CN102965116A - Heavy metal stabilizing agent and method for treating heavy metal contaminated soil by using same - Google Patents
Heavy metal stabilizing agent and method for treating heavy metal contaminated soil by using same Download PDFInfo
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- CN102965116A CN102965116A CN2012104588460A CN201210458846A CN102965116A CN 102965116 A CN102965116 A CN 102965116A CN 2012104588460 A CN2012104588460 A CN 2012104588460A CN 201210458846 A CN201210458846 A CN 201210458846A CN 102965116 A CN102965116 A CN 102965116A
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Abstract
The invention discloses a heavy metal stabilizing agent and a method for treating heavy metal contaminated soil by using the heavy metal stabilizing agent. The heavy metal stabilizing agent is prepared from the following raw materials in percentage by weight: 40 to 50 percent of phosphate, 20 to 25 percent of bentonite, 25 to 30 percent of fluor apatite and 4 to 6 percent of sodium chloride/potassium chloride. When the heavy metal stabilizing agent is used for treating the contaminated soil, the heavy metal stabilizing agent and water are mixed together to form a suspension, then the suspension is added into the heavy metal contaminated soil, and the suspension and the heavy metal contaminated soil are fully mixed. The heavy metal stabilizing agent has high stability for treating soil, and the technical problem that the conventional curing agent and curing method cause reverse dissolution easily is solved.
Description
Technical field
The present invention relates to the environmental chemistry technical field, be specifically related to a kind of heavy metal stabilizer and process the method for heavy-metal contaminated soil with it.
Background technology
China's Heavy Metals In Environment is comparatively serious and general, and Heavy Metals In Environment not only affects the yield and quality of farm crop and fishery products, and relates to atmosphere and quality of water environment, and can be by the life and health of food chain harm humans.Because sources of heavy metal is complicated, reach the interaction with other pollutents in the environment between heavy metal different shape, the different heavy metal, the complicacy that produces various combined pollutions has increased the difficulty to heavy metal research, and heavy metal has chronicity, potentiality and non-reversibility to the harm of animals and plants and human body.
Therefore, Environmental Protection in China department and government agencies at all levels have strengthened statistics and the supervision to the present situation of heavy metal content in the environment of each department, and, monitor at the stages that heavy metal contamination produces, and select to be fit to the effective reclamation activities of this area for the different situation in each department.Heavy Metal Pollution work has become the most important thing of China environmental protection work; party and state pays much attention to heavy metal pollution problem, explicitly points out in " heavy metal contamination integrated control " the 12 " planning " of recently reply of State Council and will set up fairly perfect Heavy Metal Pollution system about 2015.Therefore, the Heavy Metal Pollution Control technology will become from now on the Hot Contents in heavy metal contamination field in one period.
For example application number is the modification method that 200910194051.1 Chinese invention patent discloses a kind of heavy-metal contaminated soil, and this modification method comprises the steps: that (1) carry out whole soil to heavy-metal contaminated soil; (2) in soil, add soil improvement agent; (3) earthing, mix after, balance 0～6 month.The modification method of the heavy-metal contaminated soil of this invention suppresses the matrix oxidation by the reaction such as absorption, chelating, complexing, fixedly heavy metal ion and reduce its biology toxicity; Reduce heavy metal ion towards periphery diffusion and the seepage of soil or water body.
Application number is that 201210107906.4 Chinese invention patent application discloses a heavy metal species ambient cure agent and used the method for heavy metal in its curing heavy metal pollutent, it is composed of the following components by weight percentage in this heavy metal ambient cure agent: magnesium oxide 30.0%～40.0%, potassium primary phosphate 55.0%～65.0%, borax 3.5%～5.0%, ferric oxide 0.1%～0.5%, silicon-dioxide 0.1%～0.5%.The ambient cure agent of this invention can realize utilization of waste as resource after heavy metal waste is cured processing at normal temperatures.
The existing solidifying agent of processing for heavy-metal contaminated soil is mainly take phosphoric acid salt as main, the compound solidifying agent stabilising effect of phosphoric acid salt is general, the heavy metal phosphoric acid salt that forms after solidifying exists with insoluble or sl. sol. compound form, and after the potential of hydrogen condition changed, heavy metal ion was anti-molten easily.
Summary of the invention
The invention provides a kind of heavy metal stabilizer and process the method for heavy-metal contaminated soil with it, the good stability of stabilizer treatment soil has solved the easily anti-molten technical problem of existing solidifying agent and curing.
A kind of heavy metal stabilizer, the mass percent of its raw material is:
Under the normal temperature and pressure above-mentioned raw materials is mixed in proportion.
Described phosphoric acid salt is preferably SODIUM PHOSPHATE, MONOBASIC or potassium primary phosphate; SODIUM PHOSPHATE, MONOBASIC more preferably.
The permanent stability of phosphate mineral are better, and change of external conditions is less on the impact that the phosphoric acid salt mineral substance produces, so the present invention selects phosphoric acid salt as the main component of stablizer, and its consumption is 40～50%, is preferably 44～46%.Utilize the phosphoric acid salt compound that heavy metal is carried out stabilization, mainly utilize the reaction of phosphoric acid salt compound and heavy metal and produce stable heavy metallic mineral salt; And phosphoric acid class mineral salt can effectively be removed most heavy metal ion in the target product by surface adsorption mechanism and complex reaction.Because of price factor, the present invention adopts SODIUM PHOSPHATE, MONOBASIC as the stablizer main component.
Bentonitic mass percent is 20～25%, be preferably 21～24%, wilkinite is a kind of moisture stratiform silicate mine take montmorillonite as main component, have preferably ion-exchange and adsorptive power, be that a kind of wide material sources, green heavy metal nontoxic, non-secondary pollution are processed raw material, can realize the capture effect of heavy metal cation.And by with structure and the performance of other composition convergent improvement medicaments, make that the chemical action between the hazard component is strengthened in itself and the refuse, make it have very high River water.With stabilizer treatment Hazardous wastes of the present invention, can be when realizing that refuse is innoxious, reach the refuse perhaps not increase-volume that reduces, thereby improve overall efficiency and the economy that Hazardous wastes is processed disposal system.
The reaction mechanism that heavy metal stabilizer of the present invention is processed contaminated soil is as follows:
Heavy metal stabilizer of the present invention and water mix, and add in the contaminated soil, and the phosphoric acid salt in the stablizer and calcium ion, chlorion have multiple reaction, and wherein a kind of reaction can form Ca
10-x(HPO
4)
x(PO
4)
6-x(OH)
2-xOr Ca
10(PO
4)
6(OH)
2Carry out the calcium substitution reaction with heavy metal, form more stable heavy metal hydroxyapatite, such as CaPbHap, the heavy metallic mineral salt such as CaCdHap; Another kind of reaction is can generate chloro phosphatic rock (Ca by the hydroxyl in the halide-ions substituted hydroxy phosphatic rock or by ionic reaction
5[PO
4]
3Cl) etc., heavy metal there are capture and stabilization; Also have the reaction of a heavy metal species and phosphoric acid salt and chlorion can form brown leadd ore (Pb
5[PO
4]
3Cl) and some other phosphate compounds, for example Cd
3(PO
4)
2And CaZn (PO
4)
24H
2O, can learn from resultant: these mineral facies can play an important role to low leaching, the high stability of heavy metal phosphoric acid salt-Hazardous wastes curing system.In addition, at Pb
2+, Cu
2+, Zn
2+In the system of coexistence, phosphoric acid class mineral salt mainly is surface adsorption mechanism and complex reaction to their removal.
The present invention also provides a kind of method of utilizing described heavy metal stabilizer to process heavy-metal contaminated soil, comprising:
Described heavy metal stabilizer and water are mixed into suspension liquid, described suspension liquid is added in the described heavy-metal contaminated soil, fully mix.
The mass ratio of described heavy metal stabilizer and water is 1: 15～30.
Heavy metal ion in the described heavy-metal contaminated soil is Pb
2+, Zn
2+And Cd
2+In at least a.
Heavy metal stabilizer of the present invention carries out when processing contaminated soil at normal temperatures and pressures, and the pH value is 4～11, evenly gets final product with mixing with soil.
Beneficial effect of the present invention:
(1) the heavy metal stabilization reagent cost is lower, and mean concns can be controlled in about 12 yuan at every cubic metre for the treatment of agent cost of solid waste of 500mg/kg.
(2) chemical stabilization technique is simple, adds after medicament is mixed with tap water that mixing gets final product in the heavy metal contaminants.
(3) treatment effect is better, and the heavy metallic salt stable components of formation is anti-not molten.
The existing solidifying agent of processing for heavy-metal contaminated soil is mainly take phosphoric acid salt as main, the compound solidifying agent stabilising effect of phosphoric acid salt is general, the heavy metal phosphoric acid salt that forms after solidifying exists with insoluble or sl. sol. compound form, and after the potential of hydrogen condition changed, heavy metal ion was anti-molten easily.The present invention under the prerequisite that does not change reaction conditions, can make heavy metal form more complicated phosphate compounds by adding other components, and this compounds has physical chemistry of the earth stability, and heavy metal ion is difficult for separating out.
Stablizer of the present invention utilizes the permanent stability of composite phosphate mineral, change of external conditions is on characteristics such as the impact that the phosphoric acid salt mineral substance produces are less, adopt phosphoric acid salt, wilkinite, fluorapatite and sodium-chlor to form according to a certain percentage compound, but self-induction generates heavy metal phosphoric acid mineral substance under normal temperature and pressure conditions, some metallic cation can with the hydroxyapatite lattice in calcium ion generation ion exchange reaction and enter lattice, formation contains the hydroxyapatite of heavy metal, finally reaches the stable and environmental friendliness of heavy-metal composite pollution thing.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
Figure utilizes the technical process of heavy metal stabilizer processing contaminated soil of the present invention as follows shown in 1:
Heavy metal stabilizer is by SODIUM PHOSPHATE, MONOBASIC, wilkinite, and fluorapatite, sodium-chlor solid phase powder proportionally mix composition.With heavy metal stabilizer with join mixing in the heavy-metal contaminated soil after tap water mixes, stablizer and heavy metal form indissoluble heavy metallic mineral matter, leach leaching that sequence test shows each heavy metal species in the scope that China's " Hazardous wastes judging standard leaching characteristic identification " (GB5085.3-2007) allows by U.S. EPA standard TCLP toxicity, realized ambient stable.
The invention will be further described below in conjunction with specific examples.
Embodiment 1
Choose the Pb contaminated soil as the sample of this enforcement, Pb concentration is 864.5mg/kg.(proportioning (mass percent) is: SODIUM PHOSPHATE, MONOBASIC is 40% with heavy metal stabilizer, wilkinite is 25%, fluorapatite is 30%, sodium-chlor is 5%) with tap water according to 1: 20 stirring and dissolving of mass ratio after, according to medicament and the ratio of sample quality than 1: 400, be added in the sample, mix, leave standstill more than the 30min.Sampling drying is analyzed mensuration.Adopt convertible leaching program that sample is carried out leaching experiment, adopt atomic absorption that the leach liquor after processing is measured.
After testing, the leaching concentration of heavy metal Pb is respectively the front sample Steep cencentration 31.54mg/L of stabilization treatment, the sample Steep cencentration is 2.31mg/L after processing, and visible pedotheque after treatment satisfies national standard (Steep cencentration≤5mg/L).
Embodiment 2
Choose the Pb contaminated soil as the sample of this enforcement, Pb concentration is 859.6mg/kg.(proportioning (mass percent) is: SODIUM PHOSPHATE, MONOBASIC is 50% with heavy metal stabilizer, wilkinite is 20%, fluorapatite is 25%, sodium-chlor is 5%) with tap water according to 1: 20 stirring and dissolving of mass ratio after, according to medicament and the ratio of sample quality than 1: 500, be added in the sample, mix, leave standstill more than the 30min.Sampling drying is analyzed mensuration.Adopt convertible leaching program that sample is carried out leaching experiment, adopt atomic absorption that the leach liquor after processing is measured.
After testing, the leaching concentration of heavy metal Pb is respectively the front sample Steep cencentration 32.18mg/L of stabilization treatment, the sample Steep cencentration is 2.27mg/L after processing, and visible pedotheque after treatment satisfies national standard (Steep cencentration≤5mg/L).
Embodiment 3
Choose the Pb contaminated soil as the sample of this enforcement, Pb concentration is 389.2mg/kg.(proportioning (mass percent) is: SODIUM PHOSPHATE, MONOBASIC is 45% with heavy metal stabilizer, wilkinite is 25%, fluorapatite is 25%, sodium-chlor is 5%) with tap water according to 1: 20 stirring and dissolving of mass ratio after, according to medicament and the ratio of sample quality than 1: 1000, be added in the sample, mix, leave standstill more than the 30min, sampling drying is analyzed mensuration.Adopt convertible leaching program that sample is carried out leaching experiment, adopt atomic absorption that the leach liquor after processing is measured.
After testing, the leaching concentration of heavy metal Pb is respectively sample Steep cencentration 8.97mg/L before the stabilization treatment, and the sample Steep cencentration is 1.28mg/L after processing, and visible pedotheque after treatment satisfies national standard (Steep cencentration≤5mg/L).
Embodiment 4
Choose the Zn contaminated soil and implement sample as this, Zn concentration is 2011.5mg/kg.(proportioning (mass percent) is: SODIUM PHOSPHATE, MONOBASIC is 45% with heavy metal stabilizer, wilkinite is 25%, fluorapatite is 25%, sodium-chlor is 5%) with tap water according to 1: 15 stirring and dissolving of weight ratio after, according to medicament and the ratio of sample quality than 1: 200, be added in the sample, mix, leave standstill more than the 30min.Sampling drying is analyzed mensuration.Adopt convertible leaching program that sample is carried out leaching experiment, adopt atomic absorption that the leach liquor after processing is measured.
After testing, the leaching concentration of heavy metal Zn is respectively the front sample Steep cencentration 163.4mg/L of stabilization treatment, the sample Steep cencentration is 14.4mg/L after processing, and visible pedotheque after treatment satisfies national standard (Steep cencentration≤100mg/L).
Embodiment 5
Choose the Cd contaminated soil and implement sample as this, Cd concentration is 62.4mg/kg.(proportioning is: SODIUM PHOSPHATE, MONOBASIC is 45% with heavy metal stabilizer, wilkinite is 25%, fluorapatite is 25%, sodium-chlor is 5%) with tap water according to 1: 30 stirring and dissolving of weight ratio after, according to medicament and the ratio of sample quality than 1: 2000, be added in the sample, mix, leave standstill more than the 30min.Sampling drying is analyzed mensuration.Adopt convertible leaching program that sample is carried out leaching experiment, adopt atomic absorption that the leach liquor after processing is measured.
After testing, the leaching concentration of heavy metal Cd is respectively sample Steep cencentration 2.12mg/L before the stabilization treatment, and the sample Steep cencentration does not detect after processing, and visible pedotheque after treatment satisfies national standard (Steep cencentration≤1mg/L).
Claims (8)
1. a heavy metal stabilizer is characterized in that, the mass percent of its raw material is:
2. heavy metal stabilizer according to claim 1 is characterized in that, described phosphoric acid salt is SODIUM PHOSPHATE, MONOBASIC or potassium primary phosphate.
3. heavy metal stabilizer according to claim 2 is characterized in that, described phosphoric acid salt is SODIUM PHOSPHATE, MONOBASIC.
4. heavy metal stabilizer according to claim 1 is characterized in that, described phosphatic mass percent is 44～46%.
5. heavy metal stabilizer according to claim 1 is characterized in that, described bentonitic mass percent is 21～24%.
6. a method of utilizing the described heavy metal stabilizer of claim 1 to process heavy-metal contaminated soil is characterized in that, comprising:
Described heavy metal stabilizer and water are mixed into suspension liquid, described suspension liquid is added in the described heavy-metal contaminated soil, fully mix.
7. method according to claim 6 is characterized in that, the mass ratio of described heavy metal stabilizer and water is 1: 15～30.
8. method according to claim 6 is characterized in that, the heavy metal ion in the described heavy-metal contaminated soil is Pb
2+, Zn
2+And Cd
2+In at least a.
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| CN103145403A (en) * | 2013-03-19 | 2013-06-12 | 南京工业大学 | Method for stabilizing heavy metals in process of preparing filler from chemical sludge incineration ash |
| CN103274670A (en) * | 2013-06-09 | 2013-09-04 | 南京工业大学 | Preparation method of light porous low-toxicity chemical sludge-based filler |
| CN103524016A (en) * | 2013-10-22 | 2014-01-22 | 山东省环境保护科学研究设计院 | Stable settling agent and stable settling method of heavy-metal bottom mud |
| CN103894410A (en) * | 2014-03-27 | 2014-07-02 | 武汉都市环保工程技术股份有限公司 | Method for carrying out stabilizing and solidifying treatment on contaminated soil and applying soil to subgrade fill |
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| CN114958380A (en) * | 2021-03-01 | 2022-08-30 | 中国科学院大学 | Repairing agent for repairing lead-cadmium combined polluted soil and using method thereof |
| CN113058993A (en) * | 2021-04-08 | 2021-07-02 | 中铝环保节能集团有限公司 | Repairing agent for repairing lead, arsenic and cadmium combined polluted soil and repairing method thereof |
| CN113058993B (en) * | 2021-04-08 | 2023-09-05 | 中铝环保节能集团有限公司 | Repairing agent for repairing lead, arsenic and cadmium combined polluted soil and repairing method thereof |
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