CN101704017B - Method and device for extracting heavy metal ions from soil - Google Patents
Method and device for extracting heavy metal ions from soil Download PDFInfo
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- CN101704017B CN101704017B CN200910223493A CN200910223493A CN101704017B CN 101704017 B CN101704017 B CN 101704017B CN 200910223493 A CN200910223493 A CN 200910223493A CN 200910223493 A CN200910223493 A CN 200910223493A CN 101704017 B CN101704017 B CN 101704017B
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Abstract
The invention relates to a method and a device for extracting heavy metal ions from soil, which are used for extracting heavy metal ions from the heavy metal polluted oil. The method comprises the following steps of: forming a heavy metal ion adsorbent by adopting a compound containing carbon nano fibers, active carbon, a cationic surface active agent, acrylamide, potassium acrylate, sludge particles and potassium sulfide; putting the heavy metal ion adsorbent in a porous hard shell to form a porous hard plastic bag; and embedding the porous hard plastic bag into soil for extracting the heavy metal ions. The method and the device for extracting the heavy metal ions from soil aim at the problem of severe pollution of Cd, Cr, Cu, Hg, Pb and Zn of the soil and can effectively absorb, passivate, solidify and extract active ions such as Cd2+, Cr3+, Cu 2+, Hg2+, Pb2+, Zn2+, and the like in plow layers of the soil, maintain microzone water of the soil, release a certain K+ ions and realize the update, the purification and the circular treatment of the absorbent in the device for extracting the heavy metal ions.
Description
Technical field
The invention belongs to environmental pollution treatment technology, relate to a kind of method and device thereof that can effectively extract toxic heavy metal ion in the plough horizon particularly.
Background technology
At present, in view of the generality and the seriousness of heavy metal pollution of soil, some developed countries formulate corresponding soil remediation plan one after another.Federal Government has been formulated soil and underground water rehabilitation plan, prepares the tens billion of more than one hundred billion dollars that arrive of investment.The U.S. initiated and had set up " global soil is repaired network (Global SoilRemediation Net-work) " in 1994.
Make a general survey of domestic and international heavy metal pollution of soil reparation research, physics such as local method, soil moved in to improve the original method, electrochemical process or chemical method etc. are administered and mainly adopt soil solidification, vitrifying, leaching method, washed to traditional heavy-metal contaminated soil.These methods exist following shortcoming: (1) cost is high, and one hectare heavy metal pollution soil is often up to tens million of dollars, and is difficult to extensive use; (2) destroy ecological environment of soil, cause soil texture forfeiture, biological activity of soil to descend and soil fertility degeneration, often need carry out after-treatment; (3) secondary pollution, utilization physics, chemistry, electrochemical method often can cause the pollution once more to soil again to the process of heavy metal pollution soil remediation.
Since the eighties in 20th century; Many industrialized countries all just pay special attention to the technical research of utilization plant soil restoration; Phytoremediation (phytoremediation) is the green recovery technique of a kind of emerging heavy metal pollution original position (in situ); Plant extract technology (phytoextraction) as one of its core technology; Developed into the research and application focus of environmental science, and caused the great attention of government, academia and business circles, nearly 200 the mechanism and the company that are engaged in the developmental research of environmental organism recovery technique have only just been arranged in the North America.From current international plant extract technical research and practice progress; Remaining is also needing to solve following problem: the plant variety of (1) alternative ability enriching heavy metal Cd, Cr, Cu, Hg, Pb and Zn is less, and particularly the plant of the two or more metals of enrichment simultaneously is few; (2) super enriching plant of recommended preferential use (hyper-accumulator), general biomass is on the low side, and the overall removal efficient of heavy metal is lower, also has problems such as strange land climatic adaptation, shortage economic benefit simultaneously; (3) bioavailability of heavy metals (bioavailability) has much room for improvement in the contaminated soil; Wild plant and the crops that nature is not also seen has the high and ultra enrichment cadmium of biomass are also pointed out in research in 2003 such as Marchiol etc. 2004 and Li, and visible to seek or cultivate the big and plant can enrichment heavy metal in soil element of ground biomass still be the main subject under discussion of current soil pollution reparation research; (4) see from should being used for; The phytoremediation technology part of developed country has dropped into practical application, and has obtained environment, economic and social benefit preferably, and China still is in the starting stage; Correlation technique also is in laboratory or pilot scale stage, lacks generalization and universality.
Summary of the invention
The present invention is directed to present soil Cd, Cr, Cu, Hg, Pb and the with serious pollution problem of Zn, provide a kind of from soil the method and the device thereof of extracting heavy metal ions, it can effectively absorb-passivation-curing-extraction plough horizon in active Cd
2+, Cr
3+, Cu
2+, Hg
2+, Pb
2+And Zn
2+Plasma, can keep soil little territory moisture and discharge certain K again
+Ion, and can realize renewal, purification and the circular treatment of this extracting heavy metal ions device absorbed inside agent.
The technical scheme that the present invention adopted is following:
A kind of from soil the method for extracting heavy metal ions, be used for heavy metal ion extraction to heavy-metal contaminated soil, it is characterized in that said method comprises:
Employing comprises the composition composition adsorbent for heavy metal of carbon nano-fiber, active carbon, cationic surfactant, acrylamide, potassium acrylate, mud granule thing and potassium sulfide;
This adsorbent for heavy metal is placed on the interior porous crack hard that forms of a porous crack hard shell moulds capsule, this porous crack hard is moulded capsule be embedded in extracting heavy metal ions in the soil.
Specifically, state acrylamide and potassium acrylate and comprise acrylamide and potassium acrylate gel, the weight proportion of each component of said composition is following:
Carbon nano-fiber 0.30%～0.80%
Active carbon 8.00%～12%
Cationic surfactant 15.00%～20.00%
Acrylamide 3.00%～5.00%
Potassium acrylate 3.00%～5.00%
Mud granule thing 54.70%～68.90%.
Potassium sulfide 1.80%～2.50%.
Said cationic surfactant comprises diethanol amine CH
3N-(CH
2-CH
2OH)
2
Said mud granule thing comprises the fresh granules mud that the high-load anaerobic reactor in starch, starch sugar, citric acid, alcohol, the paper industry high-concentration sewage treatment system is produced.
Said porous crack hard is moulded capsule and is comprised a tubular high polymer material bodies, and its end spiral-lock is provided with lid, and this porous crack hard is moulded and is distributed with a plurality of penetrating holes on the capsule.
Said porous crack hard is moulded capsule and is comprised diameter 30～50mm, and length is the tubing of 100～150mm, and 60～80 diameters of distributed and arranged are the penetrating hole of 1～2mm on it.
A kind of from soil the device of extracting heavy metal ions, be used for heavy metal ion extraction to heavy-metal contaminated soil, it is characterized in that said device comprises:
Adsorbent for heavy metal comprises the composition that carbon nano-fiber, active carbon, cationic surfactant, acrylamide, potassium acrylate, mud granule thing and potassium sulfide are formed;
Porous crack hard shell is filled this adsorbent for heavy metal formation porous crack hard and is moulded capsule in it.
Specifically, the weight proportion of each component of said composition is following:
Carbon nano-fiber 0.30%～0.80%
Active carbon 8.00%～12%
Cationic surfactant 15.00%～20.00%
Acrylamide 3.00%～5.00%
Potassium acrylate 3.00%～5.00%
Mud granule thing 54.70%～68.90%.
Potassium sulfide 1.80%～2.50%.
Said cationic surfactant comprises diethanol amine CH
3N-(CH
2-CH
2OH)
2
Said mud granule thing comprises the fresh granules mud that the high-load anaerobic reactor in starch, starch sugar, citric acid, alcohol, the paper industry high-concentration sewage treatment system is produced.
Said porous crack hard is moulded capsule and is comprised a tubular high polymer material bodies, its end spiral-lock or be threaded lid is set, and this porous crack hard is moulded and is distributed with a plurality of penetrating holes on the capsule.
Said porous crack hard is moulded capsule and is comprised diameter 30～50mm, and length is the tubing of 100～150mm, and 60～80 diameters of distributed and arranged are the penetrating hole of 1～2mm on it.
The method and the device thereof that are somebody's turn to do extracting heavy metal ions from soil can be in the crops cultivation process; This device is embedded in the plough horizon bottom; For example the degree of depth is 28～40cm; Along with water translocation and content thereof in the plough horizon in the crop growthing development process, impel water-soluble attitude and the active Cd of exchangeable species in the plough horizon
2+, Cr
3+, Cu
2+, Hg
2+, Pb
2+And Zn
2+Be adsorbed agent Deng constantly through entering hard shell inside, porous crack, porous crack and absorb, and can cure potassium institute's passivation and curing, the K in the adsorbent simultaneously
+Also slowly discharge and absorb getting among the soil liquid under the effect of concentration gradient power through the porous crack and supply with the crops root system.Through reclaiming porous crack hard shell in the plough horizon after one to two period of tillage, in the laboratory, can realize renewal, purification and the circular treatment of this extracting heavy metal ions device absorbed inside agent.
The shell that this adsorbent is filled can adopt have preferable chemical resistance, the polymer composite of stronger anti-mechanical impact power, the penetrating hole that is provided with on this shell is the passage that the soil liquid and ion thereof and adsorbent carry out exchange migration.This shell has the mechanical shock performance of good anti-agricultural tillage, be placed on the ordinary production that can not influence farming activity and crops in the plough horizon and grow, and this porous crack hard shell also is convenient to reclaim and is handled and recycle.The present invention adopts by carbon nano-fiber (Carbon nanofiber), active carbon (active carbon), cationic surfactant (Cationic surface active agent), acrylamide and potassium acrylate (Acrylamide-Potassium Acrylate), mud granule thing, and formulated by a certain percentage can effectively adsorb the adsorbent of heavy metal ion in the soil liquid.The aqueous solution that wherein contains heavy metal ion in the main effect absorption of acrylamide and potassium acrylate and the gathering soil; The liquid absorbency rate of acrylamide and potassium acrylate can reach more than the 250g/g; Can reach more than the 60g/g to cationic liquid absorbency rate in the soil liquid; And in most pH in soil (4.5～9.0) scope, the imbibition adsorptivity of acrylamide and potassium acrylate is more stable.Acrylamide and potassium acrylate are harmless to soil, underground water and crops, and it also is rich in nutrient potassium and helps the crop production growth, and they have stronger stability in soil, and are favourable to the formation of soil aggregate.Inner carbon nano-fiber of being filled of the hard capsule in porous crack and active carbon are to Cd in the soil water solution
2+, Cr
3+, Cu
2+, Fe
2+, Pb
2+, Zn
2+All have stronger adsorption capacity Deng cation, and this adsorption capacity there is the trend of increase along with the mass concentration of heavy metal ion in the soil liquid.Active carbon and carbon nano-fiber also have stronger adsorption capacity to the multiple organic matter in the soil liquid simultaneously; It is to be noted and also have important facilitation for the heavy metal cation in the absorption and the maintenance soil liquid by the peripheral multiple soil organic matter of assembling of adsorbent.
The fresh granules mud that the mud granule thing can be produced for the high-load anaerobic reactor that comprises in starch, starch sugar, citric acid, alcohol, the paper industry high-concentration sewage treatment system.Mud granule has higher biologically active, high volumetric loading performance, can be as the carrier of carbon nano-fiber, activated carbon and acrylamide and potassium acrylate, and more jumbo containing and Adsorption of Heavy Metal Ions improve heavy metal ion and concentrate usefulness.
Replaced to get into again in the soil liquid or and absorbed in order to prevent to be adsorbed the adsorbed heavy metal ion of agent, just need be cured and Passivation Treatment these heavy metal ion by the crops relation.On the basis that Comprehensive Experiment is analyzed, the present invention is employed in and adds the curing-passivation complexing agent of potassium sulfide as heavy metal ion in the adsorbent, and this complexing agent in use can also constantly discharge K in soil
+, to satisfy the demand of crop growthing development to nutrient potassium, its synthetic chemistry reaction mechanism is:
K
2S＝2K
++S
2-
Cd
2++S
2-＝CdS K
sp＝8.0×10
-27
Cu
2++S
2-＝CuS K
sp＝6.3×10
-36
Pb2++S
2-＝PbS K
sp＝1.0×10
-28
Zn
2++S
2-＝ZnS K
sp＝2.93×10
-25
By solubility product (Ksp) numerical value of above-mentioned each heavy metal sulfide, the S that the electrolysis of potassium sulfide dissolving institute forms in adsorbent internal solution in the hard shell of porous crack
2-Concentration is 10
-4Mol/L (promptly is equivalent to S in the solution
2-Concentration is 3.2mg/kg) time, when above-mentioned heavy metal sulfide was in electrolytic equilibrium, the concentration of heavy metal ion was respectively in its solution:
[Cd
2+]=8.0 * 10
-23Mol/L is equivalent to 8.96 * 10
-21Mg/kg
[Cu
2+]=6.3 * 10
-32Mol/L is equivalent to 4.03 * 10
-30Mg/kg
[Pb
2+]=1.0 * 10
-24Mol/L is equivalent to 2.07 * 10
-22Mg/kg
[Zn
2+]=2.93 * 10
-25Mol/L is equivalent to 1.91 * 10
-23Mg/kg
In addition; Owing to also be equipped with acrylamide and potassium acrylate water absorbing agent in the hard shell of porous crack in the soil; And adsorbents such as active carbon, carbon nano-fiber and cationic surfactant; So just can ensure has adequate water and organic matter keeping the reproducibility state in the porous crack hard shell in the soil, to avoid the oxidized and activation of heavy metal sulfide in the housing.Absorption, passivation and curing have so just been realized fully to water-soluble attitude, exchange state heavy metal contaminants in the soil; And through collecting, handle in the soil porous crack hard shell and adsorbent wherein; But just can realize extraction to plant absorbing state heavy metal element in the soil; And water-soluble attitude in the soil, exchangeable species contents of heavy metal elements are reduced fast, to slow down its harm to crops quality and surface water quality.
In above-mentioned absorption, passivation, curing and extraction soil in the overall process of water-soluble attitude, exchangeable species heavy metal element; Its porous crack hard shell and adsorbent thereof all do not have poisonous and harmful substance to discharge; Crop growthing development is had no adverse effect, and do not have the secondary pollution phenomenon generation of soil and surface water extremely.
Beneficial effect of the present invention is, in this soil the method for extracting heavy metal ions and device thereof to present soil Cd, Cr, Cu, Hg, Pb and the with serious pollution problem of Zn, can effectively absorb-passivation-curings-the extraction plough horizon in the Cd of activity
2+, Cr
3+, Cu
2+, Hg
2+, Pb
2+And Zn
2+Plasma, can keep soil little territory moisture and discharge certain K again
+Ion, and can realize renewal, purification and the circular treatment of this extracting heavy metal ions device absorbed inside agent.
Below in conjunction with the specific embodiment the present invention is done further elaboration.
The specific embodiment
Embodiment 1 adopts the composition of carbon nano-fiber, active carbon, acrylamide and potassium acrylate, potassium sulfide to form the adsorbent for heavy metal composition; And with the carrier of commercially available mud granule as adsorbent composition; Wherein the specification of carbon nano-fiber is: OD＞50nm; ID=25-40, Length=10-20um.The weight proportion of each component is in the said composition:
Carbon nano-fiber 0.5%
Active carbon 10.00%
Cationic surfactant 18.00%
Acrylamide 3.00%
Potassium acrylate 5.00%
Potassium sulfide 2.5%
Mud granule thing 61.00%
Above-mentioned substance is fully mixed, obtain the adsorbent amalgam.Porous crack hard shell adopt have splendid chemical resistance, stronger anti-mechanical impact power, transparent Teflon-FEP material, its specification is the round bottom spiral cover structure of the long 120mm of diameter 40mm, tubing thickness is 2mm; Be designed with around the housing and on the round bottom face 60-80 be evenly distributed, penetrating hole that diameter is 1-2mm.
In this porous crack hard shell, fill above-mentioned adsorbent for heavy metal composition, form porous crack hard and mould capsule.In the process of crop seeding, it is transplanted respectively in the plough horizon bottom; According to surface slope, the soil texture, soil moisture and heavy metal in soil content status thereof; The general space density of pressing 3m * 3m is transplanted; Be that every mu of soil is transplanted about 70, regain during real tillage after the crops maturation that placement once more can be shifted.It is adapted to heavy metal pollution of soil reparation and purification to good place of irrigated land, paddy field, field, vegetable plot and soil permeability etc.Show through experiment; Under the precondition of cutting off heavy metal-polluted soil element pollution source; Migrate to the plough horizon bottom through porous of the present invention crack hard being moulded capsule; In the crop growthing development process, this compound adsorbent can constantly adsorb and curing soil solution in water-soluble attitude, exchangeable species heavy metal ion, simultaneously can also provide some crop growthing developments necessary nutrient potassium to soil; Utilization the present invention is through lasting absorption and the curing of three periods of tillage; Can reduce water-soluble attitude and exchangeable species heavy metal ion content in the soil significantly, to eliminate or to slow down of the harm of heavy metal in soil element, to reach the purpose of eliminating heavy metal pollution of soil harm and repairing contaminated soil fast to crops and surface water body water quality thereof.Use in addition that water-soluble attitude, exchangeable species heavy metal ion have remarkable economic efficiency, social benefit and environmental benefit in technology of the present invention and device absorption, passivation, curing and the extraction soil liquid; It does not destroy ecological environment of soil, does not influence the growth of crops normal growth, the generation of exhausted non-secondary pollution.
Embodiment 2 adopts the composition of carbon nano-fiber, active carbon, acrylamide and potassium acrylate to form the adsorbent for heavy metal composition, and the weight proportion of each component is in the said composition:
Carbon nano-fiber 0.30%
Active carbon 8.00%
Cationic surfactant 15.00%
Acrylamide 3.00%
Potassium acrylate 3.00%
Potassium sulfide 1.80%
Mud granule thing 68.90%
Above-mentioned substance is fully mixed; Porous crack hard shell adopt have splendid chemical resistance, stronger anti-mechanical impact power, transparent polyurethane material; Its specification is the tubing of the long 150mm of diameter 50mm, and its two ends spiral-lock is end cap fixedly, and being distributed with a plurality of diameters on body and the end cap is the penetrating hole of 1-2mm; In this porous crack hard shell, fill above-mentioned adsorbent for heavy metal composition, form porous crack hard and mould capsule.
Embodiment 3 adopts the composition of carbon nano-fiber, active carbon, acrylamide and potassium acrylate to form the adsorbent for heavy metal composition, and the weight proportion of each component is in the said composition:
Carbon nano-fiber 0.80%
Active carbon 12%
Cationic surfactant 20.00%
Acrylamide 5.00%
Potassium acrylate 5.00%
Potassium sulfide 2.50%
Mud granule thing 54.70%
Porous crack hard shell adopt have splendid chemical resistance, stronger anti-mechanical impact power, transparent makrolon material; Its specification is the tubing of the long 100mm of diameter 30mm; Its two ends spiral-lock is end cap fixedly; Being distributed with a plurality of diameters on body and the end cap is the penetrating hole of 1-2mm, in this porous crack hard shell, fills above-mentioned adsorbent for heavy metal composition, forms porous crack hard and moulds capsule.
Show through application experiment, not reaching all kinds of soil of moderate or severe heavy metal pollution as yet, through using technology of the present invention and absorption, passivation, curing and the extraction of device the water-soluble attitude in the soil liquid, exchangeable species heavy metal ion.Mould capsule for the surface water body that receives heavy metal pollution through settling fixedly porous crack hard in addition, and select suitable water depth, also can realize absorption, passivation, curing and extraction heavy metal ion in the surface water body according to hydrological characteristics and water quality condition.
According to the experiment proof; Each component of above-mentioned adsorbent composition can be carried out suitable adjustment according to the heavy metal ion content in the soil that is applied to; And can multiple proportioning compound mode; Certainly cationic surfactant mainly plays the adjustment function of the combination uniformity of other component in the mud granule thing, can adopt other cationic surfactant to replace, and does not perhaps adopt this component.
Claims (2)
1. the method for an extracting heavy metal ions from soil is used for the heavy metal ion extraction to heavy-metal contaminated soil, it is characterized in that said method comprises:
Employing comprises the composition composition adsorbent for heavy metal of carbon nano-fiber, active carbon, cationic surfactant, acrylamide, potassium acrylate, mud granule thing and potassium sulfide;
This adsorbent for heavy metal is placed on the interior porous crack hard that forms of a porous crack hard shell moulds capsule, this porous crack hard is moulded capsule be embedded in extracting heavy metal ions in the soil;
Wherein, said acrylamide and potassium acrylate comprise acrylamide and potassium acrylate gel, and the weight proportion of each component of said composition is following:
Said cationic surfactant comprises diethanol amine CH
3N-(CH
2-CH
2OH)
2
Said porous crack hard is moulded capsule and is comprised a tubular high polymer material bodies, and its end spiral-lock is provided with lid, and this porous crack hard is moulded and is distributed with a plurality of penetrating holes on the capsule;
Said porous crack hard is moulded capsule and is comprised diameter 30～50mm, and length is the tubing of 100～150mm, and 60～80 diameters of distributed and arranged are the penetrating hole of 1～2mm on it;
Said mud granule thing comprises the fresh granules mud that the high-load anaerobic reactor in starch, starch sugar, citric acid, alcohol, the paper industry high-concentration sewage treatment system is produced.
2. the device of an extracting heavy metal ions from soil is used for the heavy metal ion extraction to heavy-metal contaminated soil, it is characterized in that said device comprises:
Adsorbent for heavy metal comprises the composition that carbon nano-fiber, active carbon, cationic surfactant, acrylamide, potassium acrylate, mud granule thing and potassium sulfide are formed;
Porous crack hard shell is filled this adsorbent for heavy metal formation porous crack hard and is moulded capsule in it;
Wherein, the weight proportion of each component of said composition is following:
Said cationic surfactant comprises diethanol amine CH
3N-(CH
2-CH
2OH)
2
Said porous crack hard is moulded capsule and is comprised a tubular high polymer material bodies, its end spiral-lock or be threaded lid is set, and this porous crack hard is moulded and is distributed with a plurality of penetrating holes on the capsule;
Said porous crack hard is moulded capsule and is comprised diameter 30～50mm, and length is the tubing of 100～150mm, and 60～80 diameters of distributed and arranged are the penetrating hole of 1～2mm on it;
Said mud granule thing comprises the fresh granules mud that the high-load anaerobic reactor in starch, starch sugar, citric acid, alcohol, the paper industry high-concentration sewage treatment system is produced.
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| CN200910223493A CN101704017B (en) | 2009-11-17 | 2009-11-17 | Method and device for extracting heavy metal ions from soil |
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|---|---|---|---|
| CN200910223493A CN101704017B (en) | 2009-11-17 | 2009-11-17 | Method and device for extracting heavy metal ions from soil |
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| CN101704017B true CN101704017B (en) | 2012-10-17 |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102601104A (en) * | 2012-03-09 | 2012-07-25 | 珠海国佳高分子新材料有限公司 | Embattling treatment method of environment polluted by toxic heavy metals, inorganic matters and organic matters |
| CN102674907A (en) * | 2012-05-07 | 2012-09-19 | 珠海武大凝胶研究院有限公司 | Method for making fertilizer through rapid dehydration of sludge |
| CN104438306A (en) * | 2013-09-20 | 2015-03-25 | 重庆文理学院 | Mechanical stirring type soil heavy metal elution apparatus |
| CN103819275B (en) * | 2014-03-11 | 2016-01-13 | 天津师范大学 | Modified Nano carbon is to the regulate and control method of urban life compost heavy metal different shape |
| CN103797923B (en) * | 2014-03-11 | 2016-01-13 | 天津师范大学 | A kind of modified Nano carbon improves the method for soil matrix turfgrass reviviscence |
| CN103814744B (en) * | 2014-03-11 | 2016-01-13 | 天津师范大学 | A kind of modified Nano carbon is to the multifarious regulate and control method of soil nematodes |
| CN104307858B (en) * | 2014-10-30 | 2016-11-16 | 南京农业大学 | A kind of in-situ solidifying removes ecology bag and the application process of heavy metal-polluted soil |
| CN105618472B (en) * | 2015-12-22 | 2019-01-29 | 湖南森美思环保有限责任公司 | A kind of permanent method for removing available heavy metal in heavy-metal contaminated soil |
| CN105817470B (en) * | 2016-05-05 | 2019-04-23 | 清华大学 | The method repaired using soil of the porous media particle to heavy metal pollution |
| CN106000480B (en) * | 2016-05-24 | 2019-07-05 | 马鞍山中创环保科技有限公司 | A kind of soil remediation ion-exchange fibre and preparation method thereof |
| CN107052034A (en) * | 2017-05-23 | 2017-08-18 | 中国水稻研究所 | A kind of plunger-type heavy metal-polluted soil of suitable pot rice removes device and application |
| CN109678278A (en) * | 2019-01-21 | 2019-04-26 | 河南城建学院 | A kind of Groundwater Treatment Methodss of contaminated site |
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| CN1570021A (en) * | 2004-04-28 | 2005-01-26 | 浙江大学 | Soil organic pollution rehabilitation method by using surfactant to increasing adsorption and fixing |
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