CN107597827A - It is a kind of to remove the method for arsenic antimony and other heavy metal elements in contaminated site soil - Google Patents
It is a kind of to remove the method for arsenic antimony and other heavy metal elements in contaminated site soil Download PDFInfo
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Abstract
The method of arsenic antimony and other heavy metal elements in contaminated site soil is removed the invention discloses a kind of, this method comprises the following steps：(1) pretreatment early stage is carried out to contaminated site soil, (2) mix oxalic acid and tannic acid according to a certain percentage, and compound eluent is made；(3) using compound eluent elution contaminated site soil, (4) are eluted using ferric chloride solution, and (5) are washed using cleaning, and carry out separation of solid and liquid, soil after being repaired.The inventive method can quickly and efficiently make arsenic antimony be spun off from soil particle, and the cations such as lead zinc cadmium can be made to be transferred to liquid phase from solid phase, and yin, yang heavy metal ion is targetedly set to be spun off from soil particle, significant effect, thoroughly, the inventive method is smaller to the structure damage capability of soil, the recycling and reproducibility of soil are not influenceed, and the inventive method is especially suitable for high concentration, the contaminated soil of site of detection device for multi metallic elements combined pollution.
Description
Technical field
The invention belongs to heavy metal-polluted soil recovery technique field, more particularly to it is a kind of remove in contaminated site soil arsenic antimony and
The method of other heavy metal elements.
Background technology
In recent years, the industry such as metallurgy, chemical industry is brought to China and many environment is also brought while great economic benefit
The pollution problem of problem, especially soil becomes increasingly conspicuous.Mining, ore dressing and smelting are that the master of heavy metal is discharged into soil environment
Want one of approach.Waste mining rock, mine tailing discharge substantial amounts of heavy metal in earth's surface oxidation, leaching process, migrate vertically downward
Secondary mineral is formed to deep, causes heavy metal to be largely enriched with, pollutes lower overburden layer.Many metals are with fine ore in smelting process
Particle, oxide aerosol particle form by aerial migration, settle into soil.Produced in metal industry with heat treatment process
Aerosol particle, the row for the metal salt solution that the sewage and electroplating industry that metal flows out after acidic materials are handled use
Put, heavy metal is entered soil.Because with similar chemical activity and primary ore often with the shape of sulfide
Formula is present, and the association in ore of three kinds of lead, zinc, cadmium elements is present, and arsenic occurs with the normal association of antimony element.Much adopt, select, smelting place
The pollution of serious heavy metal pollution, particularly multielement is caused during long-term production.A variety of pollution element phase interactions
With, or mutually suppress, or mutually promote, different environmental conditions triggers different environmental effects, causes caused harm to be more difficult to
To estimate and control.
Chemical leaching technology eliminate heavy metal bring endanger influence in terms of there are huge potentiality.The technology pass through to
Soil add chemical leaching medicament, stirring chemical agent is fully contacted soil particle, by chemistry effect make heavy metal from
Spun off in soil particle, heavy metal is transferred to from solid phase of soil and be more easy in the liquid phase of processing, it is clear so as to reach
The effect of clean soil.Detection device for multi metallic elements combined pollution, because the otherness between element, cause the improvement of contaminated soil difficult
Degree increases, and only with a kind of elution medicament, is often unable to reach repairing effect, especially with arsenic antimony existing for anionic form and with
The contaminated soil that lead zinc cadmium etc. existing for cationic form coexists.
Existing patent of invention CN101362146 provides chemical leaching that is a kind of while removing removing heavy metals and arsenic, but not
It is related to heavy metal antimony.The chemical leaching is formulated by three kinds of EDTA, ammoniacal liquor and oxalic acid chemical reagent, and the purpose of ammoniacal liquor is
Dissolve EDTA, there is provided ammonium ion.Using the technology of the invention, EDTA is artificial chelating agent, expensive and be difficult to be given birth to
Thing is degraded, and is had certain bio-toxicity, is brought quadratic risk function to environment, be unfavorable for the popularization of technology.
Therefore, polluted for contaminated sites place multielement, exploitation novel environment friendly, the Heavy Metals in Soil Contaminated of economical and efficient
Treatment process, the important meaning and value having to elution technique in the scale popularization and application of heavy metal pollution place.
The content of the invention
The technical problems to be solved by the invention are to provide the low removal Pollution Field of a kind of good degrading effect, environmental protection, cost
The method of arsenic antimony and other heavy metal elements in ground soil.
The present invention solves above-mentioned technical problem with following technical scheme：
The present invention removes the method for arsenic antimony and other heavy metal elements in contaminated site soil, comprises the following steps：
(1) pretreatment early stage is carried out to contaminated site soil：Contaminated soil is carried out to air-dry removal of impurities, crosses 10 mesh sieves；
(2) compound eluent is configured：Oxalic acid and tannic acid are mixed according to a certain percentage, compound eluent is made；
(3) compound eluent elution：Pretreated contaminated soil is added into step (2) configuration according to certain liquid-solid ratio
Compound eluent, upset vibration 2-4h, elution number 1~2 time, high speed centrifugation, is allowed to separation of solid and liquid；
(4) ferric chloride solution elutes：The Polluted Soil for adding ferric chloride solution after step (3) elution according to certain liquid-solid ratio
In earth, upset vibration 2-4h, elution number 1~2 time, high speed centrifugation, separation of solid and liquid is allowed to；
(5) cleaning washing：Contaminated soil after step (4) elution is vibrated according to certain liquid-solid ratio with clean water
Elution 1~2 time, high speed centrifugation, is allowed to separation of solid and liquid, soil after being repaired.
The concentration of step (2) mesoxalic acid is 0.1-0.5mol/L, and the concentration of tannic acid is 0.01-0.1mol/L, grass
The volume proportion of acid and tannic acid is 5:1.
In the step (4), the concentration of ferric chloride solution is 0.5mol/L.
The clean water and Polluted Soil of the compound eluent of the step (3), the ferric chloride solution of step (4) and step (5)
The liquid-solid ratio of earth is 10 milliliters:1 gram.
Step (3), (4), the vibration elution described in (5) are that the container for accommodating contaminated soil is placed in into upset oscillator device
In, under normal temperature, rotating speed 30r/min, 1~4h of duration of oscillation.
The present invention uses compound eluent, elutes mode with reference to substep, joint is made using different eluent enhancing elution
With specifically there is following beneficial effect：
1) oxalic acid that the present invention uses has stronger sequestering power, oxalic acid and tannic acid to arsenic antimony existing for anionic form
The compound eluent being configured to, arsenic antimony can be quickly and efficiently set to be spun off from soil particle.
2) present invention in acid condition, the enhancing of the transfer ability of the cation such as lead zinc cadmium, the iron ion of iron chloride to
Existing for cationic form there is competitive Adsorption in the heavy metal ion such as lead zinc cadmium, the cations such as lead zinc cadmium is transferred to from solid phase
Liquid phase, intractability substantially reduce.
3) it is molten can to adjust compound eluent and iron chloride according to the height of heavy metal element zwitterion content by the present invention
The elution number of liquid, targetedly makes yin, yang heavy metal ion be spun off from soil particle, and effect is significantly, thoroughly.
4) oxalic acid, potassium dihydrogen phosphate, the iron chloride that the present invention uses are smaller to the structure damage capability of soil, do not influence soil
The recycling and reproducibility of earth.
5) the inventive method is especially suitable for high concentration, the contaminated soil of site of detection device for multi metallic elements combined pollution.
Embodiment
The present invention removes the method for arsenic antimony and other heavy metal elements in contaminated site soil, and concrete operations are as follows：
(1) pretreatment early stage is carried out to place combined contamination soil：Contaminated soil is carried out to air-dry removal of impurities, crosses 10 mesh sieves；
(2) preparation of compound eluent：Oxalic acid and tannic acid are mixed according to a certain percentage, compound eluent is made；Grass
The concentration of acid is 0.1-0.5mol/L, and the concentration of tannic acid is 0.01-0.01mol/L；The match ratio of oxalic acid and tannic acid is 5:
1。
(3) compound eluent elution：Pretreated place combined contamination soil is loaded to 150ml plastic bottle containing inner cap
In, the compound eluent of step (2) configuration is added according to certain liquid-solid ratio, upset vibration 2-4h, elutes number 1~2 time, at a high speed
Centrifugation, is allowed to separation of solid and liquid；
(4) ferric chloride solution elutes：After 0.5mol/L ferric chloride solutions are added into step (3) elution according to certain liquid-solid ratio
Place combined contamination soil in, upset vibration 2-4h, elution number 1~2 time, high speed centrifugation, be allowed to separation of solid and liquid；
(5) cleaning washing：Soil after step (4) elution, according to the clean water vibration elution 1 of certain liquid-solid ratio
~2 times, high speed centrifugation, separation of solid and liquid is allowed to, soil after being repaired.
Preferably, step (3), (4), compound eluent, ferric chloride solution, clean water and arsenic antimony described in (5) are answered
The liquid-solid ratio for closing contaminated soil is 10 milliliters:1 gram.
Preferably, step (3), (4), the vibration elution described in (5) are that plastic bottle is placed in upset oscillator device, often
Under temperature, rotating speed 30r/min, 1~4h of duration of oscillation.
Below by way of specific embodiment, the invention will be further described.
Embodiment 1：
(1) the farmland topsoil near the antimony ore place of Guangxi District is gathered, natural air drying, 10 mesh are crossed after removing debris
Sieve.Soil physico-chemical property is shown in Table 1 with content of beary metal.
The soil physico-chemical property of table 1 and content of beary metal
(2) compound eluent is prepared：By 0.1mol/L oxalic acid and 0.05mol/L tannic acid according to oxalic acid:Tannic acid=
5:1 volume ratio prepares compound eluent.
(3) soil adds the compound eluents of 100ml for the first time in 150ml plastic bottles after weighing 10g screenings, i.e. liquid is consolidated
Than for 10 milliliters：1 gram, it is placed in turnover oscillator, 2h is vibrated under the conditions of 30r/min；
(4) high speed centrifugation, after separation of solid and liquid pours out discarded leacheate, second of addition compound eluent of 100ml, i.e. liquid is consolidated
Than for 10 milliliters：1 gram, 2h is vibrated under the conditions of 30r/min；
(5) high speed centrifugation, after separation of solid and liquid pours out discarded leacheate, third time adds 100ml ferric chloride solutions, and (concentration is
0.5mol/L), i.e., liquid-solid ratio is 10 milliliters：1 gram, 2h is vibrated under the conditions of 30r/min；
(6) high speed centrifugation, after separation of solid and liquid pours out discarded leacheate, 100ml distilled water is added, i.e. liquid-solid ratio is 10 millis
Rise：1 gram, 1h is vibrated under the conditions of 30r/min；
(7) high speed centrifugation, after separation of solid and liquid pours out discarded leacheate, soil after cleaning is produced.
(8) after repeatedly elution repair process, content of beary metal and clearance in soil are shown in Table 2.
The content of beary metal and clearance of soil after table 2 elutes
Embodiment 2：
(1) topsoil in Guangxi District antimony ore place is gathered, natural air drying, 10 mesh sieves are crossed after removing debris stone.Soil
Earth physicochemical property is shown in Table 3 with content of beary metal.
The soil physico-chemical property of table 2 and content of beary metal
(2) compound eluent is prepared：By 0.3mol/L oxalic acid and 0.01mol/L tannic acid according to oxalic acid:Tannic acid
=5:1 volume ratio prepares compound eluent.
(3) soil adds the compound eluents of 100ml for the first time in 150ml plastic bottles after weighing 10g screenings, i.e. liquid is consolidated
Than for 10 milliliters：1 gram, it is placed in turnover oscillator, 2h is vibrated under the conditions of 30r/min；
(4) high speed centrifugation, after separation of solid and liquid pours out discarded leacheate, second of addition compound eluent of 100ml, i.e. liquid is consolidated
Than for 10 milliliters：1 gram, 2h is vibrated under the conditions of 30r/min；
(5) high speed centrifugation, after separation of solid and liquid pours out discarded leacheate, third time adds 100ml ferric chloride solutions, and (concentration is
0.5mol/L), i.e., liquid-solid ratio is 10 milliliters：1 gram, 2h is vibrated under the conditions of 30r/min；
(6) high speed centrifugation, after separation of solid and liquid pours out discarded leacheate, 100ml distilled water is added, i.e. liquid-solid ratio is 10 millis
Rise：1 gram, 1h is vibrated under the conditions of 30r/min；
(7) high speed centrifugation, after separation of solid and liquid pours out discarded leacheate, soil after cleaning is produced.
(8) after repeatedly elution repair process, content of beary metal and clearance in soil are shown in Table 4.
The content of beary metal and clearance of soil after table 4 elutes
Embodiment 3：
(1) topsoil near the sewage draining exit of Guangxi District lead zinc antimony ore place is gathered, natural air drying, removes debris stone
10 mesh sieves are crossed afterwards.Soil physico-chemical property is shown in Table 5 with content of beary metal.
The soil physico-chemical property of table 5 and content of beary metal
(2) compound eluent is prepared：By 0.5mol/L oxalic acid and 0.1mol/L tannic acid according to oxalic acid:Tannic acid=
5:1 volume ratio prepares compound eluent.
(3) soil adds the compound eluents of 100ml for the first time in 150ml plastic bottles after weighing 10g screenings, i.e. liquid is consolidated
Than for 10 milliliters：1 gram, it is placed in turnover oscillator, 2h is vibrated under the conditions of 30r/min；
(4) high speed centrifugation, after separation of solid and liquid pours out discarded leacheate, second adds 100ml ferric chloride solutions, and (concentration is
0.5mol/L), i.e., liquid-solid ratio is 10 milliliters：1 gram, 2h is vibrated under the conditions of 30r/min；
(5) high speed centrifugation, after separation of solid and liquid pours out discarded leacheate, third time adds 100ml ferric chloride solutions, i.e. liquid is consolidated
Than for 10 milliliters：1 gram, 2h is vibrated under the conditions of 30r/min；
(6) high speed centrifugation, after separation of solid and liquid pours out discarded leacheate, 100ml distilled water is added, i.e. liquid-solid ratio is 10 millis
Rise：1 gram, 1h is vibrated under the conditions of 30r/min；
(7) high speed centrifugation, after separation of solid and liquid pours out discarded leacheate, soil after cleaning is produced.
(8) after repeatedly elution repair process, content of beary metal and clearance in soil are shown in Table 6.
The content of beary metal and clearance of soil after table 6 elutes
In summary, the present invention removes the method for arsenic antimony and other heavy metal elements in contaminated soil of site, can be effective
The detection device for multi metallic elements content in the heavy-metal composite pollution soil of place, removal of the compound elution medicament to As, Sb must be reduced
Effect is preferable, and iron chloride is preferable to Pb, Zn, Cd removal effect, both combine elution can more thoroughly repair negative and positive heavy metal from
Sub- contaminated soil, good demonstration is provided for the reparation in heavy metal pollution place.
It the above is only and the preferred embodiments of the invention are described, protection scope of the present invention is not limited merely to
Above-described embodiment, so, it is regarded as protection model of the invention with various technical schemes of the present inventive concept without substantial differences
In enclosing.
Claims (5)
1. a kind of remove the method for arsenic antimony and other heavy metal elements in contaminated site soil, it is characterised in that it includes following
Step：
(1) pretreatment early stage is carried out to contaminated site soil：Contaminated soil is carried out to air-dry removal of impurities, crosses 10 mesh sieves；
(2) compound eluent is configured：Oxalic acid and tannic acid are mixed according to a certain percentage, compound eluent is made；
(3) compound eluent elution：Pretreated contaminated soil is added into the compound of step (2) configuration according to certain liquid-solid ratio
Eluent, upset vibration 2-4h, elution number 1~2 time, high speed centrifugation, is allowed to separation of solid and liquid；
(4) ferric chloride solution elutes：The contaminated soil for adding ferric chloride solution after step (3) elution according to certain liquid-solid ratio
In, upset vibration 2-4h, elution number 1~2 time, high speed centrifugation, it is allowed to separation of solid and liquid；
(5) cleaning washing：It will be vibrated and eluted with clean water according to certain liquid-solid ratio by the contaminated soil after step (4) elution
1~2 time, high speed centrifugation, separation of solid and liquid is allowed to, soil after being repaired.
2. removing the method for arsenic antimony and other heavy metal elements in contaminated site soil according to claim 1, its feature exists
In the concentration of step (2) mesoxalic acid is 0.1-0.5mol/L, and the concentration of tannic acid is 0.01-0.1mol/L, oxalic acid and tannic acid
Volume proportion be 5:1.
3. according to claim 1 or claim 2 remove the method for arsenic antimony and other heavy metal elements in contaminated site soil, its feature
It is, in step (4), the concentration of ferric chloride solution is 0.5mol/L.
4. according to claim 1 or claim 2 remove the method for arsenic antimony and other heavy metal elements in contaminated site soil, its feature
Be, the ferric chloride solution described in compound eluent, step (4) described in step (3) and the clean water described in step (5) with
The liquid-solid ratio of contaminated soil is 10 milliliters:1 gram.
5. the method for removing arsenic antimony and other heavy metal elements in contaminated site soil according to claim 1 or claim 2, its
It is characterised by, step (3), (4), the vibration elution described in (5) are that the container for accommodating contaminated soil is placed in into upset oscillator device
In, under normal temperature, rotating speed 30r/min, 1~4h of duration of oscillation.
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| CN110479746A (en) * | 2019-07-31 | 2019-11-22 | 招商局生态环保科技有限公司 | A kind of soil remediation and lead recovery process in lead contamination place |
| CN112852434A (en) * | 2020-12-21 | 2021-05-28 | 华南理工大学 | Preparation and application of environment-friendly heavy metal composite contaminated soil remediation eluent |
| CN113290042A (en) * | 2021-06-29 | 2021-08-24 | 新地环境科技（深圳）有限公司 | Composite eluting agent and method for repairing heavy metal composite contaminated soil by using same |
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| CN113290042A (en) * | 2021-06-29 | 2021-08-24 | 新地环境科技（深圳）有限公司 | Composite eluting agent and method for repairing heavy metal composite contaminated soil by using same |
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Application publication date: 20180119 |