CN103894404A - Method for restoring heavy metal contaminated soil - Google Patents
Method for restoring heavy metal contaminated soil Download PDFInfo
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- CN103894404A CN103894404A CN201410080088.2A CN201410080088A CN103894404A CN 103894404 A CN103894404 A CN 103894404A CN 201410080088 A CN201410080088 A CN 201410080088A CN 103894404 A CN103894404 A CN 103894404A
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Abstract
The invention discloses a method for restoring heavy metal contaminated soil. The method comprises the following steps: with crylic acid modified chitosan as a restoring agent, placing polluted soil in a restoring agent aqueous solution and stirring and eluting, or applying the restoring agent aqueous solution to a paddy field to be ploughed and ploughing so as to transfer heavy metal from the polluted soil into eluent to realize restoring of heavy metal (Pb, Cr, Cu) contaminated soil. The crylic acid modified chitosan restoring agent is prepared by Michael reaction of chitosan and crylic acid, has the advantages of environmental friendliness, non-toxic and no harm, biodegradable property, no secondary pollution and rich material source. The restoring agent is good restoring effect for heavy metal contaminated soil, and the heavy metal content of restored soil reaches the primary standard of a farmland field. The chitosan derivative restoring agent is green, good in water solubility and high in chelating capability of heavy metal.
Description
Technical field
The present invention relates to a kind of environmental friendliness and the method for restoration of soil polluted by heavy metal cheaply, be specifically related to a kind of method of restoration of soil polluted by heavy metal.
Background technology
Agricultural land soil is subject to after heavy metal pollution, can affect vegetation growth state, plant entirety growing way variation, and root system development is bad, and overground part growth is short and small, the eclipsed distortion of blade, fruit deformity, final agricultural output declines, and quality constantly declines.And the heavy metal such as lead, manganese, copper, mercury, cadmium enters human body by food chain and is difficult to equally remove, it is very long in human body metabolism's cycle, Health cost to people is huge, mainly be gathered in the each large organ of human body, destroy normal physiological metabolism, these pollutants of low dosage just can make organism metabolism get muddled, and induce an illness, even dead.Therefore, the soil of heavy metal pollution being administered and repaired is in field of environment protection, to need one of major issue solving.
At present, heavy metal-polluted soil recovery technique is mainly concentrated on to physics reparation, biotechnology, chemistry reparation etc., and physics reparation energy consumption is large, complex disposal process; Biological restoration limitation is that reparation speed is slow, limited by environmental condition, and repairing quality is difficult to ensure; Traditional chemical stabilizer precipitation recovery technique can cause secondary pollution.Comparing, adopt shitosan and derivative thereof to carry out Adsorption to heavy metal and have that environmental protection, raw material sources are extensive, simple to operate, remediation efficiency advantages of higher, is a kind of economically viable green recovery technique.For agricultural water plough (as paddy rice), suggestion can utilize spring or summer to cultivate to plough a field and harrow a field in (or loosening the soil) spreads renovation agent in water, heavy metal is transferred to water and flowed away from soil, realize the reparation of heavy-metal contaminated soil cheaply.
Summary of the invention
The invention provides a kind of method of restoration of soil polluted by heavy metal, this method adopts acrylic acid modified shitosan as renovation agent, contaminated soil is placed in to the renovation agent aqueous solution and stirs wash-out; Or the renovation agent aqueous solution is put into and treated to plough a field in cultivated paddy field and harrow a field, make in heavy metal transfer water solution, then discharge, realizes the economy reparation of contaminated soil.
The object of the invention is realized by the following technical programs:
(1) choose the serious agricultural district soil of heavy metal pollution;
(2) renovation agent of selecting is acrylic acid modified shitosan;
(3) 3 ~ 10g soil being placed in to concentration is that 0.2%wt ~ 1%wt 100 ~ 200ml renovation agent aqueous solution stirs 0.5 ~ 8h, wash-out; Or renovation agent 5 ~ 15kg is dissolved in the water of 500 ~ 1000L, is applied to 1 mu and treats to plough a field and harrow a field in cultivated paddy field, realize the reparation of heavy metal soil.
In said method, described soil is Pearl River Delta (Guangzhou, Foshan, Dongguan, Jiangmen) agricultural land soil, and all there are industrial area or integrated mill in the place of 500 ~ 1000 m collection place of described soil near; Described integrated mill comprises one or more in Battery Plant, Leather Factory and Electroplate Factory.
In said method, when selecting when soil is placed in to the renovation agent aqueous solution and stirs the method for wash-out, the method of sampling of described soil is: the soil of vertically taking arable layer 0 ~ 15 cm, adopt quincunx five point sampling methods, centered by sample point, within the scope of radius approximately 20 ~ 50 cm, get altogether five samples, and mix.
The advantages such as in said method, the acrylic acid modified shitosan of described renovation agent is that shitosan and acrylic acid are reacted and made by Michael, has environmental protection, nontoxic, biodegradable, and raw material sources are abundant.
In said method, the sample before and after described soil treatment, through pulverizing, is crossed 100 mesh sieve, dries at 120 DEG C and removes moisture, uses full decomposition method to clear up, and then measures the content of heavy metal with ICP-AES instrument.
In said method, described restorative procedure environmental protection is feasible, the water-soluble height of renovation agent, and convenient separation, can flow away along with rainfall and pouring process, departs from soil; Remediation efficiency is high, to heavy metal Pb, and Cr, the clearance best result of Cu is not 93%, 79% and 65%, after repairing, the content of beary metal of soil reaches agricultural land primary standard.
Compared with prior art, the present invention has the following advantages:
1, renovation agent raw material sources are extensive, unique.Shitosan derives from chitin, on the earth, the biosynthesis amount of annual chitin is billions of tons, wherein halobiontic growing amount, more than 1,000,000,000 tons, can be described as a kind of nexhaustible living resources, is that output is only second to cellulosic natural polymer.Shitosan has unique physicochemical property and biologically active, nontoxic, under nature, be subject to actinomyces effect, progressively degraded, is typical environment-friendly materials, can not cause secondary pollution, stronger to the complexing of heavy metal, become the focus of Recent study Adsorption of Heavy Metals.
2, renovation agent preparation process environmental protection.Compare with the building-up process of conventional EDTA, EGTA, the high pollution of polyacrylic acid isochela condensation material, high energy consumption, high harm, the former preparation process is only taking water as medium, relative environmental protection.
3, the selective height of renovation agent.More EDTA used is as chemical renovation agent both at home and abroad, and EDTA can form stable complex compound with most metal ions, but because the light metal content such as Al intrinsic in soil, Fe, Mg, Ca and K are far away higher than heavy metal.So EDTA easily reduces other tenors in soil, causes lowering soil fertility and impoverishment.And that shitosan and water-soluble modified product thereof have the chelating absorption of heavy metal is good selective, in the time that various metals exists, there is the preferential absorption behavior of obvious heavy metal, its mechanism may be more for the electronic shell of heavy metal and subgrade, there are a large amount of unoccupied orbitals atom inside, easily forms coordinate bond.
4, application innovation.With the degrade practical operation of heavy metal in soil of shitosan and modified product thereof, the present invention has directly verified the repair ability of acrylic acid modified shitosan to heavy metal by research.And restorative procedure of the present invention can be improved soil, Promoting plant growth, improve output, improve the abilities such as quality.Therefore, chitosan modified polymer has the double action of repairing heavy metal in soil and Promoting plant growth.
5, repairing effect is good.To heavy metal in soil Pb, Cr, the clearance best result of Cu is not 93%, 79% and 65%, after repairing, the content of beary metal of soil reaches agricultural land soil primary standard.
6, repair both economical.For rice terrace or water cultivated land, can utilize turns over before plantation discharges renovation agent in ploughing a field and harrowing a field in water, can realize the economy reparation of soil without special processing.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
Acrylic acid modified shitosan synthesis step is as follows: 20g shitosan is joined in the solution that 14 mL acrylic acid and 1000 mL distilled water join to stirring and dissolving.Stirring reaction 1 d at 75 DEG C, then soaks with the sodium hydroxide solution of 1 mol/L, and regulator solution is to pH=10 ~ 12, and (molecular cut off is 12000 g/mol) 2 d dialyse.After freeze-drying, be acrylic acid modified shitosan product, its quality is 22 g, water-soluble all good in the scope of pH=1 ~ 13 of product.
Renovation agent described in embodiment below synthesizes as stated above.
embodiment 1
Near agricultural land soil industrial area, Foshan City, mainly there is Pb in sample, Cr, the various heavy such as Cu are polluted, and content is higher.Earth 3.00 g that fetch earth, in the acrylic acid modified shitosan renovation agent of the 100ml 0.5%wt aqueous solution, continuous stirring 8 h, leave standstill, and filter.Measure three heavy metal species Pb of soil treatment front and back by full decomposition method, Cr, the content of Cu, before processing, the content of Pb, Cr, Cu is respectively 504,213,80.1 mg/kg, content after treatment is respectively 34.1,78.1,33.5 mg/kg, all allow Pb lower than agricultural land soil, Cr, ceiling value (GB15618-1995) 35,90,35 mg/kg of Cu content primary standard.
embodiment 2
Near the agricultural land soil Leather Factory of Guangzhou, mainly there is Pb in sample, Cr, the various heavy such as Cu are polluted, and content is higher.Earth 10.00 g that fetch earth, in the acrylic acid modified shitosan renovation agent of the 200ml 1%wt aqueous solution, continuous stirring 0.5 h, leaves standstill, and filters.Measure three heavy metal species Pb of soil treatment front and back by full decomposition method, Cr, the content of Cu, before processing, the content of Pb, Cr, Cu is respectively 214,413,78.1 mg/kg, content after treatment is respectively 21.5,89.2,31.5 mg/kg, all allow Pb lower than agricultural land soil, Cr, ceiling value (GB15618-1995) 35,90,35 mg/kg of Cu content primary standard.
embodiment 3
Near agricultural land soil Dongguan City Electroplate Factory, mainly there is Pb in sample, Cr, the various heavy such as Cu are polluted, and content is higher.Earth 6.00 g that fetch earth, in the acrylic acid modified shitosan renovation agent of the 150ml 0.2%wt aqueous solution, continuous stirring 3 h, leave standstill, and filter.Measure three heavy metal species Pb of soil treatment front and back by full decomposition method, Cr, the content of Cu, before processing, the content of Pb, Cr, Cu is respectively 257,433,108 mg/kg, content after treatment is respectively 31.8,88.7,34.9 mg/kg, all allow Pb lower than agricultural land soil, Cr, ceiling value (GB15618-1995) 35,90,35 mg/kg of Cu content primary standard.
embodiment 4
Near agricultural land soil Jiangmen city Battery Plant, mainly there is Pb in sample, Cr, the various heavy such as Cu are polluted, and content is higher.Earth 8.00 g that fetch earth, in the acrylic acid modified shitosan renovation agent of the 100ml 0.5%wt aqueous solution, continuous stirring 5 h, leave standstill, and filter.Measure three heavy metal species Pb of soil treatment front and back by full decomposition method, Cr, the content of Cu, before processing, the content of Pb, Cr, Cu is respectively 536,213,68.3 mg/kg, content after treatment is respectively 34.9,62.3,23.9 mg/kg, all allow Pb lower than agricultural land soil, Cr, ceiling value (GB15618-1995) 35,90,35 mg/kg of Cu content primary standard.
embodiment 5
Near paddy rice ground industrial area, Foshan City, cultivated and is evenly applied to 1 mu after 10kg renovation agent being dissolved in to 1000L water in ploughing a field and harrowing a field and ploughs a field in treating cultivated paddy field and harrow a field in spring.Measure three heavy metal species Pb of soil treatment front and back by full decomposition method, Cr, the content of Cu, before processing, the content of Pb, Cr, Cu is respectively 354,213,78.1 mg/kg, content after treatment is respectively 33.9,87.1,29.2 mg/kg, all allow Pb lower than agricultural land soil, Cr, ceiling value (GB15618-1995) 35,90,35 mg/kg of Cu content primary standard.
Above-mentioned specific embodiment does further and describes the present invention, but specific embodiment does not do any restriction to the present invention.
Claims (7)
1. a method for restoration of soil polluted by heavy metal, is characterized in that, concrete grammar is:
(1) choose the serious agricultural district soil of heavy metal pollution;
(2) renovation agent of selecting is acrylic acid modified shitosan;
(3) 3 ~ 10g soil being placed in to concentration is that 0.2%wt ~ 1%wt 100 ~ 200ml renovation agent aqueous solution stirs wash-out, or renovation agent 5 ~ 15kg is dissolved in the water of 500 ~ 1000L, is applied to 1 mu and treats to plough a field and harrow a field in cultivated paddy field, realize the reparation of heavy metal soil.
2. the method for a kind of restoration of soil polluted by heavy metal according to claim 1, is characterized in that, described soil is Pearl River Delta agricultural land soil, and all there are industrial area or integrated mill in the place of 500 ~ 1000 m collection place of described soil near; Described integrated mill comprises one or more in Battery Plant, Leather Factory and Electroplate Factory.
3. the method for a kind of restoration of soil polluted by heavy metal according to claim 1, it is characterized in that, when selecting when soil is placed in to the renovation agent aqueous solution and stirs the method for wash-out, the method of sampling of described soil is: the soil of vertically taking arable layer 0 ~ 15 cm, adopt quincunx five point sampling methods, centered by sample point, within the scope of radius approximately 20 ~ 50 cm, get altogether five samples, and mix.
4. the method for a kind of restoration of soil polluted by heavy metal according to claim 1, is characterized in that, the acrylic acid modified shitosan of described renovation agent is that shitosan and acrylic acid are reacted and made by Michael.
5. the method for a kind of restoration of soil polluted by heavy metal according to claim 1, is characterized in that, the mixing time of described stirring is 0.5 ~ 8h.
6. the method for a kind of restoration of soil polluted by heavy metal according to claim 1, is characterized in that, the sample before and after described soil treatment is through pulverizing, cross 100 mesh sieve, at 120 DEG C, dry and remove moisture, use full decomposition method to clear up, then measure the content of heavy metal with ICP-AES instrument.
7. the method for a kind of restoration of soil polluted by heavy metal according to claim 1, is characterized in that, described method is to heavy metal Pb, Cr, the clearance best result of Cu is not 93%, 79% and 65%, and after repairing, the content of beary metal of soil reaches agricultural land primary standard.
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Cited By (8)
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| CN104492802A (en) * | 2014-12-15 | 2015-04-08 | 山东省环境保护科学研究设计院 | Method for reducing and stabilizing chromium-contaminated soil by chemical-biological coupling |
| CN107876551A (en) * | 2017-08-24 | 2018-04-06 | 中国科学院地理科学与资源研究所 | Eight treasures (choice ingredients of certain special dishes) red-spotted stonecrop repairs method, activator and the application of cadmium and/or lead-contaminated soil |
| CN108380650A (en) * | 2018-01-30 | 2018-08-10 | 上海岩土工程勘察设计研究院有限公司 | The points distributing method that Polluted Soil stir in situ uniformity differentiates |
| CN108901559A (en) * | 2018-07-23 | 2018-11-30 | 中国水利水电科学研究院 | A kind of coal field vegetation repair method |
| CN109092888A (en) * | 2018-08-22 | 2018-12-28 | 山西华欣久泰科技有限公司 | A kind of mixing restorative procedure of heavy-metal contaminated soil |
| CN110026417A (en) * | 2019-03-29 | 2019-07-19 | 北京建工环境修复股份有限公司 | A kind of restorative procedure in heavy metal pollution arable land |
| CN110293120A (en) * | 2019-07-10 | 2019-10-01 | 广东粤风环保有限公司 | A kind of method of restoration of soil polluted by heavy metal |
| CN112342024A (en) * | 2020-09-16 | 2021-02-09 | 浙江绿农生态环境有限公司 | Soil modification method |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104492802A (en) * | 2014-12-15 | 2015-04-08 | 山东省环境保护科学研究设计院 | Method for reducing and stabilizing chromium-contaminated soil by chemical-biological coupling |
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| CN107876551A (en) * | 2017-08-24 | 2018-04-06 | 中国科学院地理科学与资源研究所 | Eight treasures (choice ingredients of certain special dishes) red-spotted stonecrop repairs method, activator and the application of cadmium and/or lead-contaminated soil |
| CN108380650A (en) * | 2018-01-30 | 2018-08-10 | 上海岩土工程勘察设计研究院有限公司 | The points distributing method that Polluted Soil stir in situ uniformity differentiates |
| CN108901559A (en) * | 2018-07-23 | 2018-11-30 | 中国水利水电科学研究院 | A kind of coal field vegetation repair method |
| CN109092888A (en) * | 2018-08-22 | 2018-12-28 | 山西华欣久泰科技有限公司 | A kind of mixing restorative procedure of heavy-metal contaminated soil |
| CN110026417A (en) * | 2019-03-29 | 2019-07-19 | 北京建工环境修复股份有限公司 | A kind of restorative procedure in heavy metal pollution arable land |
| CN110293120A (en) * | 2019-07-10 | 2019-10-01 | 广东粤风环保有限公司 | A kind of method of restoration of soil polluted by heavy metal |
| CN112342024A (en) * | 2020-09-16 | 2021-02-09 | 浙江绿农生态环境有限公司 | Soil modification method |
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