CN103740373B - A kind of heavy-metal contaminated soil stabilization agent and its preparation method and application - Google Patents
A kind of heavy-metal contaminated soil stabilization agent and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of heavy-metal contaminated soil stabilization agent and its preparation method and application, by weight percentage, its raw material consists of: bone meal 20 ~ 60%; Charcoal 10 ~ 30%; Calcined shell powder 20 ~ 70%.(1) be milled to the following particulate state of 60 order after biomass are air-dry, in pyrolyzer, cracking 6 ~ 8 hours at 400 ~ 800 DEG C, obtains charcoal; By 800 ~ 1000 DEG C of calcinings 2 ~ 4 hours in High Temperature Furnaces Heating Apparatus of the oyster shell whiting of particle diameter below 20 orders, naturally cool to room temperature, obtain calcined shell powder; (2) described charcoal, calcined shell powder and bone meal are mixed in proportion and get final product.The present invention, by composite according to specified proportion for three groups of components, solves the problems such as current heavy-metal contaminated soil stabilization agent cost is high, stabilization effect is not lasting.
Description
Technical field
The present invention relates to a kind of method of heavy-metal contaminated soil harmless treatment, be specifically related to a kind of heavy-metal contaminated soil stabilization agent and its preparation method and application.
Background technology
Heavy metal pollution of soil, due to features such as its long term latent, disguise, non-reversibilities, has become one of great environmental problem of the continued solution of China." three wastes " discharge of the industries such as mining, smelting, plating, chemical industry, electronics, process hides and agricultural chemicals, the unreasonable of chemical fertilizer use the heavy metal contamination that all can cause soil.Heavy metal in soil not only can affect the seed output and quality of farm crop, and it also along with the accumulation of the circulation of water, air and food chain, amplification, can jeopardize the health of human body.
Heavy metal stabilization technology is a kind of disposal technology being applied to heavy metal class Hazardous wastes, by the interpolation of stabilization agent, heavy metal can be converted into the higher form of stability, the health risk reducing its movability He may bring.
Such as, publication number is that the Chinese invention patent application of CN102965116A discloses a kind of heavy metal stabilizer and the method with its process heavy-metal contaminated soil, and the weight percent of the raw material of heavy metal stabilizer is: phosphoric acid salt 40 ~ 50%; Wilkinite 20 ~ 25%; Fluorapatite 25 ~ 30%; Sodium chloride/potassium chloride 4 ~ 6%.During with above-mentioned heavy metal stabilizer process contaminated soil, described heavy metal stabilizer and water are mixed into suspension liquid, described suspension liquid are added in described heavy-metal contaminated soil, fully mixes.
Publication number is that the Chinese invention patent application of CN102784452A discloses a kind of heavy metal stabilizer for removal heavy metal pollution and using method thereof.This heavy metal stabilizer contains compound lignin-base dithiocar-bamate, described lignin-base dithiocar-bamate is one or more the combination in lignin-base nabam, lignin-base dithiocarbamic acid potassium or lignin-base ammonium dithiocarbamate, can be used for the improvement of heavy metal contamination.
Publication number is that the Chinese invention patent application of CN102921713A discloses a kind of heavy metal polluted soil solidification and stabilization treatment process, this technique comprises heavy metal polluted soil argillization, permanent magnetic strong magnetic is separated, pollution level is defined the level, medicament adds stirring, extruding jolt ramming is shaping, this technique adopts the method for accurately control water to realize in the treating processes of heavy metal polluted soil without water more than needed and dust, permanent magnetic strong magnetic separation method is adopted to isolate part heavy metal in heavy metal polluted soil mud, Final pollution soil slurry curing stabilization treatment difficulty and expense is reduced from source, soil after permanent magnetic strong magnetic is separated is processed respectively according to pollution level, decrease additive amount of medicament, stablizer and solidifying agent is adopted to add also strong stirring and extrude the shaping method of jolt ramming respectively, be conducive to stablizer, Homogeneous phase mixing between solidifying agent and soil and fully reacting, ensure repairing quality.
Stabilization technology is due to features such as it are applied widely, technique is simple, easy to operate, also potentiality are had a wide range of applications in heavy metal contamination site remediation field, but the further genralrlization of shortcoming all limits this technology such as stabilization agent price is high, stabilising effect is not lasting.
Summary of the invention
The invention provides a kind of heavy-metal contaminated soil stabilization agent and its preparation method and application, solve the problems such as current heavy-metal contaminated soil stabilization agent cost is high, stabilization effect is not lasting.
A kind of heavy-metal contaminated soil stabilization agent, by weight percentage, its raw material consists of:
Bone meal 20 ~ 60%;
Charcoal 10 ~ 30%;
Calcined shell powder 20 ~ 70%.
Preferably, by weight percentage, its raw material consists of:
Bone meal 50 ~ 60%;
Charcoal 10 ~ 12%;
Calcined shell powder 30 ~ 40%.
As preferably, described bone meal is the degelatinized bone dust of at least one in pig, ox and sheep, and the content of phosphorus is greater than 12%, and particle diameter is less than 20(and 850um) order.
As preferably, described charcoal is prepared by the following method:
60 orders (i.e. 250um) following particulate state is milled to, cracking 6 ~ 8 hours at 400 ~ 800 DEG C in pyrolyzer after biomass are air-dry.The biological carbon be made under this condition has good physical adsorption performance.
Further preferably, after biomass are air-dry, be milled to 60 orders (i.e. 250um) following particulate state, cracking 7 hours at 600 DEG C in pyrolyzer.
Further preferably, described biomass are at least one in sawdust, agricultural crop straw and corn cob.
As preferably, described calcined shell powder is prepared by the following method:
By 800 ~ 1000 DEG C of calcinings 2 ~ 4 hours in High Temperature Furnaces Heating Apparatus of the oyster shell whiting of particle diameter below 20 orders, naturally cool to room temperature.Oyster shell whiting under this condition after activation has good Activity of Lime.
Further preferably, by the 900 DEG C of calcinings 3 hours in High Temperature Furnaces Heating Apparatus of the oyster shell whiting of particle diameter below 20 orders, room temperature is naturally cooled to.
The stabilization principle of calcined shell powder is that pH value controls and ion-exchange, and the stabilization principle of bone meal is chemical precipitation and ion-exchange, and biological carbon realizes stabilization mainly through physisorption.Different from common stabilization agent, the stabilization agent of the method preparation adopts the preparation of plurality of stable effective constituent, mutually act synergistically with the stabilization performance improving stabilization agent further between three kinds of compositions, to realize the diversification of chemical stabilization approach, the scope of expansion stabilization heavy metal, improves the ability of the anti-multiple environmental impact after heavy metal stabilization.
Present invention also offers a kind of as described in the preparation method of heavy-metal contaminated soil stabilization agent, comprise the steps:
(1) be milled to the following particulate state of 60 order after biomass are air-dry, in pyrolyzer, cracking 6 ~ 8 hours at 400 ~ 800 DEG C, obtains charcoal; By 800 ~ 1000 DEG C of calcinings 2 ~ 4 hours in High Temperature Furnaces Heating Apparatus of the oyster shell whiting of particle diameter below 20 orders, naturally cool to room temperature, obtain calcined shell powder;
(2) described charcoal, calcined shell powder and bone meal are mixed in proportion and get final product.
The invention also discloses a kind of utilization as described in the method for heavy-metal contaminated soil stabilization agent in-situ treatment heavy-metal contaminated soil, comprise the steps:
By rotary cultivator by contaminated soil scarifying, evenly apply described heavy-metal contaminated soil stabilization agent, then by rotary cultivator rotary tillage repeatedly, described heavy-metal contaminated soil stabilization agent is mixed with contaminated soil.
As preferably, when pollutant component main in described contaminated soil is Pb or Cd (in TCLP method leach liquor Pb >=1mg/L or Cd >=0.3mg/L), the addition of described heavy-metal contaminated soil stabilization agent with the interpolation weight ratio of bone meal in contaminated soil for 3% ~ 6%.
As preferably, when pollutant component main in described contaminated soil is Zn or Cu or Ni (in TCLP method leach liquor Zn >=100mg/L or Cu >=80mg/L or Ni >=1mg/L), the addition of described heavy-metal contaminated soil stabilization agent with the interpolation weight ratio of calcined shell powder in soil for 4% ~ 7%.
As preferably, when pollutant component in described contaminated soil more (at least two kinds in Pb, Cd, Zn, Cu and Ni) and Steep cencentration higher (i.e. Pb >=1mg/L or Cd >=0.3mg/L or Zn >=100mg/L or Cu >=80mg/L or Ni >=1mg/L in TCLP method leach liquor) time can increase the addition of stabilization agent, the addition of general stabilization agent is 4% ~ 10% of soil dry quality.
Before with medicament process contaminated soil, by harm composition main in leaching test determination contaminated soil.Fully shake after being mixed with leach liquor by soil, the content of heavy metal in mensuration leach liquor, its TCLP leaching method can with reference to HJ/T300-2007(solid waste Leaching leaching method hac buffer method).
Present invention also offers a kind of utilization as described in the method for heavy-metal contaminated soil stabilization agent dystopy process heavy-metal contaminated soil, comprise the steps:
Fully mix with stabilization agent after contaminated soil is dried, regulate contaminated soil water ratio to 10 ~ 20%, maintenance 7 ~ 14 days under normal temperature.
The problems such as the present invention is high mainly for current heavy-metal contaminated soil stabilization agent cost, stabilization effect is not lasting, propose to adopt bone meal, charcoal, oyster shell whiting to prepare the method for stabilization agent as raw material.This stabilization agent, compared with traditional medicament, has the release of stabilization stable effective ingredients, the feature that stabilization effect is lasting, simultaneously owing to have employed abandoned biomass as raw materials, reaches the effect of the treatment of wastes with processes of wastes against one another.
The present invention take biomass waste material as raw material, is added by rational proportioning, realizes the stabilization of heavy metal contaminated soil.Medicament has good pH controllability, the biological stephanoporate medium that biomass material has, effective physics can be carried out catch by heavy metal ion, containing the abundant heavy metal such as phosphatic rock, ettringite, there is efficient chemical precipitation in medicament, mineral shape can be converted into by the heavy metal of free state, there is permanently effective stabilization effect.This medicament uses simply, cost is lower, and its raw material is all common biomass waste material, also reaches the effect that waste resource utilizes simultaneously.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
To the heavy-metal contaminated soil of two kinds of different sourcess be chosen below, according to the specific embodiment of the present invention, with reference to the process flow sheet shown in Fig. 1, give and further instruction.
Charcoal is prepared by the following method:
60 orders (i.e. 250um) following particulate state is milled to, cracking 6 ~ 8 hours at 400 ~ 800 DEG C in pyrolyzer after air-dry for biomass (at least one in sawdust, agricultural crop straw and corn cob).The biological carbon be made under this condition has good physical adsorption performance; Preferably cracking 7 hours at 600 DEG C in below implementing.
Calcined shell powder is prepared by the following method:
By 800 ~ 1000 DEG C of calcinings 2 ~ 4 hours in High Temperature Furnaces Heating Apparatus of the oyster shell whiting of particle diameter below 20 orders, naturally cool to room temperature.Preferably 900 DEG C of calcinings 3 hours in High Temperature Furnaces Heating Apparatus in below implementing.
Embodiment 1
According to technical process shown in Fig. 1, obtain certain agricultural land soil, it is subject to plumbous pollution, and content plumbous in its topsoil is 381 ~ 1129mg/kg, and the lead concentration that its TCLP method leaches is 5.98mg/L.By analysis, this pollutant in soil is comparatively single, and more easily stablizes, and select stabilization agent proportioning to be bone meal 60%, oyster shell whiting 30%, charcoal 10%, the addition of stabilization agent in soil is 5%.Stabilization agent evenly point spreads to soil by artificial at twice, each point spread after by rotary cultivator by contaminated soil repeatedly scarifying, can stabilization be realized.Contrast with the sample of 5% phosphate stabilizing and 5% lime stabilization simultaneously.
The concentration of TCLP leach liquor Pb before and after table 1 stabilization
| Sample 1 | Sample 2 | Sample 3 | |
| Original soil | 6.05mg/L | 6.25mg/L | 5.65mg/L |
| Medicament of the present invention | 0.08mg/L | N.D. | 0.12mg/L |
| Potassium dihydrogen sulfate | N.D. | N.D. | 0.05mg/L |
| Lime | 0.59mg/L | 0.68mg/L | 0.61mg/L |
Embodiment 2
According to technical process shown in Fig. 1, obtain certain Pb-Zn ore district contaminated soil, the pollutent in its topsoil is mainly lead, cadmium and zinc, and its concentration is respectively 637 ~ 3128mg/kg, 3.6 ~ 17.5mg/kg and 684 ~ 2873mg/kg.By analysis, this pollutant in soil kind is comparatively complicated, and pollution level is higher, and select stabilization agent proportioning to be bone meal 50%, oyster shell whiting 40%, charcoal 10%, the addition of stabilization agent in soil is 8%.Adopt the mode of dystopy stabilization, mix with stabilization agent in stirrer after soil is dried, regulate water ratio to 10 ~ 20%, maintenance 7 ~ 14 days under normal temperature, reach best stabilization effect.Contrast with the sample of 5% phosphate stabilizing simultaneously.TCLP leach liquor heavy metal concentration before and after table 1 stabilization
| Pb | Cd | Zn | |
| Original soil | 12.96mg/L | 0.95mg/L | 118.12mg/L |
| Medicament of the present invention | 0.18mg/L | N.D. | 37.23mg/L |
| Potassium dihydrogen sulfate | 0.27mg/L | N.D. | 91.44mg/L |
The cost of manufacture price that market value according to raw material calculates this stabilization agent is about 1500 ~ 2000 yuan/ton, and the price of sodium phosphate stablizer is more than 5000 yuan/ton.Therefore it is good that the stabilization agent utilizing the present invention to prepare has stabilization effect, feature with low cost, has good market Utilization prospects.
Claims (6)
1. a heavy-metal contaminated soil stabilization agent, is characterized in that, by weight percentage, its raw material consists of:
Bone meal 20 ~ 60%;
Charcoal 10 ~ 30%;
Calcined shell powder 20 ~ 70%;
Described calcined shell powder is prepared by the following method:
By 800 ~ 1000 DEG C of calcinings 2 ~ 4 hours in High Temperature Furnaces Heating Apparatus of the oyster shell whiting of particle diameter below 20 orders, naturally cool to room temperature;
Described charcoal is prepared by the following method:
The following particulate state of 60 order is milled to, cracking 6 ~ 8 hours at 400 ~ 800 DEG C in pyrolyzer after biomass are air-dry.
2. heavy-metal contaminated soil stabilization agent according to claim 1, it is characterized in that, described bone meal is the degelatinized bone dust of at least one in pig, ox and sheep, and the content of phosphorus is greater than 12%, and particle diameter is less than 20 orders.
3. heavy-metal contaminated soil stabilization agent according to claim 1, it is characterized in that, described biomass are at least one in sawdust, agricultural crop straw and corn cob.
4. a preparation method for heavy-metal contaminated soil stabilization agent as claimed in claim 1, is characterized in that, comprise the steps:
(1) be milled to the following particulate state of 60 order after biomass are air-dry, in pyrolyzer, cracking 6 ~ 8 hours at 400 ~ 800 DEG C, obtains charcoal; By 800 ~ 1000 DEG C of calcinings 2 ~ 4 hours in High Temperature Furnaces Heating Apparatus of the oyster shell whiting of particle diameter below 20 orders, naturally cool to room temperature, obtain calcined shell powder;
(2) described charcoal, calcined shell powder and bone meal are mixed in proportion and get final product.
5. utilize a method for heavy-metal contaminated soil stabilization agent in-situ treatment heavy-metal contaminated soil as claimed in claim 1, it is characterized in that, comprise the steps:
By rotary cultivator by contaminated soil scarifying, evenly apply described heavy-metal contaminated soil stabilization agent, then by rotary cultivator rotary tillage repeatedly, described heavy-metal contaminated soil stabilization agent is mixed with contaminated soil;
When pollutant component main in described contaminated soil is Pb or Cd, the addition of described heavy-metal contaminated soil stabilization agent with the interpolation weight ratio of bone meal in contaminated soil for 3% ~ 6%;
When pollutant component main in described contaminated soil is Zn or Cu or Ni, the addition of described heavy-metal contaminated soil stabilization agent with the interpolation weight ratio of calcined shell powder in soil for 4% ~ 7%.
6. utilize a method for heavy-metal contaminated soil stabilization agent dystopy process heavy-metal contaminated soil as claimed in claim 1, it is characterized in that, comprise the steps:
Fully mix with stabilization agent after contaminated soil is dried, regulate contaminated soil water ratio to 10 ~ 20%, maintenance 7 ~ 14 days under normal temperature.
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| CN102321484A (en) * | 2011-06-09 | 2012-01-18 | 山东省农业科学院农业资源与环境研究所 | Organic environmentally-friendly soil conditioner for improving acidified or acid soil |
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