JP3247584B2 - Method for producing phosphorus adsorbent and method for removing phosphorus - Google Patents
Method for producing phosphorus adsorbent and method for removing phosphorusInfo
- Publication number
- JP3247584B2 JP3247584B2 JP18503695A JP18503695A JP3247584B2 JP 3247584 B2 JP3247584 B2 JP 3247584B2 JP 18503695 A JP18503695 A JP 18503695A JP 18503695 A JP18503695 A JP 18503695A JP 3247584 B2 JP3247584 B2 JP 3247584B2
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- JP
- Japan
- Prior art keywords
- phosphorus
- water
- granular
- adsorbent
- superabsorbent polymer
- 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 - Fee Related
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、河川、湖水、下水、一
般家庭からの排水や産業廃水等からリンを効果的に除去
することが可能な、新規リン吸着剤及びそれを用いたリ
ンの除去方法に関する。特に本発明は、河川や湖水等の
自然環境水域からリンを除去する技術に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phosphorus adsorbent capable of effectively removing phosphorus from rivers, lakes, sewage, wastewater from general households, industrial wastewater and the like, and a phosphorus adsorbent using the same. It relates to the removal method. In particular, the present invention relates to a technology for removing phosphorus from natural environmental waters such as rivers and lakes.
【０００２】[0002]
【従来技術】河川及び河川が流入する湖沼、ダム湖、海
等の富栄養化を防止するために、河川水中に含まれるリ
ンを除去する試みが近年始められている。従来の河川水
中のリン除去方法は、凝集沈殿装置を陸上に設置し、河
川水をポンプアップし硫酸アルミニウムなどの凝集剤を
添加してリンを凝集させた後、生成フロックを沈殿分離
する方法が知られている。しかし、この方法は化学プラ
ント的な凝集沈殿装置、ポンプ、配管、大きなポンプ動
力等が必要であり設備費、動力費が高価であるほか、装
置を設置する広いスペースが陸上に必要であるという欠
点があった。また観光地の河川からリン除去を行なおう
とする場合、このような装置を設置すると自然の景観を
損なうという欠点があった。また凝集沈殿処理にともな
って発生する難脱水性汚泥の処理処分が必要であるとい
う欠点もあった。2. Description of the Related Art In recent years, attempts have been made to remove phosphorus contained in river water in order to prevent eutrophication of rivers, lakes and marshes into which rivers flow, dam lakes, and the sea. The conventional method of removing phosphorus from river water is to install a coagulation and sedimentation device on land, pump up the river water, add a coagulant such as aluminum sulfate, coagulate phosphorus, and then sediment and separate the generated floc. Are known. However, this method requires coagulation and sedimentation equipment like a chemical plant, pumps, piping, large pump power, etc., which is expensive in equipment and power costs, and requires a large space for installing the equipment on land. was there. When phosphorus is to be removed from a river at a tourist spot, the installation of such a device has a disadvantage that the natural scenery is impaired. There is also a drawback that it is necessary to treat and dispose of the hardly dewaterable sludge generated by the coagulation and sedimentation treatment.
【０００３】他の方法として、活性アルミナ、鹿沼土や
アロフェン等を粒径数センチメートルの粒状に焼成し、
成型した粒状リン吸着剤を用いて河川水中のリンを除去
しようとの試みも行われている。しかしこれらの粒状リ
ン吸着剤には、以下のような欠点があり、さらに理想的
な粒状リン吸着剤の開発が望まれている。すなわち、 活性アルミナは、それ自体高価な活性アルミナ粉末を
粒状に焼成し、成型するために価格がさらに高くなり、
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。 リン吸着量が飽和に達した時、活性アルミナは、その
再生が煩雑で処理コストが高価につく。 河川に充填する場合に、濁質による閉塞を防ぐため、
活性アルミナ、鹿沼土はいずれも粒径数センチメートル
の大粒径にする必要があるが、こうすると粒状物が多孔
性でないため燐酸イオンの粒内拡散が悪く、粒状物の内
部がリン吸着に利用できない。 鹿沼土の造粒物はリン吸着容量が少なく、短期間にリ
ン吸着力を失う。 鹿沼土の造粒焼成は工程的にも生産的にも効率が悪
く、造粒焼成コストがかなり高価である。 活性アルミナ及び鹿沼土の造粒物は極めて固く、使用
後の廃物を林地に散布して肥料化する場合の適性が良く
ない。 等である。[0003] As another method, activated alumina, Kanuma soil, allophane, etc. are calcined into granules having a particle size of several centimeters,
Attempts have also been made to remove phosphorus from river water using a molded particulate phosphorus adsorbent. However, these particulate phosphorus adsorbents have the following disadvantages, and further development of an ideal particulate phosphorus adsorbent is desired. In other words, activated alumina itself is expensive because activated alumina powder, which itself is expensive, is fired into granules and molded.
It is not suitable for water treatment that requires low running cost. When the amount of adsorbed phosphorus reaches saturation, the activated alumina is complicated to regenerate and the processing cost is high. When filling rivers, to prevent clogging due to turbidity,
Both activated alumina and Kanuma soil must have a large particle size of several centimeters, but in this case, since the granular material is not porous, intragranular diffusion of phosphate ions is poor, and the inside of the granular material absorbs phosphorus. Not available. Granules of Kanuma soil have low phosphorus adsorption capacity and lose phosphorus adsorption power in a short time. Granulation and firing of Kanuma soil is inefficient in terms of process and production, and the cost of granulating and firing is considerably high. Activated alumina and granules of Kanuma soil are extremely hard, and their suitability for dispersing waste materials after use to forest land to produce fertilizer is not good. And so on.
【０００４】[0004]
【発明が解決しようとする課題】前記従来の粒状リン吸
着剤の有する欠点を解消し、 (i)（水酸化鉄や水酸化アルミニウムを用いて）多孔性
の粒状リン吸着剤とすること。 (ii)粒状リン吸着剤の製造において、焼成工程が不要
で、工程が短いこと。 (iii) 大型の粒状物としても内部まで吸着に利用でき、
リン吸着能力が大きいこと。 (iv)使用後の廃物の有効利用ができること。 等の長所を有し、かつ安価な粒状リン吸着剤を開発する
ことが望まれている。本発明は、前記のような特徴（長
所）を有する理想的な粒状リン吸着剤を提供し、それを
用いた優れたリン除去方法をを提供することにある。The disadvantages of the prior art granular phosphorus adsorbents are solved and (i) a porous granular phosphorus adsorbent (using iron hydroxide or aluminum hydroxide). (ii) In the production of the particulate phosphorus adsorbent, a calcination step is unnecessary and the step is short. (iii) It can be used as a large granular material for internal adsorption,
High phosphorus adsorption capacity. (iv) The waste can be effectively used after use. It is desired to develop an inexpensive particulate phosphorus adsorbent having the above advantages. An object of the present invention is to provide an ideal particulate phosphorus adsorbent having the above-mentioned features (advantages), and to provide an excellent phosphorus removal method using the same.
【０００５】[0005]
【課題を解決するための手段】本発明の前記課題は、下
記の本発明のリン吸着剤の製造方法及びリンの除去方法
によって達成される。すなわち、 （１）鉄塩又はアルミニウム塩水溶液を中和して得たス
ラリ状の水酸化鉄又は水酸化アルミニウムからなるリン
吸着性微粒子と高吸水性高分子粉末を混合し、その混合
物を水の存在下で混練・造粒することを特徴とする粒状
リン吸着剤の製造方法。 （２）前記混合物にセメントを添加し、水の存在下で混
練・造粒することを特徴とする前記（１）記載の粒状リ
ン吸着剤の製造方法。 （３）前記（１）又は（２）の粒状リン吸着剤の製造方
法により製造した粒状リン吸着剤を用いて、リン含有水
からリンを除去することを特徴とするリンの除去方法。 （４）前記（１）又は（２）の粒状リン吸着剤の製造方
法により製造した粒状リン吸着剤を透水性容器に充填
し、該容器をリン含有水に浸漬してリン含有水からリン
を除去することを特徴とする請求項３記載のリンの除去
方法。である。The object of the present invention is achieved by the following method for producing a phosphorus adsorbent and method for removing phosphorus according to the present invention. That is, (1) A solution obtained by neutralizing an aqueous solution of an iron salt or an aluminum salt.
The method is characterized by mixing phosphorus-adsorbing fine particles made of larytic iron hydroxide or aluminum hydroxide and superabsorbent polymer powder, and kneading and granulating the mixture in the presence of water. A method for producing a granular phosphorus adsorbent. (2) The method for producing a particulate phosphorus adsorbent according to (1), wherein cement is added to the mixture, and the mixture is kneaded and granulated in the presence of water. (3) Method for producing the particulate phosphorus adsorbent according to (1) or (2 ) above
Water containing phosphorus using a granular phosphorus adsorbent
A method for removing phosphorus, comprising: removing phosphorus from a mixture. (4) Method for producing the particulate phosphorus adsorbent according to (1) or (2 ) above
Of a granular phosphorus adsorbent manufactured by the method into a water-permeable container
The container is immersed in phosphorus-containing water to remove phosphorus from the phosphorus-containing water.
4. The removal of phosphorus according to claim 3, wherein phosphorus is removed.
Method. It is.
【０００６】リン吸着性微粒子としては、水酸化鉄、水
酸化アルミニウムが用いられる。本発明者の実験によれ
ば、リン吸着性の良い水酸化鉄、水酸化アルミスラリ
は、ポリ鉄（ポリ硫酸第２鉄）、塩化第２鉄、硫酸バン
ド、ＰＡＣ等の鉄塩、アルミニウム塩水溶液をアルカリ
でｐＨ５〜８に中和すれば良いことが判明した。アルカ
リとしては、水酸化マグネシウム、消石灰、水酸化ナト
リウムが採用できる。[0006] Phosphorus-adsorbing fine particles include iron hydroxide and water.
Aluminum oxide is used. According to the experiments of the present inventors, iron hydroxide and aluminum hydroxide slurry having good phosphorus adsorption properties include polyiron (ferric polysulfate), ferric chloride, sulfate salts, iron salts such as PAC, and aluminum salts. It turned out that the aqueous solution should be neutralized to pH 5 to 8 with alkali. As the alkali, magnesium hydroxide, slaked lime and sodium hydroxide can be employed.
【０００７】上記リン吸着性微粒子と高吸水性高分子粉
末を混合し、水を加えて混練すると、水を吸収して膨潤
した高吸水性高分子粉末が糊のような粘着力を帯び、バ
インダーとなって水酸化鉄、水酸化アルミ微粒子を効果
的に団粒化する。リン吸着性微粒子と高吸水性高分子の
構成の重量比が５：９５〜９０：１０の範囲にあると団
粒化したものは多孔性であり、成形されたリン吸着剤と
した時その内部までリンを含んだ水が侵入できるので、
優れたリン吸着剤となる。本発明の粒状リン吸着剤中の
リン吸着性微粒子と高吸水性高分子の重量の比が５：９
５より低い場合には該粒状体の強度が劣り、かつリン吸
着性微粒子が少ないのでリン吸着の効率が悪い。また、
リン吸着性微粒子と高吸水性高分子の重量の比が９０：
１０より大きい場合には該粒状体の多孔性ならびに粒子
の強度が劣る。[0007] When the above-mentioned phosphorus-adsorbing fine particles and the superabsorbent polymer powder are mixed, and water is added and kneaded, the swollen superabsorbent polymer powder which has absorbed water and has adhesive strength like a glue is obtained. As a result, iron hydroxide and aluminum hydroxide particles are effectively aggregated. When the weight ratio of the composition of the phosphorus-adsorbing fine particles to the superabsorbent polymer is in the range of 5:95 to 90:10, the agglomerated material is porous, and when formed into a shaped phosphorus adsorbent, As water containing phosphorus can enter,
It is an excellent phosphorus adsorbent. The ratio by weight of the phosphorus-adsorbing fine particles to the superabsorbent polymer in the granular phosphorus adsorbent of the present invention is 5: 9.
If it is lower than 5, the strength of the granular material is inferior and the amount of phosphorus-adsorbing fine particles is small, so that the efficiency of phosphorus adsorption is poor. Also,
The weight ratio of the phosphorus-adsorbing fine particles to the superabsorbent polymer is 90:
If it is larger than 10, the porosity of the granular material and the strength of the particles are inferior.
【０００８】また、本発明者らの実施によれば常識的な
固化法としてリン吸着性微粒子、水、セメントを混練す
ると石のように固い非多孔性の造粒物が生成してしま
い、リン吸着性が著しく悪く、自然崩壊性も悪いものし
か形成されないが、これらに高吸水性高分子粉末を添加
して混練すると驚くべきことに造粒物が多孔性の粒状団
塊になり、しかも適当な強度をもつ弾性体が形成される
ことが見出された。その構造は菓子の「おこし」のよう
に無数の小粒（これ自身リン吸着性微粒子の小集団）
が、水を吸収した高吸水性高分子ゲルを媒介として集合
し、多孔性の粒状団塊を形成していた。図１にその多孔
性の粒状団塊の模式図を示す。Further, according to the practice of the present inventors, kneading phosphorus-adsorbing fine particles, water and cement as a common-sense solidification method produces hard non-porous granules such as stones. Although the adsorbability is extremely poor and only those with poor natural disintegration are formed, when the superabsorbent polymer powder is added to these and kneaded, surprisingly, the granulated material becomes a porous granular mass, It has been found that a strong elastic body is formed. Its structure is innumerable small grains, like the confectionery "Okoshi" (this is a small group of phosphorus-adsorbing fine particles by itself)
However, they aggregated through the superabsorbent polymer gel that absorbed water to form porous granular aggregates. FIG. 1 shows a schematic diagram of the porous granular nodule.
【０００９】本発明においては、粒状リン吸着剤の強度
を高め、かつ粒状体の多孔性を向上させるために、”リ
ン吸着性微粒子と高吸水性高分子粉末”の混合物にセメ
ントを両者が重量比で４０：６０〜８０：２０である範
囲に添加することが好ましい。本発明において、”リン
吸着性微粒子と高吸水性高分子粉末の混合物”とセメン
トとの重量比が４０：６０より”リン吸着性微粒子と高
吸水性高分子粉末の混合物”の量が少ないと該粒状体の
多孔性が劣り、かつリン吸着性微粒子が少ないのでリン
吸着の効率が悪い。また、”リン吸着性微粒子と高吸水
性高分子粉末の混合物”とセメントとの重量比が８０：
２０よりセメントの量が少ないと強度はやや劣る。In the present invention, in order to increase the strength of the granular phosphorus adsorbent and to improve the porosity of the granular body, cement is added to a mixture of “phosphorus-adsorbing fine particles and superabsorbent polymer powder ”, and both are mixed by weight. It is preferable to add in a range of 40:60 to 80:20 in a ratio. In the present invention, if the weight ratio of “the mixture of the phosphorus-adsorbing fine particles and the superabsorbent polymer powder ” to the cement is less than 40:60, the amount of the “mixture of the phosphorus-adsorbing fine particles and the superabsorbent polymer powder ” is small. Since the porosity of the granular material is poor and the amount of phosphorus-adsorbing fine particles is small, the efficiency of phosphorus adsorption is poor. Further, the weight ratio of the “mixture of the phosphorus-adsorbing fine particles and the superabsorbent polymer powder ” to the cement is 80:
If the amount of cement is less than 20, the strength is slightly inferior.
【００１０】なお、セメントは一種のアルカリ剤である
ため、前記の方法によって製造した粒状脱リン剤をリン
含有水に接触させると、脱リン剤から当初アルカリ成分
（ＣａＯ等）が溶出し脱リン処理水のｐＨが９以上に上
昇することがあり、河川、湖沼からリン除去を行う場合
に生態系に悪影響を与える恐れがある。このような問題
を防止するには、水酸化鉄スラリ、水酸化アルミスラリ
に酸を添加し、スラリのｐＨを酸性（ｐＨ３〜５程度）
にしておき、該酸性のスラリにセメントを添加し、セメ
ントのアルカリ分を酸性のスラリで中和するようにすれ
ば、中性のスラリセメント混合物に高吸水性高分子粉末
を添加・混合することになり、かくして作られた脱リン
剤からアルカリ成分が溶出することはなく解決される。[0010] Since cement is a kind of alkaline agent, when the particulate dephosphorizing agent produced by the above-mentioned method is brought into contact with phosphorus-containing water, an alkali component (CaO or the like) is initially eluted from the dephosphorizing agent and dephosphorized. The pH of the treated water may rise to 9 or more, which may adversely affect the ecosystem when removing phosphorus from rivers and lakes. To prevent such a problem, an acid is added to the iron hydroxide slurry and the aluminum hydroxide slurry to adjust the pH of the slurry to acidic (about pH 3 to 5).
If the cement is added to the acidic slurry and the alkali content of the cement is neutralized with the acidic slurry, the superabsorbent polymer powder is added to and mixed with the neutral slurry cement mixture. Thus, the alkaline component is not eluted from the dephosphorizing agent thus produced, and the problem is solved.
【００１１】本発明の粒状リン吸着剤中にはリン吸着性
微粒子と高吸水性高分子以外に無機性及び／あるいは有
機性の夾雑する粒子を含んでいても良い。このような夾
雑する粒子は粒状リン吸着剤の見掛けの比重を調節する
作用をすることもある。The particulate phosphorus adsorbent of the present invention may contain inorganic and / or organic contaminating particles in addition to the phosphorus-adsorbing fine particles and the superabsorbent polymer. Such contaminating particles may act to adjust the apparent specific gravity of the particulate phosphorus adsorbent.
【００１２】本発明に用いる高吸水性高分子としては、
紙おむつ等に多用されている種々の高吸水性高分子（ポ
リアクリル酸塩、澱粉−アクリル酸塩グラフトポリマ
ー、酢酸ビニル共重合体、ポリビニルアルコール系等）
を利用できるが、特に吸水量が大きいものが好ましい。
本発明において高吸水性高分子は、粉末として添加する
ことが便利であるが、要するに本発明のリン吸着剤中に
含まれる微粒子（下記リン吸着性微粒子スラリを構成し
ている微粒子やセメント粒子等）をバインダーとして連
結するのに好適に作用する状態のものであれば特に制限
されない。また、セメントとしては、ポルトランドセメ
ント、アルミナセメント等コンクリート製造用の一般的
なセメントを利用できるが、特にアルミナセメント等の
早強性セメント、超早強性セメントが好適である。The superabsorbent polymer used in the present invention includes:
Various super absorbent polymers (polyacrylate, starch-acrylate graft polymer, vinyl acetate copolymer, polyvinyl alcohol, etc.) frequently used in disposable diapers and the like
Can be used, but those having a large water absorption are particularly preferable.
In the present invention, the superabsorbent polymer is conveniently added as a powder. In short, the fine particles contained in the phosphorus adsorbent of the present invention (fine particles or cement particles constituting the following phosphorus-adsorbing fine particle slurry) ) Is not particularly limited as long as it is in a state where it can suitably act as a binder. As the cement, general cements for concrete production such as Portland cement and alumina cement can be used, and particularly, high-strength cements such as alumina cement and ultra-high-strength cements are suitable.
【００１３】本発明の粒状脱リン剤（リン吸着剤）の代
表的製造例を図２に基づいて説明する。例えば、リン吸
着性が優れた水酸化第２鉄スラリ、または水酸化アルミ
スラリ（水分９０％程度）にセメントを添加し混合した
後、高吸水性高分子粉末を添加すると高吸水性高分子が
水酸化鉄、水酸化アルミスラリの水分を速やかに吸収
し、高吸水性高分子粒子が膨潤する。これを数分間混練
すると水を吸って膨潤した高分子が糊のような粘着力を
帯び、バインダーとなって水酸化鉄、水酸化アルミ微粒
子が効果的に団粒化する。これを適当な粒径、形状に整
形（例えば押し出し造粒法）すれば、多孔性の粒状脱リ
ン剤ができる。これを数時間以上大気中に放置すれば高
吸水性高分子粒子ゲルの硬化現象によって強度が増加
し、水中に漬けても崩壊しない脱リン剤が製造される。
従来必要であった乾燥工程、焼成工程を設けることなく
極めて簡単な工程で、短時間で多孔性の弾性のある粒状
脱リン剤が製造できる。なお、さらに強度を高めたい場
合は、高吸水性高分子とセメントを併用すれば良い。A typical production example of the granular dephosphorizing agent (phosphorus adsorbent) of the present invention will be described with reference to FIG. For example, after adding and mixing cement with ferric hydroxide slurry or aluminum hydroxide slurry (about 90% moisture) having excellent phosphorus adsorption properties, superabsorbent polymer powder is added when superabsorbent polymer powder is added. Quickly absorbs the water content of iron hydroxide and aluminum hydroxide slurry, and the superabsorbent polymer particles swell. When the mixture is kneaded for several minutes, the polymer swollen by absorbing water has an adhesive strength like a glue, and iron hydroxide and aluminum hydroxide fine particles are effectively aggregated as a binder. By shaping this into an appropriate particle size and shape (eg, extrusion granulation), a porous granular dephosphorizing agent can be obtained. If this is left in the atmosphere for several hours or more, the strength increases due to the curing phenomenon of the superabsorbent polymer particle gel, and a phosphorus removing agent that does not collapse even when immersed in water is produced.
A porous and elastic granular dephosphorizing agent can be produced in a short time in a very simple step without providing a drying step and a baking step which have been conventionally required. If it is desired to further increase the strength, a superabsorbent polymer and cement may be used in combination.
【００１４】本発明の粒状脱リン剤を用いてリン含有水
からリンを除去するには粒状脱リン剤をカラムに充填
し、リン含有水を適切な空間速度（ＳＶ）で通水すれば
良い。また、河川からリン除去を行うには粒状数センチ
に造粒した脱リン剤をネットからなる袋等透水性容器に
詰め、これを河川に水没させる方法が河川の濁質による
目詰まりが少なく、最も簡便なリン除去技術として推薦
できる。In order to remove phosphorus from phosphorus-containing water by using the granular phosphorus-removing agent of the present invention, the granular phosphorus-removing agent is packed in a column, and the phosphorus-containing water is passed at an appropriate space velocity (SV). . Also, in order to remove phosphorus from the river, the dephosphorizing agent granulated to several centimeters is packed in a permeable container such as a bag made of net, and the method of submerging this in the river is less clogging due to the turbidity of the river, It can be recommended as the simplest phosphorus removal technique.
【００１５】なお、本発明者の先願（特開平６−１５４
５９７号公報）である「金属水酸化物と高吸水性高分子
の複合粒状物」は、高吸水性高分子を利用するものであ
るが、高吸水性高分子の作用が本発明とは本質的に異な
るものである。すなわち、先願発明の技術は、「高吸水
性高分子よりなり、水中で膨潤して弾性を示すヒドロゲ
ル粒子の各々の内部に金属水酸化物を保持させるもの」
であるのに対し、本発明は、高吸水性高分子ゲル粒子の
外部にリン吸着性微粒子が存在する。また、先願発明の
技術は、ヒドロゲルは一つ一つ分散させた状態で、小粒
径のリン吸着剤として利用するものであり、大粒径の脱
リン剤は製造できない。すなわち、本発明者の先願の
「金属水酸化物と高吸水性高分子の複合粒状物」は、本
発明のような集合団粒の構造をとっていない。Incidentally, the inventor's prior application (Japanese Patent Laid-Open No. 6-154)
No. 597), “a composite particulate of a metal hydroxide and a superabsorbent polymer” utilizes a superabsorbent polymer, but the action of the superabsorbent polymer is essential to the present invention. Are different. In other words, the technology of the prior application invention is "a method of retaining a metal hydroxide inside each hydrogel particle which is made of a superabsorbent polymer and swells in water and exhibits elasticity."
On the other hand, in the present invention, the phosphorus-adsorbing fine particles exist outside the superabsorbent polymer gel particles. In the technique of the prior application, the hydrogel is used as a phosphorus adsorbent having a small particle diameter in a state of being dispersed one by one, and a dephosphorizing agent having a large particle diameter cannot be produced. In other words, the “composite particulates of metal hydroxide and superabsorbent polymer” filed by the inventor of the present invention do not have a structure of aggregated particles as in the present invention.
【００１６】[0016]
【実施例】以下に実施例により本発明を具体的に説明す
る。ただし、本発明はこの実施例のみに限定されるもの
ではない。The present invention will be specifically described below with reference to examples. However, the present invention is not limited to only this embodiment.
【００１７】実施例１ ポリ鉄原液を水道水で３倍に希釈し、これに水酸化マグ
ネシウムを添加しｐＨ６に中和してリン吸着性の良好な
水酸化第２鉄スラリを得た。このスラリ３００ｃｃに対
し、セメントを添加した後高吸水性高分子粉末７０ｇを
添加し、３分間混練したところ、容易に多孔性の団塊状
に集合した。これを粒径１０〜１２ｍｍに成型し、６時
間風乾したところ、強度が増加し、弾性のある適度な強
度（手で強く握ると壊すことができる。）の多孔性脱リ
ン剤が製造された。Example 1 A polyiron stock solution was diluted three times with tap water, and magnesium hydroxide was added to neutralize the solution to pH 6 to obtain a ferric hydroxide slurry having good phosphorus adsorption. After adding cement, 70 g of the superabsorbent polymer powder was added to 300 cc of this slurry, and the mixture was kneaded for 3 minutes. This was molded to a particle size of 10 to 12 mm, and air-dried for 6 hours. As a result, the strength was increased, and a porous dephosphorizing agent having an appropriate elasticity (can be broken when strongly grasped by hand) was produced. .
【００１８】実施例２ 実施例１において高吸水性高分子を添加する前にアルミ
ナセメントを３０ｇ添加した以外は、実施例１と同様に
行ったところ、さらに高強度の粒状脱リン剤が形成され
た。Example 2 The procedure of Example 1 was repeated, except that 30 g of alumina cement was added before the superabsorbent polymer was added. As a result, a high-strength granular dephosphorizing agent was formed. Was.
【００１９】実施例３ 液体硫酸バンド（液バン）原液を２倍に希釈したものに
水酸化ナトリウムを添加し、ｐＨ５に中和し、リン吸着
性の良い水酸化アルミスラリを得た。このスラリ３００
ｃｃに対しアルミセメント４０ｇ添加混合した後、高吸
水性高分子粉末６０ｇ添加し、２分間混練したところ同
様に容易に団塊化し、風乾後実施例１と同様の脱リン剤
が製造された。Example 3 Sodium hydroxide was added to a two-fold dilution of a liquid sulfuric acid band (liquid van) stock solution to neutralize it to a pH of 5, thereby obtaining an aluminum hydroxide slurry having good phosphorus adsorption. This slurry 300
After adding 40 g of aluminum cement to the cc and mixing, 60 g of the superabsorbent polymer powder was added and kneaded for 2 minutes. The mixture was easily agglomerated and air-dried to produce the same dephosphorizing agent as in Example 1.
【００２０】実施例４ 栃木県鹿沼市に産出する鹿沼土粉末１５０ｇにアルミナ
セメント４０ｇを混合し、さらにｐｈ４の水道水１００
ｃｃを添加した後、高吸水性高分子粉末１００ｇを添加
し、３分間混練したところ容易に多孔性の団塊になり、
風乾後、多孔性脱リン剤が製造できた。Example 4 150 g of Kanuma earth powder produced in Kanuma city, Tochigi prefecture was mixed with 40 g of alumina cement, and furthermore, 100 ph of tap water 100
After adding cc, 100 g of the superabsorbent polymer powder was added and kneaded for 3 minutes to easily form a porous nodule,
After air drying, a porous dephosphorizing agent could be produced.
【００２１】実施例５ 前記実施例１から３で製造した脱リン剤を用いてリン除
去カラム試験を行った。試験条件と試験結果を第１表に
示す。Example 5 A phosphorus removal column test was performed using the dephosphorizing agents prepared in Examples 1 to 3. Table 1 shows the test conditions and test results.
【００２２】[0022]
【表１】 [Table 1]
【００２３】第１表から、本発明のリン吸着剤は良好な
脱リン性能を示し、特に水酸化アルミスラリを素材とし
たものが好成績を示していることが認められる。なお、
原水のｐＨが７．２であるのに対して、処理水のｐＨは
いずれも７．４〜８．３の範囲にあり水質規制を満足し
た。From Table 1, it can be seen that the phosphorus adsorbent of the present invention shows good dephosphorization performance, and particularly, those made of aluminum hydroxide slurry show good results. In addition,
While the pH of the raw water was 7.2, the pH of the treated water was in the range of 7.4 to 8.3, satisfying the water quality regulations.
【００２４】[0024]
【発明の効果】本発明のリン吸着剤の製造方法によれ
ば、 （１）乾燥・焼成するこなく、極めて簡単に、かつ短時
間で多孔性で、適当な強度を有する粒状リン吸着剤を製
造することができる。従って、大量生産に適しており、
製造設備費、ランニングコストを共に従来より著しく削
減することができる。 （２）多孔性であるため、大粒径であっても、表面積が
大きくリンの吸着性能が優れている。 （３）強度が適当であり、崩壊性が優れているので、廃
吸着剤の森林への散布などの処分が容易である。According to the method for producing a phosphorus adsorbent of the present invention, (1) a porous phosphorus adsorbent having appropriate strength, which is extremely simple, can be porous in a short time, and is not dried and calcined. Can be manufactured. Therefore, it is suitable for mass production,
Both the manufacturing equipment cost and the running cost can be significantly reduced as compared with the related art. (2) Since it is porous, even if it has a large particle size, it has a large surface area and excellent phosphorus adsorption performance. (3) Since the strength is appropriate and the disintegration is excellent, it is easy to dispose of the waste adsorbent by spraying the forest.
【図１】本発明の団粒構造の粒状リン吸着剤の模式図を
示す。FIG. 1 is a schematic view of a granular phosphorus adsorbent having a granular structure according to the present invention.
【図２】本発明のリン吸着剤の製造工程を示すフロー説
明図である。FIG. 2 is a flowchart illustrating a process for producing the phosphorus adsorbent of the present invention.
１ 本発明の粒状リン吸着剤 ２ 多孔性の粒状団塊 ３ リン吸着性微粒子 DESCRIPTION OF SYMBOLS 1 The granular phosphorus adsorbent of this invention 2 Porous granular aggregate 3 Phosphorus-adsorbing fine particles
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平６−277504（ＪＰ，Ａ) 特開 平５−49857（ＪＰ，Ａ) 特開 平２−99185（ＪＰ，Ａ) 特開 昭62−183898（ＪＰ，Ａ) 特開 平６−71167（ＪＰ，Ａ) 特開 昭54−148186（ＪＰ，Ａ) 特開 平７−194971（ＪＰ，Ａ) 特開 平６−182358（ＪＰ，Ａ) 特開 平７−51564（ＪＰ，Ａ) 特開 平８−71545（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 20/26 C02F 1/28 ZAB ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-6-277504 (JP, A) JP-A-5-49857 (JP, A) JP-A-2-99185 (JP, A) 183898 (JP, A) JP-A-6-71167 (JP, A) JP-A-54-148186 (JP, A) JP-A-7-194971 (JP, A) JP-A-6-182358 (JP, A) JP-A-7-51564 (JP, A) JP-A-8-71545 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) B01J 20/26 C02F 1/28 ZAB
Claims (4)
て得たスラリ状の水酸化鉄又は水酸化アルミニウムから
なるリン吸着性微粒子と高吸水性高分子粉末を混合し、
その混合物を水の存在下で混練・造粒することを特徴と
する粒状リン吸着剤の製造方法。(1) neutralizing an aqueous solution of an iron salt or an aluminum salt;
From the slurry-like iron hydroxide or aluminum hydroxide obtained
The high water-absorbing polymer powder
A method for producing a granular phosphorus adsorbent, comprising kneading and granulating the mixture in the presence of water.
在下で混練・造粒することを特徴とする請求項１記載の
粒状リン吸着剤の製造方法。2. The method for producing a granular phosphorus adsorbent according to claim 1, wherein cement is added to the mixture, and the mixture is kneaded and granulated in the presence of water.
の製造方法により製造した粒状リン吸着剤を用いて、リ
ン含有水からリンを除去することを特徴とするリンの除
去方法。 3. The particulate phosphorus adsorbent according to claim 1 or 2.
Using the granular phosphorus adsorbent produced by the method of
Phosphorus removal from phosphorus-containing water
How to leave.
の製造方法により製造した粒状リン吸着剤を透水性容器
に充填し、該容器をリン含有水に浸漬してリン含有水か
らリンを除去することを特徴とする請求項３記載のリン
の除去方法。 4. The particulate phosphorus adsorbent according to claim 1 or 2.
Of a granular phosphorus adsorbent produced by the method for producing a water-permeable container
And immersing the container in phosphorus-containing water to remove the phosphorus-containing water.
4. The phosphorus according to claim 3, wherein phosphorus is removed.
Removal method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18503695A JP3247584B2 (en) | 1995-06-29 | 1995-06-29 | Method for producing phosphorus adsorbent and method for removing phosphorus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18503695A JP3247584B2 (en) | 1995-06-29 | 1995-06-29 | Method for producing phosphorus adsorbent and method for removing phosphorus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0910581A JPH0910581A (en) | 1997-01-14 |
| JP3247584B2 true JP3247584B2 (en) | 2002-01-15 |
Family
ID=16163673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18503695A Expired - Fee Related JP3247584B2 (en) | 1995-06-29 | 1995-06-29 | Method for producing phosphorus adsorbent and method for removing phosphorus |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3247584B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104069821A (en) * | 2014-07-09 | 2014-10-01 | 辽东学院 | Reactive dye wastewater adsorbing agent and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL2825583T3 (en) * | 2012-03-15 | 2017-07-31 | Huntsman P&A Uerdingen Gmbh | Method for granulating particle-containing material obtained from industrial processes, the granulate thus produced |
| EP3505239A1 (en) * | 2017-12-26 | 2019-07-03 | Vito NV | Sorbents from iron-rich and aluminium-rich starting materials |
-
1995
- 1995-06-29 JP JP18503695A patent/JP3247584B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104069821A (en) * | 2014-07-09 | 2014-10-01 | 辽东学院 | Reactive dye wastewater adsorbing agent and preparation method thereof |
| CN104069821B (en) * | 2014-07-09 | 2015-12-02 | 辽东学院 | A kind of Active dye waste water absorbent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0910581A (en) | 1997-01-14 |
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