CN103551376B - Method for stabilization of heavy metal contaminated soil in mining area - Google Patents
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Abstract
The invention discloses a method for stabilization of heavy metal contaminated soil in a mining area. The method comprises steps that coal ash and dried sludge are added into heavy metal contaminated soil in the mining area and are mixed uniformly, preferably, the soil is stabilized preliminarily after standing for one year, and peanut shells are added into the preliminarily stabilized soil and are mixed uniformly so as to obtain the stabilized soil. Stabilizing effects are analyzed through simulating rainwater leaching experiments, heavy metal morphological analysis, germination rate and growth of plants; all test indexes show preferable stabilizing effects; as various aspects of factors are detected, bad unexpected feedback conditions are well prevented. The stabilizer adopted by the method has wide source of feed, is cheap, can be used in repairing a spoil area of a mine so as to control the pollution by waste, and has good economic benefits and environment benefits.
Description
Technical field
The present invention relates to heavy metals mining area pollutant abatement technology field, belong to heavy-metal contaminated soil and repair field.
Background technology
For a long time, the mine tailing Solid state fermentation in metal mine ore dressing plant is all adopt the mode of Tailings Dam to stockpile waste residue with disposing generally, not only take a large amount of soils, contaminated soil, surface water, underground water, and a lot of Tailings Dam exceeds the time limit or excess load uses, make Tailings Dam there is very big potential safety hazard, Tailings Dam is built in addition and maintenance management also needs to drop into a large amount of funds.At present, the approach administering heavy metal pollution of soil is both at home and abroad summed up and mainly contains 3 kinds: one is change the occurrence status of heavy metal in soil, makes it stable or fixing, reduce it active, make its passivation, depart from food chain, to reduce its animal migration in the environment and bioavailability; Two is utilize various technology removal heavy metal from soil, reaches the dual purpose reclaiming and reduce heavy metal in soil; Three is utilize various impervious material, as cement, clay, slabstone, plastic plate etc., IA and uncontaminated area is isolated, to reduce or to stop migration and the diffusion of heavy metal.Around these 3 kinds of governance ways, various countries develop physics, chemistry and biological treating method in succession.The selective dependency of various method is in soil property, pollution level, final use and cost effectiveness analysis.At present, from large aspect, two classes are mainly divided into for the reparation of heavy-metal contaminated soil both at home and abroad: in-situ immobilization and showering.The heavy-metal contaminated soil reparation of Some Mining Districts and surrounding area generally adopts the mode of in-situ immobilization, mainly comprises physical technique: soil moved in improve the original and dig method, heat treating process, electrochemical process, isolation investment etc.; Chemical technology: fixing/stabilising, chemical leaching, chemical oxidation/reduction etc.; Bioremediation technology: phytoremediation, microorganism remediation etc., these methods respectively have pluses and minuses.The disposal cost of isolation investment is minimum, but is only isolated by heavy metal, still there is potential risk to mining soil ecology; Electrochemical process is more immature, and be only applicable to small size and pollute, execute-in-place difficulty is large; Heat treating process is not suitable for execute-in-place, and disposal cost is high, narrow application range; Chemical method easily change soil character, cause secondary pollution; Utilize hyperaccumulative plant to carry out study hotspot that phytoremediation is current heavy-metal contaminated soil Treatment process, the part but this still comes with some shortcomings, particularly most of ultraproduct tires out that the general plant of plant of heavy metal is short and small, poor growth, biomass are low, thus remediation efficiency is low, required time is long, and the with serious pollution mining soil of heavy metal, hyperaccumulative plant is generally difficult to direct growth; The carrier that microorganism remediation method utilizes is living microorganisms, and the discontinuous distribution of pollutant can cut off microorganism motion, therefore long processing period, and competes organic nutrient substance with indigenous microorganism, easily loses activity.
Curing/stabilizing technology (solidification/stabilization, be called for short S/S technology) be exactly add the physicochemical property that additive changes soil, its existing forms in soil is changed by the absorption of heavy metal or (being total to) precipitation, reduce the Leaching of heavy metal in soil environment, biological effectiveness and dissolving animal migration, reduce because rain or diafiltration work the mischief to animals and plants.Due to S/S technology have that expense is low, repair time is short, multiple Compound Heavy Metals can be processed, the advantage such as easy to operate, so it becomes a kind of more ripe and repairing and treating technology of cost-effective heavy-metal contaminated soil.For the soil of high density pollution after curing/stabilizing process, hyperaccumulative plant can be planted, improve the total amount of plants enriched heavy metal by the increase of phytomass after stabilization processes, reach the object of reparation, be conducive to the ecological recovery in mining area simultaneously; For the soil of middle low concentration pollution after curing/stabilizing process, some crops can be planted, reduce the content of heavy metal in crop, make it reach edible safety standard, realize the Commercial cultivation in soil.
At present, conventional soil solidification/stabilizing agent mainly contains: the alkaline matters such as cement, lime, flyash, siliceous fertilizer, calcium carbonate; The phosphate such as rock phosphate in powder, hydroxyapatite, calcium monohydrogen phosphate; The clay mineral such as zeolite, bentonite; Municipal sludge, the organic fertilizer such as farm manure, green manure, peat.Table 1 outlines the research and apply of several solidification/stabilizer treatment heavy metal.At present, the waste material residue of the mineral dust that some industry byproducts, environmental risk are lower, agricultural production is paid close attention in the application of heavy metal pollution in-situ passivation, but studies not enough with regard to the stabilization effect of different stabilizers combination heavy metal combined pollution.
Table 1 solidifies/research and apply of stabilizing agent
Summary of the invention
The object of the present invention is to provide a kind of method of heavy metal polluted soil in mine field stabilization processes.
The technical solution used in the present invention is:
A method for heavy metal polluted soil in mine field stabilization processes, comprises the following steps:
1) by adding flyash, dewatered sludge in heavy metal polluted soil in mine field, mixing, carrying out preliminarily stabilised process;
2) add peanut shell by the soil after preliminarily stabilised process, mix.
Further, the amount adding flyash described in step 1) is 5 ~ 20% of heavy metal polluted soil in mine field weight.
Further, the amount adding flyash described in step 1) is 5 ~ 20% of heavy metal polluted soil in mine field weight.
Further, step 2) described in add peanut shell amount be 0.5 ~ 2% of heavy metal polluted soil in mine field weight.
Further, step 2) diameter of described peanut shell is not more than 2mm.
The invention has the beneficial effects as follows:
The present invention adopts lime, flyash, dewatered sludge, pulverizing peanut shell is additive, by different stabilizing formulation, carries out stabilization processes to soil, forms the optimization of C/C composites of stabilisation.Its stabilization effect is analyzed by Simulated rainwater Leaching Experiments, Speciation Analysis of Heavy Metals experiment and the germination rate of plant, by processing mensuration, the comparative analysis of rear indices, to determine preferably stabilizing formulation, can prevent other unexpected bad feedbacks from occurring better.
The present invention is by planting experiment after stabilization processes, and the plant germination of statistics different disposal group and growing state, provide reference to the ecological effect of plant germination and growth after can be mining soil stabilization processes.
Stabilizing agent source of the present invention is relatively more extensive, and less expensive, is applied to it in the reparation of mine waste residue field, with useless pollution treatment, has good economic benefit and environmental benefit simultaneously.
Accompanying drawing explanation
Fig. 1 is the variation diagram of different shape As content in slag after stabilization processes, and EXC represents exchangeable species, and CA represents that acetic acid is in conjunction with state, and FeMOx represents that iron and manganese oxides is in conjunction with state, and OM represents combination state, and RES represents residual form;
Fig. 2 is the variation diagram of different shape Pb content in slag after stabilization processes, and EXC represents exchangeable species, and CA represents that acetic acid is in conjunction with state, and FeMOx represents that iron and manganese oxides is in conjunction with state, and OM represents combination state, and RES represents residual form;
Fig. 3 is the variation diagram of different shape Zn content in slag after stabilization processes, and EXC represents exchangeable species, and CA represents that acetic acid is in conjunction with state, and FeMOx represents that iron and manganese oxides is in conjunction with state, and OM represents combination state, and RES represents residual form;
Fig. 4 be after different disposal in leachate As containing spirogram;
Fig. 5 be after different disposal in leachate Pb containing spirogram;
Fig. 6 be after different disposal in leachate Zn containing spirogram.
Detailed description of the invention
A method for heavy metal polluted soil in mine field stabilization processes, comprises the following steps:
1) by adding flyash, dewatered sludge in heavy metal polluted soil in mine field, mixing, carrying out preliminarily stabilised process;
2) add peanut shell by the soil after preliminarily stabilised process, mix.
The amount adding flyash described in step 1) is preferably 5 ~ 20% of heavy metal polluted soil in mine field weight.
The amount adding flyash described in step 1) is preferably 5 ~ 20% of heavy metal polluted soil in mine field weight.
After mixing described in step 1), preferably place 1 year, obtain the soil of preliminarily stabilised process.
Step 2) described in add peanut shell amount be preferably 0.5 ~ 2% of heavy metal polluted soil in mine field weight.
Step 2) diameter of described peanut shell is preferably not more than 2mm.
embodiment 1
one, draw materials
Heavy-metal contaminated soil: be that the rectangular plastic hopper of 54cm × 42cm × 30cm carries out multi-point sampling from mining area composite ore slag muck and gathers 8 casees slag aggregate samples by length, width and height, they are mixed, stir, then be on average dispensed in each chest, the degree of depth of every case dress is about 25cm, and volume is about 0.048m
3, weight is about 76kg, at side face drilling one aperture of each plastic box, and with being with the rubber stopper jam-pack of plastic pipe, making every case slag slant setting a little, collecting leachate with water sample bottle.
Solidification-stabiliser materials: lime is bought from market; Flyash takes from Guangzhou Desulphurization for Coal-fired Power Plant flyash; Mud takes from the sludge drying product after the sewage treatment plants compost of Guangzhou, and content of beary metal meets " in agricultural sludge pollutant catabolic gene standard "; Peanut shell is buied from the local market of farm produce, cleans, dries, then pulverizes 2mm sieve with pulverizer, and main component is crude fibre, soluble-carbohydrate, thick protein, crude fat etc.
two, early stage stabilization processes
Gather return 8 casees mixing slag samples every two casees as a parallel laboratory test, be wherein designated as CK as blank two casees
1, CK
2; Other add a certain amount of lime, flyash, dewatered sludge by the mass ratio of slag, add 5% lime for two casees and 10% flyash is designated as A
1, A
2, add 10% flyash for two casees and 10% dewatered sludge is designated as B
1, B
2, add 5% lime for two casees and 10% dewatered sludge is designated as C in addition
1, C
2, treating depth is about 20cm, stirs and makes it mix.Place after 1 year, before peanut shell is pulverized in interpolation, every case takes out part aggregate sample, and analysis measures its basic physical and chemical and content of beary metal measures, and Primary outcome measures is as table 2.
The physicochemical property of the slag of table 2 stabilization processes premenstruum (premenstrua) and content of beary metal
As known from Table 2, non-premenstruum (premenstrua), the slag pH of stabilization processes was less than 6.5, present certain acidity, and the content of organic matter was also lower.In earlier stage, after stabilization processes, the pH of slag is increased to more than neutrality, and the content of organic matter significantly increases, and improves slag fertility, is conducive to ecology of mining areas and reclaims.Wherein the interpolation of lime and flyash raises the most obvious to the pH of slag, and after adding dewatered sludge, the content of organic matter of slag obviously increases.From the testing result of content of beary metal, warp and non-premenstruum (premenstrua) stabilization processes the content of As, Zn all exceed the standard value that soil environment quality grade III Standard (GB15618-1995) sets, wherein As exceeds standard the most serious, maximum exceeding standard rate is 723.5 times, and the content of Zn is slight exceeding standard.
Said determination data illustrate, the pH value that being combined between two of solidification-stabiliser materials flyash, lime and dewatered sludge can improve slag, the content improving organic matter.
three, after stabilization processes and stabilization processes, the content of beary metal of different shape measures
stabilization processes
After premenstruum (premenstrua) stabilization processes, by slag mass ratio respectively toward CK
2, A
2, B
2, C
2in add 1% pulverizing peanut shell, change respectively and be designated as CK
3, A
3, B
3, C
3, stir after making it fully react 3d, carry out the assay of heavy metals of different forms.
the content of beary metal of different shape measures
Heavy metal exists with 5 kinds of different forms usually:
exchangeable species: be easy to Transport And Transformation, can be absorbed by plants;
carbonate is in conjunction with state: by the impact of soil environment condition particularly pH, be easily discharged in environment; Therefore, exchangeable species and carbonate in conjunction with the state metal pair mankind and environmental hazard larger;
iron and manganese oxides in conjunction with state and
organically combine state: comparatively stable, but also can discharge when change of external conditions;
residual form: metallic element stable in properties, not easily discharges under nature normal condition.Therefore, being moved from the form that the higher form of activity is lower to activity, more stable by heavy metal and change, is the effective way reducing Heavy Metal Pollution.
the assay of different shape As
Respectively from CK
1, CK
3, A
1, A
3, B
1, B
3, C
1, C
3middle taking-up fraction slag, air-dry, grind, sieve, for heavy metal As morphological analysis experiment, the conversion between comparative analysis heavy metals of different forms, measurement result as shown in Figure 1.
As can be seen from Figure 1, slag is through B
3after stabilization processes in group, residual form As content rises the most remarkable, and amplification is 8.4%, and content is the highest, and exchangeable species As, combination state As content decline the most remarkable, and content is minimum, reduces 65.6%, 87.7% respectively.
Measurement result explanation, add the conbined usage of flyash, dewatered sludge and peanut shell simultaneously, can exchangeable species As, combination state As in slag be transformed to residual form As best, namely the conbined usage of flyash, dewatered sludge and peanut shell can solidify-stabilisation heavy metal As best.
the assay of different shape Pb
After stabilization processes, carry out analysis to the heavy metal Pb form in slag and measure, measurement result as shown in Figure 2.
As can be seen from Figure 2, compared with blank, after different stabilization processes, exchangeable species Pb changes of contents is not obvious, and acetic acid slightly increases in conjunction with state Pb content.Different stabilizers is different to the Forms Transformation of Pb, A
3in process, iron and manganese oxides is maximum in conjunction with state Pb recruitment, and amplification is 31.3%, A
1organically combining state Pb content in process reduces the most remarkable, and the range of decrease is 47.1%.But no matter through which kind of stabilization processes, in this slag, Pb content summation does not all exceed standard of soil environment quality (GB15618-1995, three grades).May when Pb content itself be very low, the change ability of each stabilization processes group to Pb form can not get better embodiment.
the assay of different shape Zn
After stabilization processes, carry out analysis to the heavy metal Zn form in slag and measure, measurement result as shown in Figure 3.
As can be seen from Figure 3, compared with blank, after stabilized process, exchangeable species Zn changes of contents is not obvious, and acetic acid slightly reduces in conjunction with state and combination state Zn content in conjunction with state, iron and manganese oxides, and residual form Zn content increases.Wherein, A
1in process, exchangeable species Zn, iron and manganese oxides are in conjunction with state Zn, combination state Zn the biggest drop, and reduce by 61.4%, 84.2%, 62.1% respectively, the increase of residual form Zn content is the most remarkable, and amplification is 44.8%.
Measurement result illustrates, the exchangeable species Zn in slag, iron and manganese oxides can be converted into residual form Zn in conjunction with state Zn, combination state Zn by interpolation lime and flyash best.
three, the mensuration of As, Pb, Zn content in leachate
Respectively to early stage stabilization processes, after stabilization processes the slag of the 3rd day, 33 days, 63 days carry out first time, for the second time, for the third time and four secondary Leaching Experiments, collect leachate, analyze the content measuring heavy metal As, Pb, Zn in leachate, measurement result as shown in figures 4-6.
As can be seen from Figure 4, in all leachates, As content is all higher, and its content exceedes surface water III class standard (GB3838-2002) limit value 0.05 mgL
-129. 6 ~ 70.8 times.But through B
3after the stabilization processes of group, in leachate, As content declines the most remarkable, stabilized process after 63 days the range of decrease be 57.4%.Illustrate after adding flyash, dewatered sludge and peanut shell best to the stabilization effect of As simultaneously, heavy metal As to be reduced in slag significantly with the diffusion mobility of rainwater;
As can be seen from Figure 5, stabilization processes just better can reduce the content of Pb in leachate, especially through B early stage
3the early stage of group, in leachate, Pb content declined the most remarkable after stabilization processes, illustrated that the mixture of flyash and dewatered sludge can to reduce in slag heavy metal Pb preferably with the diffusion mobility of rainwater.
As can be seen from Figure 6, in all leachates, Zn content does not all exceed concentration limit 1 mgL of surface water III class standard (GB3838-2002)
-1, illustrate that warp is without stabilization processes, it is all little to the harm of environment.
four, slag is on the impact of plant germination and growth
For studying the ecological effect of different stabilization processes to plant germination and growth, respectively at CK
1, CK
3, A
1, A
3, B
1, B
3, C
1, C
3sow 100 vetiver seeds in stabilization processes group, make its germination and growth under identical environment and condition, observe and add up the Germination and growth situation of plant.
According to statistics, A
1the germination rate of process vetiver is minimum, is 24%.Analyzing relevant reason, may be, after adding because of lime and flyash simultaneously, pozzolanic reaction can occur, generate more stable hydrated calcium silicate and drated calcium aluminate, cause soil hardening, thus be unfavorable for the Germination and growth of plant.Even if so lime and flyash have the effect of stabilizing heavy metal, but can not use simultaneously, namely should not contain lime and flyash two kinds of compositions in heavy metal stabilizer simultaneously.
B
3in processed group, the germination rate of vetiver is the highest, be 76%, and growing way is also best.Analyze relevant reason, may be because slag pH raises after stabilized process, the content of organic matter significantly increases, after adding peanut shell, slag becomes loose simultaneously, gas permeability is better, and in slag, the bio-available Zn concentration of heavy metal reduces, and decreases the toxic action to plant, is therefore conducive to the Germination and growth of vetiver.
To sum up result of study, flyash, dewatered sludge and the stabilization effect of peanut shell conbined usage to soil are best, soil pH can be improved significantly, increase soil organic matter content, the content of remarkable reduction heavy metal exchangeable species, reduce its toxicity, animal migration and biological effectiveness in soil environment, thus reduce heavy metal element to vegeto-animal harm, and lay the foundation for the further restoration of the ecosystem in mining area.
Claims (1)
1. a method for heavy metal polluted soil in mine field stabilization processes, is characterized in that: comprise the following steps:
To add 10% flyash and 10% dewatered sludge in heavy metal polluted soil in mine field, treating depth is about 20cm, and stir and make it mix, place after 1 year, add 1% peanut shell, peanut shell diameter is not more than 2mm, stirs;
Wherein, the As content of above-mentioned heavy metal polluted soil in mine field is 28034.62 mg/kg, Pb content be 76.50 mg/kg, Zn content is 579.34mg/kg, and the content of organic matter is 11.05mg/g, and pH value is 5.78; Or the As content of above-mentioned heavy metal polluted soil in mine field is 28834.76 mg/kg, Pb content be 75.48mg/kg, Zn content is 587.02mg/kg, and the content of organic matter is 10.33mg/g, and pH value is 5.86.
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| CN105080953B (en) * | 2015-08-26 | 2017-10-10 | 广东省农业科学院农业资源与环境研究所 | A kind of auxotype resistance control agent for reducing rice Cd contents and its application method |
| CN105855283A (en) * | 2016-06-15 | 2016-08-17 | 中科院广州化灌工程有限公司 | Treatment method for heavy metal contaminated soil |
| CN106753414B (en) * | 2016-12-29 | 2021-01-01 | 广东万山土壤修复技术有限公司 | Heavy metal passivator and preparation method and application thereof |
| CN106825011B (en) * | 2017-02-14 | 2020-04-10 | 榆林学院 | Method for removing heavy metal Pb in soil |
| CN109290364A (en) * | 2018-08-01 | 2019-02-01 | 江苏绿岩生态技术股份有限公司 | A kind of heavy metal pollution of mine soil remediation method |
| CN109622599B (en) * | 2019-02-02 | 2020-11-13 | 湖南大学 | Method for repairing farmland soil polluted by arsenic by using dehydrated sludge and biochar compounded passivator |
| CN112371712A (en) * | 2020-10-21 | 2021-02-19 | 安阳工学院 | Heavy metal contaminated soil solidification-plant cooperative remediation method |
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Effective date of registration: 20160705 Address after: 510000, Guangdong, Guangzhou, Nansha District Huandao North Road, Nansha street, Sha Lo Wan Village section 1 office building, first floor, 102 Patentee after: Guangzhou Delong Environmental Detection Technology Co., Ltd. Address before: Tianhe District West Village Guangzhou city Guangdong province 510655 No. seven compound Patentee before: South China Institute of Environmental Sciences. MEP |