CN105478467A - Method for eluting heavy metals Cu, Zn, Pb and Cd in soil by use of EDTA calcium salt - Google Patents
Method for eluting heavy metals Cu, Zn, Pb and Cd in soil by use of EDTA calcium salt Download PDFInfo
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- CN105478467A CN105478467A CN201610046852.3A CN201610046852A CN105478467A CN 105478467 A CN105478467 A CN 105478467A CN 201610046852 A CN201610046852 A CN 201610046852A CN 105478467 A CN105478467 A CN 105478467A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
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Abstract
The invention discloses a method for eluting heavy metals Cu, Zn, Pb and Cd in soil by use of EDTA calcium salt. Through adoption of the method, the heavy metals in soil can be effectively reduced. The method comprises the following steps: adopting a physical method to enable a heavy metal extracting agent, namely, EDTA to be combined with calcium oxide to form an eluting agent, namely, Ca-EDTA which has an excellent removing effect on the heavy metals in soil; determining an optima eluting condition through a series of experiments bychanging the concentration of the eluting agent, the solid-liquid ratio, the eluting time and the continuous eluting times; finally, realizing the excellent removal effect in a short time (2 h) under the condition that the lower concentration of the eluting agent is 2.5 mmol/l, the solid-liquid ratio is 1: 5 and the continuous eluting times are three. The eluting agent, namely, Ca-EDTA used in the method is lower in turbidity and has better settleability, the follow-up treatment is more convenient, the effect on soil fertility is low, and after treatment, plants can grow normally in the soil, so that convenience is brought to large trials in the future, and a certain treating time and cost can be reduced.
Description
Technical field
The present invention relates to the method for the heavy metal Cu utilized in a kind of EDTA calcium salt washed off soil, Zn, Pb, Cd.
Background technology
The adsorption mechanism of heavy metals in soil is mainly divided into two classes: (1) is adsorbed on the surface of solids in soil, exists with the form of ion; (2) exist with the form of compound, form the precipitation of heavy metal.Heavy metal-polluted soil chemical leaching recovery technique, being by reversing these courses of reaction, utilizing leacheate to be cemented out from soil by heavy metal, and by liquid wash-out technology out.At home and abroad, soil chemistry drip washing recovery technique has adaptability and more efficiently processing speed and being widely used in the application of laboratory research and Practical Project widely because of it.
Current, several eluents that in chemical leaching rehabilitating soil, heavy metal is main have: (1) artificial chelating agent: EDTA(ethylenediamine tetra-acetic acid), NTA(aminotriacetic acid), CDTA(CDTA) etc.
[42].The mechanism of chelating agent reaction is first got off by the heavy metal ion decomplexing being attached to soil particle and colloid surface by chelation, and chelating agent forms chelating nanocrystal composition by chelation and heavy metal ion, and then separates from soil.(2) natural chelators: citric acid, oxalic acid, tartaric acid etc.The mechanism of natural organic acids drip washing heavy metal is that it can form stable complex compound with heavy metal, promotes the desorb of heavy metal, H in addition
+exchange interaction and H
+also be an important mechanism to the slacking of soil mineral component.(3) surfactant.Surfactant generally can be divided into artificially synthesised surfactant and biosurfactant.Artificially synthesised surfactant mainly comprises SDBS(neopelex), SDS(lauryl sodium sulfate), Triton(song draws logical) etc.Biosurfactant mainly comprises rhamnolipid, tannic acid, saponin etc.Artificially synthesised surfactant can remove heavy metal in soil to a certain extent, but its biological degradability is poor, in use easily remains, and easily causes the secondary pollution of soil.(4) inorganic eluent.Inorganic eluent mainly comprises acid, alkali, salt etc.It is used for by acidolysis, complexing, ion-exchange etc. the complex compound that functional group and heavy metal are formed in spoiled soil, thus is resolved by heavy metal, and is leached agent and washes out.
Large quantity research shows, above eluent has drip washing effect in various degree to heavy metal in soil.The key of elution method is the selection of eluent, artificial chelating agent have not easily be degraded by microorganisms and can with the advantages such as most of heavy metal generation chelation, become the maximum a kind of eluent of Recent study and have successful Commercial Demonstration.But elution technique still exists certain drawback, as drip washing limited efficiency, need to use a large amount of leacheates, thus add the cost of reparation; After drip washing, the settling property of leacheate is poor, and liquid turbidity is high, and the difficulty of subsequent treatment is strengthened; In addition, soil is after drip washing, and the heavy metal be not only in soil is activated, also some mineral elements have wherein been activated simultaneously, nutriment in soil is leached out together in heavy metal, and cause soil nutrient elements to run off serious, the Soil Utilization after reparation is restricted.Therefore, find that a kind of elution efficiency is high, cost is low, leacheate turbidity is lower, be conducive to subsequent treatment and after can keeping drip washing, the eluent of soil fertility is the key utilizing elution technique to carry out heavy-metal contaminated soil reparation.
Summary of the invention
The object of this invention is to provide a kind of method of heavy metal Cu, Zn, Pb, Cd in EDTA calcium salt washed off soil, the drip washing effect existed in existing heavy-metal contaminated soil elution technique is poor, rehabilitation cost is high, leacheate turbidity is high, subsequent treatment is difficult to solve, be unfavorable for the problems such as plant growth after Soil leaching.
To achieve these goals, the technical solution used in the present invention is:
The present invention using be subject to heavy metal Cu, Zn, Pb, Cd combined pollution soil as handling object, utilize EDTA calcium salt as the leacheate of soil, washing tests carried out to contaminated soil, thus the heavy metal in soil is leached out.Concrete steps are: take 5.00g cross 20 mesh sieves pollute soil samples load in a series of 60ml centrifugal bottle, add a certain amount of Ca-EDTA solution respectively.Then on the oscillator with 150rmin
-1constant temperature (25 DEG C) vibration 2h, gained sample is with 4000rmin
-1centrifugal 15min, refilters recovery leacheate.
Described EDTA calcium salt soln by calcium oxide, EDTA(diethylamine tetraacethyl), configure according to the molar ratio of 2:1;
The concentration of described leacheate is: 2.5mmol/L, 5mmol/L, 10mmol/L, 20mmol/L.
The solid-to-liquid ratio of described washing tests soil and leacheate is: 1:3,1:5,1:10,1:20.
The drip washing time of described washing tests is: 0.5h, 1h, 2h, 4h, 8h, 12h, 24h be totally 7 time gradients.
The drip washing number of times of described washing tests is: 5 Continuous leaching experiments, analyzes the clearance of drip washing heavy metal each time.
The turbidity of described leacheate after washing tests is less than 3, lower than drinking water standard (GB5749-2006).
After described drip washing, soil still can keep certain fertility, and plant germination rate is more than 60%.
EDTA calcium salt of the present invention is the slaine chelate of EDTA, and the principle of its complexing heavy metal is consistent with EDTA, the H just on carboxyl
+by Ca
2+replaced.In EDTA calcium salt washed off soil, the mechanism of heavy metal is: it can form the structure of ring-type, and tightly heavy metal ion can be enclosed in surrounding, thus heavy metal ion is discharged.The stability of the complex compound that EDTA and 4 heavy metal species are formed wants height more than with during Ca complexing.Ion binding constant is respectively: logk:Ca10.2, Pb19.8, Zn18.3, Cd18.2, Cu20.5.Infer thus, Ca
2+bring impact can't to the effect of extracting of EDTA heavy metal.In addition, due to Ca
2+flocculation, Ca-EDTA leacheate has better settleability, the subsequent treatment of more easily testing.And because turbidity is lower, for carrying out providing convenient from now in large-scale experiment, reduce certain processing time and cost.
The invention has the beneficial effects as follows:
In the present invention EDTA used calcium salt heavy metal soil, Cu, Zn, Pb, Cd have certain drip washing effect, show as the clearance of different heavy metal: Cd > Pb > Cu > Zn.The concentration (2.5mmol/l) that (2h) use is lower at short notice, solid-to-liquid ratio are 1:5, Continuous leaching just can reach good removal effect three times, greatly reduce rehabilitation cost and time.The leacheate obtained after drip washing is limpider (turbidity <3) also, fullys meet the standard of life application water, reduces the difficulty of subsequent treatment.Meanwhile, after drip washing, soil can keep certain fertility, is conducive to the recovery of soil fertility, artificially can carry out the plantation of plant to soil by application of organic fertilizers, not affect the recycling in soil.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in further detail.But this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following implementation column.
Example one: test soil used and take from farmland, downstream, mining area, Chenzhou, Hunan Province Guan Xi town.Its basic physical and chemical is as table 1:
The basic physical and chemical of table 1 soil and heavy metal background values
Table2-3Physical-chemicalpropertiesandbackgroundvaluesoftheheavymetalsinsoil
The concrete practice is:
(1) Ca-EDTA eluent optium concentration measures: get 5.00g and cross 20 mesh sieve soil samples to add molar concentration be in the solution of 4 variable concentrations gradients of 2.5mmol/L, 5mmol/L, 10mmol/L, 20mmol/L, gained sample is placed on oscillator with 150r/min constant temperature (25 DEG C) vibration 2h, gained sample, with the centrifugal 15min of 4000r/min, gets the content that supernatant measures wherein heavy metal Pb, Zn, Cu, Cd, As.
Data show, along with the clearance of the increase Cu of Ca-EDTA concentration shows the variation tendency first reducing and increase afterwards, reach maximum material removal rate 16.63% when Ca-EDTA concentration is 20mmol/L.For Zn, along with the increase of concentration, the clearance of Zn shows downward trend gradually, maximum material removal rate 9.90% is reached when Ca-EDTA concentration is 2.5mmol/L, also similar variation tendency is had to Pb, Cd, when Ca-EDTA concentration is 2.5mmol/L, Pb, Cd have maximum material removal rate, are respectively 34.07%, 62.12%.Poor to As removal effect, be only 1.02%.Consider the relation of efficiency and cost, we adopt Ca-EDTA concentration to be 2.5mmol/L.
(2) the best solid-to-liquid ratio of Ca-EDTA eluent measures: arrange four solid-to-liquid ratios such as (1:3,1:5,1:10,1:20), and the ELUTION METHOD of gained sample is with (1).
Result shows: when Ca-EDTA concentration is 2.5mmol/L, solid-to-liquid ratio is reduced to the process of 1:20 from 1:3, and the removal effect of heavy metal Cu, Zn, Pb, Cd, As is without significant change, for Cu, when solid-to-liquid ratio is 1:20, its clearance reaches maximum, is 15.65%.For Zn, when solid-to-liquid ratio is 1:5, its clearance is maximum, is 9.90%.For Pb, when solid-to-liquid ratio is 1:10, it reaches maximum material removal rate: 35.93%.For Cd, when solid-to-liquid ratio is 1:10, it reaches maximum material removal rate 63.38%.Consider the adsorbance of soil to leacheate and the relation of cost, we adopt Ca-EDTA solid-to-liquid ratio to be 1:5.
(3) mensuration of Ca-EDTA eluent best drip washing time: select 2.5mmol/LCa-EDTA, arrange a series of time point and carry out sample analysis, 0.5h, 1h, 2h, 4h, 8h, 12h, 24h be totally 7 time gradients.The ELUTION METHOD of gained sample is with (1).
Result shows: the increase shown as along with the time of the clearance of 2.5mmol/LCa-EDTA to Cu, Zn, Pb, Cd first increases the trend of rear held stationary.When being when reacted 2h, clearance reaches relative efficiency, now can remove the Cd of the Cu of 15.54%, the Zn of 9.90%, the Pb of 34.07% and 62.12%, during 4-12h, clearance reaches a platform, increases the drip washing time on this basis, and clearance effect improves not obvious.When reaching 24h, all there is the phenomenon declined in the clearance of heavy metal.Therefore, in the middle of follow-up experiment, we selected 2h is the drip washing time of Ca-EDTA.
(4) mensuration of the best drip washing number of times of Ca-EDTA eluent: continuous 5 drip washing are tested to have utilized the Ca-EDTA of 2.5mmol/L to carry out, and gained sample ELUTION METHOD is with (1).
Result shows: after first time extraction, the clearance of Cu, Zn, Pb, Cd is respectively 15.54%, 9.90%, 34.07%, 62.12%.After 5 times are extracted continuously, the accumulative clearance of Cu, Zn, Pb, Cd is respectively 28.74%, 12.58%, 47.48%, 75.29%.The removal of Ca-EDTA heavy metal is mainly first three drip washing, and the accumulative clearance of first three Cu, Zn, Pb, Cd is respectively: 26.30%, 12.37%, 45.18%, 73.28%.A small amount of heavy metal can only be removed latter twice.Consider the relation of cost and efficiency, the Continuous leaching number of times that we take is 3 times.
(5) Ca-EDTA leacheate turbidimetric analysis turbidimetry, adopt the method for GB13200-91, draw a certain amount of water sample (leaving standstill 12h after Ca-EDTA washed off soil to obtain) that shakes up and be diluted to 50.0ml with turbidity free water, in 680nm wavelength, use 3cm cuvette, measure absorbance, the water sample turbidity looked into by calibration curve.
According to measurement result, Ca-EDTA leacheate absorbance and turbidity are respectively: 0.009,2.5NTU.Ca-EDTA leacheate has better settleability.
(6) soil fertility recovery experiment after drip washing: get the glass culture dish that a certain amount of Chinese Milk Vetch Seeds puts into the 90mm diameter being lined with filter paper, add a certain amount of deionized water, make filter paper fully moistening.Culture dish is put into growth cabinet, treats that Chinese Milk Vetch Seeds broken shell is sprouted.Taking 3 kinds of different soil [1. number soil (woods wash before), 2. number soil (after drip washing), 3. number soil (adding fertilizer, composite fertilizer after drip washing)] each 40g loads in test basin, regulates soil moisture content to 30% of maximum water holding capacity by deionized water.From the Chinese Milk Vetch Seeds that broken shell is sprouted, select consistent for subsequent use of size, shape, color and luster, with Medical forceps, the Chinese Milk Vetch Seeds chosen evenly is seeded in soil.Each process 10 seeds.Within 7th day, statistics germination percentage is in table 1.
Table 2 three kinds of soil are on the impact of Chinese Milk Vetch Seeds germination percentage
Table4-1Theinfluenceofthreekindsofsoilforastragalussinicusgerminationrate
| Process soil | Average germination percentage % |
| ① | 100% |
| ② | 60% |
| ③ | 87% |
The present invention adopts calcium oxide to be combined with molar ratio 2:1 with EDTA, forms a kind of eluent Ca-EDTA heavy metal-polluted soil to good removal effect.In Ca-EDTA heavy metal soil of the present invention, Cu, Zn, Pb, Cd have certain drip washing effect, show as the clearance of different heavy metal: Cd > Pb > Cu > Zn.And change eluent concentration, solid-to-liquid ratio, drip washing time, Continuous leaching number of times by series of experiments, determine optimum drip washing condition.In addition, according to the contrast of complexation constant, Ca-EDTA brings impact can not to the combination of EDTA and heavy metal.In addition, Ca-EDTA eluent turbidity is lower, has the better advantage of settleability, and subsequent treatment is for convenience, more little to Influence of Soil Fertility, and after process, edaphophyte can normal growth.For carrying out providing convenient in large-scale experiment from now on, reduce certain processing time and cost.
Claims (7)
1. utilize the heavy metal Cu in a kind of EDTA calcium salt washed off soil, its feature of method of Zn, Pb, Cd comprises the steps:
(1) take 5.00g cross 20 mesh sieves pollute soil samples load in a series of 60ml centrifugal bottle, add a certain amount of Ca-EDTA solution respectively;
(2) after step (1) being completed, centrifugal bottle is placed on the oscillator with 150rmin
-1constant temperature (25 DEG C) vibration 2h;
(3) step (2) complete after gained sample with 4000rmin
-1centrifugal 15min, refilters recovery leacheate.
2. according to claim 1 EDTA calcium salt soln by calcium oxide, EDTA(diethylamine tetraacethyl), configure according to the molar ratio of 2:1.
3. the concentration of leacheate is according to claim 1: 2.5mmol/L, 5mmol/L, 10mmol/L, 20mmol/L.
4. the solid-to-liquid ratio of washing tests soil and leacheate is according to claim 1: 1:3,1:5,1:10,1:20.
5. the drip washing time of washing tests is according to claim 1: 0.5h, 1h, 2h, 4h, 8h, 12h, 24h be totally 7 time gradients.
6. the drip washing number of times of washing tests is according to claim 1: 5 Continuous leaching experiments, analyzes the clearance of drip washing heavy metal each time.
7. the turbidity of leacheate described in after washing tests is less than 3, and lower than drinking water standard (GB5749-2006), after drip washing, soil still can keep certain fertility, and plant germination rate is more than 60%.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106238449A (en) * | 2016-08-30 | 2016-12-21 | 樊之雄 | A kind of restorative procedure of heavy-metal contaminated soil |
| CN106732832A (en) * | 2017-01-23 | 2017-05-31 | 湖南农业大学 | The method for reclaiming EDTA metal complexs and regeneration Chioro-anion exchange resin using metal salt solution |
| CN106799391A (en) * | 2017-01-16 | 2017-06-06 | 中国地质大学（北京） | A kind of method and processing equipment repaired pollution of vanadium soil and reclaim vanadium |
| CN106925604A (en) * | 2017-04-30 | 2017-07-07 | 惠州市东江园林工程有限公司 | A kind of method that plant combined chelating agent administers heavy-metal contaminated soil |
| CN108435772A (en) * | 2018-02-26 | 2018-08-24 | 中冶华天南京工程技术有限公司 | Method for restoration of soil polluted by heavy metal |
| CN108620428A (en) * | 2018-04-08 | 2018-10-09 | 杨大伟 | A kind of heavy metal-polluted soil leacheate and preparation method thereof based on ionic liquid |
| CN108841496A (en) * | 2018-07-21 | 2018-11-20 | 刘小平 | Brewed wine containing Chinese Milk Vetch Seeds in a kind of raw material |
| CN111014272A (en) * | 2019-11-19 | 2020-04-17 | 清华苏州环境创新研究院 | Method for removing heavy metals in soil or plants by using triethylamine bisulfate ionic liquid |
| CN112453041A (en) * | 2020-11-03 | 2021-03-09 | 武汉科技大学 | Soil heavy metal eluting agent, eluting method of heavy metal contaminated soil and application |
| CN112625689A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Soil composite eluting agent containing degradable chelating agent and method for repairing soil |
| CN113245358A (en) * | 2021-03-29 | 2021-08-13 | 广州珠合工程技术有限公司 | EDTA-microorganism leaching combined soil remediation method |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106238449A (en) * | 2016-08-30 | 2016-12-21 | 樊之雄 | A kind of restorative procedure of heavy-metal contaminated soil |
| CN106799391A (en) * | 2017-01-16 | 2017-06-06 | 中国地质大学（北京） | A kind of method and processing equipment repaired pollution of vanadium soil and reclaim vanadium |
| CN106732832B (en) * | 2017-01-23 | 2019-05-10 | 湖南农业大学 | EDTA metal complex is recycled using metal salt solution and regenerates the method for Chioro-anion exchange resin |
| CN106732832A (en) * | 2017-01-23 | 2017-05-31 | 湖南农业大学 | The method for reclaiming EDTA metal complexs and regeneration Chioro-anion exchange resin using metal salt solution |
| CN106925604A (en) * | 2017-04-30 | 2017-07-07 | 惠州市东江园林工程有限公司 | A kind of method that plant combined chelating agent administers heavy-metal contaminated soil |
| CN108435772A (en) * | 2018-02-26 | 2018-08-24 | 中冶华天南京工程技术有限公司 | Method for restoration of soil polluted by heavy metal |
| CN108620428B (en) * | 2018-04-08 | 2020-12-18 | 王微静 | Soil heavy metal leacheate based on ionic liquid and preparation method thereof |
| CN108620428A (en) * | 2018-04-08 | 2018-10-09 | 杨大伟 | A kind of heavy metal-polluted soil leacheate and preparation method thereof based on ionic liquid |
| CN108841496A (en) * | 2018-07-21 | 2018-11-20 | 刘小平 | Brewed wine containing Chinese Milk Vetch Seeds in a kind of raw material |
| CN112625689A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Soil composite eluting agent containing degradable chelating agent and method for repairing soil |
| CN111014272A (en) * | 2019-11-19 | 2020-04-17 | 清华苏州环境创新研究院 | Method for removing heavy metals in soil or plants by using triethylamine bisulfate ionic liquid |
| CN112453041A (en) * | 2020-11-03 | 2021-03-09 | 武汉科技大学 | Soil heavy metal eluting agent, eluting method of heavy metal contaminated soil and application |
| CN113245358A (en) * | 2021-03-29 | 2021-08-13 | 广州珠合工程技术有限公司 | EDTA-microorganism leaching combined soil remediation method |
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