CN102303041B - Composite heavy metal polluted soil in-situ fixing method - Google Patents
Composite heavy metal polluted soil in-situ fixing method Download PDFInfo
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Abstract
The invention discloses a composite heavy metal polluted soil in-situ fixing method. The method comprises the following steps of: preparing a heavy metal polluted soil restoration agent by using 80 to 90 weight parts of bentonite or kaolin serving as a filling agent, 0.5 to 15 weight parts of ferrous sulfide, 0.5 to 5 weight parts of magnesium sulfate, 1.5 to 8 weight parts of magnesium sulfite, 1 to 5 weight parts of magnesium oxide, 2 to 10 weight parts of calcium hydroxide and 1 to 5 weight parts of phosphorus-containing preparation; and mixing the components and heavy metal polluted soil according to the weight ratio of 1:(5-20), and uniformly stirring to make the humidity of the soil kept between 15 and 30 percent, wherein heavy metal ions in the polluted soil are converted into water-insoluble metal sulfides, hydroxides, multi-metal co-precipitates, basic carbonates and phosphate minerals, the biological activity of heavy metal is lost, and the heavy metal is fixed in the soil. The restored soil meets the requirement of second-level standard values of 'Environmental Quality Standard for Soil' (GB 15618-1995) in China.
Description
Technical field
The present invention relates to a kind of compound heavy-metal contaminated soil anchored in place method; Specifically; Relate to a kind of heavy metal Hg, cadmium, chromium and plumbous compound contaminated soil anchored in place restorative procedure; Through redox reaction, coprecipitation reaction with become ore deposit reaction, after being converted into water-fast metal sulfide, hydroxide, many metals coprecipitate, subcarbonate and phosphate mineral, heavy metal ion is fixed in the soil, and heavy metal loses its biologically active.Satisfy the requirement of China " soil environment quality standard " (GB 15618-1995) secondary standard value after the soil remediation.
Background technology
China's heavy metal pollution incident just gets into the high-incidence season.
2005, China Geological Survey Bureau found that there is pollution in the soil that accounts for area 13%; In all pollution types, heavy metal pollution occupies significant proportion.
2009, Chinese Ministry of Environmental Protection announced 12 heavy metal pollution incidents, caused altogether that 4035 people's blood leads exceed standard, 182 people's cadmiums exceed standard, and 32 Mass disturbances that caused by heavy metal pollution take place in the whole nation.
Since in March, 2010, the Mass disturbance that masses' blood lead exceeds standard and poisons and cause takes place again in ground such as inland river, Sichuan, Chenzhou, Hunan in succession.
Along with the exposure of " cadmium rice " incident, warning heavy metal and climbing up our dining table recently, Chinese have also reached unprecedented height to the concern of heavy metal pollution.
Cause the reason of heavy metal pollution very many; Mainly be that fields such as mining, metal smelt, electroplating industry, chemical industry, metal processing, IT industry and waste electrical equipment recovery produce and the discharging heavy metal contaminants; After getting in surface water, underground water and the atmosphere, these heavy metals finally come together in soil.Heavy metal in the soil will get into human body through food chain, when the heavy metal in the body is accumulated to a certain degree, will cause various human body diseases.Therefore, the control of heavy metal pollution of soil and reparation problem have caused governments at all levels and efforts at environmental protection person's extensive concern.
At present, the heavy-metal contaminated soil recovery technique mainly comprises following several kinds:
(1) phytoremediation method.Through plantation heavy metal is had the plant of super accumulating capability, thereby the heavy metal in the soil is extracted.The ability that ciliate desert-grass absorbs arsenic in the soil is equivalent to 200,000 times of common plant, and absorption, harvesting through ciliate desert-grass can recover by the soil of arsenic contamination.Sedum alfredii Hance has very strong accumulating capability to cadmium, and the absorption through Sedum alfredii Hance, harvesting can recover by the soil of cadmium pollution.But the time of phytoremediation method needs 3～5 years, and the time of falling into disuse that means soil is exactly 3～5 years, has influence on the production of grain and peasant's income.In addition, the cost of phytoremediation is higher, and soil per ton reaches about 200 yuan, and the rehabilitation expense of every mu of soil is up to 8～100,000 yuan, and the rehabilitation cost of per hectare soil reaches 1.2～1.5 hundred million yuans.Local government and peasant are unaffordable.
And; The super enriching plant of finding at present generally all is a wild plant; There is bigger technical difficulty in its seedling breeding; Realize that extensive seedling is just difficult more, so use now is that the way of repairing the district is transplanted in first booth breeding again, this can further increase rehabilitation cost and operation easier undoubtedly.
(2) chemical leaching method.Carry out wastewater treatment again after adopting chemical agent such as surfactant, mordant etc. that the heavy metal drip washing in the soil is come out.This method not only cost is very high, far above the phytoremediation method, and brings into soil such as new pollutant such as surfactant, mordant etc., becomes new pollution sources.The physical arrangement of soil can receive very big influence.
(3) soil moved in to improve the original method.Contaminated soil is buried inaccessiable below 25 centimetres to rice root, repair one mu of contaminated land in this way and will spend units up to a million, and contaminated soil still exists, even can continue to expand to underground water pollution.But because restorative procedure is simple, spended time is few, and this method of drinking poison to quench thirst is widely used at present.
(4) microorganism elution method.Through in soil, adding the microorganism species that heavy metal is had enrichment, heavy metal is washed out.This mode not only cost is high, for large-area soil pollution, because the microorganism leacheate is difficult to collect, in fact is difficult to operation.
(5) electrochemical process.In soil, make water-soluble heavy metal ion enrichment to cathode surface through the function of current.Should technology just grope at present in the laboratory.Because function of current distance is too little, and actual contaminated land area is too big, this technology is difficult to carry out on engineering, and no matter its high running cost is difficult to bear.
(6) heavy metal deactivation method.Only possessing bioactive heavy metal could be utilized by plant, thereby is accumulated in human body through food chain.Thereby make water-soluble heavy metal ion be converted into hydroxide to reduce its biologically active through in contaminated soil, adding passivator such as sepiolite, calcium magnesium phosphate and lime.But, by this method the heavy metal after the passivation under microbial action and environmental factor will recover its biologically active continuously when changing.Therefore, the heavy metal deactivation method has just been covered heavy metal pollution problem temporarily, momently.
(7) sulfide method.Mainly comprise vulcanized sodium and calcium sulfide, can generate the extremely low heavy metal sulfide deposition of solubility with most heavy metal, very good to the immobilization effect of heavy metal-polluted soil; But sulfide must maintain (requiring pH＞8.5 usually) among the alkaline environment to the reparation of soil, otherwise the heavy metal sulfide of these generations deposition will be converted into free heavy metal again.Strong alkaline condition makes soil lose its function of use.This restorative procedure relatively is suitable for the solidification and stabilization of heavy-metal contaminated soil to be handled, and carries out landfill then and disposes.When the super fund project of the U.S. was administered to the heavy metal pollution place, a large amount of medicaments that contain vulcanized sodium or calcium sulfide that use carried out landfill at last and dispose.
In sum, how to develop practicable heavy-metal contaminated soil recovery technique and become the bottleneck problem that following heavy metal pollution control faces.
Summary of the invention
The technical issues that need to address of the present invention just are to overcome the defective of prior art; A kind of compound heavy-metal contaminated soil anchored in place method is provided; It is through redox reaction, coprecipitation reaction and become the ore deposit reaction, is fixed in the soil after heavy metal ion is converted into water-fast metal sulfide, hydroxide, many metals coprecipitate, subcarbonate and phosphate mineral.Heavy metal loses its biologically active.Satisfy the requirement of China " soil environment quality standard " (GB 15618-1995) secondary standard value after the soil remediation.
For addressing the above problem, the present invention adopts following technical scheme:
The invention provides a kind of compound heavy-metal contaminated soil anchored in place method; Said method is for passing through redox reaction, coprecipitation reaction and becoming the ore deposit reaction; Heavy metal ion is converted into water-fast metal sulfide, hydroxide, many metals coprecipitate, subcarbonate and phosphate mineral; Heavy metal loses its biologically active, is fixed in the soil.
Concrete process for fixation comprises the following steps:
(1) heavy-metal contaminated soil is repaired preparation of medicaments: by weight ratio following raw materials according is mixed, processes heavy-metal contaminated soil and repair medicament; Bentonite or kaolin are filler for 80～90 parts, 0.5～15 part of ferrous sulfide, 0.5～5 part in magnesium sulfate, 1.5～8 parts of magnesium sulfites, 1～5 part in magnesia, 1～5 part in 2～10 parts in calcium hydroxide and phosphorous preparation;
(2) with mixing with soil: it is 1 with heavy-metal contaminated soil according to weight ratio that heavy-metal contaminated soil is repaired medicament: the weight ratio of (5～20) is mixed, is stirred, and keeps soil moisture 15～30%;
(3) reaction: through 1 month, the heavy metal ion in the contaminated soil was converted into water-fast metal sulfide, hydroxide, many metals coprecipitate, subcarbonate and phosphate mineral, and heavy metal loses its biologically active, is fixed in the soil.
Said phosphorous preparation is calcium phosphate or calcium monohydrogen phosphate or calcium dihydrogen phosphate or calcium superphosphate.
Said heavy metal is cadmium, chromium, mercury or lead.
The present invention is a reactant with ferrous sulfide, magnesium sulfate and magnesium sulfite; With the bentonite is filler; With magnesia, calcium hydroxide, phosphorous preparation is auxiliary agent, promotes heavy metal to become the ore deposit reaction, is mixed with heavy-metal contaminated soil and repairs medicament; In 1 month, heavy-metal contaminated soil is repaired fast, the soil environment quality after the reparation satisfies the requirement of China " soil environment quality standard " (GB 15618-1995) secondary standard value.
The present invention is applicable to the reparation of large tracts of land top layer heavy-metal contaminated soil, comprises the reparation in heavy metal pollution farmland, the reparation in heavy metal pollution mine and the reparation of heavy metal manufacturing enterprise contaminated site.Cost is low, and the time is fast, and efficient is high.
The specific embodiment
Embodiment 1
1), heavy-metal contaminated soil is repaired preparation of medicaments: with bentonite, ferrous sulfide, magnesium sulfate, magnesium sulfite, magnesia, calcium hydroxide and calcium dihydrogen phosphate according to 80: 15: 0.5: 8: 1: 10: 1; Mix, become heavy-metal contaminated soil and repair medicament.
2), apply heavy-metal contaminated soil and repair medicament: the hopper of polluted soil being sent into disintegrating machine with forklift; Fragmentation is after belt is sent to blender; Mix with the reparation medicament; According to soil: the weight ratio mixing of medicament=15: 1, deliver to through conveyer belt again and stack the place, obtain adding the soil behind the medicament.
3), repair: through 1 month; Heavy metal cadmium in the contaminated soil, chromium, mercury, lead are reduced into immobilized heavy metal, heavy metal precipitation thing or mineral matter at a low price; Lose its biological effectiveness; Realized the original position reparation of heavy-metal contaminated soil, the soil environment quality after the reparation satisfies the requirement of China " soil environment quality standard " (GB 15618-1995) secondary standard value.
Embodiment 2
1), heavy-metal contaminated soil is repaired preparation of medicaments: with kaolin, ferrous sulfide, magnesium sulfate, magnesium sulfite, magnesia, calcium hydroxide and calcium monohydrogen phosphate according to 90: 0.5: 5: 1.8: 5: 2: 5; Mix, become heavy-metal contaminated soil and repair medicament.
2), apply heavy-metal contaminated soil and repair medicament: polluted soil is sent into the hopper on the disintegrating machine with forklift; Fragmentation is after belt is sent to blender; Mix with the reparation medicament; According to soil: the weight ratio mixing of medicament=10: 1, deliver to through conveyer belt again and stack the place, obtain adding soil behind the medicament.
3), repair: through 1 month; Heavy metal cadmium in the contaminated soil, chromium, mercury, lead are reduced into immobilized heavy metal, heavy metal precipitation thing or mineral matter at a low price; Lose its biological effectiveness; Realized the original position reparation of heavy-metal contaminated soil, the soil environment quality after the reparation satisfies the requirement of China " soil environment quality standard " (GB 15618-1995) secondary standard value.
Embodiment 3
1), heavy-metal contaminated soil repairs preparation of medicaments: with bentonite, ferrous sulfide, magnesium sulfate, magnesium sulfite, magnesia, calcium hydroxide and calcium phosphate according to 85: 6: 2: 3: 2: 3: 4, mix, become heavy-metal contaminated soil and repair medicament.
2), apply heavy-metal contaminated soil and repair medicament: forklift is sent polluted soil into the hopper on the disintegrating machine; Fragmentation is after belt is sent to blender; Mix with the reparation medicament; According to soil: medicament=20: 1 weight ratio mixings, deliver to through conveyer belt again and stack the place, obtain adding soil behind the medicament.
3), repair: through 1 month; Heavy metal cadmium in the contaminated soil, chromium, mercury, lead are reduced into immobilized heavy metal, heavy metal precipitation thing or mineral matter at a low price; Lose its biological effectiveness; Realized the original position reparation of heavy-metal contaminated soil, the soil environment quality after the reparation satisfies the requirement of China " soil environment quality standard " (GB 15618-1995) secondary standard value.
What should explain at last is: obviously, the foregoing description only be for clearly the present invention is described and is done for example, and be not qualification to embodiment.For the those of ordinary skill in affiliated field, on the basis of above-mentioned explanation, can also make other multi-form variation or change.Here need not also can't give exhaustive to all embodiments.And conspicuous variation of being amplified out thus or change still are among protection scope of the present invention.
Claims (2)
1. compound heavy-metal contaminated soil anchored in place method; It is characterized in that: said method is for passing through redox reaction, coprecipitation reaction and becoming the ore deposit reaction; Heavy metal ion is converted into water-fast metal sulfide, hydroxide, many metals coprecipitate, subcarbonate and phosphate mineral; Heavy metal loses its biologically active, is fixed in the soil;
Comprise the following steps:
(1) heavy-metal contaminated soil is repaired preparation of medicaments: by weight ratio following raw materials according is mixed, processes heavy-metal contaminated soil and repair medicament; Bentonite or kaolin are filler for 80 ~ 90 parts, 0.5 ~ 15 part of ferrous sulfide, 0.5 ~ 5 part in magnesium sulfate, 1.5 ~ 8 parts of magnesium sulfites, 1 ~ 5 part in magnesia, 1 ~ 5 part in 2 ~ 10 parts in calcium hydroxide and phosphorous preparation;
(2) with mixing with soil: it is 1 with heavy-metal contaminated soil according to weight ratio that heavy-metal contaminated soil is repaired medicament: the weight ratio of (5 ~ 20) is mixed, is stirred, and keeps soil moisture 15 ~ 30%;
(3) reaction: through 1 month, the heavy metal ion in the contaminated soil was converted into water-fast metal sulfide, hydroxide, many metals coprecipitate, subcarbonate and phosphate mineral, and heavy metal loses its biologically active, is fixed in the soil;
Said heavy metal is cadmium, chromium, mercury or lead.
2. compound heavy-metal contaminated soil anchored in place method as claimed in claim 1 is characterized in that: said phosphorous preparation is calcium phosphate or calcium monohydrogen phosphate or calcium dihydrogen phosphate or calcium superphosphate.
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