CN101962553A - Curing agent for restoring heavy metal contaminated soil - Google Patents
Curing agent for restoring heavy metal contaminated soil Download PDFInfo
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- CN101962553A CN101962553A CN2010102884795A CN201010288479A CN101962553A CN 101962553 A CN101962553 A CN 101962553A CN 2010102884795 A CN2010102884795 A CN 2010102884795A CN 201010288479 A CN201010288479 A CN 201010288479A CN 101962553 A CN101962553 A CN 101962553A
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Abstract
The invention relates to the technical field of contaminated soil treatment, in particular to a curing agent for restoring heavy metal contaminated soil. The curing agent comprises the following components in percentage by weight: 25 to 40 percent of cement, 40 to 65 percent of high-adsorbability clay mineral and 10 to 20 percent of quicklime. The curing agent has the advantages of no risk of secondary pollution when heavy metal ions are fixed by the high-adsorbability clay mineral and no obvious change of original soil property. The components of the high-adsorbability clay mineral are close to those of the original powdered clay, so great damage to a soil structure by the cement and the quicklime is avoided. Therefore, the curing agent also has the advantages of obvious effect of restoring heavy metal plane source contaminated agricultural land and good social, economic and environmental benefits.
Description
Technical field
The present invention relates to contaminated soil and administer technical field, particularly a kind of solidifying agent that is used to be subjected to the reparation of heavy-metal contaminated soil.
Background technology
At present, the recovery technique of heavy-metal contaminated soil mainly contains: cushion, biological restoration method, chemical fixation, electronic repairing method etc.Wherein, cushion only is applicable to small area, serious pollution soil; The biological restoration method have processing costs low, can reach higher cleaning water equality advantage, but required repair time is long, contaminated thing class limitations is bigger; Electronic repairing method effect in different soil property soil differs, even adverse effect is arranged, and the high operating equipment complexity of cost, is unfavorable for the big area use.It is by adding heavy metal element in different allogenic materials (the being solidifying agent) fixing soil, reaching a kind of important method that reduces heavy metal transport property and biological effectiveness that heavy-metal contaminated soil solidifies recovery technique.Since easy to operate quick with effect, make it that not replaceable effect be arranged in the contaminated soil governance process.Adopt laboratory evaluation, can assess these fixed substances fixed efficiency to heavy metal ion in soil on the one hand; Can assess the ecological risks such as stripping, release and bio-toxicity of heavy metal on the other hand.
At present, main solidifying agent has cement, lime, flyash etc.Its main drawback has: applicable surface is narrower, and promptly some solidifying agent is effectively relatively poor for other then effect for some heavy metal ion; The cost height; Itself there is secondary pollution in some solidifying agent, as flyash; The long-term solidification effect instability of solidifying agent has the danger that discharges again thereby easily decompose the heavy metal ion that is fixed after 1 year as organic solidifying agent.
And adopt above-mentioned solidifying agent to carry out contaminated soil and administer, though the contaminated soil after administering can be used as stopping composition such as ground, roadbed and uses, but the periphery of often administering contaminated soil does not have this type of building operation operation, can not plant vegetation and add on the contaminated soil behind the solidifying agent such as cement, lime, can only be buried go into underground.
Summary of the invention
The objective of the invention is according to above-mentioned the deficiencies in the prior art part, a kind of solidifying agent that is used to be subjected to the reparation of heavy-metal contaminated soil is provided, this solidifying agent adopts high absorption clay mineral to substitute the destruction traditional solidifying agent clearly to soil such as part cement, flyash and unslaked lime, thereby the content of these materials in the reduction solidifying agent provides a kind of efficient, economy, heavy-metal contaminated soil solidifying agent that versatility is wide.And can solve the second stage employ problem of cured product.
The object of the invention realizes being finished by following technical scheme:
A kind of solidifying agent that is used to be subjected to the reparation of heavy-metal contaminated soil is characterized in that the weight percent of described solidifying agent is: cement 25-40%, high absorbability clay mineral 40%-65%, unslaked lime 10%-20%.
The weight percent of described solidifying agent is: cement 30-40%, high absorbability clay mineral 40%-60%, unslaked lime 10%-15%.
High absorbability clay mineral in the described solidifying agent is polynite.
The weight percent of described solidifying agent is: cement 30-40%, polynite 50%-55%, unslaked lime 10%-15%.
High absorbability clay mineral in the described solidifying agent is a sepiolite.
The weight percent of described solidifying agent is: cement 25%-34%, sepiolite 55%-65%, unslaked lime 10%-12%.
High absorbability clay mineral in the described solidifying agent is a diatomite.
The weight percent of described solidifying agent is: cement 25%-35%, diatomite 55%-65%, unslaked lime 10%-15%.
The using method of described solidifying agent is: described solidifying agent is added directly to heavy-metal contaminated soil and mixing, and adding proportion is the 10%-20% of contaminated soil weight.
Described solidifying agent is used for the improvement of lead pollution of soil.
Advantage of the present invention is: when the high absorbability clay mineral is fixed heavy metal ion, do not have the risk of secondary pollution, the character of original soil is not had significant change.The mineral composition of high absorbability clay is in close proximity to the original state silty clay, avoided cement and unslaked lime to soil structures cause than havoc.This advantage makes this kind solidifying agent especially remarkable for the farming land repairing effect that is subjected to the heavy metal pollution of area source, has good society, economy, environmental benefit.
Embodiment
By the following examples feature of the present invention and other correlated characteristic are described in further detail, so that technician's of the same trade understanding:
Be referred to as the high absorbability clay mineral among the present invention, thereby particle is tiny for having of specifically referring to, specific surface area and special space, clay that fibrous texture has adsorptive power or the general name of mineral, mainly is in the present invention to utilize its absorption property to adsorb heavy metal ion in the soil.Each components selection thinking of the present invention is: cement as main jointing compound under higher alkaline environment easily and heavy metal ion (as Pb, Gd etc.) form the mixture of indissoluble, thereby stable firmly heavy metal ion; Heavy metal ion in the high absorbability clay absorption soil, and can utilize the package action of cement to fix the heavy metal ion that is adsorbed; And unslaked lime is mainly used to provide a higher alkaline environment because under higher alkaline environment fixed effect the best of cured product.
The high absorbability clay is chosen as three kinds of diatomite, polynite and sepiolites in following examples, because above-mentioned three kinds of high absorbability clays are at solidification effect comparatively under the ideal prerequisite, big at the occurring in nature reserves, extract easily, complete processing is ripe, cheap, and its composition and common soil are approximate, and often use as soil improvement agent in practice, have useful effect for the plantation of vegetation.But it should be recognized by those skilled in the art that high absorbability clay mineral among the present invention also should comprise other clay with adsorptivity or mineral such as kaolin, illite.
The composition analysis of above-mentioned three kinds of high absorbability clay minerals is as follows:
| The sample title | Silty clay | Diatomite | Sepiolite | Polynite |
| Na 2O | 1.95 | — | — | 3.68 |
| MgO | 1.88 | — | 16.1 | 3.15 |
| Al 2O 3 | 9.32 | 3.35 | 2.31 | 13.9 |
| SiO 2 | 59.2 | 88.1 | 56.2 | 51.2 |
| SO 3 | 0.04 | — | — | — |
| K 2O | 1.96 | — | 0.21 | 0.77 |
| CaO | 4.12 | 2.08 | 2.87 | 2.32 |
| TiO 2 | 0.62 | — | 0.12 | 0.08 |
| Cr 2O 3 | — | — | — | — |
| MnO | 0.07 | — | 0.11 | 0.03 |
| Fe 2O 3 | 3.29 | 1.38 | 1.01 | 1.20 |
| SrO | 0.02 | — | — | 0.02 |
| BaO | — | — | — | — |
The mineral composition that can obviously find out diatomite, sepiolite and polynite from last table is in close proximity to original state silty clay used in the experiment.And in the agricultural application of reality, because the absorption property that above-mentioned three had can make clayed soil increase permeability, so can improve the soil.In the soil of plants such as plantation fruit tree, vegetables, flowers and plants, grain, admix diatomite, sepiolite and polynite and can regulate moisture and air in the soil, protect fertile water conservation, prevent from mould, mashed root and tan by the sun phenomenon such as death to occur, promote that plant grows vigorously.And can be used as the carrier of agricultural chemicals, fertilizer, be processed into long lasting fertilizer or agricultural chemicals and use.
And the main component of cement and lime is calcium oxide, is added into after the soil, and the proterties of soil is constantly alkalized, and the acid base equilibrium of plant is destroyed like this, causes growth and development of plant bad, and severe patient can be dead.
So attempt the common turfgrass of the alkali proof turf establishment industry of plantation in the soil after curing, reduce cement, lime with comparison, behind the increase adsorbing clay, for the influence of soil.
Because the effect difference that cement, lime and high absorbability clay mineral three are played, following three's proportioning experimentizes, and experimentation is as follows:
(1) in the undisturbed soil that is polluted, add heavy metal contaminants, and thorough mixing evenly obtains preparation pollution soil;
(2) interpolation solidifying agent and maintenance obtained cured product in 28 days in polluting soil;
(3) mainly with reference to toxicity leaching program (the being TCLP) standard of U.S. Environmental Protection Administration, utilize deionized water to contrast simultaneously, cured product is carried out leaching experiment with the checking solidification effect as leach liquor;
(4) cured product is packed in the ceramic jar, every altar is adorned 20 in the selected tall grass seed of native 10kg and uniform broadcasting, the back thinning of emerging, and every altar stays 10 strains, and at sowing opening entry plant height after 1 month, every 10 days records once.
Wherein, soil pollutant is a lead ion, and its pollution level is 10000 mg/L; The total volume of solidifying agent is 15%, and both addition was approximately 17.6% of soil weight.Its experimental data is as follows:
Table 1 sepiolite
| 425 cement | Lime | Sepiolite | TCLP(mg/L) | Deionized water leaches (mg/L) | Percentage of germination (%) | 40 days blade situations |
| 100% | - | - | 0.6 | 0 | 0 | - |
| 67% | 33% | - | 0 | 10.35 | 0 | - |
| 33% | - | 67% | 7.19 | 0 | 25.3 | Be grass green, blade tip is withered and yellow |
| 40% | - | 60% | 5.28 | 0 | ||
| 25% | 10% | 65% | 4.66 | 0 | 14.5 | Yellow, part is withered and yellow |
| 30% | 8% | 62% | 3.01 | 0 | ||
| 30% | 10% | 60% | 2.56 | 0 | 10.2 | Yellow, part is withered and yellow |
| 30% | 12% | 58% | 2.13 | 0.83 | ||
| 30% | 15% | 55% | 1.04 | 1.46 | 5.4 | Yellow, most of withered and yellow |
| 30% | 20% | 50% | 0.47 | 4.35 | ||
| 30% | 25% | 45% | 0.68 | 5.72 | 0 | - |
| 34% | 12% | 54% | 0.92 | 0.65 | 8.5 | Yellow, part is withered and yellow |
| 35% | 15% | 50% | 0 | 1.05 | 3.3 | Yellow, most of withered |
| 40% | 12% | 48% | 0 | 0.08 | ||
| 40% | 20% | 40% | 0 | 2.37 | 1.1 | Dead |
| 45% | 12% | 43% | 0 | 0 | ||
| 50% | 15% | 35% | 0 | 0.31 | 0.5 | Dead |
Table 2 polynite
| 425 cement | Lime | Sepiolite | TCLP(mg/L) | Deionized water leaches (mg/L) | Percentage of germination (%) | 40 days blade situations |
| 100% | - | - | 0.6 | 0 | 0 | - |
| 67% | 33% | - | 0 | 10.35 | 0 | - |
| 33% | - | 67% | 6.83 | 0 | 24.6 | Be grass green, blade tip is withered and yellow |
| 40% | - | 60% | 5.13 | 0 | ||
| 25% | 10% | 65% | 4.5 | 0 | 13.4 | Yellow, part is withered and yellow |
| 30% | 8% | 62% | 3.21 | 0 |
| 30% | 10% | 60% | 2.05 | 0 | 11.5 | Yellow, part is withered and yellow |
| 30% | 12% | 58% | 2.16 | 0.5 | ||
| 30% | 15% | 55% | 0.92 | 1.52 | 5.5 | Yellow, most of withered and yellow |
| 30% | 20% | 50% | 0.35 | 3.68 | ||
| 30% | 25% | 45% | 0.37 | 5.26 | 0 | - |
| 34% | 12% | 54% | 0.78 | 0.54 | 7.9 | Yellow, part is withered and yellow |
| 35% | 15% | 50% | 0 | 1.05 | 2.8 | Yellow, most of withered |
| 40% | 12% | 48% | 0 | 0 | ||
| 40% | 20% | 40% | 0 | 2.83 | 0.9 | Dead |
| 45% | 12% | 43% | 0 | 0 | ||
| 50% | 15% | 35% | 0 | 0.56 | 0 | - |
Table 3 diatomite
| 425 cement | Lime | Diatomite | TCLP(mg/L) | Deionized water leaches (mg/L) | Percentage of germination (%) | 40 days blade situations |
| 100% | - | - | 0.6 | 0 | 0.5 | Dead |
| 67% | 33% | - | 0 | 10.35 | 0 | - |
| 33% | - | 67% | 6.51 | 0 | 27.5 | Be grass green, blade tip is withered and yellow |
| 40% | - | 60% | 4.98 | 0 | ||
| 25% | 10% | 65% | 4.14 | 0 | 15.6 | Yellow, part is withered and yellow |
| 30% | 8% | 62% | 3.42 | 0 | ||
| 30% | 10% | 60% | 2.44 | 0 | 9.8 | Yellow, part is withered and yellow |
| 30% | 12% | 58% | 1.95 | 0.77 | ||
| 30% | 15% | 55% | 0.72 | 1.68 | 6 | Yellow, most of withered and yellow |
| 30% | 20% | 50% | 0.18 | 3.91 | ||
| 30% | 25% | 45% | 0.25 | 5.45 | 0 | - |
| 34% | 12% | 54% | 0.73 | 0.34 | 8.2 | Yellow, part is withered and yellow |
| 35% | 15% | 50% | 0.06 | 1.12 | 3.5 | Yellow, most of withered |
| 40% | 12% | 48% | 0 | 0.05 | ||
| 40% | 20% | 40% | 0 | 2.46 | 1.5 | Dead |
| 45% | 12% | 43% | 0 | 0 | ||
| 50% | 15% | 35% | 0 | 0.21 | 0.5 | Dead |
By above-mentioned data as can be seen, experimental result each components selection thinking of the present invention of having coincide preferably:
Lime mainly plays and changes soil alkalescence, so under the situation of not adding lime, the solidification effect of solidifying agent is desirable not to the utmost, but too much interpolation can not improve the effect of solidifying agent too.And in the accounting condition with higher, instead influenced the cement of other its solidifications, the accounting of high absorbability clay mineral, instead solidification effect descends.Can find out by data, when weight ratio is at 10-15% in solidifying agent, be preferred proportioning at lime.
The solidification effect of cement is better than high absorbability clay (diatomite, polynite, sepiolite).So add under the stable situation of proportioning at lime, the ratio solidification effect that improves cement is better, but also improves relatively for soil fail, the high absorbability clay improves or is reduced in the accounting of solidifying agent, and its change trend is exactly opposite with cement.
Taking all factors into consideration two kinds of trend of lead ion solidification effect and tall grass upgrowth situation, the proportioning of solidifying agent should be cement 25-40%, high absorbability clay mineral 40%-65%, unslaked lime 10%-20% substantially.Further select to be: cement 30-40%, high absorbability clay mineral 40%-60%, unslaked lime 10%-15%.
Consider the difference of three kinds of high absorbability clay characteristics selecting in the above-mentioned experiment, concrete preferred proportioning is as follows:
The weight percent of solidifying agent is: cement 30-40%, polynite 50%-55%, unslaked lime 10%-15%; Or,
The weight percent of solidifying agent is: cement 25%-34%, sepiolite 55%-65%, unslaked lime 10%-12%; Or,
The weight percent of solidifying agent is: cement 25%-35%, diatomite 55%-65%, unslaked lime 10%-15%.
More than experiment mainly is to select a kind of proper curing agents proportioning.Whether have good solidification effect equally for testing above selected solidifying agent, below further test according to above-mentioned experimental procedure (remove tall grass plantation step) for other heavy metal ion:
Following experimental result is being that select proportioning: 33% cement+12% unslaked lime+55% high absorbability clay mineral is handled contents of many kinds of heavy metal ion under 15% the level at total volume.
Table 4 sepiolite
| Heavy metal ion | Pollution level (mg/kg) | TCLP?(mg/L) | Deionized water leaches (mg/L) |
| Pb | 10000 | 0.92 | 0.65 |
| Zn | 10000 | 38.9 | 0.29 |
| Gd | 1000 | 0.05 | 0.02 |
Table 5 polynite
| Heavy metal ion | Pollution level (mg/kg) | TCLP?(mg/L) | Deionized water leaches (mg/L) |
| Pb | 10000 | 0.78 | 0.54 |
| Zn | 10000 | 30.12 | 0 |
| Gd | 1000 | 0.06 | 0 |
Table 6 diatomite
| Heavy metal ion | Pollution level (mg/kg) | TCLP?(mg/L) | Deionized water leaches (mg/L) |
| Pb | 10000 | 0.73 | 0.34 |
| Zn | 10000 | 24.5 | 0 |
| Gd | 1000 | 0.04 | 0 |
4-6 can find out by table, and the high absorbability clay has absorption, solidified effect preferably equally for the heavy metal ion of other kinds.The selection thinking of this curing agent component of the present invention that coincide too, the high absorbability clay is an inert material, mainly is the effect of utilizing its absorption, so its absorption, solidification effect are not limited by the heavy metal ion kind.
In conjunction with above-mentioned experimental result, below under the different situation of the total volume of solidifying agent, select one of them more excellent fixed mixing ratio: 33% cement+12% unslaked lime+55% high absorbability clay mineral is handled the lead ion result.Wherein, pollution level is 10000mg/kg.
Table 7 sepiolite
| Total incorporation with respect to soil | TCLP?(mg/L) | Deionized water leaches (mg/L) |
| 5% | 30.15 | 6.39 |
| 10% | 8.24 | 2.68 |
| 15% | 0.92 | 0.65 |
| 20% | 0.05 | 0 |
Table 8 polynite
| Total incorporation with respect to soil | TCLP?(mg/L) | Deionized water leaches (mg/L) |
| 5% | 24.04 | 5.22 |
| 10% | 7.35 | 2.48 |
| 15% | 0.78 | 0.54 |
| 20% | 0.07 | 0 |
Table 9 diatomite
| Total incorporation with respect to soil | TCLP?(mg/L) | Deionized water leaches (mg/L) |
| 5% | 21.62 | 4.91 |
| 10% | 6.55 | 2.56 |
| 15% | 0.73 | 0.34 |
| 20% | 0 | 0 |
Below as can be seen, be under the 10000mg/kg situation in the lead ion pollution level, the solidifying agent addition is comparatively desirable at 15%-20%.And improve under the relatively low situation addition of then corresponding increase solidifying agent in pollution level.
Claims (10)
1. a solidifying agent that is used to be subjected to the reparation of heavy-metal contaminated soil is characterized in that the weight percent of described solidifying agent is: cement 25-40%, high absorbability clay mineral 40%-65%, unslaked lime 10%-20%.
2. a kind of solidifying agent that is used to be subjected to the reparation of heavy-metal contaminated soil according to claim 1 is characterized in that the weight percent of described solidifying agent is: cement 30-40%, high absorbability clay mineral 40%-60%, unslaked lime 10%-15%.
3. a kind of solidifying agent that is used to be subjected to the reparation of heavy-metal contaminated soil according to claim 2 is characterized in that the high absorbability clay mineral in the described solidifying agent is polynite.
4. a kind of solidifying agent that is used to be subjected to the reparation of heavy-metal contaminated soil according to claim 3 is characterized in that the weight percent of described solidifying agent is: cement 30-40%, polynite 50%-55%, unslaked lime 10%-15%.
5. a kind of solidifying agent that is used to be subjected to the reparation of heavy-metal contaminated soil according to claim 2 is characterized in that the high absorbability clay mineral in the described solidifying agent is a sepiolite.
6. a kind of solidifying agent that is used to be subjected to the reparation of heavy-metal contaminated soil according to claim 5 is characterized in that the weight percent of described solidifying agent is: cement 25%-34%, sepiolite 55%-65%, unslaked lime 10%-12%.
7. a kind of solidifying agent that is used to be subjected to the reparation of heavy-metal contaminated soil according to claim 2 is characterized in that the high absorbability clay mineral in the described solidifying agent is a diatomite.
8. a kind of solidifying agent that is used to be subjected to the reparation of heavy-metal contaminated soil according to claim 7 is characterized in that the weight percent of described solidifying agent is: cement 25%-35%, diatomite 55%-65%, unslaked lime 10%-15%.
9. according to claim 1,2,3,4,5,6,7 or 8 described a kind of solidifying agent that are used to be subjected to the reparation of heavy-metal contaminated soil, the using method that it is characterized in that described solidifying agent is: described solidifying agent is added directly to heavy-metal contaminated soil and mixing, and adding proportion is the 10%-20% of contaminated soil weight.
10. according to claim 1,2,3,4,5,6,7 or 8 described a kind of solidifying agent that are used to be subjected to the reparation of heavy-metal contaminated soil, it is characterized in that: described solidifying agent is used for the improvement of lead pollution of soil.
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Application publication date: 20110202 |