CN101862749A - Repairing method of soil polluted by chromium residue - Google Patents
Repairing method of soil polluted by chromium residue Download PDFInfo
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- CN101862749A CN101862749A CN200910131680A CN200910131680A CN101862749A CN 101862749 A CN101862749 A CN 101862749A CN 200910131680 A CN200910131680 A CN 200910131680A CN 200910131680 A CN200910131680 A CN 200910131680A CN 101862749 A CN101862749 A CN 101862749A
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- restorative procedure
- 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 be subjected to 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 at a kind of soil that is subjected to 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 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, Cr VI will be converted to 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 as follows: a kind of restorative procedure of soil polluted by chromium residue comprises the steps:
Step 1, polluted soil is carried out drying handle, 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 solidifying first time processing with first curing agent;
Step 4, the polluted soil that process is solidified processing for the first time with second curing agent carry out solidifying the second time processing, the soil after can obtaining repairing.
On the basis of technique scheme, the present invention can also do following improvement.
Polluted soil is after broken and milled processed in the described 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 described step 2 is copperas solution or sodium sulfite solution or sodium metabisulfite solution etc.Dirty soil is handled as reducing agent with the solution that contains ferrous ion, hexavalent chromium compound poisonous in the dirty soil can be reduced to nontoxic substantially trivalent chromium compound.Its chemical equation is as follows:
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 described step 3 is alkaline curing agent, makes the heavy metal ion in the polluted soil generate precipitation of hydroxide.Described alkaline curing agent is limewash or sodium hydroxide solution.Its chemical equation is as follows:
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 described step 4, as last safeguard, the heavy metal ion in the polluted soil is further solidified processing.The sulfide of described solubility is vulcanized sodium or calcium sulfide.Its chemical equation is:
Zn
2++S
2-→ZnS↓
Cd
2++S
2-→CdS↓
Further, after finishing 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 under the natural conditions displays 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 be subjected to 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 by step 2 is handled, and poisonous hexavalent chromium compound is reduced to nontoxic substantially 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 solidifying the second time and handles.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 by 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 feature 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.
Embodiment at the place in plant area's transformation process, left over for certain chemical plant of object.Because be subjected to the chromium slag, electroplate waste residue, the pollution of harmful substances such as contaminated brick slag, cinder, pending polluted soil is subjected to 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 illustrated 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 drying to polluted soil and is handled, and 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 broken 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.Dirty soil is handled as reducing agent with the solution that contains reducing substanceses such as ferrous ion or pressure sulfate radical, hexavalent chromium compound poisonous in the polluted soil can be reduced to nontoxic substantially trivalent chromium compound.Its chemical equation is as follows:
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 solidifying the first time processing with first curing agent.Handle by solidifying for the first time, the most of noxious materials in the polluted soil are cured as than stable morphology, be difficult for spreading and propagating.First curing agent is alkaline curing agent, makes the heavy metal ion in the polluted soil generate precipitation of hydroxide.Described alkaline curing agent can be limewash or sodium hydroxide solution.Its chemical equation is as follows:
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, handle carrying out solidifying the second time through the polluted soil that solidifies processing for the first time with second curing agent.Handle by solidifying for the second time, further do not solidified in handling in curing for the first time in the polluted soil by completely crued material.Second curing agent is the sulfide of solubility, makes through solidifying the heavy metal ion of handling remnants for the first time and forms the sulfide precipitation that the utmost point is insoluble in water.The sulfide of described solubility is vulcanized sodium or calcium sulfide.Its chemical equation is:
Zn
2++S
2-→ZnS↓
Cd
2++S
2-→CdS↓
After finishing 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 under the natural conditions displays 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 finished and can reduce more than 90%, it leaches concentration less than the national standard requirement.Other pollution factor also reduces greatly as the same toxicity that leaches such as lead, cadmium, zinc, arsenic in the soil, meets the requirement of relevant environment risk standard.
The above only is preferred embodiment of the present invention, and is in order to restriction the present invention, within the spirit and principles in the present invention not all, 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 drying handle, 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 solidifying first time processing with first curing agent;
Step 4, the polluted soil that process is solidified processing for the first time with second curing agent carry out solidifying the second time processing, the soil after can obtaining repairing.
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 described 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 described 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 described step 3 is alkaline curing agent.
5. the restorative procedure of soil polluted by chromium residue according to claim 4 is characterized in that, described 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 described step 4.
7. the restorative procedure of soil polluted by chromium residue according to claim 6 is characterized in that, described 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 under the natural conditions and display a period of time, makes it to carry out slaking reaction.
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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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| Publication Number | Publication Date |
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| CN101862749A true CN101862749A (en) | 2010-10-20 |
| CN101862749B CN101862749B (en) | 2012-12-19 |
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| CN113426542A (en) * | 2021-07-02 | 2021-09-24 | 昆明理工大学 | Detoxification and stabilization method for hexavalent chromium-containing historical remaining tailings and surrounding soil |
| CN116174464A (en) * | 2023-03-06 | 2023-05-30 | 核工业北京化工冶金研究院 | Secondary restoration stable solidification method for 'yellowing' chromium-polluted soil |
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