CN104874585A - Comprehensive treatment method of slag heap of acidified gold ore containing heavy metal - Google Patents
Comprehensive treatment method of slag heap of acidified gold ore containing heavy metal Download PDFInfo
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Abstract
The invention relates to a stabilized and ecological remediation comprehensive treatment method of slag heap of acidified gold ore containing heavy metal, and belongs to the technical field of heavy metal pollution treatment in an ore field. The method comprises the following steps: adding a certain amount of lime, coal ash and organic sludge compost into 0-20cm soil at the upper layer of the slag heap of the gold ore containing heavy metal, mixing the ore slag and the additive according to a certain ratio and stirring so as to mix evenly, adding water into the ore slag, pouring, maintaining at the natural condition for 15-30 days so as to stabilize the slag heap of the gold core containing heavy metal; then, planting heavy metal tolerant plants including ciliate desert-grass, ramie and vetiver grass, so as to further remediate the heavy metal polluted slag heap ecologically. The method can effectively stabilize heavy metal, such as arsenic and cadmium in the gold ore slag, neutralize acid in the ore slag, improve the pH of soil in the ore field, reduce the leaching of heavy metal, enhance the soil structure, increase the soil fertility, and achieve the ecological recovery of the heavy metal polluted ore slag field.
Description
Technical field:
The present invention relates to heavy metals mining area pollutant abatement technology field, be specifically related to a kind of acidifying gold mine slag heap stabilisation containing heavy metal and repair the integrated synthesis administering method with restoration of the ecosystem.
Background technology:
Mineral Resources in China is enriched, and since reform and opening-up, the survey and exploitation of mineral resources achieves huge achievement, but digs up mine simultaneously, smelts and also result in the serious heavy metal pollution of the ecological environment such as mining area and surrounding area soil.Some gold mine of China is due to random mining for many years and adopt local method cyanide extraction of gold process, has remained a large amount of poisonous and harmful slag, due to long period of soaking and the leaching of rainwater, has defined acid wastewater in mine.Due to large, the unordered stacking of slag toxicity, mining area water, soil environment are subject to severe contamination, and ecological environment is destroyed, and mining area internal contamination thing diffuses to downstream with runoff, also result in pollution to downstream river, farmland, underground water.
For a long time, the mine tailing slag process in metal mine ore dressing plant is all generally adopt the mode of Tailings Dam to stockpile slag, not only takies a large amount of soils, contaminated soil, air, surface water, underground water, and a lot of Tailings Dam exceeds the time limit or excess load uses, and makes 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, and therefore, the research and development recovery technique of heavy metal polluted soil in mine field and the treatment technology of acid wastewater in mine just have its necessity, particularity and urgency.
At present, the reparation for heavy-metal contaminated soil is mainly divided into two classes from large aspect: 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 method of digging, heat treating process, dynamic electric repairing method, isolation investment etc.; Chemical technology: chemistry is fixing, chemical leaching, chemical oxidation/reduction etc.; Bioremediation technology: phytoremediation, microorganism remediation, compost 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; Dynamic electric repairing method technology 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, be difficult to the ecological recovery realizing place; 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; The advantages such as expense is low, applicability is strong, non-secondary pollution, recyclable valuable constituent that utilize the microbial method process mine acid slag of sulfate reducing bacteria to have, but because pure microbial method exists, organism self-ability limits, treatable pH scope is little, heavy metal ion tolerance is poor, treatment effeciency is low waits deficiency, thus fails to apply; Utilize merely plant to carry out the reparation of heavy metal pollution slag heap, due to toxicity and place lack of water, lack of water also usual lack of water organic matter and the fertilizer element of slag heap heavy metal, be thus difficult to prove effective; Place directly 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 also difficult to direct growth.
Heavy metal mobility in soil is the key factor determining its biological effectiveness, and mobility depends on its existing forms in soil, therefore by adding stabilizing agent in the soil of heavy metal pollution, by physics chemical action such as absorption, chelating, precipitation or co-precipitation, by changing the chemical form of heavy metal in soil or reducing its animal migration, increase soil fertility.First stabilizing surface treatment grows up from process radwaste, and Europe, Japan have applied for many years, and in recent years, the U.S. also takes much count of this technology.
Due to stabilizing surface treatment 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.By adding the heavy metal in soil additive stable soil, reducing the toxicity of harmful constituent, dissolving animal migration, heavy metal element being changed into the material that physics and chemistry is more stable in nature, reduce because rain or diafiltration work the mischief to environment.The patent of China in the stabilization processes of heavy metal polluted soil in mine field is less, mainly concentrates on the patent adopting the hydraulic materials such as cement, lime, gypsum.After the material of cement constituents adds soil to, can cause processing rear soil hardening, increase-volume, and the suction-operated of the C-S-H formed after leaning on hydration reaction merely and clay mineral is easily subject to the impact of external environmental condition on the fixed effect of heavy metal in soil, soil is through long-term weathering and acid-rain corrosion, heavy metal wherein also exists the potential danger that can again leach, and is also unfavorable for further ecological recovery simultaneously.、
Chinese patent (201410745013.1) discloses a kind of heavy metals immobilization agent, comprises flyash 30%-40%, lime 35%-51%, peat 19%-35%.This heavy metals immobilization agent effectively have cured the heavy metal in soil when not causing soil compaction, non-secondary pollution, but peat belongs to non-renewable resources, and cost is higher.
The present invention is containing the acid slag field of heavy metal pollution on the basis that stabilisation is repaired, then in conjunction with the plantation of heavy-metal-tolerant plant, form a kind of processing cost is low, applicability is strong, treatment effect is good method process acid slag and realize the ecological recovery new technology of slag heap.
Summary of the invention:
The object of this invention is to provide a kind of acidifying gold mine slag heap comprehensive processing method containing heavy metal, the method can effectively stablize the heavy metal such as arsenic, cadmium in gold mine slag, in and acid in slag, improve mining soil pH, reduce the leaching of heavy metal, improve soil texture, increase soil fertility, and realize the ecological recovery of heavy metal pollution slag heap.
For achieving the above object, the present invention is by the following technical solutions:
Containing an acidifying gold mine slag heap comprehensive processing method for heavy metal, comprise stabilisation reparation and restoration of the ecosystem;
Described stabilisation repair process is: stirred with stabilizing agent by slag gold mine slag heap upper strata 0-20cm soil and make it mix, after to add water pouring, and maintenance 15 ~ 30 days under field conditions (factors);
Wherein, described stabilizing agent, relative to gold mine slag heap upper strata 0-20cm slag 100wt%, comprises lime 5-20wt%, desulfurized powder coal ash 10-30wt%, sludge composting 5-20wt%;
Described restoration of the ecosystem process is: three Plants used are respectively ciliate desert-grass, vetiver, ramie, through domestication's heavy metal, there is higher patience, wherein ciliate desert-grass is the arsenic super enriching plant by screening, plants in the slag soil after stabilizer treatment and maintenance.
Preferred as technique scheme, described lime is high-quality white lime, and its main component is SiO
2, Al
2o
3, Fe
2o
3, CaO, MgO, content is respectively 3.21%, 0.45%, 0.12%, 80.26%, 4.12%.
Preferred as technique scheme, coal-burning power plant taken from by described desulfurized powder coal ash, and its main component is SiO
2, Al
2o
3, Fe
2o
3, CaO, MgO, content is respectively 55.36%, 19.25%, 7.88%, 5.56%, 2.59%.
Preferred as technique scheme, described sludge composting is from domestic sewage factory, and moisture content is lower than 30%, and organic matter is greater than 60%, and content of beary metal meets " in agricultural sludge pollutant catabolic gene standard " (GB4284-1984).
The present invention has following beneficial effect:
The present invention overcomes the deficiency of existing curing materials, does not use traditional cement class component, by adding the heavy metal in lime, flyash, sludge composting stabilization slag in slag, adopts heavy-metal-tolerant plant to implement the restoration of the ecosystem of slag heap simultaneously.Slag after stabilization processes, according in the test method of People's Republic of China (PRC) standard HJ557-2010 " solid waste Leaching leaching method-horizontal vibration method ", energy stabilization processes heavy metal pollution slag, make the Leaching of the heavy metal such as arsenic, cadmium decline more than 70%, effectively can improve the pH of leachate simultaneously.The requirement of Guangdong Province's provincial standard " Sewage Water Emissions limit value " is all met through each index of leachate of biological adsorption agent process.
Accompanying drawing illustrates:
Fig. 1: the leaching rate of different stabilization processes formula slag samples As;
Fig. 2: the leaching rate of different stabilization processes formula slag samples Cd.
Detailed description of the invention:
For a better understanding of the present invention, below by embodiment, the present invention is further described, and embodiment, only for explaining the present invention, can not form any restriction to the present invention.
The slag heap administered is positioned at Guangdong Province's Qingyuan City gold mine slag heap, this gold mine is due to random mining for many years and adopt local method cyanide extraction of gold process, remain and contained heavy metal slag in a large number, through Sampling Survey analysis, arsenic content 36521.38mg/kg in slag, cadmium content 5.897mg/kg, lead content 105.90mg/kg, Zn content 312.78mg/kg, pH=5.91, with reference to standard of soil environment quality (GB15618-1995, three grades), this slag main manifestations is that arsenic and cadmium exceed standard, and in acid.
Embodiment
(1) stabilisation reparation
Relative slag heap top layer 0-20cm slag 100 % by weight, in each embodiment, stabilizer formula is as shown in table 1, and wherein, contrast as the slag heap soil without stabilizer treatment, stabilization processes process is: use stabilizer treatment 2m
2slag heap soil, stirs stabilizing agent and slag, and then maintenance 28 days under field conditions (factors), completes stabilization procedures.Then sample is taken out, natural air drying, milled 2mm sieve, carries out leaching toxicity test with reference to HJ557-2010 " solid waste Leaching leaching method-horizontal vibration method " to sample, in leachate, content of beary metal adopts ICP-AES to analyze, and concrete measurement result is in table 2.
Stabilizer formula in each embodiment of table 1
| Lime (wt%) | Flyash (wt%) | Fertilizer (wt%) | |
| Contrast | |||
| Embodiment 1 | 5 | ||
| Embodiment 2 | 10 | ||
| Embodiment 3 | 20 | ||
| Embodiment 4 | 10 | ||
| Embodiment 5 | 20 | ||
| Embodiment 6 | 30 | ||
| Embodiment 7 | 5 | ||
| Embodiment 8 | 10 | ||
| Embodiment 9 | 20 | ||
| Embodiment 10 | 10 | 20 | |
| Embodiment 11 | 10 | 10 | |
| Embodiment 12 | 20 | 10 |
The Leaching testing result of table 2 different stabilization processes formula slag samples
PH value unit is dimensionless; The unit of all the other projects is mg/L; " L ": testing result is lower than detectability
As can be seen from Table 2: after adding lime, flyash, fertilizer, the pH value of leachate has rising, reaches more than neutrality, wherein flyash can significantly improve the pH of leachate, makes it reach meta-alkalescence.Cadmium in leachate, lead, the content of zinc does not all exceed the concentration value that " leaching characteristic identification (GB5085.3-2007) " sets.
As can be seen from Fig. 1, Fig. 2, compared with the control, when only adding lime, along with the addition of lime increases, the leaching rate of arsenic, cadmium raises, when adding 20% lime, the leaching concentration of arsenic, cadmium exceedes the leaching concentration value of contrast on the contrary, illustrates that excessive lime is unfavorable for the stabilisation of slag; When only adding flyash, along with the addition of flyash increases, the leaching of arsenic, cadmium takes the lead in reducing rear rising, when adding 20% flyash, the leaching rate of arsenic have dropped 50.4%, and the leaching rate of cadmium have dropped 51.5%, then when increasing flyash, leaching rate rises again; When only adding fertilizer, along with the addition of fertilizer increases, the leaching concentration of arsenic, cadmium first reduces rear rising, and when adding 5% fertilizer, the leaching rate of arsenic reduces 30.9%, and the leaching rate of cadmium have dropped 64.6%.Lime-flyash, lime-fertilizer, the combination of flyash-fertilizer can reduce the leaching of heavy metal, wherein lime-flyash, the treatment effect of flyash-fertilizer combination is relatively better, compared with the control, the leaching rate of arsenic have dropped 44.6% respectively, 71.3%, the leaching rate of cadmium have dropped 44.4% respectively, 71.4%, and although the combination of lime-fertilizer can make arsenic, the leaching rate of cadmium etc. declines, but with lime-flyash, the combination of flyash-fertilizer is compared, leaching effect is relatively low, compared with the control, the leaching rate of arsenic have dropped 29.5%, the leaching rate of cadmium have dropped 29.1%.
(2) restoration of the ecosystem
By the various combination process (A to lime, flyash, mud in stabilizing agent
cK, A
1, A
2, A
3, A
4, A
5, wherein A
cKfor blank), this stabilizing agent is carried out improved treatment to slag heap soil, and plants ciliate desert-grass, vetiver, ramie, carry out follow-up investigation to its growing state, investigation result is as shown in table 3.
Table 3 adds the impact of stabilizer treatment soil on different aboveground vegetation part dry weight
The different lowercase alphabet of same column is shown in 0.05 horizontal significant difference, and statistics adopts mean+SD.
As can be seen from Table 3, stabilizing agent is to after the improved treatment of slag heap soil, and polluting in slag heap the ciliate desert-grass, vetiver, the ramie biological amount that grow all has increase in various degree compared with the control, wherein, and A
2ciliate desert-grass in process, the increase of ramie Aboveground Biomass of Young dry weight significantly (P<0.01), and contrast A
cKcompare and add 4.4 times, 2.9 times respectively, this may be because lime, flyash, sludge composting can reduce the biological effectiveness of As in soil, reduce its murder by poisoning to plant, simultaneously in sludge composting containing nutrients such as abundant organic matter and N, P, K, be conducive to the growth of plant.In the change of different phytomass and process of the test, under different disposal, the growing way of plant is completely the same, i.e. control group A
cKplant strain growth is small and weak, shows stronger As poisoning symptom, and after growth a period of time, withered and yellow atrophy appears in leaf, even dead.After different modifying agent process, vegetation growth state makes moderate progress, and showing as biomass significantly increases, but after growth a period of time, plant leaf blade still there will be withered and yellow atrophy phenomenon, and this may pollute relevant with soil middle and high concentration As.There are some researches show, under high concentration As exists situation, to the toxic action of plant clearly, this toxic action main manifestations is As: plant roots is long, stem is long shortens; The dry weight of root, stem reduces; Photosynthesis and Growth of Cells are suppressed.
Additive absorbs As to vetiver and has a significant effect, and wherein aerial part As content is greater than aerial part, all shows as root > cauline leaf; KH in additive
2pO
4compared with Gao Houhui, active higher exchangeable species and carbonate in soil are significantly increased in conjunction with state As content, the mobile transfer ability of As strengthens, plant absorption As content is increased, and ramie is poor to high concentration As pollution tolerance, the As toxic action that performance process is stronger, makes its biomass reduce, is unfavorable for the growth of ramie, also illustrate that vetiver and ciliate desert-grass have stronger tolerance to high concentration As pollution, and the tolerance of ciliate desert-grass to As is greater than vetiver simultaneously.
Application Example
For inquiring into mining area slag Environmental capacity stabilization processes engineering construction scheme further, experimentally room stabilization processes lab scale research, carries out microcosm experiment to the lime-flyash elected, flyash-fertilizer, lime-fertilizer combination of two formula.
Fetch 8 casees slag aggregate samples with rectangular plastic hopper from scene, the length, width and height of plastic box outside dimension are 540 × 420 × 300mm, and inside dimension is 500 × 380 × 290mm.Carry out multi-point sampling collection mixing slag samples from composite ore slag muck, they are mixed, stirs, to be then on average dispensed in each case.The degree of depth of every case splendid attire slag is about 250mm, and the volume of slag is about 0.048m
3, slag weight is about 76kg.Gather return 8 casees mixing slag samples every two casees parallel, wherein two casees as blank, add 5% lime and 10% flyash for two casees, add 5% lime and 10% fertilizer for two casees, add 10% flyash and 10% fertilizer for two casees in addition, treating depth is 0-20cm, stirs and makes it mix, and reacts three days after adding water saturates.Then according to Guangdong Province's mean storm in rainy season amount, carry out twice simulated experiment (midfeather two days), rainfall during simulation heavy rain is tested the rain of slag, rainwater percolate is collected below with device, again the percolate collected is done to the mensuration of various index, mainly comprise the mensuration of the indexs such as pH, arsenic, cadmium, lead, zinc, compare the leaching effect before and after process, thus tentatively determine the outer draining water quality after stabilized process.Each Indexs measure result of the percolate that twice simulated experiment is collected is respectively in table 4 and table 5:
Table 4 first time percolate testing result
Table 5 second time percolate testing result
PH value unit is dimensionless; The unit of all the other projects is mg/L; " L ": testing result is lower than detectability
As can be seen from table 4,5: with compare, after treatment, the pH of the slag percolate of twice simulated test raises to some extent, reaches neutral.Cadmium in percolate, lead, the content of zinc does not all exceed the concentration value that " leaching characteristic identification (GB5085.3-2007) " sets, in twice percolate, the content of arsenic has compared decline with contrast, after adding lime and flyash, the leaching rate of arsenic have dropped 50.2%, 53.9% respectively, the leaching rate of cadmium have dropped 51.2%, 34.5% respectively, this may be that heavy metal in lime-flyash and slag reacts and generates hydroxide, illustrates that lime-flyash combination effectively can reduce the leaching of arsenic, cadmium; After adding flyash and fertilizer, the leaching rate of arsenic have dropped 60.9%, 54.4% respectively, the leaching rate of cadmium have dropped 61.8%, 54.4% respectively, this may be flyash-fertilizer combination chelating or complexation heavy metal ion, reduce its Leaching, illustrate that flyash-fertilizer combination also effectively can reduce the leaching of arsenic, cadmium; After adding lime and fertilizer, the leaching rate of arsenic have dropped 28.7%, 28.4% respectively, the leaching rate of cadmium have dropped 30.5%, 28.7% respectively, what lime-fertilizer was described adds the leaching being also conducive to reducing arsenic, cadmium, but compared with combining with lime-flyash, flyash-fertilizer, leaching effect is relatively low.This shows, the treatment effect of the combination of lime-flyash and the combination of flyash-fertilizer is obvious, effectively can control toxic heavy metal and leach.
In sum, by lime, flyash, sludge composting rational formula to the stabilization processes of slag heap, in conjunction with heavy-metal-tolerant plant plantation, effectively can realize stabilisation reparation and the ecological recovery in heavy metal pollution place.
Claims (4)
1., containing an acidifying gold mine slag heap comprehensive processing method for heavy metal, it is characterized in that: comprise stabilisation reparation and restoration of the ecosystem;
Described stabilisation repair process is: stirred with stabilizing agent by slag gold mine slag heap upper strata 0-20cm soil and make it mix, after to add water pouring, and maintenance 15 ~ 30 days under field conditions (factors);
Wherein, described stabilizing agent, relative to gold mine slag heap upper strata 0-20cm slag 100wt%, comprises lime 5-20wt%, desulfurized powder coal ash 10-30wt%, sludge composting 5-20wt%;
Described restoration of the ecosystem process is: three Plants used are respectively ciliate desert-grass, vetiver, ramie, plants in the slag heap soil after stabilizer treatment and maintenance.
2. a kind of acidifying gold mine slag heap comprehensive processing method containing heavy metal as claimed in claim 1, it is characterized in that: described lime is high-quality white lime, its main component is SiO
2, Al
2o
3, Fe
2o
3, CaO, MgO, content is respectively 3.21%, 0.45%, 0.12%, 80.26%, 4.12%.
3. a kind of acidifying gold mine slag heap comprehensive processing method containing heavy metal as claimed in claim 1, it is characterized in that: coal-burning power plant taken from by described desulfurized powder coal ash, its main component is SiO
2, Al
2o
3, Fe
2o
3, CaO, MgO, content is respectively 55.36%, 19.25%, 7.88%, 5.56%, 2.59%.
4. a kind of acidifying gold mine slag heap comprehensive processing method containing heavy metal as claimed in claim 1, it is characterized in that: described sludge composting is from domestic sewage factory, moisture content is lower than 30%, organic matter is greater than 60%, and content of beary metal meets " in agricultural sludge pollutant catabolic gene standard " (GB4284-1984).
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| CN112292957A (en) * | 2020-10-30 | 2021-02-02 | 中国科学院地理科学与资源研究所 | Method for repairing ammonia nitrogen and sulfate radical pollution of ionic storage yard |
| CN112979088A (en) * | 2021-03-09 | 2021-06-18 | 南昌航空大学 | Reduction barrier for treating slag acidic wastewater and application thereof |
| CN113042520A (en) * | 2021-05-06 | 2021-06-29 | 北京首创环境科技有限公司 | Risk management and control and ecological restoration method for metal mine polluted site |
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| CN113522931B (en) * | 2021-07-09 | 2023-03-24 | 浙江工业大学 | Mineral oxidation acid production inhibition method based on in-situ rapid film formation on surface of sulfurized mineral |
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