CN102941224B - Method for biologically detoxifying hexavalent chromium in contaminated soil - Google Patents
Method for biologically detoxifying hexavalent chromium in contaminated soil Download PDFInfo
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- CN102941224B CN102941224B CN 201210451114 CN201210451114A CN102941224B CN 102941224 B CN102941224 B CN 102941224B CN 201210451114 CN201210451114 CN 201210451114 CN 201210451114 A CN201210451114 A CN 201210451114A CN 102941224 B CN102941224 B CN 102941224B
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Abstract
The invention provides a method for biologically detoxifying hexavalent chromium in contaminated soil. The method is that the contaminated soil is closely piled up by a geomembrane, the primary humidity of the piled-up soil is 60%-85%, the closed soil is not replenished with water, a soil anaerobic condition is generated in the closed system, so that methane is generated, microorganisms generate an anaerobic atmosphere, wherein hydrogen sulfide in the methane or organic acid during the methane production process can react with hexavalent chromium in the soil, so that the hexavalent chromium is reduced to trivalent chromium, and depending on the uniform dispersion of the reduced gas after the long-term contaminant piling and moisture cycle which is generated by temperature difference between day and night, the hexavalent chromium is completely reduced and the soil is detoxified. Depending on the uniform dispersion of the reduced gas after the long-term contaminant piling and moisture cycle which is generated by temperature difference between day and night, the hexavalent chromium can be completely reduced and the soil can be detoxified, no other materials are needed, the process is simple and the treatment cost is low.
Description
Technical field
The present invention relates to chromic method in a kind of biologic detoxication polluted soil, belong to chromic biologic detoxication technical field.
Background technology
The chromium element is one of important heavy metal element in the productive life, and easily transport property and high bio-toxicity enjoy attention in soil, water body owing to its Cr VI element.The technology of existing removal Cr VI element is all based on chromic reduction and detoxication mechanism.
Chinese patent literature CN2007100492538 discloses a kind of " utilizing reducibility gas that the chromium slag is carried out method for detoxification ", and this method feeds reducibility gas after the chromium slag is heated to 350～750 ℃, keeps at last the chromium slag being cooled off more than 5 seconds.Utilize that redox reaction at high temperature takes place chromic oxidisability in the reproducibility of reducibility gas and the chromium slag
,Make Cr VI become the chromium of trivalent or lower compound, thereby separate water-soluble Cr VI and the chromic toxicity of solubility in acid in the dechromisation slag.
CN 2009100944820 discloses a kind of " utilizing the method for lake sediment in microwave detoxification of chromium slags ", be in reactor (ceramic crucible), pack into by a certain percentage chromium slag and bed mud, and mix, then crucible is put into micro-wave oven, be incubated with the mineral wool insulation material around the crucible, adopt the temperature in the armour formula thermocouple measurement microwave field of being with shielding, after treating that temperature is raised to 800～1100 degree, insulation 25～40min closes micro-wave oven, open fire door behind the 10min, after treating the material cooling, material is immersed in the distilled water, filter behind the immersion 24h.
CN2010102191861 discloses a kind of " utilizing percolate to carry out the method that chromic slag harmlessness is handled ", utilize percolate as additive, with the chromium slag with after percolate mixes by a certain percentage, send into external-heating revolving stove drying, send into the internal heat type pyrolysis oven then and carry out pyrolytic reaction, elevated temperature heat reducing gas in the internal heat type pyrolysis oven is introduced from the reduction combustion furnace, and the pyrolysis product after reduction is handled discharges after shrend.The tail gas of internal heat type pyrolysis oven with after air mixes, enters the external-heating revolving stove in order to the mixture of contact drying percolate and chromium slag through dilution trap.
CN2009102183468 discloses a kind of " method of detoxification chromium slag ", with chromium slag and walnut shell through super-dry with grind, in ceramic crucible, pack into by a certain percentage chromium slag and walnut shell, and mix, then crucible is put into micro-wave oven, be incubated with the mineral wool insulation material around the crucible, adopt the temperature in the armour formula thermocouple measurement microwave field of band shielding, treat that temperature is raised to 700～1000 ℃ after, insulation 10～20min closes micro-wave oven, open fire door behind 5～10min, after treating the material cooling, material is immersed in the distilled water, filter behind the immersion 24h, and filtrate is settled to 250ml, measure Cr in the filtrate with diphenyl carbazide spectrophotometry
6+Concentration, and conversion accounts for the percentage of sample chromium slag amount for the Cr VI quality that leaches, thus calculate the detoxifcation rate.
Above-mentioned several method all needs high-temperature process, and need be by other material, process complexity, operating cost height.
CN2008100996638 discloses a kind of " utilizing sewage plant sludge to administer the method for pollution of chromium ", be adopt sewage treatment plant's sludge discharged and hexavalent chromium polluted material through proportioning, pulverizing, mix, stirring, detoxifcation react, and reaches the purpose of hexavalent chromium polluted improvement.
CN200910043841X discloses a kind of " repairing method of microorganism in contaminated soil of chromium slag storage yard ", the single bacterium colony of picking Pannonibacter phragmitetus BB is cultivated in containing 50～250mg/L Cr (VI) fluid nutrient medium, when nutrient solution does not detect Cr (VI), the bacterial strain of choosing in this bottle is transferred, and progressively improves Cr (VI) concentration and carries out the gradient domestication; The bacterium liquid of Pannonibacter phragmitetus BB after the domestication is added in the contaminated soil, bacterium liquid addition be soil and bacterium liquid mass volume ratio (g: mL) be 1: 2, in 30 ℃ cultivate 4～5 days down after, soil obtains reparation.
CN2011101201748 discloses a kind of " removing the method for trace chromium in the aqueous solution ", this method is by cultivation and analysis to growing plant under the chromium environment, pH value with acid or alkali adjusting chromium-containing solution, add at the same time or separately and contain calcon and carbonate, through leaving standstill, post precipitation, the water of isolating containing chromium slag after testing its contained chromium content less than 0.01mg/L.
CN2010101760687 discloses a kind of " chromium slag muck field contaminated soil biochemically recharging restorative procedure and device ", comprise the soil treatment groove that pending soil is housed, middle pond, biochemistry pool and baterial cultivation pool, each several part is connected by water pipe, chromium-polluted soil through fragmentation cross 2cm sieve, the soil treatment of packing into groove is built heap, the mound height is less than 0.8m, with Cr (VI) reduction bacteria culture fluid spray soil, spraying intensity is 0.008-0.015m3/h.m2.Collect leachate to middle pond from the soil trench bottom, the bacterium liquid in middle pond lye pump suction biochemistry pool, biochemistry pool bacterium liquid is circulated sprinkling soil again.So circulated sprinkling 5-7 days, in the soil leachate, do not have till the Cr (VI).
Though above-mentioned several method does not need high-temperature process, still need be by mud, material such as reduction bacterium etc., and operation is many, the complicated height of process, particularly is difficult to be adapted to the application of large-scale engineering.
Summary of the invention
The present invention is directed to the deficiency that existing detoxifcation Cr VI technology exists, chromic biologic detoxication method in a kind of simple to operate, operating cost is low, detoxifying effect is good polluted soil is provided, and this method is applicable to the biologic detoxication of large pollutant of low toxicity such as polluted soil, chromium slag.
Chromic biologic detoxication method in the polluted soil of the present invention is that the polluted soil sealing is stored up, and detailed process is as described below:
Set up defences on the underlying basis upper berth earlier and ooze material, polluted soil is piled up on the impervious material of underlying basis, form the stockyard, the upper surface in the stockyard piles a series of trapezoidal grooves, and the hydraulic gradient on inclined-plane, groove both sides is 0.1, the ridge is formed at the top of adjacent trenches, be drilled with steam vent on the ridge, cover grave mound on the steam vent, the gutter is formed on the bottom of trapezoidal groove, the hydraulic gradient in gutter is 0.05, and the side was all sealed with impervious material around the upper surface in stockyard reached; Making the initial stage relative humidity of storing up soil is 60%-85%, no longer moisturizing after the sealing, and summer or rainy season should check the grave mound state of steam vent at any time, keep safeguarding the grave mound structure; Soil can produce anaerobic condition in this closed system, produce biogas down at 20-50 ℃, the activity of edaphon flora anaerobism produces anaerobism atmosphere (as a small amount of biogas), the organic acid of hydrogen sulfide wherein or biogas production process can with soil in Cr VI reaction, be trivalent chromium with hexavalent chrome reduction, rely on pollutant to store up the even diffusion of back reducing gas and the aqueous vapor circulation that day and night temperature produces for a long time, make chromic Restore All and make the soil detoxifcation.
Impervious material can adopt geomembrane.
The present invention only need store up contaminated large soil in the closed system, the movable anaerobism atmosphere that produces of microbiological anaerobic in this closed system, rely on pollutant to store up the even diffusion of back reducing gas and the aqueous vapor circulation that day and night temperature produces for a long time, just can guarantee chromic Restore All and make the soil detoxifcation, not need special Cr (VI) reduction bacterium, only need to have in the soil anaerobic bacteria of vigor, need not by other material, process is simple, and processing cost is low, is a kind of environment-friendly treatment method.
Description of drawings
Fig. 1 is the principle schematic of Cr VI biologic detoxication method of the present invention.
The schematic diagram that contains Cr VI leaching concentration changes with time situation in the chromium soil after Fig. 2 stores up for the stockyard is actual, 1,2,3,4 is the numbering of the soil sample in the diverse location sample point in the stockyard among the figure.
Wherein: 1, stockyard, 2, the inclined-plane, 3, the ridge, 4, steam vent, 5, the gutter.
The specific embodiment
As shown in Figure 1, chromic biologic detoxication method is stored up polluted soil exactly in the polluted soil of the present invention according to the landform sealing.Set up defences on the underlying basis upper berth earlier and ooze the material geomembrane, polluted soil is deposited on the geomembrane of underlying basis, form stockyard 1.Each stockyard 1 can be decided to be 15.6 meters of thickness 2.5m, width 1.2m, length.1 upper surface piles two pinnacles in the stockyard, forms trapezoidal groove between the adjacent pinnacle.The hydraulic gradient on inclined-plane, trapezoidal groove both sides is 0.1, and each forms the ridge 3 of width 0.3m above the pinnacle.Get out a plurality of steam vents 4 on ridge 3 downwards, steam vent 4 also can be used for sampling.Form the draining valley road of hydraulic gradient 0.05 longitudinally falling the bottom surface of trapezoidal groove.Grave mound after covering 20 centimetres on the steam vent 4, summer or rainy season should check the grave mound state of steam vent at any time, in time safeguard the grave mound structure.The side was all sealed with geomembrane around the upper surface in stockyard reached.The initial humidity of storing up soil is 60%-85%, no longer moisturizing after the sealing.
Soil can produce anaerobic condition in this closed system, produce biogas down at 20-50 ℃, the movable anaerobism atmosphere that produces of microbiological anaerobic, wherein the organic acid of the hydrogen sulfide in the biogas or biogas production process can with soil in Cr VI reaction, be trivalent chromium with hexavalent chrome reduction, rely on pollutant to store up the even diffusion of back reducing gas and the steam circulation that day and night temperature produces for a long time, make chromic Restore All and make the soil detoxifcation.Stockyard soil after the sealing or chromium slag are by the highest Cr
6+Leach concentration 67mg/L, become and in 2 years, finish chromic detoxifcation fully, can be lower than " the hazardous waste judging standard leaches toxicity and differentiates " (GB5085.3-2007) detection limit of standard appendix D solid waste metallic element flame atomic absorption spectrometry.
Fig. 2 contains actual its Cr VI of back of storing up of chromium soil to leach concentration changes with time situation, provided in the stockyard soil sample in 1,2,3,4 four diverse location sample point in the testing result of storing up initial (on April 20th, 2010), on March 15th, 2011 and three times on the 13rd July in 2012.As seen from Figure 2, the stockyard soil after the sealing or chromium slag are by the highest Cr
6+Leach concentration 67mg/L, in 3 years, can finish chromic detoxifcation fully.
Claims (1)
1. chromic biologic detoxication method in the polluted soil is characterized in that, the polluted soil sealing is stored up, and detailed process is as described below:
Set up defences on the underlying basis upper berth earlier and ooze material, polluted soil is piled up on the impervious material of underlying basis, form the stockyard, the upper surface in the stockyard piles a series of trapezoidal grooves, and the hydraulic gradient on inclined-plane, groove both sides is 0.1, the ridge is formed at the top of adjacent trenches, be drilled with steam vent on the ridge, cover grave mound on the steam vent, the gutter is formed on the bottom of trapezoidal groove, the hydraulic gradient in gutter is 0.05, and the side was all sealed with impervious material around the upper surface in stockyard reached; Making the initial stage relative humidity of storing up soil is 60%-85%, no longer moisturizing after the sealing, and summer or rainy season should check the grave mound state of steam vent at any time, keep safeguarding the grave mound structure; Soil can produce anaerobic condition in this closed system, produce biogas down at 20-50 ℃, the activity of edaphon flora anaerobism produces anaerobism atmosphere, the organic acid of hydrogen sulfide wherein or biogas production process can with soil in Cr VI reaction, be trivalent chromium with hexavalent chrome reduction, rely on pollutant to store up the even diffusion of back reducing gas and the aqueous vapor circulation that day and night temperature produces for a long time, make the Cr VI Restore All and make the soil detoxifcation.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103495602B (en) * | 2013-09-30 | 2015-07-01 | 河南金谷实业发展有限公司 | Method for restoring hexavalent chromium-polluted soil by utilizing microbial fermentation |
| CN103978026B (en) * | 2013-12-05 | 2015-10-28 | 青岛理工大学 | One utilizes debirs in-situ immobilization containing the method in Cr (VI) place |
| CN104475433A (en) * | 2014-11-19 | 2015-04-01 | 湖南广义科技有限公司 | Harmless control and resource recovery method of lands polluted by heavy metals |
| CN104759457B (en) * | 2015-04-03 | 2017-07-25 | 北京建工环境修复股份有限公司 | The method for arranging for the dystopy reaction system that chromium-polluted soil is repaired |
| CN106623399B (en) * | 2016-10-27 | 2020-01-03 | 北京市环境保护科学研究院 | Method for repairing hexavalent chromium contaminated soil by utilizing biogas slurry |
| CN111036668A (en) * | 2019-11-25 | 2020-04-21 | 南京师范大学 | Method for treating and repairing Cr (VI) slag and polluted soil thereof |
| CN113510144B (en) * | 2021-04-22 | 2022-11-08 | 贵州星硕铭越环保科技有限公司 | Method for treating heavy metal pollution of agricultural land in zinc smelting pollution area by soil method |
| CN113617832B (en) * | 2021-08-11 | 2022-06-28 | 中国热带农业科学院热带作物品种资源研究所 | Wampee tree planting soil restoration cultivation method |
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Effective date of registration: 20190704 Address after: 251414 No. 1000, Beichencun, Renfeng Town, Jiyang County, Jinan City, Shandong Province Patentee after: Ji'nan cloud water leaping Environmental Protection Technology Co., Ltd. Address before: 250100 No. 1 Hot Spring Road, Lingang Development Zone, Jinan City, Shandong Province Patentee before: SHANDONG TENGYUE CHEMICAL HAZARDOUS WASTE RESEARCH & TREATMENT CO., LTD. |