JPH0220320B2 - - Google Patents
Info
- Publication number
- JPH0220320B2 JPH0220320B2 JP5671286A JP5671286A JPH0220320B2 JP H0220320 B2 JPH0220320 B2 JP H0220320B2 JP 5671286 A JP5671286 A JP 5671286A JP 5671286 A JP5671286 A JP 5671286A JP H0220320 B2 JPH0220320 B2 JP H0220320B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphorus
- crystallized
- aqueous solution
- dephosphorization
- phosphorus removal
- 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.)
- Expired
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 72
- 239000011574 phosphorus Substances 0.000 claims description 72
- 229910052698 phosphorus Inorganic materials 0.000 claims description 72
- 239000000463 material Substances 0.000 claims description 55
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 14
- 239000011575 calcium Substances 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 239000001506 calcium phosphate Substances 0.000 claims description 4
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 4
- 235000011010 calcium phosphates Nutrition 0.000 claims description 4
- 239000004576 sand Substances 0.000 claims description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 4
- 229910052585 phosphate mineral Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 235000014653 Carica parviflora Nutrition 0.000 claims description 2
- 241000243321 Cnidaria Species 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 210000000988 bone and bone Anatomy 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 4
- 230000001172 regenerating effect Effects 0.000 claims 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- 230000000694 effects Effects 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 229910019142 PO4 Inorganic materials 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 235000021317 phosphate Nutrition 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 8
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 235000012255 calcium oxide Nutrition 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010800 human waste Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Removal Of Specific Substances (AREA)
Description
〔産業上の利用分野〕
本発明は、上水、下水、し尿系汚水、工業用
水、工場排水、ボイラー用水、その他あらゆる液
体中に存在するリン酸塩類を除去する方法におい
て晶析リン除去材の能力を回復させる方法に関す
るものである。
〔従来の技術〕
一般に自然水系に排出される上記の各種液体中
には、無機性のリン酸塩としてオルトリン酸塩や
各種の縮合リン酸塩さらに有機性リン酸塩な様々
な状態で存在しており、これらのリン酸塩類の存
在が湖沼、内海、内湾などの閉鎖水域乃至は停滞
水域の「あおこ」、「赤湖」発生の誘起因子とな
り、さらに各種の用水として使用する場合に装
置、配管内に生物学的なスライムが発生し、また
化学的なスケールが形成されて、事故発生の重大
な原因となつている。
従つて、これら液中に存在するリン酸塩を除去
する必要から、各種のリン除去方法が検討されて
いるが、その一つとして一定の粒径を持つリン酸
カルシウムを含有する晶析リン除去材を筒状ある
いは錐状の脱リン塔に充填し、被処理液のPHを６
〜11の範囲に調整し、さらに被処理液中に含まれ
ている溶解性リン酸塩類の濃度に対応して塩化カ
ルシウムなどのカルシウム剤を加え、これを一定
の流速条件で通過接触せしめることにより、充填
されている晶析リン除去材の表面にカルシウムハ
イドロキシアパタイトの結晶を晶出、固着せしめ
て溶解性リン酸塩類を除去する方法を提案した。
この方法における晶析リン除去材表面での代表的
な化学反応は次の通りである。
5Ca2+＋7OH-＋3H2PO4 -
＝Ca5（OH）（PO4）3＋6H2O ………(1)
このような脱リン方法を適用すれば、カルシウ
ムハイドロキシアパタイトが固着した接触脱リン
材の分離、脱水が極めて容易であり、従来の化学
的凝集沈澱法によるいわゆる凝沈汚泥と比較する
と、凝縮装置、脱水機、乾燥装置などの既成概念
による汚泥処理施設をまつたく必要としないだけ
でなく、資源としてのリンを回収することが出来
る優れた脱リン技術である。
〔発明が解決しようとする問題点〕
ところで従来の晶析リン除去材を各種排水に適
用する場合には以下のような問題点があつた。
即ち、被処理液中に色度成分、有機物等の吸着
性に富んだ物質が多く含まれる時、これらの物質
がカルシウムハイドロキシアパタイトの晶析と競
合して、同時に晶析材表面に固着してしまい、リ
ン除去反応を著しく阻害する場合があつた。
晶析法は適切なPH条件下でカルシウム剤を添加
して、液中に含まれる溶解性リン酸塩類を晶析材
表面にカルシウムハイドロキシアパタイトの結晶
として固着させる方法であるため晶析材の表面状
態が晶析反応に大きく影響する。従つて上記の吸
着物質の晶析材表面の被覆は晶析材の活性の低下
の原因となり、カルシウムハイドロキシアパタイ
トの生成速度が低下するために当初のリン除去性
能が失われてしまうことになる。吸着物質が被処
理液中に濃厚に存在する場合や、カルシウムハイ
ドロキシアパタイト形成に適切なPH、カルシウム
条件から逸脱した運転を続けた場合には、さらに
吸着物質の晶析材表面の被覆が促進され、晶析反
応を著しく妨害するため、晶析法の機能に致命的
な影響を与えることになる。このような問題点の
解決法として、これまでリン除去能力の低下した
晶析リン除去材をアルカリ水溶液で洗浄する方法
が確認されてきたが、その後の経験により被処理
液中にある種の有機物が存在する場合には、上記
の方法を適用しても顕著な洗浄効果が得られない
場合があり、満足した解決策となるものではなか
つた。
〔問題点を解決するための手段〕
本発明は晶析法における上記の問題点を解消
し、さらに効果的に晶析リン除去材のリン除去能
力を回復させて、安定したリン除去ができる方法
を提供することを目的とするものである。即ち、
本発明はリン吸着能力を有する晶析リン除去材を
カルシウムの存在下でリン含有液と接触させて液
中のリンを除去する方法において、該晶析リン除
去材を40℃以上に加温したアルカリ水溶液に接触
させることを特徴とするものである。
以下に本発明の一実施態様を、図面に基づき説
明すれば、まず被処理液中に多量の浮遊物質が存
在する場合には、この浮遊物質を沈澱槽又は濾過
槽などを通してあらかじめ除去する。
このように前処理操作により、予め浮遊物質を
除去された原水は、必要に応じて原水中の溶解性
リン酸塩濃度に対応してカルシウム剤が添加され
た後、酸又はアルカリのPH調整剤でPHを6.0〜
11.0に調整し、原水流入管１から脱リン塔２の上
部へ導入する。この脱リン塔２内には、リン酸カ
ルシウムを含有するリン酸塩鉱物を破砕し篩分し
て一定の粒径としたものを晶析リン除去材３とし
て充填してあり、原水はこの晶析リン除去材３と
接触しながら下降し、処理水流出管４から塔外へ
導出される。
前記晶析リン除去材３はリン酸塩鉱物又は活性
炭、活性アルミナ、含水酸化ジルコニウム、酸化
マグネシウム、骨炭、サンゴ砂、砂などの表面に
リン酸カルシウムを担持させたものが利用でき
る。
かかる脱リン操作において晶析リン除去材３に
原水中の色度成分、有機物等の不純物が吸着する
こと等により、晶析リン除去材３の表面活性が劣
化し、脱リン機能は低下するので、脱リン塔２へ
の原水の通水を行ないながら又は一定期間処理経
過後原水の通水を停止して、塔内の晶析リン除去
材３は、連続的又は間欠的に取出管５から反応槽
６に送り込まれ、該晶析リン除去材は反応槽６に
おいて、タンク７からポンプ８で供給されるアル
カリ水溶液を撹拌機９で撹拌されて接触し、晶析
リン除去材表面に吸着した阻害物質は効果的に除
去される。アルカリ水溶液と晶析リン除去剤の接
触は撹拌機にかえて空気撹拌でも、アルカリ水溶
液を循環した液流撹拌でも、これらの併用でもよ
い。アルカリ水溶液はタンク７に設置したヒータ
１０で40℃以上になるように加温してあるが、晶
析リン除去材との接触処理の間に液温が低下する
ので、必要に応じ反応槽６の温度を検知しながら
ヒータ１１を作動させ、反応槽６を40℃以上に保
つようにコントロールする。
使用するアルカリ剤は苛性ソーダでも水酸化カ
リウムでもあるいは消石炭、生石炭、水酸化マグ
ネシウムでもよい。生石灰は次式により溶解熱を
発生するので、再生操作の度に、生石灰を溶解さ
せるようにすると加温操作が大幅に省略できる利
点がある。
CaO＋H2O＝Ca（OH）2＋15.2Kcal
次に反応槽６に希釈水が導入管１２より導入さ
れ、回復された晶析リン除去剤は、ポンプ１３で
塔２に戻される。
また、晶析リン除去材を塔外へ導出することな
く、脱リン塔内で前記塔外の接触処理と同様の操
作を行なうことにより晶析リン除去材の脱リン能
力を高めることもできる。この場合、原水の通水
を停止し接触処理に用いられる40℃以上に加温し
たアルカリ水溶液を脱リン塔に上向流に通水さ
せ、晶析リン除去材を膨脹し、流動化するような
条件で接触させると更に効果的である。
このとき、晶析リン除去材と接触した後のアル
カリ水溶液は、循環使用することが好ましい。
また、アルカリ水溶液を上向流で連続的に供給
して流動層を形成させて、脱リン塔内をアルカリ
水溶液の液流で撹拌する代りに、脱リン塔底部に
設けた空気吹込管より空気を供給することや撹拌
機により、晶析リン除去材層を撹拌しても良い。
このようにアルカリ水溶液の水流、空気流ある
いは撹拌機などによつて、晶析リン除去材を撹拌
しながら40℃以上に加温したアルカリ水溶液と接
触処理させると、アルカリ水溶液を晶析リン除去
材との接触効率が向上するとともに、アルカリ水
溶液の化学的洗浄作用に、撹拌よる物理的洗浄作
用が加えられ、非常に効果的に晶析リン除去材の
回復が行なわれる利点がある。
以上述べたように本発明によれば、脱リン操作
中に晶析リン除去材を必要に応じて、アルカリ水
溶液と接触処理することにより、晶析リン除去材
の脱リン効果を長期間良好な状態に維持すること
ができ、安定した脱リン処理が可能となつた。
〔実施例〕
次に本発明の実施例を示す。
実施例 １
内径100mm〓、有効深さ2.5ｍの円筒状の脱リン
塔に、リン鉱石を破砕、篩分したもの（有効径
0.40mm、均等係数1.4）を1000mm厚充填した。粗
大固形物を大別分離した工場排水を活性汚泥法で
処理した２次処理水を被処理液とし、苛性ソーダ
により被処理液のPHを8.5〜9.0に調整し、また、
カルシウム剤と塩化カルシウムを使用し、被処理
液中の溶解性リン酸塩類の濃度に対応してCa／
PO4の重量比が1.0〜15の範囲となるように添加
した。この被処理液を前記脱リン塔に導き上方よ
り下向きにLV＝2.0ｍ／Ｈの流速で通水した。脱
リン塔には１ケ月に１回、0.5％に調整した苛性
ソーダを50℃に加温して導入し、同液に晶析リン
除去材を約12時間浸漬して接触処理した。この接
触処理操作を定期的に行ないながら約６ケ月の通
水実験を行なつた。この結果を表−１に示す。
[Industrial Application Field] The present invention is a method for removing phosphates present in tap water, sewage, human waste water, industrial water, factory wastewater, boiler water, and all other liquids. It concerns how to restore abilities. [Prior Art] Generally, in the above-mentioned liquids discharged into natural water systems, inorganic phosphates exist in various states such as orthophosphates, various condensed phosphates, and organic phosphates. The presence of these phosphates is a factor that induces the formation of "blue water" and "red lake" in closed or stagnant waters such as lakes, inland seas, and inner bays, and furthermore, when water is used for various purposes, equipment , biological slime and chemical scale are formed in the pipes, which is a major cause of accidents. Therefore, various phosphorus removal methods are being considered in order to remove the phosphates present in these liquids, and one of them is a crystallized phosphorus removal material containing calcium phosphate with a certain particle size. Packed into a cylindrical or conical dephosphorization tower, the pH of the liquid to be treated is reduced to 6.
-11, and then add a calcium agent such as calcium chloride in accordance with the concentration of soluble phosphates contained in the liquid to be treated, and allow the mixture to pass through and come into contact with it at a constant flow rate. proposed a method for removing soluble phosphates by crystallizing and fixing calcium hydroxyapatite crystals on the surface of a packed crystallized phosphorus removal material.
A typical chemical reaction on the surface of the crystallized phosphorus removal material in this method is as follows. 5Ca 2+ +7OH - +3H 2 PO 4 - = Ca 5 (OH) (PO 4 ) 3 +6H 2 O (1) If this dephosphorization method is applied, catalytic dephosphorization with fixed calcium hydroxyapatite can be achieved. It is extremely easy to separate and dewater the material, and compared to so-called flocculated sludge produced by conventional chemical coagulation and sedimentation methods, there is no need for conventional sludge treatment facilities such as condensation equipment, dewatering equipment, and drying equipment. It is an excellent dephosphorization technology that can recover phosphorus as a resource. [Problems to be Solved by the Invention] However, when the conventional crystallized phosphorus removing material is applied to various types of wastewater, the following problems occur. In other words, when the liquid to be treated contains many highly adsorbable substances such as chromaticity components and organic substances, these substances compete with the crystallization of calcium hydroxyapatite and simultaneously adhere to the surface of the crystallization material. In some cases, the phosphorus removal reaction was significantly inhibited. The crystallization method is a method in which a calcium agent is added under appropriate pH conditions to fix the soluble phosphates contained in the liquid as calcium hydroxyapatite crystals on the surface of the crystallization material. The conditions greatly affect the crystallization reaction. Therefore, coating the surface of the crystallizing material with the adsorbed substance causes a decrease in the activity of the crystallizing material, which reduces the production rate of calcium hydroxyapatite, resulting in loss of the original phosphorus removal performance. If adsorbed substances are present in a concentrated amount in the liquid to be treated, or if operation continues outside the pH and calcium conditions appropriate for calcium hydroxyapatite formation, the adsorbed substances will further promote coating on the surface of the crystallization material. , it will significantly interfere with the crystallization reaction and will have a fatal effect on the function of the crystallization method. As a solution to these problems, a method of cleaning the crystallized phosphorus removal material with a reduced phosphorus removal ability with an alkaline aqueous solution has been confirmed, but subsequent experience has shown that certain organic substances in the liquid to be treated , even if the above method is applied, it may not be possible to obtain a significant cleaning effect, and this has not been a satisfactory solution. [Means for Solving the Problems] The present invention solves the above-mentioned problems in the crystallization method, and provides a method that can more effectively restore the phosphorus removal ability of the crystallized phosphorus removal material and perform stable phosphorus removal. The purpose is to provide the following. That is,
The present invention provides a method for removing phosphorus from a liquid by bringing a crystallized phosphorus removing material having phosphorus adsorption ability into contact with a phosphorus-containing liquid in the presence of calcium, in which the crystallized phosphorus removing material is heated to 40°C or higher. It is characterized by contacting with an alkaline aqueous solution. An embodiment of the present invention will be described below with reference to the drawings. First, if a large amount of suspended solids are present in the liquid to be treated, the suspended solids are removed in advance through a sedimentation tank or a filtration tank. The raw water from which suspended solids have been removed in advance through pretreatment operations is treated with a calcium agent depending on the concentration of soluble phosphate in the raw water as necessary, and then an acidic or alkaline PH adjuster. PH at 6.0~
11.0, and introduce it into the upper part of the dephosphorization tower 2 from the raw water inlet pipe 1. This dephosphorization tower 2 is filled with phosphate minerals containing calcium phosphate crushed and sieved to a certain particle size as a crystallized phosphorus removal material 3, and the raw water is filled with this crystallized phosphorus. The treated water descends while contacting the removal material 3 and is led out of the tower from the treated water outflow pipe 4. The crystallized phosphorus removing material 3 may be a phosphate mineral, activated carbon, activated alumina, hydrous zirconium oxide, magnesium oxide, bone char, coral sand, sand, etc., with calcium phosphate supported on the surface thereof. In such a dephosphorization operation, impurities such as chromaticity components and organic substances in the raw water are adsorbed to the crystallized phosphorus removal material 3, which deteriorates the surface activity of the crystallized phosphorus removal material 3 and reduces the dephosphorization function. The crystallized phosphorus removal material 3 in the tower is continuously or intermittently removed from the take-out pipe 5 while passing the raw water to the dephosphorization tower 2 or by stopping the flow of raw water after a certain period of treatment. In the reaction tank 6, the crystallized phosphorus removing material is stirred by a stirrer 9 and comes into contact with an alkaline aqueous solution supplied by a pump 8 from a tank 7, and is adsorbed on the surface of the crystallized phosphorus removing material. Inhibitors are effectively removed. The aqueous alkaline solution and the crystallized phosphorus remover may be brought into contact with each other by air stirring instead of a stirrer, by liquid stream stirring in which the aqueous alkali solution is circulated, or by a combination of these. The alkaline aqueous solution is heated to 40°C or higher with a heater 10 installed in the tank 7, but since the liquid temperature drops during the contact treatment with the crystallized phosphorus removal material, the reaction tank 6 is heated as necessary. The heater 11 is operated while detecting the temperature of the reactor 6, and is controlled to maintain the temperature of the reaction tank 6 at 40°C or higher. The alkaline agent used may be caustic soda, potassium hydroxide, slaked coal, raw coal, or magnesium hydroxide. Since quicklime generates heat of dissolution according to the following equation, dissolving the quicklime every time a regeneration operation has the advantage that the heating operation can be greatly omitted. CaO+H 2 O=Ca(OH) 2 +15.2 Kcal Next, dilution water is introduced into the reaction tank 6 through the introduction pipe 12, and the recovered crystallized phosphorus removing agent is returned to the column 2 using the pump 13. Moreover, the dephosphorization ability of the crystallized phosphorus-removing material can be increased by performing the same operation as the contact treatment outside the tower in the dephosphorizing tower without leading the crystallized phosphorus-removing material to the outside of the tower. In this case, the flow of raw water is stopped and the alkaline aqueous solution heated to 40°C or higher used for contact treatment is passed through the dephosphorization tower in an upward flow to expand and fluidize the crystallized phosphorus removal material. It is more effective if the contact is made under suitable conditions. At this time, it is preferable that the alkaline aqueous solution that has come into contact with the crystallized phosphorus removing material be recycled. In addition, instead of continuously supplying an alkali aqueous solution in an upward flow to form a fluidized bed and stirring the inside of the dephosphorization tower with the flow of the alkali aqueous solution, air is blown from an air blowing pipe installed at the bottom of the dephosphorization tower. The crystallized phosphorus removing material layer may be stirred by supplying or using a stirrer. In this way, when the crystallized phosphorus removing material is brought into contact with the alkaline aqueous solution heated to 40℃ or higher while being stirred using an aqueous alkaline solution water stream, air stream, or a stirrer, the alkaline aqueous solution becomes the crystallized phosphorus removing material. In addition to improving the contact efficiency with the aqueous alkaline solution, the physical cleaning effect of stirring is added to the chemical cleaning effect of the alkaline aqueous solution, which has the advantage of very effectively recovering the crystallized phosphorus removal material. As described above, according to the present invention, by contacting the crystallized phosphorus removal material with an alkaline aqueous solution as necessary during the dephosphorization operation, the dephosphorization effect of the crystallized phosphorus removal material can be maintained for a long period of time. This made it possible to maintain stable dephosphorization treatment. [Example] Next, an example of the present invention will be shown. Example 1 A cylindrical dephosphorization tower with an inner diameter of 100 mm and an effective depth of 2.5 m was filled with crushed and sieved phosphate rock (with an effective diameter of
0.40mm, uniformity factor 1.4) was filled with a thickness of 1000mm. The liquid to be treated is secondary treated water obtained by treating industrial wastewater from which coarse solids have been roughly separated using the activated sludge method, and the pH of the liquid to be treated is adjusted to 8.5 to 9.0 with caustic soda.
Calcium agent and calcium chloride are used, and Ca/
It was added so that the weight ratio of PO4 was in the range of 1.0 to 15. This liquid to be treated was introduced into the dephosphorization tower and passed from above downward at a flow rate of LV=2.0 m/H. Caustic soda adjusted to 0.5% was heated to 50°C and introduced into the dephosphorization tower once a month, and the crystallized phosphorus removal material was immersed in the same solution for about 12 hours for contact treatment. The water flow experiment was carried out for about 6 months while periodically carrying out this contact treatment operation. The results are shown in Table-1.
【表】
表−１から明らかなように晶析リン除去材を加
温したアルカリ水溶液で処理しながら通水した処
理水のリン濃度は６ケ月経過しても約0.6mg／
を維持することができ脱リン性能の低下はほとん
ど認められなかつた。一方、比較例として、常温
の苛性ソーダを用いてアルカリ処理して、他は全
て同一条件で６ケ月間処理を継続した場合の対照
−１およびアルカリ処理を全く行なわず、他は全
て同一条件で６ケ月間処理を継続した場合の対照
−２の結果は、それぞれ同じく表−１に示す通り
であるが、６ケ月後の処理水のリン濃度は2.0
mg／を超え、脱リン性能は著しく悪化した。
実施例 ２
実施例１の対照−２と同一条件で調整した原水
を６ケ月間通水し、リン除去性能の低下した晶析
リン除去材を脱リン塔より抜き出し、苛性ソーダ
の濃度を0.01〜５％の範囲でそれぞれ調整して、
50℃まで加温した苛性ソーダ溶液に６時間浸漬し
て接触処理した。この場合、晶析リン除去材は
400mlずつ用い、１の三角フラスコを恒温水槽
内で振盪しながらアルカリ処理した。
各々の苛性ソーダ濃度で処理した晶析リン除去
材は、水洗後それぞれ内径30mmの脱リン塔に約
500mm厚ずつ充填し、実施例１と同様に調整した
被処理液を、LV＝1.0ｍ／Ｈで約１ケ月通水し、
リン吸着性能を比較した。結果を表−２に示す。[Table] As is clear from Table 1, the phosphorus concentration of the treated water passed through the crystallized phosphorus removal material while treating it with a heated alkaline aqueous solution was approximately 0.6 mg/ml even after 6 months.
The dephosphorization performance could be maintained with almost no decrease in dephosphorization performance. On the other hand, as a comparative example, Control-1 was treated with alkali using caustic soda at room temperature and the treatment was continued for 6 months under the same conditions. The results of Control-2 when the treatment was continued for 6 months are shown in Table 1, but the phosphorus concentration of the treated water after 6 months was 2.0.
mg/, and the dephosphorization performance deteriorated significantly. Example 2 Raw water prepared under the same conditions as Control-2 of Example 1 was passed through for 6 months, and the crystallized phosphorus removal material with decreased phosphorus removal performance was extracted from the dephosphorization tower, and the concentration of caustic soda was reduced to 0.01 to 5. Adjust each within the % range,
Contact treatment was carried out by immersing it in a caustic soda solution heated to 50°C for 6 hours. In this case, the crystallized phosphorus removal material is
Using 400 ml each, one Erlenmeyer flask was treated with alkali while being shaken in a constant temperature water bath. After washing with water, the crystallized phosphorus removal material treated with each caustic soda concentration was placed in a dephosphorization tower with an inner diameter of 30 mm.
Filled with a thickness of 500 mm, the liquid to be treated prepared in the same manner as in Example 1 was passed through at LV = 1.0 m/H for about 1 month.
The phosphorus adsorption performance was compared. The results are shown in Table-2.
【表】
表−２より明らかなように劣化した晶析リン除
去材を加温した苛性ソーダで接触処理する場合、
苛性ソーダの濃度は高いほど洗浄効果が良くなる
傾向がみられ、0.1％以上の濃度で処理したもの
は１ケ月通水しても、処理水濃度は安定してお
り、本発明法の効果を確認することができた。
実施例 ３
実施例２において苛性ソーダの液温の影響を調
べるため、0.5％苛性ソーダの液温を10℃〜100℃
の範囲で変えて、他は全て実施例２と同条件でア
ルカリ処理した。処理した晶析リン除去材は実施
例２と同じ方法で１ケ月間通水しリン吸着性能を
比較した。結果を表−３に示す。[Table] As is clear from Table 2, when the deteriorated crystallized phosphorus removal material is contacted with heated caustic soda,
There is a tendency that the higher the concentration of caustic soda, the better the cleaning effect, and when treated with a concentration of 0.1% or higher, the concentration of the treated water remained stable even after passing water for one month, confirming the effectiveness of the method of the present invention. We were able to. Example 3 In Example 2, in order to investigate the influence of the liquid temperature of caustic soda, the liquid temperature of 0.5% caustic soda was varied from 10°C to 100°C.
The alkali treatment was carried out under the same conditions as in Example 2 except that the conditions were changed within the following range. The treated crystallized phosphorus removal material was passed through water for one month in the same manner as in Example 2, and the phosphorus adsorption performance was compared. The results are shown in Table-3.
【表】
表−３から明らかなようにアルカリ水溶液の温
度が40℃以上であれば、１ケ月間通水しても安定
した処理水リン濃度が得られることが確認でき
た。一方40℃未満の液温ではアルカリ洗浄効果が
小さく１ケ月後には処理水リン濃度は2.0mg／
を超えるまでに悪化した。
実施例 ４
実施例２で使用したものと同一の、リン吸着性
能の低下した晶析リン除去材をNo.１〜３の内径30
mmの脱リン塔にそれぞれ500mm厚充填し、50℃に
液温を調節した0.5％の苛性ソーダ溶液で約５時
間接触処理した。脱リン塔No.１では苛性ソーダ導
入後そのまま静置して浸漬処理を行なつた。脱リ
ン塔No.２の上部には、循環ポンプを介して塔下部
に連結してなる液循環水管が設置してあり、接触
処理は循環ポンプを起動し、0.5ｍ／分の流速で
脱リン塔内にアルカリ水溶液を塔下部から連続的
に供給して晶析リン除去材が流動層を形成する状
態で行なつた。
脱リン塔No.３の下部には散気管が配設してあ
り、接触処理は、散気管より空気を0.5ｍ／min
の線速度で脱リン塔に１時間に10分間供給しなが
ら行なつた。接触処理した晶析リン除去材は塔下
部から水道水を供給して逆洗した後、実施例２と
同条件で１ケ月間通水し、リン吸着性能を比較し
た。結果を表−４に示す。[Table] As is clear from Table 3, it was confirmed that if the temperature of the alkaline aqueous solution was 40°C or higher, a stable phosphorus concentration in the treated water could be obtained even if the water was passed for one month. On the other hand, when the liquid temperature is below 40℃, the alkaline cleaning effect is small and the phosphorus concentration in the treated water is 2.0mg/1 month later.
It worsened to the point where it exceeded. Example 4 The same crystallized phosphorus removal material used in Example 2 with reduced phosphorus adsorption performance was used in Nos. 1 to 3 with an inner diameter of 30 mm.
Each of the dephosphorization towers was filled with a thickness of 500 mm and was contacted with a 0.5% caustic soda solution whose temperature was adjusted to 50°C for about 5 hours. In dephosphorization tower No. 1, after introducing caustic soda, the reactor was allowed to stand still for immersion treatment. A liquid circulation water pipe connected to the lower part of the tower via a circulation pump is installed at the top of dephosphorization tower No. 2. For contact treatment, the circulation pump is activated and dephosphorization is carried out at a flow rate of 0.5 m/min. The alkali aqueous solution was continuously supplied into the column from the bottom of the column, and the crystallized phosphorus removing material formed a fluidized bed. A diffuser pipe is installed at the bottom of dephosphorization tower No. 3, and the contact treatment is performed by blowing air through the diffuser pipe at 0.5 m/min.
The dephosphorization was carried out at a linear velocity of 10 minutes per hour. The contact-treated crystallized phosphorus removal material was backwashed by supplying tap water from the bottom of the tower, and then passed through water for one month under the same conditions as in Example 2, and the phosphorus adsorption performance was compared. The results are shown in Table 4.
本発明により、晶析リン除去材の表面に色度成
分、不純物の吸着して劣化するのを防ぎ、晶析リ
ン除去材の活性を維持することが可能になり、そ
の脱リン効果を長時間良好な状態に維持すること
ができ、安定した脱リン処理が可能となつた。
The present invention makes it possible to prevent chromaticity components and impurities from adsorbing and deteriorating on the surface of the crystallized phosphorus removal material, maintain the activity of the crystallized phosphorus removal material, and maintain its dephosphorizing effect for a long time. It was possible to maintain a good condition, and stable dephosphorization treatment became possible.
第１図は本発明方法の一実施態様のフローシー
トである。
１……原水流入管、２……脱リン塔、３……晶
析リン除去材、４……処理水流出管、５……晶析
リン除去材の取り出し管、６……反応槽、７……
アルカリ貯槽タンク、８，１３……移送ポンプ、
９……撹拌機、１０，１１……ヒータ、１２……
希釈水導入管。
FIG. 1 is a flow sheet of one embodiment of the method of the present invention. 1... Raw water inflow pipe, 2... Dephosphorization tower, 3... Crystallization phosphorus removal material, 4... Treated water outflow pipe, 5... Crystallization phosphorus removal material removal pipe, 6... Reaction tank, 7 ……
Alkaline storage tank, 8, 13...transfer pump,
9... Stirrer, 10, 11... Heater, 12...
Dilution water introduction pipe.
Claims (1)
シウム存在下でリン含有液と接触させて液中のリ
ンを除去する方法において、前記晶析リン除去材
を40℃以上に加温したアルカリ水溶液に接触させ
ることを特徴とする晶析リン除去材の再生方法。 ２ 前記晶析リン除去材が、リン酸塩鉱物又は活
性炭、活性アルミナ、含水酸化ジリコニウム、酸
化マグネシウム、骨炭、サンゴ砂、砂などの表面
にリン酸カルシウムを担持させたものの中から選
ばれたものの一つである特許請求の範囲第１項記
載の晶析リン除去材の再生方法。 ３ 前記アルカリ水溶液が0.1％以上の苛性ソー
ダを用いたものである特許請求の範囲第１項及び
第２項記載の晶析リン除去材の再生方法。 ４ 前記晶析リン除去材とアルカリ水溶液との接
触を、前記アルカリ水溶液の液流による撹拌状態
下、空気撹拌状態下、機械撹拌状態下のうち、少
なくとも一つの撹拌状態下で行なうものである特
許請求の範囲第１項、第２項及び第３項記載の晶
析リン除去材の再生方法。[Claims] 1. A method for removing phosphorus from a phosphorus-containing liquid by bringing a crystallized phosphorus removing material having phosphorus adsorption ability into contact with a phosphorus-containing liquid in the presence of calcium, wherein the crystallized phosphorus removing material is heated to 40°C or higher. A method for regenerating a crystallized phosphorus removing material, the method comprising bringing it into contact with a heated alkaline aqueous solution. 2. The crystallized phosphorus removing material is one of those selected from phosphate minerals, activated carbon, activated alumina, hydrated zirconium oxide, magnesium oxide, bone char, coral sand, sand, etc., with calcium phosphate supported on the surface. A method for regenerating a crystallized phosphorus removal material according to claim 1. 3. The method for regenerating a crystallized phosphorus removal material according to claims 1 and 2, wherein the alkaline aqueous solution uses 0.1% or more of caustic soda. 4. A patent in which the crystallized phosphorus removing material and the alkaline aqueous solution are brought into contact under at least one of the following agitation conditions: agitation by a liquid flow of the alkali aqueous solution, air agitation, and mechanical agitation. A method for regenerating a crystallized phosphorus removal material according to claims 1, 2, and 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5671286A JPS62213894A (en) | 1986-03-14 | 1986-03-14 | Method for regenerating precipitated phosphorus removing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5671286A JPS62213894A (en) | 1986-03-14 | 1986-03-14 | Method for regenerating precipitated phosphorus removing material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62213894A JPS62213894A (en) | 1987-09-19 |
| JPH0220320B2 true JPH0220320B2 (en) | 1990-05-08 |
Family
ID=13035091
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5671286A Granted JPS62213894A (en) | 1986-03-14 | 1986-03-14 | Method for regenerating precipitated phosphorus removing material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62213894A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5963656B2 (en) * | 2012-11-28 | 2016-08-03 | 水ｉｎｇ株式会社 | Sludge treatment apparatus and phosphorus production method |
-
1986
- 1986-03-14 JP JP5671286A patent/JPS62213894A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62213894A (en) | 1987-09-19 |
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