JPH06277504A - Production of granular dephosphorizing material - Google Patents
Production of granular dephosphorizing materialInfo
- Publication number
- JPH06277504A JPH06277504A JP8780093A JP8780093A JPH06277504A JP H06277504 A JPH06277504 A JP H06277504A JP 8780093 A JP8780093 A JP 8780093A JP 8780093 A JP8780093 A JP 8780093A JP H06277504 A JPH06277504 A JP H06277504A
- Authority
- JP
- Japan
- Prior art keywords
- phosphorus
- water
- soln
- granular
- grains
- 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
- 239000000463 material Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000008187 granular material Substances 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000010419 fine particle Substances 0.000 claims description 6
- 239000003349 gelling agent Substances 0.000 claims description 4
- 229920003169 water-soluble polymer Polymers 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 39
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 37
- 239000011574 phosphorus Substances 0.000 abstract description 37
- 239000002245 particle Substances 0.000 abstract description 15
- 238000001179 sorption measurement Methods 0.000 abstract description 15
- 235000014413 iron hydroxide Nutrition 0.000 abstract description 10
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 9
- 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 abstract description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract description 6
- 235000010413 sodium alginate Nutrition 0.000 abstract description 6
- 239000000661 sodium alginate Substances 0.000 abstract description 6
- 229940005550 sodium alginate Drugs 0.000 abstract description 6
- 239000000243 solution Substances 0.000 abstract description 6
- 239000000725 suspension Substances 0.000 abstract description 6
- 239000001110 calcium chloride Substances 0.000 abstract description 5
- 229910001628 calcium chloride Inorganic materials 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 5
- 239000000084 colloidal system Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000010304 firing Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 3
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 abstract 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract 1
- -1 phosphoric acid ions Chemical class 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 108010082455 Sebelipase alfa Proteins 0.000 description 8
- 229940041615 kanuma Drugs 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000002689 soil Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 6
- 229910001583 allophane Inorganic materials 0.000 description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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 4
- 125000004437 phosphorous atom Chemical group 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 229940085991 phosphate ion Drugs 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010865 sewage Substances 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010410 calcium alginate Nutrition 0.000 description 1
- 239000000648 calcium alginate Substances 0.000 description 1
- 229960002681 calcium alginate Drugs 0.000 description 1
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 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
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000018109 developmental process Effects 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
- 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
- 239000002367 phosphate rock Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 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
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 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)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、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し、特に固定床形成に好
適な粒状リン除去材に関する。TECHNICAL FIELD The present invention effectively adsorbs and removes a trace amount of phosphate ions (also referred to as PO 4 3− ions) contained in water such as sewage, various wastewater, dam reservoirs, lakes and rivers. The present invention relates to a novel phosphorus removing material, particularly to a granular phosphorus removing material suitable for forming a fixed bed.
【０００２】[0002]
【従来の技術】従来から鹿沼土、アロフェン、水酸化ア
ルミニウム、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（約７０万円／ｍ3 ）、
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。2. Description of the Related Art Conventionally, substances such as Kanuma soil, allophane, aluminum hydroxide, activated alumina, iron hydroxide, etc. having a large phosphorus adsorption power have been known. However, phosphorus using these substances has the following reasons. The reality is that the removal technology has not been put to practical use. Activated alumina has a high cost (about 700,000 yen / m 3 ),
It is not suitable for water treatment that requires low running costs. 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.
【０００３】原料のコストが安いアロフェン、鹿沼
土、水酸化アルミニウム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。Allophane, Kanuma soil and aluminum hydroxide, which are low in raw material cost, are difficult to put into practical use unless they are granulated because they are powdery. However, when granulated into pellets with high strength using a binder such as cement, the phosphorus adsorption power is high. However, when the amount of the binder added is reduced, the strength of the granulated product becomes weaker and the granules disintegrate in water.
【０００４】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。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.
【０００５】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
化アルミニウム、水酸化鉄や酸化鉄の微粒子及び鉄粉な
どを、粒状体に造粒してもリン吸着力の低下がなく、強
度上の欠点も現れることがなく、かつ容易に粒状化でき
る製造技術。Therefore, it has been earnestly desired to develop the following techniques. That is, 1. Although it is a promising dephosphorization material due to its low cost of raw materials, Kanuma soil, allophane, aluminum hydroxide, iron hydroxide and iron oxide fine particles and iron powder, which have problems with the conventional granulation method, are made into granular materials. A manufacturing technology that does not reduce the phosphorus adsorption power even when granulated, does not cause defects in strength, and can be easily granulated.
【０００６】２．価格が安価でリン吸着性能の良い吸着
材の製造技術。 などである。2. An adsorbent manufacturing technology that is inexpensive and has good phosphorus adsorption performance. And so on.
【０００７】[0007]
【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、水酸化アルミニウム、水酸化
鉄や酸化鉄の微粒子及び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、コストが安く、
新規な高性能脱リン材（リン吸着材）を提供することに
ある。The present invention is capable of completely solving the above-mentioned drawbacks of the prior art, and satisfies Kanuma soil, allophane, aluminum hydroxide, iron hydroxide and iron oxide fine particles, and We have developed a granulation method that can easily granulate dephosphorization materials such as iron powder that is cheap
It is to provide a new high-performance dephosphorization material (phosphorus adsorbent).
【０００８】[0008]
【課題を解決するための手段】本発明の課題は以下の新
規なリン吸着材の開発によって解決される。すなわち、
本発明はリン酸イオンを吸着する物質の微粒子と、ゲル
化剤で速効的にゲル化し得る水溶性高分子との混合物
を、ゲル化剤水溶液中に滴下して、高含水率の粒状体を
形成させた後、該粒状体内の水分を減少させることによ
って容積を縮小させて成ることを特徴とする粒状脱リン
材の製造方法である。The object of the present invention is solved by the development of the following novel phosphorus adsorbent. That is,
The present invention is to add a mixture of fine particles of a substance that adsorbs phosphate ions and a water-soluble polymer that can be rapidly gelled by a gelling agent to an aqueous solution of the gelling agent to form granules having a high water content. The method for producing a granular dephosphorization material is characterized in that the volume is reduced by reducing the water content in the granular body after the formation.
【０００９】なお、この様にして得られた粒状脱リン材
は従来に類を見ない新規な脱リン材である。The granular dephosphorization material thus obtained is a novel dephosphorization material that has never been seen before.
【００１０】本発明のリン除去材は高含水率の粒状体を
形成させた後、乾燥など任意の手段のよって粒状体内の
水分を減少させることにより、強度の大きい粒状体が得
られ、かつ水分を減少させる処理を行うことにより粒状
体内部にミクロな空隙が形成されるので、極めてポーラ
スな粒状体粒子になる。これが本発明のリン除去材の特
徴である。The phosphorus-removing material of the present invention can form a granular material having a high water content, and then reduce the water content in the granular material by any means such as drying to obtain a granular material having a high strength. By performing a treatment for reducing the amount of particles, microscopic voids are formed inside the granules, resulting in extremely porous granule particles. This is a characteristic of the phosphorus removing material of the present invention.
【００１１】ここで水溶性高分子としては、アルギン酸
ソーダ、ポリビニルアルコール（ＰＶＡ）、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。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。As the water-soluble polymer, sodium alginate, polyvinyl alcohol (PVA), polyethylene glycol, carrageenan, chitosan and the like can be used. Phosphorus can be effectively removed from phosphorus-containing water by the treatment method of contacting the phosphorus-removing material of the present invention with phosphorus-containing water.
【００１２】以下に本発明の脱リン材の製造方法を詳し
く説明する。水酸化アルミニウム、酸化アルミニウム、
水酸化鉄、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新規な多
孔性の粒状脱リン材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 powder, Kanuma soil, allophane, titanium hydroxide,
Fine particles and powders of various substances having a large phosphorus adsorption action such as zirconium hydroxide, hydroxyapatite, magnesium oxide, bone charcoal, and phosphate rock can be used as a novel porous granular dephosphorization material according to the present invention.
【００１３】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アルギン酸ソーダ
溶液と混合したのち、この混合液をオリフィスから液滴
状にして塩化カルシウム水溶液中に滴下すると、Ｆｅ
（ＯＨ）3 コロイドを包含した粒径３〜５ｍｍの球状ゲ
ル粒状体が生成される。このゲル粒状体は強度は比較的
小さいが独立して相互に融合することはない。このゲル
粒状体を塩化カルシウム水溶液から取り出した後、任意
の乾燥又は焼成手段のよって粒状体内の水分を減少させ
て、粒状体粒子の粒径を１ｍｍ以下に縮小させれば、比
重及び強度の大きい本発明の脱リン材が得られる。この
脱リン材は水分が蒸発する際、ミクロな空隙が形成され
るので、極めてポーラスな粒状体粒子になることが認め
られた。以上の工程を図１に模式的に示した。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 solution of a water-soluble polymer of sodium alginate, the mixture was made into droplets from an orifice and dropped into an aqueous solution of calcium chloride.
Spherical gel granules with a particle size of 3-5 mm containing (OH) 3 colloids are produced. The gel granules have relatively low strength but do not fuse with each other independently. After taking out the gel granules from the calcium chloride aqueous solution, if the water content in the granules is reduced by any drying or firing means to reduce the particle diameter of the granule particles to 1 mm or less, the specific gravity and the strength are high. The dephosphorization material of the present invention is obtained. It was confirmed that this dephosphorization material becomes extremely porous granular particles because microscopic voids are formed when water evaporates. The above steps are schematically shown in FIG.
【００１４】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アルギン酸
ソーダ溶液とを混合し、前記の方法と同様に塩化カルシ
ウム水溶液中に滴下した後乾燥すれば、目的物を得るこ
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, commercially available Kanuma soil for gardening is dispersed and suspended in water, impurities with a high sedimentation rate are removed and mixed with a sodium alginate solution, and the solution is added in an aqueous calcium chloride solution in the same manner as the above method. The desired product can be obtained by dropping it on and then drying.
【００１５】本発明の脱リン材粒子は水中に長時間浸漬
しても全く崩壊しない。The dephosphorizing material particles of the present invention do not disintegrate at all even when immersed in water for a long time.
【００１６】このような本発明の方法により製造された
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
せれば良い。脱リン処理の結果、通常リン濃度として１
０μｇ／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。接触方法としては、本発明の脱リン材粒子は
乾燥などの後処理により容積を縮小したことにより比重
が高く、流動し難い構成であるため、脱リン材を処理槽
乃至カラム内に装填し、固定層状態乃至移動床状態とし
てＳＶ５〜１０（１／ｈｒ）程度でリン含有水と接触さ
せるのが好適である。In order to remove phosphorus from various phosphorus-containing water by the dephosphorization material produced by the method of the present invention, the dephosphorization material of the present invention may be contacted with the phosphorus-containing water for a required time. As a result of the dephosphorization treatment, the normal phosphorus concentration is 1
It is possible to obtain low-concentration treated water of the order of 0 μg / liter. As the contacting method, the dephosphorizing material particles of the present invention have a high specific gravity due to a reduced volume due to a post-treatment such as drying, and are difficult to flow, so the dephosphorizing material is loaded into a treatment tank or a column, It is preferable to contact with phosphorus-containing water at a SV of about 5 to 10 (1 / hr) in a fixed bed state or a moving bed state.
【００１７】本発明の方法により製造さるリン吸着材
は、粒状物であって、かつ極めてポーラスなので、リン
酸イオン（ＰＯ4 3- イオン）が粒状体の内部にまで容易
に拡散でき、粒状体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。Since the phosphorus adsorbent produced by the method of the present invention is a granular material and is extremely porous, phosphate ions (PO 4 3- ions) can easily diffuse into the inside of the granular material, and There is an important property that the whole can be effectively used for phosphorus adsorption.
【００１８】[0018]
（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、４０
％ＮａＯＨを添加し、ｐＨ５．０に調整して、Ｆｅ（Ｏ
Ｈ）3 のコロイドサスペンジョンを得た。(Example 1) 1. Production of phosphorus adsorbent While stirring 1 liter of 5% FeCl 3 aqueous solution, 40%
% NaOH was added to adjust the pH to 5.0, and Fe (O
H) 3 colloidal suspension was obtained.
【００１９】このＦｅ（ＯＨ）3 サスペンジョン１リッ
トルに、２％濃度のアルギン酸ソーダ溶液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％濃度の塩化カルシウム水溶液内に滴下させた
ところ、瞬時に表面がゲル化し、図１の（Ａ）に示すよ
うな、強度が小さい粒状ゲル（粒径４．５ｍｍ、比重
１．０６）を得た。これを温度１００℃の乾燥器内で乾
燥させ、粒径０．８〜１．０ｍｍ程度の強度の大きな脱
リン材（Ｂ）を得た。To 1 liter of this Fe (OH) 3 suspension, 1 liter of a 2% concentration sodium alginate solution was added and mixed well, and then a droplet was dropped from a 3 mm diameter orifice into a 20% concentration calcium chloride aqueous solution. As a result, the surface instantly gelled, and a granular gel having a small strength (particle size 4.5 mm, specific gravity 1.06) was obtained as shown in FIG. This was dried in a dryer at a temperature of 100 ° C. to obtain a dephosphorizing material (B) having a particle size of 0.8 to 1.0 mm and high strength.
【００２０】２．リン酸イオン除去処理試験 上記脱リン材（Ｂ）を直径３ｃｍのアクリルカラムに高
さ３０ｃｍに充填し、リン原子として表した濃度が１．
５ｍｇ／リットルのリン酸イオンを含む下水の活性汚泥
処理水を下向流で、ＳＶ５（１／ｈｒ）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０．０１〜０．０２ｍｇ／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８ヶ月間維持された。また、処理水中に含まれるリン
酸イオンが、リン原子として表した濃度で０．５ｍｇ／
リットルに達した時点で、脱リン材（Ｂ）のリン吸着量
は、カラム内の脱リン材ゲルの中のＦｅ（ＯＨ）3 １ｋ
ｇあたりリン原子として４２．０ｍｇ／リットルと大き
な値であった。2. Phosphate ion removal treatment test The dephosphorizing material (B) was packed in an acrylic column having a diameter of 3 cm to a height of 30 cm, and the concentration expressed as phosphorus atoms was 1.
When the activated sludge treated water containing sewage containing 5 mg / liter of phosphate ions was passed down flow at SV5 (1 / hr), the concentration of phosphate ions (PO 4 3- ions) in the treated water was phosphorus atoms. As a result, 0.01 to 0.02 mg / liter was removed very effectively. This treated water concentration was maintained for 8 months after the start of water flow. In addition, the phosphate ion contained in the treated water is 0.5 mg / at the concentration expressed as a phosphorus atom.
At the time of reaching the liter, the phosphorus adsorption amount of the dephosphorization material (B) is determined by Fe (OH) 3 1k in the dephosphorization material gel in the column.
It was a large value of 42.0 mg / liter as a phosphorus atom per g.
【００２１】[0021]
【発明の効果】本発明の製造方法及びそれにより得られ
るリン除去材は次の効果がある。 従来、リン吸着性能を劣化させずに粒状化することが
難しかった水酸化アルミニウム、水酸化鉄、酸化鉄、鹿
沼土、アロフェンなどの微粒子のリン吸着材を容易に、
しかもリン吸着能力を劣化させずに、強度の大きな小粒
径の粒状物に成形できる。The manufacturing method of the present invention and the phosphorus removing material obtained thereby have the following effects. Conventionally, it was easy to granulate phosphorus adsorbents such as aluminum hydroxide, iron hydroxide, iron oxide, Kanuma soil, and allophane, which were difficult to granulate without degrading phosphorus adsorption performance.
Moreover, it is possible to form a granular material having a large strength and a small particle size without deteriorating the phosphorus adsorption capacity.
【００２２】製造される粒状リン除去材はポーラスな
ので、内部もリン吸着に有効利用できる。 製造される粒状リン除去材はリンの吸着能力が高く、
しかも脱リン材の製造コストが著しく安価である。（活
性アルミナの数分の１の製造コストである。）Since the granular phosphorus removing material produced is porous, the inside can be effectively utilized for phosphorus adsorption. The granular phosphorus removal material produced has a high phosphorus adsorption capacity,
Moreover, the manufacturing cost of the dephosphorization material is extremely low. (The production cost is a fraction of that of activated alumina.)
【図１】本発明の脱リン材の製造中の粒状ゲルの状態変
化を示す説明図FIG. 1 is an explanatory view showing a state change of a granular gel during production of a dephosphorization material of the present invention.
１ 水酸化鉄微粒子を含むアルギン酸ソーダ溶液の液滴 ２ アルギン酸カルシウムゲル（固形分５％程度） ３ 脱水ゲル脱リン材（粒径小、多孔性） 1 Droplets of sodium alginate solution containing iron hydroxide fine particles 2 Calcium alginate gel (solid content of about 5%) 3 Dehydrated gel dephosphorization material (small particle size, porosity)
Claims (1)
と、ゲル化剤で速効的にゲル化し得る水溶性高分子との
混合物を、ゲル化剤水溶液中に滴下して、高含水率の粒
状体を形成させた後、該粒状体内の水分を減少させるこ
とによって容積を縮小させて成ることを特徴とする粒状
脱リン材の製造方法。1. A mixture of fine particles of a substance that adsorbs phosphate ions and a water-soluble polymer that can be rapidly gelled by a gelling agent is dropped into an aqueous solution of the gelling agent to obtain a granular material having a high water content. A method for producing a granular dephosphorization material, comprising forming a body and then reducing the volume by reducing the water content in the granular body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8780093A JPH06277504A (en) | 1993-03-24 | 1993-03-24 | Production of granular dephosphorizing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8780093A JPH06277504A (en) | 1993-03-24 | 1993-03-24 | Production of granular dephosphorizing material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06277504A true JPH06277504A (en) | 1994-10-04 |
Family
ID=13925062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8780093A Pending JPH06277504A (en) | 1993-03-24 | 1993-03-24 | Production of granular dephosphorizing material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06277504A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003053565A1 (en) * | 2001-12-21 | 2003-07-03 | Muromachi Chemical Co., Ltd. | Adsorbent for phosphoric acid |
| JP2006160842A (en) * | 2004-12-06 | 2006-06-22 | Toppan Printing Co Ltd | Polyuronic acid molded article and method for producing the same |
| JP2007001835A (en) * | 2005-06-27 | 2007-01-11 | National Institute Of Advanced Industrial & Technology | Phosphorus adsorbent |
| US7267776B2 (en) | 2004-05-05 | 2007-09-11 | Lanxess Deutschland Gmbh | Foams for removing pollutants and/or heavy metals from flowable media |
| EP2733119A1 (en) * | 2012-11-20 | 2014-05-21 | Zachodniopomorski Uniwersytet Technologiczny w Szczecinie | Agent for removing dissolved phosphorus compounds from water |
-
1993
- 1993-03-24 JP JP8780093A patent/JPH06277504A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003053565A1 (en) * | 2001-12-21 | 2003-07-03 | Muromachi Chemical Co., Ltd. | Adsorbent for phosphoric acid |
| US7267776B2 (en) | 2004-05-05 | 2007-09-11 | Lanxess Deutschland Gmbh | Foams for removing pollutants and/or heavy metals from flowable media |
| JP2006160842A (en) * | 2004-12-06 | 2006-06-22 | Toppan Printing Co Ltd | Polyuronic acid molded article and method for producing the same |
| JP2007001835A (en) * | 2005-06-27 | 2007-01-11 | National Institute Of Advanced Industrial & Technology | Phosphorus adsorbent |
| JP4576560B2 (en) * | 2005-06-27 | 2010-11-10 | 独立行政法人産業技術総合研究所 | Phosphorous adsorbent |
| EP2733119A1 (en) * | 2012-11-20 | 2014-05-21 | Zachodniopomorski Uniwersytet Technologiczny w Szczecinie | Agent for removing dissolved phosphorus compounds from water |
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