JP6373257B2 - Dust cleaning method - Google Patents
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- JP6373257B2 JP6373257B2 JP2015506863A JP2015506863A JP6373257B2 JP 6373257 B2 JP6373257 B2 JP 6373257B2 JP 2015506863 A JP2015506863 A JP 2015506863A JP 2015506863 A JP2015506863 A JP 2015506863A JP 6373257 B2 JP6373257 B2 JP 6373257B2
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- 239000000428 dust Substances 0.000 title claims description 138
- 238000004140 cleaning Methods 0.000 title claims description 81
- 238000000034 method Methods 0.000 title claims description 51
- 229910052731 fluorine Inorganic materials 0.000 claims description 98
- 239000011737 fluorine Substances 0.000 claims description 98
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 94
- 239000002002 slurry Substances 0.000 claims description 64
- 239000007788 liquid Substances 0.000 claims description 37
- 238000005406 washing Methods 0.000 claims description 25
- 239000011701 zinc Substances 0.000 claims description 24
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 23
- 229910052725 zinc Inorganic materials 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052793 cadmium Inorganic materials 0.000 claims description 16
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 16
- 238000010790 dilution Methods 0.000 claims description 11
- 239000012895 dilution Substances 0.000 claims description 11
- 229910001385 heavy metal Inorganic materials 0.000 claims description 8
- -1 Fluorine ions Chemical class 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000002386 leaching Methods 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000010813 municipal solid waste Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
- Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Description
本発明は、金属製錬過程において、排出されるダスト等を亜鉛精錬用原料としてリサイクルするために必要な、ダスト類の洗浄処理に使用するダスト洗浄方法に関する。 The present invention provides a metal smelting process, required to recycle the dust discharged as zinc refining raw material, to dust washing method used in the cleaning process of the dust types.
普通鋼、ステンレス鋼を製造する際に発生するダスト、スケール、スラッジなどは、回転炉床炉や電気抵抗炉などの金属還元炉を用いて、金属成分を還元再利用している。 Dust, scale, sludge, etc. generated in the production of ordinary steel and stainless steel are reduced and reused using a metal reduction furnace such as a rotary hearth furnace or an electric resistance furnace.
その際に、金属還元炉から発生するダスト中には、重金属成分として亜鉛、鉛、カドミウムを含み、さらに、フッ素が２％以上に濃縮されるが、ダスト中のフッ素や塩素などのハロゲンは、炉中でフッ化水素や塩化水素となって、炉体を構成する耐火物を損傷するため、ダストを亜鉛製錬用原料としてリサイクルを可能にするためには、これらのハロゲン、特にフッ素を除去する必要があった。
本発明は、亜鉛精錬用原料のダストからフッ素等を洗浄除去する処理に用いる洗浄装置及び洗浄方法に関する。At that time, the dust generated from the metal reduction furnace contains zinc, lead and cadmium as heavy metal components, and further fluorine is concentrated to 2% or more, but halogens such as fluorine and chlorine in the dust are Since it becomes hydrogen fluoride and hydrogen chloride in the furnace and damages the refractories that make up the furnace body, in order to make it possible to recycle dust as a raw material for zinc smelting, these halogens, especially fluorine, are removed. There was a need to do.
The present invention relates to a cleaning apparatus and a cleaning method used for a process of cleaning and removing fluorine and the like from dust of a zinc refining raw material.
一般に、事業場や一般家庭から排出されるゴミ（「都市ゴミ」又は「一般廃棄物」と称されている。）は、都市ゴミ焼却場や産業廃棄物焼却工場等に集められ焼却処分されている。その際に焼却炉等から発生する焼却灰や飛灰（一次ダストともいう。）は、薬剤処理、又は、溶融炉、セメントキルン処理等の中間処理を施した後に最終処分場に堆積される。 Generally, trash discharged from business establishments and general households (referred to as “city trash” or “general waste”) is collected and incinerated at city trash incineration plants and industrial waste incineration plants. Yes. Incineration ash and fly ash (also referred to as primary dust) generated from the incinerator and the like at that time are deposited in the final disposal site after performing chemical treatment or intermediate treatment such as melting furnace and cement kiln treatment.
また、製鉄精錬時に発生する鉄分主体の一次ダスト（例えば、転炉ダストＴ：Ｆｅ分約６０％）は、回転炉床炉（回転炉床式還元炉、例えば、特許文献１）や還元溶融ロータリーキルン炉（例えば、特許文献２）等の還元炉で還元されて、還元鉄が製造されている。 Moreover, primary dust (for example, converter dust T: Fe content of about 60%) generated during iron refining is a rotary hearth furnace (rotary hearth type reducing furnace, for example, Patent Document 1) or a reduction melting rotary kiln. Reduced iron is produced by reduction in a reduction furnace such as a furnace (for example, Patent Document 2).
しかしながら、前記の溶融炉やセメントキルン処理等の中間処理や製鉄ダスト用の回転炉床炉等の還元炉では、蒸気圧の高い亜鉛、鉛、カドミウム等の重金属が、炉内で揮発して排ガス中に入り、この排ガスに入った重金属は排ガス処理設備内で凝縮して再び飛灰（以降、二次ダストまたは単にダストという。）となってしまう。 However, in reduction furnaces such as intermediate furnaces such as the above melting furnaces and cement kiln processes and rotary hearth furnaces for ironmaking dust, heavy metals such as zinc, lead, and cadmium with high vapor pressure volatilize in the furnace and exhaust gases. The heavy metal that enters the exhaust gas is condensed in the exhaust gas treatment facility and becomes fly ash (hereinafter referred to as secondary dust or simply dust).
この二次ダスト中には、塩素、フッ素、ナトリウム、カリウムと共に、亜鉛、鉛、カドミウム等の重金属が濃縮されて多量に含有されており、これらの回収を含めた安定した二次ダストの処理装置および処理方法が求められていた。 This secondary dust contains a large amount of heavy metals such as zinc, lead, and cadmium along with chlorine, fluorine, sodium, and potassium, and a stable secondary dust treatment system including recovery of these metals. And a processing method was sought.
この二次ダスト中の亜鉛を回収する手段として、ダストを亜鉛製錬の原料として、主原料である亜鉛精鉱等と混合し、使用する方法がある。この場合、二次ダスト中のフッ素や塩素がフッ化水素、塩化水素のガスになり、耐火物を劣化させるという問題があり、配合率を抑制せねばならないという課題があった。 As a means for recovering zinc in the secondary dust, there is a method in which dust is used as a raw material for zinc smelting and mixed with zinc concentrate as a main raw material. In this case, there is a problem that fluorine or chlorine in the secondary dust becomes a gas of hydrogen fluoride or hydrogen chloride, deteriorating the refractory, and there is a problem that the blending ratio must be suppressed.
これに対し、従来技術として、アルカリ浸出処理（特許文献３、特許文献４）が開示されている。特許文献３では、アルカリ剤を用いてｐＨ１２以上に調整した後、固液分離することにより、重金属含有澱物を得ることが開示されている。該処理では、アルカリ浸出処理後の回収殿物中の塩素濃度は、回収殿物中の液相部分を水洗し、塩素を含んだ液相部を洗い流すと、４０％から３％以下に低減できることが示されているが、フッ素の低減効果については開示されていない。
On the other hand, alkali leaching treatment (
特許文献４では、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、さらにアルカリ洗浄、水洗、乾燥することにより、該粗酸化亜鉛粉末中のハロゲン元素を除去することが示されており、フッ素は１．０％から０．３％以下に低減できることが示されているが、フッ素を２％以上含むダストの処理は考えられていない。 In Patent Document 4, the crude zinc oxide powder is put into an alkaline solution, stirred while maintaining the pH at 10 or more, and further washed with alkali, washed with water, and dried, so that the halogen element in the crude zinc oxide powder is reduced. Although it has been shown that fluorine can be reduced from 1.0% to 0.3% or less, treatment of dust containing 2% or more of fluorine is not considered.
二次ダスト中のフッ素は、形成している化合物の種類によって、アルカリ溶液への浸出速度は大きく変動する。また、二次ダスト中のフッ素濃度は、二次ダストが発生する炉の操業状態によって大きく変動する。しかしながら、特許文献３および特許文献４では、このような浸出速度の差、濃度の差が大きい二次ダストでの処理装置、処理方法についての記載はない。
The leaching rate of the fluorine in the secondary dust into the alkaline solution varies greatly depending on the type of compound formed. Further, the fluorine concentration in the secondary dust varies greatly depending on the operation state of the furnace in which the secondary dust is generated. However,
特に、ステンレス鋼および特殊鋼の製造工程では、製鋼工程での蛍石（主成分ＣａＦ2）、酸洗工程でのフッ酸の使用により、製鋼ダスト、および酸洗廃液を中和処理した場合のスラッジに多量のフッ素を含む。そのため、これらを回転炉床炉や溶融炉で処理した場合の二次ダストは２％以上のフッ素を含むことになる。In particular, in the production process of stainless steel and special steel, the use of fluorite (main component CaF 2 ) in the steelmaking process, and the use of hydrofluoric acid in the pickling process, neutralizes the steelmaking dust and pickling waste liquid. Sludge contains a large amount of fluorine. Therefore, the secondary dust when these are processed in a rotary hearth furnace or a melting furnace contains 2% or more of fluorine.
フッ素を２％以上含むダストは、効率的な洗浄装置、洗浄方法がなければ、長時間の洗浄、および多数回の洗浄を行うことになり、洗浄廃液量が増し、工程数も増えて、処理にかかるコストが非常に高くなるという課題があったが、これまでに、このようなダストの浸出処理を効率的に行う洗浄装置、洗浄方法に関する技術の開示はない。 If there is no efficient cleaning equipment and cleaning method, dust containing 2% or more of fluorine will be cleaned for a long time and many times, increasing the amount of cleaning waste liquid and increasing the number of processes. However, there has been no disclosure of a technique related to a cleaning apparatus and a cleaning method for efficiently performing such a leaching process for dust.
そこで、本発明は、上記問題に鑑み、金属成分として亜鉛、鉛、カドミウムを含み、さらに、フッ素を２％以上含有するダスト中のフッ素を安定的、効率的に低減させるためのダスト洗浄方法を提供することを目的とする。 The present invention has been made in view of the above problems, the zinc metal component comprises lead, cadmium, further, dust cleaning method for reducing fluorine stable fluorine in the dust containing 2% or more, efficiently The purpose is to provide.
前記の課題を解決するには、以下の点が必要、かつ重要となる。
（Ｉ）アルカリ領域でフッ素化合物を溶解し、ダストに含有されるフッ素を洗浄液に浸出させるために必要な条件と装置、併せて有価金属である亜鉛成分を浸出させない条件と検知する装置を明確にする。
（ＩＩ）洗浄液中のフッ素飽和濃度、および洗浄液へのフッ素浸出の終点の判別方法と必要な装置を明確にする。
（ＩＩＩ）アルカリ領域でフッ素をダストから浸出させた場合、廃液の処理上の負荷となるカドミウム成分をダストから浸出させない条件と検知する装置を明確にする。
本発明は、上記条件及び判別方法を明らかにしたものであり、その要旨とするところは以下の通りである。
（１） 本発明の一態様に係るダスト洗浄方法は、重金属成分として亜鉛、鉛、カドミウムを含み、さらに、フッ素を２％以上含有するダストと、洗浄液とを混合してスラリーとし、当該ダストからフッ素を前記洗浄液中に浸出させて洗浄するダスト洗浄方法であって、
前記ダスト洗浄方法は、前記スラリーのｐＨ値を１０〜１３とし、前記スラリー中の前記ダストの希釈率を一定にして、前記スラリー中のフッ素イオン濃度の未飽和状態における前記スラリーのフッ素イオン濃度と、前記ダストのフッ素濃度との相関関係を予め把握する工程と、
前記スラリーのフッ素イオン濃度が、前記相関関係が把握されたスラリー中のダストの希釈率において、前記洗浄対象のダストの目標のフッ素濃度に対応する前記スラリーの目標のフッ素イオン濃度になるまで、洗浄対象のダストが混合されたスラリーのｐＨ値を１０〜１３の範囲に制御しつつ、前記予め把握された相関関係における前記ダストの希釈率の範囲内で前記洗浄水を添加する工程、又は、前記スラリーの上澄み液を排水し、排水完了後、予め把握された前記ダストの希釈率の範囲内において前記洗浄水を添加する工程のいずれかの工程を１回以上行うことにより、前記スラリーのフッ素イオン濃度を前記目標のフッ素イオン濃度以下にすることを特徴としている。
（２） 本発明の一態様に係るダスト洗浄方法は、（１）に記載のダスト洗浄方法において、ダストを回収する前のスラリーのフッ素イオン濃度が５００ｍｇ/ｌ以下になるまで前記洗浄工程を１回実施または２回以上繰り返して実施するものである、
また、洗浄工程におけるｐＨ値の条件は、異なる洗浄工程毎にｐＨ値が１０〜１３の範囲内になるようにそれぞれ異なる範囲に設定しても良い。
また、図４に示されるように、スラリーのフッ素濃度が最終的に１０００ｍｇ／ｌ以下になるように制御することによって、洗浄後のダストのフッ素濃度を１．０％以下にすることができる。或いは、スラリーのフッ素濃度が最終的に５００ｍｇ／ｌ以下になるように制御することによって、洗浄後のダストのフッ素濃度を０．５％以下にすることができる。
In order to solve the above problems, the following points are necessary and important.
(I) The conditions and equipment necessary to dissolve the fluorine compound in the alkaline region and leaching fluorine contained in the dust into the cleaning liquid, as well as the equipment to detect that the zinc component, which is a valuable metal, is not leached. To do.
(II) Clarify the fluorine saturation concentration in the cleaning liquid and the method for determining the end point of fluorine leaching into the cleaning liquid and the necessary equipment.
(III) When fluorine is leached from dust in an alkaline region, a device for detecting that the cadmium component, which is a burden on the treatment of waste liquid, is not leached from dust is clarified.
The present invention clarifies the above conditions and determination method, and the gist thereof is as follows.
(1 ) A dust cleaning method according to one embodiment of the present invention includes zinc, lead, and cadmium as heavy metal components, and further, dust containing 2% or more of fluorine and a cleaning liquid are mixed to form a slurry, A dust cleaning method in which fluorine is leached into the cleaning liquid and cleaned.
In the dust cleaning method, the pH value of the slurry is 10 to 13, the dilution rate of the dust in the slurry is constant, and the fluorine ion concentration of the slurry in the unsaturated state of the fluorine ion concentration in the slurry is , A step of grasping in advance the correlation with the fluorine concentration of the dust,
Cleaning is performed until the fluorine ion concentration of the slurry reaches the target fluorine ion concentration of the slurry corresponding to the target fluorine concentration of the dust to be cleaned at the dilution ratio of dust in the slurry whose correlation has been grasped. The step of adding the washing water within the range of the dilution rate of the dust in the correlation obtained in advance while controlling the pH value of the slurry mixed with the target dust in the range of 10-13, or Fluorine ions of the slurry are drained by draining the supernatant of the slurry and performing one or more of the steps of adding the washing water within the range of the dilution rate of the dust obtained in advance after draining is completed. The concentration is set to be equal to or lower than the target fluorine ion concentration.
( 2 ) The dust cleaning method according to one aspect of the present invention is the dust cleaning method according to ( 1 ), wherein the cleaning step is performed until the fluorine ion concentration of the slurry before collecting the dust becomes 500 mg / l or less. Repeated or repeated two or more times,
Moreover, you may set the conditions of the pH value in a washing | cleaning process to a different range so that pH value may exist in the range of 10-13 for every different washing | cleaning process.
Further, as shown in FIG. 4, the fluorine concentration of the dust after cleaning can be reduced to 1.0% or less by controlling the fluorine concentration of the slurry to be finally 1000 mg / l or less. Alternatively, the fluorine concentration of the dust after cleaning can be reduced to 0.5% or less by controlling the fluorine concentration of the slurry to be finally 500 mg / l or less.
本発明によれば、還元鉄製造過程から排出されるダストや、都市ゴミ二次ダスト等のフッ素の含有量の高いダストから、環境に対して低負荷で、フッ素を安定して洗浄除去して低フッ素含有量とすることができ、該ダストを亜鉛製錬原料として、有効利用することができる洗浄装置及び洗浄方法を提供することができる。 According to the present invention, it is possible to stably wash and remove fluorine from dust discharged from the reduced iron production process and dust having a high fluorine content such as municipal waste secondary dust with low environmental impact. It is possible to provide a cleaning apparatus and a cleaning method that can have a low fluorine content and can effectively use the dust as a raw material for zinc smelting.
以下、本発明のダスト洗浄方法について詳細に説明する。まず、本発明の洗浄方法におけるｐＨ値及びフッ素飽和濃度の要件について説明する。 It will be described in detail dust washing method of the present invention. First, a description will be given pH value and fluorine saturation concentration requirements in washing method of the present invention.
図１に水溶液中のｐＨと各種金属イオン濃度の関係を示す。亜鉛と鉛はｐＨ９．２付近で最も溶解度が小さく、カドミウムはｐＨ１１．２付近で最も溶解度が小さいことが図示されている。 FIG. 1 shows the relationship between pH and various metal ion concentrations in an aqueous solution. It is illustrated that zinc and lead have the lowest solubility near pH 9.2, and cadmium has the lowest solubility near pH 11.2.
前記（Ｉ）の観点から、次の実験を行った。図２にフッ素濃度４．６％のダスト２０ｇに水（洗浄液または浸出液とも言う。）４００ｍｌを入れ、撹拌してスラリーにした後に、２０％水酸化ナトリウム水溶液で、該スラリーのｐＨをｐＨ計で監視しながら調整し、３０分撹拌を行ったときのスラリーのｐＨとダスト中フッ素濃度の関係を示す。スラリーのｐＨが高くなるほど、フッ素濃度は低くなっている。 The following experiment was performed from the viewpoint of (I). In FIG. 2, 400 ml of water (also referred to as a cleaning solution or a leachate) is added to 20 g of dust having a fluorine concentration of 4.6%, and after stirring to make a slurry, the pH of the slurry is adjusted with a pH meter with a 20% aqueous sodium hydroxide solution. It shows the relationship between the pH of the slurry and the fluorine concentration in the dust when adjusted while monitoring and stirring for 30 minutes. The higher the pH of the slurry, the lower the fluorine concentration.
これらの関係より、ｐＨ計を装備し、スラリーのｐＨ制御を行えば、スラリーの金属成分濃度およびフッ素濃度を制御できることがわかる。ダストからフッ素を浸出させ、除去するには、ｐＨを高くすれば良いが、一方、回収すべき亜鉛、鉛、カドミウムも浸出することになる。例えば、ｐＨ１２．５では亜鉛の溶解度は３ｍｇ/ｌ、鉛の溶解度は７００ｍｇ/ｌであり、洗浄液の量が多ければ、ダストから亜鉛、鉛が浸出し、ロスが大きくなる。そのため洗浄液の量をできるだけ、少なくすることが必要になる。 From these relationships, it can be seen that the metal component concentration and the fluorine concentration of the slurry can be controlled by providing a pH meter and controlling the pH of the slurry. In order to leach and remove fluorine from dust, the pH may be increased, while zinc, lead and cadmium to be recovered also leach out. For example, at a pH of 12.5, the solubility of zinc is 3 mg / l and the solubility of lead is 700 mg / l. If the amount of cleaning liquid is large, zinc and lead are leached from the dust and the loss increases. Therefore, it is necessary to reduce the amount of the cleaning liquid as much as possible.
なお、ダストを、ＮａＯＨを加えた高アルカリの洗浄液に入れると、式１および式２に示す脱ハロゲン反応が進行する。
ＰｂＣｌＦ＋２ＮａＯＨ ⇒ Ｐｂ（ＯＨ）2＋ＮａＣｌ＋ＮａＦ （式１）
ＫＺｎＦ3＋２ＮａＯＨ ⇒ Ｚｎ（ＯＨ）2＋ＫＦ＋２ＮａＦ （式２）Note that when the dust is put into a highly alkaline cleaning solution to which NaOH is added, the dehalogenation reaction shown in
PbClF + 2NaOH => Pb (OH) 2 + NaCl + NaF (Formula 1)
KZnF 3 + 2NaOH⇒Zn (OH) 2 + KF + 2NaF (Formula 2)
つまり、アルカリ剤であるＮａＯＨを消費しながら、反応が進む。そのため、スラリーのｐＨが低下する。前記ｐＨを一定に制御するには、ＮａＯＨのようなアルカリ剤を投入する制御装置が必要になる。また、ｐＨの変化がなくなり、ｐＨ制御が不要になった時点が浸出反応の終点と考えられる。 That is, the reaction proceeds while consuming NaOH which is an alkaline agent. Therefore, the pH of the slurry is lowered. In order to control the pH to be constant, a control device for introducing an alkaline agent such as NaOH is required. In addition, it is considered that the end point of the leaching reaction is a point in time when pH change is eliminated and pH control becomes unnecessary.
次に、前記（ＩＩ）の観点から、スラリー中のフッ素濃度の測定に関して述べる。フッ素濃度の測定には、一般的な方法を採用することができ、例えば市販のフッ素イオン電極を用いた方法を用いることが出来る。 Next, the measurement of the fluorine concentration in the slurry will be described from the viewpoint of (II). For the measurement of the fluorine concentration, a general method can be employed. For example, a method using a commercially available fluorine ion electrode can be used.
フッ素濃度６．６％のダスト５０ｇ、１００ｇ、１５０ｇをそれぞれ別々の容器に分取して、それぞれの容器内に洗浄液として水４００ｍｌを入れ、撹拌してスラリーにした後、該スラリーに２０％水酸化ナトリウム水溶液を加えて、該スラリーのｐＨを１１．５に狙い、ｐＨ計で監視しながら調整した。図３に、フッ素イオン電極を用いてフッ素イオン濃度を測定、記録した結果を示す。同図より、ダスト量が多いほど、フッ素濃度が高くなるが、１００ｇと１５０ｇでは大きな差はない。１２０００ｍｇ／ｌ近傍で飽和している。つまり、例えば、１１０００ｍｇ/ｌになった時点でこの処理を終了すれば、短時間の効率的なフッ素の浸出処理が行えることになる。
この後、スラリーを固液分離し、フッ素が浸出したダストを回収する。固液分離方法は特に限定されない。例えばスラリーに凝固剤を投入して、ダストが沈殿した後、上澄み液を廃棄してダストを回収することができる。
以上のフッ素を浸出させたダストを回収するまでの一連の処理を、本発明において「洗浄処理」とよぶ。
Thereafter, the slurry is subjected to solid-liquid separation, and the dust leached with fluorine is collected. The solid-liquid separation method is not particularly limited. For example, after a coagulant is added to the slurry and the dust settles, the supernatant liquid can be discarded and the dust can be recovered.
A series of processes until the dust from which the fluorine is leached is collected is called “cleaning process” in the present invention.
なお、スラリーのフッ素の飽和濃度は、スラリーのｐＨ、ダストの組成により変化して、９０００〜１４０００ｍｇ/ｌの範囲にあることを確認した。また、飽和濃度に達する時間はダストの組成および装置の撹拌条件により変化して、例えば、ダスト中のカルシウム濃度が高い場合は時間が長くなる。これは、ダスト内に強固な結合を持つＣａＦ2が生成していることに起因すると考えられる。In addition, it confirmed that the saturation density | concentration of the fluorine of a slurry changed with pH of a slurry, and the composition of dust, and was in the range of 9000-14000 mg / l. The time to reach the saturation concentration varies depending on the dust composition and the stirring conditions of the apparatus. For example, when the calcium concentration in the dust is high, the time becomes longer. This is considered to be caused by the generation of CaF 2 having a strong bond in the dust.
図３より、浸出処理を行ったスラリーからダストの固液分離を行って回収した洗浄処理後のダストは多くの水分を含み、その水分中にはアルカリ起因であるナトリウムイオンと共に、フッ素イオンを多量に含んでいることになる。この洗浄処理後のダストをさらに洗浄処理することで、これらの元素を洗い流すことが可能である。その際、ｐＨ調整を行っていない洗浄液（例えば水道水）を使用すると、ダストを洗浄している間に、ｐＨ低下が起こり、亜鉛、鉛、カドミウム等の金属が浸出して、濃度低下を招く。 As shown in FIG. 3, the dust after the washing process recovered from the leached slurry by solid-liquid separation contains a lot of moisture, and the moisture contains a large amount of fluorine ions together with sodium ions caused by alkali. Will be included. By further washing the dust after the washing treatment, these elements can be washed away. At that time, if a cleaning solution (for example, tap water) that has not been adjusted for pH is used, the pH is lowered while dust is being washed, and metals such as zinc, lead, and cadmium are leached, leading to a decrease in concentration. .
図１より、カドミウムの浸出が起こらない範囲はｐＨ１０〜１３．５である。この範囲であれば、カドミウムの排出水基準である０．１ｍｇ／ｌ以下を満足できる。つまり、ダストを洗浄する際の洗浄水のｐＨを１０〜１３、好ましくは１０〜１１に調整すれば、カドミウムの浸出は殆ど起こらない。ｐＨ調整剤としては、フッ素イオンの析出を起こさない水酸化ナトリウム水溶液もしくは水酸化カリウム水溶液が好ましい。ｐＨ１０以下でダストを洗浄した場合には、洗浄廃液中にはカドミウムイオンが混入する。カドミウムイオンは図１より、中性〜酸性領域で析出しないため、例えば、硫化物イオンを投入し、硫化カドミウムとして析出させ、洗浄水中より分離することが必要となり、非常に非効率となる。
From FIG. 1, the range in which leaching of cadmium does not occur is
以上より、ダストの洗浄処理では洗浄装置に、ｐＨ計、およびｐＨ制御装置を装着して、常に適切なｐＨを保つことで、ダストを効率的に洗浄できる。 As described above, in the dust cleaning process, the dust can be efficiently cleaned by attaching a pH meter and a pH control device to the cleaning device and always maintaining an appropriate pH.
次に、前記（ＩＩＩ）の観点から、ダストの洗浄処理の効率的な終点判定方法について検討した。金属成分として亜鉛、鉛、カドミウムを含み、さらに、フッ素を２％以上含有するダストをｐＨ１１．５でフッ素の浸出処理を行い、ダストを分離回収した。次いで、新たにダスト量の重量で１０倍量の洗浄液を回収したダストに加え、ｐＨ１０．５に調整しながら、１５分間の撹拌を行った後、さらにこのダストを分離して回収したのち、再度ダスト量の重量で１０倍量の洗浄液を回収したダストに加え、ｐＨ１０．５に調整しながら、１５分間の撹拌を行った。図４は、洗浄後のダスト中のフッ素濃度とスラリー中のフッ素濃度の関係を示す。なお、ダスト中のフッ素濃度は洗浄後のダストを乾燥後、化学分析法の吸光光度法により分析した値で、分析結果が出るまで１週間を要した。一方、洗浄液のフッ素濃度は、装置に装備したフッ素イオン濃度計の指示値である。 Next, from the viewpoint of the above (III), an efficient end point determination method for dust cleaning processing was examined. A dust containing zinc, lead and cadmium as metal components and further containing 2% or more of fluorine was subjected to a leaching treatment of fluorine at pH 11.5, and the dust was separated and recovered. Next, 10 times the amount of cleaning liquid by the amount of dust is newly added to the collected dust, and after stirring for 15 minutes while adjusting to pH 10.5, the dust is further separated and recovered, and then again. A 10-fold amount of the cleaning liquid by the amount of dust was added to the collected dust, and stirring was performed for 15 minutes while adjusting the pH to 10.5. FIG. 4 shows the relationship between the fluorine concentration in the dust after cleaning and the fluorine concentration in the slurry. The fluorine concentration in the dust is a value obtained by drying the washed dust and then analyzing it by an absorptiometric method of chemical analysis, and it took one week to obtain an analysis result. On the other hand, the fluorine concentration of the cleaning liquid is an indication value of a fluorine ion concentration meter equipped in the apparatus.
図４より多少のばらつきはあるが、両者は一次の相関関係にあり、スラリー中のフッ素濃度からダスト中のフッ素濃度を推定できる。例えば、ダスト中のフッ素濃度を０．５％以下にするには、スラリー中のフッ素濃度を５００ｍｇ／ｌ以下にすれば良いことがわかる。つまり、洗浄装置にフッ素イオン濃度計を装着し、濃度監視を行っていれば、ダストの洗浄処理の終点を把握できることになる。 Although there is some variation from FIG. 4, both have a first-order correlation, and the fluorine concentration in the dust can be estimated from the fluorine concentration in the slurry. For example, it can be seen that in order to make the fluorine concentration in the dust 0.5% or less, the fluorine concentration in the slurry should be 500 mg / l or less. That is, if a fluorine ion concentration meter is attached to the cleaning device and the concentration is monitored, the end point of the dust cleaning process can be grasped.
なお、スラリー中のフッ素濃度とダスト中のフッ素濃度の関係は、ダスト量に対する洗浄液の希釈倍率により変化する。ダスト中のフッ素濃度を同程度に低下させるには、希釈倍率が大きい場合は、スラリー中のフッ素濃度を希釈倍率が低い場合よりも下げる必要がある。そのため、前記フッ素濃度の下限は特に限定されないが、ダスト中のフッ素濃度を低減させるために大量の洗浄液が必要になるため、経済的な観点から前記下限を１００ｍｇ／ｌに設定することが好ましい。
以上のように、洗浄処理を２回以上繰り返すことにより、ダスト中のフッ素濃度を所定のフッ素濃度以下にすることができる。もちろん、１回の洗浄処理により所定のフッ素濃度が得ることもできる。また、洗浄液の調整は特に限定されず、異なるｐＨに調整された洗浄液を予め複数準備しておいても良い。或いはｐＨ値が１０〜１３のうちのいずれかに調整された単一種類の洗浄液を予め準備し、使用可能な洗浄液の量或いはスラリーの温度等の条件に応じて洗浄液のｐＨ値を再調整した後、前記洗浄液を洗浄処理に使用しても良い。The relationship between the fluorine concentration in the slurry and the fluorine concentration in the dust varies depending on the dilution ratio of the cleaning liquid with respect to the dust amount. In order to reduce the fluorine concentration in the dust to the same extent, it is necessary to lower the fluorine concentration in the slurry when the dilution ratio is large than when the dilution ratio is low. Therefore, the lower limit of the fluorine concentration is not particularly limited, but since a large amount of cleaning liquid is required to reduce the fluorine concentration in dust, it is preferable to set the lower limit to 100 mg / l from an economical viewpoint.
As described above, the fluorine concentration in the dust can be reduced to a predetermined fluorine concentration or less by repeating the cleaning process twice or more. Of course, a predetermined fluorine concentration can be obtained by a single cleaning process. The adjustment of the cleaning liquid is not particularly limited, and a plurality of cleaning liquids adjusted to different pHs may be prepared in advance. Alternatively, a single type of cleaning liquid whose pH value is adjusted to any one of 10 to 13 is prepared in advance, and the pH value of the cleaning liquid is readjusted according to conditions such as the amount of usable cleaning liquid or the temperature of the slurry. Thereafter, the cleaning liquid may be used for the cleaning process.
重金属成分として亜鉛、鉛、カドミウムを含み、さらに、フッ素を２％以上含有するダストと、アルカリ性洗浄液とを混合して、当該ダストからフッ素を浸出、洗浄する洗浄装置に関して、ｐＨ計、およびｐＨ制御装置を装着し、さらにフッ素イオン濃度計、およびフッ素イオン濃度制御装置を装着することにより、ダストからのフッ素の浸出処理に対し、ｐＨ制御を効率よく行え、浸出処理の進行状況および終点を把握できる。更に、浸出処理に続く洗浄処理に関し、ｐＨ制御を効率よく行え、洗浄処理の進行状況、追加洗浄処理の必要性の有無を判断し、かつ目標のダスト中のフッ素濃度を達成することが可能になる。 A pH meter and pH control for a cleaning device that contains zinc, lead, and cadmium as heavy metal components and further mixes a dust containing 2% or more of fluorine with an alkaline cleaning solution to leach and clean fluorine from the dust. Equipped with a device, and further equipped with a fluorine ion concentration meter and a fluorine ion concentration control device, it is possible to efficiently control pH for the leaching treatment of fluorine from dust, and to grasp the progress and end point of the leaching treatment. . Furthermore, with regard to the cleaning process following the leaching process, it is possible to efficiently control the pH, judge the progress of the cleaning process, the necessity of additional cleaning process, and achieve the target fluorine concentration in dust. Become.
図５に概要図にて本発明のダスト洗浄方法を実施するための洗浄装置の例を示す。
本発明例では全ての洗浄処理を同じ槽にて行う装置例である。洗浄槽には、攪拌機Ｍ、ｐＨ計ｐＨ、フッ素イオン濃度計Ｆが備えられている。ｐＨ制御は、前記ｐＨ計ｐＨによって測定されたダストスラリーのｐＨ値が所定の範囲内になるように、ＮａＯＨ水溶液タンクからポンプｐを介して同水溶液を前記洗浄槽内に添加することによって行う。また、フッ素濃度制御は、フッ素濃度制御ユニットＳによって行われ、前記フッ素イオン濃度計によって測定されたダストスラリーのフッ素イオン濃度が所定の範囲内になるように制御手段ＣによりバルブＶの開閉を行い、水を前記洗浄槽内へ添加する量を制御することによって行う。また、装置は水位計ＷＬを備え、水量の把握、制御が可能である。
FIG. 5 is a schematic diagram showing an example of a cleaning device for carrying out the dust cleaning method of the present invention.
The example of the present invention is an example of an apparatus that performs all cleaning processes in the same tank. The washing tank is equipped with a stirrer M, a pH meter pH, and a fluorine ion concentration meter F. The pH control is performed by adding the aqueous solution from the NaOH aqueous solution tank to the cleaning tank through the pump p so that the pH value of the dust slurry measured by the pH meter pH is within a predetermined range. Further, the fluorine concentration control is performed by the fluorine concentration control unit S, and the valve V is opened and closed by the control means C so that the fluorine ion concentration of the dust slurry measured by the fluorine ion concentration meter is within a predetermined range. , By controlling the amount of water added to the washing tank. In addition, the apparatus includes a water level gauge WL, and can grasp and control the amount of water.
次に具体的な操作方法の例を説明する。重量を測定したフッ素を２％以上含むダスト（ここではフッ素を６．５％含むダストを用いた。）をダスト収納タンクＴＤから洗浄槽に投入し、ダスト量の５倍の水を加えて撹拌を開始する。攪拌中、スラリーへのＮａＯＨ水溶液の添加を行い、スラリーのｐＨを１１．５に制御する。フッ素イオン濃度計Ｆにより、スラリーのフッ素濃度を監視し、１２０００ｍｇ／ｌのほぼ一定になった時点、すなわち、スラリーのフッ素濃度が飽和状態に達した時点で、凝集剤タンクからポンプｐにより、市販の凝集剤を加えた後、撹拌を止めて静置し、固液分離を行う。 Next, an example of a specific operation method will be described. Dust containing 2% or more of fluorine whose weight was measured (here, dust containing 6.5% of fluorine was used) was put into the washing tank from the dust storage tank TD, and 5 times the amount of dust was added and stirred. To start. During stirring, an aqueous NaOH solution is added to the slurry, and the pH of the slurry is controlled to 11.5. The fluorine concentration of the slurry is monitored by the fluorine ion concentration meter F. When the slurry concentration becomes almost constant at 12000 mg / l, that is, when the fluorine concentration of the slurry reaches a saturated state, it is commercially available from the flocculant tank by the pump p. After adding the flocculant, the stirring is stopped and the mixture is left to stand for solid-liquid separation.
界面計ＩＬにて固液分離を確認してから、上澄み液を排水ポンプＰで排水する。排水完了後、新たにダストの１０倍量の水を加えて攪拌してスラリーとし、スラリーのｐＨを１０．５に制御しながら、前記スラリーのフッ素濃度の推移を監視した。１５分経過後でフッ素濃度は２５００ｍｇ／ｌでほぼ一定になったので、凝集剤を加えた後、撹拌を止めて静置し、固液分離を行う。
After confirming the solid-liquid separation with the interface meter IL, the supernatant liquid is drained with the drainage pump P. After completion of drainage,
界面計ＩＬにて固液分離を確認してから、上澄み液を排水ポンプＰで排水する。排水完了後、新たにダストの５倍量の水を加えて攪拌してスラリーとし、スラリーのｐＨを１０．５に制御しながら、スラリーのフッ素濃度の推移を監視した。１０分経過後でフッ素濃度は６００ｍｇ／ｌでほぼ一定になったが、まだフッ素の洗浄は不十分と考えられたので、水をさらに、ダスト量の５倍加え（計１０倍量）、ｐＨを１０．５に制御して、フッ素濃度の推移を監視した。５分経過後でフッ素濃度は４００ｍｇ／ｌでほぼ一定となった。
After confirming the solid-liquid separation with the interface meter IL, the supernatant liquid is drained with the drainage pump P. After the drainage was completed,
これでダストのフッ素濃度は目標の０．５％以下を達成したと考えられたので、凝集剤を添加して、固液分離を行い、界面計ＩＬにて監視しながら、上澄み液の排水を行った。排水後、洗浄後ダストの脱水を行い、洗浄を完了した。 It was thought that the fluorine concentration in the dust had reached the target of 0.5% or less. So, flocculant was added, solid-liquid separation was performed, and the supernatant liquid was drained while monitoring with the interface meter IL. went. After draining, the dust was dehydrated after washing, and the washing was completed.
洗浄後ダストの化学分析を行ったところ、フッ素濃度は０．４％であり、目標濃度を達成した。また、洗浄前後のダストの成分バランスを確認したところ、亜鉛９９％、鉛９７％、カドミウム１００％の歩留であることが確認された。 When chemical analysis of the dust after washing was performed, the fluorine concentration was 0.4%, and the target concentration was achieved. Moreover, when the component balance of the dust before and after cleaning was confirmed, it was confirmed that the yield was 99% zinc, 97% lead, and 100% cadmium.
本発明によれば、還元鉄製造過程から排出されるダストや、都市ゴミ二次ダスト等のフッ素の含有量の高いダストから、環境に対して低負荷で、フッ素を安定して洗浄除去して低フッ素含有量とすることができ、該ダストを亜鉛製錬原料として、有効利用することができる。 According to the present invention, it is possible to stably wash and remove fluorine from dust discharged from the reduced iron production process and dust having a high fluorine content such as municipal waste secondary dust with low environmental impact. The fluorine content can be reduced, and the dust can be effectively used as a zinc smelting raw material.
Claims (2)
前記ダスト洗浄方法は、
前記スラリーのｐＨ値を１０〜１３とし、前記スラリー中の前記ダストの希釈率を一定にして、前記スラリー中のフッ素イオン濃度の未飽和状態における前記スラリーのフッ素イオン濃度と、前記ダストのフッ素濃度との相関関係を予め把握する工程と、
前記スラリーのフッ素イオン濃度が、前記相関関係が把握されたスラリー中のダストの希釈率において、前記洗浄対象のダストの目標のフッ素濃度に対応する前記スラリーの目標のフッ素イオン濃度になるまで、洗浄対象のダストが混合されたスラリーのｐＨ値を１０〜１３の範囲に制御しつつ、前記予め把握された相関関係における前記ダストの希釈率の範囲内で前記洗浄水を添加する工程、又は、前記スラリーの上澄み液を排水し、排水完了後、予め把握された前記ダストの希釈率の範囲内において前記洗浄水を添加する工程のいずれかの工程を１回以上行うことにより、前記スラリーのフッ素イオン濃度を前記目標のフッ素イオン濃度以下にする洗浄工程と、
を有することを特徴とするダスト洗浄方法。 A dust cleaning method that contains zinc, lead, cadmium as a heavy metal component and further contains dust containing 2% or more of fluorine and a cleaning liquid to form a slurry, and leaches fluorine from the dust into the cleaning liquid for cleaning. There,
The dust cleaning method includes:
The slurry has a pH value of 10 to 13, the dilution rate of the dust in the slurry is constant, and the fluorine ion concentration of the slurry in the unsaturated state of the fluorine ion concentration in the slurry, and the fluorine concentration of the dust The step of grasping the correlation with
Cleaning is performed until the fluorine ion concentration of the slurry reaches the target fluorine ion concentration of the slurry corresponding to the target fluorine concentration of the dust to be cleaned at the dilution ratio of dust in the slurry whose correlation has been grasped. The step of adding the washing water within the range of the dilution rate of the dust in the correlation obtained in advance while controlling the pH value of the slurry mixed with the target dust in the range of 10-13, or Fluorine ions of the slurry are drained by draining the supernatant of the slurry and performing one or more of the steps of adding the washing water within the range of the dilution rate of the dust obtained in advance after draining is completed. A cleaning step to bring the concentration below the target fluorine ion concentration;
A dust cleaning method comprising:
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