CN106180167A - A kind of method utilizing acidifying subcritical water to work in coordination with the pollution of heavy metal chelant repairing heavy metal in soil - Google Patents
A kind of method utilizing acidifying subcritical water to work in coordination with the pollution of heavy metal chelant repairing heavy metal in soil Download PDFInfo
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- CN106180167A CN106180167A CN201610629311.3A CN201610629311A CN106180167A CN 106180167 A CN106180167 A CN 106180167A CN 201610629311 A CN201610629311 A CN 201610629311A CN 106180167 A CN106180167 A CN 106180167A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000013522 chelant Substances 0.000 title claims abstract description 23
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000000605 extraction Methods 0.000 claims abstract description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- 230000003068 static effect Effects 0.000 claims description 7
- 239000002738 chelating agent Substances 0.000 claims description 5
- 238000003809 water extraction Methods 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 230000035699 permeability Effects 0.000 abstract description 4
- 239000004927 clay Substances 0.000 abstract description 2
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- 238000005067 remediation Methods 0.000 description 3
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- 239000003960 organic solvent Substances 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000040710 Chela Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
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- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000003583 soil stabilizing agent Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention relates to the reparation field of contaminated soil, a kind of method utilizing acidifying subcritical water to work in coordination with the pollution of heavy metal chelant repairing heavy metal in soil, by first soil being added water-soluble metal chelating agen acetylacetone,2,4-pentanedione, after insert in Subcritical Water Extraction reactor, by controlling the temperature of subcritical water, pressure, extraction time, and subcritical water acidizing degree, remove the heavy metal in soil.The present invention uses acidifying subcritical water to work in coordination with the heavy metal in heavy metal chelant rehabilitating soil, can be extracted from soil by the metallo-chelate after traditional soil huge sum of money immobilization, it is to avoid continues to remain in soil after heavy metal is stable and causes secondary pollution.Simultaneously as the special nature of subcritical water, during as the extractant of heavy metal chelate, the structure of soil and physicochemical property will not be damaged, and be applicable to the low silt of coefficient of permeability and clay.Remove the heavy metal in soil compared to root system of plant enrichment, there is the shortest characteristic.
Description
Technical field
The present invention relates to the reparation field of heavy-metal contaminated soil, specifically, be that a kind of utilization is acidified subcritical water association
The method polluted with heavy metal chelant repairing heavy metal in soil.
Background technology
Due to the discharge of Industrial " three Waste ", soil is polluted by heavy metal in various degree.Heavy metal pollution of soil, directly
It is related to agricultural product and underground drinking water safety.Heavy metal in soil can not be accumulated by biological decomposition and pass through in soil
Food chain enters human body, is detrimental to health.Therefore, the contaminated soil remediation technology of heavy metal has become current hotspot research neck
Territory.
At present, conventional heavy metal-polluted soil restorative procedure has oxidation/reducing process, elution method, curing/stabilizing method, and
Phytoremediation.Oxidation/reduction method is generally used for the reparation of specific heavy-metal contaminated soil.Such as Cd6+, pass through reduction
It is that it becomes the Cd that toxicity is less3+.But, due to oxidant present in nature, Cd3+It is oxidized into Cd6+Wind
Danger.Elution method is expensive, the soil remediation weak effect to poor permeability, and elution method is by adding chemical agent, can change
Become the physicochemical property of soil, affect the recycle value of rehabilitating soil.Curing/stabilizing technical price is cheap, but cannot be by
Heavy metal extracts from soil, elapses over time, and heavy metal has the risk separated out again.Phytoremediation utilizes natural method
Remove the heavy metal in soil, but the longest, need very long repair process.
Chelating agen can be combined by the heavy metal ion in the soil liquid, changes heavy metal existence shape in soil
State, makes heavy metal resolve from soil particle surface, not solvent is converted into soluble state, thus the huge sum of money in activating soil significantly
Belonging to, the absorption for drip washing or plant creates favorable conditions.
At present, chelating agen is applied in soil remediation engineering construction frequently as a kind of heavy metal-polluted soil stabilizer.But, chela
Mixture stop in soil environment may cause the dissolution of heavy metal in soils and sediments.Such as, after chelant ties
Heavy metal under rainfall or irrigation conditions, migration stain surface water or subsoil water.
The heavy metal ion in the soil liquid, the soil poor to permeability is removed as Soil leaching agent using chelating agen
Repairing effect is poor, and eluent is expensive, and the chelating agen simultaneously remained is likely to result in the secondary pollution of soil and groundwater.
Subcritical water refers to heat water to more than boiling point, and below critical point, and control system pressure makes water remain liquid
The water of state.The dielectric constant of subcritical water is substantially reduced and has super ionization property, and polarity reduces, and has dissolved organic matter simultaneously
Super dissolution characteristics with inorganic matter.Low polarity due to organo-metallic compound so that it is the dissolubility in water is low, but Asia is faced
The characteristic of boundary's water makes it can be effective to the extraction of organo-metallic compound.Subcritical water is as a kind of new abstraction technique tool
Have that equipment is simple, extraction time is short, and it use pure water as extractant, need not or seldom with organic solvent, therefore it is not
Environment can be caused secondary pollution.At present, the domestic research to subcritical water several fields the most below are carried out, and utilize Asia to face
Whose extraction medicinal herb components of boundary, utilizes subcritical water technology to process the pesticide in sewage and contaminated soil, explosive, PAHs.
Currently for subcritical water treatment technology, corresponding patent documentation also has certain report, such as Chinese patent literature
CN102146002A (201010580486.2, subcritical water processes town and country organic solid waste and produces fertilizer and equipment) discloses profit
The noxious substance in organic solid castoff is removed with subcritical water, larger molecular organics of degrading, improves organic solid castoff
Degradability, the ferrum in activation organic solid castoff, manganese, zinc, the trace element such as copper simultaneously.Chinese patent literature
CN104117531A (201410249466.5, a kind of method utilizing Subcritical Water Extraction to repair petroleum hydrocarbon contaminated soil) is open
The PAHs in soil is utilized to be soluble in subcritical water, the method extracted.To grinding of the heavy metals removal in soil
Study carefully, do not relate to.
Above-mentioned document is not the most reported about working in coordination with metal-chelator process heavy metal-polluted soil by acidifying subcritical water dirty
The method of dye.
Summary of the invention
It is an object of the invention to provide a kind of Subcritical Water Extraction complexed metal chelating agen that is acidified and remove the weight in soil
The method of metal.By first to soil add water-soluble metal chelating agen acetylacetone,2,4-pentanedione (also known as diacetyl methane), after insert
In Subcritical Water Extraction reactor, by controlling the temperature of subcritical water, pressure, extraction time, and subcritical water acidifying journey
Degree, removes the heavy metal in soil.
A first aspect of the present invention, it is provided that a kind of utilization acidifying subcritical water works in coordination with a heavy metal chelant rehabilitating soil huge sum of money
Belong to the method polluted, comprise the steps:
A, contaminated soil is placed in extractive reaction still, adds metal-chelator acetylacetone,2,4-pentanedione (300ml/kg soil), open
Open reactor heater；
B, question response still are warming up to reactor Pressure gauge and show (subcritical water temperature control consistent with subcritical water with thermometer
System is at 110 DEG C～130 DEG C), it is passed through the acidifying subcritical water of nitric acid volumetric concentration 0.1%～1.5%, first static extracting 30 minutes
After, the acidifying subcritical water according still further to 1kg soil 60ml/min～80ml/min flow velocity carries out dynamic extraction 10 minutes.
It is modified that the present invention carries out acid to subcritical water, with the acidifying subcritical water generation of nitric acid volumetric concentration 0.1%～1.5%
For clear water subcritical water as the extractant of contaminated soil metal heavy metal.As the equipment of Fig. 2 present invention connects shown in flow chart,
Water inlet mixes in blending tank with nitric acid.Find according to experiment, after in water, concentration of nitric acid is more than 1%, to heavy metal in soil
Clearance decline.When in water inlet, concentration of nitric acid is more than 3%, there is blocking in the pipeline of extraction equipment and valve.Optimal water inlet
Concentration of nitric acid is 1%.
In step A, contaminated soil is placed in extractive reaction still, reserved at least 15% reactor space, adds levulinic
Ketone, and fill reactor with clear water, open reactor heater.
Adding heavy-metal contaminated soil in extractive reaction still, maximum addition is the 85% of extractive reaction still, it is necessary to pre-
Being left to the space of few 15%, due to the soil effect of rising in experimentation, soil particle easily blocks reactor outlet.Reserved
15% space be effectively improved the problems referred to above.
In step A, choose to be formed and be easily soluble in the metallo-chelate acetylacetone,2,4-pentanedione of subcritical water (also known as diacetyl
Methane) as collaborative chelating agen.By searching related data, acetylacetone,2,4-pentanedione hypotoxicity, it is soluble in organic solvent, dissolves dielectric
Constant is similar with subcritical water, the most easily by Subcritical Water Extraction.To equipped with the extractive reaction still of heavy metal polluted soil adds second
Acyl acetone, according to test, acetylacetone,2,4-pentanedione addition can be adjusted with concentration according to the heavy metal component in soil.Levulinic
Ketone addition is determined by laboratory lab scale.Take a certain amount of on-the-spot soil sample, in laboratory simulation Subcritical Water Extraction condition.Root
According to laboratory result, determine acetylacetone,2,4-pentanedione addition.
In step B, subcritical water pressure 7MPa～9MPa being passed through, temperature 110 DEG C～130 DEG C.Pressure is less than
22.1MPa, when temperature is less than 374.2 DEG C, water is at subcritical state.It is found through experiments, when subcritical water temperature is 110
DEG C～130 DEG C between change time, to the heavy metal (Cu in soil2+、Cr3+、Ni2+、Pb2+、Zn2+) clearance variation effect bright
Aobvious.After subcritical water temperature is more than 140 DEG C, to the heavy metal removing rate in soil without significant change.When subcritical water pressure
When controlling between 6MPa～9MPa, the clearance of heavy metal in soil, raise with pressure and rise.
Preferably, in step B, with the flow velocity of 1kg soil subcritical water 70ml/min, contaminated soil is carried out dynamic extraction.
As shown in the process chart of Fig. 1 and the device connection diagram of Fig. 2, the utilization collaborative weight of acidifying subcritical water of the present invention
The method that metal-chelator repairing heavy metal in soil pollutes, specifically includes following steps:
A, in extractive reaction still, add heavy-metal contaminated soil, 15% space that will be reserved in extractive reaction still, it is full of
Room temperature clear water；And open extractive reaction still heater；
B, open high-pressure water inlet pump, open subcritical water preparation facilities, make subcritical water reach temperature and the pressure set；
Pressure 7MPa～9MPa, temperature 110 DEG C～130 DEG C；
C, open valve 13 and 19, close valve 7 and valve 14, when the pressure of thermocouple 9 temperature and pressure table 8 is with set
The temperature and pressure of subcritical water close to time, close high pressure water-injection pump, close valve 13,19 and 14, static extracting 30 minutes；Open
Open valve 13 and 19, regulate effusion meter 3, control the flow velocity of subcritical water；Subcritical water flow velocity is according to 1kg soil 60ml/min
～80ml/min, carry out dynamic extraction.
Waste water after d, extraction, enters heat exchanger by pressure-regulating valve, enters filtering tank, finally enters water and collects
Tank；
E, repaired after, open high-pressure water inlet pump, close subcritical water preparation facilities, open valve 7 and 14, pass valve closing
Door 12 and 19, is completely exhausted out the waste liquid in extractive reaction still.
The invention has the advantages that:
1, compared to the recovery technique of traditional heavy-metal contaminated soil, acidifying subcritical water is worked in coordination with heavy metal chelant and is repaiied
Heavy metal in earth backing earth, can extract the metallo-chelate after traditional soil huge sum of money immobilization from soil, it is to avoid
Continue to remain in soil after heavy metal is stable, it is possible to the problem that causes secondary pollution；
2 simultaneously as the special nature of subcritical water, during as the extractant of heavy metal chelate, and will not be to soil
Structure and physicochemical property damage, and are applicable to the low silt of coefficient of permeability and clay；
3, removing the heavy metal in soil compared to root system of plant enrichment, acidifying subcritical water is worked in coordination with heavy metal chelant and is repaiied
Recovering technology has again the shortest characteristic.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention.
Fig. 2 is that the equipment of the present invention connects flow chart.
The reference and the ingredient that relate in accompanying drawing are as follows:
1-blending tank, 2-high-pressure water inlet pump, 3-effusion meter, 4-subcritical water preparation facilities, 5,9-thermocouples, 6,15-pressures
Force regulating valve, 7,10,13,14,18-valves, 8,12-Pressure gauges, 11-extractive reaction still, 16-heat exchanger, 17-filtering tank
Detailed description of the invention
The detailed description of the invention provided the present invention below in conjunction with embodiment elaborates.
The process chart of the present invention is as it is shown in figure 1, as a example by heavy-metal contaminated soil, carry out being acidified subcritical water-gold
Belong to chelating agent extraction, the soil after obtaining heavy metal chelate dissolution fluid and repairing.
It is described further according to above-mentioned technological process below.
Embodiment 1
Take certain trade effluent irrigated farmland, wherein Cu2+、Cr3+、Ni2+、Pb2+、Zn2+Concentration be respectively 434ppm,
105ppm、53ppm、112ppm、1030ppm.Respectively by Pressure/Temperature 7MPa/110 DEG C, 8MPa/120 DEG C, 9MPa/130 DEG C enter
Row experiment, adds 1kg heavy-metal contaminated soil in extractive reaction still, adds 300ml acetylacetone,2,4-pentanedione chelating agen.It is passed through 1% nitre
Acid concentration subcritical water, first static extracting, after 30 minutes, needs the 1% concentration of nitric acid subcritical water of 70ml/min according to 1kg soil
Carry out dynamic extraction 10 minutes.Result is as shown in table 1.
Heavy metal removing rate under table 1 different pressures/temperature conditions
Embodiment 2
Take certain trade effluent irrigated farmland, wherein Cu2+、Cr3+、Ni2+、Pb2+、Zn2+Concentration be respectively 434ppm,
105ppm、53ppm、112ppm、1030ppm.Under conditions of Pressure/Temperature is 9MPa/130 DEG C, to acetylacetone,2,4-pentanedione chelating agen
Impact at Subcritical Water Extraction heavy metal in soil clearance is tested.1kg is added heavy metal-polluted in extractive reaction still
Dye soil, test group 2 adds 300ml acetylacetone,2,4-pentanedione chelating agen.Test group 1 is without acetylacetone,2,4-pentanedione chelating agen.It is passed through 1% nitric acid
Concentration subcritical water, first static extracting, after 30 minutes, needs the 1% concentration of nitric acid subcritical water of 70ml/min to enter according to 1kg soil
Mobile state extracts 10 minutes.Result is as shown in table 2.
The impact on nitric acid acidifying Subcritical Water Extraction heavy metal in soil of the table 2 acetylacetone,2,4-pentanedione chelating agen
Embodiment 3
Take certain trade effluent irrigated farmland, wherein Cu2+、Cr3+、Ni2+、Pb2+、Zn2+Concentration be respectively 434ppm,
105ppm、53ppm、112ppm、1030ppm.Respectively by Pressure/Temperature 9MPa/250 DEG C, 9MPa/130 DEG C test, Xiang Cui
Take addition 1kg heavy-metal contaminated soil in reactor, add 300ml acetylacetone,2,4-pentanedione chelating agen.It is passed through 1% concentration of nitric acid subcritical
Water, first static extracting, after 30 minutes, needs the 1% concentration of nitric acid subcritical water of 70ml/min to carry out dynamic extraction according to 1kg soil
10 minutes.Result is as shown in table 3.
The impact on heavy metal in soil clearance of table 3 temperature
Embodiment 4
Take certain trade effluent irrigated farmland, wherein Cu2+、Cr3+、Ni2+、Pb2+、Zn2+Concentration be respectively 434ppm,
105ppm、53ppm、112ppm、1030ppm.Test under the conditions of Pressure/Temperature 9MPa/130 DEG C, to extractive reaction still
Middle addition 1kg heavy-metal contaminated soil, adds 300ml acetylacetone,2,4-pentanedione chelating agen.Each lead into not-acidified subcritical water, 1% nitre
Acid concentration subcritical water, 1.5% concentration of nitric acid subcritical water, static extracting is after 30 minutes the most respectively, needs according to 1kg soil
The subcritical water of 70ml/min carries out dynamic extraction 10 minutes.Result is as shown in table 4.
The impact on heavy metal in soil clearance of the table 4 subcritical water acidizing degree
Below preferred embodiment to the invention is illustrated, but the invention is not limited to described
Embodiment, those of ordinary skill in the art it may also be made that all equivalents on the premise of the invention spirit
Modification or replacement, modification or the replacement of these equivalents are all contained in the application claim limited range.
Claims (8)
1. utilizing acidifying subcritical water to work in coordination with the method that heavy metal chelant repairing heavy metal in soil pollutes, its feature exists
In, comprise the steps:
A, contaminated soil is placed in extractive reaction still, adds metal-chelator acetylacetone,2,4-pentanedione, open reactor heater；
B, being passed through the acidifying subcritical water of nitric acid volumetric concentration 0.1%～1.5%, first static extracting is after 30 minutes, according still further to 1kg
The acidifying subcritical water of soil 60ml/min～80ml/min flow velocity carries out dynamic extraction 10 minutes.
Utilization acidifying subcritical water the most according to claim 1 works in coordination with what heavy metal chelant repairing heavy metal in soil polluted
Method, it is characterised in that in described step A, is placed in contaminated soil in extractive reaction still, and reserved at least 15% reactor is empty
Between, add acetylacetone,2,4-pentanedione, and fill reactor with clear water, open reactor heater.
Utilization acidifying subcritical water the most according to claim 1 works in coordination with what heavy metal chelant repairing heavy metal in soil polluted
Method, it is characterised in that in described step A, the addition of acetylacetone,2,4-pentanedione is 300ml/kg soil.
Utilization acidifying subcritical water the most according to claim 1 works in coordination with what heavy metal chelant repairing heavy metal in soil polluted
Method, it is characterised in that in described step B, in acidifying subcritical water, nitric acid volumetric concentration is 1%.
Utilization acidifying subcritical water the most according to claim 1 works in coordination with what heavy metal chelant repairing heavy metal in soil polluted
Method, it is characterised in that in described step B, acidifying subcritical water pressure 7MPa～9MPa being passed through, temperature 110 DEG C～130
℃。
Utilization acidifying subcritical water the most according to claim 1 works in coordination with what heavy metal chelant repairing heavy metal in soil polluted
Method, it is characterised in that in described step B, extracting pressure is 7MPa～9MPa.
Utilization acidifying subcritical water the most according to claim 1 works in coordination with what heavy metal chelant repairing heavy metal in soil polluted
Method, it is characterised in that in described step B, extraction temperature is 110 DEG C～130 DEG C.
Utilization acidifying subcritical water the most according to claim 1 works in coordination with what heavy metal chelant repairing heavy metal in soil polluted
Method, it is characterised in that in described step B, carries out dynamic extraction according to the flow velocity of 1kg soil subcritical water 70ml/min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109201727A (en) * | 2018-09-03 | 2019-01-15 | 杭州鸿明市政工程有限公司 | A kind of leached soil solutions, application method and equipment |
| CN109772871A (en) * | 2019-01-29 | 2019-05-21 | 天津大学 | A method for remediating glyphosate-contaminated farmland soil using subcritical low-temperature extraction technology |
| CN111872103A (en) * | 2020-07-27 | 2020-11-03 | 中国科学院重庆绿色智能技术研究院 | Method and equipment system for repairing composite contaminated soil |
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| CN109772871A (en) * | 2019-01-29 | 2019-05-21 | 天津大学 | A method for remediating glyphosate-contaminated farmland soil using subcritical low-temperature extraction technology |
| CN111872103A (en) * | 2020-07-27 | 2020-11-03 | 中国科学院重庆绿色智能技术研究院 | Method and equipment system for repairing composite contaminated soil |
| CN111872091A (en) * | 2020-07-27 | 2020-11-03 | 中国科学院重庆绿色智能技术研究院 | Green and efficient petroleum hydrocarbon contaminated soil remediation method |
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