JPH06210282A - Phosphorus removing material, its manufacture and treatment of phosphorus containing water - Google Patents
Phosphorus removing material, its manufacture and treatment of phosphorus containing waterInfo
- Publication number
- JPH06210282A JPH06210282A JP2339293A JP2339293A JPH06210282A JP H06210282 A JPH06210282 A JP H06210282A JP 2339293 A JP2339293 A JP 2339293A JP 2339293 A JP2339293 A JP 2339293A JP H06210282 A JPH06210282 A JP H06210282A
- Authority
- JP
- Japan
- Prior art keywords
- phosphorus
- water
- adsorption
- removing material
- gel
- 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.)
- Pending
Links
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 53
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000011574 phosphorus Substances 0.000 title claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000000126 substance Substances 0.000 claims abstract description 15
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 230000003100 immobilizing effect Effects 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 18
- 239000008187 granular material Substances 0.000 abstract description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract description 7
- 239000004327 boric acid Substances 0.000 abstract description 7
- 239000000725 suspension Substances 0.000 abstract description 6
- 239000000084 colloidal system Substances 0.000 abstract description 4
- 229910021538 borax Inorganic materials 0.000 abstract description 2
- 239000004328 sodium tetraborate Substances 0.000 abstract description 2
- 235000010339 sodium tetraborate Nutrition 0.000 abstract description 2
- 239000012798 spherical particle Substances 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract 3
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 abstract 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract 2
- 239000007788 liquid Substances 0.000 abstract 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract 1
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 239000003463 adsorbent Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- 108010082455 Sebelipase alfa Proteins 0.000 description 8
- 235000014413 iron hydroxide Nutrition 0.000 description 8
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 8
- 229940041615 kanuma Drugs 0.000 description 8
- 239000002689 soil Substances 0.000 description 8
- 229910001583 allophane Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000005484 gravity Effects 0.000 description 6
- 229940085991 phosphate ion Drugs 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 125000004437 phosphorous atom Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 239000000679 carrageenan Substances 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 229940113118 carrageenan Drugs 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 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 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Landscapes
- Water Treatment By Sorption (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、上水、下水、各種廃
水、ダム貯水池、湖沼、河川などの水中に含まれる微量
なリン酸イオン（ＰＯ4 3- イオンとも記載する）を効果
的に吸着除去する新規なリン除去材に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is effective for trace amounts of phosphate ions (also referred to as PO 4 3− ions) contained in water such as tap water, sewage, various waste water, dam reservoirs, lakes and rivers. The present invention relates to a novel phosphorus removing material that removes by adsorption.
【０００２】[0002]
【従来の技術】従来から鹿沼土、アロフェン、活性アル
ミナ、水酸化鉄などのリン吸着力の大きな物質が知られ
ているが、次のような理由からこれらの物質を利用した
リン除去技術は、実用化されていないのが実状である。 活性アルミナはコストが高く、低ランニングコストを
必須とする水処理には不適である。ランニングコストを
安くするためにはリン吸着が飽和に達した活性アルミナ
を再生して再利用しなければならないが、この再生が面
倒でコストも高い。 原料のコストが安いアロフェン、鹿沼土は粉末状であ
るため造粒しないと実用が難しいが、セメントなどのバ
インダーを用いて強度の大きなペレットに造粒すると、
リン吸着力が悪化してしまい、バインダー添加量を少な
くすると造粒物の強度が弱くなり、水中で崩壊してしま
うという欠点がある。2. Description of the Related Art Conventionally, substances such as Kanuma soil, allophane, activated alumina, iron hydroxide, etc. having a large phosphorus adsorption power have been known, but the phosphorus removal technology using these substances has the following reasons. The reality is that it has not been put to practical use. Activated alumina has a high cost and is not suitable for water treatment which requires low running cost. In order to reduce the running cost, it is necessary to regenerate and recycle the activated alumina whose phosphorus adsorption has reached saturation, but this regeneration is troublesome and costly. Allophane and Kanuma soil, which are low in raw material cost, are difficult to put into practical use unless they are granulated because they are powdery, but when granulating into high-strength pellets using a binder such as cement,
If the amount of the binder added is reduced, the strength of the granulated product will be weakened and the phosphorus will be disintegrated in water.
【０００３】水酸化鉄、酸化鉄粒子は、リン吸着力を
低下させずに造粒すること自体が困難であるため、リン
吸着材としての実用化例は皆無である。 造粒物の比重が２．０以上であるため、重く、リン吸
着材を流動状態でリン含有水と接触させることが困難で
あるため、固定層で使用せざるを得ず、ＳＳの多い原水
に適用すると、目詰まりが発生してしまう。 粒状活性アルミナのような粒状のリン吸着材を用いた
場合、吸着材の表面でしかリン酸イオン（ＰＯ4 3- イオ
ン）が吸着されない。従って粒状物の内部はリン吸着に
有効に利用されず無駄になっている。 廃吸着材の処理が困難である。Since it is difficult to granulate iron hydroxide and iron oxide particles without lowering the phosphorus adsorbing power, there is no practical application as a phosphorus adsorbing material. Since the specific gravity of the granulated product is 2.0 or more, it is heavy and it is difficult to bring the phosphorus adsorbent into contact with the phosphorus-containing water in a fluidized state. When applied to, it causes clogging. When a granular phosphorus adsorbent such as granular activated alumina is used, phosphate ions (PO 4 3− ions) are adsorbed only on the surface of the adsorbent. Therefore, the inside of the granular material is not effectively used for phosphorus adsorption and is wasted. It is difficult to process the waste adsorbent.
【０００４】このため、下記のような技術が開発される
ことが切望されている。すなわち、 １．原料のコストが安いため脱リン材として有望である
が、従来造粒法に問題がある鹿沼土、アロフェン、水酸
化鉄、酸化鉄微粒子や鉄粉などを容易に粒状化でき、し
かも造粒物にリン吸着力の低下がなく、かつ強度上の欠
点もない造粒法。 ２．廃吸着材の処分が容易であるか、より好ましくは有
効利用ができること。 ３．さらに、造粒物のリン吸着に使用できる面積が可能
な限り大きいこと。 などである。なお、造粒物の比重が１．０に近く軽く
て、処理槽やカラム中で容易に流動化できることが望ま
しい。Therefore, it has been earnestly desired to develop the following techniques. That is, 1. Although it is a promising dephosphorizer due to its low raw material cost, it can easily granulate Kanuma soil, allophane, iron hydroxide, iron oxide fine particles, iron powder, etc., which have problems with the conventional granulation method. Granulation method that does not reduce the phosphorus adsorption power and has no strength defects. 2. Disposal of waste adsorbent should be easy or, more preferably, effective use. 3. Furthermore, the area that can be used for phosphorus adsorption of the granulated material should be as large as possible. And so on. In addition, it is desirable that the specific gravity of the granulated material is close to 1.0 and that the granulated material can be easily fluidized in a treatment tank or a column.
【０００５】[0005]
【発明が解決しようとする課題】本発明は前記従来技術
の欠点を完全に解決することができ、上記の要請を満足
する鹿沼土、アロフェン、水酸化鉄、酸化鉄微粒子や鉄
粉などコストが安い脱リン材を容易に粒状化できる造粒
法を開発し、新規な脱リン材（リン吸着材）を提供する
ことにある。さらに本発明の課題はリン含有水から効率
よくリンを除去することにある。The present invention is capable of completely solving the above-mentioned drawbacks of the prior art, and can reduce costs such as Kanuma soil, allophane, iron hydroxide, iron oxide fine particles and iron powder which satisfy the above requirements. The purpose of the present invention is to develop a granulation method capable of easily granulating a cheap dephosphorization material and provide a new dephosphorization material (phosphorus adsorbent). A further object of the present invention is to efficiently remove phosphorus from phosphorus-containing water.
【０００６】[0006]
【課題を解決するための手段】本発明の課題は以下の新
規きなリン吸着材の開発によって解決される。すなわ
ち、リン酸イオン吸着作用をもつ物質を水溶性高分子ゲ
ル内に包括固定化してなるリン除去材である。上記本発
明のリン除去材は、リン酸イオン吸着作用をもつ物質の
少なくとも一種類を水溶性高分子と混合した後、該水溶
性高分子をゲル化せしめ、ゲル内に前記リン酸イオン吸
着作用をもつ物質を包括固定化するという従来には類例
のない新概念に基づく方法により製造される。また、リ
ン酸イオン吸着作用をもつ物質を水溶性高分子ゲル内に
包括固定化してなる本発明のリン除去材をリン含有水と
接触させる処理方法によりリン含有水からリンを効果的
に除去することができる。The object of the present invention is solved by the development of the following novel phosphorus adsorbent. That is, it is a phosphorus removing material obtained by entrapping and immobilizing a substance having a phosphate ion adsorbing action in a water-soluble polymer gel. The above phosphorus removing material of the present invention is such that after mixing at least one kind of substance having a phosphate ion adsorbing action with a water-soluble polymer, the water-soluble polymer is gelated, and the phosphate ion adsorbing action is carried out in the gel. It is manufactured by a method based on a new concept, which is unprecedented in the past, of entrapping and immobilizing a substance having Further, phosphorus is effectively removed from phosphorus-containing water by a treatment method of contacting the phosphorus-removing material of the present invention obtained by entrapping a substance having a phosphate ion-adsorbing action in a water-soluble polymer gel, with phosphorus-containing water. be able to.
【０００７】以下に本発明の脱リン材の製造方法を詳し
く説明する。水酸化アルミ、酸化アルミ、水酸化鉄、酸
化鉄、鉄粉、鹿沼土、アロフェン、水酸化チタン、水酸
化ジルコニウム、ヒドロキシアパタイト、酸化マグネシ
ウム、骨炭、リン鉱石などのリン吸着作用の大きな各種
物質の微粒子、粉末などを本発明によって容易に粒状物
にすることができる。The method for producing the dephosphorizing material of the present invention will be described in detail below. Aluminum hydroxide, aluminum oxide, iron hydroxide, iron oxide, iron powder, Kanuma soil, allophane, titanium hydroxide, zirconium hydroxide, hydroxyapatite, magnesium oxide, bone charcoal, phosphorus ore Fine particles, powder and the like can be easily made into granules by the present invention.
【０００８】以下リン吸着作用をもつ物質として水酸化
鉄を例に挙げて本発明を説明する。ＦｅＣｌ3 の水溶液
をＮａＯＨでｐＨ４〜４．５に中和するとＦｅ（ＯＨ）
3のコロイド粒子を含んだサスペンジョンが生成する。
このサスペンジョンを水溶性高分子のポリビニルアルコ
ール（ＰＶＡ）溶液と混合したのち、この混合液をオリ
フィスから液滴状にしてホウ酸あるいはホウ砂水溶液中
に滴下すると、瞬時にＦｅ（ＯＨ）3 コロイドを包含し
た径数ｍｍのＰＶＡゲルが形成される。この状態を図１
に示した。図１において、ポリビニルアルコールゲル１
の球形粒子の内部にリン酸イオン（ＰＯ4 3- イオン）吸
着作用の大きなＦｅ（ＯＨ）3 コロイド粒子２を包含し
た状態を示した。The present invention will be described below by taking iron hydroxide as an example of a substance having a phosphorus adsorption function. When an aqueous solution of FeCl 3 is neutralized with NaOH to pH 4 to 4.5, Fe (OH)
A suspension containing 3 colloidal particles is generated.
After this suspension was mixed with a polyvinyl alcohol (PVA) solution of a water-soluble polymer, this mixture was made into a droplet form from an orifice and dropped into boric acid or borax aqueous solution, and immediately Fe (OH) 3 colloid was formed. An encapsulating PVA gel with a diameter of a few mm is formed. This state is shown in Figure 1.
It was shown to. In FIG. 1, polyvinyl alcohol gel 1
2 shows a state in which Fe (OH) 3 colloidal particles 2 having a large phosphate ion (PO 4 3− ion) adsorption action are included in the spherical particles.
【０００９】このゲルをホウ酸水溶液から取り出せば、
本発明の目的とする新規脱リン材が得られる。オリフィ
スから滴下された液滴とホウ酸水溶液との接触時間は重
要ファクターであり、１〜２時間程度が好適である。接
触時間が長すぎると図１の粒子の内部全体がゲル化して
しまい、リン酸イオンの拡散速度が小さくなるので、あ
まり好ましくない。図１のように粒子表面の０．２〜
０．３ｍｍ程度の厚みの部分のみをゲル化させるのが良
い。If this gel is taken out of the aqueous boric acid solution,
The novel dephosphorization material aimed at by the present invention can be obtained. The contact time between the droplets dropped from the orifice and the boric acid aqueous solution is an important factor, and about 1 to 2 hours is preferable. If the contact time is too long, the entire interior of the particles of FIG. 1 will gel, and the diffusion rate of phosphate ions will decrease, which is not preferable. As shown in FIG.
It is preferable to gel only the portion having a thickness of about 0.3 mm.
【００１０】また、水溶性高分子としては、ＰＶＡ以外
に微生物の固定化材として知られているものの内アルギ
ン酸ソーダ、ポリエチレングリコール、カラギナン、キ
トサンなどが使える。しかし、ポリアクリルアミド、メ
ラミン、スルホン酸樹脂、ポリウレタンはゲル内の分子
拡散性が悪いので好ましくない。ＰＶＡ、アルギン酸ソ
ーダ、ポリエチレングリコールが最も拡散性が良く、強
度も問題のないゲルを形成できるので、本発明にとって
好適である。また、ゲル化手段としては、紫外線の照
射、多価金属塩の添加、架橋剤の添加、凍結など各種の
方法を採用できる。As the water-soluble polymer, sodium alginate, polyethylene glycol, carrageenan, chitosan, etc., which are known as immobilizing agents for microorganisms, can be used in addition to PVA. However, polyacrylamide, melamine, sulfonic acid resin, and polyurethane are not preferable because they have poor molecular diffusivity in the gel. PVA, sodium alginate, and polyethylene glycol are suitable for the present invention because they have the best diffusibility and can form a gel with no problem in strength. As the gelling means, various methods such as irradiation with ultraviolet rays, addition of polyvalent metal salt, addition of crosslinking agent, and freezing can be adopted.
【００１１】なお、水酸化鉄以外の前記各種リン吸着作
用をもつ物質も、全く同様に粒状化できる。例えば鹿沼
土の場合は、市販の園芸用鹿沼土を水中に分散懸濁させ
て、沈降速度の速い不純物を除去したものとＰＶＡ溶液
とを混合し、前記の方法と同様にホウ酸水溶液に滴下し
て、目的物を得ることができる。このような方法によれ
製造された本発明の脱リン材によって、各種のリン含有
水からリンを除去するには、本発明の脱リン材をリン含
有水と所要時間接触させればよく、通常リン濃度（μｇ
／リットル）として１０μｇ／リットルオーダーの低濃
度の処理水を得ることができる。It should be noted that substances other than iron hydroxide having the above-mentioned various phosphorus adsorption functions can be granulated in the same manner. For example, in the case of Kanuma soil, a commercially available Kanuma soil for gardening is dispersed and suspended in water, impurities having a high sedimentation rate are removed and mixed with a PVA solution, and the solution is dripped into a boric acid aqueous solution as in the above method. Then, the target product can be obtained. With the dephosphorization material of the present invention produced by such a method, phosphorus can be removed from various phosphorus-containing water by contacting the dephosphorization material of the present invention with phosphorus-containing water for a required time, Phosphorus concentration (μg
/ Liter), it is possible to obtain low-concentration treated water of the order of 10 μg / liter.
【００１２】接触方法としては、本脱リン材を処理槽な
いしカラム内に装填し、流動状態又は固定層状態で、リ
ン含有水と接触指せるのが好適である。本脱リン材の比
重は、１．０５〜１．３程度のオーダーであり、水の比
重に近いので、エアレーションによる空気泡の上昇運動
に乗って容易に流動化でき、ＳＳの多い原水（大雨の時
の河川水など）に対しても、層の目詰まりを生じること
なく、適用できる。本発明のリン吸着剤は、粒状物であ
っても、リン酸イオン（ＰＯ4 3- イオン）が粒子の内部
にまで容易に拡散できるので、粒状物全体をリン吸着に
有効に利用できるという重要な特性がある。As a contact method, it is preferable that the present dephosphorization material is loaded into a treatment tank or column and brought into contact with phosphorus-containing water in a fluidized state or a fixed bed state. The specific gravity of this dephosphorization material is on the order of 1.05 to 1.3, which is close to the specific gravity of water, so it can be easily fluidized by the rising motion of air bubbles due to aeration, and raw water with a lot of SS (heavy rain) It can also be applied to river water, etc.) without causing layer clogging. Even if the phosphorus adsorbent of the present invention is a granular material, since phosphate ions (PO 4 3- ions) can easily diffuse into the inside of the particle, it is important that the entire granular material can be effectively used for phosphorus adsorption. There are various characteristics.
【００１３】これに対して従来の代表的リン吸着剤とし
て著名な活性アルミナ粒状物の場合は、その表面しかリ
ン吸着に利用できない。また、本発明の脱リン材粒子の
組成は大部分（８５〜９０％程度）が水であるので、乾
燥させるとその容量が著しく減少するため、処分が容易
であり、そのまま乾燥させずに森林、畑地に散布すれ
ば、保水材とリン肥料を兼ねた物質として有効に働く。On the other hand, in the case of activated alumina granules, which are well-known as the conventional typical phosphorus adsorbent, only the surface thereof can be used for phosphorus adsorption. In addition, the composition of the dephosphorizing material particles of the present invention is mostly water (about 85 to 90%), and the volume thereof is remarkably reduced when dried, so that it is easy to dispose, and the forest is not dried as it is. If it is sprayed on the field, it works effectively as a water retaining material and a phosphorus fertilizer.
【００１４】[0014]
（実施例１） １．リン吸着剤の製造 ５％ＦｅＣｌ3 水溶液１リットルを攪拌しながら、１０
％ＮａＯＨを添加し、ｐＨ４．０に調整して、Ｆｅ（Ｏ
Ｈ）3 のコロイドサスペンジョンを得た。このＦｅ（Ｏ
Ｈ）3 サスペンジョン１リットルに、１０％濃度のＰＶ
Ａ溶液１リットルを加え、よく混合した後、直径３ｍｍ
のオリフィスから液滴を２０％濃度のホウ酸水溶液内に
落下させ、１時間接触させたところ、表面がゲル化し、
図１に示すような粒状ゲル（粒径４．５ｍｍ、比重１．
０６）を得た。(Example 1) 1. Production of phosphorus adsorbent While stirring 1 liter of 5% FeCl 3 aqueous solution, 10
% NaOH was added to adjust the pH to 4.0, and Fe (O
H) 3 colloidal suspension was obtained. This Fe (O
H) PV of 10% concentration for 1 liter of 3 suspensions
After adding 1 liter of solution A and mixing well, diameter 3 mm
When a droplet was dropped into the boric acid aqueous solution of 20% concentration from the orifice of and contacted for 1 hour, the surface gelled,
Granular gel as shown in FIG. 1 (particle size 4.5 mm, specific gravity 1.
06) was obtained.
【００１５】２．リン酸イオン除去処理試験 上記吸着剤を直径３ｃｍのアクリルカラムに高さ３０ｃ
ｍに充填し、リン原子として１．５ｍｇ／リットルのリ
ン酸イオンを含む下水の活性汚泥処理水を上向流で、Ｓ
Ｖ５で通水したところ、処理水のリン酸イオン（ＰＯ4
3- イオン）濃度はリン原子として０．０２〜０．０３
ｍｇ／リットルと極めて効果的に除去されていた。この
処理水濃度は通水開始後６ヶ月間維持された。また、処
理水のリン酸イオンがリン原子として０．５ｍｇ／リッ
トルに達した時点でのリン吸着量は、カラム内のゲルの
中のＦｅ（ＯＨ）3 １ｋｇあたりリン原子として３５．
８ｍｇ／リットルと大きな値であった。2. Phosphate ion removal treatment test The adsorbent was placed on an acrylic column with a diameter of 3 cm to a height of 30 c.
m in an upward flow of activated sludge treated water containing sewage containing 1.5 mg / liter of phosphate ions as phosphorus atoms.
When water was passed at V5, phosphate ions (PO 4
(3- ion) concentration is 0.02-0.03 as phosphorus atom
It was extremely effectively removed with mg / l. This treated water concentration was maintained for 6 months after the start of water flow. Further, the amount of phosphorus adsorbed when the phosphate ion of the treated water reached 0.5 mg / liter as the phosphorus atom was 35.50 as the phosphorus atom per 1 kg of Fe (OH) 3 in the gel in the column.
It was a large value of 8 mg / liter.
【００１６】[0016]
【発明の効果】本発明のリン除去剤は次の効果がある。 従来、リン吸着性能を劣化させずに粒状化することが
難しかった水酸化鉄、酸化鉄、鹿沼土、アロフェンなど
を容易に、しかもリン吸着能力を劣化させずに強度の大
きな粒状物に成形できる。 粒状物の内部をも、リン吸着に有効利用できる。 比重が水に近く、容易に流動化できるので、ＳＳの多
い原水にも問題なく適用できる。 廃吸着剤の有効利用（保水剤及び肥料）が可能であ
る。The phosphorus removing agent of the present invention has the following effects. Conventionally, iron hydroxide, iron oxide, Kanuma soil, allophane, etc., which had been difficult to granulate without degrading phosphorus adsorption performance, can be easily formed into granular materials with high strength without degrading phosphorus adsorption ability. . The inside of the granular material can also be effectively used for phosphorus adsorption. Since it has a specific gravity close to that of water and can be easily fluidized, it can be applied to raw water with a lot of SS without any problems. Effective use of waste adsorbent (water retention agent and fertilizer) is possible.
【図１】本発明の脱リン材の１例の断面説明図FIG. 1 is an explanatory cross-sectional view of an example of a dephosphorization material of the present invention.
１ ポリビニルアルコールゲル ２ Ｆｅ（ＯＨ）3 コロイド粒子1 polyvinyl alcohol gel 2 Fe (OH) 3 colloidal particles
Claims (3)
性高分子ゲル内に包括固定化してなるリン除去材。1. A phosphorus removing material obtained by entrapping and immobilizing a substance having a phosphate ion-adsorbing action in a water-soluble polymer gel.
くとも一種類を水溶性高分子と混合した後、該水溶性高
分子をゲル化せしめ、ゲル内に前記リン酸イオン吸着作
用をもつ物質を包括固定化することを特徴とするリン除
去材の製造方法。2. A substance having a phosphate ion-adsorbing action is mixed with at least one kind of a substance having a phosphate ion-adsorbing action, and then the water-soluble polymer is gelated to obtain the substance having a phosphate ion-adsorbing action in the gel. A method for producing a phosphorus-removing material, characterized by comprehensively immobilizing.
性高分子ゲル内に包括固定化してなるリン除去材をリン
含有水と接触させることを特徴とするリン含有水の処理
方法。3. A method for treating phosphorus-containing water, which comprises bringing a phosphorus-removing material obtained by entrapping and immobilizing a substance having a phosphate ion-adsorbing action in a water-soluble polymer gel into phosphorus-containing water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2339293A JPH06210282A (en) | 1993-01-20 | 1993-01-20 | Phosphorus removing material, its manufacture and treatment of phosphorus containing water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2339293A JPH06210282A (en) | 1993-01-20 | 1993-01-20 | Phosphorus removing material, its manufacture and treatment of phosphorus containing water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06210282A true JPH06210282A (en) | 1994-08-02 |
Family
ID=12109242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2339293A Pending JPH06210282A (en) | 1993-01-20 | 1993-01-20 | Phosphorus removing material, its manufacture and treatment of phosphorus containing water |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06210282A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000048947A1 (en) * | 1999-02-19 | 2000-08-24 | Japan Science And Technology Corporation | Method of removing phosphoric acid contained in wastewater |
| JP2006175400A (en) * | 2004-12-24 | 2006-07-06 | Hitachi Housetec Co Ltd | Phosphate ion solidification agent, phosphate ion solidification apparatus, and septic tank equipped with it |
| JP2008207095A (en) * | 2007-02-26 | 2008-09-11 | Hiroshima Univ | Phosphorus collector unit and phosphorus collection and recovery method and apparatus using the unit |
| JP2016502459A (en) * | 2012-11-01 | 2016-01-28 | ハロソース， インコーポレイテッド | Water treatment composition and method of using the same |
| CN112090391A (en) * | 2020-08-31 | 2020-12-18 | 宜兴国际环保城科技发展有限公司 | Dephosphorization water purifying agent and preparation method thereof |
| JP2021066833A (en) * | 2019-10-25 | 2021-04-30 | 日本化学工業株式会社 | Conductive adhesive, and adhesive structure and electronic component using the same |
-
1993
- 1993-01-20 JP JP2339293A patent/JPH06210282A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000048947A1 (en) * | 1999-02-19 | 2000-08-24 | Japan Science And Technology Corporation | Method of removing phosphoric acid contained in wastewater |
| US6716357B1 (en) | 1999-02-19 | 2004-04-06 | Japan Science And Technology Corporation | Method of removing phosphoric acid containting wastewater |
| JP2006175400A (en) * | 2004-12-24 | 2006-07-06 | Hitachi Housetec Co Ltd | Phosphate ion solidification agent, phosphate ion solidification apparatus, and septic tank equipped with it |
| JP2008207095A (en) * | 2007-02-26 | 2008-09-11 | Hiroshima Univ | Phosphorus collector unit and phosphorus collection and recovery method and apparatus using the unit |
| JP2016502459A (en) * | 2012-11-01 | 2016-01-28 | ハロソース， インコーポレイテッド | Water treatment composition and method of using the same |
| JP2021066833A (en) * | 2019-10-25 | 2021-04-30 | 日本化学工業株式会社 | Conductive adhesive, and adhesive structure and electronic component using the same |
| CN112090391A (en) * | 2020-08-31 | 2020-12-18 | 宜兴国际环保城科技发展有限公司 | Dephosphorization water purifying agent and preparation method thereof |
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