JP2000135480A - Treatment of residue - Google Patents

Treatment of residue

Info

Publication number
JP2000135480A
JP2000135480A JP31091698A JP31091698A JP2000135480A JP 2000135480 A JP2000135480 A JP 2000135480A JP 31091698 A JP31091698 A JP 31091698A JP 31091698 A JP31091698 A JP 31091698A JP 2000135480 A JP2000135480 A JP 2000135480A
Authority
JP
Japan
Prior art keywords
water
residue
oxide powder
calcium fluoride
zinc oxide
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
Application number
JP31091698A
Other languages
Japanese (ja)
Inventor
Hideaki Seto
英昭 瀬戸
Tomoya Anzai
知哉 安西
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Mining and Smelting Co Ltd
Original Assignee
Mitsui Mining and Smelting Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mitsui Mining and Smelting Co Ltd filed Critical Mitsui Mining and Smelting Co Ltd
Priority to JP31091698A priority Critical patent/JP2000135480A/en
Publication of JP2000135480A publication Critical patent/JP2000135480A/en
Pending legal-status Critical Current

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Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Landscapes

  • Processing Of Solid Wastes (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)

Abstract

PROBLEM TO BE SOLVED: To efficiently remove impurities in a calcium fluoride residue by using a calcium fluoride residue treatment process that comprises subjecting steelmaking dust to dechlorination treatment with lime water to obtain dechlorination water containing calcium and treated dust, adding a carbon material and water to the treated dust and pelletizing the mixture into pellects, roasting the pellets in a reduction/volatilization furnace to recover a crude zinc oxide powder, treating the crude zinc oxide powder in an alkali solution at a specified pH value. SOLUTION: Prescribed amount of chlorine in steelmaking dust in a raw material bin is removed by being sprayed dechlorinated lime water. Dechlorination water containing calcium is fed into defluorination treatment vessel. Dechlorinated steelmaking dust is baked in reduction/volatilization furnace after pelletizd. Crude zinc oxide powder volatized by baking is recovered by bag filter. Zinc oxide powder containing lead halide and zinc halide is agitated in a dehalogenation vessel with an alkali aqueos solution (>pH10). After solid liquid separation. The mixture is separated into calucium fluoride residue and waste water in the defluorination residue vessel with alkali aqueous solution of above pH11.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、残渣の処理方法に
関し、詳しくは製鋼煙灰中に含まれる有価金属である亜
鉛を粗酸化亜鉛粉末として回収した後のカルシウムを含
有する脱塩素水とフッ素を含有する脱ハロゲン水とを混
合し、反応させることによって得られるフッ化カルシウ
ム残渣中に含まれる鉛、亜鉛、イオウ等の不純物を効率
良く除去する残渣の処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating a residue, and more particularly, to a method for recovering zinc, which is a valuable metal contained in steelmaking ash, as crude zinc oxide powder and then removing dechlorinated water and fluorine containing calcium. The present invention relates to a residue treatment method for efficiently removing impurities such as lead, zinc, and sulfur contained in a calcium fluoride residue obtained by mixing and reacting with dehalogenated water to be contained.

【０００２】[0002]

【従来の技術及び発明が解決しようとする課題】鉄屑を
電気炉にて溶解して鋼を製造する際に発生する製鋼煙灰
には有価金属である亜鉛や鉛が含まれている。亜鉛は製
鋼煙灰を還元、揮発することによって粗酸化亜鉛粉末と
して回収される。2. Description of the Related Art Steel fumes produced when steel is produced by melting iron scraps in an electric furnace contain zinc and lead, which are valuable metals. Zinc is recovered as crude zinc oxide powder by reducing and volatilizing steelmaking fumes.

【０００３】この粗酸化亜鉛粉末を回収した後の脱ハロ
ゲン水には、フッ素、塩素等のハロゲン元素や鉛、亜鉛
等が含まれている。また、製鋼煙灰を脱塩素散水によっ
て脱塩素されるが、脱塩素後の脱塩素水中にはカルシウ
ム、塩素等が含まれている。[0003] The dehalogenated water after recovery of the crude zinc oxide powder contains halogen elements such as fluorine and chlorine, lead, zinc and the like. Further, the steelmaking ash is dechlorinated by dechlorination and sprinkling, and the dechlorinated water after dechlorination contains calcium, chlorine and the like.

【０００４】これら脱ハロゲン水と脱塩素水は、脱フッ
素残渣処理槽に導かれ、フッ化カルシウムが生成し、フ
ィルタープレスによって固液分離され、排水とフッ化カ
ルシウムを主成分とするフッ化カルシウム残渣とに分離
される。[0004] These dehalogenated water and dechlorinated water are led to a defluorination residue treatment tank, where calcium fluoride is generated and separated into solid and liquid by a filter press. Separated from the residue.

【０００５】このフッ化カルシウム残渣中には、鉛、亜
鉛、イオウ等の不純物が含まれており、従来において
は、これらフッ化カルシウム残渣はそのまま野積みさ
れ、放置されているのが実状であった。[0005] The calcium fluoride residue contains impurities such as lead, zinc, and sulfur. Conventionally, these calcium fluoride residues are piled up as they are and left as they are. Was.

【０００６】ところで、鉄鋼の製鋼工程、具体的には溶
銑予備処理や転炉、電炉において、スラグの流動性を向
上し、反応を促進するために、フッ化カルシウム原料と
して蛍石が使用されている。この蛍石はフッ化カルシウ
ム８０重量％、イオウ０．０５重量％以下、鉛０．０４
重量％以下、水分１．０重量％以下である。この蛍石は
輸入に依存しており、新たなフッ化カルシウム源が要望
されている。Fluorite is used as a raw material of calcium fluoride in the steelmaking process of iron and steel, specifically in hot metal pretreatment, a converter and an electric furnace, in order to improve the fluidity of slag and promote the reaction. I have. This fluorite contains 80% by weight of calcium fluoride, 0.05% by weight or less of sulfur, and 0.04% of lead.
% By weight and water content by weight is 1.0% by weight or less. This fluorite depends on imports, and a new calcium fluoride source is required.

【０００７】脱フッ素残渣は新たなフッ化カルシウム源
として有望であり、資源の再利用の点からも好ましいも
のであるが、上述のように、フッ化カルシウム残渣中に
は、鉛、亜鉛、イオウ等の不純物が含まれており、フッ
化カルシウム源としてそのまま使用することは困難であ
った。Although the defluoridation residue is promising as a new calcium fluoride source and is preferable from the viewpoint of resource recycling, as described above, the calcium fluoride residue contains lead, zinc and sulfur. And it was difficult to use it directly as a calcium fluoride source.

【０００８】そして、このフッ化カルシウム残渣の不純
物処理においては、効率性に優れた連続的な処理方法が
要望されている。[0008] In the treatment of impurities of the calcium fluoride residue, there is a demand for a highly efficient continuous treatment method.

【０００９】従って、本発明の目的は、製鋼煙灰に石灰
水を脱塩素散水することによって得られたカルシウムを
含有する脱塩素水と、製鋼煙灰を還元揮発炉で焙焼して
得られた粗酸化亜鉛をアルカリ溶液中に投入してｐＨを
１０以上に保持しながら撹拌し、その後濾別して得られ
たフッ素を含有する脱ハロゲン水とを反応させて得られ
たフッ化カルシウム残渣の不純物を効率性をもって除去
できる残渣の連続的な処理方法を提供することにある。[0009] Accordingly, an object of the present invention is to provide calcium-containing dechlorinated water obtained by dechlorinating lime water onto steelmaking ash, and crude steel obtained by roasting steelmaking ash in a reduction volatilization furnace. Pour zinc oxide into an alkaline solution, stir while maintaining the pH at 10 or higher, and then filter the impurities of the calcium fluoride residue obtained by reacting with fluorine-containing dehalogenated water obtained by filtration. It is an object of the present invention to provide a method for continuously treating a residue that can be removed with a property.

【００１０】[0010]

【課題を解決するための手段】本発明者らは、検討の結
果、フッ化カルシウム残渣を回収し、これをアルカリ溶
液中に投入し、ｐＨを１１以上に保持することによっ
て、上記目的が達成し得ることを知見した。Means for Solving the Problems As a result of the study, the present inventors have collected calcium fluoride residue, poured it into an alkaline solution, and maintained the pH at 11 or more, thereby achieving the above object. It was found that it could be done.

【００１１】本発明は、上記知見に基づきなされたもの
で、製鋼煙灰に石灰水を脱塩素散水することによって得
られたカルシウムを含有する脱塩素水と、製鋼煙灰に炭
素材料と水を加えてペレット化し、これを還元揮発炉で
焙焼した後、粗酸化亜鉛粉末を回収し、該粗酸化亜鉛粉
末をアルカリ溶液中に投入してｐＨを１０以上に保持し
ながら撹拌し、その後濾別して得られたフッ素を含有す
る脱ハロゲン水とを反応させて得られたフッ化カルシウ
ム残渣をアルカリ溶液中に投入して、ｐＨを１１以上に
保持しながら撹拌し、さらにアルカリ洗浄、水洗、乾燥
し、該フッ化カルシウム残渣中の不純物を除去すること
を特徴とする残渣の処理方法を提供するものである。The present invention has been made on the basis of the above-mentioned findings. The present invention relates to a method of adding decalcified water containing calcium obtained by dechlorinating lime water to steel making ash, and adding a carbon material and water to steel making ash. After pelletizing and roasting this in a reduction volatilization furnace, the crude zinc oxide powder is recovered, and the crude zinc oxide powder is put into an alkaline solution, stirred while maintaining the pH at 10 or more, and then filtered to obtain. The obtained calcium fluoride residue obtained by reacting with the fluorine-containing dehalogenated water is put into an alkaline solution, stirred while maintaining the pH at 11 or more, and further washed with alkali, washed with water, and dried. An object of the present invention is to provide a method for treating a residue, characterized by removing impurities in the calcium fluoride residue.

【００１２】[0012]

【発明の実施の形態】以下、本発明を図面に基づいて詳
細に説明する。図１は、製鋼煙灰から粗酸化鉛粉末を回
収し、濾液を処理する工程を示す概略フロー図である。
同図においては、簡略化して説明するために、ロッドミ
ル、バッグフィルター、シックナー等は省略してある。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic flow chart showing the steps of recovering crude lead oxide powder from steelmaking ash and treating the filtrate.
In the figure, a rod mill, a bag filter, a thickener, and the like are omitted for simplification.

【００１３】本発明では、製鋼煙灰から亜鉛成分を粗酸
化亜鉛粉末として回収する。この製鋼煙灰は、鉄屑を電
気炉にて溶解して鋼を製造する際に発生するもので、亜
鉛を１０〜４０重量％程度含有する。In the present invention, the zinc component is recovered from the steelmaking ash as crude zinc oxide powder. This steelmaking ash is generated when iron scrap is melted in an electric furnace to produce steel, and contains about 10 to 40% by weight of zinc.

【００１４】図１に示されるように、原料ビン中の製鋼
煙灰は、石灰水を脱塩素散水することによって塩素分が
一定量除去される。カルシウムと塩素分を含有する脱塩
素水は脱フッ素処理槽に導入される。一方、脱塩素処理
された製鋼煙灰は、炭素材料と水、さらに所望の添加剤
を加えてペレット化される。ペレット化は、これらの各
成分を混合し、転動して造粒し、ロッドミルと製団機に
よって行う。炭素材料としては、石炭、コークス等が例
示される。製鋼煙灰をペレット化するのは、製鋼煙灰の
飛散等を防止するためである。As shown in FIG. 1, a certain amount of chlorine is removed from steelmaking ash in a raw material bottle by demineralizing and sprinkling lime water. The dechlorinated water containing calcium and chlorine is introduced into the defluorination treatment tank. On the other hand, the steel ash subjected to the dechlorination treatment is pelletized by adding a carbon material, water, and a desired additive. Pelletization is performed by mixing these components, tumbling and granulating, and using a rod mill and a forming machine. Examples of the carbon material include coal and coke. The purpose of pelletizing the steelmaking ash is to prevent the scattering of the steelmaking ash.

【００１５】次に、この炭素材料等と共にペレット化し
た製鋼煙灰を還元揮発炉に投入して焙焼を行い、粗酸化
亜鉛粉末を揮発させ、バッグフィルターによって、粗酸
化亜鉛粉末を回収する。この粗酸化亜鉛粉末中には、鉛
やフッ素、塩素といったハロゲン元素が存在し、例えば
ハロゲン化鉛、ハロゲン化亜鉛として存在する。Next, the steelmaking ash pelletized together with the carbon material and the like is put into a reduction and volatilization furnace and roasted to volatilize the crude zinc oxide powder, and the crude zinc oxide powder is recovered by a bag filter. Halogen elements such as lead, fluorine and chlorine are present in the crude zinc oxide powder, for example, as lead halide and zinc halide.

【００１６】この粗酸化亜鉛粉末は脱ハロゲン処理槽中
に投入される。この脱ハロゲン処理槽には、アルカリ溶
液が導入されており、ｐＨを１０以上、好ましくはｐＨ
を１１〜１４に保持しながら撹拌する。撹拌時間は２時
間程度である。撹拌時のｐＨを１０以上とすることによ
って、例えばハロゲン化鉛は、ＨＰｂＯ2 - 、ＰｂＯ 2
- となり、またハロゲン元素もイオン化してスラリー中
に溶解される。アルカリ溶液としては水酸化ナトリウ
ム、炭酸ナトリウム等の水溶液が例示される。This crude zinc oxide powder is placed in a dehalogenation treatment tank.
It is thrown into. This dehalogenation treatment tank contains
Solution is introduced, and the pH is adjusted to 10 or more, preferably pH
While keeping at 11-14. Stir time is 2 o'clock
It is about between. By adjusting the pH during stirring to 10 or more,
Thus, for example, lead halide is HPbOTwo -, PbO Two
-And the halogen element is also ionized into the slurry
Dissolved in Sodium hydroxide as alkaline solution
And aqueous solutions of sodium carbonate and the like.

【００１７】この粗酸化亜鉛を含むスラリーは、フィル
タープレスで固液分離される。この際には、アルカリ洗
浄、水洗が行われる。アルカリ洗浄をするのは、単に水
洗のみではｐＨが１０以下となるので、スラリー中のハ
ロゲン元素が粗酸化亜鉛粉末中に再度含まれる恐れがあ
り、これを防止するためである。また、このアルカリ洗
浄、水洗は、後述するような多段向流洗浄としてもよ
い。The slurry containing the crude zinc oxide is separated into a solid and a liquid by a filter press. At this time, alkali washing and water washing are performed. The alkali cleaning is performed to prevent the halogen element in the slurry from being re-contained in the crude zinc oxide powder because the pH is reduced to 10 or less simply by washing with water. The alkali washing and the water washing may be a multi-stage countercurrent washing as described later.

【００１８】このようにして、フッ素、塩素等のハロゲ
ン元素含有量が大幅に低減された粗酸化亜鉛粉末が得ら
れる。この粗酸化亜鉛粉末は、亜鉛製錬における原料と
して好適に使用できる。特に、粗酸化亜鉛粉末中のフッ
素含有量は０．１重量％以下とすることが望ましい。こ
の粗酸化亜鉛粉末はそのまま、亜鉛製錬の原料として用
いられる。In this way, a crude zinc oxide powder having a greatly reduced content of halogen elements such as fluorine and chlorine can be obtained. This crude zinc oxide powder can be suitably used as a raw material in zinc smelting. In particular, the fluorine content in the crude zinc oxide powder is desirably 0.1% by weight or less. This crude zinc oxide powder is used as it is as a raw material for zinc smelting.

【００１９】一方、ハロゲン元素、鉛、亜鉛等を含む脱
ハロゲン濾液は、上記した脱塩素水と同様に脱フッ素残
渣処理槽に導入される。この脱フッ素残渣処理槽では、
脱塩素水中に含まれるカルシウムが脱ハロゲン水（濾
液）中のフッ素と反応しフッ化カルシウムを主成分とす
るフッ化カルシウム残渣が生成する。この脱フッ素処理
槽には、ｐＨ調整のためにアルカリ溶液が添加され、ｐ
Ｈは好ましくは８〜１２、さらに好ましくは９〜１１に
維持される。On the other hand, a dehalogenated filtrate containing a halogen element, lead, zinc and the like is introduced into a defluorination residue treatment tank in the same manner as the above-mentioned dechlorinated water. In this defluoridation residue treatment tank,
Calcium contained in the dechlorinated water reacts with fluorine in the dehalogenated water (filtrate) to form a calcium fluoride residue containing calcium fluoride as a main component. An alkaline solution is added to this defluorination treatment tank for pH adjustment, and p
H is preferably maintained at 8-12, more preferably 9-11.

【００２０】次に、このフッ化カルシウム残渣を含むス
ラリーは、フィルタープレスにて固液分離され、フッ化
カルシウム残渣と排水とに分離される。Next, the slurry containing the calcium fluoride residue is subjected to solid-liquid separation by a filter press to separate the calcium fluoride residue and waste water.

【００２１】このアルカリ洗浄及び水洗の詳細を示すフ
ロー図を図２に示す。脱ハロゲン濾液中のフッ素は、脱
フッ素残渣処理槽で、上述のように、カルシウムと反応
しフッ化カルシウムを主成分とするフッ化カルシウム残
渣を生成する。また、この脱フッ素残渣処理槽はアルカ
リ溶液によってｐＨ調整される。次に、このフッ化カル
シウム残渣を含むスラリーは、撹拌槽１でアルカリ洗浄
される。次に、スラリーはフィルタープレスで脱水され
る。このフィルタープレスでは濾液は排水とされ、排水
処理工程へ導かれる。スラリーは続いて撹拌槽２に導入
され、アルカリ洗浄された後、フィルタープレスに導入
される。さらに、このスラリーは、撹拌槽３に導入さ
れ、水洗された後、フィルタープレスに導入され、固液
分離される。FIG. 2 is a flowchart showing details of the alkali washing and the water washing. Fluorine in the dehalogenated filtrate reacts with calcium in the defluoridation residue treatment tank as described above to produce a calcium fluoride residue containing calcium fluoride as a main component. The pH of the defluoridation residue treatment tank is adjusted by an alkaline solution. Next, the slurry containing the calcium fluoride residue is alkali-washed in the stirring tank 1. Next, the slurry is dewatered in a filter press. In this filter press, the filtrate is drained and guided to a wastewater treatment step. The slurry is subsequently introduced into the stirring tank 2, washed with alkali, and then introduced into a filter press. Further, the slurry is introduced into the stirring tank 3, washed with water, and then introduced into a filter press to be separated into a solid and a liquid.

【００２２】撹拌槽１のスラリーは、フィルタープレス
で固液分離され、この濾液は、排水とされる。一方、フ
ッ化カルシウム残渣は撹拌槽２にてアルカリ洗浄（第２
段洗浄）される。このアルカリ洗浄に用いられた濾液１
は不純物の含有量が少ないため、上記撹拌槽１における
アルカリ溶液として用いられる。次いで、フッ化カルシ
ウム残渣は撹拌槽３にて水洗（第３段洗浄）される。こ
の水洗に用いられた濾液２も不純物の含有量が少ないた
め、調合槽にてこれにアルカリ溶液を加え、上記のアル
カリ洗浄に用いられる。すなわち、アルカリ洗浄及び水
洗においては多段向流洗浄がなされる。このような多段
向流洗浄を行うことによって、フッ化カルシウム残渣中
の不純物処理が高い効率性をもって連続的になされる。The slurry in the stirring tank 1 is separated into solid and liquid by a filter press, and the filtrate is drained. On the other hand, the calcium fluoride residue is washed with alkali in the stirring tank 2 (second
Step washing). The filtrate 1 used for this alkali washing
Is used as an alkaline solution in the stirring tank 1 because the content of impurities is small. Next, the calcium fluoride residue is washed with water (third stage washing) in the stirring tank 3. Since the filtrate 2 used for the water washing also has a low content of impurities, an alkali solution is added to the filtrate in a mixing tank and used for the above alkali washing. That is, in the alkali washing and the water washing, multi-stage countercurrent washing is performed. By performing such multi-stage countercurrent cleaning, the treatment of impurities in the calcium fluoride residue is continuously performed with high efficiency.

【００２３】このようなアルカリ洗浄及び／又は水洗の
多段向流洗浄は、上記に限らず、例えばフィルタープレ
スでの切り替えによる機内洗浄や多段向流シックナーに
採用してもよく、上記と同様に行われる。The multi-stage countercurrent washing of the alkali washing and / or water washing is not limited to the above, and may be employed in, for example, in-machine washing by switching with a filter press or a multi-stage countercurrent thickener. Will be

【００２４】このようにして、鉛、亜鉛、イオウが大幅
に低減されたフッ化カルシウムが得られる。このフッ化
カルシウムは、鉄鋼の製鋼工程におけるフッ化カルシウ
ム原料として好適に使用できる。特に、フッ化カルシウ
ム中の鉛、亜鉛、イオウ含有量はそれぞれ０．１重量％
以下とすることが望ましい。[0024] In this way, calcium fluoride having significantly reduced lead, zinc and sulfur can be obtained. This calcium fluoride can be suitably used as a calcium fluoride raw material in a steelmaking process of steel. In particular, the contents of lead, zinc and sulfur in calcium fluoride are each 0.1% by weight.
It is desirable to make the following.

【００２５】[0025]

【実施例】以下、本発明を実施例等に基づき具体的に説
明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments and the like.

【００２６】〔実施例１〜３〕図１に基づいて、脱塩素
散水により脱塩素した製鋼煙灰に石炭と水を加え、ロッ
ドミル及び製団機においてペレット化し、これを還元揮
発炉で焙焼し、バックフィルターにおいて粗酸化亜鉛粉
末を回収した。この粗酸化亜鉛粉末中には、亜鉛６１．
７重量％、鉛９．０９重量％、塩素３．５４重量％、フ
ッ素０．９重量％、イオウ１．０７重量％が含まれてい
た。[Examples 1 to 3] Based on FIG. 1, coal and water are added to steelmaking smoke ash dechlorinated by dechlorination and sprinkling, pelletized in a rod mill and a sizing machine, and roasted in a reduction volatilization furnace. The crude zinc oxide powder was recovered in a back filter. In this crude zinc oxide powder, zinc 61.
It contained 7% by weight, 9.09% by weight of lead, 3.54% by weight of chlorine, 0.9% by weight of fluorine and 1.07% by weight of sulfur.

【００２７】脱ハロゲン処理槽中に導入された水酸化ナ
トリウム溶液中に、この粗酸化亜鉛粉末を投入し、水酸
化ナトリウム導入量を調節することによって、スラリー
のｐＨを１２に保持しながら、６０℃で２時間撹拌を行
った。The crude zinc oxide powder is introduced into the sodium hydroxide solution introduced into the dehalogenation treatment tank, and the pH of the slurry is maintained at 12 by adjusting the amount of sodium hydroxide introduced. Stirring was performed for 2 hours at ° C.

【００２８】次いで、フィルタープレスで固液分離さ
れ、さらに水酸化ナトリウム洗浄、水洗を行った。脱ハ
ロゲン粗酸化亜鉛粉末はその後、乾燥を行った。Next, the mixture was separated into solid and liquid by a filter press, and further washed with sodium hydroxide and water. Thereafter, the dehalogenated crude zinc oxide powder was dried.

【００２９】脱ハロゲン濾液は、上記の脱塩素した脱塩
素水と共に、脱フッ素処理槽に導入された。この脱ハロ
ゲン濾液中には、鉛６００ｐｐｍ、亜鉛５０ｐｐｍ、フ
ッ素２０００ｐｐｍが含まれていた。The dehalogenated filtrate was introduced into a defluorination treatment tank together with the dechlorinated dechlorinated water described above. This dehalogenated filtrate contained 600 ppm of lead, 50 ppm of zinc, and 2000 ppm of fluorine.

【００３０】この脱フッ素残渣処理槽において、脱ハロ
ゲン濾液と脱塩素水とを混合し、フッ化カルシウムを主
成分とするフッ化カルシウム残渣を生成させた。また、
この脱フッ素残渣処理槽は、水酸化ナトリウムを添加す
ることによってｐＨを９．５に維持した。このフッ化カ
ルシウム残渣中には、不純物として鉛５．０重量％、亜
鉛０．５重量％、イオウ２．９重量％が含まれていた。In this defluoridation residue treatment tank, the dehalogenated filtrate and dechlorinated water were mixed to form a calcium fluoride residue containing calcium fluoride as a main component. Also,
The pH of the defluoridation residue treatment tank was maintained at 9.5 by adding sodium hydroxide. The calcium fluoride residue contained 5.0% by weight of lead, 0.5% by weight of zinc, and 2.9% by weight of sulfur as impurities.

【００３１】次いで、フッ化カルシウム残渣を含むスラ
リーは、フィルタープレスで固液分離され、さらに水酸
化ナトリウム洗浄、水洗を逐次バッチ式で行った。フッ
化カルシウムはその後、乾燥を行った。この際のアルカ
リ洗浄液のｐＨをそれぞれ１１（実施例１）、１２（実
施例２）、１３（実施例３）とした。バッチ式における
アルカリ洗浄後のフッ化カルシウム中の鉛、亜鉛、イオ
ウの含有量を表１に示す。Next, the slurry containing the calcium fluoride residue was subjected to solid-liquid separation by a filter press, and washing with sodium hydroxide and washing with water were successively performed in batch mode. The calcium fluoride was then dried. At this time, the pH of the alkaline cleaning liquid was set to 11 (Example 1), 12 (Example 2), and 13 (Example 3), respectively. Table 1 shows the contents of lead, zinc, and sulfur in calcium fluoride after alkali washing in a batch system.

【００３２】[0032]

【表１】 [Table 1]

【００３３】表１の結果から明らかなように、バッチ式
において、実施例１〜３は、アルカリ洗浄後のフッ化カ
ルシウム中の不純物（鉛、亜鉛、イオウ）濃度が低減さ
れており、特にスラリーのｐＨを１３とした実施例３
は、この傾向が顕著である。このフッ化カルシウムは、
鉄鋼の製鋼工程におけるフッ化カルシウム原料として使
用できる。As is evident from the results in Table 1, in the batch method, Examples 1 to 3 show that the concentration of impurities (lead, zinc, and sulfur) in calcium fluoride after the alkali washing is reduced. Example 3 in which the pH of water was 13
This tendency is remarkable. This calcium fluoride
It can be used as a raw material for calcium fluoride in the steelmaking process of steel.

【００３４】〔実施例４及び５〕上記で得られたフィル
タープレスされたフッ化カルシウム残渣について、水酸
化ナトリウム洗浄、水洗を図２のフローに基づいて多段
向流洗浄を行った。フッ化カルシウムはその後、乾燥を
行った。この際のアルカリ洗浄液のｐＨをそれぞれ１１
（実施例４）、１３（実施例５）とした。多段向流洗浄
後のフッ化カルシウム中の鉛、亜鉛、イオウの含有量を
表２に示す。Examples 4 and 5 The filter-pressed calcium fluoride residue obtained above was washed with sodium hydroxide and washed with water in a multistage countercurrent manner based on the flow shown in FIG. The calcium fluoride was then dried. At this time, the pH of the alkaline cleaning solution was set
(Example 4) and 13 (Example 5). Table 2 shows the contents of lead, zinc and sulfur in the calcium fluoride after the multi-stage countercurrent washing.

【００３５】[0035]

【表２】 [Table 2]

【００３６】表２の結果から、多段向流洗浄を行った実
施例４及び５は、フッ化カルシウム中の不純物濃度を大
幅に低減することができる。また、上記のように、水酸
化ナトリウム（アルカリ）洗浄及び水洗を連続的に多段
向流洗浄することによって、バッチ式の洗浄に比べて、
アルカリの必要量をバッチ式の洗浄に比べて１／２程度
することができるため、非常に効率的にアルカリ洗浄を
行うことができる。From the results shown in Table 2, in Examples 4 and 5 in which multi-stage countercurrent cleaning was performed, the impurity concentration in calcium fluoride can be significantly reduced. Further, as described above, by performing sodium hydroxide (alkali) washing and water washing continuously in multi-stage countercurrent washing, compared with batch-type washing,
Since the required amount of alkali can be reduced to about １ ／ compared with the batch type cleaning, the alkali cleaning can be performed very efficiently.

【００３７】[0037]

【発明の効果】以上説明したように、本発明の処理方法
によって、製鋼煙灰を原料とし、粗酸化亜鉛粉末を回収
する工程において、生成するフッ化カルシウム残渣中の
不純物を除去できる。従って、このフッ化カルシウム
は、鉄鋼の製鋼工程における蛍石に代わるフッ化カルシ
ウム原料として好適に使用できる。また、従来放置され
ていたフッ化カルシウム残渣を再利用することがで可能
なので、省資源に寄与することができる。特に、多段向
流洗浄を行うことによって、高い効率性をもって連続的
にフッ化カルシウム残渣中の不純物を除去できる。As described above, according to the treatment method of the present invention, impurities in the generated calcium fluoride residue can be removed in the step of recovering crude zinc oxide powder from steelmaking smoke ash as a raw material. Therefore, this calcium fluoride can be suitably used as a calcium fluoride raw material instead of fluorite in the steelmaking process of steel. In addition, since the calcium fluoride residue that has been conventionally left can be reused, it is possible to contribute to resource saving. In particular, by performing the multi-stage countercurrent cleaning, impurities in the calcium fluoride residue can be continuously removed with high efficiency.

【図面の簡単な説明】[Brief description of the drawings]

【図１】図１は、製鋼煙灰から粗酸化鉛粉末を回収し、
濾液を処理する工程を示す概略フロー図である。FIG. 1 is a diagram illustrating a method for recovering crude lead oxide powder from steelmaking smoke ash.
FIG. 4 is a schematic flowchart showing a step of treating a filtrate.

【図２】図２は、アルカリ洗浄及び水洗における多段向
流洗浄の詳細を示すフロー図である。FIG. 2 is a flowchart showing details of multi-stage countercurrent cleaning in alkali cleaning and water cleaning.

フロントページの続き Ｆターム(参考） 4D004 AA43 AA50 AB03 AB10 AC05 BA05 CA10 CA14 CA30 CA34 CA35 CA37 CC11 CC12 4K001 AA10 AA20 AA30 AA42 BA14 CA16 CA25 DA06 DB08 DB23 DB37 4K056 AA12 AA16 CA06 CA20 Continued on the front page F term (reference) 4D004 AA43 AA50 AB03 AB10 AC05 BA05 CA10 CA14 CA30 CA34 CA35 CA37 CC11 CC12 4K001 AA10 AA20 AA30 AA42 BA14 CA16 CA25 DA06 DB08 DB23 DB37 4K056 AA12 AA16 CA06 CA20

Claims (3)

【特許請求の範囲】[Claims] 【請求項１】 製鋼煙灰に石灰水を脱塩素散水すること
によって得られたカルシウムを含有する脱塩素水と、製
鋼煙灰に炭素材料と水を加えてペレット化し、これを還
元揮発炉で焙焼した後、粗酸化亜鉛粉末を回収し、該粗
酸化亜鉛粉末をアルカリ溶液中に投入してｐＨを１０以
上に保持しながら撹拌し、その後濾別して得られたフッ
素を含有する脱ハロゲン水とを反応させて得られたフッ
化カルシウム残渣をアルカリ溶液中に投入して、ｐＨを
１１以上に保持しながら撹拌し、さらにアルカリ洗浄、
水洗、乾燥し、該フッ化カルシウム残渣中の不純物を除
去することを特徴とする残渣の処理方法。Claims: 1. A dechlorinated water containing calcium obtained by dechlorinating lime water on steelmaking ash, and a carbon material and water added to the steelmaking ash to pelletize and roast in a reduction volatilization furnace. After that, the crude zinc oxide powder is recovered, and the crude zinc oxide powder is poured into an alkaline solution, stirred while maintaining the pH at 10 or more, and then filtered to remove fluorine-containing dehalogenated water. The calcium fluoride residue obtained by the reaction is put into an alkaline solution, and the mixture is stirred while maintaining the pH at 11 or more.
A residue treatment method, comprising washing with water and drying to remove impurities in the calcium fluoride residue. 【請求項２】 上記アルカリ洗浄及び／又は水洗を多段
向流洗浄で行う請求項１記載の残渣の処理方法。2. The method for treating a residue according to claim 1, wherein said alkali washing and / or water washing is performed by multi-stage countercurrent washing. 【請求項３】 上記不純物が鉛、亜鉛及びイオウである
請求項１又は２記載の残渣の処理方法。3. The method according to claim 1, wherein the impurities are lead, zinc and sulfur.
JP31091698A 1998-10-30 1998-10-30 Treatment of residue Pending JP2000135480A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002285255A (en) * 2001-03-28 2002-10-03 Sumitomo Metal Mining Co Ltd Method for manufacturing zinc oxide calcine or zinc oxide briquette
JP2002332529A (en) * 2001-05-07 2002-11-22 Sumitomo Metal Mining Co Ltd Method for removing fluorine from crude zinc oxide
TWI511792B (en) * 2012-11-26 2015-12-11 A method for wet sorting mineral powders with multiple impurities
CN105188968A (en) * 2013-03-22 2015-12-23 新日铁住金不锈钢株式会社 Dust cleaning device and dust cleaning method
CN113787088A (en) * 2021-10-29 2021-12-14 深圳市龙岗区东江工业废物处置有限公司 CVD dust treatment method
US11512368B2 (en) 2017-04-06 2022-11-29 Montanuniversität Leoben Method for removing fluoride from a zinc-containing solution or suspension, defluoridated zinc sulfate solution and use thereof, and method for producing zinc and hydrogen fluoride or hydrofluoric acid

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002285255A (en) * 2001-03-28 2002-10-03 Sumitomo Metal Mining Co Ltd Method for manufacturing zinc oxide calcine or zinc oxide briquette
JP4506017B2 (en) * 2001-03-28 2010-07-21 住友金属鉱山株式会社 Method for producing zinc oxide sinter or zinc oxide briquette
JP2002332529A (en) * 2001-05-07 2002-11-22 Sumitomo Metal Mining Co Ltd Method for removing fluorine from crude zinc oxide
TWI511792B (en) * 2012-11-26 2015-12-11 A method for wet sorting mineral powders with multiple impurities
CN105188968A (en) * 2013-03-22 2015-12-23 新日铁住金不锈钢株式会社 Dust cleaning device and dust cleaning method
US11512368B2 (en) 2017-04-06 2022-11-29 Montanuniversität Leoben Method for removing fluoride from a zinc-containing solution or suspension, defluoridated zinc sulfate solution and use thereof, and method for producing zinc and hydrogen fluoride or hydrofluoric acid
CN113787088A (en) * 2021-10-29 2021-12-14 深圳市龙岗区东江工业废物处置有限公司 CVD dust treatment method

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