JP4565836B2 - Phosphorus remover - Google Patents
Phosphorus remover Download PDFInfo
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- JP4565836B2 JP4565836B2 JP2003435065A JP2003435065A JP4565836B2 JP 4565836 B2 JP4565836 B2 JP 4565836B2 JP 2003435065 A JP2003435065 A JP 2003435065A JP 2003435065 A JP2003435065 A JP 2003435065A JP 4565836 B2 JP4565836 B2 JP 4565836B2
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Description
本発明は、リンの除去剤に関し、さらに詳しくはたとえばリンを含む水中のリンの除去剤に関する。 The present invention relates to a phosphorus remover, and more particularly to a phosphorus remover in water containing, for example, phosphorus.
従来、河川、湖、沼もしくは貯水池等の水、ならびに産業排水および生活排水等に含まれるリン酸もしくはその塩等のリン含有化合物(以下「リン」ということがある)は富栄養化の原因となるため、その効率的な除去が必要とされている。たとえば、消石灰を用いる凝集沈殿法が一般的であるが、多量の消石灰を用いるためにスラッジの精製が多くなり、さらに煩雑な後処理工程を必要とする難点がある。そこで、このような難点を解決するために種々の方法が提案されており、ケイ酸カルシウム水和物を脱リン材として用いる方法も提案されている(特許文献1)。この方法は、改良された脱リン方法を提供するが、ケイ酸カルシウム水和物の耐水性があまりよいとはいえないために、繰り返し使用するとケイ酸カルシウム水和物の崩壊を生じ、脱リン効果が低減してしまう傾向がある。 Conventionally, phosphorus-containing compounds (hereinafter sometimes referred to as “phosphorus”) such as phosphoric acid or its salts contained in water from rivers, lakes, swamps or reservoirs, as well as industrial wastewater and domestic wastewater, are the causes of eutrophication. Therefore, its efficient removal is required. For example, a coagulation sedimentation method using slaked lime is common, but since a large amount of slaked lime is used, purification of sludge increases, and there is a difficulty that requires a complicated post-treatment process. Therefore, various methods have been proposed to solve such difficulties, and a method using calcium silicate hydrate as a dephosphorizing material has also been proposed (Patent Document 1). Although this method provides an improved dephosphorization method, the water resistance of calcium silicate hydrate is not very good, so repeated use causes the calcium silicate hydrate to disintegrate and dephosphorization. The effect tends to decrease.
本発明は、結晶性がよく、ろ過抵抗の小さく、特定の天然物もしくは改質した天然物を用いたリン除去剤を提供するものである。 The present invention provides a phosphorus removal agent using a specific natural product or a modified natural product having good crystallinity and low filtration resistance.
本発明は、層間にカルシウムが導入されたバーミキュライトを有効成分とするリン除去剤、さらにはリンを含む水をこのリン除去剤と接触させてリンを水から除去することを特徴とするリンの除去方法、を要旨とする。 The present invention relates to a phosphorus removal agent comprising vermiculite having calcium introduced between layers as an active ingredient, and further removing phosphorus from water by bringing water containing phosphorus into contact with the phosphorus removal agent. The method is the gist.
本発明によれば、結晶性がよく、ろ過抵抗が小さい、特定の天然物もしくは改質した天然物を用いたリン除去剤が得られ、簡易な設備で効率的に水中のリンをヒドロキシアパタイトとして除去し得る。 According to the present invention, a phosphorus removing agent using a specific natural product or modified natural product having good crystallinity and low filtration resistance can be obtained, and phosphorus in water can be efficiently converted into hydroxyapatite with simple equipment. Can be removed.
本発明に係るリン除去剤はバーミキュライトを有効成分とする。本発明で使用されるバーミキュライト(ヒル石)は、黒雲母に類似した粘土鉱物であり、高温で脱水により層に垂直の方向に著しく膨張して、ヒルのように伸び多孔体となる。すなわち、本発明において使用されるバーミキュライトは、SiO2、MgO、Al2O3を主成分とする薄片状の鉱物であり、一般的な黒雲母系、緑泥石系のいずれでもよく、産地により組成等に差異があっても使用し得る。比表面積(窒素吸着法)は通常10m2/g以下である。粒径も特に制限されないが、通常、5mm以下、好ましくは3mm以下,そして表面積を大きくするのに好ましくは0.5mm以下である。 The phosphorus removing agent according to the present invention contains vermiculite as an active ingredient. Vermiculite (hillstone) used in the present invention is a clay mineral similar to biotite, and expands remarkably in a direction perpendicular to the layer by dehydration at a high temperature to become a porous body like a hill. That is, the vermiculite used in the present invention is a flaky mineral mainly composed of SiO 2 , MgO, Al 2 O 3 , and may be any of a general biotite system or a chlorite system, depending on the production area. Even if there is a difference, it can be used. The specific surface area (nitrogen adsorption method) is usually 10 m 2 / g or less. The particle size is not particularly limited, but is usually 5 mm or less, preferably 3 mm or less, and preferably 0.5 mm or less for increasing the surface area.
本発明においては、このようなバーミキュライトを実質的に未膨張の状態で使用する。すなわち、バーミキュライトは、通常10〜20%程度の水を含んでおり、高温(層間水が脱離し始める約320℃から1000℃)での急激な加熱により脱水され著しく膨張する(多くは1000℃、1〜2秒で、もとの厚さの10〜30倍)。本発明においては実質的にこのような膨張を得ていないもの(層間水が存在し、実質的に未膨張バーミキュライトの構造を保持している程度まで膨張したものを含む)、および層間水が存在しない程度まで膨張させたバーミキュライトのいずれも使用されうる。 In the present invention, such vermiculite is used in a substantially unexpanded state. That is, vermiculite usually contains about 10 to 20% of water, and is dehydrated and expanded significantly by rapid heating at a high temperature (about 320 ° C. to 1000 ° C. at which interlayer water begins to desorb). 1-2 seconds, 10-30 times the original thickness). In the present invention, those that have not substantially obtained such expansion (including those in which interlayer water is present and expanded to such an extent that the structure of unexpanded vermiculite is substantially retained), and interlayer water is present. Any vermiculite expanded to such an extent that it does not do can be used.
本発明におけるリン除去剤は、好適には上記のバーミキュライトの層間にカルシウムを導入したものを有効成分とする。バーミキュライトの層間にカルシウムを導入する方法は特に制限されないが、好適にはカルシウム化合物水溶液にバーミキュライトを浸漬させるか、またはバーミキュライトおよびカルシウム化合物の混合物を常圧ないし加圧下に加熱処理、たとえばオートクレーブ処理、することにより得られる。上記のカルシウム化合物水溶液としては、硝酸カルシウム、塩化カルシウム、酢酸カルシウム等の水溶液が好適である。 The phosphorus removal agent in the present invention preferably contains an active ingredient obtained by introducing calcium between the layers of the above vermiculite. The method for introducing calcium between the layers of vermiculite is not particularly limited, but preferably vermiculite is immersed in an aqueous calcium compound solution, or a mixture of vermiculite and calcium compound is heated under normal pressure or under pressure, for example, autoclaving. Can be obtained. As the above calcium compound aqueous solution, an aqueous solution of calcium nitrate, calcium chloride, calcium acetate or the like is preferable.
さらに、上記オートクレーブ処理による場合にはカルシウム化合物としては、固体もしくは液体のいずれでもよく、たとえば消石灰、硝酸カルシウム、塩化カルシウム、酢酸カルシウム等が好適に用いられ、通常、混合物中のカルシウム化合物がバーミキュライトの1〜10wt%、好ましくは2〜5wt%である。このオートクレーブ処理は、通常100〜200℃、10kg以下程度で行われる。 Further, in the case of the above autoclave treatment, the calcium compound may be either solid or liquid. For example, slaked lime, calcium nitrate, calcium chloride, calcium acetate and the like are preferably used. Usually, the calcium compound in the mixture is vermiculite. 1 to 10 wt%, preferably 2 to 5 wt%. This autoclave process is normally performed at 100-200 degreeC and about 10 kg or less.
本発明においては上記のリン除去剤を、リンを含む水と接触させてリンを水から除去する。リン除去剤の使用量は、水に対して通常5〜20%程度であり、水中のリンはヒドロキシアパタイトとして水から除去される。リンを含む水のpHは8〜10に調節されるのが好適であり、pHが5程度以下の場合には水酸化ナトリウムによりpHを上昇させるのが好適である。リンを含む水との接触により、リン除去剤の表面にヒドロキシアパタイトの核が発生、成長することによりリンが迅速に除去される。生成するヒドロキシアパタイトは、ヘドロ状ではなく、バーミキュライト表面に付着した顆粒状であり、リン回収、肥料化等の後処理も容易である。 In the present invention, the phosphorus removing agent is brought into contact with water containing phosphorus to remove phosphorus from the water. The usage-amount of a phosphorus removal agent is about 5 to 20% normally with respect to water, and phosphorus in water is removed from water as a hydroxyapatite. The pH of water containing phosphorus is preferably adjusted to 8 to 10, and when the pH is about 5 or less, it is preferable to increase the pH with sodium hydroxide. By contact with water containing phosphorus, nuclei of hydroxyapatite are generated and grown on the surface of the phosphorus removing agent, so that phosphorus is rapidly removed. The produced hydroxyapatite is not sludge, but is a granule attached to the surface of vermiculite, and post-treatment such as phosphorus recovery and fertilization is easy.
このようにリンを含む水を反応槽でリン除去剤と接触させる際に、消費されるカルシウムを補充するためにカルシウム化合物をさらに添加するのが好適である。このカルシウム化合物としては、消石灰、塩化カルシウム等が挙げられるが、消石灰であるのが好適であり、飽和水溶液の形態で添加するのがさらに好適である。 Thus, when water containing phosphorus is brought into contact with the phosphorus removing agent in the reaction vessel, it is preferable to further add a calcium compound in order to supplement the consumed calcium. Examples of the calcium compound include slaked lime and calcium chloride, but slaked lime is preferable, and it is more preferable to add in the form of a saturated aqueous solution.
本発明において、リンを含む水としては特に制限されず、河川、湖、沼もしくは貯水池等の水、ならびに産業排水および生活排水等が挙げられる。 In this invention, it does not restrict | limit especially as water containing phosphorus, Water, such as a river, a lake, a swamp, or a reservoir, industrial waste water, domestic waste water, etc. are mentioned.
次に、本発明を実施例によりさらに詳細に説明するが、本発明はこれらの実施例により限定されるものではない。なお部は質量部を表わす。
実施例1
水道水にKH2PO4を溶解し、リン濃度約20〜100mg/Lの原水を調製した。未膨張バーミキュライト300gを充填した3Lの噴流型反応槽に反応槽の2〜10倍/分の流量でその原水を導入し、さらに反応槽内のpHを8〜10に維持するために、塩化カルシウム飽和水溶液を反応槽に供給した。反応槽出口のリン濃度は約4〜20mg/Lであり、リンの除去率は約80%であった。
実施例2
実施例1において未膨張バーミキュライトに代えて、層間にカルシウムを導入した未膨張バーミキュライト(未膨張バーミキュライトに消石灰3wt%を添加し、180℃、5kgで3時間、オートクレーブ処理)を用いる以外は実施例1と同様にしてリンの除去を行なった。実施例1の場合よりもさらにヒドロキシアパタイトの核発生、成長が容易であり、リンがさらに迅速に除去された。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples. The part represents part by mass.
Example 1
KH 2 PO 4 was dissolved in tap water to prepare raw water having a phosphorus concentration of about 20 to 100 mg / L. In order to introduce the raw water into a 3 L jet-type reaction tank filled with 300 g of unexpanded vermiculite at a flow rate of 2 to 10 times / min of the reaction tank, and to maintain the pH in the reaction tank at 8 to 10 calcium chloride A saturated aqueous solution was fed to the reaction vessel. The phosphorus concentration at the outlet of the reaction vessel was about 4 to 20 mg / L, and the phosphorus removal rate was about 80%.
Example 2
In Example 1, instead of unexpanded vermiculite, unexpanded vermiculite in which calcium was introduced between layers (3 wt% of slaked lime was added to the unexpanded vermiculite and autoclaved at 180 ° C., 5 kg for 3 hours) was used. In the same manner, phosphorus was removed. The nucleation and growth of hydroxyapatite was easier than in Example 1, and phosphorus was removed more rapidly.
本発明のリン除去剤を用いて、簡易な設備で効率的に水中のリンをヒドロキシアパタイトとして除去し得る。 Using the phosphorus removing agent of the present invention, phosphorus in water can be efficiently removed as hydroxyapatite with simple equipment.
Claims (11)
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JP2003435065A JP4565836B2 (en) | 2003-12-26 | 2003-12-26 | Phosphorus remover |
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JP4565836B2 true JP4565836B2 (en) | 2010-10-20 |
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CN111704221A (en) * | 2020-05-21 | 2020-09-25 | 阿拉尔市中泰纺织科技有限公司 | Polyamine modified expanded vermiculite flocculant and preparation method and application thereof |
CN113354146B (en) * | 2021-06-08 | 2022-08-12 | 葛新星 | Phosphorus-containing sewage environment treatment method and treatment device |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6075394A (en) * | 1983-09-30 | 1985-04-27 | Kurita Water Ind Ltd | Dephosphorizing method |
JPS6078692A (en) * | 1983-10-07 | 1985-05-04 | Kurita Water Ind Ltd | Dephosphorization |
JPH038495A (en) * | 1989-06-05 | 1991-01-16 | Kanatsu Giken Kogyo Kk | Denitrifying and dephosphorizing composition and method for denitrification and dephosphorization |
JPH09174045A (en) * | 1995-12-27 | 1997-07-08 | Toyo Denka Kogyo Kk | Agent for removing phosphate |
JPH10118638A (en) * | 1996-10-24 | 1998-05-12 | Japan Vilene Co Ltd | Water treatment material |
JPH10230254A (en) * | 1997-02-19 | 1998-09-02 | Ebara Corp | Lightweight dephosphorizing agent and removing method of phosphorus in organic waste water using the same |
JPH10309585A (en) * | 1997-05-08 | 1998-11-24 | Tamuraya:Kk | Water quality purifying method |
JP2001520578A (en) * | 1997-03-26 | 2001-10-30 | コモンウエルス サイエンティフィック アンド インダストリアル リサーチ オーガナイゼーション | Precipitate improvement material and improvement method |
JP2002316850A (en) * | 2001-02-13 | 2002-10-31 | Tomita Pharmaceutical Co Ltd | Environment cleaning-type inorganic material |
JP2003305481A (en) * | 2002-04-17 | 2003-10-28 | Kurita Water Ind Ltd | Crystallization dephosphorization method and crystallization dephosphorization apparatus |
JP2005028272A (en) * | 2003-07-11 | 2005-02-03 | Kunimine Industries Co Ltd | Phosphorus-component adsorbent and method for wastewater treatment by using the adsorbent |
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2003
- 2003-12-26 JP JP2003435065A patent/JP4565836B2/en not_active Expired - Fee Related
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6075394A (en) * | 1983-09-30 | 1985-04-27 | Kurita Water Ind Ltd | Dephosphorizing method |
JPS6078692A (en) * | 1983-10-07 | 1985-05-04 | Kurita Water Ind Ltd | Dephosphorization |
JPH038495A (en) * | 1989-06-05 | 1991-01-16 | Kanatsu Giken Kogyo Kk | Denitrifying and dephosphorizing composition and method for denitrification and dephosphorization |
JPH09174045A (en) * | 1995-12-27 | 1997-07-08 | Toyo Denka Kogyo Kk | Agent for removing phosphate |
JPH10118638A (en) * | 1996-10-24 | 1998-05-12 | Japan Vilene Co Ltd | Water treatment material |
JPH10230254A (en) * | 1997-02-19 | 1998-09-02 | Ebara Corp | Lightweight dephosphorizing agent and removing method of phosphorus in organic waste water using the same |
JP2001520578A (en) * | 1997-03-26 | 2001-10-30 | コモンウエルス サイエンティフィック アンド インダストリアル リサーチ オーガナイゼーション | Precipitate improvement material and improvement method |
JPH10309585A (en) * | 1997-05-08 | 1998-11-24 | Tamuraya:Kk | Water quality purifying method |
JP2002316850A (en) * | 2001-02-13 | 2002-10-31 | Tomita Pharmaceutical Co Ltd | Environment cleaning-type inorganic material |
JP2003305481A (en) * | 2002-04-17 | 2003-10-28 | Kurita Water Ind Ltd | Crystallization dephosphorization method and crystallization dephosphorization apparatus |
JP2005028272A (en) * | 2003-07-11 | 2005-02-03 | Kunimine Industries Co Ltd | Phosphorus-component adsorbent and method for wastewater treatment by using the adsorbent |
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