WO2020238479A1 - Procédé amélioré pour détoxification par voie humide de résidu de déchets contenant du chrome hexavalent ou de sol pollué par du chrome hexavalent - Google Patents

Procédé amélioré pour détoxification par voie humide de résidu de déchets contenant du chrome hexavalent ou de sol pollué par du chrome hexavalent Download PDF

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Publication number
WO2020238479A1
WO2020238479A1 PCT/CN2020/085701 CN2020085701W WO2020238479A1 WO 2020238479 A1 WO2020238479 A1 WO 2020238479A1 CN 2020085701 W CN2020085701 W CN 2020085701W WO 2020238479 A1 WO2020238479 A1 WO 2020238479A1
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Prior art keywords
slurry
hexavalent chromium
chromium
tank
hexavalent
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PCT/CN2020/085701
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English (en)
Chinese (zh)
Inventor
李淑彩
方华祥
李来顺
吕正勇
闾文景
宋登慧
苗竹
朱湖地
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北京高能时代环境技术股份有限公司
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Publication of WO2020238479A1 publication Critical patent/WO2020238479A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/08—Reclamation of contaminated soil chemically

Definitions

  • the present invention relates to the technical field of pollution control, in particular to an improved process for wet detoxification of hexavalent chromium-containing waste residue or hexavalent chromium-contaminated soil, so as to realize the harmless treatment of hexavalent chromium-containing pollutants.
  • the waste slag containing hexavalent chromium has been harmlessly treated.
  • the soil of the chromium slag deposits has also been seriously polluted.
  • the site contains hexavalent chromium waste residue mixed with contaminated soil.
  • the harmless treatment of the hexavalent chromium-containing waste residue and the heavily polluted soil of hexavalent chromium is an important link in the comprehensive treatment of hexavalent chromium-contaminated sites.
  • the reducing agent and the acidified hexavalent chromium slurry are matured in a mixing tank. If the aging time is not long enough, it will be unfavorable for the reduction of hexavalent chromium. If the aging time is too long, energy consumption will be high on the one hand, Reduce the efficiency of the wet detoxification system.
  • the present invention provides an improved process for wet detoxification of hexavalent chromium-containing waste residue or hexavalent chromium-contaminated soil to improve the thoroughness and long-term effectiveness of the wet detoxification.
  • the present invention discloses an improved process for wet detoxification of hexavalent chromium-containing waste residue or hexavalent chromium-contaminated soil, including:
  • the hexavalent chromium-containing waste residue or hexavalent chromium-contaminated soil is subjected to wet grinding treatment to obtain a slurry;
  • the trivalent chromium slurry after the reduction reaction is subjected to solid-liquid separation, the separated filtrate is partially recycled for acidification treatment, and the separated filter cake is subjected to external curing treatment.
  • the wet grinding treatment of waste slag containing hexavalent chromium or soil contaminated with hexavalent chromium to obtain a slurry comprising:
  • the hexavalent chromium waste residue or hexavalent chromium contaminated soil that has been sieved and ground is put into a wet milling device, and it is ground to 100-150 meshes to obtain the slurry.
  • the said conveying the said slurry into the sulfuric acid-acetic acid mixed liquid for acidification treatment to obtain the slurry comprising:
  • the slurry is gradually transported to the acidification reaction tank, stirred and mixed with the sulfuric acid-acetic acid mixture in the acidification reaction tank, so that the pH of the slurry is maintained at 5-6 and aged for 5-6 hours.
  • the mass percentage of the sulfuric acid is 10%-20%
  • the mass percentage of the acetic acid is 5%-10%
  • the volume ratio of the sulfuric acid to the acetic acid is 1:1-3:1.
  • the said transferring the slurry to the reducing agent solution to carry out a reduction reaction, so that the hexavalent chromium in the slurry is converted into trivalent chromium; comprising:
  • the slurry is gradually transported to the reduction reaction tank, stirred and mixed with the reducing agent solution in the reduction reaction tank, and the reaction time is 5-8 hours to convert the hexavalent chromium in the slurry into trivalent chromium.
  • the reducing agent solution is a solution of ferrous sulfate and sodium metabisulfite dissolved in water, and the molar ratio of the ferrous sulfate to sodium metabisulfite is 4:1 to 6:1.
  • the concentration of ferrous sulfate is 15%-20%.
  • the trivalent chromium slurry after the reduction reaction is subjected to solid-liquid separation, the separated filtrate is partially recycled for acidification treatment, and the separated filter cake is subjected to external curing treatment; including:
  • the separated filtrate enters the filtrate tank, and a part of the filtrate in the filtrate tank is recycled to the acidification reaction tank for acidification treatment; the separated filtration
  • the cake pile is placed in the curing tank for airtight curing.
  • the filter cake is cured in a curing tank for 7-15 days. During the curing, the filter cake is sprayed with filtrate to ensure that the filter cake remains moist.
  • the curing tank is a circular tank with HDPE film and impermeable cement anti-seepage treatment. It is located 2 to 3 meters below the ground and has a diameter of 4 to 6 meters. The top is covered with HDPE film and the center is at the top. The location is equipped with a nozzle for spraying filtrate, and the nozzle is connected to the filtrate tank through a pipe.
  • the wet-milled slurry is gradually added to the sulfuric acid-acetic acid solution, so as to promote the full contact between the slurry and the acid solution, and maintain a microenvironment that is conducive to the acidification reaction on the reaction interface;
  • the present invention reduces the generation of calcium sulfate precipitation in the wet detoxification process by adding acetic acid, thereby avoiding calcium sulfate precipitation to wrap the hexavalent chromium pollutant particles and improving the dissolution of hexavalent chromium in the acid leaching stage;
  • the acidified slurry is gradually added to the reducing agent solution, thereby promoting full contact between the hexavalent chromium pollutant particles and the reducing agent, and maintaining a microenvironment that is conducive to the occurrence of the reduction reaction on the reaction interface;
  • the present invention places the separated filter cake in an external curing tank for curing, reduces the aging time in the reduction reaction tank, improves the production efficiency of the wet detoxification system and prolongs the reaction time of hexavalent chromium and the reducing agent. Conducive to the complete reduction of hexavalent chromium to trivalent chromium.
  • Figure 1 is a flow chart of an improved process for wet detoxification of hexavalent chromium-containing waste residue or hexavalent chromium-contaminated soil disclosed in an embodiment of the present invention.
  • the present invention provides an improved process for wet detoxification of hexavalent chromium-containing waste residue or hexavalent chromium-contaminated soil, including:
  • the hexavalent chromium waste residue or hexavalent chromium contaminated soil that has been sieved and ground is put into a wet grinding equipment, and it is ground to 100-150 mesh to obtain a slurry.
  • the sulfuric acid-acetic acid mixture First add the sulfuric acid-acetic acid mixture to the acidification reaction tank, and then gradually transport the slurry to the acidification reaction tank for acidification, so that the pH of the slurry is maintained at 5-6 and aged for 5-6 hours; among them, the mass percentage of sulfuric acid It is 10% to 20%, the mass percentage of acetic acid is 5% to 10%, and the volume ratio of sulfuric acid to acetic acid is 1:1 to 3:1.
  • the principle of the addition sequence of the acidification process of the present invention is: different from the traditional wet detoxification process, the acid solution is not added to the slag slurry, but the slag slurry is gradually added to the acid solution to make the slag slurry and the acid solution have sufficient To ensure that the microenvironment on the reaction interface is most conducive to the acidification of the slurry.
  • the principle of selecting the sulfuric acid-acetic acid mixture for acidification in the present invention is:
  • the solubility of calcium acetate at 20°C is about 340g/L, which facilitates the stirring of the slurry and avoids the problem that calcium sulfate precipitation can wrap the chromium slag particles and cannot react with acid. .
  • the slurry is gradually transported to the reduction reaction tank and stirred and mixed with the reducing agent solution.
  • the reaction time is 5-8 hours, and the hexavalent chromium in the slurry is converted into trivalent chromium; wherein the reducing agent solution is sulfurous acid dissolved in water
  • the molar ratio of iron and sodium metabisulfite solution, ferrous sulfate and sodium metabisulfite is 4:1 to 6:1, and the concentration of ferrous sulfate in the prepared solution is 15% to 20%.
  • the hexavalent chromium-containing waste residue or hexavalent chromium-contaminated soil slurry is added to the reducing agent In the solution, make the slurry and the reducing agent have sufficient contact to ensure that the reaction interface is the most favorable micro-environment for the reduction of hexavalent chromium.
  • the separated filtrate enters the filtrate tank, and a part of the filtrate in the filtrate tank is recycled to the acidification reaction tank for acidification treatment; the separated filter cake stack Place it in the curing tank for airtight curing; among them, the filter cake is cured in the curing tank for 7-15 days. During the curing period, the filter cake is sprayed with the filtrate to ensure that the filter cake remains moist.
  • the curing tank is a circular tank with HDPE membrane and impermeable cement anti-seepage treatment. It is located 2 to 3 meters below the ground and has a diameter of 4 to 6 meters.
  • the top is covered with HDPE membrane, and the top center is equipped with a nozzle for spraying filtrate. The nozzle is connected to the filtrate tank through a pipe.
  • the filter cake after reduction reaction and dehydration treatment needs to be cured in the curing tank for 7-15 days, thereby reducing the aging time in the reduction reaction tank, improving the production efficiency of the wet detoxification system and prolonging the reaction of hexavalent chromium with the reducing agent Time is conducive to the complete reduction of hexavalent chromium to trivalent chromium.
  • the mixture of chromium residue and soil at the original site of a chromium salt production enterprise in Baiyin, Gansu, has a hexavalent chromium content of 2000-3000mg/kg.
  • the acidified slurry is gradually pumped to the reduction reaction tank and mixed with the reducing agent.
  • the pumping takes 2 hours.
  • the ratio of the reducing agent aqueous solution in the reduction reaction tank is as follows: the molar ratio of ferrous sulfate to sodium metabisulfite is 6:1, the concentration of ferrous sulfate in the reducing agent aqueous solution is 15%, and the reaction time is 5 hours;
  • the filter cake is cured in a curing tank (2 meters deep and 4 meters in diameter). During the curing, the filter cake is sprayed with the filtrate in the filtrate storage tank to ensure that the filter cake remains moist. After 7 days, take 3 mixed samples in the curing tank, and the contents of hexavalent chromium were detected as: 0.14mg/kg, 0.20mg/L, 0.12mg/L; 1 month later, take the detoxified residue In the three mixed samples, the contents of hexavalent chromium detected were: 0.13mg/kg, 0.17mg/L, 0.18mg/L.
  • the mixture of chromium residue and soil at the original site of a chromium salt production enterprise in Zhangye, Gansu, has a hexavalent chromium content of 4000-5000mg/kg.
  • the acidified slurry is gradually pumped to the reduction reaction tank and mixed with the reducing agent.
  • the pumping takes 2 hours.
  • the ratio of the reducing agent aqueous solution in the reduction reaction tank is as follows: the molar ratio of ferrous sulfate to sodium metabisulfite is 4:1, the concentration of ferrous sulfate in the reducing agent aqueous solution is 20%, and the reaction time is 8 hours;
  • the filter cake is cured in a curing tank (3 meters deep and 5 meters in diameter). During the curing, the filter cake is sprayed with the filtrate in the filtrate storage tank to ensure that the filter cake remains moist.
  • three mixed samples were taken in the curing tank, and the contents of hexavalent chromium were detected as: 0.25mg/kg, 0.18mg/L, 0.19mg/L.

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  • Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Processing Of Solid Wastes (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

L'invention concerne un procédé amélioré pour la détoxification par voie humide d'un résidu de déchets contenant du chrome hexavalent ou d'un sol pollué par du chrome hexavalent, consistant à soumettre le résidu de déchets contenant du chrome hexavalent ou le sol pollué par du chrome hexavalent à un traitement de broyage humide pour obtenir une bouillie de résidu; distribuer la bouillie de résidu à une solution mélangée d'acide sulfurique-acide acétique pour un traitement d'acidification pour obtenir une bouillie de matière; distribuer la bouillie de matière à une solution d'un agent réducteur pour une réaction de réduction, de telle sorte que le chrome hexavalent dans la bouillie de matière est transformé en un chrome trivalent; et soumettre la bouillie de matière au chrome trivalent après la réaction de réduction à une séparation solide-liquide, le filtrat séparé étant partiellement recyclé pour le traitement d'acidification, et le gâteau de filtration séparé étant soumis à un traitement de conditionnement externe. La génération d'un précipité de sulfate de calcium au cours du procédé de détoxification par voie humide est réduite par l'ajout d'acide acétique, ce qui empêche le précipité de sulfate de calcium de recouvrir des particules polluantes au chrome hexavalent, et augmente la dissolution du chrome hexavalent au cours de l'étape de lixiviation par acide; en outre, la bouillie de matière acidifiée est progressivement ajoutée à une solution d'un agent réducteur, ce qui favorise un contact complet entre les particules polluantes au chrome hexavalent et l'agent réducteur, et maintient un micro-environnement qui est propice à la survenue de réactions de réduction sur une interface de réaction.
PCT/CN2020/085701 2019-05-29 2020-04-20 Procédé amélioré pour détoxification par voie humide de résidu de déchets contenant du chrome hexavalent ou de sol pollué par du chrome hexavalent WO2020238479A1 (fr)

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CN201910456664.1 2019-05-29
CN201910456664.1A CN110125164A (zh) 2019-05-29 2019-05-29 用于含六价铬废渣或六价铬污染土壤湿法解毒的改进工艺

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CN110125164A (zh) * 2019-05-29 2019-08-16 北京高能时代环境技术股份有限公司 用于含六价铬废渣或六价铬污染土壤湿法解毒的改进工艺
CN111607401A (zh) * 2020-05-27 2020-09-01 重庆大学 一种用于原位修复六价铬污染的修复剂及其制备方法和应用

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