CN101862749B - Recovering method of soil polluted by chromium residue - Google Patents
Recovering method of soil polluted by chromium residue Download PDFInfo
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- CN101862749B CN101862749B CN 200910131680 CN200910131680A CN101862749B CN 101862749 B CN101862749 B CN 101862749B CN 200910131680 CN200910131680 CN 200910131680 CN 200910131680 A CN200910131680 A CN 200910131680A CN 101862749 B CN101862749 B CN 101862749B
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- soil
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- chromium residue
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Abstract
The invention relates to a method for repairing and processing the soil polluted by heavy metals such as chromium and the like and semimetal elements such as arsenic and the like, and eliminating the pollution influence. The method mainly comprises the following steps: carrying out the dry treatment on the polluted soil, and carrying out the crushing and grinding treatment; carrying out the reduction treatment by a reducing agent on the polluted soil which is crushed and ground; carrying out a first curing process by a first curing agent on the polluted soil which undergoes the reduction treatment; carrying out a second curing process by a second curing agent on the polluted soil which undergoes the first curing process, thus obtaining the repaired soil. By the processing programs, harmful substances such as the heavy metals and the like in the polluted oil are solidified into the stable state; and the toxicity of the harmful substances is obviously reduced and is not easily diffused.
Description
Technical field
The present invention relates to a kind of to received heavy metal such as chromium and and semimetallic elements contaminated soil such as arsenic carry out the restorative procedure that repair process, pollution abatement influence, especially to a kind of soil that receives heavy metal pollution such as Cr VI.
Background technology
Heavy metal pollution is the environmental pollution that is caused by heavy metal or its compound.Mainly by due to the human factors such as mining, sewage discharge and use heavy metal goods.Its extent of injury depends on concentration and the chemical form that heavy metal exists in environment.
Chromium is a kind of common source of heavy metal pollution, and the different forms that exist directly have influence on the toxicity property and the transportable property of chromium.Cr VI has stronger oxidisability, and toxicity is bigger, for reducing or eliminating its toxicity and prevent its diffusion, will convert Cr VI into trivalent chromium usually.In addition, elements such as lead, cadmium, zinc, arsenic also are common pollution sources, and especially when it was in ionic forms, bamboo telegraph soluble in water caused the pollution of wider and the bigger degree of depth.
Landfill has on the spot been carried out to a large amount of noxious industry discarded objects in certain chemical plant in plant area's transformation process, mainly contain the chromium slag, electroplate waste residue, contaminated brick slag, cinder etc.Cause heavy metals such as containing a large amount of chromium, lead, cadmium, zinc, arsenic in the soil, all belong to strong toxic pollutant.Be the influence that reduces to pollute, need carry out repair process, make the innoxious and renewable resources utilization of contaminated soil contaminated soil.
Summary of the invention
Technical problem to be solved by this invention provides a kind of restorative procedure of soil polluted by chromium residue; Contaminated soil is carried out harmless treatment; Make semimetallic elements such as heavy metal elements such as chromium in the soil and arsenic change a kind of stable morphology into, prevent its diffusion.
The technical scheme that the present invention solves the problems of the technologies described above is following: a kind of restorative procedure of soil polluted by chromium residue comprises the steps:
Step 1, polluted soil is carried out dried, and carry out fragmentation and milled processed;
Step 2, the polluted soil after fragmentation and milled processed is reduced processing with reducing agent;
Step 3, the polluted soil after handling through reduction is carried out the cured first time with first curing agent;
Step 4, with second curing agent to carrying out the cured second time, the soil after can obtaining repairing through the polluted soil of cured for the first time.
On the basis of technique scheme, the present invention can also do following improvement.
Polluted soil is after broken and milled processed in the said step 1, and its particle order number is above (particle diameter is less than 198 microns), preferably 80 ∽, 120 orders of 80 orders.
Reducing agent in the said step 2 is copperas solution or sodium sulfite solution or sodium metabisulfite solution etc.Solution with containing ferrous ion is handled dirty soil as reducing agent, can hexavalent chromium compound poisonous in the dirty soil be reduced to nontoxic basically trivalent chromium compound.Its chemical equation is following:
CrO
4 2-+3Fe
2++8H
+→3Fe
3++Cr
3++4H
2O
2CrO
4 2-+3SO
3 2-+10H
+→2Cr
3++3SO
4 2-+5H
2O
4CrO
4 2-+3S
2O
5 2-+14H
+→4Cr
3++6SO
4 2-+7H
2O
First curing agent in the said step 3 is alkaline curing agent, makes the heavy metal ion in the polluted soil generate precipitation of hydroxide.Said alkaline curing agent is limewash or sodium hydroxide solution.Its chemical equation is following:
Cr
3++3(OH)
-→Cr(OH)
3↓
Pb
2++2(OH)
-→Pb(OH)
2↓
Cd
2++2(OH)
-→Cd(OH)
2↓
Zn
2++2(OH)
-→Zn(OH)
2↓
As
3++3(OH)
-→As(OH)
3↓
Second curing agent is the sulfide of solubility in the said step 4, as last safeguard, the heavy metal ion in the polluted soil is carried out further cured.The sulfide of said solubility is vulcanized sodium or calcium sulfide.Its chemical equation is:
Zn
2++S
2-→ZnS↓
Cd
2++S
2-→CdS↓
Further, after accomplishing above-mentioned steps,, the soil after repairing is done further processing, make the soil after repairing carry out slaking reaction for reaching better regulation effect.Soil after being about to handle places natural conditions held a period of time, makes the chemical reaction in the abovementioned steps abundant more, thorough, carries out fully to guarantee first curing reaction and second curing reaction.Its chemical reaction mechanism with the reacting phase in the aforementioned step together.
This technology at first adopts grinding technique; To receive the chromium slag muck to put contaminated soil in ball milling; Fully mix, levigate to a certain degree; Destroyed the colloform texture and the residual chromium slag chromate crystal structure of polymerism in the soil, increased specific area, for follow-up half-dried solid phase reduction, curing reaction lay the first stone.
Reduction through step 2 is handled, and poisonous hexavalent chromium compound is reduced to nontoxic basically trivalent chromium compound in the polluted soil.Step 3 adopts first curing agent such as limewash; To being cured processing in the contaminated soil; Make lead in the contaminated soil, cadmium, zinc, arsenic plasma generate the precipitation of hydroxide of indissoluble; Simultaneously, the chromium ion that also first step is reduced to trivalent has carried out stabilization processes, promptly is converted into chromium hydroxide precipitation.Step 4 adopts vulcanized sodium or calcium sulfide as second curing agent polluted soil to be carried out the cured second time.The solubility of metal sulfide is generally all smaller, and therefore making curing agent with vulcanized sodium or calcium sulfide can more effectively handle the contaminated soil that contains heavy metal ion, and zinc, cadmium ion generate the sulfide precipitation that the utmost point is insoluble in water through reaction again.Through above handling procedure, harmful substances such as the heavy metal in the polluted soil are cured as a kind of stable morphology, and its toxicity obviously reduces, and also are difficult for diffusion.
Description of drawings
Fig. 1 is the process chart of soil polluted by chromium residue restorative procedure of the present invention.
The specific embodiment
Below in conjunction with accompanying drawing principle of the present invention and characteristic are described, institute gives an actual example and only is used to explain the present invention, is not to be used to limit scope of the present invention.
The place that the object that embodiment was directed against is left in plant area's transformation process for certain chemical plant.Because receive the chromium slag, electroplate waste residue, the pollution of harmful substances such as contaminated brick slag, cinder, pending polluted soil receives chromium, lead, cadmium, zinc, arsenic contamination serious: chromium content is 23.35～20836.33mg/kg in the soil, and maximum exceeds standard 54.8 times; Lead content is 6.00～49423.56mg/kg, and maximum exceeds standard 93.3 times; Zinc content is 13.26～110000mg/kg, and maximum exceeds standard 152.8 times; Cadmium content is 0～3400mg/kg, and maximum exceeds standard 283.3 times; Arsenic content is 0.45～1918.68mg/kg, and maximum exceeds standard 34.9 times.
Fig. 1 has explained the technological process of the restorative procedure of soil polluted by chromium residue of the present invention on the whole, and this method adopts half-dried multistage electronation/fixation to administer technology.As shown in Figure 1, below be to utilize this method to handle the key step of the polluted soil that contains toxic components such as heavy metal.
The first step 10 is carried out dried to polluted soil, makes it dehydration; Utilize special-purpose ball mill that dried polluted soil is carried out fragmentation and milled processed again.Through broken and grinding, the abundant mixing and stirring of polluted soil is ground into fine particle, and particle order number reaches 80 orders above (particle diameter is less than 198 microns), preferably 80～120 orders.Broken and grinding has destroyed the colloform texture and the residual chromium slag chromate crystal structure of polymerism in the soil, has increased the specific area of soil, for half-dried solid phase reduction, curing reaction in the subsequent treatment program lay the first stone.
In second step 20, the polluted soil after fragmentation and milled processed is reduced processing with reducing agent.The reducing agent here can be selected copperas solution or solution such as sodium sulfite, sodium pyrosulfite for use.Solution with containing reducing substanceses such as ferrous ion or pressure sulfate radical is handled dirty soil as reducing agent, can hexavalent chromium compound poisonous in the polluted soil be reduced to nontoxic basically trivalent chromium compound.Its chemical equation is following:
CrO
4 2-+3Fe
2++8H
+→3Fe
3++Cr
3++4H
2O
2CrO
4 2-+3SO
3 2-+10H
+→2Cr
3++3SO
4 2-+5H
2O
4CrO
4 2-+3S
2O
5 2-+14H
+→4Cr
3++6SO
4 2-+7H
2O
In the 3rd step 30, the polluted soil after handling through reduction is carried out the cured first time with first curing agent.Through the cured first time, the most of noxious materials in the polluted soil are cured as than stable morphology, be difficult for diffusion and propagation.First curing agent is alkaline curing agent, makes the heavy metal ion in the polluted soil generate precipitation of hydroxide.Said alkaline curing agent can be limewash or sodium hydroxide solution.Its chemical equation is following:
Cr
3++3(OH)
-→Cr(OH)
3↓
Pb
2++2(OH)
-→Pb(OH)
2↓
Cd
2++2(OH)
-→Cd(OH)
2↓
Zn
2++2(OH)
-→Zn(OH)
2↓
As
3++3(OH)
-→As(OH)
3↓
In the 4th step 40, the polluted soil of cured carries out the cured second time to passing through for the first time with second curing agent.Through the cured second time, further do not solidified in the cured in the first time in the polluted soil by completely crued material.Second curing agent is the sulfide of solubility, makes through the remaining heavy metal ion of the cured first time and forms the sulfide precipitation that the utmost point is insoluble in water.The sulfide of said solubility is vulcanized sodium or calcium sulfide.Its chemical equation is:
Zn
2++S
2-→ZnS↓
Cd
2++S
2-→CdS↓
After accomplishing above-mentioned steps, the soil that meets the requirement of relevant environment risk standard after can obtaining repairing.
For reaching better regulation effect, also can do further and handle the soil after repairing, make the soil after repairing carry out slaking reaction.Soil after being about to handle places natural conditions held a period of time, makes the chemical reaction in the abovementioned steps abundant more, thorough, carries out fully to guarantee first curing reaction and second curing reaction.Its chemical reaction mechanism with the reacting phase in the aforementioned step together.
Half-dried multistage electronation/fixation is administered technology need adopt the corresponding engineering measure; The detoxifcation deadline is by the hydrogeological characteristics in place; Place and final multiple factor decisions such as engineering design plan (EDP) are repaired in pollutant distribution, pollution; The fastest deadline is 6 months, and special circumstances are about 9 months.Perch the Cr VI leaching toxicity that reaches in the contaminated soil in the underground water after reparation is accomplished and can reduce more than 90%, it leaches concentration less than the national standard requirement.Other pollution factor also reduces like the same toxicity that leaches such as lead, cadmium, zinc, arsenic greatly in the soil, meets the requirement of relevant environment risk standard.
The above is merely preferred embodiment of the present invention, and is in order to restriction the present invention, not all within spirit of the present invention and principle, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. the restorative procedure of a soil polluted by chromium residue is characterized in that comprising the steps:
Step 1, polluted soil is carried out dried, and carry out fragmentation and milled processed;
Step 2, the polluted soil after fragmentation and milled processed is reduced processing with reducing agent;
Step 3, the polluted soil after handling through reduction is carried out the cured first time with first curing agent;
Step 4, with second curing agent to carrying out the cured second time, the soil after can obtaining repairing through the polluted soil of cured for the first time.
2. the restorative procedure of soil polluted by chromium residue according to claim 1 is characterized in that, the particle order number of polluted soil after broken and milled processed is more than 80 orders in the said step 1.
3. the restorative procedure of soil polluted by chromium residue according to claim 1 is characterized in that, the reducing agent in the said step 2 is copperas solution or sodium sulfite solution or sodium metabisulfite solution.
4. the restorative procedure of soil polluted by chromium residue according to claim 1 is characterized in that, first curing agent in the said step 3 is alkaline curing agent.
5. the restorative procedure of soil polluted by chromium residue according to claim 4 is characterized in that, said alkaline curing agent is limewash or sodium hydroxide solution.
6. the restorative procedure of soil polluted by chromium residue according to claim 1 is characterized in that, second curing agent is a dissolvable sulfide in the said step 4.
7. the restorative procedure of soil polluted by chromium residue according to claim 6 is characterized in that, said dissolvable sulfide is vulcanized sodium or calcium sulfide.
8. the restorative procedure of soil polluted by chromium residue according to claim 1 is characterized in that, also comprises step 5, the soil after will handling places natural conditions held a period of time, makes it to carry out slaking reaction.
Priority Applications (1)
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|---|---|---|---|
| CN 200910131680 CN101862749B (en) | 2009-04-14 | 2009-04-14 | Recovering method of soil polluted by chromium residue |
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|---|---|---|---|
| CN 200910131680 CN101862749B (en) | 2009-04-14 | 2009-04-14 | Recovering method of soil polluted by chromium residue |
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| CN101862749A CN101862749A (en) | 2010-10-20 |
| CN101862749B true CN101862749B (en) | 2012-12-19 |
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| CN103894402A (en) * | 2012-12-28 | 2014-07-02 | 苏州中科慧盛生物科技有限公司 | Hexavalent chromium-containing soil purification method |
| CN103071670B (en) * | 2013-01-24 | 2016-03-16 | 韩清洁 | A kind of equipment for chromium slag contaminated soil Detoxified treatment |
| CN103084385A (en) * | 2013-01-28 | 2013-05-08 | 韩清洁 | Repairation method of chromium-polluted soil and corresponding equipment thereof |
| CN104138895A (en) * | 2013-05-09 | 2014-11-12 | 苏州中科慧盛生物科技有限公司 | Hexavalent chromium-containing soil purifying method |
| CN103275725B (en) * | 2013-06-07 | 2015-01-21 | 中南大学 | Chemical fixing agent for heavy metal contaminated soil remediation and preparation and application thereof |
| CN103521513B (en) * | 2013-10-18 | 2015-04-01 | 中国科学院南京土壤研究所 | Leaching method of soil polluted by hexavalent chromium |
| CN103949468B (en) * | 2014-03-18 | 2016-03-23 | 北京国环建邦环保科技有限公司 | A kind of total chromium dystopy administering method of chromium-polluted soil |
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| CN107523302A (en) * | 2016-06-22 | 2017-12-29 | 上海宝钢工业技术服务有限公司 | Administer the hexavalent chromium polluted soil remediation medicament in metallurgical place and preparation method |
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| CN107641511A (en) * | 2017-07-24 | 2018-01-30 | 中冶华天工程技术有限公司 | For the preparation method and soil remediation method of the stabilization material for administering soil |
| CN109226233A (en) * | 2018-08-07 | 2019-01-18 | 广西博世科环保科技股份有限公司 | Height repairs target heavy-metal contaminated soil administering method |
| CN110449455A (en) * | 2019-08-07 | 2019-11-15 | 光大环境修复(江苏)有限公司 | A kind of restorative procedure for the contaminated soil that heavy metal lead is exceeded |
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