CN102876330A - Curing agent for heavy metal contaminated soil restoration and heavy metal contaminated soil restoration method - Google Patents
Curing agent for heavy metal contaminated soil restoration and heavy metal contaminated soil restoration method Download PDFInfo
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- CN102876330A CN102876330A CN2012103833183A CN201210383318A CN102876330A CN 102876330 A CN102876330 A CN 102876330A CN 2012103833183 A CN2012103833183 A CN 2012103833183A CN 201210383318 A CN201210383318 A CN 201210383318A CN 102876330 A CN102876330 A CN 102876330A
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Abstract
The invention discloses a curing agent for heavy metal contaminated soil restoration and a heavy metal contaminated soil restoration method. The curing agent for the heavy metal contaminated soil restoration comprises sulphoaluminate cement, and composition containing active silica and quick lime can be further added in the curing agent. After the sulphoaluminate cement is mixed with soil contaminated by heavy metal, firstly calcium sulphoaluminate in the sulphoaluminate cement is reacted with water to form monosulfate calcium hydroaluminosulfate, then heavy metal compound chemical bond is broken, heavy metal and atoms in ettringite are subjected to recombination of the chemical bond, metal atoms are constrained in a crystal lattice in space and not prone to be precipitated, thereby the purpose of curing heavy metal can be achieved, and the leaching toxicity of the heavy metal is reduced. A test proves that an obvious restorative effect can be achieved after the sulphoaluminate cement is used for 24 hours, namely after restoration, the soil leaching concentration is reduced and maintained within specified requirements, and the heavy metal can be effectively cured.
Description
Technical field
The present invention relates to environmental protection technical field, relate in particular to a kind of heavy-metal contaminated soil reparation solidifying agent, heavy-metal contaminated soil restorative procedure.
Background technology
Heavy metal generally refer to proportion at the about 60 kinds of elements more than 4.0 or proportion at the about 45 kinds of elements more than 5.0.Heavy metal in Study on environmental pollution mainly refers to the significant elements of bio-toxicity such as Pb, Cd, Hg, Cr and metalloid As, also comprises the elements such as heavy metal Zn, Cu, Co, Ni and Sn with certain toxicity.Some heavy metal element is human body and the essential element of other organism, will cause poisoning but its concentration surpasses certain limit.
Heavy metal pollution of soil refers to that mankind's activity inputs heavy metal in the soil, causes heavy metal content in soil apparently higher than background content, and the phenomenon that causes eco-environmental quality to worsen.
The cardinal principle of heavy-metal contaminated soil restorative procedure has two kinds at present: change the existence form of heavy metal in soil, reduce its toxicity; Heavy metal in soil is removed.Mainly contain following several according to the present typical restorative procedure of principle:
The first, Electroremediation: plug electrode at the contaminated soil two ends, behind the plugged, on the charged particle galvanotropism electrode in the soil, to reach the purpose of removing Heavy Metals in Contaminated Soils.In Europe, this technology not only is applied to lead pollution of soil, also is applied to the reparation of the contaminated soils such as copper, zinc, chromium, nickel and good fortune simultaneously.(" research of remediation of heavy metal-contaminated soil ")
The second, phytoremediation: phytoremediation mainly absorbs heavy metal in soil by super enriching plant,
Heavy metal is transferred to plant shoot divide, then the plant shoot with enriching heavy metal divides harvesting,
Reclaim heavy metal after burning, reach and repair the purpose of polluting.
Four, fixing-stable: fixing-stableization generally adopts heavy metal organic sequestering agent or solidifying agent and Heavy Metals in Contaminated Soils reaction, generates stable material, thereby reduces the Leaching of heavy metal, reaches the purpose of reparation.The inorganic soil solidifying agent that adopts at present cooperates other gelling material generally take ordinary Portland cement as main raw material, and alkali-activator and tensio-active agent carry out soil remediation after mixing.
In above-mentioned four kinds for the treatment of processs, the heavy metals immobilization stabilization technology is because its repairing effect is good, and the advantage such as rehabilitation cost is lower is remediation of heavy metal-contaminated soil relatively more commonly used at present.At present the heavy-metal contaminated soil solidification and stabilization is the remediation of heavy metal-contaminated soil of relatively commonly using, and its solidifying agent is divided into two kinds of organic sequestering agent and inorganic medicaments.Wherein, heavy metal chelant generally all is organic chemicals, some sequestrant itself just has certain harm to environment, as it being rendered to the secondary pollution that may cause soil in the soil, simultaneously the product of sequestrant and heavy metal for a long time and may decompose under severe environment, Leaching Heavy Metals increases, thereby causes the Re-pollution of heavy metal.And inorganic materials generally forms take gelling material as configurations in the heavy metals immobilization agent, generally take phosphoric acid salt and silicate as main.This class solidifying agent is that heavy metal in soil is fixed in the mineral, to reach the purpose that reduces its Leaching Heavy Metals.But present inorganic materials exists consumption large, and repairing efficiency is longer, and the long-term repair poor effect is to shortcomings such as soil fail are larger.
Summary of the invention
The object of the invention is to propose a kind of heavy-metal contaminated soil reparation solidifying agent, heavy-metal contaminated soil restorative procedure, the secondary pollution that produces when avoiding Heavy metal contaminated soil repaired, simultaneously, further shorten repairing efficiency, improve repairing effect.
First aspect the invention discloses a kind of heavy-metal contaminated soil reparation solidifying agent, and this solidifying agent comprises aluminosulfate cement.
Further, above-mentioned heavy-metal contaminated soil reparation also comprises with solidifying agent: the composition that contains active silica.
Further, above-mentioned heavy-metal contaminated soil reparation also comprises unslaked lime with solidifying agent.
Further, above-mentioned heavy-metal contaminated soil reparation is with in the solidifying agent, and the described composition that contains active silica is the silicon ash; And in the described solidifying agent, the mass percentage content of aluminosulfate cement is 40%-60%; The mass percentage content of silicon ash is 30%-45%, and the mass percentage content of unslaked lime is 5%-15%.
Further, above-mentioned heavy-metal contaminated soil reparation is with in the solidifying agent, and the mass ratio of the aluminosulfate cement in this cured article, silicon ash and unslaked lime is 5:4:1; And, in the described silicon ash, SiO
2Content is greater than 80% of silicon ash quality, Al
2O
3Content is greater than 10% of silicon ash quality; Described unslaked lime is powder, and the specific surface area of unslaked lime is greater than 100m
2/ kg.
Further, above-mentioned heavy-metal contaminated soil reparation solidifying agent also comprises surfactant.
Second aspect the invention also discloses a kind of heavy-metal contaminated soil restorative procedure, comprises following two steps:
Powder is repaired in step 1, preparation, and this reparation powder comprises aluminosulfate cement;
Step 2, contaminated by heavy metals soil is mixed spray water in the mixing process with described reparation powder.
Further, in the above-mentioned soil remediation method, during the reparation powder of described step 1 preparation, also add the composition that contains active silica.
Further, in the above-mentioned soil remediation method, during the reparation powder of described step 1 preparation, also be added with unslaked lime.
Further, in the above-mentioned soil remediation method, during the reparation powder of described step 1 preparation, the composition of the described active silica of interpolation is the silicon ash; And in the described reparation powder, the mass ratio of aluminosulfate cement, silicon ash and unslaked lime is 5:4:1; And in the described silicon ash, SiO. content is greater than 80% of silicon ash quality, Al
2O
3Content is greater than 10% of silicon ash quality; Described unslaked lime is powder, and specific surface area is greater than 100m2/kg.
Further, in the above-mentioned soil remediation method, when powder is repaired in described step 1 preparation, also be added with tensio-active agent.
Among the present invention, after aluminosulfate cement and the contaminated by heavy metals mixing with soil: at first, calcium sulphoaluminate in the aluminosulfate cement and water reaction form single sulphur type calcium hydroaluminosulfate (mineral are called ettringite), then heavy metal compound chemical bond fracture, heavy metal and ettringite Atom carry out the restructuring of chemical bond, and atoms metal spatially is bound in the lattice and is difficult for separating out.So just reach the purpose of curing heavy metal, reduced the Leaching of heavy metal.Evidence adopts aluminosulfate cement after 24 hours, can present obvious repairing effect, is reduced in the specified requirement with the soil leaching concentration after namely repairing, and reaches the purpose that heavy metal is effectively solidified.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art, the below will do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art, apparently,
Accompanying drawing in the following describes only is some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain according to these accompanying drawings other accompanying drawing.
After Fig. 1 is the active silica hydration reaction, the C-S of generation-H gel networks synoptic diagram;
Fig. 2 is C-S behind the heavy metals immobilization-H gel networks synoptic diagram;
Fig. 3 is the preparation method schematic diagram that a preferred embodiment of solidifying agent is used in heavy-metal contaminated soil reparation of the present invention.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the invention, the technical scheme in the embodiment of the invention is clearly and completely described, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making the every other embodiment that obtains under the creative work prerequisite.
The first embodiment
In one embodiment of the invention, the heavy-metal contaminated soil reparation is aluminosulfate cement with the main component of solidifying agent.
When adopting this solidifying agent that heavy-metal contaminated soil is repaired, comprise following two steps: step 1, use aluminosulfate cement prepare solidifying agent,, repair powder that is; Step 2, contaminated by heavy metals soil is mixed spray water in the mixing process with described reparation powder.
The hydration reaction of the main reacting thiourea aluminate cement that occurs in the solidification process
3CaO·Al
2O
3·CaSO
4+nH
2O→3CaO·Al
2O
3·CaSO
4·(30-32)H
2O+
The aluminosulfate cement hydration rate is very fast, finishes near aquation in 24 hours, so the initial stage mainly be the hydration reaction of aluminosulfate cement in reaction.
Notice that the aluminosulfate cement powder should be noted absolute waterproof with before contaminated soil mixes, preservation period generally should not be above three days.When being cured processing, soil and the aluminate cement powder that preferably will need to administer mix in stirrer, spray water in the mixing process, and adding quality is powder quality, it is even that whipping process keeps adding water as far as possible.The soil that stirs is poured out from stirrer.Mix complete after, under physical environment, keep mixing Soil conservation and avoided sunlight to be exposed to the sun in 24 hours as far as possible, sunlight is crossed and should be sprinkled water when strong.Forbid large rainwash.
In the present embodiment, after aluminosulfate cement and the contaminated by heavy metals mixing with soil: at first, calcium sulphoaluminate in the aluminosulfate cement and water reaction form single sulphur type calcium hydroaluminosulfate (mineral are called ettringite), then heavy metal compound chemical bond fracture, heavy metal and ettringite Atom carry out the restructuring of chemical bond, atoms metal spatially is bound in the lattice, and is difficult for separating out.So just reach the purpose of curing heavy metal, reduced the Leaching of heavy metal.Evidence adopts aluminosulfate cement after 24 hours, can present obvious repairing effect, is reduced in the specified requirement with the soil leaching concentration after namely repairing, and reaches the purpose that heavy metal is effectively solidified.
The second embodiment
In another embodiment, the heavy-metal contaminated soil reparation, can also be added and contain the active silica composition except the aluminosulfate cement powder with solidifying agent.Here, contain the active silica composition and can be silicon ash, flyash or volcanic ash.For example, in the present embodiment, can select to add the silicon ash.
By the adding of silicon ash, strengthen the solidification effect of heavy metal, especially the long-term effectiveness of repairing there is extraordinary effect.Can strengthen the heavy metals immobilization effect, heavy metal-polluted soil can not reactivate contaminate environment after guaranteeing to repair under envrionment conditions.
Concrete reaction mechanism is described as follows, and the main reaction that occurs has following two:
It at first is the hydration reaction of aluminosulfate cement
3CaO·Al
2O
3·CaSO
4+nH
2O→3CaO·A
l2O
3·CaSO
4·(30-32)H
2O+
What secondly occur is pozzolanic reaction
SiO
2+ H
2O+Ca (OH)
2→ C-S-H (gel)
The aluminosulfate cement hydration rate is very fast, finishes near aquation in 24 hours, so the initial stage mainly be the hydration reaction of aluminosulfate cement in reaction.The pozzolanic reaction speed of active silica is slow, and is less at the initial stage reacting weight, but the later stage continues to react.
The aluminosulfate cement main component is calcium sulphoaluminate, and itself and water reaction form single sulphur type calcium hydroaluminosulfate, and mineral are called ettringite.
Active silica and water, calcium hydroxide reaction have generated stable C-S-H gel.C-S-H gel structure more complicated forms different structures according to Si/Ca than difference.But it all is the structure at the occurring in nature stable existence.
Heavy metal compound in above-mentioned reaction process, its chemical bond fracture, metal and ettringite or C-S-H crystal gel Atom carries out the restructuring of chemical bond, atoms metal spatially is bound in the lattice, and is difficult for separating out.So just reach the purpose of curing heavy metal, reduced the Leaching of heavy metal.
Take C-S-H crystal gel as example, behind the active silica hydration reaction, the C-S of generation-H gel networks synoptic diagram as shown in Figure 1.Through wherein containing certain heavy metal element after the medicament curing, take nickel as example, its structure as shown in Figure 2.Need to prove that the amount of Ni is amplified several times for convenience of explanation among the figure, the Ni amount of element that in fact replaces in the structure seldom.
In the present embodiment, by the adding of silicon ash, strengthen the solidification effect of heavy metal, especially the long-term effectiveness of repairing is had extraordinary effect.Can strengthen the heavy metals immobilization effect, heavy metal-polluted soil can not reactivate and the Re-pollution environment under envrionment conditions after guaranteeing to repair.
A same embodiment notes, the solidifying agent for preparing should be noted absolute waterproof with before contaminated soil mixes, and preservation period generally should not be above three days.When being cured processing, soil and the aluminate cement powder that preferably will need to administer mix in stirrer, spray water in the mixing process, and adding quality is powder quality, it is even that whipping process keeps adding water as far as possible.The soil that stirs is poured out from stirrer.Mix complete after, under physical environment, keep mixing Soil conservation and avoided sunlight to be exposed to the sun in 24 hours as far as possible, sunlight is crossed and should be sprinkled water when strong.Forbid large rainwash.
Need to prove that the quality of aluminosulfate cement powder and silicon ash can obtain according to on-the-spot needs debugging.Present embodiment is not done restriction at this.
The 3rd embodiment
The below introduces a preferred embodiment of the present invention.
In this embodiment, the heavy-metal contaminated soil reparation can also be on the basis of the second embodiment with solidifying agent, has increased the unslaked lime powder and as the glucose of tensio-active agent.Also namely, the heavy-metal contaminated soil reparation comprises aluminosulfate cement with solidifying agent, silicon ash, unslaked lime and glucose.
In the specific implementation, the mass percent of aluminosulfate cement in solidifying agent preferably is controlled to be 40%-60%, and the mass percent of silicon ash in solidifying agent preferably is controlled to be 30%-45%, and the mass percent of unslaked lime in solidifying agent preferably is controlled to be 5%-15%.But in fact, if mass percentage content falls into outside the above-mentioned interval, the solidifying agent that the three mixes also can play solidification to contaminated by heavy metals soil, and just effect is not good in above-mentioned interval.
Below, describe by a specific examples.
With reference to Fig. 3, Fig. 3 is the preparation method schematic diagram that solidifying agent is used in heavy-metal contaminated soil reparation of the present invention.As can be seen from the figure, with the unslaked lime in the silicon in the aluminosulfate cement in the cement bin, silicon ash silo ash, the unslaked lime storehouse and as the glucose of tensio-active agent by measuring chute according to the ratio weighing of setting, namely can be used for the heavy-metal contaminated soil reparation after then fully mixing.
In the solidifying agent of the below to present embodiment, the content of each component makes a detailed description:
(1) in the silicon ash, requires active SiO
2Content is greater than 80%, Al
2O
3Content is greater than 10%;
(2) aluminosulfate cement adopts the commodity cement of label 425 on the market;
(3) unslaked lime is powder, and specific surface area is greater than 100m
2/ kg.
(4) mass ratio of aluminosulfate cement, silicon ash and unslaked lime is 5:4:1.
(5) quality of glucose accounts for the 0.5%-3% of other three kinds of material total masses.
And the solidifying agent for preparing will mix complete before engineering begins, and the powder that mixes needs absolute waterproof to preserve, and preservation period generally should not be above three days.
Can throw in the following manner solidifying agent: add solidifying agent according to 5%-10% of soil quality, soil and solidifying agent are mixed in stirrer, spray water in the mixing process, adding quality is the solidifying agent quality, it is even that whipping process keeps adding water as far as possible.The soil that stirs is poured out from stirrer, keeps mixing Soil conservation and avoided sunlight to be exposed to the sun in 24 hours as far as possible under physical environment, and sunlight is crossed and should be sprinkled water when strong, and forbids large rainwash.
As described in above-mentioned two embodiment, the adding of aluminosulfate cement, what can guarantee contaminated by heavy metals soil just can have positive effect after repairing 24 hours, namely, be reduced in the specified requirement with the soil leaching concentration after repairing, reach the purpose that heavy metal is effectively solidified.
By the adding of silicon ash, strengthen the solidification effect of heavy metal, especially the long-term effectiveness of repairing there is extraordinary effect.Can strengthen the heavy metals immobilization effect, heavy metal-polluted soil can not reactivate and the Re-pollution environment under envrionment conditions after guaranteeing to repair.Certainly, the silicon ash can be had by other material substitution of active silica, such as flyash or volcanic ash etc.The present invention does not do restriction at this.
By adding the unslaked lime powder, can regulate P in soil H value, promote the carrying out of reaction.
By adding glucose, play the effect of tensio-active agent, be conducive to the carrying out of heavy metals immobilization reaction.Glucose plays Action of Surfactant in solidifying agent, be conducive to pulvis and disperse and react.Certainly, the tensio-active agent of other types also has equal effect not affecting in the situation of repairing permanent stability.The present invention does not do restriction at this.
Medicament curing heavy metal reaction mechanism is as follows:
The main reaction that occurs has following two in the solidification process:
At first, generation is the hydration reaction of aluminosulfate cement
3CaO·Al
2O
3·CaSO
4+nH
2O→3CaO·Al
2O
3CaSO
4·(30-32)H
2O+
Secondly, generation is pozzolanic reaction
SiO
2+ H
2O+Ca (OH)
2→ C-S-H (gel)
The aluminosulfate cement hydration rate is very fast, finishes near aquation in 24 hours, so the initial stage mainly be the hydration reaction of aluminosulfate cement in reaction.The pozzolanic reaction speed of active silica is slow, and is less at the initial stage reacting weight, but the later stage continues to react.
The aluminosulfate cement main component is calcium sulphoaluminate, and itself and water reaction form single sulphur type calcium hydroaluminosulfate, and mineral are called ettringite.
Active silica and water, calcium hydroxide reaction have generated stable C-S-H gel.C-S-H gel structure more complicated forms different structures according to Si/Ca than difference.But it all is the structure at the occurring in nature stable existence.
Heavy metal compound in above-mentioned reaction process, its chemical bond fracture, metal and ettringite or C-S-H crystal gel Atom carries out the restructuring of chemical bond, atoms metal spatially is bound in the lattice, and is difficult for separating out.So just reach the purpose of curing heavy metal, reduced the Leaching of heavy metal.The synoptic diagram that can see figures.1.and.2 is understood the restructuring of chemical bond.
Below, the testing data of associative list 1, the repairing effect that the solidifying agent that adopts this enforcement is repaired contaminated by heavy metals soil describes.
Table 1 solidifying agent repairing effect is analyzed
When utilizing this solidifying agent to carry out the soil remediation test, the compliance test result after the soil fixing is shown,
Solidifying agent is not exclusively the same for different heavy metal element fixed effects, but can both be effectively fixing; The effect of repairing in rear 24 hours namely satisfies national requirements, and along with the time increases, fixed rate all increases, and repairing effect has increase trend.
To sum up, have following advantage in heavy-metal contaminated soil reparation of the present invention with solidifying agent:
The first, with respect to Electroremediation, the present invention have soil itself is required low, the advantage such as repairing efficiency is short, and repairing effect is good.
The advantages such as the second, the employing inorganic materials than phytoremediation, has the repairing efficiency weak point to the contaminated soil stabilization treatment, and repairing effect is good.
Three, inorganic materials without any harm, belongs to the environmental friendliness shaped material to environment, thereby also can not produce secondary pollution problems.With respect to other inorganic medicaments, the present invention has selected the combination of aluminosulfate cement and silicon ash etc., guarantees to repair to finish in the short period of time, and repairing effect is steady in a long-term.
In addition, the invention also discloses a kind of embodiment of heavy-metal contaminated soil restorative procedure, each step and principle of work have all been done fully explanation in above-mentioned three embodiment, and relevant part gets final product with reference to above-mentioned explanation, does not repeat them here.
The above only is preferred embodiment of the present invention, and is in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a heavy-metal contaminated soil reparation solidifying agent is characterized in that this solidifying agent comprises aluminosulfate cement.
2. heavy-metal contaminated soil reparation solidifying agent according to claim 1 is characterized in that, also comprises: the composition that contains active silica.
3. heavy-metal contaminated soil reparation solidifying agent according to claim 1 is characterized in that, also comprises unslaked lime.
4. heavy-metal contaminated soil reparation solidifying agent according to claim 3 is characterized in that,
The described composition that contains active silica is the silicon ash; And, in the described solidifying agent,
The mass percentage content of aluminosulfate cement is: 40%-60%;
The mass percentage content of silicon ash is: 30%-45%,
The mass percentage content of unslaked lime is: 5%-15%.
5. heavy-metal contaminated soil reparation solidifying agent according to claim 4 is characterized in that,
The mass ratio of the aluminosulfate cement in this cured article, silicon ash and unslaked lime is 5:4:1; And, in the described silicon ash, SiO
2Content is greater than 80% of silicon ash quality, Al
2O
3Content is greater than 10% of silicon ash quality; Described unslaked lime is powder, and the specific surface area of unslaked lime is greater than 100m
2/ kg.
According to claim 5 in each described heavy-metal contaminated soil reparation solidifying agent, it is characterized in that also comprises surfactant.
7. a heavy-metal contaminated soil restorative procedure is characterized in that,
Powder is repaired in step 1, preparation, and this reparation powder comprises aluminosulfate cement;
Step 2, contaminated by heavy metals soil is mixed spray water in the mixing process with described reparation powder.
8. soil remediation method according to claim 7 is characterized in that, during the reparation powder of described step 1 preparation, also adds and contains the active silica composition.
9. soil remediation method according to claim 8 is characterized in that,
During the reparation powder of described step 1 preparation, also be added with unslaked lime.
10. each described soil remediation method in 9 according to claim 6 is characterized in that, when powder is repaired in described step 1 preparation, also is added with tensio-active agent.
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