JP3741269B2 - Waste water treatment agent, waste water treatment method and apparatus - Google Patents
Waste water treatment agent, waste water treatment method and apparatus Download PDFInfo
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【０００１】
【発明の属する技術分野】
本発明は排水処理剤、排水の処理方法及びその装置に関するものである。
【０００２】
【従来の技術】
硫酸アルミニウムは、通常、耐熱、耐酸性材よりなる反応槽に硫酸を仕込み、これに水酸化アルミニウムを投入して加熱させ、得られた濃厚硫酸アルミニウム溶液を反応槽で水希釈して貯蔵し、冷却後濃度調整して製品としている。
【０００３】
その用途としては、下水や工場排水、上水等の排水処理剤（無機凝集剤）として使用されたり、紙用サイズ剤、皮革のなめしや油脂の清澄剤、各種触媒等として広く使用されている工業用薬品である。
【０００４】
ところで、前述の排水処理剤として使用する場合、他の処理剤、例えば、ＰＡＣ（ポリ塩化アルミニウム）と比べると、薬剤を多く加えないと満足すべき凝集速度が得られないと言う問題点を有しているため、近年、硫酸アルミニウムがＰＡＣに置き換えられるケースが増加してきているが、硫酸アルミニウムは原料として硫酸廃液を使用出来ることから、資源の有効利用（省資源）の観点より、ＰＡＣと同等以上の凝集性能を有するものが渇望される状況になってきている。
【０００５】
【発明が解決しようとする課題】
本発明は、従来の硫酸アルミニウムより優れかつＰＡＣと同等以上の凝集性能を有する硫酸アルミニウム含有組成物を提供することを目的とするものである。
【０００６】
【課題を解決するための手段】
本発明者は、上記の目的を達成するために鋭意研究を重ねた結果、予想外にも硫酸アルミニウムに硝酸を共存させることで凝集性能が向上されることを見出し、さらに検討を重ねて、本発明を完成させるに至った。
【０００７】
すなわち本発明は、
〔１〕 硝酸と硫酸アルミニウムを含有し、８重量％のＡｌ 2 Ｏ 3 を含む液状硫酸アルミニウムに換算した液状硫酸アルミニウムに対して、硝酸が１０〜２０００ｐｐｍ含有されていることを特徴とする排水処理剤に係わるものであり、
〔２〕 硝酸がすでにある目的で使用された硝酸である、前記〔１〕に記載した排水処理剤、
〔３〕 硫酸アルミニウムがすでにある目的で使用された硫酸と硝酸から製造された粗硫酸アルミニウムである、前記〔１〕に記載した排水処理剤とするのがよく、また、
〔４〕 前記〔１〕〜〔３〕のいずれか１項に記載した排水処理剤を使用することを特徴とする、排水の処理方法、及び、
〔５〕 前記〔１〕〜〔３〕のいずれか１項に記載した排水処理剤を搭載した排水処理装置、
も提供するものである。
【０００８】
【発明の実施の形態】
本発明で使用される硫酸アルミニウムは、公知の硫酸アルミニウムの製造に準じて行なわれた液状物や粉末物のどちらであってもよいし、その品質は工業グレード（工業用規格：ＪＩＳ Ｋ１４２３−１９７０、水道用規格：ＪＩＳ Ｋ１４５０−１９７７）や試薬グレードのいずれのレベルであってもよいし、もしくは、使用済みの廃硫酸や廃水酸化アルミニウムを用いて製造された粗硫酸アルミニウムであってもよい。
【０００９】
本発明で使用される硝酸としては、濃度や品質は試薬グレードおよび工業グレードのいずれのものであって良いし、一度ある目的、例えば有機合成、半導体生産時のレジスト剥離、各種洗浄等に使用された硝酸を含有する廃液であってもよい。また、発煙硝酸や同廃液を硝酸として使用してもよい。資源の有効利用、コストダウンの観点から、一度ある目的に使用された廃硝酸を用いることが望ましい。あるいは、上記硫酸中に含まれている硝酸であってもよい。例えば、特開平１１−１５７８１２や特開平１１−３１９８４９で提案されているように、硫酸廃液中の過酸化水素水を分解するために添加された硝酸、つまり、硫酸廃液中に含まれる硝酸分を利用することも可能である。硝酸は、硝酸を含有する廃液、廃硝酸等を含む。
【００１０】
上記のすでにある目的に使用された硝酸とは、硝酸を含有する廃液、廃硝酸等を含む。
【００１１】
本発明の組成物（排水処理剤）は硝酸と硫酸アルミニウムとを配合することにより容易に製造できる。本発明の組成物には、通常水がさらに含まれている。なお、本発明の組成物において硫酸アルミニウムは液状硫酸アルミニウムとして存在する。従って、液状硫酸アルミニウムとは、組成物中に存在する水と硫酸アルミニウムから構成されている。
【００１２】
本発明では、硫酸アルミニウムに硝酸を存在させることで凝集特性の向上を図るが、その添加量としては、液状硫酸アルミニウム［Ａｌ2Ｏ3の含有量８重量％、又はＡｌ2（ＳＯ4）3の含有量２６．８重量％］の重量に換算した液状硫酸アルミニウムに対して約１０〜２０００ｐｐｍとすべきである。硝酸の濃度がこれより低いと凝集効果の向上が期待できず、また、これより高くなると経済的ではない。この硝酸は、液状の硫酸アルミニウムにそのまま所定量添加されてもよいし、もしくは前述のように硫酸アルミニウムを製造する際や同製造原料（硫酸等）中に含まれていたものであってもよい。
【００１３】
また、本発明の組成物は硫酸と水酸化アルミニウムとを硝酸の存在下に反応させる方法によっても容易に製造することができる。
【００１４】
本方法で使用される硫酸は、濃度に関しては特に限定は無く、約９０重量％以下の濃度においても十分使用可能であり、通常は約５０重量％以上が好ましい。なお、従来法では、硫酸の濃度は約９０重量％以上が標準的であった。また、本発明に使用される硫酸の品質としては、工業用や試薬グレードのもの、または、半導体工業等で利用される高純度品であってもよいし、各種部品や製品の洗浄液として使用されたもの、特に、半導体の製造工程でレジスト剥離や洗浄液として利用されたものであってもよい。また、発煙硫酸や無水硫酸もしくはこれらの廃液であってもよい。なお、資源の有効利用、コストダウンの観点から、一度ある目的に使用された廃硫酸を用いることが望ましい。硫酸は、硫酸を含有する廃液、廃硫酸等を含む。
【００１５】
本方法で使用される水酸化アルミニウムとしては、アルミニウム塩、陶磁器、ガラス、耐火物、触媒もしくは触媒担体、樹脂、ゴム、紙の難燃剤、人工大理石等の原料として工業用に用いられているものであってもよいし、ＩＣ（集積回路）や光学用ガラス原料、高純度アルミニウム化合物原料、触媒用、医薬用に用いられている高純度水酸化アルミニウムであってもよいし、水酸化アルミニウムを含有するこれらの廃材（使用済みのもの）であってもよい。なお、コスト面と資源の有効利用面の観点から、工業用水酸化アルミニウムや一度他の目的に使用された水酸化アルミニウムを原料として用いることがより好ましい。水酸化アルミニウムは、水酸化アルミニウムを含有する廃材等を含む。
【００１７】
以上に示した原料である硫酸、水酸化アルミニウムおよび硝酸以外に、所望により他の添加物、例えば水を反応系に存在させて硫酸アルミニウムの製造を行うこともできる。反応方法としては、硝酸を反応系に存在させる以外は公知の硫酸アルミニウムの製造に従って行われてよく、硫酸に水酸化アルミニウムを粉末状で添加してもよいし、水酸化アルミニウムを水でスラリー化したものを硫酸に添加してもよい。または、水酸化アルミニウムと水のスラリーに硫酸を加えてもよい。また、硝酸は、反応前や反応途中のどちらで添加してもよいし、硫酸や水、水酸化アルミニウムと水のスラリー中に予め添加した状態で使用してもよい。前述で述べた特開平１１−１５７８１２や特開平１１−３１９８４９の記載に従う再生硫酸中にはすでに硝酸が含有されている。このような硫酸を原料として使用することで硝酸を反応系に存在させることもできる。本発明の反応は好ましくは水酸化アルミニウムと硝酸の混合物に硫酸を滴下することにより行われる。
【００１８】
同反応系への硝酸の添加量としては、反応系のトータル重量に対して約１〜３０００ｐｐｍで、好ましくは、約１０〜１０００ｐｐｍである。硝酸の添加量がこれより少ないと反応の促進効果が得られにくくなり、これより多くなると経済的に不利となる。
【００１９】
また、硝酸入りの硫酸を原料として用いる場合は、硫酸中の硝酸濃度は約１０〜５０００ｐｐｍが好ましい。この場合も、硝酸の添加量がこれより少ないと反応の促進効果が充分に得られにくくなり、これより多くなると経済的に不利となる。
なお、硝酸入りの硫酸を用いて、さらに反応系に硝酸を添加してもよい。
【００２０】
硝酸を添加することで硫酸の反応性を向上させることができるため、従来方法に比べて、低濃度の硫酸を用い低温かつ短時間で、効率良く反応が促進されることになる。そのメカニズムは明らかでないが、下記反応H2SO4＋HNO3→ NO2+＋HSO4 -が硫酸アルミニウムの反応に関与しているものと予想される。
【００２１】
反応系の加熱については、前述の硝酸により反応促進効果があることや、硫酸と水との水和熱やアルミニウムとの反応熱を利用することができるため、特に加熱源を設けることは必ずしも必要ない。そのため反応温度は、仕込み時は室温からスタートし、水和熱や反応熱を利用することで約６０〜１１０℃にまで到達し、あとはこの温度で熟成することで求める硫酸アルミニウムを効率よく製造することができる。なお、所望に応じて例えばスチーム等を利用した強制加熱を行ってもよい。
【００２２】
反応時間は通常は約１分〜１時間で終了する。滴下時間は約１〜２０分（通常：約５分）、熟成時間は約１〜２０分（通常：約５分）であるが、反応温度等の条件によってこれ以外でもよい。
【００２３】
硫酸に対する水酸化アルミニウムの添加量は、約１.０〜１.２倍モルが好ましい。
【００２４】
また、同反応のさらなる効率アップを図るため、さらに過酸化水素水を添加してもよい。
【００２５】
なお、反応終了後は、水による希釈で所定の濃度に調整した液状物としてもよいし、固化床に流し完全に固化するまで冷却した後、これを粉砕して本方法の組成物としてもよい。
【００２６】
以上のようにして得られた硝酸と硫酸アルミニウムを包含することを特徴とする工業用組成物は、従来の硫酸アルミニウムやＰＡＣと同様にして排水処理剤として利用できる。
【００２７】
なお、硝酸を硫酸アルミニウムに存在させることにより、硫酸イオンは硝酸イオンと会合し易くなるため、硫酸イオンとアルミニウムイオンとの会合が弱くなり、アルミニウムのイオン強度が高められて排水中の懸濁粒子を吸着する効果が向上されると考えられ、硫酸アルミニウムを含む組成物をＰＡＣと同等以上の凝集性能を有する排水処理剤に転換することが可能となる。
【００２８】
また、本発明の組成物は、従来の硫酸アルミニウム含有組成物と同様にして排水処理剤以外の紙用サイズ剤、皮革のなめし剤、油脂の清澄剤、各種触媒等の工業分野で使用することが可能である。
【００２９】
さらに、本発明の組成物は、従来の排水処理装置に搭載することが可能である。
【００３０】
【実施例】
以下、実施例により本発明をさらに説明するが、本発明はこれに限定されるものではない。なお、硫酸アルミニウム中の酸化アルミニウムの定量分析は、ＪＩＳ Ｋ１４５０-1996法に従って行った。
【００３１】
実施例１ 下記比較例１に記載した水道用硫酸アルミニウムに工業用硝酸（７０重量％）を５００ｐｐｍ添加したもの。
【００３２】
実施例２ 保温材により反応釜外壁を覆った撹拌機付きの反応釜に水：１８gと粉末状水酸化アルミニウム（試薬）：９.８gと７０重量％硝酸（工業品）：０.０５gを加えて撹拌を行ったものに、８０重量％の硫酸：２２.５gを撹拌下に室温下で５分かけて滴下した。滴下終了後５分間熟成を行った後、反応液に水：２８gを加えて希釈を行った。得られた反応液をフィルターでろ過して、未反応の水酸化アルミニウムの分離を行ったものについてｐＨとＡｌ２Ｏ３（重量％）を測定した。この液のｐＨは３.３３で、Ａｌ２Ｏ３（重量％）は８.１０であった。
【００３３】
実施例３ 硝酸そのものを添加するのでは無く、硝酸を３００ｐｐｍ含有した半導体工場からの廃硫酸（８０重量％）を用いて実施例１と同じ方法で反応を行った。最終的に得られた反応液のｐＨは３.１２で、Ａｌ２Ｏ３（重量％）は８.１４であった。
【００３４】
比較例１ 水道用硫酸アルミニウム（Ａｌ２Ｏ３：８重量％）、ｐＨは３.１０で、Ａｌ２Ｏ３（重量％）は８.１０。
【００３５】
比較例２ 排水処理用ＰＡＣ（ポリ塩化アルミニウム：工業品；アルミナ１０重量％）。
【００３６】
以上のサンプル５種類を用いて、半導体工場排水にて凝集効果を比較評価した。なお、同排水原水中にはＦイオンが３０ｐｐｍ含まれていたが（他にも、硫酸、硝酸、塩酸等が同排水中に含まれる）、これに消石灰を添加してｐＨ＝８.７とした懸濁液を用いて、各サンプルを添加した場合や、引き続き高分子凝集剤（ポリアクリルアミド系凝集剤）を添加した場合について、凝集速度、濁度、Ｆイオン濃度の項目で比較検討を行った。なお、凝集速度については、沈降管を用いて所定の距離を通過する時間の測定を目視で行った。排水の濁度は京都電子工業（株）ポータブル濁度計ＰＣ−０６を、Ｆイオン濃度はＤＫＫコーポレーションＩＬＯ−３０を用いて測定を行った。
【００３７】
実施例１〜３、比較例１，２について凝集速度、濁度、Ｆイオン濃度を評価した結果を図１〜３に示す。
【００３８】
図１の結果から分かるように、硝酸が存在する実施例１〜３の方が比較例１，２より優れた凝集速度を示している。また、サンプルの添加量が多いほどより優れた凝集速度を示している。
【００３９】
図２の結果から分かるように、硝酸が存在する実施例１〜３の方が比較例１、２より濁度が低下することを示している。また、さらに他の高分子凝集剤を添加するとより濁度が低下することを示している。
【００４０】
図３の結果から分かるように、硝酸が存在する実施例１〜３の方が比較例１，２よりＦイオン濃度が低下することを示している。また、他の高分子凝集剤をさらに添加するとよりＦイオン濃度が低下することを示している。
【００４１】
【発明の効果】
本発明の硝酸を含有する硫酸アルミニウム組成物は、ＰＡＣより優れた凝集性能を示す。凝集性能は処理能力である凝集速度と処理水の水質を示す濁度とＦイオン濃度で評価する。
【００４２】
また、廃硫酸、廃硝酸を使用することができるので資源の有効利用を図ることが可能となる。
【図面の簡単な説明】
【図１】 実施例１〜３の組成物と比較例１、２の組成物との凝集速度に関する比較を示す。
【図２】 実施例１〜３の組成物と比較例１、２の組成物との濁度に関する比較を示す。
【図３】 実施例１〜３の組成物と比較例１、２の組成物とのＦイオン濃度に関する比較を示す。[0001]
BACKGROUND OF THE INVENTION
The present invention is waste water treatment agent, to a processing method and apparatus of the drainage.
[0002]
[Prior art]
Aluminum sulfate is usually charged with sulfuric acid in a reaction tank made of heat-resistant and acid-resistant material, and aluminum hydroxide is added to it and heated, and the resulting concentrated aluminum sulfate solution is diluted with water in the reaction tank and stored. After cooling, the concentration is adjusted to make a product.
[0003]
As its use, it is widely used as a wastewater treatment agent (inorganic flocculant) for sewage, factory effluent, tap water, etc., as a paper sizing agent, leather tanning, oil refining agent, various catalysts, etc. It is an industrial chemical.
[0004]
By the way, when used as the above-mentioned wastewater treatment agent, there is a problem that a satisfactory agglomeration rate cannot be obtained unless a large amount of chemical is added compared to other treatment agents such as PAC (polyaluminum chloride). because you are, in recent years, but aluminum sulfate has been increasing cases be replaced with a PAC, since the usable sulfate waste as aluminum sulfate raw material, from the viewpoint of effective use of resources (resource saving) and PAC Those having a cohesion performance equal to or higher than that have been craved.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide an aluminum sulfate-containing composition that is superior to conventional aluminum sulfate and has a coagulation performance equal to or higher than that of PAC.
[0006]
[Means for Solving the Problems]
As a result of intensive research to achieve the above-mentioned object, the present inventor has unexpectedly found that coagulation performance is improved by coexisting nitric acid with aluminum sulfate. The invention has been completed.
[0007]
That is, the present invention
[1] contains nitrate and aluminum sulfate, with respect to the liquid aluminum sulfate in terms of liquid aluminum sulfate containing 8 wt% Al 2 O 3, waste water treatment, characterized in that nitric acid is contained 10~2000ppm Related to the agent ,
[2] nitric acid is nitric acid used in existing purposes, waste water treatment agents described above [1],
[3] is a crude aluminum sulfate produced from sulfuric acid and nitric acid used in the aluminum sulphate is already interest, often to a waste water treatment agent described in the above [1], also,
[4] characterized in that said the use of waste water treatment agents described in any one of [1] to [3], the processing method of waste water and,
[ 5 ] A wastewater treatment apparatus equipped with the wastewater treatment agent according to any one of [1] to [3] ,
It is also intended to provide.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The aluminum sulfate used in the present invention may be either a liquid material or a powder material prepared in accordance with the production of a known aluminum sulfate, and the quality thereof is an industrial grade (industrial standard: JIS K1423-1970). Standards for water supply: JIS K1450-1977) and reagent grade levels, or crude aluminum sulfate produced using used waste sulfuric acid or waste aluminum hydroxide.
[0009]
The concentration and quality of the nitric acid used in the present invention may be any of reagent grade and industrial grade, and once used for a certain purpose, such as organic synthesis, resist stripping during semiconductor production, various washings, etc. It may also be a waste liquid containing nitric acid . Further, fuming nitric acid or the waste liquid may be used as nitric acid. From the viewpoint of effective use of resources and cost reduction, it is desirable to use waste nitric acid once used for a certain purpose. Alternatively, it may be nitric acid contained in the sulfuric acid. For example, as proposed in JP-A-11-157812 and JP-A-11-319849, nitric acid added to decompose the hydrogen peroxide solution in the sulfuric acid waste solution, that is, the nitric acid content contained in the sulfuric acid waste solution. It can also be used. Nitric acid includes waste liquid containing nitric acid, waste nitric acid and the like.
[0010]
The nitric acid used for the above-mentioned purposes includes waste liquid containing nitric acid, waste nitric acid and the like.
[0011]
The composition (waste water treatment agent) of the present invention can be easily produced by blending nitric acid and aluminum sulfate. The composition of the present invention usually further contains water. In the composition of the present invention, aluminum sulfate exists as liquid aluminum sulfate. Therefore, liquid aluminum sulfate is comprised from the water and aluminum sulfate which exist in a composition.
[0012]
In the present invention, the aggregation property is improved by making nitric acid present in aluminum sulfate. The amount of addition is liquid aluminum sulfate [Al 2 O 3 content of 8% by weight, or Al 2 (SO 4 ) 3. The content should be about 10 to 2000 ppm with respect to the liquid aluminum sulfate converted to the weight of 26.8 wt%. If the concentration of nitric acid is lower than this, an improvement in the coagulation effect cannot be expected, and if it is higher than this, it is not economical. The nitric acid may be added as a predetermined amount of aluminum sulfate of the liquid, or when and the raw material for producing aluminum sulfate as described above may be those contained in the (sulfuric acid) .
[0013]
The composition of the present invention can also be easily produced by a method in which sulfuric acid and aluminum hydroxide are reacted in the presence of nitric acid.
[0014]
Sulfuric acid used in the present method is not limited especially in terms of concentration, are also possible sufficiently used at a concentration of about 90 wt% or less, usually preferably at least about 50 wt%. In the conventional method, the standard concentration of sulfuric acid is about 90% by weight or more. In addition, the quality of sulfuric acid used in the present invention may be industrial or reagent grade, or high purity products used in the semiconductor industry, etc., and may be used as a cleaning liquid for various parts and products. In particular, it may be used as a resist peeling or cleaning solution in a semiconductor manufacturing process. Further, fuming sulfuric acid, sulfuric anhydride, or a waste liquid thereof may be used. From the viewpoint of effective use of resources and cost reduction, it is desirable to use waste sulfuric acid once used for a certain purpose. Sulfuric acid includes waste liquid containing sulfuric acid, waste sulfuric acid, and the like.
[0015]
Aluminum hydroxide used in this method includes those used for industrial purposes as raw materials for aluminum salts, ceramics, glass, refractories, catalysts or catalyst carriers, resins, rubber, paper flame retardants, artificial marble, etc. It may be IC (integrated circuit) , optical glass raw materials, high-purity aluminum compound raw materials, catalysts, high-purity aluminum hydroxide used for pharmaceuticals, or aluminum hydroxide. These waste materials (used ones) may be included. In view of cost and effective use of resources, it is more preferable to use industrial aluminum hydroxide or aluminum hydroxide once used for other purposes as a raw material. Aluminum hydroxide includes waste materials containing aluminum hydroxide .
[0017]
In addition to sulfuric acid, aluminum hydroxide and nitric acid which are the raw materials shown above, if desired, other additives such as water may be present in the reaction system to produce aluminum sulfate. As a reaction method, except that nitric acid is present in the reaction system, it may be carried out in accordance with the production of a known aluminum sulfate. Aluminum hydroxide may be added to sulfuric acid in powder form, or aluminum hydroxide is slurried with water. The product may be added to sulfuric acid. Alternatively, sulfuric acid may be added to a slurry of aluminum hydroxide and water. Nitric acid may be added either before or during the reaction, or may be used in a state of being added in advance to a slurry of sulfuric acid, water, aluminum hydroxide and water. Nitric acid is already contained in the regenerated sulfuric acid according to the description of JP-A-11-157812 and JP-A-11-319849 described above. Such a sulfuric acid nitric acid by using as a raw material may be present in the reaction system. The reaction of the present invention is preferably carried out by dropping sulfuric acid into a mixture of aluminum hydroxide and nitric acid.
[0018]
The amount of nitric acid added to the reaction system is about 1 to 3000 ppm, preferably about 10 to 1000 ppm, based on the total weight of the reaction system. If the amount of nitric acid added is less than this, it becomes difficult to obtain the reaction promoting effect, and if it is more than this, it becomes economically disadvantageous.
[0019]
When sulfuric acid containing nitric acid is used as a raw material, the concentration of nitric acid in sulfuric acid is preferably about 10 to 5000 ppm. In this case as well, if the amount of nitric acid added is less than this, the effect of promoting the reaction cannot be obtained sufficiently, and if it exceeds this, it becomes economically disadvantageous.
Nitric acid may be added to the reaction system using sulfuric acid containing nitric acid.
[0020]
Since the reactivity of sulfuric acid can be improved by adding nitric acid, the reaction is efficiently promoted at a low temperature and in a short time by using a low concentration sulfuric acid as compared with the conventional method. The mechanism is not clear, but the following reaction H 2 SO 4 + HNO 3 → NO 2+ + HSO 4 − is expected to be involved in the reaction of aluminum sulfate.
[0021]
Regarding the heating of the reaction system, it is necessary to provide a heating source in particular because the above-mentioned nitric acid has a reaction promoting effect, the heat of hydration of sulfuric acid and water and the heat of reaction of aluminum can be used. Absent. Therefore, the reaction temperature starts from room temperature at the time of preparation, reaches about 60-110 ° C by using heat of hydration and heat of reaction, and then efficiently produces the aluminum sulfate required by aging at this temperature. can do. For example, forced heating using steam or the like may be performed as desired.
[0022]
The reaction time is usually about 1 minute to 1 hour. The dropping time is about 1 to 20 minutes (usually: about 5 minutes), and the aging time is about 1 to 20 minutes (usually: about 5 minutes), but other conditions may be used depending on conditions such as reaction temperature.
[0023]
The amount of aluminum hydroxide added to sulfuric acid is preferably about 1.0 to 1.2 times mole.
[0024]
In order to further increase the efficiency of the reaction, hydrogen peroxide water may be further added.
[0025]
In addition, after completion | finish of reaction, it is good also as the liquid substance adjusted to the predetermined density | concentration by dilution with water, It is good to make it the composition of this method by grind | pulverizing this after pouring to a solidification bed and fully solidifying. .
[0026]
The industrial composition characterized by including nitric acid and aluminum sulfate obtained as described above can be used as a wastewater treatment agent in the same manner as conventional aluminum sulfate and PAC.
[0027]
When nitric acid is present in aluminum sulfate, sulfate ions are likely to associate with nitrate ions, so the association between sulfate ions and aluminum ions is weakened, and the ionic strength of aluminum is increased, resulting in suspended particles in waste water. It is considered that the effect of adsorbing water is improved, and the composition containing aluminum sulfate can be converted into a wastewater treatment agent having a coagulation performance equal to or higher than that of PAC.
[0028]
In addition, the composition of the present invention is used in industrial fields such as paper sizing agents other than waste water treatment agents, leather tanning agents, oil clarifiers, and various catalysts in the same manner as conventional aluminum sulfate-containing compositions. Is possible.
[0029]
Furthermore, the composition of this invention can be mounted in the conventional waste water treatment equipment.
[0030]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. The quantitative analysis of aluminum oxide in aluminum sulfate was performed according to JIS K1450-1996 method.
[0031]
Example 1 To the aluminum sulfate for water supply described in Comparative Example 1 below, 500 ppm of industrial nitric acid (70% by weight) was added.
[0032]
Example 2 Water: 18 g, powdered aluminum hydroxide (reagent): 9.8 g and 70 wt% nitric acid (industrial product): 0.05 g were added to a reaction kettle with a stirrer whose outer wall was covered with a heat insulating material. Then, 22.5 g of 80% by weight sulfuric acid was added dropwise over 5 minutes at room temperature with stirring. After completion of dropping, the mixture was aged for 5 minutes, and diluted by adding 28 g of water to the reaction solution. The obtained reaction solution was filtered through a filter, and the pH and Al 2 O 3 (% by weight) of the product obtained by separating unreacted aluminum hydroxide were measured. The pH of this solution was 3.33, and Al 2 O 3 (wt%) was 8.10.
[0033]
Example 3 Instead of adding nitric acid itself, the reaction was carried out in the same manner as in Example 1 using waste sulfuric acid (80% by weight) from a semiconductor factory containing 300 ppm nitric acid. The pH of the finally obtained reaction solution was 3.12, and Al 2 O 3 (% by weight) was 8.14.
[0034]
Comparative Example 1 Aluminum sulfate for water supply (Al 2 O 3 : 8% by weight), pH is 3.10, and Al 2 O 3 (% by weight) is 8.10.
[0035]
Comparative Example 2 PAC for wastewater treatment (polyaluminum chloride: industrial product;
[0036]
Using the above five types of samples, the coagulation effect was comparatively evaluated with semiconductor factory wastewater. The drainage raw water contained 30 ppm of F ions (in addition, sulfuric acid, nitric acid, hydrochloric acid, etc. were contained in the wastewater), and slaked lime was added to this to obtain pH = 8.7. Using each suspension, when each sample is added or when a polymer flocculant (polyacrylamide flocculant) is subsequently added, a comparative study is performed on the items of aggregation rate, turbidity, and F ion concentration It was. In addition, about the aggregation rate, the measurement of the time which passes a predetermined distance was performed visually using the sedimentation tube. The turbidity of the wastewater was measured using a portable turbidimeter PC-06 manufactured by Kyoto Electronics Industry Co., Ltd., and the F ion concentration was measured using a DKK Corporation ILO-30.
[0037]
The results of evaluating the aggregation rate, turbidity, and F ion concentration for Examples 1 to 3 and Comparative Examples 1 and 2 are shown in FIGS.
[0038]
As can be seen from the results in FIG. 1, Examples 1 to 3 in which nitric acid is present show a better aggregation rate than Comparative Examples 1 and 2. Further, the larger the amount of sample added, the better the aggregation rate.
[0039]
As can be seen from the results of FIG. 2, Examples 1 to 3 in which nitric acid is present show that the turbidity is lower than those of Comparative Examples 1 and 2. Further, it is shown that the turbidity is further lowered when another polymer flocculant is added.
[0040]
As can be seen from the results of FIG. 3, Examples 1 to 3 where nitric acid is present show that the F ion concentration is lower than those of Comparative Examples 1 and 2. Further, it is shown that the F ion concentration is further decreased when another polymer flocculant is further added.
[0041]
【The invention's effect】
The aluminum sulfate composition containing nitric acid of the present invention exhibits a better agglomeration performance than PAC. The agglomeration performance is evaluated by the agglomeration rate, which is the treatment capacity, turbidity indicating the quality of the treated water, and F ion concentration.
[0042]
Moreover, since waste sulfuric acid and waste nitric acid can be used, it is possible to effectively use resources.
[Brief description of the drawings]
FIG. 1 shows a comparison of the aggregation rate between the compositions of Examples 1 to 3 and the compositions of Comparative Examples 1 and 2. FIG.
FIG. 2 shows a comparison of turbidity between the compositions of Examples 1 to 3 and the compositions of Comparative Examples 1 and 2.
FIG. 3 shows a comparison regarding the F ion concentration between the compositions of Examples 1 to 3 and the compositions of Comparative Examples 1 and 2;
Claims (5)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001356387A JP3741269B2 (en) | 2001-11-21 | 2001-11-21 | Waste water treatment agent, waste water treatment method and apparatus |
| TW091133512A TWI256943B (en) | 2001-11-21 | 2002-11-15 | Production method for aluminum sulfate, aluminum sulfate, method for improving for improving yield of aluminum sulfate, use of nitric acid, industrial composition, method for processing waste water, and device for processing waste water |
| KR1020020071648A KR101165425B1 (en) | 2001-11-21 | 2002-11-18 | A method for manufacturing sulfuric acid aluminum and a wastewater treatment apparatus for using an industrial composition |
| US10/298,525 US7067099B2 (en) | 2001-11-21 | 2002-11-19 | Method for preparing aluminum sulfate, aluminum sulfate, method for improving yield of aluminum sulfate, and use of nitric acid |
| EP02292887.3A EP1314696B1 (en) | 2001-11-21 | 2002-11-21 | Method for preparing aluminum sulfate |
| CNB021505810A CN1296281C (en) | 2001-11-21 | 2002-11-21 | Aluminium sulfate, its preparation method and use thereof |
| KR1020100057633A KR101101333B1 (en) | 2001-11-21 | 2010-06-17 | Wastewater treatment agent |
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| JP2001356387A JP3741269B2 (en) | 2001-11-21 | 2001-11-21 | Waste water treatment agent, waste water treatment method and apparatus |
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| JP2003154207A JP2003154207A (en) | 2003-05-27 |
| JP3741269B2 true JP3741269B2 (en) | 2006-02-01 |
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| JP4457027B2 (en) * | 2005-02-22 | 2010-04-28 | 新日本製鐵株式会社 | Disposal water treatment method |
| JP5877600B2 (en) * | 2011-03-31 | 2016-03-08 | アクアス株式会社 | Aggregation processing equipment |
| JP5492335B1 (en) * | 2013-08-08 | 2014-05-14 | 株式会社ケイ・アール・ジー | Method for producing flocculant and flocculant |
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