CN105567247A - Heavy metal-contaminated soil remediation agent and preparation method thereof - Google Patents
Heavy metal-contaminated soil remediation agent and preparation method thereof Download PDFInfo
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- CN105567247A CN105567247A CN201610079918.9A CN201610079918A CN105567247A CN 105567247 A CN105567247 A CN 105567247A CN 201610079918 A CN201610079918 A CN 201610079918A CN 105567247 A CN105567247 A CN 105567247A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
The invention provides a heavy metal-contaminated soil remediation agent. The remediation agent is prepared from, by weight, 30%-45% of quick lime, 10%-25% of biomass charcoal, 10%-15% of kieselguhr, 10%-15% of sodium bentonite, 10%-15% of activated aluminum oxide, 5%-10% of nitrilotriacetic acid, 1%-5% of sodium lignin sulfonate and 1%-5% of sodium dodecyl sulfate. A preparation method comprises the steps that the quick lime, the biomass charcoal, the kieselguhr, the sodium bentonite, activated aluminum oxide, nitrilotriacetic acid, sodium lignin sulfonate and sodium dodecyl sulfate are stirred and mixed to be uniform according to the weight ratio, and then the soil remediation agent is prepared. The prepared soil remediation agent has the good effect when cadmium-lead-zinc-mercury compound contaminated soil is remedied.
Description
Technical field:
The invention belongs to soil pollution recovery technique field, be specifically related to a kind of heavy-metal contaminated soil renovation agent and preparation method thereof.
Technical background:
" national Soil Pollution Investigation publication " display within 2014, is announced: national edatope situation totally allows of no optimist according to Environmental Protection Department and Ministry of Land and Resources; some areas soil pollution is heavier; arable soil environmental quality causes anxiety, industry and mining discarded ground edatope outstanding problem.The human activity such as industry and mining, agricultural and Environmental Background Values of Soils height are the major causes causing soil pollution or exceed standard.Soil total exceeding standard rate in the whole nation is 16.1%, and wherein slightly, slightly, moderate and serious pollution point position ratio be respectively 11.2%, 2.3%, 1.5% and 1.1%.Pollution type is based on inorganic type, and organic type takes second place, and compound pollution proportion is less, and an inorganic pollutant figure place that exceeds standard accounts for 82.8% of all super punctuation bits.
From pollution distribution situation, soils in south china pollutes and overweights the north; The subregion soil contamination problem such as Yangtze River Delta, the Delta of the Pearl River, Northeastern rust belt are comparatively outstanding, and southwest, variable charge soil heavy metals exceeding standard scope is larger; Cadmium, mercury, arsenic, plumbous 4 kinds of level of inorganic contaminants distribution present the situation raised gradually from northwest to the southeast, from northeast to southwestward.
Principal pollutant are cadmium, nickel, copper, arsenic, mercury, lead, dichlorodiphenyl trichloroethane and polycyclic aromatic hydrocarbons.If be as the criterion with second national land investigation result, China's arable land latest data is 2,030,770,000 mu and calculates, and the cultivated area of middle serious pollution accounts for 2.9%, has reached 5,889 ten thousand mu.
Administering method at present for heavy metal pollution of soil mainly contains immobilization/stabilization, drip-rinsing process, washes local method, electromotion repairing technique method, chemical reduction method, phytoremediation, microorganism remediation, totally there is the problems such as remediation efficiency is low, processing cost is high.Traditional restorative procedure is as large in quantities such as landfill, drip washing, electrochemistry, and cost is high and usually cause Soil structure to destroy and some nutritive element loss.Therefore, develop a kind of low cost, simple, efficient, eco-friendly soil remediation medicament is significant.
Chemical passivation renovation agent is a kind of controlling area-source pollution technology of efficient economy, and this technology also meets the needs of China's Sustainable development.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of heavy-metal contaminated soil renovation agent and preparation method thereof, the present invention adopts unslaked lime, biomass charcoal, diatomite, sodium bentonite, activated alumina, nitrilotriacetic acid(NTA), sodium lignosulfonate, sodium laurylsulfonate is mixed in proportion, make soil-repairing agent, add to by a certain percentage in heavy-metal contaminated soil according to pollution level, by absorption, ion-exchange, heavy metal in the synergies such as chelating and soil reacts, heavy metal is made to form stable chemical form, stop its environmental transport and transfer and diffusion, reduce heavy metal murder by poisoning degree in the environment.
For solving the problems of the technologies described above, the invention provides a kind of heavy-metal contaminated soil renovation agent, its raw material is made up of unslaked lime, biomass charcoal, diatomite, sodium bentonite, activated alumina, nitrilotriacetic acid(NTA), sodium lignosulfonate, sodium laurylsulfonate, and the weight percent of each raw material of described soil-repairing agent is:
Unslaked lime 30-45%;
Biomass charcoal 10-25%;
Diatomite 10-15%;
Sodium bentonite 10-15%;
Activated alumina 10-15%;
Nitrilotriacetic acid(NTA) 5-10%;
Sodium lignosulfonate 1-5%;
Sodium laurylsulfonate 1-5%;
The mass percent sum of each raw material is 100%.
Further, in described renovation agent, the mass percent of each raw material is:
Unslaked lime 45%;
Biomass charcoal 10%;
Diatomite 10%;
Sodium bentonite 10%;
Activated alumina 10%;
Nitrilotriacetic acid(NTA) 5%;
Sodium lignosulfonate 5%;
Sodium laurylsulfonate 5%.
A kind of heavy-metal contaminated soil renovation agent of the present invention, described biomass charcoal be with stalk, Pericarppium arachidis hypogaeae, wood chip one or more for raw material, be 3kPa at system pressure, pyrolysis temperature is that the condition vacuum pyrolysis 30min of 500 DEG C makes, and is obtained the pressed powder of below 3mm by milled processed.
Described unslaked lime, diatomite, activated alumina are respectively the pressed powder of below 2mm;
Described sodium bentonite is that alkaline coefficient is greater than 1, smectite content is 60-88%, particle diameter is 2mm
Following pressed powder;
Described nitrilotriacetic acid(NTA) is the pressed powder of below 2mm;
Described sodium lignosulfonate, sodium laurylsulfonate are the pressed powder of below 2mm.
A kind of heavy-metal contaminated soil renovation agent of the present invention, by unslaked lime, biomass charcoal, diatomite, sodium bentonite, activated alumina, nitrilotriacetic acid(NTA), sodium lignosulfonate, sodium laurylsulfonate are uniformly mixed according to the above ratio, namely obtain repairing medicament.
A kind of heavy-metal contaminated soil renovation agent of the present invention, after obtaining mixture by said process, add in heavy-metal contaminated soil, the reparation pharmaceutical quantities of adding is the 1-10% of contaminated soil weight, then sprays a small amount of water and make Soil conservation moistening.
This medicament may be used for the improvement of single heavy metal contaminated soil, also the improvement of Compound Heavy Metals is applicable to, be applicable to the reparation of big area heavy-metal contaminated soil, comprise the mine reparation of heavy metal contamination and the reparation of heavy metal use manufacturing enterprise contaminated site.Compared with prior art, reparation medicament of the present invention has the advantage that preparation method is simple, feasible, regulation effect is good.
Relative to prior art, beneficial effect of the present invention is:
Biomass charcoal in renovation agent is obtained by vacuum pyrolysis biomass, and biomass charcoal porosity obtained is under vacuum high, and adsorptive value is high; With biomass such as stalks for raw material, make full use of resource, avoid causing environmental pollution because of its burning.By the biomass charcoal that vacuum pyrolysis obtains, have specific surface area large, duct is enriched, and easily all kinds of heavy metal ion of absorption, reduces the concentration of transport property heavy metal ion in soil.
The chemical composition of unslaked lime is calcium oxide, and making soil pH value improve soil surface negative charge on the one hand increases, thus the affinity of soil heavy metal increases; On the other hand pH value raises, and is also conducive to the existence of MOH+ and improves the adsorptive capacity of heavy metal ion, impels heavy metal in soil to form oxyhydroxide or combined precipitation or co-precipitation simultaneously.
Sodium bentonite is the clay mineral based on montmorillonite, and primary chemical formula is Nax (H
2o)
4(AI
2-xmg
0.83) Si
4o
10) (OH)
2, its structure presss from both sides by two silicon-oxy tetrahedrons the crystalline structure that one deck alumina octahedral forms.Mainly there is sodium ion in the laminate structure that sodium bentonite structure cell is formed, easily by other cation replacements, has good ion exchangeable, can carry out ion-exchange with the heavy metal in soil, reduces the bio-toxicity of heavy metal-polluted soil.
Activated alumina has many capillary channels, and specific surface area is large, has stronger avidity to water, oxide compound etc.
Nitrilotriacetic acid(NTA) can provide four coordinate bonds for metal ion, and its molecule is less again, and thus it has very strong complex ability, can form stable inner complex with each metal ion species.
Sodium lignosulfonate is a kind of natural polymers, has very strong dispersive ability, is suitable for by solid dispersal in water medium, can be adsorbed on the surface of various solid particle, can carry out metal ion exchanged effect; Adding of sodium lignosulfonate, promote to greatest extent to repair the dispersion of other components in soil in medicament, self also there is the sequestering action with heavy metal ion simultaneously.
Sodium laurylsulfonate is a kind of anion surfactant efficiently, and easily with various additive compound, cost is lower, and synthesis technique is ripe, with the hydrophobicity in sequestrant complex treatment soil containing heavy metal substance, improves soil remediation effect.
Except said components absorption separately, sequestering action, adding of biomass charcoal, diatomite, sodium bentonite, activated alumina can improve soil physico-chemical property well, greatly strengthens the permeability of soil; Under the effect of sodium laurylsulfonate, the good water solubility of nitrilotriacetic acid(NTA), sodium lignosulfonate, easily and biomass charcoal, diatomite, sodium bentonite, activated alumina cooperatively interact and to react with heavy metal ion, sodium lignosulfonate has dissemination simultaneously, in the edatope having water, promote that other components are disperseed in soil, to greatest extent with soil contact reacts.
Play synergy by said components, the leaching yield of heavy metal in soil is reduced greatly, reach and be better than the primary standard of country " standard of soil environment quality " (GB15618-1995).
Embodiment:
Embodiment 1
Test soil collecting is from certain heavy metal contamination region, and the heavy metal content in this regional soil top layer is higher than the grade III Standard of " standard of soil environment quality " (GB15618-1995).Practical situation according to polluting are repaired:
(a), sample from soil, detect and adopt turnover oscillator to carry out leaching test to soil according to solid waste " Leaching leaching method sulfonitric method " (HJ/T299-2007), detect preprosthetic heavy metal-polluted soil concentration;
B prepared by (), soil-repairing agent: be retrieved as the pulverous unslaked lime of below 2mm; Taking stalk as raw material, is 3kPa at system pressure, and pyrolysis temperature is the condition vacuum pyrolysis 30min of 500 DEG C, and milled processed obtains the solid particulate of below 3mm, makes the biomass charcoal that particle diameter is less than 3mm; Obtain that alkaline coefficient is greater than 1, smectite content is 80%, particle diameter is less than the sodium bentonite of 2mm; Obtain pulverous unslaked lime, diatomite, nitrilotriacetic acid(NTA), activated alumina, sodium lignosulfonate, sodium laurylsulfonate that particle diameter is less than 2mm.The mass percent of each raw material is:
Unslaked lime 45%;
Biomass charcoal 10%;
Diatomite 10%;
Sodium bentonite 10%;
Activated alumina 10%;
Nitrilotriacetic acid(NTA) 5%;
Sodium lignosulfonate 5%;
Sodium laurylsulfonate 5%;
Carry out Homogeneous phase mixing according to the above ratio, namely complete preparation, obtain repairing medicament.
(c), heavy-metal contaminated soil is dug out, send into crusher in crushing, through Belt Conveying to mixing tank, reparation medicament for soil quality 10% is fully mixed with contaminated soil, in mixing process, spraying a small amount of water makes Soil conservation moistening, leaves standstill 10 days, namely complete reparation after mixing.
(d), effect detection: sample from the soil after reparation, detecting adopts turnover oscillator to carry out leaching test to soil according to solid waste " Leaching leaching method sulfonitric method " (HJ/T299-2007), detect the heavy metal-polluted soil concentration after repairing, result is as shown in table 1:
Table 1
| Cadmium (Cd) | Plumbous (Pb) | Zinc (Zn) | Mercury (Hg) | |
| Before process (mg/kg) | 33.3 | 2876 | 1892 | 5.9 |
| After process (mg/kg) | 0.009 | 0.06 | 0.5 | Do not detect |
Cadmium in Soil after reparation, lead, zinc, mercury content meet the primary standard of " standard of soil environment quality " (GB15618-1995).
Embodiment 2
Test soil collecting is from certain heavy metal contamination region, and the heavy metal content in this regional soil top layer is higher than the grade III Standard of " standard of soil environment quality " (GB15618-1995).Practical situation according to polluting are repaired:
(a), sample from soil, detect and adopt turnover oscillator to carry out leaching test to soil according to solid waste " Leaching leaching method sulfonitric method " (HJ/T299-2007), detect preprosthetic heavy metal-polluted soil concentration;
B prepared by (), soil-repairing agent: be retrieved as the pulverous unslaked lime of below 2mm; Taking stalk as raw material, is 3kPa at system pressure, and pyrolysis temperature is the condition vacuum pyrolysis 30min of 500 DEG C, and milled processed obtains the solid particulate of below 3mm, makes the biomass charcoal that particle diameter is less than 3mm; Obtain that alkaline coefficient is greater than 1, smectite content is 80%, particle diameter is less than the sodium bentonite of 2mm; Obtain pulverous unslaked lime, diatomite, nitrilotriacetic acid(NTA), activated alumina, sodium lignosulfonate, sodium laurylsulfonate that particle diameter is less than 2mm.The mass percent of each raw material is:
Unslaked lime 30%;
Biomass charcoal 25%;
Diatomite 10%;
Sodium bentonite 15%;
Activated alumina 10%;
Nitrilotriacetic acid(NTA) 8%;
Sodium lignosulfonate 1%;
Sodium laurylsulfonate 1%;
Carry out Homogeneous phase mixing according to the above ratio, namely complete preparation, obtain repairing medicament.
(c), heavy-metal contaminated soil is dug out, send into crusher in crushing, through Belt Conveying to mixing tank, reparation medicament for soil quality 1% is fully mixed with contaminated soil, in mixing process, sprays a small amount of water and make Soil conservation moistening, leave standstill 10 days after mixing, namely complete reparation.
(d), effect detection: sample from the soil after reparation, detecting adopts turnover oscillator to carry out leaching test to soil according to solid waste " Leaching leaching method sulfonitric method " (HJ/T299-2007), detect the heavy metal-polluted soil concentration after repairing, result is as shown in table 2:
Table 2
| Cadmium (Cd) | Plumbous (Pb) | Zinc (Zn) | Mercury (Hg) | |
| Before process (mg/kg) | 9.1 | 931 | 653 | 4.2 |
| After process (mg/kg) | 0.01 | 0.2 | 0.9 | Do not detect |
Cadmium in Soil after reparation, lead, zinc, mercury content meet the primary standard of " standard of soil environment quality " (GB15618-1995).
Embodiment 3
Test soil collecting is from certain heavy metal contamination region, and the heavy metal content in this regional soil top layer is higher than the grade III Standard of " standard of soil environment quality " (GB15618-1995).Practical situation according to polluting are repaired:
(a), sample from soil, detect and adopt turnover oscillator to carry out leaching test to soil according to solid waste " Leaching leaching method sulfonitric method " (HJ/T299-2007), detect preprosthetic heavy metal-polluted soil concentration;
B prepared by (), soil-repairing agent: be retrieved as the pulverous unslaked lime of below 2mm; Taking stalk as raw material, is 3kPa at system pressure, and pyrolysis temperature is the condition vacuum pyrolysis 30min of 500 DEG C, and milled processed obtains the solid particulate of below 3mm, makes the biomass charcoal that particle diameter is less than 3mm; Obtain that alkaline coefficient is greater than 1, smectite content is 80%, particle diameter is less than the sodium bentonite of 2mm; Obtain pulverous unslaked lime, diatomite, nitrilotriacetic acid(NTA), activated alumina, sodium lignosulfonate, sodium laurylsulfonate that particle diameter is less than 2mm.The mass percent of each raw material is:
Unslaked lime 30%;
Biomass charcoal 10%;
Diatomite 15%;
Sodium bentonite 10%;
Activated alumina 15%;
Nitrilotriacetic acid(NTA) 10%;
Sodium lignosulfonate 5%;
Sodium laurylsulfonate 5%;
Carry out Homogeneous phase mixing according to the above ratio, namely complete preparation, obtain repairing medicament.
(c), heavy-metal contaminated soil is dug out, send into crusher in crushing, through Belt Conveying to mixing tank, reparation medicament for soil quality 5% is fully mixed with contaminated soil, in mixing process, sprays a small amount of water and make Soil conservation moistening, leave standstill 10 days after mixing, namely complete reparation.
(d), effect detection: sample from the soil after reparation, detecting adopts turnover oscillator to carry out leaching test to soil according to solid waste " Leaching leaching method sulfonitric method " (HJ/T299-2007), detect the heavy metal-polluted soil concentration after repairing, result is as shown in table 3:
Table 3
| Cadmium (Cd) | Plumbous (Pb) | Zinc (Zn) | Mercury (Hg) | |
| Before process (mg/kg) | 11.1 | 876 | 581 | 4.7 |
| After process (mg/kg) | 0.01 | 0.09 | 0.6 | Do not detect |
Cadmium in Soil after reparation, lead, zinc, mercury content meet the primary standard of " standard of soil environment quality " (GB15618-1995).
Claims (6)
1. a heavy-metal contaminated soil renovation agent, it is characterized in that: raw material is made up of unslaked lime, biomass charcoal, diatomite, sodium bentonite, activated alumina, nitrilotriacetic acid(NTA), sodium lignosulfonate, sodium laurylsulfonate, the mass percent of each raw material of described soil-repairing agent is:
Unslaked lime 30-45%;
Biomass charcoal 10-25%;
Diatomite 10-15%;
Sodium bentonite 10-15%;
Activated alumina 10-15%;
Nitrilotriacetic acid(NTA) 5-10%;
Sodium lignosulfonate 1-5%;
Sodium laurylsulfonate 1-5%;
The mass percent sum of each raw material is 100%.
2. a kind of heavy-metal contaminated soil renovation agent according to claim 1, is characterized in that: the mass percent of each raw material of described soil-repairing agent is:
Unslaked lime 45%;
Biomass charcoal 10%;
Diatomite 10%;
Sodium bentonite 10%;
Activated alumina 10%;
Nitrilotriacetic acid(NTA) 5%;
Sodium lignosulfonate 5%;
Sodium laurylsulfonate 5%.
3. a kind of heavy-metal contaminated soil renovation agent according to claim 1 and 2, it is characterized in that: in described soil-repairing agent biomass charcoal be with stalk, Pericarppium arachidis hypogaeae, wood chip one or more for raw material, system pressure be 3kPa, pyrolysis temperature be the condition of 500 DEG C under vacuum pyrolysis 30min, then obtained the pressed powder of below 3mm by milled processed.
4. a kind of heavy-metal contaminated soil renovation agent according to claim 1 and 2, is characterized in that: the sodium bentonite in described soil-repairing agent is the pressed powder that alkaline coefficient is greater than 1, smectite content is 60-88%, particle diameter is less than 2mm.
5. a kind of heavy-metal contaminated soil renovation agent according to claim 1 and 2, is characterized in that: described unslaked lime, diatomite, activated alumina, nitrilotriacetic acid(NTA), sodium lignosulfonate, sodium laurylsulfonate are respectively the pressed powder of below 2mm.
6. the preparation method of a kind of heavy-metal contaminated soil renovation agent described in claim 1 to 5 any one, it is characterized in that: unslaked lime, biomass charcoal, diatomite, sodium bentonite, activated alumina, nitrilotriacetic acid(NTA), sodium lignosulfonate, sodium laurylsulfonate are uniformly mixed by above-mentioned mass ratio, obtain the soil-repairing agent prepared.
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Application publication date: 20160511 |