JPS6044996B2 - How to remove phosphates from liquid - Google Patents
How to remove phosphates from liquidInfo
- Publication number
- JPS6044996B2 JPS6044996B2 JP8313079A JP8313079A JPS6044996B2 JP S6044996 B2 JPS6044996 B2 JP S6044996B2 JP 8313079 A JP8313079 A JP 8313079A JP 8313079 A JP8313079 A JP 8313079A JP S6044996 B2 JPS6044996 B2 JP S6044996B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphates
- liquid
- dephosphorization
- calcium carbonate
- calcium
- 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
- 239000007788 liquid Substances 0.000 title claims description 42
- 229910019142 PO4 Inorganic materials 0.000 title claims description 34
- 150000003013 phosphoric acid derivatives Chemical class 0.000 title claims description 30
- 235000021317 phosphate Nutrition 0.000 title claims description 29
- 238000000034 method Methods 0.000 claims description 51
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 50
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 22
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 20
- 239000011707 mineral Substances 0.000 claims description 20
- 235000010755 mineral Nutrition 0.000 claims description 20
- 239000002131 composite material Substances 0.000 claims description 16
- 229910001424 calcium ion Inorganic materials 0.000 claims description 15
- 239000004568 cement Substances 0.000 claims description 15
- 229910052585 phosphate mineral Inorganic materials 0.000 claims description 15
- 239000011575 calcium Substances 0.000 claims description 12
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 7
- 239000000920 calcium hydroxide Substances 0.000 claims description 7
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000001506 calcium phosphate Substances 0.000 claims description 5
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 5
- 235000011010 calcium phosphates Nutrition 0.000 claims description 5
- 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 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 238000006114 decarboxylation reaction Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- -1 marl Substances 0.000 description 11
- 239000010802 sludge Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 9
- 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 8
- 239000003513 alkali Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002367 phosphate rock Substances 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 235000014653 Carica parviflora Nutrition 0.000 description 3
- 241000243321 Cnidaria Species 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000010800 human waste Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[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 VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000010151 yanghe Substances 0.000 description 1
Landscapes
- Removal Of Specific Substances (AREA)
- Water Treatment By Sorption (AREA)
Description
【発明の詳細な説明】
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関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for removing phosphates present in tap water, sewage, human waste water, industrial water, factory wastewater, boiler water, and all other liquids.
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どが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」、「赤潮」
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。The various liquids mentioned above that are generally discharged into natural water systems include:
Orthophosphates, various condensed phosphates, and organic phosphates exist in various states as inorganic phosphates, and the presence of these phosphates causes the closure of lakes, inland seas, and inner bays. "Blue water" and "red tide" in water or stagnant water
Biological slime is generated in equipment and piping when water is used for various purposes.
In addition, chemical scale is formed, which is a serious cause of accidents.
したがつて、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おり、そ
の代表的なものとして、生物学的処理法、イオン交換樹
脂法、化学的凝集沈殿法などがあげられるが、このうち
、化学的凝集沈殿法は現時点で一応完成された処理技術
として評価され、すでにかなりのところで実際処理規模
の処理装置が稼動している。Therefore, various phosphorus removal methods are being considered in order to remove the phosphates present in these liquids, and the representative ones include biological treatment, ion exchange resin method, and chemical treatment. Among these methods, the chemical coagulation-sedimentation method is regarded as a somewhat completed treatment technology, and treatment equipment on an actual treatment scale is already in operation in many places.
この化学的凝集処理法によるリン酸塩類の除去は、液中
に存在するリン酸塩類を特定の凝集剤を添加することに
よつて不溶性リン酸塩として除去する方法であり、凝集
剤としては、通常、消石灰〔Ca(0H)2〕、硫酸ア
ルミニウム〔Al.(SO4)3〕、塩化第2鉄〔Fe
Cl3〕などが用いられる。The removal of phosphates by this chemical flocculation treatment is a method of removing phosphates present in the liquid as insoluble phosphates by adding a specific flocculant. Usually, slaked lime [Ca(0H)2], aluminum sulfate [Al. (SO4)3], ferric chloride [Fe
Cl3] etc. are used.
ところが、化学的凝集沈殿法の最大の欠点は、使用する
凝集剤の種類にあまり関係なく、1一般に大量の凝集剤
を必要とし、処理コストが高いこと。2大なる薬注量に
比例的に大量の汚泥が発生し、この汚泥の沈降性、濃縮
性が極めて悪いこと(石灰汚泥は例外)。However, the biggest drawback of the chemical coagulation-sedimentation method is that it generally requires a large amount of flocculant and the processing cost is high, regardless of the type of flocculant used. A large amount of sludge is generated in proportion to the amount of two major chemical injections, and the settling and thickening properties of this sludge are extremely poor (with the exception of lime sludge).
3さらにこの汚泥は脱水性が劣ること(石灰汚泥は例外
)。3 Furthermore, this sludge has poor dewatering properties (lime sludge is an exception).
であり、大なる汚泥処理施設と処理費用を必要とするた
めに、現用技術であるにもかかわらず、実用上多くの問
題をかかえている。However, because it requires a large sludge treatment facility and processing costs, it has many practical problems despite being a current technology.
また、本発明者等によつて従来にない新規な処理方法と
して一定の粒径をもつリン酸カルシウムを含有するリン
酸塩鉱物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
いるリン酸塩鉱物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
を除去する方法も提案されるに至つた。In addition, the inventors of the present invention have developed a novel treatment method in which a cylindrical or conical dephosphorization tower is filled with phosphate minerals containing calcium phosphate having a certain particle size, and the PH of the liquid to be treated is is adjusted to a range of 6 to 11, and the solubility contained in the liquid to be treated is adjusted to a range of 6 to 11. By adding a calcium agent such as calcium chloride according to the concentration of phosphates and bringing them into contact with each other at a constant flow rate, calcium hydroxyapatite crystals are crystallized on the surface of the filled phosphate minerals. , fixed with soluble phosphoric acid. Methods for removing salts have also been proposed.
この楊合、リン酸塩鉱物表での代表的な化学反応は次の
通りである。このような新規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リン酸
塩鉱物の分離、脱水が極めて容易であり、従来の化学的
凝集沈殿法によるいわゆる凝沈汚泥と比較すると、濃縮
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はなく、資源として
のリンを回収することができる優れた脱リン技術である
。The typical chemical reactions in this Yanghe phosphate mineral table are as follows. By applying this new dephosphorization method, it is extremely easy to separate and dehydrate phosphate minerals with fixed calcium hydroxyapatite. This is an excellent dephosphorization technology that not only does not require conventional sludge treatment facilities such as equipment, dehydrators, and dryers, but also can recover phosphorus as a resource.
しかしながら、この新しい接触脱リン法では、液中に含
まれている溶解性リン酸塩類をカルシウムハイドロキシ
アパタイト 〔Ca5(0H)(PO4)3〕の結晶と
して固定するために、適当なPH条件下でカルシウム剤
としてCaCI2,Ca(0H)2−などが添加される
が、被処理液中にアルカリ度成分が含まれていると次に
示すような反応式にしたがつて炭酸カルシウムが生成さ
れる。However, in this new catalytic dephosphorization method, in order to fix the soluble phosphates contained in the liquid as crystals of calcium hydroxyapatite [Ca5(0H)(PO4)3], appropriate pH conditions are required. CaCI2, Ca(0H)2-, etc. are added as calcium agents, but if the liquid to be treated contains an alkalinity component, calcium carbonate is produced according to the following reaction formula.
この炭酸カルシウムは液のPHがカルシウムハイドロキ
シアパタイトが生成されるに適したPH範囲にあるか、
あるいは調整されていれば、アパタイトの生成速度のほ
うが炭酸カルシウムの生成速度よりも大きいために生成
されないが、現実の実際処理装置では完全なPHコント
ロールは難しく、またアルカリ度成分が濃厚な場合には
、カルシウム剤を添加した瞬間に前記(2)式の反応が
ある程度進行することは避けられない。Is the pH of this calcium carbonate liquid in a pH range suitable for producing calcium hydroxyapatite?
Alternatively, if the pH was adjusted, the apatite production rate would be higher than the calcium carbonate production rate, so it would not be produced, but it is difficult to completely control the pH in actual processing equipment, and if the alkalinity component is concentrated. It is inevitable that the reaction of formula (2) proceeds to some extent the moment the calcium agent is added.
このような条件で生成される炭酸カルシウムの結晶は極
めて少量であるが、長期間中に徐々に炭酸カルシウムの
結晶がリン酸塩鉱物の表面に固着成長する。Although the amount of calcium carbonate crystals produced under these conditions is extremely small, the calcium carbonate crystals gradually grow fixedly on the surface of the phosphate mineral over a long period of time.
その結果、リン酸塩鉱物の表面活性が劣化し、脱リン機
能は低減し、当初ほどの脱リン効果は期待できなくなる
。このように接触脱リン法は、液中にアルカリ度成分が
多量に含まれ、かつ溶解性リン酸塩類も含まれている液
についてはその適用に限界があるが、何らかの方法でア
ルカリ度成分を除去すれば、接触脱リン法の適用範囲は
拡大される。As a result, the surface activity of the phosphate mineral deteriorates, the dephosphorization function decreases, and the dephosphorization effect can no longer be expected to be as high as it was initially. In this way, the catalytic dephosphorization method has limited applicability to liquids that contain large amounts of alkalinity components and also soluble phosphates, but it is possible to remove alkalinity components by some method. If removed, the scope of application of the catalytic dephosphorization method will be expanded.
液中のアルカリ度成分を除去する従来法、すなわち軟化
の方法の主たるものは、液酸性下におけるストリツピン
グ法とCa(0H)2添加による軟化法(一種の凝集沈
殿処理)とがあるが、これらの方法にはそれぞれ重大な
欠点がある。すなわち、前者の液酸性下におけるストリ
ツピング法は、液を酸性にするための酸と、さらに処理
後再度PHを元にもどすためのアルカリ剤が必要であり
、処理費用が高くなるだけでなく、プロセスとして複雑
であり、かつ処理の安定性に欠ける。The main conventional methods for removing alkalinity components in liquids, that is, the main softening methods, are the stripping method under acidic conditions and the softening method by adding Ca(0H)2 (a type of coagulation-sedimentation treatment). Each method has significant drawbacks. In other words, the former method of stripping under acidic conditions requires an acid to make the liquid acidic and an alkaline agent to return the pH to the original level after treatment, which not only increases processing costs but also increases process costs. It is complex and lacks processing stability.
また、後者のCa(0H)2添加による化学的軟化法は
、大量の軟化剤(消石灰)が必要であるだけでなく、処
理しにくい大量の汚泥が発生し、事後処理も煩雑・不経
済である。本発明は、これら従来の問題を解決する有効
な方法であつて、リン酸塩類を適確で効率よく除去し、
長期にわたり安定した処理操作を可能にし稼動率を大巾
に向上できる方法を提供することを目的としたものであ
る。In addition, the latter chemical softening method by adding Ca(0H)2 not only requires a large amount of softener (slaked lime), but also generates a large amount of sludge that is difficult to treat, and post-treatment is also complicated and uneconomical. be. The present invention is an effective method for solving these conventional problems, and is an effective method for removing phosphates accurately and efficiently.
The purpose of this invention is to provide a method that enables stable processing operations over a long period of time and greatly improves the operating rate.
また本発明方法の他の目的は、きわめて簡単な処理操作
で質的に著しく良質な処理水が経済的に得られ処埋設備
費並ひに処理経費の節減をも容易にできる有益な方法と
することにある。Another object of the method of the present invention is to provide a useful method that can economically obtain treated water of extremely high quality through extremely simple treatment operations, and that can easily reduce treatment equipment costs and treatment costs. It's about doing.
本発明は、リン酸塩類を含む液を、セメント−アルカリ
剤一炭酸カルシウム含有鉱物からなる複合体と接触させ
、その後リン酸カルシウムを主成分とするリン酸塩鉱物
と接触させて処理することを特徴とする液中に存在する
リン酸塩類の除去方法である。The present invention is characterized in that a liquid containing phosphates is brought into contact with a cement-alkaline agent composite consisting of a calcium monocarbonate-containing mineral, and then brought into contact with a phosphate mineral whose main component is calcium phosphate for treatment. This is a method for removing phosphates present in the liquid.
本発明方法において用いられるセメント−アルカリ剤一
炭酸カルシウム含有鉱物からなる複合体一としてはセメ
ントニアルカリ剤+炭酸カルシウム含有鉱物=3:1〜
1:15、さらにアルカリ剤:炭酸カルシウム含有鉱物
=1:1〜1:10の配合組成からなる複合体を使用す
るのが有効である。The composite consisting of cement-alkaline agent monocalcium carbonate-containing mineral used in the method of the present invention is cement-alkali agent+calcium carbonate-containing mineral=3:1~
It is effective to use a composite having a blending composition of 1:15, and further alkali agent:calcium carbonate-containing mineral=1:1 to 1:10.
この場合セメントには、ボルトランドセメント、スラツ
グセメント、シリカセメント、アルミナセメント、混合
セメント等があり、アルカリ剤には消石灰、生石灰、力
性ソーダ、力性カリ等があり、また炭酸カルシウム含有
鉱物には大理石、泥灰岩、ドロマイト、方解石、サンゴ
質石灰岩、サンゴ砂等があり、これらを単独又は二種以
上組合せて用いるが、このセメント、アルカリ剤、炭酸
カルシウム含有鉱物を粒状、粉粒状、塊状、粉状にして
混合し、そのままあるいはこれに適当量の水を加えてよ
く練り、粒径0.37T$t〜10077w!に成型し
て複合体とする。なお複合体の形状は必要に応じ粉状、
粉粒状、粒状、塊状のものの任意のものでよい。いずれ
にしても、セメント−アルカリ剤一炭酸カルシウム含有
鉱物からなる複合体に被処理液を接触させることにより
、該複合体、とりわけアルカリ剤からは0H−イオン、
セメントあるいは炭酸カルシウム含有鉱物からCa2+
イオンが溶解するため、被処理液に含まれるアルカリ度
成分は前記(2)式に従い炭酸カルシウムとなり、生成
した炭酸カルシウムは結晶化作用により該複合体の溶解
しない部分、とりわけ炭酸カルシウム含有鉱物表面に固
着して脱炭酸工程による軟化処理が行なわれ、したがつ
て、従来のCa(0H)2添加の軟化法と違つて汚泥の
発生がなく、汚泥の処理、処分が不必要となる。In this case, the cements include boltland cement, slag cement, silica cement, alumina cement, mixed cement, etc., and the alkaline agents include slaked lime, quicklime, hydrocarbon soda, hydropotassium, etc., and minerals containing calcium carbonate. There are marble, marl, dolomite, calcite, coralline limestone, coral sand, etc., and these are used alone or in combination of two or more types, but this cement, alkali agent, calcium carbonate-containing minerals are used in granular, powdered, granular, Mix it into a lump or powder, and knead it as it is or add an appropriate amount of water to it to obtain a particle size of 0.37T$t~10077W! It is molded into a composite. The shape of the composite can be powdered or
Any powder, granule, or block may be used. In any case, by bringing the liquid to be treated into contact with a composite consisting of a cement-alkaline agent calcium monocarbonate-containing mineral, 0H- ions,
Ca2+ from cement or calcium carbonate-containing minerals
Since the ions are dissolved, the alkalinity component contained in the liquid to be treated becomes calcium carbonate according to equation (2) above, and the generated calcium carbonate is crystallized into the undissolved parts of the complex, especially the surface of calcium carbonate-containing minerals. After solidification, a softening process is performed through a decarboxylation process. Therefore, unlike the conventional softening method of adding Ca(0H)2, no sludge is generated, and sludge treatment and disposal are unnecessary.
本発明方法による前記軟化法では、被処理液の性状に応
じて、該複合体のセメント−アルカリ剤−炭酸カルシウ
ム含有鉱物の含有率を変えること、あるいは該複合体と
被処理液との接触時間を変えることにより、該複合体か
らの0H−イオン、Ca2+イオンの溶解量を被処理液
の軟化に十分な量に制御できることから、従来の軟化法
のような薬注設備、PH調整設備は不必要となる。つぎ
に、該複合体に接触し化学的軟化の終了した被処理液に
は、炭酸カルシウムの生成にあずからない0H−イオン
、Ca2+イオンが残存しているため、モル比としてC
a/PO4≧0.7好ましくは1〜5、PH=8〜1C
iffましくはPH=8.5〜9.5の条件下でカルシ
ウムハイドロオキシアパタイトの結晶を晶出、固着せし
めることにより、被処理液からリン酸塩類を除去するこ
とができる。このリン酸塩鉱物表面での化学反応式は前
記(1)式の通りである。さらに、化学的軟化の終了し
た被処理液にカルシウムイオンが被処理液のリン酸塩類
に対してモル比としてCa/PO4く0.7の場合であ
れば、被処理液中にカルシウムイオンを添加することに
よつて、リン酸塩鉱物表面にカルシウムハイドロオキシ
アパタイトの結晶を晶出、固着せしめて、被処理液から
除去することが可能となるが、該複合体のアルカリ剤と
して、消石灰を用いると、消石灰から、0H−イオン、
Ca2+イオンが溶解するため、被処理液のアルカリ度
成分の軟化、リン酸塩類の除去いずれの反応にも寄与す
ることで、その効果は大きい。In the softening method according to the method of the present invention, depending on the properties of the liquid to be treated, the content of cement-alkaline agent-calcium carbonate-containing mineral in the composite may be changed, or the contact time of the composite and the liquid to be treated may be changed. By changing the amount of 0H- ions and Ca2+ ions dissolved in the complex, it is possible to control the amount of 0H- ions and Ca2+ ions that are sufficient to soften the liquid to be treated. It becomes necessary. Next, in the liquid to be treated that has come into contact with the composite and has been chemically softened, 0H- ions and Ca2+ ions that do not participate in the production of calcium carbonate remain, so the molar ratio of C
a/PO4≧0.7 preferably 1-5, PH=8-1C
Phosphates can be removed from the liquid to be treated by crystallizing and fixing calcium hydroxyapatite crystals, preferably under conditions of pH=8.5 to 9.5. The chemical reaction formula on the surface of this phosphate mineral is as shown in formula (1) above. Furthermore, if the molar ratio of calcium ions to the phosphates in the liquid to be treated is Ca/PO4=0.7, calcium ions are added to the liquid to be treated after chemical softening. By doing this, it becomes possible to crystallize and fix calcium hydroxyapatite crystals on the surface of the phosphate mineral and remove them from the liquid to be treated, but slaked lime is used as an alkali agent for the complex. And from slaked lime, 0H- ion,
Since Ca2+ ions are dissolved, they contribute to both the softening of the alkalinity components of the liquid to be treated and the removal of phosphates, and are therefore highly effective.
また前記脱リン工程では、一定の粒径をもつリン酸カル
シウムを含有するリン酸塩鉱物、例えばLヨルダン産、
フロリダ産、メキシコ産、カナダ産、神奈川県玄倉産、
栃木県足尾銅山産、与論島産、福岡県長垂産、北海道大
玖鉱山産などのリン鉱石を充填した充填塔に通液するこ
をによつて行なわれるものであるが、該充填塔での通液
方法としては流動層方式又は固定層方式のいずれでもよ
く固定層方式では上向流、下向流のいずれでもよい。In addition, in the dephosphorization step, phosphate minerals containing calcium phosphate having a certain particle size, such as L Jordan,
From Florida, from Mexico, from Canada, from Kurokura, Kanagawa Prefecture,
It is carried out by passing liquid through a packed tower filled with phosphate rock from Ashio Copper Mine in Tochigi Prefecture, Yoron Island, Nagatari in Fukuoka Prefecture, Daiku Mine in Hokkaido, etc. The liquid passing method may be either a fluidized bed method or a fixed bed method, and in the fixed bed method, either an upward flow or a downward flow may be used.
この通液条件は流動層方式では一般にS■として10〜
100d/7T1−Hr、固定層方式ではSVとして1
〜10d/d−Hrの範囲が適当である。さらに通液処
理に際して液のPH値は普通8.0〜11.0の範囲で
行なうのがよく、カルシウムイオンの注入率は液中に溶
存する各種リン酸塩類の濃度によつて異なるが通常Ca
/PO4として0.5〜2CEましくは1.0〜5.0
の範囲で添加処理される。さらに本発明の一実施態様を
図面について説明すれは、リン酸塩類、アルカリ度成分
を含む被処理液を、沈殿池もしくは簡単な砂ろ過機によ
つて液中に残存する浮遊物質を除去したるのち流入管1
より第一槽2内に導入する。In the fluidized bed method, this liquid passing condition is generally 10~10 as S■.
100d/7T1-Hr, 1 as SV in fixed layer method
A range of ~10 d/d-Hr is suitable. Furthermore, during the liquid passage treatment, the pH value of the liquid should normally be in the range of 8.0 to 11.0, and the injection rate of calcium ions varies depending on the concentration of various phosphates dissolved in the liquid, but usually Ca
/0.5~2CE or 1.0~5.0 as PO4
It is added within the range of . Further, one embodiment of the present invention will be explained with reference to the drawings. The liquid to be treated containing phosphates and alkalinity components is filtered through a sedimentation tank or a simple sand filter to remove suspended substances remaining in the liquid. Later inflow pipe 1
and introduced into the first tank 2.
この第一槽2内には、セメント−アルカリ剤一炭酸カル
シウム含有鉱物からなる複合体3の一定粒径に調整され
たものが或る高さに充填されているので、被処理液がこ
の第一槽2を通過する際に該複合体3と接触して、複合
体3を溶解し、0H−イオンおよびCa2+イオンが溶
出し、被処理液中のアルカリ度成分は炭酸カルシウムと
なつて該複合体の未溶解の部分に晶出、固着する。第二
槽6にはリン酸カルシウムを主成分とするリン酸塩鉱物
7を一定の粒径に調整したものが充填され、第一槽2を
出た流出液一は流入管4より第二槽6に導入され、第二
槽6を通過する際に、液中のリン酸塩類はヒドロキシア
パタイトとなつてリン酸塩鉱物7の表面に晶出、固着す
ることにより除去されたのち、流出管8から良質な処理
水を流出する。さらに、ヒドロキシアパタイトの生成に
充分なCa2+イオンが不足する場合、例えばモル比と
してCa/PO4〈0.7の場合は、流入管5よりCa
2+イオンを添加して、モル比としてCa/PO43−
ニ1〜5にすれはよい。This first tank 2 is filled to a certain height with composites 3 made of cement-alkaline agent calcium monocarbonate-containing minerals whose particle size has been adjusted to a certain level. When passing through the tank 2, it comes into contact with the complex 3, dissolves the complex 3, 0H- ions and Ca2+ ions are eluted, and the alkalinity component in the liquid to be treated becomes calcium carbonate and the complex 3 is dissolved. Crystallizes and adheres to undissolved parts of the body. The second tank 6 is filled with phosphate mineral 7 whose main component is calcium phosphate, which has been adjusted to a certain particle size. When the liquid is introduced and passes through the second tank 6, the phosphates in the liquid become hydroxyapatite, which crystallizes and adheres to the surface of the phosphate mineral 7, and is removed. discharge treated water. Furthermore, if there is insufficient Ca2+ ion to generate hydroxyapatite, for example, if the molar ratio is Ca/PO4<0.7, Ca
By adding 2+ ions, the molar ratio Ca/PO43-
D 1-5 is good.
以上のべたように本発明は、液中に含まれているアルカ
リ度成分を、セメント−アルカリ剤一炭酸カルシウム含
有鉱物からなる複合体と接触させることにより、アルカ
リ度成分を可及的に除去し、後続するリン酸塩鉱物との
接触工程におけるリン酸塩類除去効果をもたらすCa2
ソオンの増大とPH調節のためのアルカリ剤の添加を省
略するなど極めて簡単な操作で液中のリン酸塩類を長期
間除去することができ、さらに処埋設備とも軽減させる
ことができるものである。As described above, the present invention removes alkalinity components contained in the liquid as much as possible by bringing the alkalinity components contained in the liquid into contact with a composite consisting of cement and an alkaline agent and minerals containing calcium monocarbonate. , Ca2 which brings about the effect of removing phosphates in the subsequent contact step with phosphate minerals.
Phosphate salts in the liquid can be removed for a long period of time with extremely simple operations such as omitting the addition of alkaline agents to increase the amount of SOON and adjust the pH, and furthermore, the need for disposal equipment can be reduced. .
次に本発明の実施例をのべる。Next, examples of the present invention will be described.
実施例1
セメント−アルカリ剤一炭酸カルシウム含有鉱物からな
る複合体をセメントを2重量部、アルカリ剤として消石
灰を1重量部、炭カル含有鉱物としてサンゴ砂7重量部
、これに水5重量部を加え、良く練りペースト状にした
。Example 1 Cement-alkali agent A composite consisting of calcium monocarbonate-containing minerals was prepared by adding 2 parts by weight of cement, 1 part by weight of slaked lime as an alkali agent, 7 parts by weight of coral sand as a charcoal-containing mineral, and 5 parts by weight of water. The mixture was added and kneaded well to form a paste.
このペースト状物から粒径0.5Tm〜1.0T!Rl
nの粒状物を成型調整した。軟化用のカラムとして直径
20cm1高さ200C71の容器に、上記粒状複合体
を32e(充填高さとして100cm)充填した。From this paste-like material, the particle size is 0.5Tm to 1.0T! Rl
n granules were molded and adjusted. The above granular composite was packed into a container having a diameter of 20 cm and a height of 200C71 as a softening column (32e (filling height: 100 cm)).
脱リン用のカラムとして直径10cm1高さ100cm
の容器に粒径0.6Tf$l〜0.8TfUTLのヨル
ダン産リン鉱石を8e(充填高さとして100cm)充
填した。第1表に示した下水の活性汚泥処理水を原水と
して上記の軟化用カラムに上向流で通水したのち脱リン
用カラムに上向流て通水した。Diameter 10cm 1 height 100cm as a column for dephosphorization
A container was filled with 8e (filling height: 100 cm) of Jordanian phosphate rock having a particle size of 0.6 Tf$l to 0.8 TfUTL. The activated sludge-treated sewage water shown in Table 1 was used as raw water and was passed through the above-mentioned softening column in an upward flow, and then passed through the dephosphorization column in an upward flow.
通水速度として軟化用カラムはSV=1(1/Hr)、
脱リン用カラムはS■=4(1/Hr)とした。この実
験を約4ケ月継続し、長期間通水した場合のリン鉱石の
活性劣化をチェックするために、運転開始後1週間目、
3ケ月目に最終処理水について精密分析を行なつた。The water flow rate for the softening column is SV=1 (1/Hr),
The dephosphorization column was set to S■=4 (1/Hr). This experiment continued for about 4 months, and in order to check the deterioration of the activity of phosphate rock when water was passed for a long period of time, during the first week after the start of operation,
A precise analysis was conducted on the final treated water in the third month.
この結果は第1表に示す通りであり、本発明によれば通
水開始1週間後と3ケ月後でも脱リン効果の低減は全く
認められなかつた。The results are shown in Table 1, and according to the present invention, no reduction in the dephosphorization effect was observed at all even after one week and three months after the start of water flow.
一方比較例として、上記原水を軟化カラムに通水せずに
、PHを8.8〜9.2に調整して直接脱リンカラム(
通水条件は同一)に通水した結果を第2表に示す。On the other hand, as a comparative example, the pH was adjusted to 8.8 to 9.2 without passing the raw water through the softening column, and the raw water was directly passed through the dephosphorization column (
Table 2 shows the results of water flow under the same water flow conditions.
通水当初は脱リン効果は顕著であつても3ケ月後には、
脱リン性能は著しく劣化した。実施例2軟化用カラムお
よび脱リンカラムの形状は実施例−1と同様のものを用
いた。Although the dephosphorization effect is noticeable at the beginning of water flow, after 3 months,
The dephosphorization performance deteriorated significantly. Example 2 The shapes of the softening column and dephosphorization column were the same as in Example-1.
セメント−アルカリ剤一炭酸カルシウム含有鉱物からな
る複合体をセメントを3重量部、アルカリ剤として粒状
力性ソーダを1重量部、炭酸カルシウム含有鉱物として
サンゴ砂6重量部、これに水5重量部を加えよく練りペ
ースト状にした。Cement - alkaline agent A complex consisting of calcium monocarbonate-containing minerals is prepared by adding 3 parts by weight of cement, 1 part by weight of granular soda as an alkali agent, 6 parts by weight of coral sand as a calcium carbonate-containing mineral, and 5 parts by weight of water. Add it and knead it well to make a paste.
このペースト状物から粒径0.5Tm!n〜1.07T
$Lの粒状物を成型調整した。軟化用のカラムには上記
粒状複合体を32e充填し、脱リン用のカラムには粒径
0.4薗〜0.6Tnmのヨルダン産リン鉱石を8′充
填した。From this paste-like material, the particle size is 0.5Tm! n~1.07T
A granular material of $L was molded and adjusted. The column for softening was packed with 32e of the above granular composite, and the column for dephosphorization was packed with 8' of Jordanian phosphate rock having a particle size of 0.4 Tnm to 0.6 Tnm.
第3表に示したし尿の硝化脱窒素法の処理水(生し尿の
1@希釈水)を原水として軟化用カラムに上向流で通水
した。The treated water of the nitrification and denitrification method of human waste shown in Table 3 (1@diluted water of human waste) was used as raw water and passed through the softening column in an upward flow.
通水速度として軟化用カラムはS■=0.5(1/h)
、脱リン用カラムはSV=2(1/Hr)とした。原水
のリン酸濃度はPO43−として40〜60mg/lで
ありCa2+イオン濃度は10〜20mg/′である。
Ca2+イオンを軟化用カラムの処理水に100mg/
f添加して脱リン処理を1ケ月継続して行なつた。通水
開始後3週間目の結果を第3表に示す。The water flow rate for the softening column is S = 0.5 (1/h)
The dephosphorization column was set at SV=2 (1/Hr). The phosphoric acid concentration of the raw water is 40 to 60 mg/l as PO43-, and the Ca2+ ion concentration is 10 to 20 mg/'.
Add 100mg/Ca2+ ion to the treated water of the softening column.
The dephosphorization treatment was continued for one month by adding f. Table 3 shows the results 3 weeks after the start of water flow.
一方、比較例として、上記軟化用カラムの処理水にCa
2+イオンを添加せずに行なづた結果を第4表に示す。
この第4表の結果から、Ca2+イオンを添加しない場
合の脱リン性能は著るしく劣化した。On the other hand, as a comparative example, Ca was added to the treated water of the softening column.
Table 4 shows the results obtained without adding 2+ ions.
From the results in Table 4, the dephosphorization performance was significantly degraded when Ca2+ ions were not added.
図面は本発明方法の一実施態様を示す系統説図てある。 The drawings are schematic diagrams illustrating one embodiment of the method of the invention.
Claims (1)
剤−炭酸カルシウム含有鉱物から成る複合体と接触して
液中のアルカリ度成分を炭酸カルシウムとして除去した
のち、リン酸カルシウムを主成分とするリン酸塩鉱物と
接触させて処理することを特徴とする液中のリン酸塩類
の除去方法。 2 前記脱炭酸工程が、セメント:アルカリ剤+炭酸カ
ルシウム含有鉱物=3:1〜1:15で、アルカリ剤:
炭酸カルシウム含有鉱物=1:1〜1:10の複合体に
接触処理されるものである特許請求の範囲第1項記載の
リン酸塩類の除去方法。 3 前記脱リン工程が、脱リン塔に供給する脱炭酸工程
流出液にCa/PO_4として1.0〜20の範囲のカ
ルシウムイオンを注入して処理するものである特許請求
の範囲第1項又は第2項記載のリン酸塩類の除去方法。 4 前記セメント−アルカリ剤−炭酸カルシウム含有鉱
物からなる複合体が、消石灰をアルカリ剤として用いた
もので処理されるものである特許請求の範囲第1項、第
2項又は第3項記載のリン酸塩類の除去方法。5 前記
脱リン工程が、粒径0.1〜1.0mmのリン酸塩鉱物
を充填した脱リン塔へ固定層方式或いは流動層方式とし
て通液するものである特許請求の範囲第1項、第2項、
第3項又は第4項記載のリン酸塩類の除去方法。 6 前記脱リン工程が、軟化処理液にカルシウムイオン
をCa/PO_4として1.0〜5.0の範囲添加して
処理するものである特許請求の範囲第1項、第2項、第
3項、第4項又は第5項記載のリン酸塩類の除去方法。[Claims] 1. A solution to be treated containing phosphates is brought into contact with a composite consisting of cement, an alkaline agent, and a calcium carbonate-containing mineral to remove alkalinity components in the solution as calcium carbonate, and then the calcium phosphate is removed. A method for removing phosphates from a liquid, the method comprising treating the phosphates by bringing them into contact with phosphate minerals as the main component. 2 The decarboxylation step is performed using cement: alkaline agent + calcium carbonate-containing mineral = 3:1 to 1:15, and alkaline agent:
The method for removing phosphates according to claim 1, wherein the method is carried out in contact with a complex of calcium carbonate-containing minerals in a ratio of 1:1 to 1:10. 3. Claim 1 or 3, wherein the dephosphorization process is performed by injecting calcium ions in the range of 1.0 to 20 as Ca/PO_4 into the decarboxylation process effluent supplied to the dephosphorization tower. The method for removing phosphates according to item 2. 4. The phosphor according to claim 1, 2, or 3, wherein the composite consisting of cement, alkaline agent, and calcium carbonate-containing mineral is treated with slaked lime as an alkaline agent. Method for removing acid salts. 5. Claim 1, wherein the dephosphorization step involves passing the liquid through a dephosphorization tower filled with phosphate minerals having a particle size of 0.1 to 1.0 mm in a fixed bed system or a fluidized bed system, Section 2,
The method for removing phosphates according to item 3 or 4. 6. Claims 1, 2, and 3, wherein the dephosphorization step is performed by adding calcium ions as Ca/PO_4 in a range of 1.0 to 5.0 to the softening treatment solution. , the method for removing phosphates according to item 4 or 5.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8313079A JPS6044996B2 (en) | 1979-06-30 | 1979-06-30 | How to remove phosphates from liquid |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8313079A JPS6044996B2 (en) | 1979-06-30 | 1979-06-30 | How to remove phosphates from liquid |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS567680A JPS567680A (en) | 1981-01-26 |
JPS6044996B2 true JPS6044996B2 (en) | 1985-10-07 |
Family
ID=13793608
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8313079A Expired JPS6044996B2 (en) | 1979-06-30 | 1979-06-30 | How to remove phosphates from liquid |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6044996B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4707270A (en) * | 1985-01-31 | 1987-11-17 | Ube Industries, Ltd. | Process for treating waste water containing phosphorus compounds and/or organic cod substances |
-
1979
- 1979-06-30 JP JP8313079A patent/JPS6044996B2/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
JPS567680A (en) | 1981-01-26 |
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