CN105170620B - A kind of method of magnetic active carbon collaboration activator restoration of soil polluted by heavy metal - Google Patents
A kind of method of magnetic active carbon collaboration activator restoration of soil polluted by heavy metal Download PDFInfo
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- CN105170620B CN105170620B CN201510635125.6A CN201510635125A CN105170620B CN 105170620 B CN105170620 B CN 105170620B CN 201510635125 A CN201510635125 A CN 201510635125A CN 105170620 B CN105170620 B CN 105170620B
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Abstract
The invention discloses a kind of methods of magnetic active carbon collaboration activator restoration of soil polluted by heavy metal, include the following steps：（1）Activator is added into heavy-metal contaminated soil, turns over uniformly, activates 20~30d；（2）Magnetic active carbon is added in the soil of heavy metal pollution after activation, turns over uniformly, adsorbs 20~30d；（3）The magnetic active carbon is recycled using the mode of magnetic separation；（4）By step（3）The magnetic active carbon of middle recycling uses 1~2h of acid soak of 0.1mol/L~0.5mol/L, then is washed with deionized water to neutrality, and magnetic active carbon recycles；（5）By step（4）The heavy metal removal in acid solution after elution；（6）Circulation step（1）~（5）, until heavy metal in soil content is up to standard.After method using the present invention recycles reparation three times, the content of the heavy metal in soil of heavy metal pollution can reach secondary standard, and this method is simple, and efficiently, the period is short.
Description
Technical field
The present invention relates to contaminated soils to administer field, more particularly to a kind of magnetic active carbon collaboration activator remediating heavy metal
The method of contaminated soil.
Background technology
The existing heavy metal pollution in China is ploughed about 300,000,000 mu, and the overwhelming majority is not administered reasonably, and with work
The discharge for the waste that the industries such as the fast development of agricultural, mining, smelting, plating, chemical industry generate and irrigation, agriculture chemical
Unreasonable utilization also aggravating soil heavy metal pollution situation.
There are mainly two types of the approach for administering heavy metal pollution of soil in the prior art, first, changing heavy metal in the soil
Existence reduces its migration and bioavailability in the environment, including deep ploughing, casting method and modifying agent method
Deng wherein deep ploughing can cause the pollutant in topsoil to spread, and heavy metal is possible to be activated in deep soil；
Although casting method can be greatly reduced content of beary metal, the soil for can also cause surface layer fertile soil loss simultaneously, digging out is difficult
The problems such as to post-process；Temporarily heavy metal can only be fixed in the soil using modifying agent, heavy metal is reduced and entered by plant
Human body, but cannot thoroughly dispose heavy metal from soil, also there are hidden danger.Another method is that duplicate removal is removed from soil
Metal, the method that heavy metal is removed from soil include chemical leaching method and phytoremediation, and chemical leaching method can reduce weight
The Phyto-availability of metal, but can make to lose a large amount of nutritional ingredient in soil simultaneously, while use the side of chemical leaching
Method is it is also possible to can cause the acidification of soil either to be alkalized；And use phytoremediation method be drawn by botanical system,
Accumulation, volatilization and heavy metal removed from soil to reduce heavy metal pollution, the cost of this method than less expensive, and
It is environmentally protective, but plant to the suction-operated of heavy metal there are one saturation capacity, and the period of phytoremediation is long,
The recycling problem of heavy metal is also a very big problem.Therefore, the weight in the soil of heavy metal pollution how is efficiently removed
Metal, and the heavy metal in soil can also be recycled, it is a urgent problem to be solved.
Invention content
In order to solve the above technical problems, the object of the present invention is to provide a kind of magnetic active carbon collaboration activators to repair a huge sum of money
Belong to the method for contaminated soil, this method can efficiently remove heavy metal in heavy-metal contaminated soil and to heavy metal into
Row recycling.
In order to achieve the above objectives, the technical solution adopted by the present invention is：
A kind of method of magnetic active carbon collaboration activator restoration of soil polluted by heavy metal, includes the following steps：
（1）Activator is added into heavy-metal contaminated soil, turns over uniformly, activates 20~30d；
（2）Magnetic active carbon is added into the heavy-metal contaminated soil after activation, turns over uniformly, adsorbs 20~30d；
（3）Utilize the mode recycling step of magnetic separation（2）In magnetic active carbon；
（4）By step（3）1~2h of acid soak of the magnetic active carbon of middle recycling 0.1mol/L~0.5mol/L, then
It is washed with deionized water to neutrality；
（5）Recycling step（4）Heavy metal in the acid solution used；
（6）Circulation step（1）~（5）, until heavy metal in soil content is up to standard；
The step（1）Middle activator includes the raw material of following parts by weight：30~50 parts of fruit/vegetable waste, weathered coal 30~
50 parts and 20~30 parts of organic fertilizer.
Preferably, the step（1）The additive amount of middle activator is 15~20g/m2。
Preferably, the step（2）The additive amount of middle magnetic active carbon is 8~10g/m2。
Preferably, the step（4）In acid solution be HCl, H2SO4And HNO3In one kind.
Preferably, the step（1）The preparation of middle activator includes the following steps：
Fruit/vegetable waste and weathered coal are weighed, is 20~30 DEG C in temperature, moisture is retting under conditions of 50~60%
After 20~30d, drying to water content is 10%~15%, smashes it through 30~50 mesh sieve, is uniformly mixed, that is, is prepared into organic fertilizer
To activator.
Preferably, the organic fertilizer is feces of livestock and poultry through organic fertilizer made of retting.
Preferably, the step（2）The preparation method of middle magnetic active carbon is：
By 10~15 parts by weight FeSO4·7H2O and 10~25 parts by weight FeCl3·6H2O is dissolved in deionized water, then
30~60 parts by weight of activated carbon are added in, are heated to 40~60 DEG C, stir 40min~60min；Alkaline solution is added dropwise extremely while stirring
Then solution alkaline cures 3h~4h in 100 DEG C of water-baths, is cooled to 20~30 DEG C, is washed with deionized to neutrality,
The magnetisable material of generation is isolated with magnet, 4h~5h is dried at 100~110 DEG C, that is, magnetic active carbon is prepared.
Preferably, the alkaline solution is NaOH, KOH and NH3·H2One kind in O.
The beneficial effects of the invention are as follows：
The present invention cooperates with activator come the soil of repairing heavy metal pollution using magnetic active carbon, first will be native using activator
Then heavy metallic activation in earth is adsorbed the heavy metal in soil using magnetic active carbon, finally recycles magnetic active carbon, wash
Recycling after de-, and the heavy metal in eluent can be then recovered.
Activator is to be mixed using after fruit/vegetable waste and weathered coal retting with organic fertilizer, and fruit/vegetable waste is to use
The waste of fruits and vegetables in daily life, such as apple, lemon, grape and the pericarp of orange and vegetables are discarded
Object containing a large amount of organic matter, the elements such as cellulose and N, P, K in these fruit/vegetable wastes, and is nontoxic；Wind
Change and then contain a large amount of humic acid in coal；After fruit/vegetable waste and the fermentation of weathered coal retting, the humic acid in weathered coal will
It can be activated, and humic acid is the conditioner of soil, can improve the physicochemical property of soil, increasing soil fats up, activating soil
In metallic element；And containing a large amount of organic acid in the fruit/vegetable waste after fermenting, and organic acid can dissociate in the soil
Into proton and low molecular organic acid, proton can cause the variation of the pH value and oxidation-reduction potential in environment, promote soil
The weathering course of dissolution of heavy metal host mineral in earth.And the organic fertilizer used in activator is feces of livestock and poultry through made of retting
Organic fertilizer contains in the organic fertilizer there are many organic acid, peptides and the abundant nutrient including nitrogen, phosphorus, potassium, not only
Full nutrition can be provided, and fertilizer efficiency is long for crops, can increase and update the soil organism, promote microbial reproduction, improved
The physicochemical property and bioactivity of soil.
The magnetic active carbon used in the present invention is prepared ferrite load using infusion process on the activated carbon, activity
Containing a large amount of micropore on charcoal, there is very big specific surface area, there is very strong adsorption capacity, load iron to the heavy metal in soil
Activated carbon after oxysome is magnetic.It, will be magnetic using the mode of magnetic separation after magnetic active carbon adsorbs heavy metal in the soil
Activated carbon recycles, and is eluted the heavy metal on magnetic active carbon using acid solution after recycling, and the magnetism after elution is living
Property charcoal can also recycle after being washed till neutrality using deionized water, environmentally protective.
Therefore, it is of the invention that activator is cooperateed with come the beneficial of the method for restoration of soil polluted by heavy metal using magnetic active carbon
Effect is mainly reflected in：
（1）It, can be in activating soil containing a large amount of organic acid, humic acid and abundant nutrient in activator
Heavy metal, increase and the update soil organism, promote microbial reproduction, improve the physicochemical property and soil activation of soil；
（2）The heavy metal in the soil through overactivation, suction of the magnetic active carbon to heavy metal are adsorbed using magnetic active carbon
Attached ability is strong, and the magnetic active carbon for adsorbing heavy metal can be recycled by way of magnetic separation, and the magnetism after recycling is living
Property charcoal using acid soak elution after, the heavy metal of magnetic active carbon absorption is eluted into acid solution, then will magnetic activity
Charcoal is washed to neutrality, and magnetic active carbon is recycled after drying, and the heavy metal in acid solution is recycled, environmentally protective
Efficiently.
Specific embodiment
With reference to specific embodiment, the invention will be further described.
Experiment soil is selected from contaminated by heavy metals one piece of arable land near the mining area of Henan, and pollutant includes zinc, lead,
Cadmium, copper, mercury, arsenic.The arable land is divided into 7 pieces of regions, each region difference label 1#, 2#, 3#, 4#, 5#, 6# and 7#, every piece
40 × 50m of region, every piece of region set 5 sampled points, acquire total 35 of the soil sample of 0~20cm in heavy-metal contaminated soil, mix
After closing uniformly, according to GB5085.3-2007《Hazardous waste judging standard leaching characteristic identification》In the method listed to soil
In content of beary metal be measured.After testing, the heavy metal Zn in the soil of the heavy metal pollution, Pb, Cd, Cu, Hg, As,
Cr concentration is respectively：380.6mg/kg, 150.3 mg/kg, 25.87 mg/kg, 300.1mg/kg, 19.43 mg/kg,
68.5mg/kg, 389.2 mg/kg, pH value 6.6.
According to GB15618-2008《National Soil-environmental standard》The environment second level standard value of middle soil inorganic pollutant,
Zn, Pb, Cd during agriculture nonirrigated farmland pH6.5~7.5, Cu, Hg, the secondary standard value of As, Cr are respectively 250,80,0.45,100,
0.7,30,200mg/kg, therefore, there is more serious heavy metal pollution in block arable land.
Embodiment 1
A kind of method of magnetic active carbon collaboration activator restoration of soil polluted by heavy metal, includes the following steps：
（1）Activator is added into 1# heavy-metal contaminated soils, the additive amount of activator is 15g/m2, turn over the soil on surface layer
Earth is turned over uniformly, makes soil activating 20d；
（2）Magnetic active carbon is added in the soil of heavy metal pollution after activation, the additive amount of magnetic active carbon is 8g/
m2, the soil on surface layer is turned over, is turned over uniformly, keeping soil moisture, magnetic adsorbent acts on 20d in the soil 15%~20%,
The heavy metal in soil is made to be attracted on magnetic active carbon；
（3）It is uniform that magnetic active carbon is made into used Soil tillage, magnetic active carbon is isolated using magnetic separator；
（4）By step（3）The magnetic active carbon of middle recycling impregnates 1h using 0.5mol/L HCl liquid, then is washed with deionized water
To neutrality, magnetic active carbon can be recycled；
（5）Recycling step（4）Heavy metal in middle acid solution；
（6）If by detection, the content of beary metal in soil is exceeded, recycles above-mentioned steps（1）~（5）, until in soil
Content of beary metal comply with standard until.
Wherein activator includes the raw material of following parts by weight：20 parts of 30 parts of fruit/vegetable waste, 50 parts of weathered coal and organic fertilizer.
The preparation method of activator is：The fruit/vegetable waste and 50 parts by weight weathered coals of 30 parts by weight are weighed, is in temperature
20 DEG C, for retting after 20 days, drying to water content is 10% under conditions of moisture is 50%, 30 mesh sieve is smashed it through, with 20 weights
Amount part organic fertilizer is uniformly mixed, that is, activator is prepared.
The preparation method of wherein organic fertilizer is：By chicken manure, pig manure and cow dung, moisture contains at a temperature of 20 DEG C~30 DEG C
Measure be 30% under the conditions of retting 30d, dry to water content is 10%, smashes it through 30 mesh sieve, that is, organic fertilizer is prepared.
The preparation method of wherein magnetic active carbon is：By 10 parts by weight FeSO4·7H2O and 25 parts by weight FeCl3·6H2O
It is dissolved in deionized water, then adds in 30 parts by weight of activated carbon, be heated to 40 DEG C, stir 60min；It is added dropwise while stirring
Then 0.5mol/LNaOH cures 3h in 100 DEG C of water-baths, is cooled to 20~30 DEG C, is washed with deionized water to solution alkaline
It washs to neutrality, the magnetisable material of generation is isolated with magnet, be placed in baking oven at 100 DEG C dry 5h, that is, magnetism is prepared
Activated carbon.
It recycles after repairing three times, the content of pH value and heavy metal in detection soil, Zn, Pb, Cd, Cu in soil,
The content of Hg, As, Cr are respectively 180.8mg/kg, 75.9 mg/kg, 0.4 mg/kg, 89.6 mg/kg, 0.7 mg/kg, 24.5
Mg/kg, 180.6 mg/kg, pH value 6.8, heavy metal in soil content reach soil safety standard.
Embodiment 2
A kind of method of magnetic active carbon collaboration activator restoration of soil polluted by heavy metal, includes the following steps：
（1）Activator is added into 2# heavy-metal contaminated soils, the additive amount of activator is 16g/m2, turn over the soil on surface layer
Earth is turned over uniformly, makes soil activating 22d；
（2）Magnetic active carbon is added in the soil of heavy metal pollution after activation, the additive amount of magnetic active carbon is 9g/
m2, the soil on surface layer is turned over, is turned over uniformly, keeping soil moisture, magnetic active carbon acts on 23d in the soil 15%~20%,
The heavy metal in soil is made to be attracted on magnetic active carbon；
（3）It is uniform that magnetic active carbon is made into used Soil tillage, magnetic active carbon is isolated using magnetic separator；
（4）By step（3）The magnetic active carbon of middle recycling uses 0.1mol/LHNO3Liquid impregnates 2h, then is washed with deionized water
To neutrality, magnetic active carbon can be recycled；
（5）Recycling step（4）Heavy metal in middle acid solution；
（6）If by detection, the content of beary metal in soil is exceeded, recycles above-mentioned steps（1）~（5）, until in soil
Content of beary metal comply with standard until.
Wherein activator includes the raw material of following parts by weight：30 parts of 35 parts of fruit/vegetable waste, 45 parts of weathered coal and organic fertilizer.
The preparation method of activator is：The fruit/vegetable waste and 45 parts by weight weathered coals of 35 parts by weight are weighed, is in temperature
30 DEG C, for retting after 24 days, drying to water content is 15% under conditions of moisture is 53%, smashes it through 50 mesh sieve；With 30 weights
Amount part organic fertilizer is uniformly mixed, that is, activator is prepared.
The preparation method of wherein organic fertilizer is：By chicken manure, pig manure and cow dung, moisture is at 20 DEG C~30 DEG C
Retting 20d under the conditions of 50%, drying to water content are 15%, smash it through 50 mesh sieve, that is, organic fertilizer is prepared.
The preparation method of wherein magnetic active carbon is：
By 12 parts by weight FeSO4·7H2O and 10 parts by weight FeCl3·6H2O is dissolved in deionized water, then adds in 40 weights
Part activated carbon is measured, is heated to 50 DEG C, stirs 55min；The KOH of 0.5mol/L is added dropwise while stirring to solution alkaline, Ran Hou
4h is cured in 100 DEG C of water-baths, 20 DEG C~30 DEG C is cooled to, is washed with deionized to neutrality, generation is isolated with magnet
Magnetisable material is placed in baking oven at 105 DEG C dry 4h, that is, magnetic active carbon is prepared.
It recycles after repairing three times, the content of pH value and heavy metal in detection soil, Zn, Pb, Cd, Cu in soil,
The content of Hg, As, Cr are respectively 170.9 mg/kg, 68.3 mg/kg, 0.36 mg/kg, 89.2 mg/kg, 0.64 mg/kg,
22.6 mg/kg, 160.7 mg/kg, pH value 6.8, heavy metal in soil content reach soil safety standard.
Embodiment 3
A kind of method of magnetic active carbon collaboration activator restoration of soil polluted by heavy metal, includes the following steps：
（1）Activator is added into 3# heavy-metal contaminated soils, the additive amount of activator is 17g/m2, turn over the soil on surface layer
Earth is turned over uniformly, makes soil activating 25d；
（2）Magnetic active carbon is added in the soil of heavy metal pollution after activation, the additive amount of magnetic active carbon is
10g/m2, the soil on surface layer is turned over, is turned over uniformly, keeping soil moisture, magnetic active carbon acts in the soil 15%~20%
26d makes the heavy metal in soil be attracted on magnetic active carbon；
（3）It is uniform that magnetic active carbon is made into used Soil tillage, magnetic active carbon is isolated using magnetic separator；
（4）By step（3）The magnetic active carbon of middle recycling uses 0.1mol/LH2SO4Liquid impregnates 1.5h, then uses deionized water
Neutrality is washed till, magnetic active carbon can be recycled；
（5）Recycling step（4）Heavy metal in middle acid solution；
（6）If by detection, the content of beary metal in soil is exceeded, recycles above-mentioned steps（1）~（5）, until in soil
Content of beary metal comply with standard until.
Wherein activator includes the raw material of following parts by weight：25 parts of 40 parts of fruit/vegetable waste, 40 parts of weathered coal and organic fertilizer.
The preparation method of activator is：The fruit/vegetable waste and 40 parts by weight weathered coals of 40 parts by weight are weighed, is in temperature
25 DEG C, for retting after 26 days, drying to water content is 12% under conditions of moisture is 56%, smashes it through 40 mesh sieve；With 25 weights
Amount part organic fertilizer is uniformly mixed, that is, activator is prepared.
The preparation method of wherein organic fertilizer is：By chicken manure, pig manure and cow dung, moisture is at 20 DEG C~30 DEG C
Retting 26d under the conditions of 40%, drying to water content are 12%, smash it through 40 mesh sieve, that is, organic fertilizer is prepared.
The preparation method of wherein magnetic active carbon is：
By 13 parts by weight FeSO4·7H2O and 15 parts by weight FeCl3·6H2O is dissolved in deionized water, then adds in 50 weights
Part activated carbon is measured, is heated to 45 DEG C, stirs 45min；The NH of 0.5mol/L is added dropwise while stirring3·H2O is to solution alkaline, so
3.5h is cured in 100 DEG C of water-baths afterwards, 20 DEG C~30 DEG C is cooled to, is washed with deionized to neutrality, is isolated with magnet
The magnetisable material of generation is placed in baking oven at 110 DEG C dry 4.5h, that is, magnetic active carbon is prepared.
After cycle is repaired three times, Zn, Pb, Cd, Cu in the content soil of the pH value and heavy metal in soil are detected,
The content of Hg, As, Cr are respectively 100.5 mg/kg, 60.5 mg/kg, 0.29 mg/kg, 85.0 mg/kg, 0.59 mg/kg,
20.8 mg/kg, 130.1 mg/kg, pH value 7.0, heavy metal in soil content reach soil safety standard.
Embodiment 4
A kind of method of magnetic active carbon collaboration activator restoration of soil polluted by heavy metal, includes the following steps：
（1）Activator is added into 4# heavy-metal contaminated soils, the additive amount of activator is 18g/m2, turn over the soil on surface layer
Earth is turned over uniformly, makes soil activating 28d；
（2）Magnetic active carbon is added in the soil of heavy metal pollution after activation, the additive amount of magnetic active carbon is
8.5g/m2, the soil on surface layer is turned over, is turned over uniformly, keeping soil moisture, magnetic active carbon acts in the soil 15%~20%
28d makes the heavy metal in soil be attracted on magnetic active carbon；
（3）It is uniform that magnetic active carbon is made into used Soil tillage, magnetic activity is isolated using magnetic separator；
（4）By step（3）The magnetic active carbon of middle recycling uses 0.2mol/LH2SO4Liquid impregnates 2h, then is washed with deionized water
To neutrality, magnetic active carbon can be recycled；
（5）Recycling step（4）Heavy metal in middle acid solution；
（6）If by detection, the content of beary metal in soil is exceeded, recycles above-mentioned steps（1）~（5）, until in soil
Content of beary metal comply with standard until.
Wherein activator includes the raw material of following parts by weight：22 parts of 45 parts of fruit/vegetable waste, 35 parts of weathered coal and organic fertilizer.
The preparation method of activator is：The fruit/vegetable waste and 35 parts by weight weathered coals of 45 parts by weight are weighed, is in temperature
28 DEG C, under conditions of moisture is 58% after retting 28d, drying to water content is 13%, smashes it through 35 mesh sieve；With 22 weight
Part organic fertilizer is uniformly mixed, that is, activator is prepared.
The preparation method of organic fertilizer is：By chicken manure, pig manure and cow dung, moisture is 45% at 20 DEG C~30 DEG C
Retting 28d under part, drying to water content are 12%, smash it through 35 mesh sieve, that is, organic fertilizer is prepared.
The preparation method of wherein magnetic active carbon is：
By 14 parts by weight FeSO4·7H2O and 20 parts by weight FeCl3·6H2O is dissolved in deionized water, then adds in 60 weights
Part activated carbon is measured, is heated to 55 DEG C, stirs 50min；The NH of 0.5mol/L is added dropwise while stirring3·H2O is to solution alkaline, so
3.5h is cured in 100 DEG C of water-baths afterwards, 20 DEG C~30 DEG C is cooled to, is washed with deionized to neutrality, is isolated with magnet
The magnetisable material of generation is placed in baking oven at 110 DEG C dry 4.5h, that is, magnetic active carbon is prepared.
It recycles after repairing three times, the content of pH value and heavy metal in detection soil, Zn, Pb, Cd, Cu in soil,
The content of Hg, As, Cr are respectively 145.8 mg/kg, 74.2 mg/kg, 0.32 mg/kg, 83.2 mg/kg, 0.52 mg/kg,
25.8 mg/kg, 150.9 mg/kg, pH value 7.2, heavy metal in soil content reach soil safety standard.
Embodiment 5
A kind of method of magnetic active carbon collaboration activator restoration of soil polluted by heavy metal, includes the following steps：
（1）Activator is added into 5# heavy-metal contaminated soils, the additive amount of activator is 20g/m2, turn over the soil on surface layer
Earth is turned over uniformly, makes soil activating 30d；
（2）Magnetic active carbon is added in the soil of heavy metal pollution after activation, the additive amount of magnetic active carbon is
9.5g/m2, the soil on surface layer is turned over, is turned over uniformly, keeping soil moisture, magnetic active carbon acts in the soil 15%~20%
30d makes the heavy metal in soil be attracted on magnetic active carbon；
（3）It is uniform that magnetic active carbon is made into used Soil tillage, magnetic active carbon is isolated using magnetic separator；
（4）By step（3）The magnetic active carbon of middle recycling uses 0.3mol/LH2SO4Liquid impregnates 2h, then is washed with deionized water
To neutrality, magnetic active carbon can be recycled；
（5）Recycling step（4）Heavy metal in middle acid solution.
（6）If by detection, the content of beary metal in soil is exceeded, recycles above-mentioned steps（1）~（5）, until in soil
Content of beary metal comply with standard until.
Wherein activator includes the raw material of following parts by weight：28 parts of 50 parts of fruit/vegetable waste, 30 parts of weathered coal and organic fertilizer.
The preparation method of activator is：The fruit/vegetable waste and 30 parts by weight weathered coals of 50 parts by weight are weighed, is in temperature
22 DEG C, for retting after 30 days, drying to water content is 15% under conditions of moisture is 60%, smashes it through 45 mesh sieve；With 28 weights
Amount part organic fertilizer is uniformly mixed, that is, activator is prepared.
The preparation method of wherein organic fertilizer is：By chicken manure, pig manure and cow dung, moisture is at 20 DEG C~30 DEG C
Retting 30d under the conditions of 40%, drying to water content are 15%, smash it through 45 mesh sieve, that is, organic fertilizer is prepared.
The preparation method of wherein magnetic active carbon is：
By 15 parts by weight FeSO4·7H2O and 23 parts by weight FeCl3·6H2O is dissolved in deionized water, then adds in 45 weights
Part activated carbon is measured, is heated to 60 DEG C, stirs 40min；The NaOH of 0.5mol/L is added dropwise while stirring to solution alkaline, Ran Hou
4h is cured in 100 DEG C of water-baths, 20 DEG C~30 DEG C is cooled to, is washed with deionized to neutrality, generation is isolated with magnet
Magnetisable material is placed in baking oven at 105 DEG C dry 4.5h, that is, magnetic active carbon is prepared.
It recycles after repairing three times, the content of pH value and heavy metal in detection soil, Zn, Pb, Cd, Cu in soil,
The content of Hg, As, Cr are respectively 120.8 mg/kg, 76.8 mg/kg, 0.42 mg/kg, 86.7 mg/kg, 0.61 mg/kg,
27.6 mg/kg, 154.8 mg/kg, pH value 7.1, heavy metal in soil content reach soil safety standard.
Comparative example 1
Comparative example 1 repairs the soil of 6# heavy metal pollutions using condition same as Example 3, and the difference lies in do not make
Use activator.
After cycle is repaired three times, the content of the pH value and heavy metal in soil is detected, content of beary metal has been in earth
Decline, but soil safety standard is not fully achieved, Zn in soil, Pb, Cd, Cu, Hg, As, the content of Cr is respectively 256.3
Mg/kg, 78.0 mg/kg, 1.96 mg/kg, 94.3 mg/kg, 5.81 mg/kg, 27.9 mg/kg, 250.7 mg/kg, pH value
It is 6.6.
Comparative example 2
Comparative example 1 repairs the soil of 7# heavy metal pollutions using condition same as Example 3, and the difference lies in use
The organic fertilizer prepared in embodiment 3 replaces activator.
After cycle is repaired three times, the content of the pH value and heavy metal in soil is detected, content of beary metal has been in earth
Decline, but soil safety standard is not fully achieved, Zn in soil, Pb, Cd, Cu, Hg, As, the content of Cr is respectively 200.4
Mg/kg, 70.6mg/kg, 1.02 mg/kg, 90.4mg/kg, 3.28mg/kg, 49.7mg/kg, 210.3mg/kg, pH value are
6.7。
The repairing effect of heavy-metal contaminated soil
The heavy metal pollution of 7 pieces of 40 × 50m is repaired by above-described embodiment 1~5 and this 7 kinds of methods of comparative example 1 and 2
Arable land, the initial content of pH value, heavy metal before reparation in heavy-metal contaminated soil（mg/kg）And heavy metal after repairing
Content（mg/kg）Three aspects test to restorative procedure, as shown in table 1.
1 heavy-metal contaminated soil of table repairs testing result
After being repaired using the method for Examples 1 to 5 to the soil of 1#~5# heavy metal pollutions, pH value exists in soil
In the range of 6.8~7.1, according to GB15618-2008《National Soil-environmental standard》The environment second of middle soil inorganic pollutant
Grade standard value, Zn, Pb, Cd during agriculture nonirrigated farmland pH6.5~7.5, Cu, Hg, the secondary standard value of As, Cr are respectively 250,80,
0.45,100,0.7,30,200mg/kg, as can be seen from Table 1, the heavy metal before repairing in the soil of the block heavy metal pollution
Content is all above secondary standard value, and testing result shows that the restorative procedure of Examples 1 to 5 can will be native by cycle three times
Content of beary metal in earth is reduced to secondary standard value；And without using activator in comparative example 1, by cycle reparation three times
Afterwards, the content of beary metal in the 6# regions does not reach the standard value of two level then；Manure use replaces activator in comparative example 2,
Content of beary metal after recycling three times in 7# regional soils does not also reach secondary standard, but comparative example 2 is to heavy metal
Removal rate be better than comparative example 1, if it is indicated above that soil without overactivation, the heavy metal in soil is deposited mostly with reference state
Heavy metal existing for reference state is not easy to be adsorbed by magnetic active carbon, and the heavy metal in Organic Manure on Soil has certain work
Change acts on, and activator is added into soil, heavy metal that can be in activating soil, and heavy metal is promoted to change to ionic condition,
It is adsorbed by magnetic active carbon.
Claims (6)
- A kind of 1. method of magnetic active carbon collaboration activator restoration of soil polluted by heavy metal, which is characterized in that including following step Suddenly：（1）Activator is added into heavy-metal contaminated soil, turns over uniformly, activates 20~30d；（2）Magnetic active carbon is added into the heavy-metal contaminated soil after activation, turns over uniformly, adsorbs 20~30d；（3）Utilize the mode recycling step of magnetic separation（2）In magnetic active carbon；（4）By step（3）1~2h of acid soak of the magnetic active carbon of middle recycling 0.1mol/L~0.5mol/L, then spend Ion is washed to neutrality；（5）Recycling step（4）Heavy metal in the acid solution used；（6）Circulation step（1）~（5）, until heavy metal in soil content is up to standard；The step（1）Middle activator includes the raw material of following parts by weight：30~50 parts of fruit/vegetable waste, 30~50 parts of weathered coal With 20~30 parts of organic fertilizer；The step（2）The preparation method of middle magnetic active carbon is：By 10~15 parts by weight FeSO4·7H2O and 10~25 parts by weight FeCl3·6H2O is dissolved in deionized water, then adds in 30 ~60 parts by weight of activated carbon are heated to 40~60 DEG C, stir 40min~60min；Alkaline solution to solution is added dropwise while stirring is in Then alkalinity cures 3h~4h in 100 DEG C of water-baths, is cooled to 20~30 DEG C, is washed with deionized to neutrality, use magnet The magnetisable material of generation is isolated, 4h~5h is dried at 100~110 DEG C, that is, magnetic active carbon is prepared；The step（1）The preparation of middle activator includes the following steps：Weigh fruit/vegetable waste and weathered coal, temperature be 20~30 DEG C, moisture be 50~60% under conditions of retting 20~ After 30d, drying to water content is 10%~15%, smashes it through 30~50 mesh sieve, is uniformly mixed with organic fertilizer, that is, work is prepared Agent.
- 2. the method for magnetic active carbon collaboration activator restoration of soil polluted by heavy metal according to claim 1, feature It is, the step（1）The additive amount of middle activator is 15~20g/m2。
- 3. the method for magnetic active carbon collaboration activator restoration of soil polluted by heavy metal according to claim 1, feature It is, the step（2）The additive amount of middle magnetic active carbon is 8~10g/m2。
- 4. the method for magnetic active carbon collaboration activator restoration of soil polluted by heavy metal according to claim 1, feature It is, the step（4）In acid solution be HCl, H2SO4And HNO3In one kind.
- 5. the method for magnetic active carbon collaboration activator restoration of soil polluted by heavy metal according to claim 1, feature It is, the organic fertilizer is feces of livestock and poultry through organic fertilizer made of retting.
- 6. the method for magnetic active carbon collaboration activator restoration of soil polluted by heavy metal according to claim 1, feature It is, the alkaline solution is NaOH, KOH and NH3·H2One kind in O.
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