CN103966439B - In a kind of copper and sulfide tailings, the leachate separating-purifying of metal rubidium resource reclaim processes technique - Google Patents
In a kind of copper and sulfide tailings, the leachate separating-purifying of metal rubidium resource reclaim processes technique Download PDFInfo
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- CN103966439B CN103966439B CN201310040833.6A CN201310040833A CN103966439B CN 103966439 B CN103966439 B CN 103966439B CN 201310040833 A CN201310040833 A CN 201310040833A CN 103966439 B CN103966439 B CN 103966439B
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Abstract
The leachate separating-purifying that the invention discloses metal rubidium resource reclaim in a kind of copper and sulfide tailings processes technique, can be used for rubidium potassium and separates and the purification of rubidium.The most neutralized precipitation of solution removes removing heavy metals and calcium ions and magnesium ions, regulation feed liquid basicity extracts the rubidium in filtrate with the t BAMBP extractant of sulfonated kerosene dilution by comparing 2: 1 (O/A) multitple extraction to 0.5mol/L NaOH, again with pure water by comparing 10: 1 (O/A) wash load organic phase, then the organic phase after washing with 1mol/L nitric acid back extraction, makes the rubidium in organic phase be transferred in strip liquor.Repeat two-section extraction washing anti-extraction process after regulation strip liquor basicity, product purity can be made to reach 99%.
Description
Technical field
The present invention relates to the recoverying and utilizing method of tailing leaching liquid rubidium, be specifically related to, with extraction separation rubidium and potassium, obtain
Highly purified rubidium product salt.
Background technology
Rubidium is found in 1861 the earliest, and pure rubidium is silvery white, and fusing point is 39 DEG C, is the alkali of periodic table of elements first family
Metallic element, atomic number 37, atomic weight 85.47, because atomic radius and ionic radius are big, easily lose valence electron, chemically
Matter is active.Rubidium is particularly important rare precious metal resource, has great meaning in economy, strategy.Rubidium metal and chemical combination thereof
Thing uses the most extensive at biochemistry, molecular biosciences, catalyst, electronic device, photoelectric tube, special glass etc., and consumption is
Many.The overall thermal efficiency in power station can be brought up to 55%～65% with rubidium salt as medium, this is that tradition firepower steam turbine is sent out
2 times of electricity overall thermal efficiency；The voyage carrying rubidium ion propeller aircraft is about carrying equal quality conventional propellant 150
Times, the speed of service is up to 116 × 105km/h。
Rubidium is typical dispersed elements, and character is close with potassium, is often the accompanying element of potassium, at mineral, rock in nature
The content of stone and meteoritic abundance, rubidium and potassium be respectively provided with significant correlation, feldspar and mica containing rubidium be usually direct crystallization or with
Fluid carries out cation exchange and is formed, containing in rubidium ore, owing to the quantity of potassium accounts for absolute advantage.The extraction of rubidium includes well
Making from brine salting liquid, containing rubidium feldspar, lepidolite extracted lithium mother liquor, acid magmatic rock weathering crust or ionic adsorption Rare Earth Mine etc., rubidium,
Caesium is sufficiently close to element physics, chemical property such as potassium, sodium, lithium, calcium, magnesium, therefore brings great difficulty to separation and Extraction.Mesh
The separating-purifying of front rubidium is divided into selective precipitation method, ion exchange adsorption, solvent extraction three kinds.
Rubidium ion can react generation precipitation with some precipitating reagent (such as heteropoly acid, complexing hydrochlorate, halide, vitriol etc.), logical
The conditions such as control precipitant concentration, acidity of crossing can make rubidium and other magazins' layout.Due to the reagent price for selective precipitation rubidium
Universal the most costly, therefore the precipitation method are primarily adapted for use in the further purification of thick product.
Ion-exchange is the important means separating rubidium, and this method is divided into two big classes by the composition of exchanger: organic
The ion-exchange of resin and the ion-exchange of inorganic material.But owing to exchanger is relatively big by environmental influence, and rubidium from
The back suction of son is accompanied by and in leachate, the competitive Adsorption of metal all can have influence on adsorption effect so that the reality of ion-exchange should
Bigger by difficulty.
Solvent extraction technology separation rubidium is that Recent study is more, it is relatively wide to apply, a kind of isolation technics that is that make fast progress, molten
Main agents used by agent extraction includes crown ether, phenol alcohol reagent etc..The progress that extract and separate rubidium obtains at present is mainly used in
Rubidium contains quantitative analysis, and the diluent of use mostly is dimethylbenzene etc. and has more highly toxic reagent, for the reality extraction containing rubidium solution
Take production and have no relevant report.Owing to rubidium is the relatively low element of a wealth of species, in actual production solution, content is relatively low, and due to
The character of rubidium and potassium is the most close, and the content of rubidium and potassium is respectively provided with significant correlation, is often rubidium containing the potassium content in rubidium solution
About 100 times, therefore the research low concentration rubidium separating-purifying containing rubidium solution has particularly important meaning for the production of rubidium.
Summary of the invention
It is an object of the invention to provide a kind of technique simple, efficiency is high, low cost, the extraction separation method that environmental pollution is little,
From containing low concentration rubidium, high potassium concentration copper and sulfide tailings leachate separating-purifying rubidium, obtain pure rubidium strip liquor, use evaporative crystallization
Method obtain high-purity rubidium salt, it is achieved the extraction and recovery of low concentration rubidium, and reduce production cost, produce certain social benefit
And environmental benefit.
In order to overcome the deficiencies in the prior art, technical scheme uses multistage extraction-washing-back extraction associating,
Tenor design according to each section of solution produces progression, and it is characterized in that and achieves low rubidium content, high potassium content solution
The separating-purifying of rubidium, comprises the steps of
1, pretreatment: in tailing leaching liquid, rubidium content is about 600mg/L, contain simultaneously the metals such as iron, copper, zinc, manganese, calcium from
Son, sends out the impurity such as the iron removed in leachate, copper, zinc, manganese, calcium initially with chemical precipitation, and regulates leachate basicity and be
0.5mol/L。
2, multitple extraction: using t-BAMBP as extractant, sulfonated kerosene as diluent, configuration t-BAMBP concentration is
The extractant of 1mol/L, by comparing 2: 1 (O/A) multitple extraction leachate, makes the recovery of extraction of rubidium reach 100%.
3, washing: using pure water as washing agent, by comparing 10: 1 (O/A) two-stage wash load organic phase, reduces organic phase
Middle potassium content.
4, back extraction: the salpeter solution with concentration as 1mol/L is as back washing agent, after comparing 2: 1 (O/A) back extraction washing
Load organic phases, makes the rubidium in organic phase be transferred in strip liquor, it is thus achieved that one section of strip liquor.
5, two-stage extraction/washing/back extraction: the strip liquor produced with step (4), as stoste, repeats step (2), (3), (4),
Obtain two sections of strip liquors.
6, three sections of extraction/washing/back extractions: the two sections of strip liquors produced with step (5) as stoste, repeat step (2), (3),
(4), it is thus achieved that three sections of strip liquors, as back washing agent, the organic phase after follow-up third wash is carried out back extraction using three sections of strip liquors, follow
After ring 5 times, it is thus achieved that the final strip liquor that rubidium content is 3400mg/L, purity is 99%.
7, by the final strip liquor evaporating, concentrating and crystallizing obtained by step (6), the rubidium nitrate crystal that purity is 99% is obtained.
The present invention utilizes extraction separation method to purify the rubidium in solution, uses organic reagent t-BAMBP to extract completely in feed liquid
Low content rubidium, through flow process separation rubidium and potassium such as extraction-washing-back extraction, and by multistage extraction process purify rubidium, finally
Obtain high-purity rubidium solution, and obtain high-purity rubidium product salt by evaporative crystallization technique.
Accompanying drawing explanation
Fig. 1 is the typical process flow diagram of the present invention, in actual implementation process, can according to required product purity,
Suitably adjust extraction process hop count.
Fig. 2 is strip liquor Metal Ion Chromatography map analysis in three sections of flow processs, and the change of metal rubidium purity in strip liquor is described.
Detailed description of the invention
For being more fully understood that the present invention, it is further elucidated with present disclosure below in conjunction with embodiment, but the present invention's is interior
Hold and be not limited solely to the following examples.
Embodiment 1
This test uses laboratory preparation containing Rb+0.5g/L、K+The solution extraction of 100g/L, is diluted to sulfonated kerosene
The t-BAMBP of 1mol/L is extractant, and extraction is in a ratio of 2: 1 (O/A), extracts 5 grades, with pure water load organic phases, washs 3
Level, washing is in a ratio of 10: 1 (O/A), washs back loading organic phase with the nitric acid back extraction of 1mol/L, and back extraction is in a ratio of 2: 1 (O/A).
Liquid, strip liquor tenor more than analytical extraction, and calculate the rate of recovery, obtain result of the test and be shown in Table 1.
Strip liquor Rb: the K mass ratio obtained after one-section abstraction PROCESS FOR TREATMENT is increased to 1: 7 by the 1: 200 of stoste, second segment
Strip liquor Rb: the K mass ratio that extraction process obtains after processing is increased to 1.5: 1, and it is anti-that the 3rd section of extraction process obtains after processing
Extraction liquid Rb: K mass ratio is increased to 99: 1, and in strip liquor, rubidium content reaches 432.5mg/L, and potassium content is 4.4mg/L.Evaporative crystallization
The rubidium purity salt obtained is up to 98.5%, and the rate of recovery of rubidium is 81.7%.
The high potassium of table 1 solution extraction test result Han rubidium
Embodiment 2
After fired slags leachate after the sorted enrichment of copper and sulfide tailings, chloridising roasting is processed by removing heavy metals, decalcification magnesium,
The content of Rb and K is respectively 0.645g/L and 46g/L, takes 30ml sample and carries out three sections by high potassium concn solution extraction test method
Continuous extraction experimental study, result of the test is shown in Table 2.In the strip liquor obtained after three sections of extraction process, Rb: K mass ratio is increased to
82: 1, the rubidium purity salt that evaporative crystallization obtains has reached 98.5%.
Table 2 copper and sulfide tailings leachate extraction test result
Embodiment 3
After fired slags leachate after the sorted enrichment of copper and sulfide tailings, chloridising roasting is processed by removing heavy metals, decalcification magnesium,
The content of Rb and K is respectively 0.5g/L and 19.7g/L, and first paragraph, by comparing O/A=2, carries out 5 grades of extractions, and recovery of extraction can
Reach 100%, carry out two-stage back extraction by comparing O/A=2 with pure water by comparing after O/A=10 carries out 3 grades of washings.Strip liquor regulates
Basicity carries out second segment extraction to 0.5mol/LNaOH, and second segment presses O/A=2, carries out 4 sections of extractions, and recovery of extraction is
100%, with pure water by compare O/A=10 carry out 3 sections washing after two-stage back extraction again.The 3rd section of extraction is carried out after regulation basicity
Taking-back extraction, result of the test is shown in Table 3.In the strip liquor obtained after three sections of extraction process, Rb: K mass ratio is increased to 246: 1,
The rubidium purity salt that evaporative crystallization obtains has reached 99.4%.
Table 3 copper and sulfide tailings leachate extraction test result
In three sections of flow processs, Fig. 2 is shown in strip liquor Metal Ion Chromatography map analysis.As seen from the figure, in 1 section of strip liquor, rubidium ion contains
Amount is far below potassium, and in the strip liquor after 3 sections of extraction-washing-back extraction, rubidium ion content is far above the content of potassium ion.
Claims (3)
1. in a copper and sulfide tailings, the leachate separating-purifying of metal rubidium resource reclaim processes technique, it is characterised in that have following
Processing method and step:
(1) pretreatment: in tailing leaching liquid, rubidium content is 600mg/L, contains iron, copper, zinc, manganese, calcium metal ion, first simultaneously
Use chemical precipitation method to remove the iron in leachate, copper, zinc, manganese, calcium impurities, and to regulate leachate basicity be 0.5mol/L；
(2) multitple extraction: using t-BAMBP as extractant, sulfonated kerosene as diluent, configuration t-BAMBP concentration is 1mol/L
Extractant, by volume ratio 2: the 1 multitple extraction leachate of organic phase Yu aqueous phase；
(3) washing: using pure water as washing agent, by volume ratio 10: the 1 two-stage wash load organic phase of organic phase Yu aqueous phase, fall
Potassium content in low organic phase；
(4) back extraction: the salpeter solution with concentration as 1mol/L is as back washing agent, by volume ratio 2: 1 back extraction of organic phase Yu aqueous phase
Load organic phases after washing, makes the rubidium in organic phase be transferred in strip liquor, it is thus achieved that one section of strip liquor；
(5) two-stage extraction/washing/back extraction: the strip liquor produced with step (4), as stoste, repeats step (2), (3), (4), obtains
Obtain two sections of strip liquors；
(6) three sections of extraction/washing/back extractions: the two sections of strip liquors produced with step (5) as stoste, repeat step (2), (3),
(4), it is thus achieved that three sections of strip liquors, as back washing agent, the organic phase after follow-up third wash is carried out back extraction using three sections of strip liquors, follow
After ring 5 times, it is thus achieved that the final strip liquor that rubidium content is 3400mg/L, purity is 99%；
(7) by the final strip liquor evaporating, concentrating and crystallizing obtained by step (6), the rubidium nitrate crystal that purity is 99% is obtained.
Science and engineering at the leachate separating-purifying of metal rubidium resource reclaim in a kind of copper and sulfide tailings the most according to claim 1
Skill, it is characterised in that: after pretreatment, in leachate, iron, copper, zinc, manganese, calcium tenor are respectively lower than 0.5mg/L, and with hydrogen
Sodium oxide molybdena regulation leachate basicity is 0.5mol/L.
Science and engineering at the leachate separating-purifying of metal rubidium resource reclaim in a kind of copper and sulfide tailings the most according to claim 1
Skill, it is characterised in that: step (3) washing process organic phase is 10: 1 with the volume ratio of aqueous phase, and cleaning solution recycles to washing
After potassium ion in liquid reaches saturated concentration, evaporative crystallization reclaims sylvite.
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| CN106086470B (en) * | 2016-06-12 | 2017-12-22 | 宋玉军 | A kind of method that rubidium salt is obtained using Kaolin Tailings as raw material |
| CN110983041A (en) * | 2019-12-31 | 2020-04-10 | 江西南氏锂电新材料有限公司 | Purification and impurity removal method for lepidolite leaching solution |
| CN112239221B (en) * | 2020-10-19 | 2023-02-28 | 广东省科学院资源综合利用研究所 | Method for extracting rubidium chloride from rubidium-containing high-salinity brine |
| CN115491520B (en) * | 2022-02-09 | 2023-08-04 | 江西东鹏新材料有限责任公司 | Separation and extraction process of dilute alkali metal |
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| CN102206748A (en) * | 2011-04-13 | 2011-10-05 | 江西本源新材料科技有限公司 | Method for extracting potassium, rubidium, caesium and vanadium |
| CN102828052A (en) * | 2012-08-27 | 2012-12-19 | 张勇 | Method for separating potassium, rubidium, cesium and vitriol after extracting lithium from lepidolite |
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| CN102206748A (en) * | 2011-04-13 | 2011-10-05 | 江西本源新材料科技有限公司 | Method for extracting potassium, rubidium, caesium and vanadium |
| CN102828052A (en) * | 2012-08-27 | 2012-12-19 | 张勇 | Method for separating potassium, rubidium, cesium and vitriol after extracting lithium from lepidolite |
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