CN102766465A - Ion mineralization stabilizer for treating soil with heavy metal pollution and application method thereof - Google Patents
Ion mineralization stabilizer for treating soil with heavy metal pollution and application method thereof Download PDFInfo
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Abstract
The invention discloses ion mineralization stabilizer for treating soil with heavy metal pollution and an application method thereof. The ion mineralization stabilizer comprises, by weight percent, 5-30% of sulfur-based compound, 10-50% of phosphor-based compound, 10-50% of calcium-based compound, and 10-30% of silicon-based compound. The materials are respectively ground into powders with particle size not less than 200 meshes, and the powders are proportionally mixed well. The application method of the ion mineralization stabilizer for treating soil with heavy metal pollution includes: detecting arsenic content and leaching toxicity of the soil to be treated, placing the ion mineralization stabilizers in different proportions on the surface of the soil to be treated according to pollution level, well mixing to form mixed soil by ploughing and stirring, adding water to keep the water content of the mixed soil no less than 25%, covering the mixed soil with moisturizing material, curing for at least 5 days to keep heavy metals in the mixed soil to form stable minerals.
Description
Technical field
The present invention relates to environmental technology field, particularly relate to a kind of ion mineralising stablizer and method of use of the improvement heavy-metal contaminated soil that various heavy-metal contaminated soils are administered.
Background technology
Heavy metal-pollutedly have a finger in every pie the environmental pollution that causes by heavy metal or its compound, mainly by due to the human factors such as mining, exhaust gas emission, sewage irrigation and use heavy metal goods.Heavy metal pollution of soil has the characteristics of disguise, chronicity and non-reversibility; Harmful heavy metal runs up to a certain degree in the soil; Not only can cause Soil degradation, crop yield and quality descend, but also can pass through runoff, leaching loss effect polluted surface water and underground water; Worsen hydrological environment, and direct poisonous plant or be detrimental to health through the food chain approach.At the beginning of 2011 4 months, China first " 12 " ad hoc planning---" heavy metal contamination integrated control " 12 " planning " obtains State Council and formally gives an written reply, and control program makes every effort to control 5 heavy metal species.At present, extensive studies is carried out to the heavy metal pollution of soil recovery technique in countries in the world, and following several kinds of reclamation activitiess are specifically arranged.
1 engineering repairing method: the engineering repairing method mainly contains soil moved in to improve the original method, soil replacement method and the method for digging, and the soil moved in to improve the original method is in contaminated soil, to add a large amount of clean soils, covers top layer or mixing, and Pollutant levels are reduced.Soil replacement method is taken contaminated soil away exactly, changes to new clean soil.The method of digging adopts the mode of deep ploughing to make the pollutent that accumulates in the top layer be distributed to deep layer, the purpose that reaches dilution and handle certainly.The method of digging is mainly used in the soil of slight pollution, and soil moved in to improve the original method and soil replacement method are mainly used in the soil of serious pollution.The engineering reparation is the classical heavy metal pollution of soil control measures of comparison, and it has thorough, stable advantage, its weak point: the enforcement quantities is big, investment cost is high, can destroy soil structures during improper measures, causes soil fertility to descend.The dirty soil that swaps out also needs properly to stack to dispose, and prevents secondary pollution, the investment of its corresponding increase engineering with move.
2 physical chemistry repairing methods: the physical chemistry repairing method mainly contains soil drip-rinsing process, vitrifying method, electrochemical process etc.The soil drip-rinsing process utilizes eluent drip washing contaminated soil, and the heavy metal in the solid phase of soil is transferred in the liquid phase of soil, reduces pollutent toxicity; The vitrifying method is to use electrically heated at the scene, and with the contaminated soil fusing, the cooling back forms stiff glass body technique chemically inert, non-diffusion; Electrochemical process is to utilize electrokinetic effects that extra electric field produces to drive pollutent in the soil along the direction of an electric field directional migration, and the pollutent of enrichment can be focused on or separates at electrode district.Arsenic in the clayed soil of, conductivity difference not high for perviousness can destroy the principle of metal-soil key according to electric current, but the Applied Electrochemistry method is removed.But the weak point that this method exists: rehabilitation cost is high, energy consumption is big even have secondary pollution.
3 phytoremediation methods: the phytoremediation method is to utilize certain kind of plant of plantation to purify soil and the water body that receives arsenic contamination.The phytoremediation method by the mechanism of its reparation and process can be divided into that plant extraction, plant are fixed, phytovolatilization, root system filter, plant degradation.Wherein, plant extraction is meant and utilizes root system of plant absorption soil contaminant and be transported to plant shoot, reaches a kind of method of removing pollutant in soil through harvesting overground part material.The weak point of this method: the improvement cycle is very long, and later stage plant collection, treatment process be complicacy comparatively, and the maintenance management cycle is long.
4 chemistry are repaired: chemical repair method is exactly to drop into modifying agent to soil, through absorption, redox, antagonism or the precipitating action to heavy metal, to reduce the biological effectiveness of heavy metal.This key problem in technology is to select cost-effective modifying agent.Modifying agent commonly used has the organic substance of lime, zeolite, lime carbonate, phosphoric acid salt, silicate and promotion reductive action, and different modifying agents are different to the mechanism of action of heavy metal.Chemical repair method adopts the stable curing technology that the soil that receives heavy metal contamination is repaired usually.
The stable curing technology is to wait water-soluble, diffustivity and the biological effectiveness that reduces soil pollutant through using the chemical passivation agent, thereby reduces the ability that their get into plant materials, microbe body and water body, alleviates the harm to the ecosystem.Along with the widespread demand to the soil remediation low-cost technologies, low-cost stable curing technology will be developed fast.
China also is being in the starting stage aspect the heavy-metal contaminated soil stable curing recovery technique at present; Mainly be to adopt lime, phosphoric acid salt, cement etc. to make heavy metal ion with oxyhydroxide or phos-phate forms passivation; Exist long-lasting poor, dosing big, only be fit to the shortcoming of low contaminated soil, and China's soil pollution particularly has compound and high-load characteristics with the peripheral heavy-metal contaminated soil in smeltery in the mining area.Therefore, new stabilization curing recovery technique and the medicament of exploitation is the key that improves China's heavy-metal contaminated soil stable curing recovery technique.
Summary of the invention
The objective of the invention is to overcome existing deficiency; Unsettled heavy metal ion generation mineralising reaction in a kind of employing ion mineralising stabilization stablizer and the heavy-metal contaminated soil is provided, heavy metal is converted into the ion mineralising stablizer and the method for use of the improvement heavy-metal contaminated soil of the most stable compound.
The object of the invention is achieved through following technical proposals:
Ion mineralising stablizer of the present invention comprises following raw material, and its mass percent is:
Sulfur-based compound is 5-30%;
Phosphorio compound is 10-50%;
The calcium based compound is 10-50%;
Silicon base compound is 10-30%;
Each raw material is ground into granularity respectively be not less than 200 purpose materials, mix in proportion, obtain described ion mineralising stablizer.
Described sulfur-based compound is any one of Iron sulfuret, sodium sulphite, sodium polysulphide, sulfurated lime, ammonium sulfide, potassium sulphide, potassium polysulfide, calcium polysulfide, or multiplely arbitrarily press the arbitrary proportion mixing.
Described phosphorio compound be secondary calcium phosphate, tricalcium phosphate, dicalcium phosphate, phosphoric acid, Secondary ammonium phosphate, ammonium phosphate, sodium phosphate, fused(calcium magnesium)phosphate, Rock Phosphate (72Min BPL) phosphorus bone meal, potassiumphosphate, potassium hydrogenphosphate any one or multiplely arbitrarily mix by arbitrary proportion.
Described calcium based compound be Wingdale, chalk, rhombspar, lime, calcium hydroxide, silicate cement any one or multiplely arbitrarily mix by arbitrary proportion.
Described silicon base compound be kaolin, smectite, attapulgite, wilkinite, zeyssatite, volcanical ash, zeolite, flyash any one or multiplely arbitrarily mix by arbitrary proportion.
The method of use that ion mineralising stablizer of the present invention is used to administer heavy-metal contaminated soil may further comprise the steps:
(1) content of heavy metal and leaching toxicity in the pending contaminated soil of detection;
(2) according to detected result, by quality than heavy-metal contaminated soil: ion mineralising stablizer=5 ~ 50:1 adds ion mineralising stablizer, with ion mineralising stablizer equably spreading on the surface of pending soil;
(3) adopt the mode of the stirring of turning over that the ion mineralising stablizer of pending soil together with spreading on it mixed 3 times at least, form mixed soil; Through adding the water mode, keep the water cut of mixed soil to be not less than 25%;
(4) on mixed soil, cover material which can retain moisture, curing time at least 5 days lets heavy metal reacts in ion mineralising stablizer and the heavy-metal contaminated soil in the mixed soil, forms stable mineral form;
(5) the leaching toxicity of heavy metal in the sample detecting mixed soil; Do not meet environmental requirement if detect, increase curing time, add water in case of necessity, up to the detected result compliance with environmental protection requirements.
Advantages such as compared with prior art, it is extensive that ion mineralising stablizer of the present invention has raw material, draws materials easily, and the preparation method is simple; Advantages such as the method for use of ion mineralising stablizer of the present invention has simple to operate, and regulation effect is good.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Ion mineralising stablizer of the present invention comprises following raw material, and its mass percent is:
Sulfur-based compound is 5-30%;
Phosphorio compound is 10-50%;
The calcium based compound is 10-50%;
Silicon base compound is 10-30%;
Each raw material is ground into granularity respectively be not less than 200 purpose materials, mix in proportion, obtain described ion mineralising stablizer.
Described sulfur-based compound is any one of Iron sulfuret, sodium sulphite, sodium polysulphide, sulfurated lime, ammonium sulfide, potassium sulphide, potassium polysulfide, calcium polysulfide, or multiplely arbitrarily press the arbitrary proportion mixing.
Described phosphorio compound be secondary calcium phosphate, tricalcium phosphate, dicalcium phosphate, phosphoric acid, Secondary ammonium phosphate, ammonium phosphate, sodium phosphate, fused(calcium magnesium)phosphate, Rock Phosphate (72Min BPL) phosphorus bone meal, potassiumphosphate, potassium hydrogenphosphate any one or multiplely arbitrarily mix by arbitrary proportion.
Described calcium based compound be Wingdale, chalk, rhombspar, lime, calcium hydroxide, silicate cement any one or multiplely arbitrarily mix by arbitrary proportion.
Described silicon base compound be kaolin, smectite, attapulgite, wilkinite, zeyssatite, volcanical ash, zeolite, flyash any one or multiplely arbitrarily mix by arbitrary proportion.
The method of use that ion mineralising stablizer of the present invention is used to administer heavy-metal contaminated soil may further comprise the steps:
(1) content of heavy metal and leaching toxicity in the pending contaminated soil of detection; Detection method is a known prior art.
(2) according to detected result, by quality than heavy-metal contaminated soil: ion mineralising stablizer=5 ~ 50:1 adds ion mineralising stablizer, with ion mineralising stablizer equably spreading on the surface of pending soil.
(3) adopt the mode of the stirring of turning over that the ion mineralising stablizer of pending soil together with spreading on it mixed 3 times at least, form mixed soil; Through adding the water mode, keep the water cut of mixed soil to be not less than 25%; The mode of stirring of turning over is a known prior art.
(4) on mixed soil, cover material which can retain moisture, curing time at least 5 days lets heavy metal reacts in ion mineralising stablizer and the heavy-metal contaminated soil in the mixed soil, forms stable mineral form; Material which can retain moisture is straw bag, gunnysack or other material known.
(5) the leaching toxicity of heavy metal in the sample detecting mixed soil; Do not meet environmental requirement if detect, increase curing time, add water in case of necessity, up to the detected result compliance with environmental protection requirements.Detection method is a known prior art.Environmental requirement is the regulation of the relevant environmental protection of country.
The embodiment 1 of ion mineralising stablizer:
Raw material sulfurated lime, secondary calcium phosphate, Wingdale and kaolin are ground into granularity be not less than 200 purpose materials, weigh according to mass percent: sulfurated lime is 15%, and secondary calcium phosphate is 30%; Wingdale is 30%; Kaolin is 25%, mixes then, promptly obtains described ion mineralising stablizer.
The embodiment 2 of ion mineralising stablizer:
Raw material time Iron sulfuret, sulfurated lime, secondary calcium phosphate, tricalcium phosphate, Wingdale, chalk, kaolin are ground into granularity with smectite and is not more than 200 purpose materials, Iron sulfuret and sulfurated lime are mixed into component A according to arbitrary proportion, secondary calcium phosphate and tricalcium phosphate are mixed into component B according to arbitrary proportion; Wingdale and chalk are mixed into component C according to arbitrary proportion; Kaolin and smectite are mixed into component D according to arbitrary proportion, weigh according to mass percent: becoming component A is 10%, and component B is 35%; Component C is 35%; Component D is 20%, mixes then, promptly obtains described ion mineralising stablizer.
On the basis of embodiment 2, change the composition of component A, B, C, D, just can develop out a lot of embodiment, draw inferences about other cases from one instance, repeat no more.
The embodiment 1 of ion mineralising stablizer method of use:
(1) detecting the main polluted heavy metals in heavy metal contamination zone, Chenzhou is Cd, Pb, As, Hg; Be higher than national soil environment quality standard (GB15618-1995) grade III Standard; Confirm as the soil of combined pollution or heavily contaminated, the regional area heavy metals exceeding standard reaches 2000 times.Heavy metal deformation analysis heavy metal existence is main with exchangeable species mainly, causes the soil can't the farming farm crop.
(2) according to detected result, add the ion mineralising stabilization medicament of " embodiment 1 of ion mineralising stablizer " by 10% mass ratio, with ion mineralising stablizer equably spreading on the surface of pending soil.
(3) adopt the mode of the stirring of turning over that the ion mineralising stablizer of pending soil together with spreading on it mixed 3 times at least, form mixed soil; Through adding the water mode, keep the water cut of mixed soil to be not less than 25%;
(4) the material which can retain moisture gunnysack that on mixed soil, covers, curing time 5 days lets heavy metal reacts in ion mineralising stablizer and the heavy-metal contaminated soil in the mixed soil, forms stable mineral form.
(5) detect after the maintenance: the content of heavy metal in the leach liquor that soil is measured through lixiviate mode of regulation in the solid waste " leach toxicity leaching method sulfuric acid nitrate method " (HJ/T299-2007); The leaching value of handling back Cd is less than 0.01mg/L; The leaching value of Pb is less than 0.05mg/L; The leaching value of As all is lower than " the requirement of III class water concentration limit value among the groundwater quality standard 》 ﹙ GB/T14848-93 ﹚ less than 0.05mg/L.
The embodiment 2 of ion mineralising stablizer method of use:
(1) detecting the main polluted heavy metals in Tianyuan District heavy metal contamination zone, Zhuzhou is Cd, Pb, and cadmium, lead content have all surpassed national soil environment quality III grade standard.Wherein: soil cadmium content exceeding standard rate is 88.2%, the highlyest exceeds standard 23.7 times; The lead content exceeding standard rate is 82.4%, the highlyest exceeds standard 3.7 times; What cadmium, lead exceeded standard simultaneously has 27, and exceeding standard rate is 79.4%.
(2) according to detected result, add the ion mineralising stabilization medicament of " embodiment 2 of ion mineralising stablizer " by 6% mass ratio, with ion mineralising stablizer equably spreading on the surface of pending soil.
(3) adopt the mode of the stirring of turning over that the ion mineralising stablizer of pending soil together with spreading on it mixed 3 times at least, form mixed soil; Through adding the water mode, keep the water cut of mixed soil to be not less than 25%;
(4) the material which can retain moisture gunnysack that on mixed soil, covers, curing time 5 days lets heavy metal reacts in ion mineralising stablizer and the heavy-metal contaminated soil in the mixed soil, forms stable mineral form.
(5) detect after the maintenance: the content of heavy metal in the leach liquor that soil is measured through lixiviate mode of regulation in the solid waste " leach toxicity leaching method sulfuric acid nitrate method " (HJ/T299-2007); The leaching value of handling back Cd is less than 0.01mg/L; The leaching value of Pb all is lower than " the requirement of III class water concentration limit value among the groundwater quality standard 》 ﹙ GB/T14848-93 ﹚ less than 0.03mg/L.
Claims (8)
1. ion mineralising stablizer of administering heavy-metal contaminated soil, it is characterized in that: said ion mineralising stablizer comprises following raw material, and its mass percent is:
Sulfur-based compound is 5-30%;
Phosphorio compound is 10-50%;
The calcium based compound is 10-50%;
Silicon base compound is 10-30%;
Each raw material is ground into granularity respectively be not less than 200 purpose materials, mix in proportion, obtain described ion mineralising stablizer.
2. ion mineralising stablizer according to claim 1; It is characterized in that: described sulfur-based compound is any one of Iron sulfuret, sodium sulphite, sodium polysulphide, sulfurated lime, ammonium sulfide, potassium sulphide, potassium polysulfide, calcium polysulfide, or multiplely arbitrarily press the arbitrary proportion mixing.
3. ion mineralising stablizer according to claim 1 and 2 is characterized in that: described phosphorio compound be secondary calcium phosphate, tricalcium phosphate, dicalcium phosphate, phosphoric acid, Secondary ammonium phosphate, ammonium phosphate, sodium phosphate, fused(calcium magnesium)phosphate, Rock Phosphate (72Min BPL) phosphorus bone meal, potassiumphosphate, potassium hydrogenphosphate any one or multiplely arbitrarily mix by arbitrary proportion.
4. ion mineralising stablizer according to claim 1 and 2 is characterized in that: described calcium based compound be Wingdale, chalk, rhombspar, lime, calcium hydroxide, silicate cement any one or multiplely arbitrarily mix by arbitrary proportion.
5. ion mineralising stablizer according to claim 1 and 2 is characterized in that: described silicon base compound be kaolin, smectite, attapulgite, wilkinite, zeyssatite, volcanical ash, zeolite, flyash any one or multiplely arbitrarily mix by arbitrary proportion.
6. ion mineralising stablizer according to claim 3 is characterized in that: described silicon base compound be kaolin, smectite, attapulgite, wilkinite, zeyssatite, volcanical ash, zeolite, flyash any one or multiplely arbitrarily mix by arbitrary proportion.
7. ion mineralising stablizer according to claim 4 is characterized in that: described silicon base compound be kaolin, smectite, attapulgite, wilkinite, zeyssatite, volcanical ash, zeolite, flyash any one or multiplely arbitrarily mix by arbitrary proportion.
8. the method for use that will be used to administer heavy-metal contaminated soil according to the said ion mineralising of claim 1 stablizer is characterized in that, said method comprising the steps of:
(1) content of heavy metal and leaching toxicity in the pending contaminated soil of detection;
(2) according to detected result, by quality than heavy-metal contaminated soil: ion mineralising stablizer=5 ~ 50:1 adds ion mineralising stablizer, with ion mineralising stablizer equably spreading on the surface of pending soil;
(3) adopt the mode of the stirring of turning over that the ion mineralising stablizer of pending soil together with spreading on it mixed 3 times at least, form mixed soil; Through adding the water mode, keep the water cut of mixed soil to be not less than 25%;
(4) on mixed soil, cover material which can retain moisture, curing time at least 5 days lets heavy metal reacts in ion mineralising stablizer and the heavy-metal contaminated soil in the mixed soil, forms stable mineral form;
(5) the leaching toxicity of heavy metal in the sample detecting mixed soil; Do not meet environmental requirement if detect, increase curing time, add water in case of necessity, up to the detected result compliance with environmental protection requirements.
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