CN110076192A - A kind of in-situ remediation method of heavy-metal contaminated soil - Google Patents
A kind of in-situ remediation method of heavy-metal contaminated soil Download PDFInfo
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- CN110076192A CN110076192A CN201910466171.6A CN201910466171A CN110076192A CN 110076192 A CN110076192 A CN 110076192A CN 201910466171 A CN201910466171 A CN 201910466171A CN 110076192 A CN110076192 A CN 110076192A
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- soil
- heavy
- chitosan
- metal contaminated
- contaminated soil
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
Abstract
The invention discloses a kind of in-situ remediation methods of heavy-metal contaminated soil；Spinning solution is hybridly prepared into using chitosan, molysite, chitosan/zeroth order Nanoscale Iron composite fibre is obtained through electrostatic spinning, it is twisted into again via twisting machine and glass fibre with heavy metal adsorption reducing power and has the composite adsorption rope of some strength, and net is made, it is embedded in the soil of heavy metal pollution, it takes out, complete the absorption in situ of heavy metal-polluted soil and removes after a period of time.It is environment-friendly high-efficiency, easy to operate the method achieve the in-situ immobilization of heavy-metal contaminated soil, it overcomes traditional adsorbent material and is difficult to the drawbacks of separating from soil.
Description
Technical field
The present invention relates to soil remediation more particularly to a kind of in-situ remediation methods of heavy-metal contaminated soil.
Background technique
Heavy-metal contaminated soil has the characteristics that the period is long, difficult, and soil remediation method effect is poor, costly at present,
So the soil remediation of heavy metal pollution has become the key subjects of environment protection field.Heavy metal pollution not only causes the group of soil
At the variation of, structure and function, additionally it is possible to inhibit crop root growth and photosynthesis, crop failure is caused even to have no harvest.More
To seriously endanger animal, human health importantly, heavy metal is also possible to move to animal by food chain, in human body.Cadmium
The heavy metal pollutions such as rice, arsenic poison, blood lead endanger all reports common in recent years.
The mainly fixed passivating technique of heavy metals exceeding standard soil in-situ Treatment process, phytoremediation technology and adsorbent method.
Fixed passivating technique refers to by the way that fixative is added into soil, adjusts and change the physical chemistry of heavy metal in the soil
Matter makes it generate the series reactions such as precipitating, absorption, ion exchange, humification and oxidationreduction, reduces it in soil environment
In biological effectiveness and transportable property, to reduce these heavy metal elements to the toxicity of animals and plants.But no matter which kind of is applied
Fixative, the heavy metal for being finally adsorbed passivation all stay in the soil, and may be with the change of environmental condition, biological effectiveness
It may also restore, soil is caused to pollute repeatedly；A kind of pollution control means of the phytoremediation as green, ecology with higher
The shortcomings that benefit, but that there are kinds is insufficient, takes a long time, the agriculture underproduction.Adsorbent then can adsorb or convert heavy metal, be allowed to send out
Raw migration, but it enter soil after be difficult to separate, and may leak downwards, polluted underground water.Therefore, it studies a kind of without secondary dirt
The heavy-metal adsorption material and processing method contaminate, is cheap, easily separating from soil have prior meaning to soil remediation
Justice.
Summary of the invention
The shortcomings that it is an object of the invention to overcome the above-mentioned prior art and deficiency provide a kind of heavy-metal contaminated soil
In-situ remediation method.Spinning solution is hybridly prepared into using chitosan, molysite, obtains chitosan/zeroth order Nanoscale Iron through electrostatic spinning
Composite fibre, then be twisted into glass fibre with heavy metal adsorption reducing power via twisting machine and have answering for some strength
Absorption rope is closed, and net is made, is embedded in the soil of heavy metal pollution, is taken out after a period of time, complete heavy metal-polluted soil
Absorption and removal in situ.It is environment-friendly high-efficiency, easy to operate the method achieve the in-situ immobilization of heavy-metal contaminated soil, it overcomes
Traditional adsorbent material is difficult to the drawbacks of separating from soil.The present invention have it is heavy metal ion adsorbed it is high-efficient, without secondary
The advantages of pollution, adsorbent material are easily separated from soil.
The present invention is achieved through the following technical solutions:
A kind of in-situ remediation method of heavy-metal contaminated soil, the specific steps are as follows:
Step 1: being dissolved in acetic acid or formic acid for chitosan, molysite be added thereto, is passed through nitrogen 1~2h of deoxygenation, and machinery stirs
Mix it is lower be added potassium borohydride into mixed solution, stir 0.5~1h to obtain mixed solution；Polyethylene is added into mixed solution
Alcohol, 80~95 DEG C of 3~5h of closed stirring, is made into spinning solution, and carry out electrostatic spinning, it is compound to obtain chitosan/zeroth order Nanoscale Iron
Fiber；
Step 2: using twisting machine by the chitosan of step 1/zeroth order Nanoscale Iron composite fibre and glass fibre composite twist
It is made for a composite adsorption rope, and is made into netted, obtains composite adsorption net；
Step 3: the composite adsorption net of step 2 being embedded in the soil of heavy metal pollution, from soil after placing 10~30 days
It is taken out in earth, completes the in-situ immobilization of soil.
Acetic acid described in above-mentioned steps one or formic acid concn are 15%~25%；The molysite be ferric sulfate, ferric phosphate,
One or more of ferric nitrate；The mixing speed is 300~5000 revs/min.
Spinning solution described in above-mentioned steps one forms by weight, wherein 15~20 parts of chitosan, acetic acid or formic acid 25
~30 parts, 10~15 parts of molysite, 3~4 parts of potassium borohydride, 60~80 parts of polyvinyl alcohol.
During electrostatic spinning described in above-mentioned steps one, humidity is 40~50%, and voltage is 25~30kV, and syringe needle is to connecing
Distance by plate is 18~25cm.
The mass ratio of chitosan/zeroth order Nanoscale Iron composite fibre and glass fibre is 1.5:1~2.5 in above-mentioned steps two:
1。
Twisting machine described in above-mentioned steps two uses ring doubling frame, and the composite adsorption rope diameter being twisted into is 2~4mm,
2~20mm of mesh diameter of composite web.
Heavy metal described above is chromium, cadmium, arsenic, mercury, any one or a few in lead.
Composite adsorption net described above places into the soil earth's surface depth as 20~30cm；The soil moisture content be 40~
90%, soil pH value is 3~7 or soil pH value is 4~7.
The present invention compared with the existing technology, have following advantages and effects
There is a large amount of-NH in chitosan2, the functional groups such as-OH, not only there is charge attraction work to heavy metal ion
With, while there are also chelations；Zeroth order Nanoscale Iron has small partial size, extra specific surface area, high reaction activity, strong reducing property and suction
Attached property is even more to show very strong removal ability for heavy metal ion.
The present invention is hybridly prepared into spinning solution using chitosan, molysite, obtains chitosan/zeroth order Nanoscale Iron through electrostatic spinning
Composite fibre, then be twisted into glass fibre with heavy metal adsorption reducing power via twisting machine and have answering for some strength
It closes absorption to restrict and be made into net, is embedded in heavy metals exceeding standard soil, is taken out after a period of time, complete the original position of heavy metal-polluted soil
Absorption and removal.It is environment-friendly high-efficiency, easy to operate the method achieve the in-situ immobilization of heavy-metal contaminated soil, overcome tradition
Adsorbent material is difficult to the problem of separating from soil.
Specific embodiment
The present invention is more specifically described in detail combined with specific embodiments below.
Embodiment 1
(1) chitosan is dissolved in 15% acetic acid solution, ferric sulfate is added thereto, be passed through nitrogen deoxygenation 1h, mechanical stirring
Potassium borohydride is added under (300 revs/min) into mixed solution, high-speed stirred (3000 revs/min) 1h to obtain mixed solution,
Polyvinyl alcohol is added into mixed solution, after the completion of addition, 85 DEG C of closed stirring (500 revs/min) 3h are made into spinning solution,
Middle spinning solution forms by weight, 15 parts of chitosan, 28 parts of acetic acid, 15 parts of ferric sulfate, 4 parts of potassium borohydride, polyvinyl alcohol 80
Part.Electrostatic spinning humidity is 40%, voltage 25kV, and the distance of syringe needle to receiver sheet is 19cm, obtains chitosan/zeroth order nanometer
Iron composite fibre；
(2) chitosan of step (1)/zeroth order Nanoscale Iron composite fibre and glass fibre are pressed by quality using ring doubling frame
It is made for composite adsorption rope, diameter 2mm than 1.5:1 composite twist, and the net that mesh diameter is 2mm is made；
(3) by the soil of composite adsorption net embedment pollution of chromium (3000ppm) of step (2), (water content 70%, pH value are
5) it in, places 15 days, composite adsorption net places into the soil earth's surface depth as 25cm；
The composite adsorption net for adsorbing heavy metal is taken out from soil, completes the in-situ immobilization of soil.It is surveyed by standard HJ491
Determine chromium total amount in soil, residual quantity 200ppm, removal rate 93%.
Embodiment 2
(1) chitosan is dissolved in 20% formic acid solution, ferric phosphate is added thereto, be passed through nitrogen deoxygenation 2h, mechanical stirring
Potassium borohydride is added under (500 revs/min) into mixed solution, high-speed stirred (5000 revs/min) 1h to obtain mixed solution,
Polyvinyl alcohol is added into mixed solution, after the completion of addition, 90 DEG C of closed stirring (1000 revs/min) 3.5h are made into spinning solution,
Wherein spinning solution forms by weight, wherein 17 parts of chitosan, 30 parts of formic acid, 13 parts of ferric phosphate, 3 parts of potassium borohydride, poly- second
75 parts of enol.Electrostatic spinning humidity is 45%, voltage 28kV, and the distance of syringe needle to receiver sheet is 22cm, obtains chitosan/zero
Valence Nanoscale Iron composite fibre；
(2) chitosan of step (1)/zeroth order Nanoscale Iron composite fibre and glass fibre are pressed by quality using ring doubling frame
It is made for composite adsorption rope, diameter 3mm than 2.5:1 composite twist, and the net that mesh diameter is 5mm is made.
(3) the composite adsorption net embedment cadmium of step (2) is stained to the soil (water content 60%, pH value 4) of (10ppm)
In, it places 18 days, composite adsorption net places into the soil earth's surface depth as 22cm；
The composite adsorption net for adsorbing heavy metal is taken out from soil, completes the in-situ immobilization of soil.By standard GB/
T17141 measures cadmium total amount in soil, residual quantity 1ppm, removal rate 90%.
Embodiment 3
(1) chitosan is dissolved in 25% acetic acid solution, ferric sulfate is added thereto, be passed through nitrogen deoxygenation 1h, mechanical stirring
Potassium borohydride is added under (1000 revs/min) into mixed solution, high-speed stirred (4000 revs/min) 1h is molten to obtain mixing
Polyvinyl alcohol is added into mixed solution for liquid, and after the completion of addition, 95 DEG C of closed stirring (400 revs/min) 5h are made into spinning solution,
Wherein spinning solution forms by weight, wherein 19 parts of chitosan, 25 parts of acetic acid, 12 parts of ferric sulfate, 4 parts of potassium borohydride, poly- second
70 parts of enol.Electrostatic spinning humidity is 50%, voltage 25kV, and the distance of syringe needle to receiver sheet is 23cm, obtains chitosan/zero
Valence Nanoscale Iron composite fibre；
(2) chitosan of step (1)/zeroth order Nanoscale Iron composite fibre and glass fibre are pressed by quality using ring doubling frame
It is made for composite adsorption rope, diameter 4mm than 2:1 composite twist, and the net that mesh diameter is 10mm is made；
(3) by the soil of composite adsorption net embedment arsenic pollution (300ppm) of step (2), (water content 40%, pH value are
4) it in, places 22 days, composite adsorption net places into the soil earth's surface depth as 25cm；
(4) the composite adsorption net for adsorbing heavy metal is taken out from soil, completes the in-situ immobilization of soil.By standard GB/
T22105.2 measures arsenic total amount in soil, residual quantity 20ppm, removal rate 93%.
Embodiment 4
(1) chitosan is dissolved in 25% formic acid solution, ferric nitrate is added thereto, be passed through nitrogen deoxygenation 1.5h, machinery stirs
It mixes and potassium borohydride is added under (2000 revs/min) into mixed solution, high-speed stirred (3500 revs/min) 0.5h is to be mixed
Polyvinyl alcohol is added into mixed solution for solution, and after the completion of addition, 85 DEG C of closed stirring (600 revs/min) 4h are made into spinning
Liquid, wherein spinning solution composition by weight, wherein 20 parts of chitosan, 30 parts of formic acid, 15 parts of ferric nitrate, 4 parts of potassium borohydride, poly-
80 parts of vinyl alcohol.Electrostatic spinning humidity is 40%, voltage 29kV, and the distance of syringe needle to receiver sheet is 25cm, obtain chitosan/
Zeroth order Nanoscale Iron composite fibre；
(2) chitosan of step (1)/zeroth order Nanoscale Iron composite fibre and glass fibre are pressed by quality using ring doubling frame
It is made for composite adsorption rope, diameter 3mm than 1.5:1 composite twist, and the net that mesh diameter is 8mm is made；
(3) by the soil (water content 40%, pH value 5) of composite adsorption net embedment mercury pollution (10ppm) of step (2)
In, it places 25 days, composite adsorption net places into the soil earth's surface depth as 30cm；
(4) the composite adsorption net for adsorbing heavy metal is taken out from soil, completes the in-situ immobilization of soil.By standard GB/
T22105.1 measures mercury in soils total amount, residual quantity 1ppm, removal rate 90%.
Embodiment 5
(1) chitosan is dissolved in 21% formic acid solution, ferric phosphate is added thereto, be passed through nitrogen deoxygenation 2h, mechanical stirring
Potassium borohydride is added under (700 revs/min) into mixed solution, high-speed stirred (4500 revs/min) 0.5h is molten to obtain mixing
Polyvinyl alcohol is added into mixed solution for liquid, and after the completion of addition, 95 DEG C of closed stirring (700 revs/min) 3h are made into spinning solution,
Wherein spinning solution forms by weight, wherein 19 parts of chitosan, 28 parts of formic acid, 13 parts of ferric phosphate, 3 parts of potassium borohydride, poly- second
70 parts of enol.Electrostatic spinning humidity is 45%, voltage 26kV, and the distance of syringe needle to receiver sheet is 19cm, obtains chitosan/zero
Valence Nanoscale Iron composite fibre；
(2) chitosan of step (1)/zeroth order Nanoscale Iron composite fibre and glass fibre are pressed by quality using ring doubling frame
It is made for composite adsorption rope, diameter 3mm than 1.8:1 composite twist, and the net that mesh diameter is 20mm is made；
(3) by the soil of composite adsorption net embedment lead contamination (1000ppm) of step (2), (water content 80%, pH value are
6) it in, places 24 days, composite adsorption net places into the soil earth's surface depth as 25cm；
(4) the composite adsorption net for adsorbing heavy metal is taken out from soil, completes the in-situ immobilization of soil.By standard GB/
T17141 measures lead total amount in soil, residual quantity 80ppm, removal rate 92%.
Embodiment 6
(1) chitosan is dissolved in 23% acetic acid solution, ferric sulfate is added thereto, be passed through nitrogen deoxygenation 1h, mechanical stirring
Potassium borohydride is added under (500 revs/min) into mixed solution, high-speed stirred (4500 revs/min) 1h to obtain mixed solution,
Polyvinyl alcohol is added into mixed solution, after the completion of addition, 90 DEG C of closed stirring (800 revs/min) 4h are made into spinning solution,
Middle spinning solution forms by weight, wherein 18 parts of chitosan, 26 parts of acetic acid, 14 parts of ferric sulfate, 4 parts of potassium borohydride, polyethylene
75 parts of alcohol.Electrostatic spinning humidity is 50%, voltage 28kV, and the distance of syringe needle to receiver sheet is 22cm, obtains chitosan/zeroth order
Nanoscale Iron composite fibre；
(2) chitosan of step (1)/zeroth order Nanoscale Iron composite fibre and glass fibre are pressed by quality using ring doubling frame
It is made for composite adsorption rope, diameter 2mm than 2.2:1 composite twist, and the net that mesh diameter is 15mm is made；
(3) soil by the composite adsorption net embedment cadmium of step (2), lead contamination (respectively 10ppm and 1000ppm) (contains
Water is 90%, pH value 7) in, it places 28 days, composite adsorption net places into the soil earth's surface depth as 27cm；
(4) the composite adsorption net for adsorbing heavy metal is taken out from soil, completes the in-situ immobilization of soil.By standard GB/
T17141 measures cadmium and lead total amount in soil, and residual quantity is respectively 1ppm and 100ppm, removal rate 90%.
As described above, the present invention can be better realized.
Embodiment of the present invention are not limited by the above embodiments, other are any without departing from Spirit Essence of the invention
With changes, modifications, substitutions, combinations, simplifications made under principle, equivalent substitute mode should be, be included in of the invention
Within protection scope.
Claims (9)
1. a kind of in-situ remediation method of heavy-metal contaminated soil, which is characterized in that specific step is as follows:
Step 1: being dissolved in acetic acid or formic acid for chitosan, molysite be added thereto, is passed through nitrogen 1~2h of deoxygenation, under mechanical stirring
Potassium borohydride is added into mixed solution, stirs 0.5~1h to obtain mixed solution；Polyvinyl alcohol is added into mixed solution,
80~95 DEG C of 3~5h of closed stirring, are made into spinning solution, and carry out electrostatic spinning, obtain chitosan/compound fibre of zeroth order Nanoscale Iron
Dimension；
Step 2: using twisting machine by the chitosan of step 1/zeroth order Nanoscale Iron composite fibre with glass fibre is compound is twisted into
It for a composite adsorption rope, and is made into netted, obtains composite adsorption net；
Step 3: the composite adsorption net of step 2 being embedded in the soil of heavy metal pollution, after placing 10~30 days from soil
It takes out, completes the in-situ immobilization of soil.
2. the in-situ remediation method of heavy-metal contaminated soil according to claim 1, it is characterised in that: described in step 1
Acetic acid or formic acid concn be 15%~25%；The molysite is one or more of ferric sulfate, ferric phosphate, ferric nitrate；Institute
Stating mixing speed is 300~5000 revs/min.
3. the in-situ remediation method of heavy-metal contaminated soil according to claim 1, it is characterised in that: described in step 1
Spinning solution forms by weight, wherein 25~30 parts of 15~20 parts of chitosan, acetic acid or formic acid, 10~15 parts of molysite, boron hydrogen
Change 3~4 parts of potassium, 60~80 parts of polyvinyl alcohol.
4. the in-situ remediation method of heavy-metal contaminated soil according to claim 1, it is characterised in that: described in step 1
During electrostatic spinning, humidity is 40~50%, and voltage is 25~30kV, and the distance of syringe needle to receiver sheet is 18~25cm.
5. the in-situ remediation method of heavy-metal contaminated soil according to claim 1, it is characterised in that: shell is poly- in step 2
The mass ratio of sugar/zeroth order Nanoscale Iron composite fibre and glass fibre is 1.5:1~2.5:1.
6. the in-situ remediation method of heavy-metal contaminated soil according to claim 1, it is characterised in that: described in step 2
Twisting machine uses ring doubling frame, and the composite adsorption rope diameter being twisted into is 2~4mm, 2~20mm of mesh diameter of composite web.
7. the in-situ remediation method of heavy-metal contaminated soil according to claim 1, it is characterised in that: the heavy metal is
Chromium, cadmium, arsenic, mercury, any one or a few in lead.
8. the in-situ remediation method of heavy-metal contaminated soil according to claim 1, it is characterised in that: the composite adsorption
Net places into the soil earth's surface depth as 20~30cm；The soil moisture content is 40~90%, and soil pH value is 3~7.
9. the in-situ remediation method of heavy-metal contaminated soil according to claim 1, it is characterised in that: the composite adsorption
Net places into the soil earth's surface depth as 20~30cm；The soil moisture content is 40~90%, and soil pH value is 4~7.
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Cited By (1)
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|---|---|---|---|---|
| CN112062876A (en) * | 2020-08-28 | 2020-12-11 | 华南理工大学 | Phosphorylated chitosan derivative and preparation method and application thereof |
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