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WO2005084838A1 - Méthode de traitement des cendres légères - Google Patents

Méthode de traitement des cendres légères Download PDF

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Publication number
WO2005084838A1
WO2005084838A1 PCT/JP2005/002377 JP2005002377W WO2005084838A1 WO 2005084838 A1 WO2005084838 A1 WO 2005084838A1 JP 2005002377 W JP2005002377 W JP 2005002377W WO 2005084838 A1 WO2005084838 A1 WO 2005084838A1
Authority
WO
WIPO (PCT)
Prior art keywords
washing
fly ash
solution
solid
residue
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.)
Ceased
Application number
PCT/JP2005/002377
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English (en)
Japanese (ja)
Inventor
Taro Aichi
Hiroshi Asada
Akiyoshi Horiuchi
Tetsuo Dohi
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.)
Dowa Holdings Co Ltd
Original Assignee
Dowa Mining 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 Dowa Mining Co Ltd filed Critical Dowa Mining Co Ltd
Publication of WO2005084838A1 publication Critical patent/WO2005084838A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
    • B09B3/38—Stirring or kneading
    • 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
    • B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/06—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/20—Waste processing or separation

Definitions

  • the present invention is intended for fly ash collected from combustion exhaust gas at the time of incineration of municipal solid waste or the like, or fly ash collected from exhaust gas generated at the time of melting ash or dust during incineration or the like.
  • the present invention relates to a wet treatment method, and particularly to a treatment method for separating and recovering C a, P b, gangue components, Zn content and the like contained in the fly ash in a form that can be effectively used.
  • Waste from general establishments and households (referred to as “municipal waste” or “general waste”) is collected at municipal waste incineration facilities, industrial waste incineration plants, etc., and incinerated. I have. At that time, incineration ash and fly ash generated from the incinerator are deposited at the final disposal site through intermediate treatment such as chemical treatment, melting treatment, and cement kiln treatment.
  • Patent Document 1 JP-A-7-1095333
  • Patent Literature 2 Japanese Patent Application Laid-Open No. Hei 8-1-1 7 7 2 4
  • Patent Literature 3 Japanese Patent Application Laid-Open No. H08-14141539 ''
  • Patent Document 4 Japanese Patent Application Laid-Open No. 2000-01-1 1 3 2 4 2
  • Patent Document 5 Japanese Patent Application Laid-Open No. 2000-01-34 8 6 2 7
  • Patent Document 7 JP-A-8-36555 No.
  • Patent Document 8 JP-A-8-3 2 3 3 2 1
  • Patent Document 9 Japanese Patent Application Laid-Open No. 2000-11017
  • Patent Document 10 Japanese Patent Application Laid-Open No. 2000-2004
  • Patent Literature 1 Japanese Patent Application Laid-Open No. 2000-2111
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2000-200501 Problem to be Solved by the Invention
  • wet treatment methods disclosed in the above patent documents are effective in separating and recovering heavy metals contained in fly ash in a stable form.
  • these technologies focus on the recovery of heavy metals, and further improvement is desired from the viewpoint of effective use of Ca and effective use of gangue components.
  • fly ash contains a large amount of Ca, so it is not possible to obtain in the intermediate process.
  • gangue residue byproducts gypsum C a S 0 4
  • this residue has a high Pb grade, it is desired to use it effectively for lead production.
  • it since it has a large gypsum content, its use as a raw material for lead production has a problem in terms of thermal energy.
  • the present invention relates to a process for recovering heavy metals by treating fly ash, i) Effective use of Ca,
  • Fly ash contains a large amount of Zn and often Pb. In order to use these metals effectively, it is preferable to use Zn for wet zinc herb and Pb for lead with other gangue components.
  • the inventors of the present invention have studied the process of treating fly ash that enables the use of Zn and Pb, and as a result, firstly, in the washing step, as much Ca as possible is dissolved in the liquid "as much as possible” and separated and collected. However, it was found that it would be extremely advantageous to reduce the amount of Ca remaining on the solids side of the washed fly ash as much as possible.
  • the Ca may be separated and recovered as the calcium carbonate (CAC0 3) and gypsum (CaS 0 4).
  • the present invention has been completed based on these findings.
  • the solution after decalcification obtained in the step [4] can be returned to the step [1] and reused as water for washing fly ash.
  • the after-liquid obtained in the step [9] can be reused by returning it to the steps [6] and [8] as [1] or [5] or as lipanolep water.
  • step [10] the by leaching with sulfuric acid-containing aqueous solution solids containing ⁇ and CaS 0 4 obtained in step [9], the step of shifting the Zn leachate side (sulfuric leaching step 2),
  • the method for treating fly ash according to the present invention has the following advantages.
  • the Ca in the fly ash is separated and recovered as CaCOa from the solution after washing and as CaS04 from the washing residue side, so it can be effectively used for various purposes.
  • FIG. 1 is a flowchart showing an example of a fly ash treatment process to which the present invention is applied. Preferred embodiments of the invention
  • the fly ash treatment method of the present invention can be applied to various fly ash discharged from incinerators and melting furnaces of waste treatment facilities and the like, or mixed fly ash thereof. Above all, it is effective to apply to fly ash having a high Ca content of, for example, 15 to 30% by mass.
  • FIG. 1 shows an example of the processing flow of the present invention.
  • [1] to [11] in FIG. 1 correspond to the steps [1] to [11] described in the claims.
  • the steps [1] to [11] will be described in order.
  • ⁇ Process [1] (Washing process)> make a fly ash mixture with a low pulp concentration. If the fly ash is agglomerated and clumped, such as when the fly ash is conditioned, it is desirable to grind it beforehand. This is because if the fly ash does not become well dispersed in the liquid during washing, the dissolution of Ca will not proceed easily.
  • the liquid for washing may be water, but after the step [4], the liquid can be reused.
  • a fly ash mixture having a very low pulp concentration (PD) of 5 to 100 g / L is used for washing.
  • PD pulp concentration
  • Pulp concentration is within the range of 0.01 to 100 g / L. Possible pulp concentration is too low, and the amount of liquid to be treated by solid-liquid separation increases. It is better to do it within the range. Practically, it is preferably from 10 to 100 g / L, and more preferably from 30 to 50 g.ZL.
  • the fly ash be dispersed in the liquid and that the Ca mass in the fly ash be vigorously stirred to a level at which the mass transfer coefficient of the film is negligible to promote the dissolution of Ca.
  • the pH during washing does not need to be particularly controlled, but it is possible to increase the amount of dissolved Ca by adding an acid or the like.
  • the pH value varies depending on the composition of the fly ash, but usually falls within the range of 7 to 13.
  • the time (residence time) of the cleaning treatment may be generally set to 10 to 150 minutes.
  • the optimal time varies depending on the degree of agglomeration of the agglomerates and the intensity of stirring, but it is desirable to use a sufficiently pulverized fly ash for a processing time of about 10 to 80 minutes.
  • stirring should be performed at a temperature of 20 to 90 ° C and a processing time of 10 to 150 minutes with a strength that stabilizes the pH 5 to 120 minutes after the start of the processing. Is desirable.
  • the slurry after washing is subjected to solid-liquid separation.
  • the Ca dissolved in the washing solution is collected as a solution after washing.
  • the amount of cleaning residue is greatly reduced compared to the original fly ash, and the Ca content is also reduced.
  • various means can be selected, such as thickening with a thickener, a filter, a press, a belt-type vacuum filter, an Oliver, and a screw counter.
  • the dissolved Ca is precipitated as Ca CO 3 by blowing CO 2 gas into the solution after washing.
  • CO 2 gas it is preferable to blow the co 2 gas so as to have a pH of 8 to 11, preferably 9 to 10. It is desirable to perform stirring.
  • C0 2 concentration and the G / L ratio ( "volume of the gas blown per minute (L) / slurries volume (L)") so much regardless CAC0 3 gas used is precipitated.
  • the C0 2 amount you introduced is excessive CAC0 3 will be redissolved, if when high C 0 2 concentration of the gas or GZL ratio of blowing high tricky.
  • the GL ratio is preferably set to 0.001 to 0.01.
  • the temperature is preferably from 10 to 40 ° C.
  • the processing time is preferably about 5 to 40 minutes, which is the time required for the pH value to fall within the above range.
  • the step [3] obtained CaC 0 3 containing slurry to solid-liquid was separated, the separating and recovering CAC0 3 as solids.
  • This can be used as a neutralizing agent in the production process.
  • Ca since Ca is removed from the post-solution, it can be returned to step [1] and used for washing water.
  • salts NaCl and C1 will be concentrated, so it is desirable to perform effluent treatment by partially bleeding off.
  • the washing residue obtained in the step [2] is subjected to a process for recovering a Pb-containing gangue residue that can be used for lead smelting and a Zn-containing liquid that can be used for wet zinc smelting. It is.
  • step [5] repulp and sulfuric acid leaching are performed.
  • the pulp concentration is preferably about 100 to 300 g / L before leaching.
  • sulfuric acid Zn is transferred to the leaching solution side, and Pb and gangue components are retained on the leaching residue side. However, some gangue components also migrate to the leachate side.
  • the pH during leaching is controlled between 1 and 3.5.
  • the temperature can be between 20 and 90 ° C and the leaching time can be between 30 and 120 minutes.
  • Neutralization is performed following leaching. This process precipitates gangue components that have been leached once. NaO H and CaO is as a neutralizing agent, Ca (OH) 2, CaC 0 3 power can be used. Here, it is possible to utilize the CaC 0 3 obtained in the step [4]. Even if Pb is contained in CaCOs, it is favorable for Pb-bearing gangue residue by neutralization.
  • the pH at the time of neutralization is controlled to 3.5 to 5, preferably 3.5 to 4. Most of the Ca content in fly ash has been removed by the previous washing process, so gypsum will not be produced in large quantities in this neutralization process.
  • the temperature can be 20 to 90 ° C, and the reaction time can be 5 to 120 minutes.
  • the neutralized slurry is subjected to solid-liquid separation, and the post-solution containing Zn and the residue containing Pb are recovered.
  • the post-Zn-containing solution can be used as, for example, a wet zinc raw material by treating in the following step [8].
  • Pb-containing residue includes Pb component and Si0 2 and [alpha] 1 2 0 gangue components such as mainly comprising PBS O. Since this Pb-containing residue has a small amount of accompanying gypsum, it can be suitably used as a raw material for lead production.
  • solution excluding the Pb-containing residue is the [7] (Zn-containing after liquid)
  • further pH neutralized with the liquid which had increased to 5-9 and to produce a Zn compound and CaS 0 4 such Zetaitashita. If the pH exceeds 9, Zn goes in the direction of redissolution. More preferably, the pH is 7-8.
  • CaO or Ca (OH) 2 can be used as a neutralizing agent.
  • the temperature can be 20 to 90 ° C, and the reaction time can be 5 to 120 minutes.
  • the solids containing the Zn compound and CaS 0 4 obtained in the step [9] repulped and leached with sulfuric acid.
  • the pulp concentration is desirably about 100 to 100 g / L before leaching.
  • the pH during leaching should be controlled between 0.1 and 4.
  • the temperature is 20-90. C.
  • the leaching time can be 5 to 120 minutes.
  • the post-solution containing ZnS 04 can be used as an electrolytic solution made of wet zinc.
  • CaS 04 can be used in various industrial fields.
  • composition analysis was performed. The results are shown in Table 2. On the other hand, a composition analysis was also performed on the solution after washing. The results are shown in Table 3.
  • composition analysis was performed. Table 6 shows the results. On the other hand, a composition analysis was also performed on the solution after washing. Table 7 shows the results.
  • Sulfuric acid leaching was carried out (step [5]).
  • the liquid temperature was 30 ° C.
  • solid-liquid separation was performed (step [7]) to obtain a Zn-containing post-solution and a Pb-containing residue.
  • Table 8 shows the analysis results of the solution containing Zn. After the Pb-containing residue was sufficiently dried at 1 G at 5 ° C, the composition was analyzed. Table 9 shows the results.
  • the invention example shows that Pb grade is higher than comparative example. Also, the amount of Ca was greatly reduced. In other words, the amount of gypsum accompanying the P-containing residue as a by-product is greatly reduced by using the washing residue in which most of the Ca is dissolved and removed on the liquid side in the washing step. This Pb-containing residue can be effectively used for lead production together with gangue components.
  • Example 2
  • the composition was analyzed. Table 10 shows the results. Composition analysis was also performed on the after solution (after Ca removal). Table 11 shows the results. As described above, the analyzed solution after the removal of Ca was returned to the washing solution, and the bleed-off operation was repeated about 30 L each time. This is the solution obtained by performing the above charging, that is, the solution after the removal of Ca after performing five consecutive chargings. The composition change due to the repetition is almost stable. As can be seen from Tables 10 and 11, from the post-washing solution obtained according to the present invention, for example, CaCOs of a grade usable as an alkali in step [6] was recovered. In addition, the amount of Ca dissolved in the solution after decalcification was smaller than that in the solution after washing, and it was confirmed that the solution could be repeatedly used as washing water.
  • the Zn-containing post-liquid (Table 8) obtained in Step [7] was subjected to the treatment of Step [8] and subsequent steps. That is, slurried lime Ca was added to the solution after the Zn content while stirring to neutralize (step [8]). At that time, pH The pH was monitored so that it was 9. The temperature was 30 ° C and the reaction time was 60 minutes. The slurry was solid-liquid separation (step [9]), was recovered Zn compound and CaS 0 4 of ZnO mainly as solids. In addition, the post-solution was recovered. The liquid after this could be reused as water, for example, returned to step [1] or step [5].

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Processing Of Solid Wastes (AREA)
  • Removal Of Specific Substances (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

Méthode pour le traitement des cendres légères qui comprend [1]une étape (étape de lavage) consistant à laver les cendres légères dans un liquide ayant une concentration de pulpe de 5 à 100 g/l, pour dissoudre un composant Ca des cendres légères dans de l’eau, et [2]une étape consistant à soumettre la boue formée dans l’étape de lavage expliquée ci-dessus à une séparation solide-liquide pour ainsi récupérer le composant Ca dissout dans une solution après lavage et récupérer aussi un composant solide sous forme de lessivat. Le soufflement d’un gaz CO2 dans la solution ci-dessus après lavage forme du CaCO3. Par ailleurs, le lessivat ci-dessus a une faible teneur en Ca, ce qui se traduit par la production de dérivés contenant du Pb, ayant une faible teneur en gypse en soumettant le lessivat à la lixiviation à l’acide sulfurique et le résidu contenant du Pb est utile dans le raffinage du Pb. Ensuite, la solution obtenue après la séparation du résidu contenant du Pb peut être utilisée comme matière première pour le raffinage du Zn.
PCT/JP2005/002377 2004-03-03 2005-02-09 Méthode de traitement des cendres légères Ceased WO2005084838A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004-59852 2004-03-03
JP2004059852A JP2005246226A (ja) 2004-03-03 2004-03-03 飛灰の処理方法

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WO2005084838A1 true WO2005084838A1 (fr) 2005-09-15

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104529011A (zh) * 2015-01-05 2015-04-22 北京建筑材料科学研究总院有限公司 垃圾焚烧飞灰水洗液去硬度降pH值装置和方法
CN111479939A (zh) * 2017-12-04 2020-07-31 昭和电工株式会社 钒酸盐的制造方法
WO2022203517A1 (fr) * 2021-03-24 2022-09-29 Noah Solutions As Procédé et appareil de neutralisation et de stabilisation de cendres volantes
CN115301711A (zh) * 2022-08-04 2022-11-08 江山市虎鼎环保科技有限公司 一种飞灰水洗压滤的防堵塞方法

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JP4878605B2 (ja) * 2008-03-31 2012-02-15 太平洋セメント株式会社 フライアッシュの湿式脱炭における前処理装置
CN102448885B (zh) * 2009-07-23 2015-09-30 日立造船株式会社 钠和钾的分离提取装置及分离提取方法
JP5072919B2 (ja) * 2009-07-23 2012-11-14 日立造船株式会社 焼却炉からの焼却灰の処理装置および処理方法
JP7780141B2 (ja) * 2021-08-31 2025-12-04 住友大阪セメント株式会社 炭酸カルシウム生成方法及びシステム
CN115446096B (zh) * 2022-08-29 2023-08-08 北京科技大学 废旧轮胎裂解炭黑制备高炉喷吹燃料及碳酸锌的方法
JP7485125B1 (ja) 2023-02-27 2024-05-16 住友大阪セメント株式会社 セメント製造プロセスから生じる廃棄物の再利用循環方法及びそのシステム
TWI893876B (zh) * 2024-07-02 2025-08-11 綠碳永續科技股份有限公司 焚化爐飛灰水洗系統

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JP2003225633A (ja) * 2002-02-01 2003-08-12 Taiheiyo Cement Corp 塩化物含有ダストの処理方法

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JPH08117724A (ja) * 1994-10-26 1996-05-14 Dowa Mining Co Ltd 焼却炉または溶融炉からの飛灰の処理方法
JP2000144271A (ja) * 1998-11-13 2000-05-26 Yoshizawa Lime Industry 溶融飛灰からの重金属の回収方法
JP2000212654A (ja) * 1999-01-19 2000-08-02 Dowa Mining Co Ltd 重金属と塩素を含有する物質からの重金属の回収方法
JP3633840B2 (ja) * 1999-11-29 2005-03-30 株式会社タクマ 溶融飛灰の処理方法

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JP2003211127A (ja) * 2002-01-29 2003-07-29 Taiheiyo Cement Corp 塩化物含有ダストの処理方法
JP2003225633A (ja) * 2002-02-01 2003-08-12 Taiheiyo Cement Corp 塩化物含有ダストの処理方法

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104529011A (zh) * 2015-01-05 2015-04-22 北京建筑材料科学研究总院有限公司 垃圾焚烧飞灰水洗液去硬度降pH值装置和方法
CN111479939A (zh) * 2017-12-04 2020-07-31 昭和电工株式会社 钒酸盐的制造方法
WO2022203517A1 (fr) * 2021-03-24 2022-09-29 Noah Solutions As Procédé et appareil de neutralisation et de stabilisation de cendres volantes
CN115301711A (zh) * 2022-08-04 2022-11-08 江山市虎鼎环保科技有限公司 一种飞灰水洗压滤的防堵塞方法

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