WO2005084837A1 - Méthode de traitement des cendres légères impliquant la fixation du dioxyde de carbonne - Google Patents

Méthode de traitement des cendres légères impliquant la fixation du dioxyde de carbonne Download PDF

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Publication number
WO2005084837A1
WO2005084837A1 PCT/JP2005/002375 JP2005002375W WO2005084837A1 WO 2005084837 A1 WO2005084837 A1 WO 2005084837A1 JP 2005002375 W JP2005002375 W JP 2005002375W WO 2005084837 A1 WO2005084837 A1 WO 2005084837A1
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WIPO (PCT)
Prior art keywords
fly ash
washing
liquid
solid
solution
Prior art date
Application number
PCT/JP2005/002375
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English (en)
Japanese (ja)
Inventor
Taro Aichi
Hiroshi Asada
Akiyoshi Horiuchi
Tetsuo Dohi
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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 WO2005084837A1 publication Critical patent/WO2005084837A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • 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
    • 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
    • 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
    • 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
    • C02F1/62—Heavy metal 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.
  • This is a wet treatment method that also fixes carbon dioxide.Specifically, after a process that consumes a large amount of carbon dioxide, the C a component, pb component, gangue component, Zn component, etc. contained in the fly ash are removed.
  • the present invention relates to a processing method for separating and recovering 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. H08-117177
  • Patent Literature 3 Japanese Patent Application Laid-Open No. H08-141459
  • Patent Document 4 Japanese Unexamined Patent Application Publication No. 2000-1-1103
  • Patent Document 5 Japanese Patent Application Laid-Open Publication No. 2000-1-3 4 8 6 2 7
  • Patent Document 6 Japanese Patent Application Laid-Open Publication No. 2003-16664 829
  • Patent Document 7 JP-A-8-36555
  • Patent Document 8 Japanese Patent Application Laid-Open No. 8-323231
  • Patent Document 9 Japanese Unexamined Patent Application Publication No. 2000-111
  • Patent Document 10 Japanese Patent Application Laid-Open No. 2000-2004-271
  • Patent Literature 11 Japanese Patent Application Laid-Open No. 200-02-111429
  • Patent Document 12 Japanese Patent Application Laid-Open Publication No. 2003-202015 Problem to be Solved by the Invention
  • fly ash contains a large amount of Ca, so it is not possible to obtain in the intermediate process.
  • the gangue residue byproducts gypsum (C a S 0 4) and contains a lot Mau. Since this residue has high Pb quality, it is desired to use it effectively for lead production. However, 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
  • Fly ash contains a large amount of Zn and often Pb. To use these metals effectively, it is preferable to use Zn for wet zinc smelting and Pb for lead sintering together with other gangue components.
  • the present inventors have conducted intensive studies on the process of treating fly ash that makes it possible to use Zn and pb, and as a result, firstly, in the washing step, as much Ca as possible was dissolved in “liquid” as much as possible and separated and collected. It has been found that it is extremely advantageous to reduce the amount of Ca remaining on the solids side of the washed fly ash as much as possible.
  • Ca is calcium carbonate (Ca CO
  • the present invention has been completed based on these findings.
  • a method for treating fly ash, which also serves to fix carbon dioxide, is provided.
  • the solution after decalcification obtained in the step [4] is returned to the step [1] and reused as a liquid for washing fly ash.
  • a method for treating fly ash is also provided.
  • the after-liquid obtained in the step [9] can be reused by returning it to the step [6] or [8] as [1] or [5], or as repulping water.
  • step [10] the by leaching with sulfuric acid-containing aqueous solution solids containing the Zn compound and CaS 0 4 obtained in step [9], the step of shifting the Zn leachate side (sulfuric leaching step 2) ,
  • the present invention has the following advantages.
  • the gypsum content in the Pb-containing gangue residue obtained as a by-product can be reduced when treated by a process using sulfuric acid immersion. Therefore, the Pb-containing residue is obtained in a form that can be easily used for lead production, and recycling can be promoted.
  • 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.
  • description will be given along the steps [1] to [11].
  • fly ash mixture with a low pulp concentration. If the fly ash is agglomerated and agglomerated, as in the case where the fly ash is conditioned, it is desirable to grind it in advance. This is because if the fly ash does not become well dispersed in the liquid at the time of 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 as the washing ash mixture during washing.
  • the pulp concentration can be in the range of 0.01 to 100 g / L, but if the pulp concentration is too low, the amount of liquid to be treated by solid-liquid separation increases and it becomes uneconomical. It is better to do within the range. Practically, it is preferably from 10 to 100 g / L, and more preferably from 30 to 50 g / L.
  • GZL ratio 0.01 ⁇ ; L. 0, temperature 5 ⁇ 50 ° C, treatment time 10 ⁇ : pH stable within 5 ⁇ 60 minutes after the start of treatment It is desirable to perform the stirring with such strength as to cause
  • Carbon dioxide in this step is fixed as Ca (HC0 3) 2.
  • carbon dioxide remains in fixed as CaC 0 3.
  • the amount of carbon dioxide fixed in the washing step of the present invention is about twice the amount fixed by the conventional method such as Patent Documents 7 and 8, The effect of fixing carbon dioxide is great.
  • the C0 2 gas generated in about manufacturing ⁇ such as Cu or Zn utilized in the present process, it can contribute to reducing carbon dioxide emissions complexes.
  • the slurry after washing is subjected to solid-liquid separation. Since Ca (HC0 3) 2 is dissolved in the liquid, It can be recovered as a solution after washing. In addition, the amount of cleaning residue is greatly reduced compared to the original fly ash due to the decrease in the amount of Ca.
  • the treatment time may be such that the added Ca0 or Ca (0H) 2 reacts and the pH is settled (for example, 5 to 60 minutes).
  • the temperature may be about 10 to 50 ° C.
  • the cleaning residue obtained in the step [2] is subjected to a process of recovering a Pb-containing gangue residue usable for lead production and a Zn-containing liquid usable for wet sub-dust production.
  • 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. Increasing the acid concentration so that the pH is less than 1 does not significantly change the leaching rate of Zn. Leaching at a pH of 1.5 to 2.5 is more preferred, including economics. It is desirable that the temperature be 20 to 90 ° C and the leaching time be 30 to 120 minutes.
  • Neutralization is performed following leaching. This process precipitates gangue components that have been leached once.
  • As the neutralizing agent and NaOH, CaO, Ca (OH) 2, CaC 0 3 can be used.
  • the pH at the time of middle-handed mouth is controlled to 3.5 to 5, preferably 3.5 to 4. Most of the Ca in the fly ash has been removed by the previous washing process, so a large amount of gypsum will not be generated in this neutralization process.
  • the temperature can be between 20 and 90 ° C.
  • the neutralized slurry is subjected to solid-liquid separation to recover the post-solution containing Zn and the residue containing Pb.
  • the after-solution containing Zn can be used as a raw material for wet zinc production.
  • Pb-containing residue includes Pb component and Si0 2, gangue components such as AI2O3 mainly comprising pb S 0. Since this Pb-containing residue has a small amount of accompanying gypsum, it can be suitably used as a raw material for lead production.
  • This solid content is used as a raw material for wet zinc production by, for example, treating it in the following step [10].
  • the back solution can be used as [1] or [5], or returned to the process of [6] or [8] as repulp water.
  • the step [9] Zn compound obtained in, repulped solids containing CaS 0 4, leaching with sulfuric acid. This transfers Zn to the leachate side in the form of ZnS O ⁇ . No ,.
  • the lump concentration is preferably about 100 to 100 g / L before leaching.
  • the pH during leaching should be controlled between 0.1 and 4.
  • the temperature can be between 20 and 90 ° C and the leaching time can be between 5 and 120 minutes.
  • the leached slurry is subjected to solid-liquid separation to recover the post-solution containing ZnS O and the solid content of CaS C (gypsum).
  • ZnS 0 4 containing after liquid can be used as an electrolyte of the wet zinc made ⁇ .
  • CaS0 4 is available in a variety of 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.
  • the water to be used repeatedly is defined as [30] after about 30 L of the post-solution obtained in the step [4] of Example 2 is returned as washing water each time, and after the same treatment process has already been repeated for 4 charges, This is the post-liquid obtained in step 4) (however, distilled water is used for the first charge).
  • the mixture was stirred at 30 ° C for 60 minutes while blowing C02 gas into the mixed fly ash at a flow rate of 30 L / min.
  • the C0 2 gas was used to collect the gas discharged from the neutralization step of the Zn-made ⁇ field.
  • the obtained slurry was subjected to solid-liquid separation with a filter to obtain a liquid after washing and a washing residue.
  • 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 performed by stirring (step [5]).
  • CaCOa was added to the treatment liquid (the slurry after leaching) to adjust the pH to 4, and the mixture was stirred for 60 minutes to perform neutralization (step [6]).
  • 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 105 ° C, the composition was analyzed.
  • Table 9 shows the results. Comparing Table 4 (Comparative Example) and Table 8 (Inventive Example), in the inventive example, the Zn concentration in the liquid after Zn-containing was higher than that in the comparative example, and the C1 concentration was lower. In other words, in the invention example The resulting Zn-containing post-solution is very advantageous for use as a raw material for wet zinc production.
  • 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 post-Ca-removed solution was used as described above, and at this stage, 30 de-Ca-removed solution was returned as washing water, and about 3 L of the bleed-off operation was already repeated four times. This is a solution obtained by performing the above charge, that is, a solution after removing Ca after performing five consecutive charges, and the composition fluctuation due to repetition is almost stable. Table 1 0, as can be seen from Table 1 1, the CaC 0 3 available in the resulting species s field from the wash after liquid quality is recovered according to the present invention.
  • the amount of Ca dissolved in the solution after Ca removal was significantly smaller than that in the solution after washing even though Ca 0 was added, confirming that the solution can be used repeatedly as washing water. Was done.
  • the carbon dioxide consumed in the cleaning process was consequently fixed in the form of CaCO 3 , and an effect of reducing the amount released to the atmosphere was recognized.
  • the post-treatment liquid containing Zn obtained in the step [7] (the one in Table 8) was subjected to the treatment of the step [8] and thereafter. That is, slurried lime Ca 0 was added to the solution after the Zn content while stirring to neutralize (step [8]). At that time, the pH was monitored so that the pH became 9. The temperature was 40 ° C and the reaction time was 60 minutes. This slurry was subjected to solid-liquid separation (step [9]), and a Zn compound mainly composed of Zn ⁇ and CaSO 4 were recovered 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].
  • Pa was repulped residue containing Zn compound and CaS 0 4 recovered as solids Sulfuric acid was added to the mixture to adjust the pH to 2, and the mixture was stirred at 60 ° C. for 20 minutes to perform sulfuric acid leaching (step [10]). Then solid-liquid fraction leaving the performed (step [11]), were recovered after liquid and CAS0 4 (gypsum) solids principal containing ZnS04. The post-solution containing ZnSO was gradely usable as a raw material for wet zinc production. On the other hand, the obtained gypsum had relatively few impurities and could be used in various fields.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Hydrology & Water Resources (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Processing Of Solid Wastes (AREA)
  • Removal Of Specific Substances (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

Méthode pour le traitement des cendres légères impliquant la fixation du dioxyde de carbone, 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, et à souffler en même temps le CO2 dans le liquide, pour ensuite dissoudre un composant Ca tel que Ca(HCO3)2 et [2]une étape consistant à soumettre la boue formée dans l’étape de lavage expliquée ci-dessus à une séparation solide - liquide pour ensuite récupérer Ca(HCO3)2 dans une solution après lavage et récupérer aussi un composant solide sous forme de lessivat. La solution après lavage obtenue ci-dessus peut être utilisée pour produire 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/JP2005/002375 2004-03-03 2005-02-09 Méthode de traitement des cendres légères impliquant la fixation du dioxyde de carbonne WO2005084837A1 (fr)

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JP2004/059847 2004-03-03
JP2004059847A JP2005246225A (ja) 2004-03-03 2004-03-03 二酸化炭素の固定を兼ねた飛灰の処理方法

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102825059A (zh) * 2012-09-05 2012-12-19 沈阳航空航天大学 一种焚烧飞灰资源化利用的安全预处理方法
CN113634114A (zh) * 2021-08-02 2021-11-12 中煤科工清洁能源股份有限公司 一种利用粉煤灰捕集烟气中co2的方法
CN113957260A (zh) * 2021-08-31 2022-01-21 江西盖亚环保科技有限公司 飞灰的重金属回收工艺

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JP5317421B2 (ja) * 2007-03-19 2013-10-16 太平洋セメント株式会社 塩含有粉体の処理方法及び処理システム
CN102303036B (zh) * 2011-07-06 2014-01-15 东江环保股份有限公司 碱激发固化稳定处理垃圾焚烧飞灰的方法
EP2732887B1 (fr) * 2012-11-15 2015-07-15 S.VE.D.A. S.R.L. Società Veneta Depuratori e Affini Procédé pour traiter des cendres lourdes ou de scories en général
CN108680707B (zh) * 2018-05-18 2021-04-27 光大环保技术研究院（南京）有限公司 一种飞灰全组分定量分析方法
CN114950005A (zh) * 2022-06-29 2022-08-30 格林爱科(荆门)新能源材料有限公司 三元正极前驱体生产再生废液回收系统及回收方法
CN115594429B (zh) * 2022-09-25 2023-06-09 浙江大学 基于氨基碳酸化改性联合水泥固化飞灰建材化利用的方法

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN102825059A (zh) * 2012-09-05 2012-12-19 沈阳航空航天大学 一种焚烧飞灰资源化利用的安全预处理方法
CN113634114A (zh) * 2021-08-02 2021-11-12 中煤科工清洁能源股份有限公司 一种利用粉煤灰捕集烟气中co2的方法
CN113957260A (zh) * 2021-08-31 2022-01-21 江西盖亚环保科技有限公司 飞灰的重金属回收工艺

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