WO2020238479A1 - Improved process for wet detoxification of hexavalent-chromium-containing waste residue or hexavalent chromium polluted soil - Google Patents

Improved process for wet detoxification of hexavalent-chromium-containing waste residue or hexavalent chromium polluted soil Download PDF

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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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slurry
hexavalent chromium
chromium
tank
hexavalent
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PCT/CN2020/085701
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French (fr)
Chinese (zh)
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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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    • 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

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  • 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.

Abstract

Disclosed is an improved process for wet detoxification of a hexavalent-chromium-containing waste residue or hexavalent chromium polluted soil, comprising subjecting the hexavalent-chromium-containing waste residue or the hexavalent chromium polluted soil to a wet grinding treatment to obtain a residue slurry; delivering the residue slurry to a sulfuric acid-acetic acid mixed solution for an acidification treatment to obtain a material slurry; delivering the material slurry to a solution of a reducing agent for a reduction reaction, such that the hexavalent chromium in the material slurry is transformed into a trivalent chromium; and subjecting the trivalent chromium material slurry after the reduction reaction to solid-liquid separation, wherein the separated filtrate is partly recycled for the acidification treatment, and the separated filter cake is subjected to an external conditioning treatment. The generation of a calcium sulfate precipitate during the wet detoxification process is reduced by adding acetic acid, thus preventing the calcium sulfate precipitate from covering hexavalent chromium pollutant particles, and increasing the dissolution of the hexavalent chromium during the acid leaching stage; in addition, the acidified material slurry is gradually added to a solution of a reducing agent, thus promoting full contact between the hexavalent chromium pollutant particles and the reducing agent, and maintaining a microenvironment that is conducive to the occurrence of reduction reactions on a reaction interface.

Description

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Improved process for wet detoxification of hexavalent chromium-containing waste residue or hexavalent chromium polluted soil 技术领域Technical field
本发明涉及污染治理技术领域，具体涉及一种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，实现含六价铬污染物的无害化处理。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.
背景技术Background technique
目前对含六价铬废渣已经得到了无害化处理，但由于大部分铬渣堆场堆存时间久远且缺少防止六价铬扩散的措施，铬渣堆放地的土壤也受到了严重污染，部分场地含六价铬废渣与污染土壤混合在一起。对场地中的含六价铬废渣、六价铬重度污染土壤进行无害化处理，是对六价铬污染场地进行综合治理的重要环节。At present, the waste slag containing hexavalent chromium has been harmlessly treated. However, due to the long storage time of most of the chromium residues and the lack of measures to prevent the diffusion of hexavalent chromium, 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.
现有的用于铬渣湿法解毒的工艺存在解毒后“返黄”、解毒不彻底等问题，无法达到新标准的要求。Existing processes for wet detoxification of chromium slag have problems such as "yellowing" after detoxification and incomplete detoxification, which cannot meet the requirements of the new standard.
现有用于铬渣湿法解毒的工艺存在以下问题：The existing technology for wet detoxification of chromium slag has the following problems:
1、在渣浆酸化过程中，将酸加入到含六价铬废渣或六价铬污染土壤渣浆中，不利于酸化彻底；1. During the acidification of the slurry, adding acid to the hexavalent chromium-containing waste residue or hexavalent chromium-contaminated soil slurry is not conducive to thorough acidification;
2、添加硫酸进行酸化处理，由于大部分铬渣钙含量较高，当添加硫酸时，硫酸根与钙形成硫酸钙，由于料浆加水量少，浆液中硫酸钙的浓度过高容易形成硫酸钙沉淀(硫酸钙的溶解度约为是2g/L)，导致料浆变粘稠不易搅拌；2. Add sulfuric acid for acidification treatment. Since most of the chromium residue has a high calcium content, when sulfuric acid is added, sulfate radicals and calcium form calcium sulfate. Due to the small amount of water added to the slurry, the concentration of calcium sulfate in the slurry is too high to easily form calcium sulfate Precipitation (the solubility of calcium sulfate is about 2g/L), causing the slurry to become thick and difficult to stir;
3、在还原反应过程中，将还原剂添加到含六价铬废渣或六价铬污染土壤料浆中，不利于还原反应的发生；3. During the reduction reaction, adding the reducing agent to the hexavalent chromium-containing waste residue or hexavalent chromium-contaminated soil slurry is not conducive to the occurrence of the reduction reaction;
4、将还原药剂与酸化后的六价铬浆液在搅拌罐中熟化，若熟化时间不够长，不利与六价铬的还原，若熟化时间过长，一方面能耗高，另一方面也会降低湿法解毒系统的效率。4. 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.
发明内容Summary of the invention
针对上述问题中存在的不足之处，本发明提供一种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，提高湿法解毒的彻底性和长效性。In view of the deficiencies in the above problems, 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.
本发明公开了一种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，包括：The present invention discloses an improved process for wet detoxification of hexavalent chromium-containing waste residue or hexavalent chromium-contaminated soil, including:
将含六价铬废渣或六价铬污染土壤进行湿磨处理，得到渣浆；The hexavalent chromium-containing waste residue or hexavalent chromium-contaminated soil is subjected to wet grinding treatment to obtain a slurry;
将所述渣浆输送至硫酸-醋酸混合液中进行酸化处理，得到料浆；Transporting the slurry to the sulfuric acid-acetic acid mixed liquid for acidification treatment to obtain a slurry;
将所述料浆输送至还原剂溶液中进行还原反应，使所述料浆中的六价铬转化为三价铬；Transporting the slurry to the reducing agent solution for reduction reaction, so that the hexavalent chromium in the slurry is converted into trivalent chromium;
将还原反应后的三价铬料浆进行固液分离，分离后的滤液部分循环用于酸化处理，分离后的滤饼进行外部养护处理。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.
作为本发明的进一步改进，所述将含六价铬废渣或六价铬污染土壤进行湿磨处理，得到渣浆；包括：As a further improvement of the present invention, the wet grinding treatment of waste slag containing hexavalent chromium or soil contaminated with hexavalent chromium to obtain a slurry; comprising:
将经过筛分磨碎的六价铬废渣或六价铬污染土壤置入湿磨设备，将其磨碎至100～150目，得到所述渣浆。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.
作为本发明的进一步改进，所述将所述渣浆输送至硫酸-醋酸混合液中进行酸化处理，得到料浆；包括：As a further improvement of the present invention, the said conveying the said slurry into the sulfuric acid-acetic acid mixed liquid for acidification treatment to obtain the slurry; comprising:
将所述渣浆逐渐输送到酸化反应罐中，与酸化反应罐内的硫酸-醋酸混合液搅拌混合，使所述料浆的pH维持在5～6，老化5～6小时。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.
作为本发明的进一步改进，所述硫酸的质量百分数为10％～20％，所述醋酸的质量百分数为5％～10％，所述硫酸与醋酸的体积比为1:1～3:1。As a further improvement of the present invention, the mass percentage of the sulfuric acid is 10%-20%, the mass percentage of the acetic acid is 5%-10%, and the volume ratio of the sulfuric acid to the acetic acid is 1:1-3:1.
作为本发明的进一步改进，所述将所述料浆输送至还原剂溶液中进行还原反应，使所述料浆中的六价铬转化为三价铬；包括：As a further improvement of the present invention, 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:
将所述料浆逐渐输送到还原反应罐中，与还原反应罐内的还原剂溶液搅拌混合，反应时间5-8小时，将所述料浆中的六价铬转化为三价铬。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.
作为本发明的进一步改进，所述还原剂溶液为溶解在水中的硫酸亚铁与焦亚硫酸钠溶液，所述硫酸亚铁与焦亚硫酸钠的摩尔比为4:1～6:1，配置好的溶液中硫酸亚铁的浓度为15％～20％。As a further improvement of the present invention, 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%.
作为本发明的进一步改进，所述将还原反应后的三价铬料浆进行固液分离，分离后的滤液部分循环用于酸化处理，分离后的滤饼进行外部养护处理；包括：As a further improvement of the present invention, 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:
将还原反应后的料浆泵入板框压滤机进行固液分离，分离后的滤液进入滤液罐，所述滤液罐中的一部分滤液循环至酸化反应罐，用于酸化处理；分离后的滤饼堆置于养护槽内进行密闭养护。Pump the reduction reaction slurry into a plate and frame filter press for solid-liquid separation, 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.
作为本发明的进一步改进，还包括：As a further improvement of the present invention, it also includes:
所述滤饼在养护槽内养护7～15天，养护期间，用滤液喷洒滤饼，确保滤饼保持湿润状态。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.
作为本发明的进一步改进，所述养护槽是经过HDPE膜和抗渗水泥防渗处理的圆形槽，位于地面下2～3米，直径4～6米，顶部覆盖HDPE膜，并在顶部中心位置配备有用于喷洒滤液的喷头，喷头通过管道与滤液罐相连。As a further improvement of the present invention, 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.
与现有技术相比，本发明的有益效果为：Compared with the prior art, the beneficial effects of the present invention are:
1、本发明将湿磨处理后的渣浆逐渐加入到硫酸-醋酸溶液中，从而促进渣浆与酸溶液的充分接触，并在反应界面上保持利于酸化反应进行的微环境；1. In the present invention, 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;
2、本发明通过添加醋酸来减少湿法解毒过程硫酸钙沉淀的产生，从而避免硫酸钙沉淀将六价铬污染物颗粒包裹，提高酸浸阶段六价铬的溶出；2. 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;
3、本发明将酸化后的料浆逐渐加入到还原剂溶液中，从而促进六价铬污染物颗粒与还原剂充分接触，并在反应界面上保持利于还原反应发生的微环境；3. In the present invention, 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;
4、本发明将分离后的滤饼进行置于外部养护槽内进行养护，减少在还原反应罐内的老化时间，提高湿法解毒系统的生产效率并延长六价铬与还原剂的反应时间，利于六价铬被彻底还原为三价铬。4. 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.
附图说明Description of the drawings
图1为本发明一种实施例公开的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的流程图。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.
具体实施方式Detailed ways
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be described clearly and completely in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments It is a part of the embodiments of the present invention, but not all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present invention.
下面结合附图对本发明做进一步的详细描述：The present invention will be further described in detail below in conjunction with the accompanying drawings:
如图1所示，本发明提供一种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，包括：As shown in Figure 1, the present invention provides an improved process for wet detoxification of hexavalent chromium-containing waste residue or hexavalent chromium-contaminated soil, including:
S1、将含六价铬废渣或六价铬污染土壤进行湿磨处理，得到渣浆；S1. Perform wet grinding treatment on waste slag containing hexavalent chromium or soil contaminated with hexavalent chromium to obtain a slurry;
具体为：Specifically:
将经过筛分磨碎的六价铬废渣或六价铬污染土壤置入湿磨设备，将其磨碎至100～150目，得到渣浆。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.
S2、将渣浆逐渐加入至硫酸-醋酸混合液中进行酸化处理，得到料浆；S2. Gradually add the slurry to the sulfuric acid-acetic acid mixed liquid for acidification treatment to obtain slurry;
具体为：Specifically:
先在酸化反应罐中加入硫酸-醋酸混合液，再将渣浆逐渐输送到酸化反应罐中进行酸化，使料浆的pH维持在5～6，老化5～6小时；其中，硫酸的质量百分数为10％～20％，醋酸的质量百分数为5％～10％，硫酸与醋酸的体积比为1:1～3:1。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.
本发明上述酸化过程添加顺序的原理为：与传统的湿法解毒工艺不同，不是将酸溶液加入到渣浆中，而是将渣浆逐渐添加到酸溶液中，使渣浆与酸溶液有充分的接触，确保在反应界面上是最有利于渣浆酸化的微环境。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.
本发明选用硫酸-醋酸混合液进行酸化处理的原理为：The principle of selecting the sulfuric acid-acetic acid mixture for acidification in the present invention is:
由于大部分铬渣钙含量较高，当添加硫酸时，硫酸根与钙形成硫酸钙，由于料浆加水量少，浆液中硫酸钙的浓度过高容易形成硫酸钙沉淀(硫酸钙的溶解度约为是2g/L)，导致料浆变粘稠不易搅拌。醋酸的加入，可以减少硫酸钙沉淀的产生，醋酸钙20℃的溶解度约为340g/L，从而利于对浆液进行搅拌，并避免硫酸钙沉淀将铬渣颗粒包裹起来后无法与酸发生反应的问题。Due to the high calcium content of most chromium residues, when sulfuric acid is added, sulfate radicals and calcium form calcium sulfate. Due to the small amount of water added to the slurry, the concentration of calcium sulfate in the slurry is too high to easily form calcium sulfate precipitation (the solubility of calcium sulfate is about It is 2g/L), which causes the slurry to become viscous and difficult to stir. The addition of acetic acid can reduce the generation of calcium sulfate precipitation. 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. .
S3、将料浆输送至还原剂溶液中进行还原反应，使料浆中的六价铬转化为三价铬；S3. Transporting the slurry to the reducing agent solution for reduction reaction to convert the hexavalent chromium in the slurry into trivalent chromium;
具体为：Specifically:
将料浆逐渐输送到还原反应罐中与还原剂溶液搅拌混合，反应时间5-8小时，将料浆中的六价铬转化为三价铬；其中，还原剂溶液为溶解在水中的硫酸亚铁与焦亚硫酸钠溶液，硫酸亚铁与焦亚硫酸钠的摩尔比为4:1～6:1，配置好的溶液中硫酸亚铁的浓度为15％～20％。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%.
本发明上述还原反应添加顺序的原理为：The principle of the above-mentioned reduction reaction addition sequence of the present invention is:
与传统的湿法解毒工艺不同，不是将还原剂添加到含六价铬废渣或六价铬污染土壤料浆中，而是将含六价铬废渣或六价铬污染土壤料浆加入到还原 剂溶液中，使料浆与还原剂有充分的接触，确保在反应界面上是最有利于六价铬被还原的微环境。Different from the traditional wet detoxification process, instead of adding the reducing agent to the hexavalent chromium-containing waste residue or hexavalent chromium-contaminated soil slurry, 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.
S4、将还原反应后的三价铬料浆进行固液分离，分离后的滤液部分循环用于酸化处理，分离后的滤饼进行外部养护处理；S4. 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;
具体为：Specifically:
将还原反应后的料浆泵入板框压滤机进行固液分离，分离后的滤液进入滤液罐，滤液罐中的一部分滤液循环至酸化反应罐，用于酸化处理；分离后的滤饼堆置于养护槽内进行密闭养护；其中，滤饼在养护槽内养护7～15天，养护期间，用滤液喷洒滤饼，确保滤饼保持湿润状态。养护槽是经过HDPE膜和抗渗水泥防渗处理的圆形槽，位于地面下2～3米，直径4～6米，顶部覆盖HDPE膜，并在顶部中心位置配备有用于喷洒滤液的喷头，喷头通过管道与滤液罐相连。Pump the reduction reaction slurry into a plate and frame filter press for solid-liquid separation. 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.
本发明上述养护处理的原理为：The principle of the above-mentioned curing treatment of the present invention is:
经还原反应、脱水处理后的滤饼需要在养护槽内养护7～15天，从而减少在还原反应罐内的老化时间，提高湿法解毒系统的生产效率并延长六价铬与还原剂的反应时间，利于六价铬被彻底还原为三价铬。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.
实施例1：Example 1:
甘肃白银某铬盐生产企业原址的铬渣与土壤的混合物，六价铬含量2000-3000mg/kg。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.
S1、将经过筛分磨碎的渣土混合物置入球磨机中进行湿磨，使其可以通过100目筛；S1. Put the sieved and ground residue mixture into a ball mill for wet grinding, so that it can pass through a 100-mesh sieve;
S2、先将体积比为1:1的硫酸(10％溶液)-醋酸(5％溶液)混合液泵入酸化反应罐中，再将通过100目筛的料浆逐渐泵入酸化反应罐与酸溶液混合搅拌，使料浆的pH维持在5～6范围，老化6小时；S2. First, pump the sulfuric acid (10% solution)-acetic acid (5% solution) mixture with a volume ratio of 1:1 into the acidification reaction tank, and then gradually pump the slurry passing through the 100 mesh sieve into the acidification reaction tank and the acid The solution is mixed and stirred to maintain the pH of the slurry in the range of 5-6, aging for 6 hours;
S3、将酸化后的料浆逐渐泵送到还原反应罐中与还原药剂搅拌混合，泵送用时2小时，还原反应罐中的还原剂水溶液配比如下：硫酸亚铁与焦亚硫酸钠的摩尔比为6:1，还原剂水溶液中硫酸亚铁的浓度为15％，反应时间5小时；S3. 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;
S4、将还原反应罐中料浆泵入板框压滤机进行固液分离，分离后的滤液进入滤液罐储存；S4. Pump the slurry in the reduction reaction tank into the plate and frame filter press for solid-liquid separation, and the separated filtrate enters the filtrate tank for storage;
S5、滤饼在养护槽内(深2米，直径4米)养护，养护期间，用滤液储存罐中的滤液喷洒滤饼，确保滤饼保持湿润状态。7天后，在养护槽中取3个混合样，检测得到六价铬的含量分别为：0.14mg/kg、0.20mg/L、0.12mg/L；1个月后，对解毒后的渣土取3个混合样，检测得到六价铬的含量分别为：0.13mg/kg、0.17mg/L、0.18mg/L。S5. 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.
S6、将滤液储存罐中的滤液泵入酸化反应罐进行循环利用。S6. Pump the filtrate in the filtrate storage tank into the acidification reaction tank for recycling.
实施例2：Example 2:
甘肃张掖某铬盐生产企业原址的铬渣与土壤的混合物，六价铬含量4000-5000mg/kg。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.
S1、将经过筛分磨碎的渣土混合物置入球磨机中进行湿磨，使其可以通过150目筛；S1. Put the sieved and ground residue mixture into a ball mill for wet grinding, so that it can pass through a 150-mesh sieve;
S2、将体积比为3:1的硫酸(20％溶液)-醋酸(10％溶液)混合液泵入酸化反应罐，再将通过150目筛的料浆逐渐泵入酸化反应罐与酸溶液混合搅拌，使料浆的pH维持在5～6范围，老化6小时；S2. Pump the sulfuric acid (20% solution)-acetic acid (10% solution) mixture with a volume ratio of 3:1 into the acidification reaction tank, and then gradually pump the slurry passing through the 150 mesh sieve into the acidification reaction tank and mix with the acid solution Stir to maintain the pH of the slurry in the range of 5 to 6, and age for 6 hours;
S3、将酸化后的料浆逐渐泵送到还原反应罐中与还原药剂搅拌混合，泵送用时2小时，还原反应罐中的还原剂水溶液配比如下：硫酸亚铁与焦亚硫酸钠的摩尔比为4:1，还原剂水溶液中硫酸亚铁的浓度为20％，反应时间8小时；S3. 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;
S4、将还原反应罐中料浆泵入板框压滤机进行固液分离，分离后的滤液进入滤液罐储存；S4. Pump the slurry in the reduction reaction tank into the plate and frame filter press for solid-liquid separation, and the separated filtrate enters the filtrate tank for storage;
S5、滤饼在养护槽内(深3米，直径5米)养护，养护期间，用滤液储存罐中的滤液喷洒滤饼，确保滤饼保持湿润状态。15天后，在养护槽中取3个混合样，检测得到六价铬的含量分别为：0.25mg/kg、0.18mg/L、0.19mg/L，1个月后，对解毒后的渣土取3个混合样，检测得到六价铬的含量分别为：0.15mg/kg、0.20mg/L、0.13mg/L。S5. 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. After 15 days, 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. One month later, take the detoxified residue In the three mixed samples, the contents of hexavalent chromium were detected as follows: 0.15mg/kg, 0.20mg/L and 0.13mg/L.
S6、将滤液储存罐中的滤液泵入酸化反应罐进行循环利用。S6. Pump the filtrate in the filtrate storage tank into the acidification reaction tank for recycling.
以上仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above are only preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various modifications and changes. Any modification, equivalent replacement, improvement, etc., made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

  1. 一种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，其特征在于，包括：An improved process for wet detoxification of hexavalent chromium-containing waste residue or hexavalent chromium-contaminated soil, which is characterized in that it comprises:
    将含六价铬废渣或六价铬污染土壤进行湿磨处理，得到渣浆；The hexavalent chromium-containing waste residue or hexavalent chromium-contaminated soil is subjected to wet grinding treatment to obtain a slurry;
    将所述渣浆输送至硫酸-醋酸混合液中进行酸化处理，得到料浆；Transporting the slurry to the sulfuric acid-acetic acid mixed liquid for acidification treatment to obtain a slurry;
    将所述料浆输送至还原剂溶液中进行还原反应，使所述料浆中的六价铬转化为三价铬；Transporting the slurry to the reducing agent solution for reduction reaction, so that the hexavalent chromium in the slurry is converted into trivalent chromium;
    将还原反应后的三价铬料浆进行固液分离，分离后的滤液部分循环用于酸化处理，分离后的滤饼进行外部养护处理。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.
  2. 如权利要求1所述的改进工艺，其特征在于，所述将含六价铬废渣或六价铬污染土壤进行湿磨处理，得到渣浆；包括：The improved process according to claim 1, wherein the wet grinding treatment is performed on waste slag containing hexavalent chromium or soil contaminated with hexavalent chromium to obtain a slurry; comprising:
    将经过筛分磨碎的六价铬废渣或六价铬污染土壤置入湿磨设备，将其磨碎至100～150目，得到所述渣浆。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.
  3. 如权利要求1所述的改进工艺，其特征在于，所述将所述渣浆输送至硫酸-醋酸混合液中进行酸化处理，得到料浆；包括：The improved process according to claim 1, characterized in that said transporting said slurry to a sulfuric acid-acetic acid mixture for acidification treatment to obtain slurry; comprising:
    将所述渣浆逐渐输送到酸化反应罐中，与酸化反应罐内的硫酸-醋酸混合液搅拌混合，使所述料浆的pH维持在5～6，老化5～6小时。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.
  4. 如权利要求3所述的改进工艺，其特征在于，所述硫酸的质量百分数为10％～20％，所述醋酸的质量百分数为5％～10％，所述硫酸与醋酸的体积比为1:1～3:1。The improved process according to claim 3, wherein the mass percentage of the sulfuric acid is 10%-20%, the mass percentage of the acetic acid is 5%-10%, and the volume ratio of the sulfuric acid to acetic acid is 1. :1～3:1.
  5. 如权利要求1所述的改进工艺，其特征在于，所述将所述料浆输送至还原剂溶液中进行还原反应，使所述料浆中的六价铬转化为三价铬；包括：5. The improved process according to claim 1, wherein said transferring said slurry to a reducing agent solution for reduction reaction to convert hexavalent chromium in said slurry into trivalent chromium; comprising:
    将所述料浆逐渐输送到还原反应罐中，与还原反应罐内的还原剂溶液搅拌混合，反应时间5-8小时，将所述料浆中的六价铬转化为三价铬。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.
  6. 如权利要求5所述的改进工艺，其特征在于，所述还原剂溶液为溶解在水中的硫酸亚铁与焦亚硫酸钠溶液，所述硫酸亚铁与焦亚硫酸钠的摩尔比为4:1～6:1，配置好的溶液中硫酸亚铁的浓度为15％～20％。The improved process according to claim 5, wherein 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 in the prepared solution is 15%-20%.
  7. 如权利要求1所述的改进工艺，其特征在于，所述将还原反应后的三价铬料浆进行固液分离，分离后的滤液部分循环用于酸化处理，分离后的滤饼进行外部养护处理；包括：The improved process of claim 1, wherein 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 externally cured Processing; including:
    将还原反应后的料浆泵入板框压滤机进行固液分离，分离后的滤液进入 滤液罐，所述滤液罐中的一部分滤液循环至酸化反应罐，用于酸化处理；分离后的滤饼堆置于养护槽内进行密闭养护。Pump the reduction reaction slurry into a plate and frame filter press for solid-liquid separation, 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.
  8. 如权利要求7所述的改进工艺，其特征在于，还包括：The improved process according to claim 7, characterized in that it further comprises:
    所述滤饼在养护槽内养护7～15天，养护期间，用滤液喷洒滤饼，确保滤饼保持湿润状态。The filter cake is cured in the curing tank for 7-15 days. During the curing, the filter cake is sprayed with the filtrate to ensure that the filter cake remains moist.
  9. 如权利要求8所述的改进工艺，其特征在于，所述养护槽是经过HDPE膜和抗渗水泥防渗处理的圆形槽，位于地面下2～3米，直径4～6米，顶部覆盖HDPE膜，并在顶部中心位置配备有用于喷洒滤液的喷头，喷头通过管道与滤液罐相连。The improved process according to claim 8, characterized in that, 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. HDPE membrane, and is equipped with a spray head for spraying filtrate at the top center, which is connected to the filtrate tank through a pipe.
PCT/CN2020/085701 2019-05-29 2020-04-20 Improved process for wet detoxification of hexavalent-chromium-containing waste residue or hexavalent chromium polluted soil WO2020238479A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110125164A (en) * 2019-05-29 2019-08-16 北京高能时代环境技术股份有限公司 Improvement technique for waste residue containing Cr VI or hexavalent chromium polluted soil wet method detoxifcation
CN111607401A (en) * 2020-05-27 2020-09-01 重庆大学 Repairing agent for in-situ repairing hexavalent chromium pollution and preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102614620A (en) * 2012-03-15 2012-08-01 中国科学院过程工程研究所 Wet detoxification method of hexavalent chromium contained alkali waste residues
JP2013116465A (en) * 2011-10-31 2013-06-13 Jfe Steel Corp Material for reducing harmful element, and method for reducing harmful element
KR101349073B1 (en) * 2013-08-30 2014-01-09 한국지질자원연구원 Heavy metal-contaminated soil washing method using soil washing solution including siderophore and heavy metal-contaminated soil washing device
CN103894406A (en) * 2014-03-18 2014-07-02 江苏维尔利环保科技股份有限公司 Method for restoring polluted chromium-containing soil by combining wet detoxification and stabilization
CN103071670B (en) * 2013-01-24 2016-03-16 韩清洁 A kind of equipment for chromium slag contaminated soil Detoxified treatment
CN108723071A (en) * 2018-05-22 2018-11-02 河北省冀信环保科技有限公司 One kind harmless treatment device containing chromium soil and processing method
CN110125164A (en) * 2019-05-29 2019-08-16 北京高能时代环境技术股份有限公司 Improvement technique for waste residue containing Cr VI or hexavalent chromium polluted soil wet method detoxifcation

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102189093B (en) * 2010-03-09 2015-02-04 刘杰 Method for detoxicating chromium residues and comprehensive utilization of detoxicated chromium residues
CN103586273A (en) * 2012-08-14 2014-02-19 江苏盖亚环境工程有限公司 Method for treating contaminated soil by utilizing wedge-shape high-strength isolated leaching reaction tank
CN103934256B (en) * 2014-04-21 2019-06-04 江苏维尔利环保科技股份有限公司 Chromium slag and wet method detoxifcation method containing chromium pollutant
CN204148233U (en) * 2014-09-23 2015-02-11 中科华南（厦门）环保有限公司 A kind of modular optimizes integrated-type high chromium concentration contaminated soil remediation system adopting recirculating
CN109304356A (en) * 2018-11-07 2019-02-05 长沙汇聚环境技术有限公司 A kind of method of zinc and organic material contaminated soil reparation

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013116465A (en) * 2011-10-31 2013-06-13 Jfe Steel Corp Material for reducing harmful element, and method for reducing harmful element
CN102614620A (en) * 2012-03-15 2012-08-01 中国科学院过程工程研究所 Wet detoxification method of hexavalent chromium contained alkali waste residues
CN103071670B (en) * 2013-01-24 2016-03-16 韩清洁 A kind of equipment for chromium slag contaminated soil Detoxified treatment
KR101349073B1 (en) * 2013-08-30 2014-01-09 한국지질자원연구원 Heavy metal-contaminated soil washing method using soil washing solution including siderophore and heavy metal-contaminated soil washing device
CN103894406A (en) * 2014-03-18 2014-07-02 江苏维尔利环保科技股份有限公司 Method for restoring polluted chromium-containing soil by combining wet detoxification and stabilization
CN108723071A (en) * 2018-05-22 2018-11-02 河北省冀信环保科技有限公司 One kind harmless treatment device containing chromium soil and processing method
CN110125164A (en) * 2019-05-29 2019-08-16 北京高能时代环境技术股份有限公司 Improvement technique for waste residue containing Cr VI or hexavalent chromium polluted soil wet method detoxifcation

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