CN103834410A - Heavy metal immobilizing agent and method for immobilization and stabilization of soil heavy metals by using heavy metal immobilizing agent - Google Patents
Heavy metal immobilizing agent and method for immobilization and stabilization of soil heavy metals by using heavy metal immobilizing agent Download PDFInfo
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Abstract
The invention belongs to the technical field of restoration of heavy metal-contaminated soil and especially relates to a heavy metal immobilizing agent and a method for immobilization and stabilization of soil heavy metals by using the heavy metal immobilizing agent. The heavy metal immobilizing agent is composed of an immobilizing agent A and an immobilizing agent B, wherein the immobilizing agent A comprises, by mass, 40 to 80% of fly ash, 5 to 20% of cement and 20 to 40% of carbide slag, and the immobilizing agent B is an aqueous alkali (with a solid-liquid ratio of 0.2 to 0.6). The invention has the following advantages: (1) used raw materials are cheap, and a part of industrial waste is utilized, thereby realizing treatment of wastes with the waste; and (2) the prepared heavy metal immobilizing agent has a good immobilization effect, and the heavy metal leaching rate of immobilized heavy metal-contaminated soil meet requirements prescribed in Identification Standards for Hazardous Wastes (GB5085.3-2007).
Description
Technical field
The invention belongs to remediation of heavy metal-contaminated soil field, relate in particular to a kind of heavy metals immobilization agent and use the method for this heavy metals immobilization agent solidification and stabilization heavy metal-polluted soil.
Background technology
Current, heavy metal contamination is to people's quality of life and healthyly brought very large impact, and grievous injury health of the masses, jeopardizes environmental safety, affects social stability.Heavy metal contamination has the features such as chronicity, cumulative bad, latent and non-reversibility, its harm is large, difficulty of governance is large, cost is high, especially the eco-toxicity risk that heavy metal brings out more and more receives publicity, and particularly the heavy metal pollution of soil associated with grain-production generally paid attention to especially.
In recent years, China also pays much attention to Heavy Metal Pollution work, and in April, 2011, " heavy metal contamination integrated control " 12 " planning " is implemented through State Council approved.Planning proposes, to set up fairly perfect Heavy Metal Pollution system, accident emergency system and environment and health risk evaluation system by 2015, solve the outstanding problem of a collection of infringement health of the masses, substantially stop sudden heavy metal contamination event situation occurred frequently.The heavy metal contaminants of preferential control is classified heavy metal lead (Pb), mercury (Hg), cadmium (Cd), chromium (Cr) and metalloid arsenic (As) as in planning.
At present, solidification and stabilization heavy metal contamination also has many pieces of public technology bibliographical informations.In the prior art having disclosed, report (application number: a 201210107906.4) heavy metal species ambient cure agent and use the method for heavy metal in its curing heavy metal pollutent, the solidifying agent that utilizes magnesium oxide, potassium primary phosphate, borax, ferric oxide and silicon-dioxide to prepare, under normal temperature condition, solidification effect is good.Also there is report (application number: the 201010533363.3) heavy metal zinc polluted soil curing agent take industrial waste carbide slag as raw material, take cement, carbide slag and wilkinite as raw material, under the hydration reaction effect of cement, make the objectionable impurities in contaminated soil be closed in cured body inside, thereby reach object innoxious, stabilization.
Summary of the invention
The present invention, take flyash as main raw material, take cement, carbide slag as adulterant, prepares a kind of solidifying agent for solidification and stabilization heavy metal pollution of soil by the excitation of alkaline solution.The raw material using is cheap, both utilized a part of trade waste, the treatment of wastes with processes of wastes against one another, the solidification effect of the solidifying agent of preparation is better simultaneously, and the leaching yield of the heavy-metal contaminated soil after solidifying can reach " Hazardous wastes judging standard leaching characteristic identification " related request (GB5085.3-2007).
The object of the invention is to disclose a kind of heavy metals immobilization agent.
Another object of the present invention has been to disclose the method for the above-mentioned heavy metals immobilization agent of a kind of right to use solidification and stabilization heavy metal-polluted soil.
The object of the invention is to be achieved through the following technical solutions:
A kind of heavy metals immobilization agent, wherein, described heavy metals immobilization agent is made up of solidifying agent A and solidifying agent B, and in described solidifying agent A, the mass percent of each component is: flyash 40%～80%, cement 5%～20% and carbide slag 20%～40%; Described solidifying agent B is alkaline solution.
A kind of heavy metals immobilization agent described in technique scheme, wherein, described solidifying agent B is that modulus is 2.0 sodium silicate.Water glass is the soluble alkali metal silicate material being formed by alkalimetal oxide and silica bound, claims again sodium silicate.Water glass can be divided into sodium silicate (being water glass (Na2OnSiO2) aqueous solution) and potash water glass (being the aqueous solution of potassium silicate (K2OnSiO2)) according to alkali-metal kind, the coefficient n that its molecular formula is respectively in Na2OnSiO2 and K2OnSiO2. formula is called modulus of water glass, is silicon oxide in water glass and the molecular ratio (or mol ratio) of alkalimetal oxide; Modulus of water glass is the important parameter of water glass, generally between 1.5-3.5.Modulus of water glass is larger, and solid water glass is more insoluble in water, and n is that 1 o'clock normal-temperature water can be dissolved, and n needs hot water to dissolve while increasing, and n is greater than at 3 o'clock needs 4 steam more than normal atmosphere to dissolve; Modulus of water glass is larger, and silica content is more, and water glass viscosity increases, and is easy to decompose sclerosis, and cohesive force increases.
A kind of heavy metals immobilization agent described in technique scheme, wherein, the mass ratio between heavy-metal contaminated soil and solidifying agent A is (10～40): 100; The amount of described solidifying agent B is solid-to-liquid ratio 0.2W/W～0.6W/W, and described solid-to-liquid ratio is solidifying agent A and heavy-metal contaminated soil sum and the ratio of alkaline solution.
A method that uses the heavy metals immobilization agent solidification and stabilization heavy metal-polluted soil described in technique scheme, comprises the steps:
(1), prepare solidifying agent A by the mass percent of flyash 40%～80%, cement 5%～20% and carbide slag 20%～40%;
(2), by heavy-metal contaminated soil and solidifying agent A (10～40) in mass ratio: 100 choose heavy-metal contaminated soil, and heavy-metal contaminated soil is mixed, stirred with solidifying agent A, obtain uniform compound;
(3), add solidifying agent B by solid-to-liquid ratio 0.2W/W～0.6W/W, stir, pack mould molding into;
(4), the demoulding after 24h, under natural condition, maintain.
The method of the solidification and stabilization heavy metal-polluted soil described in technique scheme, wherein, the churning time in step (2) is 5min～10min; Churning time in step (3) is 10min～20min.
The method of the solidification and stabilization heavy metal-polluted soil described in technique scheme, wherein, described method also comprises the step of step (2) gained compound being dried in the baking oven of 105 ℃ to 2h～4h.
The present invention, take flyash as main raw material, take cement, carbide slag as adulterant, makes a kind of heavy metals immobilization agent for solidification and stabilization heavy metal pollution of soil by the excitation of alkaline solution.Raw material used in the present invention is cheap, has both utilized a part of trade waste, the treatment of wastes with processes of wastes against one another; The solidification effect of the solidifying agent of preparation is better simultaneously, and the leaching yield of the heavy-metal contaminated soil after solidifying can reach " Hazardous wastes judging standard leaching characteristic identification " related request (GB5085.3-2007).
The main raw material of the present invention using flyash, cement and carbide slag as solidifying agent A, the main raw material using alkaline solution as solidifying agent B; The mechanism of its solidification and stabilization heavy metal-polluted soil is:
Take flyash as main raw material, cement and carbide slag are adulterant, excite at alkaline solution under the effect of solution, the active aluminum silicate phase containing in solidifying agent A is dissolved into the aluminosilicate oligopolymer of oligomeric state, oligomer reacts condensation by dehydroxylation and is positive aluminosilicate polymer, and the positive aluminosilicate polymer generating further by polycondensation formed by-O-Si-O-Si-and-the gelling matrix with complex three-dimensional network-like structure that O-Al-O-Si-connects into;
On the one hand, due to feldspar phase, (feldspar is a kind of aluminosilicate mineral phase producing after flyash, cement, carbide slag and heavy-metal contaminated soil react under the effect of alkali-activator mutually, a kind of reaction product) existence, not only can be preferably for the generation of new feldspar in polymerization process provides more crystalline basement and nucleus, and heavy metal in soil ion can be adhered to and catch again to the existence of the substrate of feldspar phase and nucleus preferably, thereby heavy metal ion is solidificated in gel-in-matrix, thereby plays the effect of solidification and stabilization.On the other hand, because the aluminium silicate mineral in raw material is under the alkaline environment condition of alkaline solution, has occurred to dissolve and discharged free state silicon (OH)
2siO
2 2-, Al (OH)
4 -(OH)
2siO
3 3-deng negatively charged ion, the heavy metal cation (Pb of stripping in these negatively charged ion and soil
2+, Cd
2+, Cr
3+, Cr
6+, As
3+) etc. react, also can make the heavy metal in heavy-metal contaminated soil obtain solidification and stabilization;
Flyash and cement can hydration reactions in soil-solidified-agent in the present invention, play binding agent; Carbide slag plays the effect that regulates P in soil H in soil-solidified-agent, strengthens the effect of alkali-activator (alkaline solution);
Cement in the present invention in solidifying agent A is ordinary portland cement clinker.
The present invention has following beneficial effect:
1, use heavy metals immobilization agent of the present invention to be cured after processing heavy-metal contaminated soil, the solidification effect of heavy metals immobilization agent is good, and the leaching yield of the heavy-metal contaminated soil after solidifying can reach " Hazardous wastes judging standard leaching characteristic identification " related request (GB5085.3-2007).
2, in the raw materials of heavy metals immobilization agent of the present invention, a part is industrial waste, has played the effect of the treatment of wastes with processes of wastes against one another.
3, because a part in raw material of the present invention is industrial waste, therefore compared with the solidifying agent prepared with traditional method of heavy metals immobilization agent of preparation, reduce the cost of manufacture of heavy metals immobilization agent, the heavy metals immobilization agent making is cheap.
4, cheap due to heavy metals immobilization agent of the present invention, has therefore also reduced the cost of solidification and stabilization heavy metal-polluted soil, and processing enterprise or the individual of contaminated soil are happy to promote the use of.
Embodiment:
For making technical scheme of the present invention be convenient to understand, below in conjunction with concrete test example to a kind of heavy metals immobilization agent in the present invention and use the method for this heavy metals immobilization agent solidification and stabilization heavy metal-polluted soil to do the explanation of a step.
The analysis of the chemical composition of soil in the embodiment of the present invention adopts X-ray diffraction instrument to carry out diffraction quantitative analysis, arsenic Leaching leaching method adopts " solid waste Leaching leaching method sulfuric acid nitrate method " (HJ/T299-2007), and in leach liquor, the mensuration of arsenic adopts siliver diethyldithiocarbamate spectrophotometer method to measure.
The sodium silicate that the solidifying agent B using in all embodiment is below 2.0 for modulus.
The chemical composition of the heavy-metal contaminated soil using in all embodiment is below in table 1.
Table 1 heavy-metal contaminated soil chemical composition (wt%)
| Chemical composition | MgO | Si 2O 3 | Fe 2O 3 | Al 2O 3 | Ni 2O 3 | Cr 2O 3 | MnO | Na 2O |
| Content | 16.9 | 15.3 | 10.9 | 1.07 | 0.686 | 0.382 | 0.127 | 0.112 |
| Chemical composition | CaO | Co 2O 3 | TiO 2 | ZnO | K 2O | CuO | As 2O 3 | Loss on ignition |
| Content | 0.078 | 0.019 | 0.017 | 0.01 | 0.008 | 0.007 | 0.003 | 5.34 |
embodiment 1:
In the present embodiment, the shared mass percent of each component of solidifying agent A is: flyash 70%, cement 10%, carbide slag 20%; The solid-to-liquid ratio of solidifying agent B is 0.3W/W.Concrete grammar step is as follows:
A, heavy-metal contaminated soil and solidifying agent A are chosen to heavy-metal contaminated soil in mass ratio at 20: 100, heavy-metal contaminated soil is mixed, stirred with solidifying agent A, obtain uniform compound;
B, the compound that step a is mixed dry 2h～4h in the baking oven of 105 ℃;
C, add solidifying agent B by solid-to-liquid ratio 0.3W/W, stir, pack mould molding into;
The demoulding after d, 24h, maintains respectively 28d under natural condition.
F, employing " solid waste Leaching leaching method sulfuric acid nitrate method " (HJ/T299-2007) are carried out toxicity leaching to solidifying agent heavy-metal contaminated soil after treatment, leaching concentration is far below " Hazardous wastes judging standard leaching characteristic identification " (GB5085.3-2007) specified standards value
Toxicity leaches and the results are shown in Table in 2 shown in " embodiment 1 ".
Table 2 heavy-metal contaminated soil process before, leaching concentration after treatment (mg/L)
embodiment 2:
In the present embodiment, the shared mass percent of each component of solidifying agent A is: flyash 65%, cement 10%, carbide slag 25%; The solid-to-liquid ratio of solidifying agent B is 0.3W/W.Concrete grammar step is as follows:
A, heavy-metal contaminated soil and solidifying agent A are chosen to heavy-metal contaminated soil in mass ratio at 25: 100, heavy-metal contaminated soil is mixed, stirred with solidifying agent A, obtain uniform compound;
B, the compound that step a is mixed dry 2h～4h in the baking oven of 105 ℃;
C, add solidifying agent B by solid-to-liquid ratio 0.3W/W, stir, pack mould molding into;
The demoulding after d, 24h, maintains respectively 28d under natural condition.
F, employing " solid waste Leaching leaching method sulfuric acid nitrate method " (HJ/T299-2007) to solidifying agent heavy-metal contaminated soil after treatment carry out toxicity leaching, leaching concentration is far below " Hazardous wastes judging standard leaching characteristic identification " (GB5085.3-2007) specified standards value.
Toxicity leaches and the results are shown in Table in 2 shown in " embodiment 2 ".
embodiment 3:
In the present embodiment, the shared mass percent of each component of solidifying agent A is: flyash 60%, cement 15%, carbide slag 25%; The solid-to-liquid ratio of solidifying agent B is 0.4W/W.Concrete grammar step is as follows:
A, heavy-metal contaminated soil and solidifying agent A are chosen to heavy-metal contaminated soil in mass ratio at 30: 100, heavy-metal contaminated soil is mixed, stirred with solidifying agent A, obtain uniform compound;
B, the compound that step a is mixed dry 2h～4h in the baking oven of 105 ℃;
C, add solidifying agent B by solid-to-liquid ratio 0.4W/W, stir, pack mould molding into;
The demoulding after d, 24h, maintains respectively 28d under natural condition.
F, employing " solid waste Leaching leaching method sulfuric acid nitrate method " (HJ/T299-2007) to solidifying agent heavy-metal contaminated soil after treatment carry out toxicity leaching, leaching concentration is far below " Hazardous wastes judging standard leaching characteristic identification " (GB5085.3-2007) specified standards value.Toxicity leaches and the results are shown in Table in 2 shown in " embodiment 3 ".
embodiment 4:
In the present embodiment, the shared mass percent of each component of solidifying agent A is: flyash 55%, cement 15%, carbide slag 30%; The solid-to-liquid ratio of solidifying agent B is 0.4W/W.Concrete grammar step is as follows:
A, heavy-metal contaminated soil and solidifying agent A are chosen to heavy-metal contaminated soil in mass ratio at 35: 100, heavy-metal contaminated soil is mixed, stirred with solidifying agent A, obtain uniform compound;
B, the compound that step a is mixed dry 2h～4h in the baking oven of 105 ℃;
C, add solidifying agent B by solid-to-liquid ratio 0.4W/W, stir, pack mould molding into;
The demoulding after d, 24h, maintains respectively 28d under natural condition.
F, employing " solid waste Leaching leaching method sulfuric acid nitrate method " (HJ/T299-2007) to solidifying agent heavy-metal contaminated soil after treatment carry out toxicity leaching, leaching concentration is far below " Hazardous wastes judging standard leaching characteristic identification " (GB5085.3-2007) specified standards value.Toxicity leaches and the results are shown in Table in 2 shown in " embodiment 4 ".
embodiment 5:
In the present embodiment, the shared mass percent of each component of solidifying agent A is: flyash 55%, cement 20%, carbide slag 25%; The solid-to-liquid ratio of solidifying agent B is 0.5W/W.Concrete grammar step is as follows:
A, heavy-metal contaminated soil and solidifying agent A are chosen to heavy-metal contaminated soil in mass ratio at 40: 100, heavy-metal contaminated soil is mixed, stirred with solidifying agent A, obtain uniform compound;
B, the compound that step a is mixed dry 2h～4h in the baking oven of 105 ℃;
C, add solidifying agent B by solid-to-liquid ratio 0.5W/W, stir, pack mould molding into;
The demoulding after d, 24h, maintains respectively 28d under natural condition.
F, employing " solid waste Leaching leaching method sulfuric acid nitrate method " (HJ/T299-2007) to solidifying agent heavy-metal contaminated soil after treatment carry out toxicity leaching, leaching concentration is far below " Hazardous wastes judging standard leaching characteristic identification " (GB5085.3-2007) specified standards value.Toxicity leaches and the results are shown in Table in 2 shown in " embodiment 5 ".
Toxicity from embodiment in table 2 1～5 leaches result, heavy metals immobilization agent prepared by the present invention stabilization treatment that is cured to heavy-metal contaminated soil, leaching concentration is lower than " Hazardous wastes judging standard leaching characteristic identification " concentration limit (GB5085.3-2007), and solidification effect is good.
The above, it is only preferred embodiment of the present invention, not the present invention is done to any formal and substantial restriction, all those skilled in the art, do not departing within the scope of technical solution of the present invention, when utilizing disclosed above technology contents, and the equivalent variations of a little change of making, modification and differentiation is equivalent embodiment of the present invention; Meanwhile, the change of any equivalent variations that all foundations essence technology of the present invention is done above embodiment, modification and differentiation, all still belong in the scope of technical scheme of the present invention.
Claims (6)
1. a heavy metals immobilization agent, is characterized in that, described heavy metals immobilization agent is made up of solidifying agent A and solidifying agent B, and in described solidifying agent A, the mass percent of each component is: flyash 40%～80%, cement 5%～20% and carbide slag 20%～40%; Described solidifying agent B is alkaline solution.
2. a kind of heavy metals immobilization agent according to claim 1, is characterized in that: described solidifying agent B is that modulus is 2.0 sodium silicate.
3. a kind of heavy metals immobilization agent according to claim 1, is characterized in that: the mass ratio between heavy-metal contaminated soil and solidifying agent A is (10～40): 100; The amount of described solidifying agent B is solid-to-liquid ratio 0.2W/W～0.6W/W, and described solid-to-liquid ratio is solidifying agent A and heavy-metal contaminated soil sum and the ratio of alkaline solution.
4. right to use requires a method for heavy metals immobilization agent solidification and stabilization heavy metal-polluted soil described in 1, comprises the steps:
(1), prepare solidifying agent A by the mass percent of flyash 40%～80%, cement 5%～20% and carbide slag 20%～40%:
(2), by heavy-metal contaminated soil and solidifying agent A (10～40) in mass ratio: 100 choose heavy-metal contaminated soil, and heavy-metal contaminated soil is mixed, stirred with solidifying agent A, obtain uniform compound;
(3), add solidifying agent B by solid-to-liquid ratio 0.2W/W～0.6W/W, stir, pack mould molding into;
(4), the demoulding after 24h, under natural condition, maintain.
5. the method for solidification and stabilization heavy metal-polluted soil as claimed in claim 4, is characterized in that: the churning time in step (2) is 5min～10min; Churning time in step (3) is 10min～20min.
6. the method for the solidification and stabilization heavy metal-polluted soil as described in claim 4 or 5, is characterized in that: described method also comprises the step of step (2) gained compound being dried in the baking oven of 105 ℃ to 2h～4h.
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