CN105668702B - The method that Chioro-anion exchange resin removes Cu, Zn, Pb, Cd in Ca-EDTA leached soil solutions - Google Patents
The method that Chioro-anion exchange resin removes Cu, Zn, Pb, Cd in Ca-EDTA leached soil solutions Download PDFInfo
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- CN105668702B CN105668702B CN201610046850.4A CN201610046850A CN105668702B CN 105668702 B CN105668702 B CN 105668702B CN 201610046850 A CN201610046850 A CN 201610046850A CN 105668702 B CN105668702 B CN 105668702B
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- resin
- leacheate
- edta
- anion exchange
- chioro
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The present invention prepares the Ca EDTA solution of 2.5mmol/L using physical method, and contaminated soil is eluted, its leacheate is collected, Chioro-anion exchange resin is used in combination to be mixed with Ca EDTA leached soil solutions, then resin is detached with leacheate, resin trap is in case reuse.Chioro-anion exchange resin used in the present invention has a preferable adsorption capacity to heavy metal in Ca EDTA leacheates, and resin can have good adsorption effect in the case that dosage is lower to the heavy metal in leacheate.Resin can be regenerated by two-stage regeneration process simultaneously, to reuse, and equally have preferable adsorption effect, be also beneficial to reduce cost, reduced the secondary pollution to environment.
Description
Technical field
The present invention relates to a kind of Chioro-anion exchange resins to remove Cu, Zn, Pb, Cd in Ca-EDTA leached soil solutions
Method.
Background technology
Currently, will produce many leacheates during Soil leaching, due to containing EDTA and heavy metal in leacheate, such as
Fruit can cause environmental pollution if directly being discharged leacheate, while in view of EDTA prices are more expensive, work as processing
When a large amount of polluted soils, required cost is higher.Therefore EDTA is recycled, the cost of Soil leaching can be reduced.
The method of processing EDTA eluates common are the precipitation method, including neutralization precipitation method, sulphide precipitation, iron at present
Oxysome coprecipitation, chemical reduction method, electrochemical reducing and high molecular heavy metals trapping agent method etc..Separately having makes in waste water
The method that heavy metal is adsorbed under conditions of not changing its chemical form, concentrated, detached, including absorption, solvent extraction, steaming
Hair and freezing method, ion exchange and UF membrane etc..Or the effects that by the flocculation of microorganism or plant, absorption, accumulation, enrichment
The method for removing heavy metal in waste water(Chen Jinxiu etc., 2013).One of which method is Na2The S precipitation method, this method are in alkalinity
Under environment, make Ca-EDTA leached soil solutions and Na2S solution reacts, make in leacheate heavy metal formed sulfide precipitation from
And be recycled, then use HNO3Adjust recycling EDTA solution pH value, then by the EDTA solution of recycling continue to
Soil leaching, but compared with when eluting first time, the removal rate of each heavy metal element all decreases, while generating a large amount of
The subsequent processes of sediment bring problem(Zeng Qingru, 2003).Song Jiming etc.(2000)The study found that chelate exchange resin can
The heavy metal ion in water removal is gone, and resin can regenerate, and be reused.But this method deposits recovery processing EDTA
The heavy metal in solution still has the low defect for the treatment of effeciency under conditions.So far, the chlorine type anion exchange used in the present invention
Resin is not yet used to handle Ca-EDTA leached soil solutions, in this, as the innovative point of the present invention.
Chioro-anion exchange resin used in the present invention passes through the suction to heavy metallic salt in Ca-EDTA leached soil solutions
It is attached, so as to achieve the effect that remove heavy metal and recycling EDTA in Ca-EDTA leached soil solutions.In addition, resin after absorption
Can by with it is certain density(Acid, alkali or salt)Exchange reaction occurs for solution, and the ion adsorbed on resin is fallen in removing, to make
The resin to fail in resin layer restores the ability that absorption exchanges again, so that it is regenerated and is used for follow-up washing tests, is likewise supplied with
Preferable elution effect.It is also beneficial to save the cost of processing leacheate in this way, while operating more easy.
Invention content
The object of the present invention is to provide a kind of Chioro-anion exchange resin remove Ca-EDTA leached soil solutions in Cu, Zn,
The method of Pb, Cd
The side of Cu, Zn, Pb, Cd in Chioro-anion exchange resin removal Ca-EDTA leached soil solutions provided by the invention
Method step is:
1)2.5mmol/L Ca-EDTA solution is by EDTA(Diethylamine tetraacethyl), calcium oxide, according to 1:2 molar ratios are matched
It sets;
2)The preparation of leacheate:It takes the soil 300g for crossing 2mm sieves after air-drying to be added in the beaker of 2L, 1500ml is added
The Ca-EDTA solution of 2.5mmolL-1, at ambient temperature electric blender 2 h are stirred with the speed of 150 rmin-1,
12h is stood, the eluate in beaker is poured into 100ml centrifuge tubes and centrifuges 15min, filtering, leacheate with 4000 rmin-1
It is tested for subsequent recovery after collection.
3)Anion exchange resin adsorbs:2.00g anion exchange resin is weighed to be fitted into a series of 60 ml centrifugal bottles,
Respectively according to solid-to-liquid ratio 1:5、1:10、1:20 are added the leacheate prepared, then on the oscillator with 150 rmin-1
Constant temperature(25℃)2 h are vibrated, filters, resin is detached with leacheate, resin trap is in case reuse, the huge sum of money in leacheate
It is to be measured to belong to content.In triplicate, results are averaged for each processing.
4)Anion exchange resin regeneration test:The used resin for taking collection, by crossing column experiments, using two steps
Method of reproduction:The first step is eluted from resin heavy metal ion with acid;This experiment uses 0.1mol/L HCl.Second step,
Resin is restored to its original state with lye;This experiment uses 0.1mol/L NaOH.Distilled water flushing is then used, tree is cleaned
Remaining lye in lipid layer.Resin after regeneration is continued on for into the adsorption test to leacheate, operating procedure is same as above.
The present invention prepares the Ca-EDTA solution of 2.5mmol/L using physical method, and after being mixed with soil, collects its leaching
Washing lotion is used in combination 2.00g Chioro-anion exchange resins to be mixed with Ca-EDTA leacheates with different solid ratio, then by resin with
Leacheate detaches, and resin trap is in case reuse.The present invention adsorbs Ca-EDTA leacheates using Chioro-anion exchange resin
Middle heavy metal, and resin can have good adsorption effect in the case that dosage is lower to the heavy metal in leacheate.Simultaneously
Resin can be reused by regeneration, and equally have preferable adsorption effect, be also beneficial to reduce cost, be reduced
Secondary pollution to environment.
Specific implementation mode
Example one:Anion exchange resin adsorbs:It weighs 2.00g anion exchange resin and is packed into a series of 60 ml centrifugations
In bottle, respectively according to solid-to-liquid ratio 1:5、1:10、1:20 are added the leacheate prepared, then on the oscillator with 150 r
Min-1 constant temperature(25℃)2 h are vibrated, filters, resin is detached with leacheate, resin trap is in case reuse, in leacheate
Content of beary metal it is to be measured.In triplicate, results are averaged for each processing.After measured:Chioro-anion exchange resin is to leaching
Cu, Zn, Pb, Cd in washing lotion have preferable adsorption effect, and under different solid-to-liquid ratios, to the removal efficiency base of heavy metal
This is consistent, is 1 in solid-to-liquid ratio:Under conditions of 20, the removal rate of Cu, Pb, Cd are respectively 100%, 96%, 95% in leacheate.And Zn
Removal rate want more slightly lower, under the same conditions, removal rate 74%.
Example two:The recycling of EDTA and recycling:Test operation step is same as above.After measured:The EDTA obtained by recycling
Solution still has the ability of certain removal heavy metal in soil.The EDTA solution of recycling to the removal rate of Cd still close to 50%, but with
It is compared when eluting for the first time, the removal rate of each heavy metal element is all greatly reduced, and removal efficiency reduces by more than 30%.
Example three:Anion exchange resin regenerates:In view of the relationship of cost and efficiency, using solid-to-liquid ratio 1:20 are inhaled
Adhesion test.The used resin for taking collection, by crossing column experiments, using two-stage regeneration process:The first step, with acid by heavy metal
Ion is eluted from resin;This experiment uses 0.1mol/L hydrochloric acid.Resin is restored to its initial shape by second step with lye
State;This experiment uses 0.1mol/L sodium hydroxides.Distilled water flushing is then used, remaining lye in eluted resin layer.It will regeneration
Resin afterwards continues on for the adsorption test to leacheate, and operating procedure is same as above.It analyzes after measured:Resin pair after regeneration
Heavy metal in leacheate has preferable adsorption effect, and the removal rate to Cu, Zn, Pb, Cd is respectively:95.65%、74.56%、
99.69%、100%。
The present invention prepares the Ca-EDTA solution of 2.5mmol/L using physical method, and after being mixed with soil, collects its leaching
Washing lotion is used in combination Chioro-anion exchange resin leached soil solutions to mix, then detaches resin with leacheate, collects in case repeating
It uses.Chioro-anion exchange resin used in the present invention can have metal ion in leacheate preferable adsorption capacity, and
And resin can have good adsorption effect in the case that dosage is lower to the heavy metal in leacheate.Resin can pass through simultaneously
Two-stage regeneration process is regenerated, and to reuse, and is equally had preferable adsorption effect, is also beneficial to reduce cost,
Reduce the secondary pollution to environment.
Claims (1)
1. its feature packet of the method for Cu, Zn, Pb, Cd in a kind of Chioro-anion exchange resin removal Ca-EDTA leached soil solutions
Include following steps:
(1) by EDTA, calcium oxide according to 1:2 molar ratios configure 2.5mmol/L Ca-EDTA solution;
(2) preparation of leacheate:It takes the soil 300g for crossing 2mm sieves after air-drying to be added in the beaker of 2L, adds 1500ml
2.5mmol·L-1Ca-EDTA solution, at ambient temperature use electric blender with 150rmin-1Speed stir 2h,
12h is stood, the eluate in beaker is poured into 100ml centrifuge tubes with 4000rmin-115min, filtering are centrifuged, leacheate is received
It is tested for subsequent recovery after collection;
(3) anion exchange resin adsorbs:2.00g Chioro-anion exchange resins are weighed to be fitted into a series of 60ml centrifugal bottles,
Respectively according to solid-to-liquid ratio 1:5、1:10、1:20 are added the leacheate prepared, then on the oscillator with 150rmin-1It is permanent
25 DEG C of oscillation 2h of temperature, filtering detach resin with leacheate, in case reusing, the heavy metal in leacheate contains resin trap
It measures to be measured;
(4) anion exchange resin regenerates:
The first step takes step(3)The used resin collected, by crossing column experiments, using the salt of a concentration of 0.1mol/L
Acid elutes heavy metal ion from resin;
Resin is restored to its original state by second step using a concentration of 0.1mol/L sodium hydroxides;
Third walks, and then uses distilled water flushing, remaining lye in eluted resin layer;
Resin after regeneration is continued on for the adsorption test to leacheate by the 4th step.
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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 |
CN107303586B (en) * | 2017-08-07 | 2018-09-14 | 燕山大学 | A kind of in-situ remediation method of heavy-metal contaminated soil |
CN110589991B (en) | 2019-09-10 | 2020-11-27 | 同济大学 | Method for removing calcium ions in high-concentration organic wastewater |
CN113387407A (en) * | 2021-06-15 | 2021-09-14 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Method for separating and recovering cadmium from base metal solution |
CN113354230B (en) * | 2021-06-30 | 2023-10-24 | 清华大学深圳国际研究生院 | Treatment method of heavy metal polluted bottom mud |
Citations (3)
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JPS5367682A (en) * | 1976-11-30 | 1978-06-16 | Ebara Infilco Co Ltd | Regenerating method for condensate water demineralization apparatus |
GB2063094B (en) * | 1979-11-10 | 1983-07-20 | Permutit Boby Ltd | Water purification by ion exchange |
CN1787971A (en) * | 2004-02-09 | 2006-06-14 | 日立麦克赛尔株式会社 | Apparatus for forming ion-exchanged water and method for regenerating ion exchange resin therein |
-
2016
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS5367682A (en) * | 1976-11-30 | 1978-06-16 | Ebara Infilco Co Ltd | Regenerating method for condensate water demineralization apparatus |
GB2063094B (en) * | 1979-11-10 | 1983-07-20 | Permutit Boby Ltd | Water purification by ion exchange |
CN1787971A (en) * | 2004-02-09 | 2006-06-14 | 日立麦克赛尔株式会社 | Apparatus for forming ion-exchanged water and method for regenerating ion exchange resin therein |
Non-Patent Citations (1)
Title |
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"Removal of trace metals from contaminated soils using EDTA incorporating resin trapping techniques";R.STejowulana等;《Environmental Pollution》;19981001;第103卷(第1期);第135-142页摘要、材料与方法部分 * |
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