CN103966439A - Leachate separation and purification treatment process for recovery of metal rubidium resources from copper sulfur tailings - Google Patents
Leachate separation and purification treatment process for recovery of metal rubidium resources from copper sulfur tailings Download PDFInfo
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- CN103966439A CN103966439A CN201310040833.6A CN201310040833A CN103966439A CN 103966439 A CN103966439 A CN 103966439A CN 201310040833 A CN201310040833 A CN 201310040833A CN 103966439 A CN103966439 A CN 103966439A
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Abstract
The invention discloses a leachate separation and purification treatment process for recovery of metal rubidium resources from copper sulfur tailings, and the process can be used for separation of rubidium and potassium and purification of rubidium. The process includes: firstly subjecting a solution to neutralization and precipitation to remove heavy metals and calcium and magnesium ions, adjusting the alkalinity of the material liquid to 0.5mol/L NaOH, then taking a sulfonated kerosene diluted t-BAMBP extracting agent and conducting multistage extraction to extract rubidium from a filtrate according to a phase ratio of 2:1 (O/A), then taking pure water to wash a loaded organic phase according to a phase ratio of 10:1 (O/A), then using 1mol/L nitric acid to conduct back extraction on the washed organic phase so as to transfer rubidium in the organic phase into the back extracted liquid, and repeating the two-stage extraction-washing-back extraction process after adjusting the alkalinity of the back extracted liquid, thus making the product purity reach 99%.
Description
Technical field
The present invention relates to the recoverying and utilizing method of tailing leaching liquid rubidium, be specifically related to separate rubidium and potassium with extraction process, 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 metal of periodic table of elements first family, ordination number 37, nucleidic mass 85.47, because of atomic radius and ionic radius large, easily lose valence electron, chemical property is active.Rubidium is very important rare precious metal resource, has great meaning in economy, strategy.Rubidium metal and compound thereof use the most extensive at biological chemistry, molecular biosciences, catalyzer, electron device, phototube, special glass etc., consumption is also maximum.The overall thermal efficiency in power station can be brought up to 55%～65% taking rubidium salt as medium, this is 2 times of traditional firepower steam turbine generation overall thermal efficiency; The voyage of carrying rubidium ion thruster aircraft is approximately to carry 150 times of equal quality conventional propellants, and travelling speed can reach 116 × 10
5km/h.
Rubidium is typical dispersed elements, character and potassium are close, be often the associated element of potassium at occurring in nature, at mineral, rock and meteoritic abundance, the content of rubidium and potassium all has significant dependency, feldspar and mica are containing generally direct crystallization or carry out cationic exchange with fluid and form of rubidium, containing in rubidium ore, because the quantity of potassium accounts for absolute advantage.The extraction of rubidium comprises well making from brine salts solution, contains rubidium feldspar, lepidolite extracted lithium mother liquor, acid magmatic rock weathering crust or ionic adsorption rare-earth mineral etc., element physics, the chemical property such as rubidium, caesium and potassium, sodium, lithium, calcium, magnesium are very approaching, therefore bring great difficulty to separation and Extraction.At present the separating-purifying of rubidium is divided into three kinds of selective precipitation methods, ion exchange adsorption, solvent extration.
Rubidium ion can react with some precipitation agent (as heteropolyacid, complexing hydrochlorate, halogenide, vitriol etc.) and produce precipitation, can make rubidium separate with other impurity by controlling the conditions such as precipitation agent concentration, acidity.Because the reagent price for selective precipitation rubidium is generally more expensive, therefore the precipitator method are mainly applicable to the further purification of thick product.
Ion exchange method is the important means that separates rubidium, and this method can be divided into two large classes by the composition of exchanger: the ion exchange method of organic resin and the ion exchange method of inorganic materials.But because exchanger is subject to environmental influence larger, and the back suction of rubidium ion is accompanied by and leach liquor in the competitive adsorption of metal all can have influence on adsorption effect, make the practical application difficulty of ion exchange method larger.
It is a kind of isolation technique that Recent study is more, apply extensively, make fast progress that solvent extraction technology separates rubidium, and solvent extration main agents used comprises crown ether, phenol alcohol reagent etc.The progress that at present extracting and separating rubidium is obtained is mainly used in rubidium containing quantitative analysis, and the thinner of use mostly is dimethylbenzene etc. and has more highly toxic reagent, produces and has no relevant report containing the extraction of rubidium solution for reality.Because rubidium is the element that a wealth of species is lower, in actual production solution, content is lower, and because the character of rubidium and potassium is very close, the content of rubidium and potassium all has significant dependency, be often 100 times of left and right of rubidium containing the potassium content in rubidium solution, therefore study lower concentration and there is very important meaning containing the rubidium separating-purifying of rubidium solution for the production of rubidium.
Summary of the invention
The object of this invention is to provide a kind of technique simple, efficiency is high, cost is low, the extraction separation method that environmental pollution is little, separating-purifying rubidium from the copper sulphur tailing leaching liquid containing lower concentration rubidium, high potassium concentration, obtains pure rubidium strip liquor, adopt the method for evaporative crystallization to obtain high purity rubidium salt, realize the extraction of lower concentration rubidium and reclaim, and reduce production costs, produce certain social benefit and environmental benefit.
In order to overcome the deficiencies in the prior art, technical scheme of the present invention adopts the multistage extraction-washing-associating of stripping, produce progression according to the metal content design of each section of solution, its special character is the separating-purifying of having realized low rubidium content, high potassium content solution rubidium, comprises following steps:
1, pre-treatment: in tailing leaching liquid, rubidium content is about 600mg/L, contain the metal ions such as iron, copper, zinc, manganese, calcium simultaneously, the impurity such as the iron that first adopts chemical precipitation to send out to remove in leach liquor, copper, zinc, manganese, calcium, and to regulate leach liquor basicity be 0.5mol/L.
2, multi-stage solvent extraction: using t-BAMBP as extraction agent, sulfonated kerosene is as thinner, the extraction agent that configuration t-BAMBP concentration is 1mol/L, by (O/A) multi-stage solvent extraction leach liquor of comparing 2: 1, makes the recovery of extraction of rubidium reach 100%.
3, washing: using pure water as washing composition, by (O/A) two-stage wash load organic phase of comparing 10: 1, reduce potassium content in organic phase.
4, strip: the salpeter solution taking concentration as 1mol/L is reverse-extraction agent, by the load organic phases after (O/A) back extraction of comparing 2: 1 washing, the rubidium in organic phase is transferred in strip liquor, obtain one section of strip liquor.
5, two-stage extraction/washing/back extraction: the strip liquor producing taking step (4) is as stoste, and repeating step (2), (3), (4), obtain two sections of strip liquors.
6, three sections of extraction/washing/back extractions: two sections of strip liquors that produce taking step (5) are as stoste, repeating step (2), (3), (4), obtain three sections of strip liquors, organic phase using three sections of strip liquors as reverse-extraction agent after to follow-up third wash is carried out back extraction, circulate after 5 times, obtaining rubidium content is the final strip liquor that 3400mg/L, purity are 99%.
7, final strip liquor evaporating, concentrating and crystallizing step (6) being obtained, obtains purity and is 99% rubidium nitrate crystal.
The present invention utilizes the rubidium in extraction separation method purification solution, adopt organic reagent t-BAMBP to extract the low levels rubidium in feed liquid completely, separate rubidium and potassium through flow processs such as extraction-washing-reextraction, and by multistage extraction process purification rubidium, finally obtain high purity rubidium solution, and obtain high purity rubidium product salt by evaporative crystallization technique.
Brief description of the drawings
Fig. 1 is typical process flow figure of the present invention, in actual implementation process, can, according to desired product purity, suitably adjust extraction process hop count.
Fig. 2 is strip liquor metal ion color atlas analysis in three sections of flow processs, and the variation of metal rubidium purity in strip liquor is described.
embodiment
For understanding better the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1
This test adopts laboratory preparation containing Rb
+0.5g/L, K
+the solution extraction of 100g/L, the t-BAMBP that is diluted to 1mol/L taking sulfonated kerosene is extraction agent, extraction is in a ratio of 2: 1 (O/A), extract 5 grades, with pure water wash load organic phase, wash 3 grades, washing is in a ratio of 10: 1 (O/A), with the nitric acid back extraction washing back loading organic phase of 1mol/L, back extraction is in a ratio of 2: 1 (O/A).The remaining liquid of analytical extraction, strip liquor metal content, and calculate recovery rate, obtain test-results in table 1.
The strip liquor Rb obtaining after one-section abstraction art breading: K mass ratio is increased to 1: 7 by stoste at 1: 200, the strip liquor Rb that second segment extraction process obtains after processing: K mass ratio is increased to 1.5: 1, the strip liquor Rb that the 3rd section of extraction process obtains after processing: K mass ratio is increased to 99: 1, in strip liquor, rubidium content reaches 432.5mg/L, and potassium content is 4.4mg/L.The rubidium purity salt that evaporative crystallization obtains can reach 98.5%, and the rate of recovery of rubidium is 81.7%.
The high potassium of table 1 is containing rubidium solution extraction test-results
Embodiment 2
After the fired slags leach liquor of copper sulphur mine tailing after sorting enrichment, chloridizing roasting processed by removing heavy metals, decalcification magnesium, the content of Rb and K is respectively 0.645g/L and 46g/L, get 30ml sample and carry out three sections of continuous extraction experimental studies by high potassium concn solution extraction test method, test-results is in table 2.Rb in the strip liquor obtaining after three sections of extraction process: K mass ratio is increased to 82: 1, the rubidium purity salt that evaporative crystallization obtains has reached 98.5%.
Table 2 copper sulphur tailing leaching liquid extraction test result
Embodiment 3
After the fired slags leach liquor of copper sulphur mine tailing after sorting enrichment, chloridizing roasting processed by removing heavy metals, decalcification magnesium, the content of Rb and K is respectively 0.5g/L and 19.7g/L, first paragraph is by comparing O/A=2, carry out 5 grades of extractions, recovery of extraction can reach 100%, is undertaken carrying out two-stage reextraction by comparing O/A=2 after 3 grades of washings with pure water by comparing O/A=10.Strip liquor regulates basicity to carry out second segment extraction to 0.5mol/LNaOH, and second segment press O/A=2, carries out 4 sections of extractions, and recovery of extraction is 100%, carries out two-stage reextraction again after 3 sections of washings with pure water by comparing O/A=10.After adjusting basicity, carry out the 3rd section of extracting-back extraction and get, test-results is in table 3.Rb in the strip liquor obtaining after three sections of extraction process: K mass ratio is increased to 246: 1, the rubidium purity salt that evaporative crystallization obtains has reached 99.4%.
Table 3 copper sulphur tailing leaching liquid extraction test result
In three sections of flow processs, Fig. 2 is shown in the analysis of strip liquor metal ion color atlas.As seen from the figure, in 1 section of strip liquor, rubidium ion content is far below potassium, and in the strip liquor after 3 sections of extraction-washing-reextraction, rubidium ion content is far above the content of potassium ion.
Claims (8)
1. the leach liquor separating-purifying treatment process that in copper sulphur mine tailing, metal rubidium resource reclaims, is characterized in that having following treatment process and step:
(1) pre-treatment: in tailing leaching liquid, rubidium content is about 600mg/L, contain the metal ions such as iron, copper, zinc, manganese, calcium simultaneously, first adopt chemical precipitation method to remove the impurity such as iron in leach liquor, copper, zinc, manganese, calcium, and to regulate leach liquor basicity be 0.5mol/L.
(2) multi-stage solvent extraction: using t-BAMBP as extraction agent, sulfonated kerosene is as thinner, the extraction agent that configuration t-BAMBP concentration is 1mol/L, by (O/A) multi-stage solvent extraction leach liquor of comparing 2: 1.
(3) washing: using pure water as washing composition, by (O/A) two-stage wash load organic phase of comparing 10: 1, reduce potassium content in organic phase.
(4) strip: the salpeter solution taking concentration as 1mol/L is reverse-extraction agent, by the load organic phases after (O/A) back extraction of comparing 2: 1 washing, the rubidium in organic phase is transferred in strip liquor, obtain one section of strip liquor.
(5) two-stage extraction/washing/back extraction: the strip liquor producing taking step (4) is as stoste, and repeating step (2), (3), (4), obtain two sections of strip liquors.
(6) three sections of extraction/washing/back extractions: two sections of strip liquors that produce taking step (5) are as stoste, repeating step (2), (3), (4), obtain three sections of strip liquors, organic phase using three sections of strip liquors as reverse-extraction agent after to follow-up third wash is carried out back extraction, circulate after 5 times, obtaining rubidium content is the final strip liquor that 3400mg/L, purity are 99%.
(7) final strip liquor evaporating, concentrating and crystallizing step (6) being obtained, obtains purity and is 99% rubidium nitrate crystal.
2. the leach liquor separating-purifying treatment process that in a kind of copper sulphur mine tailing according to claim 1, metal rubidium resource reclaims, it is characterized in that: after pretreatment, in leach liquor, the metal content such as iron, copper, zinc, manganese, calcium is respectively lower than 0.5mg/L, and regulates leach liquor basicity as 0.5mol/L taking sodium hydroxide.
3. the leach liquor separating-purifying treatment process that in a kind of copper sulphur mine tailing according to claim 1, metal rubidium resource reclaims, is characterized in that: using sulfonated kerosene as thinner, and dilution extraction agent t-BAMBP to 1mol/L.
4. the leach liquor separating-purifying treatment process that in a kind of copper sulphur mine tailing according to claim 1, metal rubidium resource reclaims, is characterized in that: (O/A) multi-stage solvent extraction solution of comparing 2: 1, is extracted the rubidium ion in feed liquid completely.
5. the leach liquor separating-purifying treatment process that in a kind of copper sulphur mine tailing according to claim 1, metal rubidium resource reclaims, it is characterized in that: with pure water by (O/A) two-stage wash load organic phase of comparing 10: 1, washings recycles, to the concentration that reaches capacity of the potassium ion in washings, washings evaporative crystallization reclaims sylvite.
6. the leach liquor separating-purifying treatment process that in a kind of copper sulphur mine tailing according to claim 1, metal rubidium resource reclaims, it is characterized in that: the nitric acid using concentration as 1mol/L is as reverse-extraction agent the organic phase of stripping after washing by (O/A) single-stage of comparing 2: 1.
7. the leach liquor separating-purifying treatment process that in a kind of copper sulphur mine tailing according to claim 1, metal rubidium resource reclaims, it is characterized in that: for improving content and the purity of metal rubidium in strip liquor, adopt three sections of extraction/washing/stripping process, each section using the last period strip liquor as stoste.
8. the leach liquor separating-purifying treatment process that in a kind of copper sulphur mine tailing according to claim 1, metal rubidium resource reclaims, it is characterized in that: for improving content and the purity of metal rubidium in strip liquor, the reverse-extraction agent of organic phase after using the 3rd section of strip liquor as follow-up third wash, recycle 5 times, can make that in final strip liquor, rubidium content reaches 3400mg/L, purity reaches 99%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106086470A (en) * | 2016-06-12 | 2016-11-09 | 宋玉军 | A kind of method obtaining rubidium salt with Kaolin Tailings for 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 |
| CN112239221A (en) * | 2020-10-19 | 2021-01-19 | 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 |
| CN115491520A (en) * | 2022-02-09 | 2022-12-20 | 江西东鹏新材料有限责任公司 | Separation and extraction process for 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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2013
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106086470A (en) * | 2016-06-12 | 2016-11-09 | 宋玉军 | A kind of method obtaining rubidium salt with Kaolin Tailings for raw material |
| 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 |
| CN112239221A (en) * | 2020-10-19 | 2021-01-19 | 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 |
| 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 |
| CN115491520A (en) * | 2022-02-09 | 2022-12-20 | 江西东鹏新材料有限责任公司 | Separation and extraction process for dilute alkali metal |
| 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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