CN105060384A - Method for synergistic extraction and separation of heavy metal ions from waste water in copper waste rock field - Google Patents
Method for synergistic extraction and separation of heavy metal ions from waste water in copper waste rock field Download PDFInfo
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- CN105060384A CN105060384A CN201510485792.0A CN201510485792A CN105060384A CN 105060384 A CN105060384 A CN 105060384A CN 201510485792 A CN201510485792 A CN 201510485792A CN 105060384 A CN105060384 A CN 105060384A
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Abstract
The invention relates to a method for synergistic extraction and separation of heavy metal ions from waste water in a copper waste rock field, and belongs to the field of hydrometallurgy. The method provided by the invention is characterized in that a saponified carboxylic acid extraction solvent and non-saponified oxime, an oxime extraction agent are mixed in a certain proportion, and the mixture is adopted as a synergistic extraction agent; the heavy metal ions(Cu<2+>,Pb<2+>,Zn<2+>,Cd<2+>) and impurity ions (Ca<2+>,Mg<2+>) from waste water in the copper waste rock field are extracted and separated; the heavy metal ions enters an organic tank, so as to greatly reduce concentration of heavy metal ions in a raffinate solution to meet an emission standard; and the pH value is about 7.0, and direct emission will not lead to land acidification, thereby achieving a purpose of purifying waste water of mines from the source. The method has characteristics of being low in cost, high in efficiency and simple in flow and the like.
Description
Technical field:
The present invention relates to a kind of method of synergistic extraction separating copper waste rock pile heavy metal ions in wastewater, for the treatment of the acid waste water of cupric, cadmium, lead and zine ion, belong to field of hydrometallurgy.
Background technology:
In April, 2015, country put into effect water prevention and cure of pollution action plan, required to take charge of industrial pollution control severely, and wherein non-ferrous metal industry is one of important source of pollution.Mine wastewater discharge causes river, soil by heavy metal contamination area cumulative year after year, is the aggravation of preventing pollution problem, solves heavy metal wastewater thereby emission problem extremely urgent from source.
The domestic treatment process to acidic mine waste water is a lot, but cuts both ways.Such as chemical Treatment cost is high, effect is unstable.Although microbial method safe ready, heavy metal ion has selectivity, is difficult to remove heavy metal contaminants comprehensively.Solvent extration is as the operating process of separating metal ions in hydrometallurgical processes flow process, its technology has developed into the comparatively ripe stage, solvent extration is used for reference in heavy metal containing wastewater treatment, well can improve heavy metal waste water treatment process, and strengthen the recovery of heavy metal ion, there is good environmental benefit and economic benefit.
Mine wastewater complicated component, adopt single extraction system separation of metal ions difficulty large, technical process is long, and separating effect is undesirable.And synergistic system has and improves extraction rate and extraction selectivity, strengthen extracted species stability, improve extracted species a series of advantage such as solubleness in organic phase.Investigator is had to adopt Versatic10 and LIX63 synergistic extractant system from containing separating nickel the isoionic solution of copper, zinc and manganese and cobalt ion (ChengC.Y., Hydrometallurgy, 2006) abroad.Chinese patent adopts the elements such as synergistic extraction method separating nickel (CN103184337A, CN103421952A), rare earth (CN102041384A, CN101294244B).Lower for concentration of metal ions, the solution of complicated component needs the synergistic system exploring good separation further.
Summary of the invention:
The present invention is the heavy metal ion in high-level efficiency separating copper waste rock pile waste water, solves heavy metal wastewater thereby pollution problem from source, provides a kind of method of synergistic extraction separating copper waste rock pile heavy metal ions in wastewater.This synergistic extraction method can by the heavy metal ion (Cu in waste water
2+, Pb
2+, Zn
2+, Cd
2+) be enriched in organic phase, foreign ion (Ca
2+, Mg
2+) remain in aqueous phase, concentration of heavy metal ion in aqueous phase is reduced greatly, reaches heavy metal wastewater thereby emission standard.
Concrete technical scheme of the present invention, comprises the following steps:
The present invention forms synergic reagent after adopting carboxylic acid extraction agent to mix by a certain percentage with aldoxime, ketoxime extractants, then through thinner dilution, with the extracting and separating heavy metal ion (Cu that reacts containing the solution of heavy metal ion or mine wastewater
2+, Pb
2+, Zn
2+, Cd
2+) and foreign ion (Ca
2+, Mg
2+), be extracted heavy metal ion and strip obtain metal product through washing, substep.
In described synergic reagent, carboxylic acid extraction agent is MextralV10.
In described synergic reagent, aldoxime, ketoxime extractants are Mextral622H or Mextral973H.
In described synergic reagent, carboxylic acid extraction agent needs saponification, and aldoxime, ketoxime extractants are without the need to saponification.
In described synergic reagent, carboxylic acid extraction agent is through the saponification of 10mol/LNaOH solution, and saponification degree is 50%, 60%, 70% and 80%.
In described synergic reagent, carboxylic acid extraction agent mixes according to a certain volume with aldoxime, ketoxime extractants, and wherein carboxylic acid extraction agent accounts for 50%-95%, and aldoxime, ketoxime extractants account for 50%-5%.
Described thinner is DT-100 or sulfonated kerosene.
Described synergic reagent and thinner 1: 9,1: 8,1: 7,1: 6,1: 5 and 1: 4 to mix by volume.
Described organic phase is made up of synergist and thinner, and aqueous phase is solution to be extracted or mine wastewater, and organic phase and aqueous phase 2: 1,1: 1,1: 1.5,1: 2,1: 3 and 1: 4 mix and react by volume.
Described synergic reagent is the acidic mine waste water of 1.5-5.0 for the treatment of pH value.
The present invention has the following advantages:
(1) compared with single extraction system, synergistic system is extracted heavy metal ion enrichment in organic phase by a step, simplifies heavy metal ion and foreign ion separation process scheme, has important actual application value.
(2) adopt this synergistic extraction method to obtain raffinate pH value about 7.0, without the need to acid-base neutralisation, directly discharge can not cause acidification, and reduces production cost.
Embodiment:
Embodiment 1:
Large for some representative quantity discharged, the contaminated serious mine wastewater of periphery carries out Field Research, and sum up general acidic mine waste water feature, table 1 is depicted as according to metal cation component in mine wastewater and content preparation simulated solution, adopts the heavy metal ion (Cu in synergistic system separation solution
2+, Pb
2+, Zn
2+, Cd
2+) and foreign ion (Ca
2+, Mg
2+).
Metal cation component and content in table 1 simulated solution
In synergist, saponification carboxylic acid extraction agent MextralV10 and non-saponified aldoxime extractants Mextral622H volume ratio are 2: 3, and the volume ratio of synergist and thinner is 1: 5, and saponification carboxylic acid extraction agent adopts 10mol/LNaOH saponification, and saponification degree is 75%.Aqueous phase is preparation simulated solution, and the volume ratio of organic phase (being made up of synergist and thinner) and aqueous phase is 1: 1, and mixing is placed on shaking table vibrates, and hunting speed is 150rpm, and extraction time is 10min.
Metal cation component and content in raffinate is obtained as shown in table 2 through extraction.Raffinate pH value is 6.89, Cu
2+, Pb
2+, Cd
2+and Zn
2+percentage extraction is respectively 99.9%, 96.6%, 99.8% and 95.8%, Ca
2+, Mg
2+percentage extraction is respectively 16.7%, 13%.
Metal cation component and content in table 2 raffinate
Embodiment 2
With saponification carboxylic acid extraction agent MextralV10 and non-saponified aldoxime and ketoxime extractants Mextral973H for synergist, to the heavy metal ion (Cu in simulated solution
2+, Pb
2+, Zn
2+, Cd
2+) and foreign ion (Ca
2+, Mg
2+) be separated, in synergist, carboxylic acid extraction agent MextralV10 and aldoxime and ketoxime extractants Mextral973H volume ratio are 1: 1, and the volume ratio of synergist and thinner is 1: 5, and carboxylic acid extraction agent adopts 10mol/LNaOH saponification, and saponification degree is 75%.Aqueous phase is preparation simulated solution, composition and content as shown in table 1, the volume ratio of organic phase (being made up of synergist and thinner) and aqueous phase is 1: 1, and mix and be placed on shaking table and vibrate, hunting speed is 150rpm, and extraction time is 10min.
Metal cation component and content in raffinate is obtained as shown in table 3 through extraction.Raffinate pH value is 6.44, Cu
2+, Pb
2+, Cd
2+and Zn
2+percentage extraction is respectively 99.3%, 98.3%, 98% and 99.3%, Ca
2+, Mg
2+percentage extraction is respectively 11.4%, 6.5%.
Metal cation component and content in table 3 raffinate
Embodiment 3
Adopt the synergistic extractant system of carboxylic acid extraction agent MextralV10 and aldoxime extractants Mextral622H mixing to certain copper mine waste rock pile Acid water reservoir hydrops pond heavy metal ions in wastewater (Cu
2+, Pb
2+, Zn
2+) and foreign ion (Ca
2+, Mg
2+) carry out extracting and separating.In synergist, saponification carboxylic acid extraction agent MextralV10 and non-saponified aldoxime extractants Mextral622H volume ratio are 2: 1, and the volume ratio of synergist and thinner is 1: 5, and carboxylic acid extraction agent saponification degree is 75%.Aqueous phase is certain copper mine waste rock pile Acid water reservoir hydrops pond waste water, and pH value is 2.2, composition and content as shown in table 4.The volume ratio of organic phase (being made up of synergist and thinner) and aqueous phase is 1: 2, and mixing is placed on shaking table vibrates, and hunting speed is 150rpm, and extraction time is 10min.
Metal cation component and content in raffinate is obtained as shown in table 5 through extraction.Raffinate pH value is 3.83, Cu
2+, Pb
2+and Zn
2+percentage extraction is respectively 99.1%, 100% and 66.1%, Ca
2+, Mg
2+percentage extraction is respectively 5.2%, 0.41%.
Table 4 certain copper mine hydrops pond acid waste water chemical constitution and content
Metal cation component and content in table 5 raffinate
Claims (8)
1. the present invention is a kind of method of synergistic extraction separating copper waste rock pile heavy metal ions in wastewater, it is characterized in that: after adopting carboxylic acid extraction agent to mix by a certain percentage with aldoxime, ketoxime extractants, form synergic reagent, again through thinner dilution, with the extracting and separating heavy metal ion (Cu that reacts containing the acid waste water of heavy metal ion
2+, pb
2+, Zn
2+, Cd
2+) and foreign ion (Ca
2+, Mg
2+).
2. the method for synergistic extraction separating copper waste rock pile heavy metal ions in wastewater as claimed in claim 1, it is characterized in that: in described synergic reagent, carboxylic acid extraction agent is MextralV10, aldoxime, ketoxime extractants are Mextral622H or Mextral973H.
3. the method for synergistic extraction separating copper waste rock pile heavy metal ions in wastewater as claimed in claim 1, it is characterized in that: in described synergic reagent, carboxylic acid extraction agent needs saponification, aldoxime, ketoxime extractants are without the need to saponification.
4. the method for synergistic extraction separating copper waste rock pile heavy metal ions in wastewater as claimed in claim 1, is characterized in that: the volume ratio of described synergic reagent and mixing diluents is 1: 9,1: 8,1: 7,1: 6,1: 5 and 1: 4.
5. the method for synergistic extraction separating copper waste rock pile heavy metal ions in wastewater as claimed in claim 1, it is characterized in that: in described synergic reagent, carboxylic acid extraction agent is through the saponification of 10mol/LNaOH solution, saponification degree is 50%, 60%, 70% and 80%.
6. the method for synergistic extraction separating copper waste rock pile heavy metal ions in wastewater as claimed in claim 1, it is characterized in that: in described synergic reagent, carboxylic acid extraction agent mixes according to a certain volume with aldoxime, ketoxime extractants, wherein carboxylic acid extraction agent accounts for 50%-95%, and aldoxime, ketoxime extractants account for 50%-5%.
7. the method for synergistic extraction separating copper waste rock pile heavy metal ions in wastewater as claimed in claim 1, it is characterized in that: described organic phase is made up of synergist and thinner, aqueous phase is solution to be extracted or copper waste rock pile acid waste water, and organic phase and aqueous phase are 2: 1,1: 1,1: 1.5,1: 2,1: 3 and 1: 4 mix and react by volume.
8. the method for synergistic extraction separating copper waste rock pile heavy metal ions in wastewater as claimed in claim 1, is characterized in that: described synergic reagent is the acidic mine waste water of 1.5-5.0 for the treatment of pH value.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106756011A (en) * | 2016-11-25 | 2017-05-31 | 桂林理工大学 | The method that saponification directly extracts calcium is exempted from a kind of synergic solvent extraction from solution |
| CN106906369A (en) * | 2015-12-22 | 2017-06-30 | 北京有色金属研究总院 | The technique that a kind of utilization synergic solvent extraction technology reclaims copper, zinc, nickel, cadmium from heavy metal wastewater thereby |
| CN110339592A (en) * | 2019-07-22 | 2019-10-18 | 山东大学 | Heavy metal ion extracting agent based on fatty acid, preparation method and extraction method |
| CN111410217A (en) * | 2020-04-10 | 2020-07-14 | 吉林吉恩镍业股份有限公司 | Method for removing nickel and cobalt in magnesium sulfate solution by adopting extraction separation method |
Citations (3)
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|---|---|---|---|---|
| CN101003396A (en) * | 2006-01-16 | 2007-07-25 | 陈尚林 | System and method for treating wastewater of containing copper from microetching printed circuit board |
| CN101173326A (en) * | 2007-11-30 | 2008-05-07 | 浙江工业大学 | Method for recovery utilization of acid waste liquid generated in waste lead acid accumulator lead -recovery process |
| CN103566623A (en) * | 2012-07-24 | 2014-02-12 | 中国科学院大连化学物理研究所 | Dispersive liquid-liquid microextraction method of heavy metal ions by using alkyl carboxylic acid as extracting agent |
-
2015
- 2015-08-03 CN CN201510485792.0A patent/CN105060384B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003396A (en) * | 2006-01-16 | 2007-07-25 | 陈尚林 | System and method for treating wastewater of containing copper from microetching printed circuit board |
| CN101173326A (en) * | 2007-11-30 | 2008-05-07 | 浙江工业大学 | Method for recovery utilization of acid waste liquid generated in waste lead acid accumulator lead -recovery process |
| CN103566623A (en) * | 2012-07-24 | 2014-02-12 | 中国科学院大连化学物理研究所 | Dispersive liquid-liquid microextraction method of heavy metal ions by using alkyl carboxylic acid as extracting agent |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106906369A (en) * | 2015-12-22 | 2017-06-30 | 北京有色金属研究总院 | The technique that a kind of utilization synergic solvent extraction technology reclaims copper, zinc, nickel, cadmium from heavy metal wastewater thereby |
| CN106906369B (en) * | 2015-12-22 | 2018-10-26 | 北京有色金属研究总院 | A kind of technique recycling copper, zinc, nickel, cadmium from heavy metal wastewater thereby using synergic solvent extraction technology |
| CN106756011A (en) * | 2016-11-25 | 2017-05-31 | 桂林理工大学 | The method that saponification directly extracts calcium is exempted from a kind of synergic solvent extraction from solution |
| CN110339592A (en) * | 2019-07-22 | 2019-10-18 | 山东大学 | Heavy metal ion extracting agent based on fatty acid, preparation method and extraction method |
| CN110339592B (en) * | 2019-07-22 | 2020-05-08 | 山东大学 | Heavy metal ion extracting agent based on fatty acid, preparation method and extraction method |
| CN111410217A (en) * | 2020-04-10 | 2020-07-14 | 吉林吉恩镍业股份有限公司 | Method for removing nickel and cobalt in magnesium sulfate solution by adopting extraction separation method |
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