CN109772871A - A method of glyphosate polluted farmland soil is repaired using subcritical low-temperature extraction technology - Google Patents
A method of glyphosate polluted farmland soil is repaired using subcritical low-temperature extraction technology Download PDFInfo
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- CN109772871A CN109772871A CN201910083381.7A CN201910083381A CN109772871A CN 109772871 A CN109772871 A CN 109772871A CN 201910083381 A CN201910083381 A CN 201910083381A CN 109772871 A CN109772871 A CN 109772871A
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Abstract
The present invention relates to a kind of methods for repairing glyphosate polluted farmland soil using subcritical low-temperature extraction technology.Soil sample is weighed from glyphosate polluted farmland soil；Soil sample is placed in subcritical abstraction kettle, closed extraction kettle, pressure in extraction kettle is promoted to 0.6MPa, organic extractant is made to liquefy at normal temperature；Organic extractant is passed through extraction kettle, organic extractant is made to be in subcritical state, carries out continuous dynamic extraction with soil sample；After the completion of extraction, extract liquor is put into solvent recovery kettle, obtains glyphosate polluted farmland soil extract liquor；Glyphosate polluted farmland soil extract liquor is added to FeSO4In aqueous solution；Then it is added sodium peroxydisulfate, after stir process, glyphosate is almost completely degraded, and realizes the reparation of glyphosate polluted farmland soil.The content of glyphosate is lower than 0.1mg/kg after processing, and more than 99%, the glyphosate polluted in soil sample is almost completely degraded degradation rate.
Description
Technical field
The invention belongs to contaminated soil remediation fields, and in particular to a kind of sweet using subcritical low-temperature extraction technology reparation grass
The method of phosphine polluted farmland soil.
Background technique
Pesticide (Pesticide) refers to agriculturally for preventing and treating the chemical agent of pest and disease damage and coordinate plant growth, in agriculture
It is play an important role in industry production.With the continuous development of modern agriculture, the usage amount and environment remaining quantity of pesticide increase year by year.
Although pesticide plays an important role in plant growing process, all kinds of pest and disease damages can be effectively prevent, promote farming produce
Amount.But pesticide application technology and it is unscientific use etc. due to, cause pesticide residue in soil environment, to human health and
Environmental organism generates pollution and harm.Pesticide has caused people to it from crop or farmland as a kind of environmental contaminants
It is diffused into the concern of agricultural product.
Glyphosate (Glyphosate) is also known as " agriculture reaches ", is organophosphorus herbicide, is that usage amount is maximum in the world at present
One of herbicide kind is widely applied in farmland due to having the feature of efficient, wide spectrum and low toxicity.Glyphosate it is a large amount of
Using the environmental pollution got worse and disruption of ecological balance is caused, have to edaphophyte, animal and microorganism a degree of
Toxic action, and be enriched in the mammalian body along with food chain, to threaten human health.The high usage amount institute of glyphosate
Bring safety problem causes enough concerns of people, how to remove residual contamination of the glyphosate in agricultural land soil and has become
Current urgent problem to be solved.
CN106478291A discloses a kind of method that glyphosate contaminated soil is repaired using soil conditioner, by adding
Enter soil conditioner and promote microorganism growth, to accelerate the solidification and degradation of glyphosate, but the method cannot be in short-term
Interior degradation soil glyphosate.CN104117531A discloses a kind of utilization Subcritical Water Extraction reparation petroleum hydrocarbon contaminated soil
Method, Subcritical Water Extraction has the characteristics that green, efficient, but extraction temperature required for the method is high, energy consumption is high.
Summary of the invention
It is an object of the invention to the glyphosate pollution situations generally existing for agricultural land soil, and it is sweet mainly to provide a kind of grass
The restorative procedure of phosphine polluted farmland soil.Subcritical low-temperature extraction technology is specifically first passed through to separate from soil of getting dirty, extract mesh
Pollutant glyphosate is marked, oxidative degradation then is carried out to the glyphosate of extraction.The technology is expected to be applied to practical farmland glyphosate
Contaminated soil remediation.
The purpose of the present invention is realized by following scheme:
1) soil sample is weighed from glyphosate polluted farmland soil, and 120~200 meshes are crossed after drying, grinding；Soil sample is set
In subcritical abstraction kettle, pressure in extraction kettle is promoted to 0.6MPa by closed extraction kettle, makes organic extractant liquid at normal temperature
Change；
2) organic extractant is passed through extraction kettle, adjusts temperature in extraction kettle to 30~55 DEG C, pressure to 0.71~
1.30Mpa makes organic extractant be in subcritical state, carries out continuous dynamic extraction with soil sample；After the completion of extraction, by extract liquor
Solvent recovery kettle is put into, hermetic reclaim kettle adjusts pressure in kettle and gasifies to 0.25~0.78Mpa, organic extractant and recycle again
It utilizes, obtains glyphosate polluted farmland soil extract liquor；
3) glyphosate polluted farmland soil extract liquor obtained in the step 2) is added to FeSO4In aqueous solution, extraction
Take liquid and FeSO4The volume ratio of solution is 1:1~1:3；Then it is added sodium peroxydisulfate, after stir process, glyphosate is almost complete
Degradable realizes the reparation of glyphosate polluted farmland soil.
The preferred steps 1) in drying temperature be 105~110 DEG C.
The preferred steps 2) in adjust soil sample be passed through organic extractant quality of soil sample and be passed through organic extractant body
Long-pending solid-to-liquid ratio is 40~180min of 1:5~1:15 (kg:L) dynamic extraction.
The preferred steps 2) described in organic extractant be butane or dimethyl ether.
The preferred steps 3) in FeSO4The concentration of solution is 0.02~0.04mol/L, and sodium peroxydisulfate and FeSO is added4's
Molar ratio is 1:1~3:1.
The preferred steps 3) in gained mixed liquor will be added after sodium peroxydisulfate stir 80 with the speed of 180~260r/min
~120min.
Compared with existing glyphosate polluted farmland soil restorative procedure, present invention has the advantage that
The present invention utilize subcritical low-temperature extraction technology, use low temperature subcritical abstraction solvent butane or dimethyl ether as
Organic extractant, can realize effective extraction to contaminated soil glyphosate at a lower temperature, and rate of extraction is fast, efficiency
It is high.After the activated persulfate system oxidation of obtained glyphosate contaminated soil extract liquor, glyphosate is almost completely degraded, should
Method can realize industrialization large-scale production and be expected to be applied to practical glyphosate polluted farmland soil reparation.
Implementation through the invention, glyphosate content are more than the pollution soil sample of 50mg/kg, after processing the content of glyphosate
Lower than 0.1mg/kg, more than 99%, the glyphosate polluted in soil sample is almost completely degraded degradation rate.
Specific embodiment
The present invention is further elaborated below by specific case study on implementation.
Embodiment 1
1) soil sample is weighed from glyphosate polluted farmland soil, is dried at a temperature of 105 DEG C, polished 120 mesh of mistake.
Soil sample is placed in subcritical abstraction kettle, closed extraction kettle, pressure in extraction kettle is promoted to 0.6MPa, organic extractant is made to exist
It liquefies under room temperature；
2) organic extractant butane is passed through extraction kettle, adjusting soil sample with the solid-to-liquid ratio for being passed through organic extractant is 1:5
(kg:L).The temperature in extraction kettle is adjusted to 30 DEG C, pressure to 0.71MPa makes organic extractant be in subcritical state, with soil
Sample carries out continuous dynamic extraction 40min.After the completion of extraction, extract liquor is put into solvent recovery kettle, hermetic reclaim kettle is adjusted in kettle
Pressure obtains glyphosate polluted farmland soil extract liquor to 0.25Mpa, organic extractant gasification and recycling and reusing；
3) glyphosate polluted farmland soil extract liquor obtained in the step 2) is added to the FeSO of 0.02mol/L4
In aqueous solution, extract liquor and FeSO4The volume ratio of solution is 1:1.Then sodium peroxydisulfate is added, sodium peroxydisulfate and FeSO is added4's
Molar ratio is 1:1.It will be added after gained mixed liquor after sodium peroxydisulfate stirs 80min with the speed of 180r/min, glyphosate is almost
It is completely degraded, realizes the reparation of glyphosate polluted farmland soil.
Embodiment 2
1) soil sample is weighed from glyphosate polluted farmland soil, is dried at a temperature of 108 DEG C, polished 150 mesh of mistake.
Soil sample is placed in subcritical abstraction kettle, closed extraction kettle, pressure in extraction kettle is promoted to 0.6MPa, organic extractant is made to exist
It liquefies under room temperature；
2) organic extractant butane is passed through extraction kettle, adjusting soil sample with the solid-to-liquid ratio for being passed through organic extractant is 1:8
(kg:L).The temperature in extraction kettle is adjusted to 42 DEG C, pressure to 0.95MPa makes organic extractant be in subcritical state, with soil
Sample carries out continuous dynamic extraction 120min.After the completion of extraction, extract liquor is put into solvent recovery kettle, hermetic reclaim kettle adjusts kettle
Interior pressure obtains glyphosate polluted farmland soil extract liquor to 0.48Mpa, organic extractant gasification and recycling and reusing；
3) glyphosate polluted farmland soil extract liquor obtained in the step 2) is added to the FeSO of 0.03mol/L4
In aqueous solution, extract liquor and FeSO4The volume ratio of solution is 1:2.Then sodium peroxydisulfate is added, sodium peroxydisulfate and FeSO is added4's
Molar ratio is 2:1.To be added after sodium peroxydisulfate after the speed stirring 105min of gained mixed liquor 210r/min, glyphosate almost by
It is degradable, realize the reparation of glyphosate polluted farmland soil.
Embodiment 3
1) soil sample is weighed from glyphosate polluted farmland soil, is dried at a temperature of 110 DEG C, polished 200 mesh of mistake.
Soil sample is placed in subcritical abstraction kettle, closed extraction kettle, pressure in extraction kettle is promoted to 0.6MPa, organic extractant is made to exist
It liquefies under room temperature；
2) organic extractant butane is passed through extraction kettle, adjusting soil sample with the solid-to-liquid ratio for being passed through organic extractant is 1:15
(kg:L).The temperature in extraction kettle is adjusted to 55 DEG C, pressure to 1.30MPa makes organic extractant be in subcritical state, with soil
Sample carries out continuous dynamic extraction 180min.After the completion of extraction, extract liquor is put into solvent recovery kettle, hermetic reclaim kettle adjusts kettle
Interior pressure obtains glyphosate polluted farmland soil extract liquor to 0.78Mpa, organic extractant gasification and recycling and reusing；
3) glyphosate polluted farmland soil extract liquor obtained in the step 2) is added to the FeSO of 0.04mol/L4
In aqueous solution, extract liquor and FeSO4The volume ratio of solution is 1:3.Then sodium peroxydisulfate is added, sodium peroxydisulfate and FeSO is added4's
Molar ratio is 3:1.To be added after sodium peroxydisulfate after the speed stirring 120min of gained mixed liquor 260r/min, glyphosate almost by
It is degradable, realize the reparation of glyphosate polluted farmland soil.
Embodiment 4
1) soil sample is weighed from glyphosate polluted farmland soil, is dried at a temperature of 108 DEG C, polished 150 mesh of mistake.
Soil sample is placed in subcritical abstraction kettle, closed extraction kettle, pressure in extraction kettle is promoted to 0.6MPa, organic extractant is made to exist
It liquefies under room temperature；
2) organic extractant dimethyl ether is passed through extraction kettle, adjusting soil sample with the solid-to-liquid ratio for being passed through organic extractant is 1:10
(kg:L).The temperature in extraction kettle is adjusted to 48 DEG C, pressure to 1.20MPa makes organic extractant be in subcritical state, with soil
Sample carries out continuous dynamic extraction 120min.After the completion of extraction, extract liquor is put into solvent recovery kettle, hermetic reclaim kettle adjusts kettle
Interior pressure obtains glyphosate polluted farmland soil extract liquor to 0.47Mpa, organic extractant gasification and recycling and reusing；
3) glyphosate polluted farmland soil extract liquor obtained in the step 2) is added to the FeSO of 0.03mol/L4
In aqueous solution, extract liquor and FeSO4The volume ratio of solution is 1:2.Then sodium peroxydisulfate is added, sodium peroxydisulfate and FeSO is added4's
Molar ratio is 2:1.To be added after sodium peroxydisulfate after the speed stirring 110min of gained mixed liquor 210r/min, glyphosate almost by
It is degradable, realize the reparation of glyphosate polluted farmland soil.
Glyphosate content before and after detection processing in pollution soil sample, measurement result are as shown in the table:
What the present invention was disclosed and proposed a kind of repairs glyphosate polluted farmland soil using subcritical low-temperature extraction technology
Method, those skilled in the art can be by using for reference present disclosure, and the appropriate links such as condition route that change are realized, although of the invention
Method and technology of preparing are described by preferred embodiment, and related technical personnel can obviously not depart from the present invention
Hold, methods and techniques described herein route is modified or is reconfigured in spirit and scope, to realize final preparation
Technology.In particular, it should be pointed out that all similar replacements and change are apparent to those skilled in the art,
They are considered as being included in spirit of that invention, range and content.
Claims (7)
1. a kind of method for repairing glyphosate polluted farmland soil using subcritical low-temperature extraction technology；It is characterized in that step is such as
Under:
1) soil sample is weighed from glyphosate polluted farmland soil, and 120~200 meshes are crossed after drying, grinding；Soil sample is placed in Asia
In critical extraction kettle, pressure in extraction kettle is promoted to 0.6MPa, organic extractant is made to liquefy at normal temperature by closed extraction kettle；
2) organic extractant is passed through extraction kettle, adjusts temperature in extraction kettle to 30~55 DEG C, pressure to 0.71~
1.30Mpa makes organic extractant be in subcritical state, carries out continuous dynamic extraction with soil sample；After the completion of extraction, by extract liquor
Solvent recovery kettle is put into, hermetic reclaim kettle adjusts pressure in kettle and gasifies to 0.25~0.78Mpa, organic extractant and recycle again
It utilizes, obtains glyphosate polluted farmland soil extract liquor；
3) glyphosate polluted farmland soil extract liquor obtained in the step 2) is added to FeSO4In aqueous solution, extract liquor with
FeSO4The volume ratio of solution is 1:1~1:3；Then it is added sodium peroxydisulfate, after stir process, glyphosate is almost completely degraded,
Realize the reparation of glyphosate polluted farmland soil.
2. the method as described in claim 1, it is characterized in that drying temperature is 105~110 DEG C in the step 1).
3. the method as described in claim 1, it is characterized in that adjusting soil sample and the soil for being passed through organic extractant in the step 2)
Sample quality is 1:5~1:15 (kg:L) with the solid-to-liquid ratio for being passed through organic extractant volume.
4. the method as described in claim 1, it is characterized in that 40~180min of dynamic extraction in the step 2).
5. the method as described in claim 1, it is characterized in that organic extractant described in step 2) described in the step 2)
For butane or dimethyl ether.
6. the method as described in claim 1, it is characterized in that FeSO in the step 3)4The concentration of solution be 0.02~
Sodium peroxydisulfate and FeSO is added in 0.04mol/L4Molar ratio be 1:1~3:1.
7. the method as described in claim 1, it is characterized in that will be added in the step 3) after sodium peroxydisulfate gained mixed liquor with
The speed of 180~260r/min stirs 80~120min.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995033541A1 (en) * | 1994-06-09 | 1995-12-14 | Idaho Research Foundation, Inc. | Fluid extraction of metals and/or metalloids |
| CN103230932A (en) * | 2013-04-11 | 2013-08-07 | 华北电力大学 | A device for remediation of organic contaminated soil by using supercritical CO2 fluid and a remediation method |
| US20140051902A1 (en) * | 2011-04-29 | 2014-02-20 | Tongji University | Process for eliminating or reducing persistent organic pollutants contained in particles |
| CN104998899A (en) * | 2015-07-07 | 2015-10-28 | 东南大学 | Microbial remediation method capable of mineralizing heavy metal ions based on glyphosate degradation |
| CN106180167A (en) * | 2016-08-03 | 2016-12-07 | 上海市环境工程设计科学研究院有限公司 | A kind of method utilizing acidifying subcritical water to work in coordination with the pollution of heavy metal chelant repairing heavy metal in soil |
| CN107513388A (en) * | 2017-07-25 | 2017-12-26 | 康泽波 | It is a kind of to be used to administer medicament of soil arsenic pollution and preparation method thereof |
| CN108246790A (en) * | 2018-01-02 | 2018-07-06 | 昆明理工大学 | A kind of method for repairing phenol organic matter contaminated soil |
| CN108405595A (en) * | 2018-03-02 | 2018-08-17 | 南京农业大学 | A kind of organic contamination agricultural land soil fertilizing-growth-promoting-attenuation treatment and detection method |
-
2019
- 2019-01-29 CN CN201910083381.7A patent/CN109772871B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995033541A1 (en) * | 1994-06-09 | 1995-12-14 | Idaho Research Foundation, Inc. | Fluid extraction of metals and/or metalloids |
| US20140051902A1 (en) * | 2011-04-29 | 2014-02-20 | Tongji University | Process for eliminating or reducing persistent organic pollutants contained in particles |
| CN103230932A (en) * | 2013-04-11 | 2013-08-07 | 华北电力大学 | A device for remediation of organic contaminated soil by using supercritical CO2 fluid and a remediation method |
| CN104998899A (en) * | 2015-07-07 | 2015-10-28 | 东南大学 | Microbial remediation method capable of mineralizing heavy metal ions based on glyphosate degradation |
| CN106180167A (en) * | 2016-08-03 | 2016-12-07 | 上海市环境工程设计科学研究院有限公司 | A kind of method utilizing acidifying subcritical water to work in coordination with the pollution of heavy metal chelant repairing heavy metal in soil |
| CN107513388A (en) * | 2017-07-25 | 2017-12-26 | 康泽波 | It is a kind of to be used to administer medicament of soil arsenic pollution and preparation method thereof |
| CN108246790A (en) * | 2018-01-02 | 2018-07-06 | 昆明理工大学 | A kind of method for repairing phenol organic matter contaminated soil |
| CN108405595A (en) * | 2018-03-02 | 2018-08-17 | 南京农业大学 | A kind of organic contamination agricultural land soil fertilizing-growth-promoting-attenuation treatment and detection method |
Non-Patent Citations (1)
| Title |
|---|
| 殷瑞君等: "土壤中PAHs提取纯化和测定方法研究进展 ", 《山西农业科学》 * |
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