CN109821878A - Vermiculite loads nanometer iron-based material to the fixing means of heavy metal-polluted soil lead - Google Patents
Vermiculite loads nanometer iron-based material to the fixing means of heavy metal-polluted soil lead Download PDFInfo
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- CN109821878A CN109821878A CN201910078555.0A CN201910078555A CN109821878A CN 109821878 A CN109821878 A CN 109821878A CN 201910078555 A CN201910078555 A CN 201910078555A CN 109821878 A CN109821878 A CN 109821878A
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Abstract
The invention discloses a kind of vermiculites to load nanometer iron-based material to the fixing means of heavy metal-polluted soil lead, 0 to 5 parts of vermiculite load nano zero valence irons are added in the soil of specially every 100 parts of contaminated heavy metal leads or vermiculite loads nano ferriferrous oxide, wherein, sodium borohydride solution the preparation method comprises the following steps: be added dropwise in the ferrum sulfuricum oxydatum solutum that vermiculite is added by vermiculite load nano zero valence iron in nitrogen environment, washed, drying obtains vermiculite load nano zero valence iron.Wherein, vermiculite loads nano ferriferrous oxide the preparation method comprises the following steps: by FeCl2And FeCl3It is dissolved in oxygen deionized water, and vermiculite stirring is added, instill sodium hydroxide solution, it is cooling, the washing of oxygen deionized water is spent, drying obtains vermiculite load nano ferriferrous oxide.The present invention can use the nanometer iron-based material of vermiculite load and effectively fix to heavy metal-polluted soil lead；Have the effect of to improvement heavy metal-polluted soil lead fabulous.
Description
Technical field
Present invention relates particularly to a kind of soil modification method, specially vermiculite loads nanometer iron-based material to heavy metal-polluted soil
The fixing means of lead.
Background technique
As important living guarantee, soil not only has productivity, also has buffering and purification function.But with society
Economic fast development, mankind's activity bring serious harm to soil environment.Heavy metal is as a kind of lasting and not degradable
Pollutant, threaten underground water security, agricultural production and human health.In past 50 years, in global range about
There is 7.83 × 105 tons of lead to be discharged into environment, significant portion enters soil.Feelings of China's soil by heavy metal pollution
Shape is similarly severe, and for the arable land more than national 1/6 by heavy metal pollution, accumulative contaminated area reaches 20,000,000 hectares.By
The grain annual amount of heavy metal pollution is up to 12,000,000 t, and economic loss is at 20,000,000,000 yuan or more.Wherein lead is heavy compared to other
Metal has the characteristics that highly dissoluble, high biochemical activity and strong carcinogenicity.The intake of lead will lead to human kidney, reproductive system
With the problem of nervous system etc., human health is caused to seriously threaten, Lead Pollution in Soil has become environmental problem urgently to be resolved.
Currently, the relatively early country for carrying out contaminated soil remediation work such as the U.S., Japan is to part soil pollution by heavy metal
Recovery technique complete apply work, be concentrated mainly on dystopy fixing/stabilising technology, dystopy soil elution technology, fixation in situ/
Stabilization technology, phytoremediation for soil technology, soil barrier Landfill etc..Dystopy fixing/stabilising technology is completed at 200
Heavy-metal contaminated soil recovery project, dystopy soil elution technology, fixation in situ/stabilization technology (account for entire recovery technique
7%), phytoremediation for soil technology, soil obstruct Landfill also extensive utilization.But all kinds of technology spininess are to heavy metal classes, needle
To lead-contaminated soil it is still necessary to further screen.Meanwhile by document retrieval (sci-tech novelty-search) the results show that existing literature is reported
Lead-contaminated soil disposal technology mainly have the technologies such as fixation, strong magnetic separation, wherein chemical fastening techniques are in economy and timeliness
It is upper that there is unrivaled advantage and obtain extensive concern.Chemical fastening techniques rely primarily on application fixative and are achieved, Gu
Determine heavy metal can be greatly lowered in agent biological effectiveness and toxicity, and cost of investment easy to operate is low.But conventional chemical is solid
The application for determining agent such as calcium oxide, hydroxyapatite etc. may change soil physico-chemical property, change soil structure, cause the two of soil
Secondary pollution, therefore seek a kind of pollution that can efficiently administer heavy metal-polluted soil lead, and environment amenable fixed agent material is
As urgent need.Wherein one of the nonmetallic ore as China's potential advantages, major product-vermiculite of the great vermiculite deposit of yield
Due to fabulous cationic exchangeability and adsorptivity, its constituent is mainly siliceous in addition, magnesium, iron, potassium, titanium etc. are to ring
Border beneficial element, undoubtedly soil remediation and improvement most suitable selection material.
Vermiculite is the secondary metamorphic mineral containing magnesium, irony aluminosilicate, is to be made by mica mineral hydrothermal alteration or weathering
With the regeneration mineral of formation, by chlorite, hydromica and clay mineral etc lattice stratiform mineral composition, there is zeolite and certain
The ion-exchange performance of clay.Vermiculite is usually sheet, scale aggregate.In the interlayer structure of vermiculite, contain commutative sun
Ion and intermediary water, volume expansion when heating.
For vermiculite as soil conditioner, plastic soil especially high to viscosity has positive effect, and expanded vermiculite has
The moisture holding capacity and laminated structure of height, keep soil aeration good.The cation exchange capacity (CEC) of vermiculite is strong, in the molecular structure may be used
It to keep nutrient, is then released slowly into somatomedin, pretends as the separation interlayer of water fruits and vegetables, plant growth；Low-density
Vermiculite, the permeability and water-retaining property of soil can be improved, improve the delay and ventilation of water, beneficial element in soil easy to control
Absorption and desorption also have good heat insulation effect to soil.
Make the wetting agent of peat soil or the regulator of soil with vermiculite, acid soil can be made to become neutral soil, play buffer function,
It can prevent the change dramatically of soil pH value.
Vermiculite more also serves as the carrier of fertilizer and pesticide, and to the harmful heavy metal of soil, it can be used as weight for absorption
The absorbent and fixative of metallic element, so that the content of beary metal mouth reduced in crop draws.And vermiculite is to arid area sand
The improved effect of matter soil is more prominent.
But since vermiculite is often applied in the form of expanded vermiculite practical, expanded vermiculite porosity is big but light specific gravity, because
This is difficult to mix with soil, and cladding degree is not high, and conjugation is lower, needs to carry out modification or modification for this disadvantage thus,
It can be come into full contact with contaminated soil, be greatly improved the fixed efficiency to heavy metal lead.
Summary of the invention
To solve the above-mentioned problems, the purpose of the present invention is to overcome the shortcomings of the existing technology, provides a kind of vermiculite load
Fixing means of the nanometer iron-based material to heavy metal-polluted soil lead.
Vermiculite provided by the invention loads nanometer iron-based material to the fixing means of heavy metal-polluted soil lead, specifically, by leech
Stone loads nanometer iron-based material and mixes with by the soil of heavy metal lead pollution, obtains the fixed soil of heavy metal lead.
Vermiculite as described above loads nanometer iron-based material to the fixing means of heavy metal-polluted soil lead, further explains
To load the mixed proportion of nanometer iron-based material by weight by the soil of heavy metal lead pollution and vermiculite are as follows:
By 100 parts of soil of heavy metal lead pollution, nanometer iron-based material 0.2-5 parts of vermiculite load.
Vermiculite as described above loads nanometer iron-based material to the fixing means of heavy metal-polluted soil lead, further explains
To load the mixed proportion of nanometer iron-based material by weight by the soil of heavy metal lead pollution and vermiculite are as follows:
By 100 parts of soil of heavy metal lead pollution, nanometer iron-based material 0.2-1.6 parts of vermiculite load.
Vermiculite as described above loads nanometer iron-based material to the fixing means of heavy metal-polluted soil lead, further explains
To be loaded the mixed method of nanometer iron-based material by the soil of heavy metal lead pollution and vermiculite are as follows:
(1), vermiculite is loaded nanometer iron-based material to be added in proportion in the soil by heavy metal lead pollution, makes its mixing
Uniformly；Obtain mixed soil；
(2), deionized water is added into mixed soil again, so that water content in mixed soil is greater than 30%, mixes well；
(3), the mixed soil after mixing thoroughly is in ventilation curing, cured 15-20 days；Make the heavy metal in mixed soil
Lead is fixed.
Vermiculite as described above loads nanometer iron-based material to the fixing means of heavy metal-polluted soil lead, further explains
For it is that vermiculite loads nano zero valence iron that the vermiculite, which loads nanometer iron-based material,.
Vermiculite as described above loads nanometer iron-based material to the fixing means of heavy metal-polluted soil lead, further explains
For the vermiculite load nano zero valence iron is prepared as follows:
(1), vermiculite is placed in reaction container bottom；
(2), ferric sulfate solution in ethyl alcohol and aqueous solution and is mixed in another reaction container, obtains ferric sulfate mixing
Liquid；
(3), ferric sulfate mixed liquor is placed in reaction vessel, and is passed through in nitrogen removal reaction vessel into reaction vessel
Oxygen in solution；
(4), sodium borohydride is dissolved in ethyl alcohol and aqueous solution in another vessel, sodium borohydride solution obtained；
(5), in nitrogen environment, sodium borohydride solution is added dropwise in reaction vessel, after being added dropwise to complete, lasting stirring makes
Fully reacting obtains support type vermiculite suspension；
Its chemical equation is as follows:
(6), filtration load type vermiculite suspension obtains black particle object, then washs black with the deionized water of deoxidation
Particulate matter, then black particle object is washed with the dehydrated alcohol of deoxidation, black particle object is dried with vacuum drier, obtains vermiculite load
Nano zero valence iron.
Vermiculite as described above loads nanometer iron-based material to the fixing means of heavy metal-polluted soil lead, further explains
For,
The granularity of the vermiculite is 180-220 mesh；
The ethyl alcohol and aqueous solution are formulated by volume by 1 part of ethyl alcohol and 1 part of water；
Vermiculite additional amount ratio in the reaction vessel are as follows: a ferric sulfate mixed liquor is added in 0.45g vermiculite；Every portion sulphur
The amount ratio of ferric sulfate and ethyl alcohol and aqueous solution in sour iron mixed liquor are as follows: 0.5356g is added in the ethyl alcohol and aqueous solution of every 5ml
Ferric sulfate；
In obtained sodium borohydride solution step, the amount ratio of ethyl alcohol and aqueous solution and sodium borohydride are as follows: the second of every 10ml
The sodium borohydride of 0.4g is used in pure and mild aqueous solution；
Described is added dropwise to sodium borohydride solution in reaction vessel, specifically: sodium borohydride solution is poured into buret
In, it is added dropwise in reaction vessel with the speed of 1~2 drop per second；
The lasting stirring makes fully reacting, specifically: persistently stir 20-40min；
The method of the filtration load type vermiculite suspension are as follows: carried out support type vermiculite suspension using miillpore filter
Filtering removal, obtains black particle object；
The deionized water of the importing deoxidation washs black particle object, specifically: import the deionized water of 150ml deoxidation
Wash black particle object, and in this way and wash repeatedly three times；
The dehydrated alcohol for importing deoxidation washs black particle object, specifically: import the dehydrated alcohol of 100ml- deoxidation
Wash black particle object, and in this way and wash repeatedly three times.
Vermiculite as described above loads nanometer iron-based material to the fixing means of heavy metal-polluted soil lead, further explains
For it is that vermiculite loads nano ferriferrous oxide that the vermiculite, which loads nanometer iron-based material,.
Vermiculite as described above loads nanometer iron-based material to the fixing means of heavy metal-polluted soil lead, further explains
For the vermiculite load nano ferriferrous oxide is prepared as follows:
(1), FeCl2 is dissolved in oxygen deionized water in a reservoir, going oxygen deionized water is 80 DEG C, is obtained
FeCl2 solution；
(2), FeCl3 is dissolved in oxygen deionized water by another extracting container, and going oxygen deionized water is 80 DEG C, is obtained
FeCl3 solution；
(3), FeCl2 solution and FeCl3 solution are mixed into a container, and mole of FeCl2 therein and FeCl3
Mass ratio 1:2；It is heated using 98-100 DEG C；Vermiculite is added, it is lasting to stir, obtain vermiculite mixed liquor；
(4), the sodium hydroxide solution of 5molL-1 is instilled in vermiculite mixed liquor, and pH is adjusted to 9-11, must loaded
Type vermiculite suspension, lasting stirring are warming up to 90 DEG C or more until support type vermiculite suspension；Fixed 30min；
(5), stop heating and naturally cool to room temperature；
(6), oxygen deionized water washing vermiculite suspension is spent, until pH reaches 6.3-7.8；
(7), the material after washing is dried and is pulverized, obtain vermiculite load nano ferriferrous oxide.
Vermiculite as described above loads nanometer iron-based material to the fixing means of heavy metal-polluted soil lead, further explains
For the oxygen deionized water of going is 80 DEG C；
It is described when being dissolved in FeCl3 in oxygen deionized water, the FeCl3 of addition is 1.05 times excessive or more；
The addition vermiculite is specifically, be added vermiculite 0.9g；
Described dries the material after washing, specifically, the material after washing is dried in vacuum drying oven with 105 DEG C
It does, obtains solid pharmaceutical preparation, solid pharmaceutical preparation is pulverized to obtain vermiculite load nano ferriferrous oxide；
The vermiculite load nano ferriferrous oxide saves in vacuum desiccator.
The invention has the benefit that
The present invention can use the nanometer iron-based material of vermiculite load and effectively fix to heavy metal-polluted soil lead；It is native to administering
Earth heavy metal lead has the effect of fabulous.
Detailed description of the invention
Fig. 1 vermiculite and support type vermiculite scanning electron microscope result.
The variation of Fig. 2 vermiculite and support type vermiculite to soil pH.
The variation of Fig. 3 vermiculite and support type vermiculite to Lead speciation in soil.
The fixed effect of Fig. 4 vermiculite and support type vermiculite to lead in soil.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the specific embodiment of the invention and
Technical solution of the present invention is clearly and completely described in corresponding attached drawing.
Embodiment one:
Vermiculite is loaded nanometer iron-based material to mix with by the soil of heavy metal lead pollution, it is fixed to obtain heavy metal lead
Soil, its ratio be (by weight): by 100 parts of soil of heavy metal lead pollution, vermiculite loads nanometer iron-based material 0.2-5
Part.
Vermiculite is loaded nanometer iron-based material to be added to according to the above ratio in the soil of heavy metal lead pollution, keeps its mixing equal
It is even, obtain mixed soil.
Then deionized water is added in mixed soil, so that water content in mixed soil is greater than 30%, mixes well.
Mixed soil after mixing thoroughly is in ventilation curing, is cured 15-20 days；Consolidate mixed soil heavy metal lead
It is fixed.
Embodiment two:
Vermiculite is loaded nanometer iron-based material to mix with by the soil of heavy metal lead pollution, it is fixed to obtain heavy metal lead
Soil, its ratio be (by weight): by 100 parts of soil of heavy metal lead pollution, vermiculite loads nanometer iron-based material 0.2-1.6
Part.
Vermiculite is loaded nanometer iron-based material to be added to according to the above ratio in the soil of heavy metal lead pollution, keeps its mixing equal
It is even, obtain mixed soil.
Then deionized water is added in mixed soil, so that water content in mixed soil is greater than 30%, mixes well.
Mixed soil after mixing thoroughly is in ventilation curing, is cured 15-20 days；Make in the soil by heavy metal lead pollution
Heavy metal lead be fixed.
In the present invention, vermiculite loads nano zero valence iron preparation method, and the specific method is as follows:
Firstly, reaction based on theory be following formula:
Therefore the present invention production vermiculite load nano zero valence iron process in, various reagents, material additive amount press
Above-mentioned formula derives.
The synthetic reaction of vermiculite load nano zero valence iron carries out in the three-neck flask of 500mL.
Ethyl alcohol used in during it and aqueous solution are formulated by volume by 1 part of ethyl alcohol and 1 part of water.
First by 0.45g vermiculite (200 mesh) be placed in three-neck flask bottom, weigh 0.5356g ferric sulfate, be dissolved in second alcohol and water
In solution, mechanical stirring makes it be uniformly mixed acquisition ferric sulfate mixed liquor, and then ferric sulfate mixed liquor is placed in three-neck flask,
It is passed through the oxygen in nitrogen removal reaction vessel in solution.Excessive sodium borohydride 0.4g, which is weighed, according to reaction equation is dissolved in 10mL
Ethyl alcohol and aqueous solution in, then sodium borohydride solution obtained pours into sodium borohydride solution in buret.In the guarantor of nitrogen
Under shield, sodium borohydride solution is added in three-neck flask with the speed of 1~2 drop per second, is added dropwise to complete to sodium borohydride solution
Afterwards, continue to stir 30min, make fully reacting, obtain support type vermiculite suspension.
After reaction, black particle object is attracted to focus on three-neck flask bottom with strong magnets, it will using miillpore filter
Support type vermiculite suspension is filtered, and collects black particle object, and the deionized water of deoxidation is then imported into black particle object
Washed product three times, uses water 150ml every time.Finally import the anhydrous second of deoxidation again into the black particle object after washing three times again
Alcohol washed product three times, finally dried with vacuum drier, obtain leech by each dosage 100ml by the black particle object that washing is completed
Stone loads nano zero valence iron.And it is placed in vacuum equipment and saves.
In the present invention, vermiculite load nano ferriferrous oxide the preparation method is as follows:
In a reservoir by FeCl2It is dissolved in 150mL oxygen deionized water, going oxygen deionized water is 80 DEG C, is obtained
FeCl2Solution.
Another device is by FeCl3It is dissolved in 150mL to go in oxygen deionized water, going oxygen deionized water is 80 DEG C, obtains FeCl3
Solution；
The FeCl that will be obtained in above-mentioned two step2Solution and FeCl3Solution is mixed into a container, and therein
FeCl2With FeCl3Molal weight ratio 1:2；The FeCl being added in the above process2It is preferably appropriate excessive.
Container is placed in 98-100 DEG C of water-bath.
Then 0.9g vermiculite is added into container and obtains vermiculite suspension under lasting stirring.
By 5molL-1Sodium hydroxide solution instilled in vermiculite suspension dropwise pH be adjusted to 9-11, lasting stirring is straight
90 DEG C or more are warming up to vermiculite suspension, fixed 30min.
From being taken out after container is cooled to room temperature in water-bath, the washing of oxygen deionized water is spent, until pH is close to neutrality
(pH6.3-7.8), it is dried in vacuum drying oven with 105 DEG C, obtains vermiculite load nano ferriferrous oxide.It is being dried in vacuo after grinding
It is saved in device.
It is as follows that nanometer iron-based material characterization situation is loaded using vermiculite made from the above method:
This test loads nano zero-valence to vermiculite after vermiculite (V) before loading and load using field emission scanning electron microscope (SEM)
Iron (V@nZVI), vermiculite load surface nano ferriferrous oxide (V@Fe3O4) carry out analysis comparison.
The detection of support type vermiculite fixed effect:
(1), more parts of 50.0g soil sample are accurately weighed, is placed in 250ml beaker.
(2), respectively add vermiculite, vermiculite load nano zero valence iron, vermiculite load three kinds of materials of nano ferriferrous oxide into
The fixed test of row.And during the test, vermiculite or the vermiculite load that every 1kg in the soil of heavy metal lead pollution, is added
The additive amount of nano zero valence iron or vermiculite load nano ferriferrous oxide is equal are as follows: 0,2.0,4.0,8.0,16.0g.3 weights are set
Retrial is tested, and after three kinds of materials are added, 20ml deionized water is added in each beaker, mixes well, and is placed in ventilation and is cured 2 weeks.
After fixation, with quartering obtain it is fixed after soil, sieved with 100 mesh sieve after being ground it is to be measured, it is subsequent testing soil pH, solid
Fixed front and back Lead speciation variation, Pb in Soil exchange state changes of contents and toxicity characteristic leaching procedure.
Test result:
Sem analysis, with reference to Fig. 1 vermiculite and support type vermiculite scanning electron microscope result.
A:3000 times of vermiculite in Fig. 1；B:10000 times of vermiculite in Fig. 1；
C:10000 times of vermiculite in Fig. 1 loads nano zero valence iron；D:30000 times of vermiculite in Fig. 1 loads nano zero-valence；
D:10000 times of vermiculite in Fig. 1 loads nano ferriferrous oxide；F:30000 times of vermiculite in Fig. 1 loads nanometer four
Fe 3 O.
It is found by scanning electron microscope, all vermiculite surface smoothers of this test, stratiform gully space structure is presented, and have
By high surface area (a and b in Fig. 1), this structure facilitates iron-based material in the fixation on its surface.By test process,
One layer of uniform particle covering is secured on the surface of vermiculite otherwise smooth, and graininess covering can be derived for magnetism zero
Valence iron (c and d in Fig. 1) and magnetic ferroferric oxide (e and f in Fig. 1), by being surveyed under Electronic Speculum to iron-based material partial size
Amount finds that its partial size is less than 100nm, shows that iron-based material of this test load on vermiculite is four oxygen of nano zero valence iron and nanometer
Change three-iron.
Influence of the support type vermiculite to soil pH:
It can be seen from the variation of Fig. 2 vermiculite and support type vermiculite to soil pH vermiculite, vermiculite load nano zero valence iron,
The addition of vermiculite load nano ferriferrous oxide produces influence to soil pH value, and with the increase of fixative dosage, soil
Earth pH is gradually increased, but different to two kinds of support type vermiculite influence degrees.When increasing to 16g/kg with applied amount, leech
The soil pH that stone, vermiculite load nano zero valence iron, vermiculite load nano ferriferrous oxide is increased to respectively by original 6.76
Maximum value 7.01,7.90,7.28, improves 0.25,1.14,0.52 respectively.Vermiculite after loading iron-based material is than unsupported
Vermiculite pH improves 0.27~0.89.Unsupported vermiculite is still greater than in the elevation amplitude of support type vermiculite soil pH, and through receiving
Influence of the vermiculite of rice Zero-valent Iron load to soil is much larger than the vermiculite loaded through nano ferriferrous oxide.
Influence of the support type vermiculite to Lead speciation in soil:
After adding fixative, 4 kinds of chemical form changes of contents of heavy metal in soil Pb are shown in Fig. 3 (vermiculite and support type leech
Variation of the stone to Lead speciation in soil).
From figure 3, it can be seen that three kinds of material processing reduce Acid extractable lead content in soil, wherein vermiculite is loaded
The effect of nano zero valence iron is the most significant, and Acid extractable lead content is reduced to 546.87mg/kg from 718.81mg/kg, reduces
Amplitude reaches 23.92%.The reduction sequence of three kinds of processing is vermiculite load nano zero valence iron (23.92%) > vermiculite load nanometer
Ferroso-ferric oxide (13.25%) > vermiculite (7.51%).Support type vermiculite can promote reduced rate than unsupported vermiculite highest
16.41%.Meanwhile three kinds of material processing increase residual form lead content in soil, wherein vermiculite loads nano zero valence iron
Effect is the most significant, and residual form lead content is increased to 222.58mg/kg from 128.94, and elevation amplitude reaches 42.07%.At three kinds
The raising sequence of reason is vermiculite load nano zero valence iron (42.07%) > vermiculite load nano ferriferrous oxide (34.49%) >
Vermiculite (27.73%).Support type vermiculite can promote rate of rise 14.34% than unsupported vermiculite highest.In addition to this, three kinds of materials
It handles while reducing iron and manganese oxides reference state lead content in soil, and increase organically combine state lead content in soil, but
It is unobvious to increase the range of decrease.
It can be seen that the addition of fixative reduces the weak acid extractable lead content of Pb in soil and improves residual form
Lead content, the Acid extractable of lead is most easily by bio-absorbable, and residual form cannot be bioavailable, and illustrate the addition of fixative
Its biological effectiveness is reduced, the effect that vermiculite loads nano zero valence iron is the most obvious.
Fixed effect of the support type vermiculite to Pb in Soil:
From Fig. 4 (fixed effect of vermiculite and support type vermiculite to lead in soil) as can be seen that vermiculite, vermiculite load nanometer
The addition of Zero-valent Iron, vermiculite load nano ferriferrous oxide can reduce the content of exchange state Pb in soil, and can inhibit it
Leaching content illustrates that vermiculite and support type vermiculite have certain fixed effect to Pb in soil.Also, with the increasing of fixed dosage
Add, the content of exchange state Pb and leaching content gradually decrease in soil, and bioavailability reduces, and fixed efficiency increases.Meanwhile it is negative
Load type vermiculite than vermiculite fixed effect more preferably.
From the point of view of the content of exchange state Pb in soil, when reaching 16g/kg with vermiculite additive amount, exchange state Pb in soil
Content 116.88mg/kg is reduced to by original 274.65mg/kg, reduce 57.45%, and vermiculite loads nano zero-valence
The content of exchange state Pb is then reduced to 32.28mg/kg, 99.93mg/ in iron, vermiculite load nano ferriferrous oxide soil
Kg reduces 88.25%, 63.62% respectively, therefore, it can be seen that vermiculite load nano zero valence iron can significantly reduce soil
The content of middle exchange state lead, it is suppressed that the activity of lead in soil, and vermiculite is compared, it is negative that vermiculite loads nano zero valence iron, vermiculite
It carries nano ferriferrous oxide and improves 30.80% and 6.17% respectively than vermiculite.Thus illustrate, support type vermiculite in soil to handing over
The reduction amplitude for changing state Pb content is bigger, and vermiculite load nano zero valence iron loads nano ferriferrous oxide reducing effect than vermiculite
It is more significant.
From the point of view of the toxicity leaching content of Pb in soil, when reaching 16g/kg with vermiculite additive amount, the leaching of Pb in soil
Amount has been gradually lowered to 288.00mg/kg from 400.14mg/kg, and fixed efficiency reaches 28.03%.And add vermiculite load nanometer
Zero-valent Iron and vermiculite load nano ferriferrous oxide, and when additive amount reaches 16g/kg, the leaching content of Pb is respectively reached in soil
218.54mg/kg, 261.68mg/kg, fixed efficiency improve 45.38%, 34.60%, therefore illustrate that vermiculite loads nanometer
Zero-valent Iron and vermiculite load nano ferriferrous oxide fixed efficiency are higher than vermiculite, and load the fixed effect of the vermiculite of nano zero valence iron
The fixed efficiency of vermiculite of the rate than loading nano ferriferrous oxide is more significant.
Above embodiment is used to illustrate the present invention, rather than limits the invention, in spirit of the invention
In scope of protection of the claims, to any modifications and changes that the present invention makes, protection scope of the present invention is both fallen within.
Claims (10)
1. vermiculite loads nanometer iron-based material to the fixing means of heavy metal-polluted soil lead, which is characterized in that vermiculite is loaded nanometer
Iron-based material is mixed with by the soil of heavy metal lead pollution, obtains the fixed soil of heavy metal lead.
2. vermiculite as described in claim 1 loads nanometer iron-based material to the fixing means of heavy metal-polluted soil lead, feature exists
In loading the mixed proportion of nanometer iron-based material by weight by the soil of heavy metal lead pollution and vermiculite are as follows:
By 100 parts of soil of heavy metal lead pollution, nanometer iron-based material 0.2-5 parts of vermiculite load.
3. vermiculite as described in claim 1 loads nanometer iron-based material to the fixing means of heavy metal-polluted soil lead, feature exists
In loading the mixed proportion of nanometer iron-based material by weight by the soil of heavy metal lead pollution and vermiculite are as follows:
By 100 parts of soil of heavy metal lead pollution, nanometer iron-based material 0.2-1.6 parts of vermiculite load.
4. the vermiculite as described in claim 2-3 loads nanometer iron-based material to the fixing means of heavy metal-polluted soil lead, feature
It is, the mixed method of nanometer iron-based material is loaded by the soil of heavy metal lead pollution and vermiculite are as follows:
(1), vermiculite is loaded nanometer iron-based material to be added in proportion in the soil by heavy metal lead pollution, keeps its mixing equal
It is even；Obtain mixed soil；
(2), deionized water is added into mixed soil again, so that water content in mixed soil is greater than 30%, mixes well；
(3), the mixed soil after mixing thoroughly is in ventilation curing, cured 15-20 days；Make the heavy metal lead quilt in mixed soil
It is fixed.
5. vermiculite as described in claim 1 loads nanometer iron-based material to the fixing means of heavy metal-polluted soil lead, feature exists
In it is that vermiculite loads nano zero valence iron that the vermiculite, which loads nanometer iron-based material,.
6. vermiculite as claimed in claim 5 loads nanometer iron-based material to the fixing means of heavy metal-polluted soil lead, feature exists
In the vermiculite load nano zero valence iron is prepared as follows:
(1), vermiculite is placed in reaction container bottom；
(2), ferric sulfate solution in ethyl alcohol and aqueous solution and is mixed in another reaction container, obtains ferric sulfate mixed liquor；
(3), ferric sulfate mixed liquor is placed in reaction vessel, and is passed through solution in nitrogen removal reaction vessel into reaction vessel
In oxygen；
(4), sodium borohydride is dissolved in ethyl alcohol and aqueous solution in another vessel, sodium borohydride solution obtained；
(5), in nitrogen environment, sodium borohydride solution is added dropwise in reaction vessel, after being added dropwise to complete, lasting stirring makes to react
Completely, support type vermiculite suspension is obtained；
Its chemical equation is as follows:
(6), filtration load type vermiculite suspension obtains black particle object, then washs black particle with the deionized water of deoxidation
Object, then black particle object is washed with the dehydrated alcohol of deoxidation, black particle object is dried with vacuum drier, obtains vermiculite load nanometer
Zero-valent Iron.
7. vermiculite as claimed in claim 6 loads nanometer iron-based material to the fixing means of heavy metal-polluted soil lead, feature exists
In the granularity of the vermiculite is 180-220 mesh；
The ethyl alcohol and aqueous solution are formulated by volume by 1 part of ethyl alcohol and 1 part of water；
Vermiculite additional amount ratio in the reaction vessel are as follows: a ferric sulfate mixed liquor is added in 0.45g vermiculite；Every portion ferric sulfate
The amount ratio of ferric sulfate and ethyl alcohol and aqueous solution in mixed liquor are as follows: 0.5356g sulfuric acid is added in the ethyl alcohol and aqueous solution of every 5ml
Iron；
In obtained sodium borohydride solution step, the amount ratio of ethyl alcohol and aqueous solution and sodium borohydride are as follows: the ethyl alcohol of every 10ml and
The sodium borohydride of 0.4g is used in aqueous solution；
Described is added dropwise to sodium borohydride solution in reaction vessel, specifically: sodium borohydride solution is poured into buret, with
The speed of 1~2 drop per second is added dropwise in reaction vessel；
The lasting stirring makes fully reacting, specifically: persistently stir 20-40min；
The method of the filtration load type vermiculite suspension are as follows: be filtered support type vermiculite suspension using miillpore filter
Removal obtains black particle object；
The deionized water of the importing deoxidation washs black particle object, specifically: import the deionized water washing of 150ml deoxidation
Black particle object, and in this way and wash repeatedly three times；
The dehydrated alcohol for importing deoxidation washs black particle object, specifically: the dehydrated alcohol washing for importing 100ml deoxidation is black
Coloured particles object, and in this way and wash repeatedly three times.
8. vermiculite as described in claim 1 loads nanometer iron-based material to the fixing means of heavy metal-polluted soil lead, feature exists
In it is that vermiculite loads nano ferriferrous oxide that the vermiculite, which loads nanometer iron-based material,.
9. vermiculite as claimed in claim 8 loads nanometer iron-based material to the fixing means of heavy metal-polluted soil lead, feature exists
In the vermiculite load nano ferriferrous oxide is prepared as follows:
(1), in a reservoir by FeCl2It is dissolved in oxygen deionized water, going oxygen deionized water is 80 DEG C, obtains FeCl2It is molten
Liquid；
(2), another extracting container is by FeCl3It is dissolved in oxygen deionized water, going oxygen deionized water is 80 DEG C, obtains FeCl3It is molten
Liquid；
(3), by FeCl2Solution and FeCl3Solution is mixed into a container, and FeCl therein2With FeCl3Molal weight ratio
1:2；It is heated using 98-100 DEG C；Vermiculite is added, it is lasting to stir, obtain vermiculite mixed liquor；
(4), by 5molL-1Sodium hydroxide solution instill in vermiculite mixed liquor, and pH is adjusted to 9-11, obtains support type leech
Stone suspension, lasting stirring are warming up to 90 DEG C or more until support type vermiculite suspension；Fixed 30min；
(5), stop heating and naturally cool to room temperature；
(6), oxygen deionized water washing vermiculite suspension is spent, until pH reaches 6.3-7.8；
(7), the material after washing is dried and is pulverized, obtain vermiculite load nano ferriferrous oxide.
10. vermiculite as claimed in claim 9 loads nanometer iron-based material to the fixing means of heavy metal-polluted soil lead, feature exists
In the oxygen deionized water of going is 80 DEG C；
It is described by FeCl3When being dissolved in oxygen deionized water, the FeCl of addition3It is 1.05 times excessive or more；
The addition vermiculite is specifically, be added vermiculite 0.9g；
Described dries the material after washing, specifically, the material after washing is dried in vacuum drying oven with 105 DEG C, obtains
Solid pharmaceutical preparation, by solid pharmaceutical preparation pulverize to obtain vermiculite load nano ferriferrous oxide；
The vermiculite load nano ferriferrous oxide saves in vacuum desiccator.
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