CN103551376A - 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 pollution control technical field, belong to heavy-metal contaminated soil and repair field.
Background technology
For a long time, it is all generally to adopt the mode of Tailings Dam to stockpile waste residue that the mine tailing waste residue in metal mine ore dressing plant is processed with disposing, not only take a large amount of soils, contaminated soil, surface water, underground water, and a lot of Tailings Dams exceed the time limit or excess load is used, make Tailings Dam have 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 of administering heavy metal pollution of soil is both at home and abroad summed up and mainly contains 3 kinds: the one, change the occurrence status of heavy metal in soil, and make it stable or fixing, reduce its activity, make its passivation, depart from food chain, to reduce its animal migration and bioavailability in environment; The 2nd, utilize various technology removal heavy metal from soil, reach the dual purpose that reclaims and reduce heavy metal in soil; The 3rd, utilize various impervious materials, as cement, clay, slabstone, plastic plate etc., by IA and the isolation of uncontaminated area, to reduce or to stop migration and the diffusion of heavy metal.Around these 3 kinds of governance ways, various countries have developed physics, chemistry and biological treating method in succession.The selective dependency of the whole bag of tricks is in soil property, pollution level, final use and cost effectiveness analysis.At present, the domestic and international reparation for heavy-metal contaminated soil is mainly divided into two classes from large aspect: original position reparation and showering.The mode that the heavy-metal contaminated soil reparation of Some Mining Districts and surrounding area generally adopts original position to repair, mainly comprises physical technique: soil moved in to 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 reparation etc., these methods respectively have pluses and minuses.The disposal cost of isolation investment is minimum, but only heavy metal is isolated, and mining soil ecology is still existed to potential risk; Electrochemical process is more immature, is only applicable to small size and pollutes, and 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 the study hotspot that phytoremediation is current heavy-metal contaminated soil improvement technology, the part but this still comes with some shortcomings, particularly short and small, the poor growth of the general plant of plant of the tired heavy metal of most of ultraproduct, biomass is low thereby remediation efficiency is low, required time is long, and the mining soil serious to heavy metal pollution, hyperaccumulative plant is generally difficult to direct growth; The carrier of microorganism repairing method utilization is microorganism live body, and the discontinuous distribution of pollutant can cut off microorganism motion, so 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 to add additive to change the physicochemical property of soil, absorption by heavy metal or (being total to) precipitation change it and have a form in soil, reduce Leaching, biological effectiveness and the dissolving animal migration of heavy metal in soil environment, reduce because rain or diafiltration work the mischief to animals and plants.Because S/S technology has that expense is low, repair time is short, can process multiple Compound Heavy Metals, the advantage such as easy to operate, so it becomes a kind of repairing and treating technology of more ripe and cost-effective heavy-metal contaminated soil.For the soil of high density pollution after curing/stabilizing is processed, can plant hyperaccumulative plant, by the increase of phytomass after stabilization processes, improve the total amount of plants enriched heavy metal, 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 is processed, can plant some crops, reduce the content of heavy metal in crop, make it reach edible safety standard, realize the production utilization 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 has been summarized research and the application of several solidify/stabilizer treatment heavy metals.At present, some industry byproducts, the mineral dust that environmental risk is lower, the waste material residue of agricultural production are paid close attention in the application of heavy metal pollution in-situ passivation, but with regard to different stabilizers combination to the stabilization effect research of heavy-metal composite pollution not enough.
Research and the application of solidify/stabilizing agent of table 1
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, mix, carry out preliminarily stabilised processing;
2) by adding peanut shell in the soil after preliminarily stabilisedization processing, mix.
Further, described in step 1), adding the amount of flyash is 5~20% of heavy metal polluted soil in mine field weight.
Further, described in step 1), adding the amount of flyash is 5~20% of heavy metal polluted soil in mine field weight.
Further, the amount that adds peanut shell step 2) is 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:
It is additive that the present invention adopts lime, flyash, dewatered sludge, pulverizing peanut shell, by different stabilizing formulation, soil is carried out to stabilization processes, forms the optimization of C/C composites of stabilisation.By the germination rate of the experiment of simulation rain, Speciation Analysis of Heavy Metals experiment and plant, analyze its stabilization effect, by processing mensuration, the comparative analysis of rear indices, to determine preferably stabilizing formulation, can prevent better that other unexpected bad feedbacks from occurring.
The present invention is by planting experiment after stabilization processes, and plant germination and the growing state of statistics different disposal group, provide reference to the ecological effect of plant germination and growth after can be mining soil stabilization processes.
Stabilizing agent of the present invention source is more extensive, and less expensive, is applied to it in the reparation of mine waste residue field, with the pollution treatment of giving up, 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 to organically combine 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 to organically combine 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 to organically combine 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.
The specific embodiment
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, mix, carry out preliminarily stabilised processing;
2) by adding peanut shell in the soil after preliminarily stabilisedization processing, mix.
Described in step 1), add the amount of flyash to be preferably 5~20% of heavy metal polluted soil in mine field weight.
Described in step 1), add the amount of flyash to be 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 that preliminarily stabilisedization is processed.
Step 2) described in, add the amount of peanut shell to be preferably 0.5~2% of heavy metal polluted soil in mine field weight.
Step 2) diameter of described peanut shell is preferably and is not more than 2mm.
one, draw materials
Heavy-metal contaminated soil: carry out multi-point sampling with the rectangular plastic hopper of the high 54cm * 42cm * 30cm of being of length and width from mining area mixing slagheap and gather 8 casees slag aggregate samples, they are mixed, stir, then within average minute, install in each chest, the degree of depth of every case dress is about 25cm, and volume is about 0.048m
3, the about 76kg of weight, at side face drilling one aperture of each plastic box, and with the rubber stopper jam-pack with plastic pipe, makes every case slag slant setting a little, with water sample bottle, collects leachate.
Solidify-stabiliser materials: lime is bought from market; Flyash is taken from Guangzhou Desulphurization for Coal-fired Power Plant flyash; Mud is taken from the sludge drying product after Guangzhou sanitary sewage disposal factory compost, and content of beary metal meets pollutant control criterion > > in the agricultural mud of < <; Peanut shell is buied from the local market of farm produce, cleans, dries, then pulverized 2mm sieve with pulverizer, and main component is crude fibre, soluble-carbohydrate, thick protein, crude fat etc.
two, early stage stabilization processes
Gather mix for 8 casees slag samples every two casees as a parallel laboratory test, wherein as blank, be designated as CK two casees
1, CK
2; Other mass ratioes by slag add a certain amount of lime, flyash, dewatered sludge, add for two casees 5% lime and 10% flyash to be designated as A
1, A
2, add for two casees 10% flyash and 10% dewatered sludge to be designated as B
1, B
2, other 5% lime and 10% dewatered sludge of adding for two casees is designated as C
1, C
2, process the about 20cm of the degree of depth, stir it is mixed.Place after 1 year, before adding pulverizing peanut shell, every case takes out part aggregate sample, analyzes its basic physical and chemical of mensuration and content of beary metal and measures, and mainly measurement result is as table 2.
Physicochemical property and the content of beary metal of the slag of table 2 stabilization processes premenstruum (premenstrua)
As known from Table 2, not premenstruum (premenstrua) stabilization processes slag pH be less than 6.5, present certain acidity, and the content of organic matter is also lower.In earlier stage after stabilization processes, more than the pH of slag is increased to neutrality, the content of organic matter significantly increases, and has improved slag fertility, is conducive to ecology of mining areas and reclaims.Wherein the interpolation of lime and flyash is the most obvious to the pH rising of slag, and after interpolation dewatered sludge, the content of organic matter of slag obviously increases.Testing result from content of beary metal, warp and not premenstruum (premenstrua) stabilization processes the standard value all set over soil environment quality grade III Standard (GB15618-1995) of the content of As, Zn, 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 declaration, solidify-stabiliser materials flyash, lime and dewatered sludge be combined with between two can improve slag pH value, improve organic content.
three, after stabilization processes and stabilization processes, the content of beary metal of different shape is measured
After premenstruum (premenstrua) stabilization processes, press 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 it is fully reacted after 3d, carry out the assay of heavy metals of different forms.
Heavy metal exists with 5 kinds of different forms conventionally:
exchangeable species: be easy to Transport And Transformation, can be absorbed by plants;
carbonate is in conjunction with state: be subject to the particularly impact of pH of soil environment condition, be easily discharged in environment; Therefore, exchangeable species and carbonate are larger in conjunction with the state metal pair mankind and environmental hazard;
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 is difficult for discharging under nature normal condition.Therefore by heavy metal, from the higher form of activity to activity lower, more stable form migration and transformation, be, the effective way that reduces Heavy Metal Pollution.
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 is as shown in Figure 1.
As can be seen from Figure 1, slag is through B
3after stabilization processes in group, it is the most remarkable that residual form As content rises, and amplification is 8.4%, and content is the highest, and exchangeable species As, organically combine state As content and decline the most significantly, and content is minimum, has reduced respectively 65.6%, 87.7%.
Measurement result explanation, add the use of combining of flyash, dewatered sludge and peanut shell simultaneously, can be best by exchangeable species As in slag, organically combine state As and transform to residual form As, flyash, dewatered sludge and peanut shell combines can solidify best-stabilisation of use heavy metal As.
After stabilization processes, the heavy metal Pb form in slag is analyzed to mensuration, measurement result as shown in Figure 2.
As can be seen from Figure 2, compare 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 processing, iron and manganese oxides is maximum in conjunction with state Pb recruitment, and amplification is 31.3%, A
1in processing, organically combine the reduction of state Pb content the most remarkable, 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 be in the situation that Pb content itself be very low, each stabilization processes group can not get better embodiment to the change ability of Pb form.
After stabilization processes, the heavy metal Zn form in slag is analyzed to mensuration, measurement result as shown in Figure 3.
As can be seen from Figure 3, compare with blank, after stabilized processing, 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 processing, exchangeable species Zn, iron and manganese oxides, in conjunction with state Zn, combination state Zn the biggest drop, reduce respectively 61.4%, 84.2%, 62.1%, and the increase of residual form Zn content is the most remarkable, and amplification is 44.8%.
Measurement result explanation, adding lime and flyash can be converted into residual form Zn by the exchangeable species Zn in slag, iron and manganese oxides in conjunction with state Zn, combination state Zn best.
three, the mensuration of As, Pb, Zn content in leachate
Respectively to the slag of the 3rd day, 33 days, 63 days after early stage stabilization processes, stabilization processes carry out for the first time, for the second time, for the third time with four Leaching Experiments, collect leachate, analyze the content of measuring heavy metal As, Pb, Zn in leachate, measurement result is as shown in Fig. 4~6.
As can be seen from Figure 4, in all leachates, As content is all higher, and its content surpasses 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 decline the most remarkable, stabilized processing after 63 days the range of decrease be 57.4%.Illustrate and add after flyash, dewatered sludge and peanut shell preferably to the stabilization effect of As simultaneously, can reduce significantly in slag heavy metal As with the diffusion mobility of rainwater;
As can be seen from Figure 5, early stage, stabilization processes just can better reduce the content of Pb in leachate, especially through B
3the early stage of group is after stabilization processes, and in leachate, Pb content declines the most significantly, and the mixture that flyash and dewatered sludge be described can 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 surpass concentration limit 1 mgL of surface water III class standard (GB3838-2002)
-1, illustrating that warp is without stabilization processes, it is all little to the harm of environment.
four, the impact of slag on 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
3in stabilization processes group, sow 100 vetiver seeds, 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 processing vetiver is minimum, is 24%.Analyzing relevant reason, may be because after lime and flyash adds, can there is pozzolanic reaction simultaneously, generates more stable hydrated calcium silicate and drated calcium aluminate, causes soil hardening, thereby is unfavorable for the Germination and growth of plant.Even so lime and flyash have the effect of stabilizing heavy metal, but can not use simultaneously, in heavy metal stabilizer, should not contain two kinds of compositions of lime and flyash 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 processing, the content of organic matter significantly increases, after adding peanut shell, slag becomes loose simultaneously, gas permeability is better, and in slag, the available state content of heavy metal reduces, and has reduced the toxic action to plant, is therefore conducive to the Germination and growth of vetiver.
Result of study to sum up, it is best to the stabilization effect of soil that flyash, dewatered sludge and peanut shell are combined use, can improve significantly soil pH, increase soil organic matter content, significantly reduce the content of heavy metal exchangeable species, reduce its toxicity, animal migration and biological effectiveness in soil environment, thereby reduce heavy metal element to vegeto-animal harm, and lay the foundation for the further restoration of the ecosystem in mining area.
Claims (5)
1. a method for heavy metal polluted soil in mine field stabilization processes, is characterized in that: comprise the following steps:
1) by adding flyash, dewatered sludge in heavy metal polluted soil in mine field, mix, carry out preliminarily stabilised processing;
2) by adding peanut shell in the soil after preliminarily stabilisedization processing, mix.
2. the method for a kind of heavy metal polluted soil in mine field stabilization processes according to claim 1, is characterized in that: the amount that adds flyash described in step 1) is 5~20% of heavy metal polluted soil in mine field weight.
3. the method for a kind of heavy metal polluted soil in mine field stabilization processes according to claim 1, is characterized in that: the amount that adds flyash described in step 1) is 5~20% of heavy metal polluted soil in mine field weight.
4. the method for a kind of heavy metal polluted soil in mine field stabilization processes according to claim 1, is characterized in that: step 2) described in to add the amount of peanut shell be 0.5~2% of heavy metal polluted soil in mine field weight.
5. the method for a kind of heavy metal polluted soil in mine field stabilization processes according to claim 1, is characterized in that: step 2) diameter of described peanut shell is not more than 2mm.
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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 |