0.5〜5倍
の高さの水頭を設ける。この場合、リン吸着塔では、水
は水頭圧による重量濾過方式で通水する。In supplying the treated water to the phosphorus adsorption tower, a head having a height of preferably 0.5 to 5 times the diameter of the tower is provided at the top of the adsorption tower. In this case, in the phosphorus adsorption tower, water is passed by a weight filtration method using a head pressure.
【0012】膜分離処理水をリン吸着塔の頂部で分散さ
せることも好ましい。この分散は、例えば、処理水流れ
方向に直交する平板状分散板を用いて行う。この分散に
よって、膜分離処理水を吸着塔内に均一に供給し、十分
なリン吸着処理をすることができる。It is also preferable to disperse the membrane separation treatment water at the top of the phosphorus adsorption tower. This dispersion is performed using, for example, a flat dispersion plate orthogonal to the flow direction of the treated water. By this dispersion, the water for membrane separation treatment can be uniformly supplied into the adsorption tower, and sufficient phosphorus adsorption treatment can be performed.
【0013】第1の脱リン方法で用いるリン吸着剤は、
ジルコニウムフェライト水和物をベースとするものであ
って、例えば武田薬品工業(株)製の「セブントール
P」が好適に使用される。これは、ジルコニウムフェラ
イト水和物が保有する表面水酸基に由来するイオン交換
性を利用して、リン酸イオンを選択的に吸着除去するも
のであり、使用後、再生して再使用可能なリン吸着剤で
ある。The phosphorus adsorbent used in the first dephosphorization method is
It is based on zirconium ferrite hydrate. For example, "Seventor P" manufactured by Takeda Pharmaceutical Co., Ltd. is preferably used. This is to selectively adsorb and remove phosphate ions by utilizing the ion exchangeability derived from the surface hydroxyl groups possessed by zirconium ferrite hydrate. Agent.
【0014】第1の脱リン方法で用いるリン吸着剤の平
均粒径は、好ましくは0.1〜4.0mm、より好まし
くは0.2〜1.5mmである。The average particle diameter of the phosphorus adsorbent used in the first phosphorus removal method is preferably 0.1 to 4.0 mm, more preferably 0.2 to 1.5 mm.
【0015】第1の脱リン方法は、ある時間実施すると
破過点に達する。破過後、リン吸着塔内のリン吸着剤を
薬液洗浄するには、薬剤供給ラインからリン吸着塔に洗
浄剤を供給するのが好ましい。薬剤供給ラインは吸着処
理すべき液の供給ラインに接続されている。洗浄剤とし
ては苛性ソーダ等のアルカリ水溶液が好ましい。この洗
浄によってリン吸着剤からリン酸塩が脱離される。つい
で、吸着剤活性化のため硫酸や塩酸等の酸を薬剤供給ラ
インから吸着剤充填部へ通水し、リン吸着剤の再生を行
う。[0015] The first dephosphorization method reaches a breakthrough point when it is carried out for a certain time. After the breakthrough, in order to wash the phosphorus adsorbent in the phosphorus adsorption tower with a chemical solution, it is preferable to supply a detergent from the chemical supply line to the phosphorus adsorption tower. The drug supply line is connected to a supply line for the liquid to be subjected to the adsorption treatment. As the cleaning agent, an aqueous alkali solution such as caustic soda is preferable. This washing removes phosphate from the phosphorus adsorbent. Next, in order to activate the adsorbent, an acid such as sulfuric acid or hydrochloric acid is passed from the drug supply line to the adsorbent filling section to regenerate the phosphorus adsorbent.
【0016】リン吸着塔としては、リン吸着剤を充填し
た複数カラムからなるカートリッジをリン吸着塔内に取
り替え可能に組み込んだものが好ましい。カートリッジ
の使用により、吸着剤の取り替え操作が簡単になし得、
またリン吸着塔のメンテナンスが楽である。The phosphorus adsorption tower is preferably one in which a cartridge comprising a plurality of columns filled with a phosphorus adsorbent is replaceably incorporated in the phosphorus adsorption tower. The use of cartridges makes it easy to replace the adsorbent,
Also, maintenance of the phosphorus adsorption tower is easy.
【0017】また、受け槽から放流槽へオーバーフロー
ラインを設けることも好ましい。何らかの原因で膜分離
装置の膜が破損等を生じ浮遊物質が同装置から流出しリ
ン吸着塔が目詰まりを起こしたときでも、同ラインによ
って、受け槽のオーバーフローを放流槽へ流出させて吸
着塔の水溢れを防止できる。It is also preferable to provide an overflow line from the receiving tank to the discharge tank. Even if the membrane of the membrane separation device is damaged for any reason and suspended matter flows out of the device and the phosphorus adsorption tower is clogged, the overflow of the receiving tank flows out to the discharge tank by the same line and the adsorption tower Water can be prevented.
【0018】本発明による第2の脱リン方法は、膜分離
装置内において膜の原水側に、ジルコニウムフェライト
水和物を構成材料とするリン吸着剤を投入して排水をリ
ン吸着処理し、ついで膜分離処理することを特徴とする
方法である。In a second method for removing phosphorus according to the present invention, a phosphorus adsorbent containing zirconium ferrite hydrate as a constituent material is charged into a raw water side of a membrane in a membrane separation apparatus, and the wastewater is subjected to a phosphorus adsorption treatment. This is a method characterized by performing a membrane separation treatment.
【0019】膜分離装置内の底部はホッパー形状にする
ことが好ましい。膜分離装置内に散気することも好まし
い。散気によりリン吸着剤が膜分離装置内に均一に攪拌
され、脱リン処理が効率よくなされる。膜分離装置の底
部から堆積した汚泥および吸着剤を、通常は間欠的に引
き抜く。これによって、吸着剤の交換を容易に行うこと
ができる。It is preferable that the bottom of the membrane separation device is formed in a hopper shape. It is also preferable to diffuse air into the membrane separation device. By the aeration, the phosphorus adsorbent is uniformly stirred in the membrane separation device, and the phosphorus removal treatment is efficiently performed. Sludge and adsorbent deposited from the bottom of the membrane separator are usually withdrawn intermittently. Thereby, the replacement of the adsorbent can be easily performed.
【0020】膜分離装置内の排水のpHは好ましくは
5.8〜8.6、より好ましくは6.5〜7.5の範囲
である。The pH of the waste water in the membrane separation device is preferably in the range of 5.8 to 8.6, more preferably in the range of 6.5 to 7.5.
【0021】また、膜分離装置内の排水のpHを1.0
〜6.5に調整し、リン吸着処理水のpHを5.8〜
8.6に調整することも好ましい。pH値の選択は、膜
分離装置内の膜や排水中の活性汚泥等の耐酸性を考慮し
て行われる。pH調整剤としては硫酸、塩酸等の一般的
な酸性水溶液や、苛性ソーダ、苛性カリ等の一般的なア
ルカリ性水溶液が用いられる。Further, the pH of the waste water in the membrane separation device is adjusted to 1.0
~ 6.5 and adjust the pH of the phosphorus adsorption treated water to 5.8 ~
Adjustment to 8.6 is also preferable. The selection of the pH value is performed in consideration of the acid resistance of the membrane in the membrane separation device and the activated sludge in the wastewater. As the pH adjusting agent, a general acidic aqueous solution such as sulfuric acid or hydrochloric acid, or a general alkaline aqueous solution such as caustic soda or caustic potash is used.
【0022】第2の脱リン方法で用いるリン吸着剤も、
ジルコニウムフェライト水和物をベースとするものであ
って、例えば武田薬品工業(株)製の「セブントール
P」が好適に使用される。The phosphorus adsorbent used in the second dephosphorization method also includes
It is based on zirconium ferrite hydrate. For example, "Seventor P" manufactured by Takeda Pharmaceutical Co., Ltd. is preferably used.
【0023】第2の脱リン方法で用いる吸着剤の平均粒
径は、好ましくは0.1〜4.0mm、より好ましくは
0.2〜1.5mmである。The average particle size of the adsorbent used in the second dephosphorization method is preferably from 0.1 to 4.0 mm, more preferably from 0.2 to 1.5 mm.
【0024】[0024]
【発明の実施の形態】つぎに、実施例に基づき、本発明
を具体的に説明する。なお、全図面を通じて同一物およ
び同一部分には同一符号を付して重複する説明を省略す
る。Next, the present invention will be specifically described based on examples. Note that the same components and portions are denoted by the same reference symbols throughout the drawings, and redundant description will be omitted.
【0025】実施例1 図1において、膜分離装置(1) の槽内には、複数の中空
状平膜モジュールを備えた濾過膜ユニット(2) が配置さ
れている。図示は省略したが、各平膜モジュールは、対
向状に配置された2枚の平膜と、両平膜の周縁部間に配
置された額縁状スペーサとよりなる。各平膜モジュール
に、その中空部内と連通するように吸引管が接続され、
すべての吸引管が1つの吸引ポンプ(3) に接続されてい
る。なお、濾過膜ユニット(2) には、平膜を用いた平膜
モジュールに代えて、中空糸状膜を用いたモジュールを
適用することもできる。濾過膜ユニット(2) の下には複
数の散気管(4) が配され、散気管(4) にブロワ(5) によ
り空気が送り込まれる。膜分離装置(1) の下端部は、下
方に向かって細くなったホッパ状となされるとともにそ
の底部に排水管(6) が設けられている。Embodiment 1 In FIG. 1, a filtration membrane unit (2) having a plurality of hollow flat membrane modules is arranged in a tank of a membrane separation device (1). Although not shown, each flat membrane module is composed of two flat membranes arranged in opposition, and a frame-shaped spacer arranged between the peripheral portions of both flat membranes. A suction tube is connected to each flat membrane module so as to communicate with the inside of the hollow portion,
All suction pipes are connected to one suction pump (3). Note that, as the filtration membrane unit (2), a module using a hollow fiber membrane can be applied instead of a flat membrane module using a flat membrane. A plurality of air diffusion tubes (4) are arranged below the filtration membrane unit (2), and air is sent into the air diffusion tubes (4) by a blower (5). The lower end of the membrane separation device (1) is shaped like a hopper tapered downward, and a drain pipe (6) is provided at the bottom.
【0026】上記構成の膜分離装置(1) によって排水を
処理し活性汚泥等を除いた後、この膜透過水を吸引ポン
プ(3) で、リン吸着塔(9) より高い位置にある受け槽
(7) に送る。ついで、この膜透過水を受け槽(7) から流
量自動調整弁(8) により、リン吸着塔(9) 内の通水条件
がLV=約150(cm/h)、SV=約3(1/h)
となるように、一定流量でリン吸着塔(9) に供給する。
リン吸着塔入口の膜分離処理水のpHは=6.5〜7.
5である。リン吸着塔入口の膜分離処理水の全リン酸イ
オンは7〜8(mg−P/リットル)である。After treating the wastewater by the membrane separation device (1) having the above structure to remove activated sludge and the like, the membrane permeated water is collected by a suction pump (3) at a position higher than the phosphorus adsorption tower (9).
Send to (7). Next, the membrane permeated water is supplied from the receiving tank (7) by the automatic flow rate regulating valve (8) so that the water passing condition in the phosphorus adsorption tower (9) is LV = about 150 (cm / h) and SV = about 3 (1). / H)
Is supplied to the phosphorus adsorption tower (9) at a constant flow rate.
The pH of the membrane separation treatment water at the inlet of the phosphorus adsorption tower is 6.5 to 7.
5 The total phosphate ions in the membrane separation treatment water at the inlet of the phosphorus adsorption tower are 7 to 8 (mg-P / liter).
【0027】リン吸着塔(9) には、塔底から約半分の高
さまでリン吸着剤(21)が充填され、底部に脱リン処理水
ライン(10)が配されている。脱リン処理水ライン(10)
は、吸着剤充填部の上に塔直径の約3倍の高さの水頭が
生じるよう、塔外部を塔底から塔頂レベルまで上行しつ
いで放流槽(11)に至る。The phosphorus adsorption tower (9) is filled with a phosphorus adsorbent (21) to a height of about half from the bottom of the tower, and a dephosphorized water line (10) is arranged at the bottom. Dephosphorization treatment water line (10)
Goes up the outside of the column from the bottom of the column to the top of the column, and then reaches the discharge tank (11) so that a head of about three times the diameter of the column is formed above the adsorbent packed section.
【0028】リン吸着塔(9) としては、リン吸着剤を充
填した複数のカラムからなるカートリッジをリン吸着塔
内に取り替え可能に組み込んだものが設けられ、吸着剤
の取り替えの必要性が生じたときカートリッジを取り替
える。As the phosphorus adsorption tower (9), there is provided one in which a cartridge comprising a plurality of columns filled with a phosphorus adsorbent is exchangeably incorporated in the phosphorus adsorption tower, and the necessity of replacing the adsorbent arises. When replacing the cartridge.
【0029】吸着剤(21)としては、ジルコニウムフェラ
イト水和物をベースとする武田薬品工業(株)製の「セ
ブントールP」を使用する。この吸着剤は平均粒径約1
mmの造粒品である。As the adsorbent (21), "Seventor P" manufactured by Takeda Pharmaceutical Co., Ltd. based on zirconium ferrite hydrate is used. This adsorbent has an average particle size of about 1
mm granulated product.
【0030】脱リン処理を上記流量である時間実施する
と破過点に達する。これを図5のグラフに示す。破過点
は、全リン酸イオン出口濃度/全リン酸イオン入口濃度
=0.1とする。When the dephosphorization treatment is carried out for the above-mentioned flow rate for a certain time, the breakthrough point is reached. This is shown in the graph of FIG. The breakthrough point is defined as total phosphate ion outlet concentration / total phosphate ion inlet concentration = 0.1.
【0031】本発明方法で用いるリン吸着剤は、pH約
1〜7の範囲でリン酸イオンをより多量に選択的に吸着
するが、アルカリ側では殆ど吸着しないという特性を有
している。したがって、この吸着剤を用いてpH1〜
8.6の酸性から中性域の液中でリン酸イオンの吸着操
作を行った後、アルカリ性水溶液でリン酸イオンを脱離
させ、ついでこの吸着剤を酸性水溶液で処理することに
より、再生することができる。例えば、リン酸イオンを
吸着させた本吸着剤を5重量%の水酸化ナトリウム水溶
液中に数時間浸すことにより、吸着したリン酸イオンは
脱着する。これを水洗して、0.5%の硫酸水溶液に数
時間浸すことにより、本吸着剤は再活性化され初期の吸
着性能を回復する。脱着に用いるアルカリ性水溶液は、
水酸化カリウムなど他のアルカリを含む水溶液であって
もよい。またアルカリ性水溶液のアルカリ濃度は0.1
〜20重量%程度であればよい。活性化に用いる酸性水
溶液は塩酸、硝酸などの酸を含む水溶液であってよい。
酸の濃度は0.1〜10重量%程度であればよい。The phosphorus adsorbent used in the method of the present invention has a property that it selectively adsorbs a large amount of phosphate ions in the pH range of about 1 to 7, but hardly adsorbs phosphate ions on the alkali side. Therefore, using this adsorbent,
After performing a phosphate ion adsorption operation in a liquid in an acidic to neutral range of 8.6, phosphate ions are desorbed with an alkaline aqueous solution, and then the adsorbent is treated with an acidic aqueous solution to regenerate. be able to. For example, when the present adsorbent having adsorbed phosphate ions is immersed in a 5% by weight aqueous sodium hydroxide solution for several hours, the adsorbed phosphate ions are desorbed. This is washed with water and immersed in a 0.5% sulfuric acid aqueous solution for several hours, whereby the adsorbent is reactivated and the initial adsorption performance is restored. The alkaline aqueous solution used for desorption is
An aqueous solution containing another alkali such as potassium hydroxide may be used. The alkali concentration of the alkaline aqueous solution is 0.1
It may be about 20% by weight. The acidic aqueous solution used for the activation may be an aqueous solution containing an acid such as hydrochloric acid or nitric acid.
The concentration of the acid may be about 0.1 to 10% by weight.
【0032】この一連の脱着、活性化操作は、カラムに
吸着剤を充填したまま行うことができる。すなわち、吸
着剤を充填したカラムに、吸着操作終了後、アルカリ性
水溶液、酸性水溶液を順番にカラムに通水することによ
り、容易に再生を行うことができる。この場合の通液方
向は上向流、下向流のいずれでもよい。This series of desorption and activation operations can be performed while the column is filled with the adsorbent. That is, the regeneration can be easily performed by passing an alkaline aqueous solution and an acidic aqueous solution through the column in order after the adsorption operation to the column filled with the adsorbent. In this case, the flow direction may be either an upward flow or a downward flow.
【0033】この再生操作において、目詰まり等の防止
のため水や空気を用いて、洗浄操作をすることができ
る。洗浄水は、処理原水へ戻す。In this regeneration operation, a washing operation can be performed using water or air to prevent clogging and the like. The washing water is returned to the treated raw water.
【0034】また、この再生操作において脱着したリン
酸イオンはリン酸塩の形で回収することができる。例え
ば、水酸化ナトリウムで脱着したリン酸イオンは、一般
に行われている晶析法を用いてリン酸ナトリウムの結晶
で回収することが可能である。これは貴重なリン資源と
して再使用することができる。The phosphate ions desorbed in this regeneration operation can be recovered in the form of phosphate. For example, phosphate ions desorbed with sodium hydroxide can be recovered as sodium phosphate crystals by using a commonly used crystallization method. This can be reused as a valuable phosphorus resource.
【0035】リン吸着塔内のリン吸着剤を洗浄するに
は、吸着処理すべき液の供給ラインに設けられた薬剤供
給ライン(13)から、苛性ソーダ水溶液を吸着塔内に流
し、吸着剤からリン酸塩を脱離させる。その後、吸着剤
活性化のため硫酸を薬剤供給ラインから通水し、吸着剤
の再生を行う。To wash the phosphorus adsorbent in the phosphorus adsorption tower, a caustic soda aqueous solution is flowed into the adsorption tower from a chemical supply line (13) provided in the supply line of the liquid to be subjected to the adsorption treatment, and the phosphorus is removed from the adsorbent. The acid salt is eliminated. Thereafter, sulfuric acid is passed through the chemical supply line to activate the adsorbent, and the adsorbent is regenerated.
【0036】リン吸着塔(9) の底部から出た脱リン処理
水はライン(10)によって放流槽(11)へ送られる。また、
吸着剤の洗浄に用いられた薬剤液はライン(14)によって
塔底部から抜出される。Dephosphorized water discharged from the bottom of the phosphorus adsorption tower (9) is sent to a discharge tank (11) by a line (10). Also,
The chemical solution used for washing the adsorbent is withdrawn from the bottom of the column by the line (14).
【0037】受け槽(7) から放流槽(11)へオーバーフロ
ーライン(12)を設ける。これによって、何らかの原因で
膜分離装置の膜が破損等を生じ浮遊物質が同装置から流
出しリン吸着塔(9) が目詰まりを起こしたときでも、同
ラインによって、受け槽(7)のオーバーフローを放流槽
(11)へ流出させて吸着塔の水溢れを防止できる。An overflow line (12) is provided from the receiving tank (7) to the discharge tank (11). As a result, even if the membrane of the membrane separation device is damaged for some reason and suspended matter flows out of the device and the phosphorus adsorption tower (9) is clogged, overflow of the receiving tank (7) is performed by the line. The discharge tank
The water is discharged to (11) to prevent overflow of the adsorption tower.
【0038】上記処理によって得られた処理水のリン除
去率を図6のグラフに示す。このグラフより、本発明に
よる脱リン方法が優れた脱リン効果を示すことが確認で
きた。The phosphorus removal rate of the treated water obtained by the above treatment is shown in the graph of FIG. From this graph, it was confirmed that the phosphorus removal method according to the present invention exhibited an excellent phosphorus removal effect.
【0039】実施例2 図2において、この実施例では、受け槽(7) からリン吸
着塔(9) への流量を、空転防止機能付き水中ポンプ(15)
と、三角堰を備えた計量器(16)との組合せによって調整
する。計量器(16)は三角堰の働きにより水を一定流量ず
つリン吸着塔(9) に供給するものであり、三角堰の堰板
は上下にスライド自在であり、これにより供給量を変え
ることができる。水の過剰分は計量器(16)から受け槽
(7) へ戻される。Embodiment 2 In FIG. 2, in this embodiment, the flow rate from the receiving tank (7) to the phosphorus adsorption tower (9) is controlled by the submersible pump (15)
And a measuring device (16) having a triangular weir. The measuring device (16) supplies water to the phosphorus adsorption tower (9) at a constant flow rate by the function of the triangular weir, and the weir plate of the triangular weir is slidable up and down, so that the supply amount can be changed. it can. Excess water is received from the measuring device (16)
Returned to (7).
【0040】計量器(16)からリン吸着塔(9) へのライン
の先端には、処理水流れ方向に直交する円板状分散板(1
7)が、リン吸着塔(9) の液面を臨むように配設されてい
る。分散板(17)は、図4に示すように、下面に4つの分
散孔(20)を有している。これによって、膜透過水はリン
吸着塔(9) へ液面全体に均等な流速で分散供給される。
その他の点は、実施例1と同じである。At the end of the line from the measuring device (16) to the phosphorus adsorption tower (9), a disc-shaped dispersion plate (1
7) is disposed so as to face the liquid level of the phosphorus adsorption tower (9). As shown in FIG. 4, the dispersion plate (17) has four dispersion holes (20) on the lower surface. Thereby, the permeated water is dispersed and supplied to the phosphorus adsorption tower (9) at a uniform flow rate over the entire liquid surface.
Other points are the same as the first embodiment.
【0041】実施例3 図8において、この実施例では、受け槽(7) において膜
透過水に酸水溶液槽(22)から給液ポンプ(23)によって硫
酸水溶液を添加して、膜透過水のpHを3.0に調整す
る。また、放流槽(11)において脱リン処理水にアルカリ
水溶液槽(24)から給液ポンプ(25)によって苛性ソーダ水
溶液を添加して、脱リン処理水のpHを7.0に調整す
る。その他の点は、実施例1と同じである。Embodiment 3 Referring to FIG. 8, in this embodiment, a sulfuric acid aqueous solution is added to the membrane permeated water from the acid aqueous solution tank (22) by the feed pump (23) in the receiving tank (7). Adjust the pH to 3.0. Further, in the discharge tank (11), an aqueous caustic soda solution is added to the dephosphorized water from the alkaline aqueous solution tank (24) by the liquid supply pump (25), and the pH of the dephosphorized water is adjusted to 7.0. Other points are the same as the first embodiment.
【0042】その結果、処理水の全リン除去率が90%
になる破過点に達するまでの日数は45日であり、図6
との比較から明らかなように、実施例1の日数の約3倍
に伸びた。As a result, the total phosphorus removal rate of the treated water was 90%.
The number of days required to reach the breakthrough is 45 days.
As can be seen from the comparison with Example 1, the number of days increased to about three times the number of days in Example 1.
【0043】実施例4 図3において、この実施例では、膜分離装置(1) 内にお
いて濾過膜ユニット(2) の原水側にリン吸着剤(18)を直
接投入して排水をリン吸着処理し、ついで膜分離処理す
る。膜透過水は吸引ポンプ(3) で膜分離装置(1) から排
出する。吸着剤としては、実施例1のものと同じく、ジ
ルコニウムフェライト水和物をベースとする武田薬品工
業(株)製の「セブントールP」を使用する。吸着剤の
使用量は、膜分離装置有効容量60リットルに対し約2
500gである。Embodiment 4 In FIG. 3, in this embodiment, a phosphorus adsorbent (18) is directly charged into the raw water side of the filtration membrane unit (2) in the membrane separation device (1) to subject the waste water to a phosphorus adsorption treatment. Then, a membrane separation treatment is performed. The permeated water is discharged from the membrane separator (1) by the suction pump (3). As the adsorbent, "Seventor P" manufactured by Takeda Pharmaceutical Co., Ltd. based on zirconium ferrite hydrate is used as in Example 1. The amount of adsorbent used is approximately 2 for an effective volume of 60 liters of the membrane separation device.
500 g.
【0044】膜分離装置(1) の槽内における濾過膜ユニ
ット(2) よりも下方の部分に複数の散気管(4) が配置さ
れている。散気管(4) にはブロワ(5) により空気が送り
込まれる。散気によりリン吸着剤が膜分離装置内に均一
に攪拌され、脱リン処理が効率よくなされる。A plurality of air diffusion tubes (4) are arranged below the filtration membrane unit (2) in the tank of the membrane separation device (1). Air is blown into the air diffuser (4) by the blower (5). By the aeration, the phosphorus adsorbent is uniformly stirred in the membrane separation device, and the phosphorus removal treatment is efficiently performed.
【0045】また、膜分離装置(1) の槽底部は、下方に
向かって細くなったホッパ状となされる。The bottom of the tank of the membrane separation device (1) is formed in a hopper shape tapered downward.
【0046】リン吸着剤が破過点を超えた場合は散気を
停止する。リン吸着剤(18)は活性汚泥より比重が高いの
で、優先的に沈殿する。ホッパ底部の引き抜きライン(1
9)から汚泥の一部と共に吸着剤を取り出し、新たに吸着
剤を上部から投入する。取り出した吸着剤は再生して再
び使用する。When the phosphorus adsorbent exceeds the breakthrough point, the air diffusion is stopped. Since the phosphorus adsorbent (18) has a higher specific gravity than activated sludge, it precipitates preferentially. Pullout line at bottom of hopper (1
Take out the adsorbent together with a part of the sludge from 9) and add a new adsorbent from above. The removed adsorbent is regenerated and reused.
【0047】膜分離装置内の排水のpHは好ましくは
5.8〜8.6、より好ましくは6.5〜7.5の範囲
である。The pH of the waste water in the membrane separation device is preferably in the range of 5.8 to 8.6, more preferably in the range of 6.5 to 7.5.
【0048】吸着剤の吸着能力は確認されているので、
リン吸着量、破過の時期等は、膜分離槽内に投入する吸
着剤の量により事前に予測される。Since the adsorption capacity of the adsorbent has been confirmed,
The phosphorus adsorption amount, breakthrough time, and the like are predicted in advance based on the amount of the adsorbent charged into the membrane separation tank.
【0049】上記処理によって得られた処理水のリン除
去率を図7のグラフに示す。このグラフより、本発明に
よる脱リン方法が優れた脱リン効果を示すことが確認で
きた 実施例5 図9において、この実施例では、膜分離装置(1) の槽に
おいて処理すべき排水に酸水溶液槽(22)から給液ポンプ
(23)によって硫酸水溶液を添加して、排水のpHを6.
0に調整する。また、膜透過水は吸引ポンプ(3) で放流
槽(11)に貯え、ここで膜透過水にアルカリ水溶液槽(24)
から給液ポンプ(25)によって苛性ソーダ水溶液を添加し
て、脱リン処理水のpHを7.0に調整する。その他の
点は、実施例4と同じである。FIG. 7 is a graph showing the phosphorus removal rate of the treated water obtained by the above treatment. From this graph, it was confirmed that the phosphorus removal method according to the present invention exhibited an excellent phosphorus removal effect. Example 5 In FIG. 9, in this example, acid was added to wastewater to be treated in the tank of the membrane separation device (1). Liquid supply pump from aqueous solution tank (22)
5. A sulfuric acid aqueous solution was added according to (23) to adjust the pH of the waste water to 6.
Adjust to 0. The permeated water is stored in the discharge tank (11) by the suction pump (3).
The pH of the dephosphorized water is adjusted to 7.0 by adding an aqueous solution of caustic soda with the feed pump (25). Other points are the same as the fourth embodiment.
【0050】その結果、処理水の全リン除去率が90%
になる破過点に達するまでの日数は22日であり、図7
との比較から明らかなように、実施例4の日数の約1.
5倍に伸びた。As a result, the total phosphorus removal rate of the treated water was 90%.
The number of days required to reach the breakthrough is 22 days, as shown in FIG.
As is clear from the comparison with Example 1, the number of days in Example 4 was about 1.
It grew 5 times.
【0051】[0051]
【発明の効果】本発明による排水の脱リン方法処理によ
れば、処理コストが少なくてすみ、厄介な凝集沈殿物の
発生がなく、また吸着したリンを再資源化することがで
きる。According to the method for removing phosphorus from wastewater according to the present invention, the processing cost can be reduced, no troublesome aggregates are generated, and the adsorbed phosphorus can be recycled.
【図1】 本発明の実施例1を示すフロー図である。FIG. 1 is a flowchart showing Embodiment 1 of the present invention.
【図2】 本発明の実施例2を示すフロー図である。FIG. 2 is a flowchart showing a second embodiment of the present invention.
【図3】 本発明の実施例4を示すフロー図である。FIG. 3 is a flowchart showing a fourth embodiment of the present invention.
【図4】 円板状分散板を示す底面図である。FIG. 4 is a bottom view showing a disk-shaped dispersion plate.
【図5】 破過曲線を示すグラフである。FIG. 5 is a graph showing a breakthrough curve.
【図6】 全リン除去率を示すグラフである。FIG. 6 is a graph showing the total phosphorus removal rate.
【図7】 全リン除去率を示すグラフである。FIG. 7 is a graph showing the total phosphorus removal rate.
【図8】 本発明の実施例3を示すフロー図である。FIG. 8 is a flowchart showing a third embodiment of the present invention.
【図9】 本発明の実施例5を示すフロー図である。FIG. 9 is a flowchart showing Example 5 of the present invention.
(1) :膜分離装置 (7) :受け槽 (8) :流量自動調整弁 (9) :リン吸着塔 (11):放流槽 (15):空転防止機能付き水中ポンプ (16):三角堰を備えた計量器 (17):分散板 (19):引き抜きライン (18)(21):吸着剤 (22):酸水溶液槽 (24):アルカリ水溶液槽 (1): Membrane separation device (7): Receiving tank (8): Automatic flow control valve (9): Phosphorus adsorption tower (11): Discharge tank (15): Submersible pump with anti-spin function (16): Triangular weir (17): Dispersion plate (19): Extraction line (18) (21): Adsorbent (22): Acid aqueous solution tank (24): Alkaline aqueous solution tank
───────────────────────────────────────────────────── フロントページの続き (72)発明者 松本 智樹 大阪市住之江区南港北1丁目7番89号 日 立造船株式会社内 (72)発明者 毛利 元哉 大阪府吹田市山田南50番B−101号 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Tomoki Matsumoto 1-7-89 Minami Kohoku, Suminoe-ku, Osaka-shi Inside Tachibana Shipbuilding Co., Ltd. issue
Claims (22)
ムフェライト水和物を構成材料とするリン吸着剤でリン
吸着処理することを特徴とする排水の脱リン方法。1. A method for removing phosphorus from wastewater, comprising subjecting the wastewater to membrane separation treatment, and then subjecting the wastewater to a phosphorus adsorption treatment using a zirconium ferrite hydrate as a constituent material.
調製することを特徴とする請求項1記載の方法。2. The method according to claim 1, wherein the pH of the membrane separation treatment water is adjusted to 5.8 to 8.6.
調整することを特徴とする請求項2記載の方法。3. The method according to claim 2, wherein the pH of the membrane separation treatment water is adjusted to 6.5 to 7.5.
調整し、リン吸着処理水のpHを5.8〜8.6に調整
することを特徴とする請求項1記載の方法。4. The method according to claim 1, wherein the pH of the membrane separation treatment water is adjusted to 1.0 to 6.5, and the pH of the phosphorus adsorption treatment water is adjusted to 5.8 to 8.6. Method.
500(cm/h)、SVで1〜10(1/h)である
ことを特徴とする請求項1〜4のうち1項記載の方法。5. The water passing condition in the phosphorus adsorption tower is 50 to 50 in LV.
The method according to claim 1, wherein the method is 500 (cm / h) and the SV is 1 to 10 (1 / h).
〜250(cm/h)、SVで2〜5(1/h)である
ことを特徴とする請求項5記載の方法。6. The water passing condition in the phosphorus adsorption tower is 100 at LV.
The method according to claim 5, characterized in that it is 250 to 250 (cm / h) and SV is 2 to 5 (1 / h).
る受け槽に一旦受け、ここからリン吸着塔へ送り、吸着
塔への流量を流量調整バルブによって、または、水中ポ
ンプと三角堰を備えた計量器との組合せによって調整す
ることを特徴とする請求項1〜6のうち1項記載の方
法。7. The membrane separation treatment water is temporarily received in a receiving tank located at a position higher than the adsorption tower, and then sent to the phosphorus adsorption tower, and the flow to the adsorption tower is controlled by a flow control valve, or a submersible pump and a triangular weir are used. 7. The method according to claim 1, wherein the adjustment is carried out by means of a combination with a weighing device.
通水するに当たり、吸着剤充填部の上に塔直径の0.5
〜5倍の高さの水頭を設けることを特徴とする請求項1
〜7のうち1項記載の方法。8. When the membrane separation treatment water is passed through the adsorbent filled section of the adsorption tower, a 0.5 mm diameter of the tower is placed on the adsorbent filled section.
2. A water head having a height of about 5 to 5 times is provided.
The method according to any one of claims 1 to 7.
させることを特徴とする請求項1〜8のうち1項記載の
方法。9. The method according to claim 1, wherein the membrane separation treatment water is dispersed at the top of the phosphorus adsorption tower.
剤で洗浄することを特徴とする請求項1〜9のうち1項
記載の方法。10. The method according to claim 1, wherein the phosphorus adsorbent in the phosphorus adsorption tower is washed with a chemical detergent.
らなるカートリッジをリン吸着塔内に取り替え可能に組
み込むことを特徴とする請求項1〜10のうち1項記載
の方法。11. The method according to claim 1, wherein a cartridge comprising a plurality of columns filled with the phosphorus adsorbent is replaceably incorporated in the phosphorus adsorption tower.
0mmであることを特徴とする請求項1〜11のうち1
項記載の方法。12. The phosphorus adsorbent has an average particle size of 0.1 to 4.
12. The method according to claim 1, wherein the distance is 0 mm.
The method described in the section.
5mmであることを特徴とする請求項12記載の方法。13. The phosphorus adsorbent having an average particle size of 0.2 to 1.
13. The method according to claim 12, wherein the distance is 5 mm.
ジルコニウムフェライト水和物を構成材料とするリン吸
着剤を投入して排水をリン吸着処理し、ついで膜分離処
理することを特徴とする排水の脱リン方法。14. A raw water side of a membrane in a membrane separation device,
A method for removing phosphorus from wastewater, comprising introducing a phosphorus adsorbent containing zirconium ferrite hydrate as a constituent material, subjecting the wastewater to a phosphorus adsorption treatment, and then subjecting the wastewater to a membrane separation treatment.
8.6に制御することを特徴とする請求項14項記載の
方法。15. The pH of wastewater in the membrane separation device is adjusted to 5.8 to
The method according to claim 14, wherein the control is performed at 8.6.
7.5に制御することを特徴とする請求項15項記載の
方法。16. The pH of the waste water in the membrane separation device is adjusted to 6.5 to 16.
The method according to claim 15, wherein the control is performed at 7.5.
し、リン吸着処理水のpHを5.8〜8.6に調整する
ことを特徴とする請求項14記載の方法。17. The method according to claim 14, wherein the pH of the waste water is adjusted to 1.0 to 6.5, and the pH of the phosphorus adsorption treated water is adjusted to 5.8 to 8.6.
することを特徴とする請求項14〜17のうち1項記載
の方法。18. The method according to claim 14, wherein the bottom of the membrane separation device is formed in a hopper shape.
する請求項14〜18のうち1項記載の方法。19. The method according to claim 14, wherein air is diffused into the membrane separation device.
よびリン吸着剤を引き抜くことを特徴とする請求項14
〜19のうち1項記載の方法。20. The sludge and the phosphorus adsorbent deposited from the bottom of the membrane separation device are withdrawn.
20. The method according to any one of claims 19 to 19.
0mmであることを特徴とする請求項14〜20のうち
1項記載の方法。21. The phosphorus adsorbent having an average particle size of 0.1 to 4.
21. The method according to claim 14, wherein the distance is 0 mm.
5mmであることを特徴とする請求項21記載の方法。22. The phosphorus adsorbent having an average particle size of 0.2-1.
22. The method according to claim 21, wherein the distance is 5 mm.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002370086A (en) * | 2001-06-15 | 2002-12-24 | Bio Oriented Technol Res Advancement Inst | Dephosphorization method for wastewater |
JP2006130402A (en) * | 2004-11-05 | 2006-05-25 | Yuuhei Inamori | Phosphorus removal method, phosphorus recovery method, and phosphorus adsorbing cartridge |
JP2008532763A (en) * | 2005-08-30 | 2008-08-21 | エルジー・ケム・リミテッド | Method and apparatus for collecting powder from which soluble components have been removed |
JP2010522068A (en) * | 2007-03-19 | 2010-07-01 | イージーマイニング スウェーデン エービー | Phosphorus recovery |
JP2010264457A (en) * | 2010-09-03 | 2010-11-25 | National Agriculture & Food Research Organization | Method of removing phosphorus in waste water |
JP4647814B2 (en) * | 2001-03-27 | 2011-03-09 | 住友重機械エンバイロメント株式会社 | Organic wastewater treatment equipment |
-
1998
- 1998-09-04 JP JP25052198A patent/JP3845758B2/en not_active Expired - Fee Related
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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JP4647814B2 (en) * | 2001-03-27 | 2011-03-09 | 住友重機械エンバイロメント株式会社 | Organic wastewater treatment equipment |
JP2002370086A (en) * | 2001-06-15 | 2002-12-24 | Bio Oriented Technol Res Advancement Inst | Dephosphorization method for wastewater |
JP4618937B2 (en) * | 2001-06-15 | 2011-01-26 | 独立行政法人農業・食品産業技術総合研究機構 | How to remove phosphorus from wastewater. |
JP2006130402A (en) * | 2004-11-05 | 2006-05-25 | Yuuhei Inamori | Phosphorus removal method, phosphorus recovery method, and phosphorus adsorbing cartridge |
JP2008532763A (en) * | 2005-08-30 | 2008-08-21 | エルジー・ケム・リミテッド | Method and apparatus for collecting powder from which soluble components have been removed |
JP4738476B2 (en) * | 2005-08-30 | 2011-08-03 | エルジー・ケム・リミテッド | Method and apparatus for collecting powder from which soluble components have been removed |
JP2010522068A (en) * | 2007-03-19 | 2010-07-01 | イージーマイニング スウェーデン エービー | Phosphorus recovery |
JP2010264457A (en) * | 2010-09-03 | 2010-11-25 | National Agriculture & Food Research Organization | Method of removing phosphorus in waste water |
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