CN107937733A - Process for extracting lithium potassium rubidium cesium from lepidolite - Google Patents
Process for extracting lithium potassium rubidium cesium from lepidolite Download PDFInfo
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- CN107937733A CN107937733A CN201711211614.4A CN201711211614A CN107937733A CN 107937733 A CN107937733 A CN 107937733A CN 201711211614 A CN201711211614 A CN 201711211614A CN 107937733 A CN107937733 A CN 107937733A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/262—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds using alcohols or phenols
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to a process for extracting lithium potassium rubidium cesium from lepidolite. The process for extracting lithium potassium, rubidium and cesium from the lepidolite adopts staged extraction, and lithium salt, cesium salt, rubidium salt and potassium salt can be sequentially extracted, so that lithium potassium, rubidium and cesium can be comprehensively extracted from the lepidolite ore, the lithium potassium, rubidium and cesium can be effectively recovered, and the resource utilization rate is high.
Description
Technical field
The present invention relates to mineral products field of comprehensive utilization, more particularly to a kind of work that lithium potassium rubidium caesium is extracted from zinnwaldite
Skill.
Background technology
Lithium has high strategic value, is known as " industrial monosodium glutamate ", " Energy Star " and " member for promoting the world to advance
Element ", is one of military project, the most important rare metal in civilian two fields.Potassium, rubidium and caesium are three kinds of chemical property and its active
Alkali metal, has excellent photoelectric properties, has emphatically in catalyst, photocell, magnetohydrodynamic generator and medicine and other fields
The purposes wanted.With the development of the strategic emerging industries such as China's new energy, ecological construction, to lithium, rubidium, caesium strategic resources
Demand also necessarily increases.
In nature, lithium potassium rubidium caesium is rich in zinnwaldite ore, however, there has been no from zinnwaldite ore at present
The technique of comprehensive extraction lithium potassium rubidium caesium.
The content of the invention
Based on this, it is necessary to for how from zinnwaldite ore the problem of comprehensive extraction lithium potassium rubidium caesium, there is provided a kind of
The technique that lithium potassium rubidium caesium can be extracted from zinnwaldite.
A kind of technique that lithium potassium rubidium caesium is extracted from zinnwaldite, includes the following steps：
Zinnwaldite ore deposit is worn into zinnwaldite powder, wherein, the zinnwaldite powder of -100 mesh accounts for whole zinnwaldite powder
More than 80wt%；
The zinnwaldite powder is uniformly mixed with reconstructors, fluxing agent, afterwards in 700 DEG C~1000 DEG C of temperature conditionss
Lower carry out calcination, so that lithium potassium rubidium caesium changes into water-soluble compound, obtains zinnwaldite clinker；
The zinnwaldite clinker is subjected to leaching operation, separation of solid and liquid is carried out afterwards and retains leachate, obtain lithium potassium
The pregnant solution of rubidium caesium；
Alkali is added into the pregnant solution of the lithium potassium rubidium caesium and adjusts pH value to 8.5~9.5, solid-liquid is carried out after the reaction was complete
Separate and retain the first filtrate；
Carbonate is added into first filtrate, separation of solid and liquid is carried out after the reaction was complete and retains the second filtrate；
It is 10g/L~20g/L that second filtrate, which is evaporated, and is concentrated into the concentration of lithium ion, is added afterwards soluble
Carbonate, separation of solid and liquid obtains precipitation and the 3rd filtrate after reaction, and the precipitation is washed and dried, obtains lithium carbonate；
Adjust the concentration of basicity hydroxide ion into the 3rd filtrate of the 3rd filtrate for 0.1mol/L~
0.4mol/L, then carries out fractional extraction using extractant, the first load organic phases and the first raffinate is obtained after separation；
First load organic phases are stripped using back washing agent, retain the first strip liquor, it is anti-to described first
Extraction liquid is enriched with, and obtains cesium salt；
The concentration for adjusting basicity hydroxide ion into first raffinate of first raffinate is 0.5mol/L
~1.0mol/L, then carries out fractional extraction using extractant, the second load organic phases and the second raffinate is obtained after separation；
Second load organic phases are stripped using back washing agent, retain the second strip liquor, it is anti-to described second
Extraction liquid is enriched with, and obtains rubidium salt；
Second raffinate is enriched with, obtains sylvite.
The above-mentioned technique that lithium potassium rubidium caesium is extracted from zinnwaldite can be extracted to obtain lithium successively using extracting stage by stage
Salt, cesium salt, rubidium salt and sylvite, so as to the comprehensive extraction lithium potassium rubidium caesium from zinnwaldite ore, realize lithium potassium rubidium caesium
Effectively recycling, resource utilization are high.
In one of the embodiments, the mass ratio of the zinnwaldite powder, the reconstructors and the fluxing agent is 1:
0.4~1:0.3~0.5.
In one of the embodiments, the reconstructors are selected from least one of inorganic compound of calcic；It is described to help
Flux is selected from least one of inorganic compound containing sodium or potassium.
In one of the embodiments, it is by the operation of zinnwaldite clinker progress leaching operation：By the zinnwaldite
Clinker water logging at room temperature.
In one of the embodiments, the alkali in sodium hydroxide, potassium hydroxide, lithium hydroxide and milk of lime extremely
Few one kind.
In one of the embodiments, added into first filtrate in the step of carbonate is reacted, reaction temperature
Spend for 50 DEG C~70 DEG C.
In one of the embodiments, the precipitation is washed and the step of dried, obtain lithium carbonate in, using washing
Liquid is washed to wash the precipitation；The cleaning solution is that unsaturated carbonate lithium solution, ethanol or temperature are 75 DEG C~95 DEG C
Deionized water；
The quality of the cleaning solution is 0.5 times~2.0 times of the weight in wet base of the precipitation.
In one of the embodiments, the extractant is the 4- tert-butyl groups -2- (α-methylbenzyl) phenol；The extractant and institute
The volume ratio for stating the 3rd filtrate is 0.1~0.3:1, the volume ratio of the extractant and first raffinate is 0.6~0.9:
1。
In one of the embodiments, the back washing agent is hydrochloric acid, sulfuric acid or carbon dioxide；First load is organic
It is mutually 5~12 with the volume ratio of the back washing agent, the volume ratio of second load organic phases and the back washing agent is 3~10.
In one of the embodiments, the operation being enriched with to second raffinate is：By second raffinate
It is 85g/L~95g/L to be evaporated at a temperature of 90 DEG C~120 DEG C and be concentrated into the concentration of potassium ion, afterwards at -5 DEG C~10 DEG C
At a temperature of crystallisation by cooling, obtain sylvite after separation.
Embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, below to the specific reality of the present invention
The mode of applying is described in detail.Many details are elaborated in the following description in order to fully understand the present invention.But
The invention can be embodied in many other ways as described herein, and those skilled in the art can be without prejudice to this hair
Similar improvement is done in the case of bright intension, therefore the present invention is from the limitation of following public specific embodiment.
The technique that lithium potassium rubidium caesium is extracted in the slave zinnwaldite of one embodiment, includes the following steps：
S10, by zinnwaldite ore deposit wear into zinnwaldite powder, wherein, the zinnwaldite powder of -100 mesh accounts for whole zinnwaldites
More than the 80wt% of powder.
Wherein, the zinnwaldite powder of -100 mesh refers to that particle size is less than the zinnwaldite powder of 100 mesh.Zinnwaldite powder
Size it is smaller, be conducive to zinnwaldite powder in roasting process and come into full contact with reconstructors, fluxing agent, the reaction was complete.
Zinnwaldite powder, be uniformly mixed by S20 with reconstructors, fluxing agent, afterwards in 700 DEG C~1000 DEG C of temperature conditionss
Lower carry out calcination, so that lithium potassium rubidium caesium changes into water-soluble compound, obtains zinnwaldite clinker.
Preferably, the mass ratio of zinnwaldite powder, reconstructors and fluxing agent is 1:0.4~1:0.3~0.5.It can make iron
Lepidolite is destructurized, fully discharges the valuable elements such as lithium potassium rubidium caesium.
Preferably, reconstructors are selected from least one of inorganic compound of calcic；Fluxing agent is selected from the nothing containing sodium or potassium
At least one of machine compound.The reconstructors of these species can make zinnwaldite destructurized, fully discharge lithium potassium
The valuable elements such as rubidium caesium, fluxing agent, which mainly rises, reduces material fusing point, accelerates the effect of reaction.
Wherein, the compound of calcium is preferably calcium chloride or calcium carbonate.The compound of sodium is preferably sodium chloride.The chemical combination of potassium
Thing is preferably potassium chloride.
S30, by zinnwaldite clinker carry out leaching operation, carries out separation of solid and liquid and retaining leachate afterwards, obtains lithium potassium
The pregnant solution of rubidium caesium.
Preferably, it is by zinnwaldite clinker progress leaching operation：By the water logging at room temperature of zinnwaldite clinker.
Leaching operation can be such that valuable element lithium potassium rubidium caesium enters in leachate, and water logging slag can be used as dispensing to prepare ceramics
Product.
Preferably, the quality of water used is 2~5 times of zinnwaldite clinker quality.
S40, add alkali adjusting pH value to 8.5~9.5 into the pregnant solution of lithium potassium rubidium caesium, and solid-liquid is carried out after the reaction was complete
Separate and retain the first filtrate.
Preferably, alkali is selected from least one of sodium hydroxide, potassium hydroxide, lithium hydroxide and milk of lime.Purpose is to remove
Remove the impurity such as iron in the pregnant solution of lithium potassium rubidium caesium, manganese, aluminium.Specifically, these impurity are made to be converted into hydroxide precipitation, reaction
Separation of solid and liquid is carried out after completely, removes precipitation.
S50, add carbonate into the first filtrate, and separation of solid and liquid is carried out after the reaction was complete and retains the second filtrate.
Ca is remained in first filtrate2+, adding carbonate can be by Ca2+Precipitation of calcium carbonate is converted into, after the reaction was complete
Separation of solid and liquid is carried out, above-mentioned precipitation of calcium carbonate can be removed, so as to remove remaining Ca2+。
Preferably, added into the first filtrate in the step of carbonate is reacted, reaction temperature is 50 DEG C~70 DEG C.This
Sample can reduce the loss of valuable element (for example, lithium).
It should be noted that alkali can be added to lithium potassium in the form of its pure compound solid or in the form of its aqueous solution
In the pregnant solution of rubidium caesium.
Second filtrate, is evaporated that to be concentrated into the concentration of lithium ion be 10g/L~20g/L by S60, is added afterwards soluble
Carbonate, separation of solid and liquid obtains precipitation and the 3rd filtrate after reaction, and precipitation is washed and dried, obtains lithium carbonate.
Wherein, the dosage of soluble carbonate salt is the 110% of theoretical amount.Soluble carbonate salt is in the form of its aqueous solution
It is added in the second filtrate after concentration.
Preferably, soluble carbonate salt is selected from sodium carbonate or potassium carbonate.The soluble carbonate salt of these species will not introduce
New impurity.
In order to improve the rate of deposition for separating out lithium carbonate, the temperature of solution can be properly increased to 90 DEG C~110 DEG C, while
Reacted under stirring condition.
Preferably, in the step of being washed to precipitation and being dried, obtain lithium carbonate, precipitation is washed using cleaning solution
Wash；Cleaning solution is the deionized water that unsaturated carbonate lithium solution, ethanol or temperature are 75 DEG C~95 DEG C；The quality of cleaning solution is heavy
0.5 times of the weight in wet base in shallow lake~2.0 times.
Precipitation is washed using the cleaning solution of mentioned kind, can avoid introducing new impurity, so as to improve carbonic acid
The purity of lithium product.
S70, adjust the 3rd filtrate basicity hydroxide ion into the 3rd filtrate concentration for 0.1mol/L~
0.4mol/L, then carries out fractional extraction using extractant, the first load organic phases and the first raffinate is obtained after separation.
Preferably, extractant is the 4- tert-butyl groups -2- (α-methylbenzyl) phenol (t-BAMBP), concentration for 0.7mol/L~
1.0mol/L.The volume ratio of extractant and the 3rd filtrate is 0.1~0.3:1.
S80, using back washing agent be stripped the first load organic phases, retains the first strip liquor, to the first strip liquor
It is enriched with, obtains cesium salt.
Preferably, back washing agent is hydrochloric acid, sulfuric acid or carbon dioxide.First load organic phases and the volume ratio of back washing agent are
5~12.
The operation being enriched with to the first strip liquor is：First strip liquor is subjected to high temperature concentration, cryogenic freezing, obtains caesium
Product.
S90, adjust the first raffinate basicity hydroxide ion into the first raffinate concentration for 0.5mol/L~
1.0mol/L, then carries out fractional extraction using extractant, the second load organic phases and the second raffinate is obtained after separation.
Preferably, extractant is the 4- tert-butyl groups -2- (α-methylbenzyl) phenol (t-BAMBP), concentration for 0.7mol/L~
1.0mol/L.The volume ratio of extractant and the first raffinate is 0.6~0.9:1.
S100, using back washing agent be stripped the second load organic phases, retains the second strip liquor, to the second strip liquor
It is enriched with, obtains rubidium salt.
Preferably, back washing agent is hydrochloric acid, sulfuric acid or carbon dioxide.Second load organic phases and the volume ratio of back washing agent are
3~10.
The operation being enriched with to the second strip liquor is：Second strip liquor is subjected to high temperature concentration, cryogenic freezing, obtains rubidium
Product.
S110, be enriched with the second raffinate, obtains sylvite.
Preferably, the operation being enriched with to the second raffinate is：By the second raffinate at a temperature of 90 DEG C~120 DEG C into
The concentration of row evaporation and concentration to potassium ion is 85g/L~95g/L, afterwards the crystallisation by cooling at a temperature of -5 DEG C~10 DEG C, after separation
Obtain sylvite.
The above-mentioned technique that lithium potassium rubidium caesium is extracted from zinnwaldite can be extracted to obtain lithium successively using extracting stage by stage
Salt, cesium salt, rubidium salt and sylvite, so as to the comprehensive extraction lithium potassium rubidium caesium from zinnwaldite ore, realize lithium potassium rubidium caesium
Effectively recycling, resource utilization are high.
In addition, the present invention using roasting method processing zinnwaldite, using cheap calcium chloride, calcium oxide, sodium salt etc. as
Auxiliary agent is roasted, production cost is low, and lithium, potassium, rubidium, caesium leaching rate are high.Purification and impurity removal process is simple, due in roasting process iron,
The impurity such as aluminium, fluorine are retained in solid phase in the form of water-insoluble, and only a small amount of impurity enters leachate, cleaning procedure second step
Add the calcium slag that sodium carbonate deliming obtains to can be used as roasting auxiliary agent use, reduce production cost.
The present invention controls suitable condition to obtain the extremely low caesium organic phase of impurity content and rubidium using fractional extraction means
Organic phase, lays a good foundation for the follow-up caesium for preparing high-purity or rubidium product；Strip liquor concentration is improved by circulating back extraction, is subtracted
Material circulation is lacked, so as to reduce the follow-up evaporation and concentration cost for preparing rubidium, caesium product.
The present invention has the advantages that product recovery rate is high and to integrate cost low etc., meets national development circular economy and mineral products provide
Source comprehensively utilizes the requirement of policy.
It is embodiment below：
Embodiment 1
The zinnwaldite concentrate of the present embodiment, consisting of：
Li2O 3.57%, Na2O 2.56%, K2O 6.64%, Rb2O 1.01%, Cs2O 0.16%, CaO 0.11%,
MgO 0.008%, Al2O321.42%, SiO234.81%, MnO 0.38%, FeO 3.92%, F 5.02%.
The technique that lithium potassium rubidium caesium is extracted from zinnwaldite is as follows：
500g zinnwaldite ore deposits are worn into zinnwaldite powder, wherein, the zinnwaldite powder of -100 mesh accounts for whole zinnwaldites
The 82.9% of powder.
By zinnwaldite powder and calcium chloride, sodium chloride according to 1:0.5:0.5 (mass ratio) is uniformly mixed, afterwards at 850 DEG C
Temperature conditionss under roast 45min so that lithium potassium rubidium caesium changes into water-soluble compound, obtain zinnwaldite clinker.
By the 2L water leachings of zinnwaldite clinker, separation of solid and liquid is carried out afterwards and retains leachate, obtains lithium potassium rubidium
The pregnant solution of caesium.In the pregnant solution of lithium potassium rubidium caesium, Li2O、K2O、Rb2O and Cs2The leaching rate of O successively up to 89.72%,
90.63%th, 93.26% and 91.01%.
Milk of lime is added into the pregnant solution of lithium potassium rubidium caesium, it is 8.5 to adjust pH value, and separation of solid and liquid is carried out after the reaction was complete
And retain the first filtrate.First filtrate is heated to 70 DEG C, and adds sodium carbonate liquor, stirs 30min, carries out separation of solid and liquid
And retain the second filtrate, to remove impurity calcium.The removal rate of Ca is up to 98.05%.Wherein, lithium, potassium, rubidium, caesium loss late are smaller,
It is followed successively by 1.73%, 1.50%, 0.50%, 0.80%.
It is 11.39g/L that second filtrate, which is evaporated at 95 DEG C, and is concentrated into the concentration of lithium ion.At this time, lithium, potassium, rubidium
With the loss very little of caesium, loss late is followed successively by 2.42%, 4.62%, 3.95% and 1.55%.Afterwards by after evaporation and concentration
Second filtrate is heated with stirring to boiling, adds saturated sodium carbonate solution reaction 40min, and separation of solid and liquid obtains precipitation and the after reaction
Three filtrates, use hot water (quality of hot water for precipitate 1.2 times of weight in wet base) to wash and dry precipitation, are met state
Mark the carbon lithium carbonate of GB/T 11075-2013, lithium rate of deposition is up to 83.40%.
The concentration for adjusting basicity hydroxide ion into the 3rd filtrate of the 3rd filtrate is 0.4mol/L, then using extraction
Agent t-BAMBP carries out fractional extraction.Wherein, the concentration of extractant t-BAMBP is 0.70mol/L, extractant and the 3rd filtrate
Volume ratio is 0.18.O/A=1 is compared in the sodium chloride solution of wash water 0.10mol/L, washing.Carry out seven grades of fractional extractions (two
Level extraction, Pyatyi washing) after, caesium extraction yield is higher up to caesium purity in 99.90%, first load organic phases, major impurity rubidium,
Potassium content is all very low, only 0.020g/L, 0.002g/L.Back washing agent is the hydrochloric acid solution of 0.50mol/L, and back extraction is in a ratio of 10.
After being stripped by single-stage, caesium back extraction ratio 97.56%, caesium concentration 14.44g/L.It is stripped by 3 circulations, caesium concentration reaches
56.96g/L, reduces the follow-up evaporation capacity for preparing product sequence.First strip liquor high temperature evaporation-cryogenic freezing is obtained pure
Spend the cesium chloride product for 98.73%.
First raffinate hydrogenation sodium oxide molybdena adjusts basicity to 0.55mol/L, and extractant t-BAMBP concentration is 1.0mol/L,
The volume ratio of extractant and the first raffinate is 0.76.O/A=3 is compared in the sodium chloride solution of wash water 0.10mol/L, washing.
After carrying out ten grades of fractional extractions (three-level extraction, seven grades of washings), rubidium extraction yield is up to rubidium in 99.80%, second load organic phases
Purity is higher, and major impurity potassium content only has 0.023g/L.Back washing agent is 1.0mol/L hydrochloric acid solutions, and back extraction is in a ratio of 10, warp
Single-stage back extraction is crossed, rubidium back extraction ratio 96.44%, rubidium concentration 10.30g/L, is stripped by 2 circulations, and caesium concentration reaches 30.0g/L, is dropped
The low evaporation capacity for subsequently preparing product sequence.Second strip liquor high temperature evaporation-cryogenic freezing is obtained into purity as 98.06%
Rubidium chloride product.
It is 91.46g/L that second raffinate, which is evaporated at 105 DEG C, and is concentrated into the concentration of potassium ion, afterwards at 0 DEG C
Lower crystallisation by cooling, obtains the agricultural potassium chloride product of qualification after separation.
After above-mentioned processing, the lithium of the present embodiment, potassium, rubidium, the overall recovery of caesium to be followed successively by 71.75%,
55.06%th, 76.07%, 81.16%.
Embodiment 2
The zinnwaldite concentrate of the present embodiment, consisting of：
Li2O 2.79%, Na2O 2.79%, K2O 5.75%, Rb2O 0.89%, Cs2O 0.15%, CaO 0.14%,
MgO 0.02%, Al2O318.42%, SiO246.92%, FeO 8.23%, F 4.06%.
The technique that lithium potassium rubidium caesium is extracted from zinnwaldite is as follows：
300g zinnwaldite ore deposits are worn into zinnwaldite powder, wherein, the zinnwaldite powder of -100 mesh accounts for whole zinnwaldites
The 83.5% of powder.
By zinnwaldite powder and calcium chloride, calcium carbonate, sodium chloride according to 1:0.4:0.2:0.4 (mass ratio) is uniformly mixed,
50min is roasted under 800 DEG C of temperature conditionss afterwards, so that lithium potassium rubidium caesium changes into water-soluble compound, obtains iron lithium
Mica clinker.
By the 0.6L water leachings of zinnwaldite clinker, separation of solid and liquid is carried out afterwards and retains leachate, obtains lithium potassium
The pregnant solution of rubidium caesium.In the pregnant solution of lithium potassium rubidium caesium, Li2O、K2O、Rb2O and Cs2The leaching rate of O successively up to 87.13%,
88.92%th, 90.78%, 90.66%.
Milk of lime is added into the pregnant solution of lithium potassium rubidium caesium, it is 9.5 to adjust pH value, and separation of solid and liquid is carried out after the reaction was complete
And retain the first filtrate.First filtrate is heated to 50 DEG C, and adds sodium carbonate liquor, stirs 30min, carries out separation of solid and liquid
And retain the second filtrate, to remove impurity calcium.The removal rate of Ca is up to 97.87%.Wherein, lithium, potassium, rubidium, caesium loss late are smaller,
It is followed successively by 4.89%, 2.80%, 1.56%, 1.07%.
It is 15.26g/L that second filtrate, which is evaporated at 105 DEG C, and is concentrated into the concentration of lithium ion.At this time, lithium, potassium, rubidium
With the loss very little of caesium, loss late is followed successively by 3.58%, 4.17%, 3.64% and 1.77%.Afterwards by after evaporation and concentration
Second filtrate is heated with stirring to boiling, adds saturated sodium carbonate solution reaction 40min, and separation of solid and liquid obtains precipitation and the after reaction
Three filtrates, use hot water (quality of hot water for precipitate 1.2 times of weight in wet base) to wash and dry precipitation, are met state
Mark the carbon lithium carbonate of GB/T 11075-2013, lithium rate of deposition is up to 85.18%.
The concentration for adjusting basicity hydroxide ion into the 3rd filtrate of the 3rd filtrate is 0.3mol/L, then using extraction
Agent t-BAMBP carries out fractional extraction.Wherein, the concentration of extractant t-BAMBP is 0.70mol/L, extractant and the 3rd filtrate
Volume ratio is 0.18.O/A=1 is compared in the sodium chloride solution of wash water 0.10mol/L, washing.Carry out seven grades of fractional extractions (two
Level extraction, Pyatyi washing) after, caesium extraction yield loads that the organic phase purity of caesium is very high, and major impurity rubidium, potassium contain up to 98.11%
Amount is all very low, only 0.087g/L, 0.015g/L.Back washing agent is the hydrochloric acid solution of 0.50mol/L, and back extraction is in a ratio of 10.By
After single-stage back extraction, caesium back extraction ratio 96.15%, caesium concentration 13.28g/L.It is stripped by 1 circulation, caesium concentration reaches 26.44g/L,
Reduce the follow-up evaporation capacity for preparing product sequence.First strip liquor high temperature evaporation-cryogenic freezing is obtained purity and is
99.01% cesium chloride product.
First raffinate hydrogenation sodium oxide molybdena adjusts basicity to 0.65mol/L, and extractant t-BAMBP concentration is 1.0mol/L,
The volume ratio of extractant and the first raffinate is 0.76.O/A=3 is compared in the sodium chloride solution of wash water 0.10mol/L, washing.
After carrying out ten grades of fractional extractions (three-level extraction, seven grades of washings), rubidium extraction yield is up to rubidium in 97.80%, second load organic phases
Purity is higher, and major impurity potassium content only has 0.037g/L.Back washing agent is 1.0mol/L hydrochloric acid solutions, and back extraction is in a ratio of 10, warp
Single-stage back extraction is crossed, rubidium back extraction ratio 97.58%, rubidium concentration 9.70g/L, is stripped by 2 circulations, and caesium concentration reaches 29.05g/L, is dropped
The low evaporation capacity for subsequently preparing product sequence.Second strip liquor high temperature evaporation-cryogenic freezing is obtained into purity as 99.23%
Rubidium chloride product.
It is 87.86g/L that second raffinate, which is evaporated at 95 DEG C, and is concentrated into the concentration of potassium ion, afterwards at 5 DEG C
Crystallisation by cooling, obtains the agricultural potassium chloride product of qualification after separation.
After above-mentioned processing, the lithium of the present embodiment, potassium, rubidium, the overall recovery of caesium to be followed successively by 68.06%,
50.19%th, 73.22%, 74.79%.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope that this specification is recorded all is considered to be.
Embodiment described above only expresses the several embodiments of the present invention, its description is more specific and detailed, but simultaneously
Cannot therefore it be construed as limiting the scope of the patent.It should be pointed out that come for those of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of technique that lithium potassium rubidium caesium is extracted from zinnwaldite, it is characterised in that include the following steps：
Zinnwaldite ore deposit is worn into zinnwaldite powder, wherein, the zinnwaldite powder of -100 mesh accounts for whole zinnwaldite powder
More than 80wt%；
The zinnwaldite powder is uniformly mixed with reconstructors, fluxing agent, afterwards under 700 DEG C~1000 DEG C of temperature conditionss into
Row calcination, so that lithium potassium rubidium caesium changes into water-soluble compound, obtains zinnwaldite clinker；
The zinnwaldite clinker is subjected to leaching operation, separation of solid and liquid is carried out afterwards and retains leachate, obtain lithium potassium rubidium caesium
Pregnant solution；
Alkali is added into the pregnant solution of the lithium potassium rubidium caesium and adjusts pH value to 8.5~9.5, separation of solid and liquid is carried out after the reaction was complete
And retain the first filtrate；
Carbonate is added into first filtrate, separation of solid and liquid is carried out after the reaction was complete and retains the second filtrate；
It is 10g/L~20g/L that second filtrate, which is evaporated, and is concentrated into the concentration of lithium ion, adds soluble carbonic acid afterwards
Salt, separation of solid and liquid obtains precipitation and the 3rd filtrate after reaction, and the precipitation is washed and dried, obtains lithium carbonate；
It is 0.1mol/L~0.4mol/ to adjust the basicity of the 3rd filtrate concentration of hydroxide ion into the 3rd filtrate
L, then carries out fractional extraction using extractant, the first load organic phases and the first raffinate is obtained after separation；
First load organic phases are stripped using back washing agent, retain the first strip liquor, to first strip liquor
It is enriched with, obtains cesium salt；
Adjust the concentration of basicity hydroxide ion into first raffinate of first raffinate for 0.5mol/L~
1.0mol/L, then carries out fractional extraction using extractant, the second load organic phases and the second raffinate is obtained after separation；
Second load organic phases are stripped using back washing agent, retain the second strip liquor, to second strip liquor
It is enriched with, obtains rubidium salt；
Second raffinate is enriched with, obtains sylvite.
2. the technique according to claim 1 that lithium potassium rubidium caesium is extracted from zinnwaldite, it is characterised in that the iron lithium cloud
The mass ratio of female powder, the reconstructors and the fluxing agent is 1:0.4~1:0.3~0.5.
3. the technique according to claim 1 that lithium potassium rubidium caesium is extracted from zinnwaldite, it is characterised in that the reconstructors
At least one of inorganic compound selected from calcic；The fluxing agent in the inorganic compound containing sodium or potassium at least one
Kind.
4. the technique according to claim 1 that lithium potassium rubidium caesium is extracted from zinnwaldite, it is characterised in that by zinnwaldite
Clinker carry out leaching operation operation be：By the zinnwaldite clinker water logging at room temperature.
5. the technique according to claim 1 that lithium potassium rubidium caesium is extracted from zinnwaldite, it is characterised in that the alkali is selected from
At least one of sodium hydroxide, potassium hydroxide, lithium hydroxide and milk of lime.
6. the technique according to claim 1 that lithium potassium rubidium caesium is extracted from zinnwaldite, it is characterised in that to described first
Added in filtrate in the step of carbonate is reacted, reaction temperature is 50 DEG C~70 DEG C.
7. the technique according to claim 1 that lithium potassium rubidium caesium is extracted from zinnwaldite, it is characterised in that to the precipitation
In the step of being washed and being dried, obtain lithium carbonate, the precipitation is washed using cleaning solution；The cleaning solution is full
With the deionized water that Lithium carbonate solution, ethanol or temperature are 75 DEG C~95 DEG C；
The quality of the cleaning solution is 0.5 times~2.0 times of the weight in wet base of the precipitation.
8. the technique according to claim 1 that lithium potassium rubidium caesium is extracted from zinnwaldite, it is characterised in that the extractant
For the 4- tert-butyl groups -2- (α-methylbenzyl) phenol；The volume ratio of the extractant and the 3rd filtrate is 0.1~0.3:1, the extraction
The volume ratio for taking agent and first raffinate is 0.6~0.9:1.
9. the technique according to claim 1 that lithium potassium rubidium caesium is extracted from zinnwaldite, it is characterised in that the back washing agent
For hydrochloric acid, sulfuric acid or carbon dioxide；The volume ratio of first load organic phases and the back washing agent is 5~12, described the
Two load organic phases and the volume ratio of the back washing agent are 3~10.
10. the technique according to claim 1 that lithium potassium rubidium caesium is extracted from zinnwaldite, it is characterised in that to described the
The operation that two raffinates are enriched with is：Second raffinate is evaporated at a temperature of 90 DEG C~120 DEG C and is concentrated into potassium
The concentration of ion is 85g/L~95g/L, and the crystallisation by cooling at a temperature of -5 DEG C~10 DEG C, sylvite is obtained after separation afterwards.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109777948A (en) * | 2019-02-25 | 2019-05-21 | 广东省矿产应用研究所 | Technological method for extracting rubidium by flash cycle leaching of silicate |
| CN109987619A (en) * | 2019-04-26 | 2019-07-09 | 核工业北京化工冶金研究院 | The method for preparing battery-level lithium carbonate from lepidolite leachate by strengthening washing |
| CN111996392A (en) * | 2020-07-22 | 2020-11-27 | 中国地质科学院郑州矿产综合利用研究所 | Method for extracting cesium and rubidium from lepidolite |
| EP3894605A4 (en) * | 2018-12-12 | 2022-09-28 | XPS Expert Process Solutions - Glencore Canada Corporation | Lithium recovery and purification |
| CN116605892A (en) * | 2023-07-11 | 2023-08-18 | 唐山鑫丰锂业有限公司 | Process for producing lithium hydroxide from mica ore |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974678A (en) * | 2010-11-24 | 2011-02-16 | 中南大学 | Method for extracting lithium and other alkali metal elements from lepidolite mineral |
| CN103320626A (en) * | 2013-06-18 | 2013-09-25 | 赣州有色冶金研究所 | Method and system for recovering lithium, rubidium and/or cesium from lepidolite |
| CN104326496A (en) * | 2014-10-14 | 2015-02-04 | 中国地质科学院郑州矿产综合利用研究所 | Method for extracting rubidium salt from brine and method for extracting cesium salt from brine |
| CN104649302A (en) * | 2013-11-18 | 2015-05-27 | 湖南厚道矿业有限公司 | Method for acquiring lithium carbonate in zinnwaldite |
| CN104817099A (en) * | 2015-04-28 | 2015-08-05 | 中南大学 | Improved method for extracting alkali metal compound from solid fluorine reconstruction lepidolite |
| CN105803188A (en) * | 2016-05-30 | 2016-07-27 | 江西旭锂矿业有限公司 | Method for preferential segregation of potassium, rubidium and cesium through chloridizing roasting treatment of lepidolite |
| CN106222450A (en) * | 2016-07-21 | 2016-12-14 | 温岭市亿林投资有限公司 | Lithium, rubidium and the extracting method of caesium in a kind of zinnwaldite ore deposit |
| CN106929693A (en) * | 2015-12-29 | 2017-07-07 | 核工业北京化工冶金研究院 | A kind of caesium rubidium potassium extraction separating method |
-
2017
- 2017-11-28 CN CN201711211614.4A patent/CN107937733B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974678A (en) * | 2010-11-24 | 2011-02-16 | 中南大学 | Method for extracting lithium and other alkali metal elements from lepidolite mineral |
| CN103320626A (en) * | 2013-06-18 | 2013-09-25 | 赣州有色冶金研究所 | Method and system for recovering lithium, rubidium and/or cesium from lepidolite |
| CN104649302A (en) * | 2013-11-18 | 2015-05-27 | 湖南厚道矿业有限公司 | Method for acquiring lithium carbonate in zinnwaldite |
| CN104326496A (en) * | 2014-10-14 | 2015-02-04 | 中国地质科学院郑州矿产综合利用研究所 | Method for extracting rubidium salt from brine and method for extracting cesium salt from brine |
| CN104817099A (en) * | 2015-04-28 | 2015-08-05 | 中南大学 | Improved method for extracting alkali metal compound from solid fluorine reconstruction lepidolite |
| CN106929693A (en) * | 2015-12-29 | 2017-07-07 | 核工业北京化工冶金研究院 | A kind of caesium rubidium potassium extraction separating method |
| CN105803188A (en) * | 2016-05-30 | 2016-07-27 | 江西旭锂矿业有限公司 | Method for preferential segregation of potassium, rubidium and cesium through chloridizing roasting treatment of lepidolite |
| CN106222450A (en) * | 2016-07-21 | 2016-12-14 | 温岭市亿林投资有限公司 | Lithium, rubidium and the extracting method of caesium in a kind of zinnwaldite ore deposit |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3894605A4 (en) * | 2018-12-12 | 2022-09-28 | XPS Expert Process Solutions - Glencore Canada Corporation | Lithium recovery and purification |
| CN109777948A (en) * | 2019-02-25 | 2019-05-21 | 广东省矿产应用研究所 | Technological method for extracting rubidium by flash cycle leaching of silicate |
| CN109987619A (en) * | 2019-04-26 | 2019-07-09 | 核工业北京化工冶金研究院 | The method for preparing battery-level lithium carbonate from lepidolite leachate by strengthening washing |
| CN109987619B (en) * | 2019-04-26 | 2022-03-22 | 核工业北京化工冶金研究院 | Method for preparing battery-grade lithium carbonate from lepidolite leaching solution through intensive washing |
| CN111996392A (en) * | 2020-07-22 | 2020-11-27 | 中国地质科学院郑州矿产综合利用研究所 | Method for extracting cesium and rubidium from lepidolite |
| CN116605892A (en) * | 2023-07-11 | 2023-08-18 | 唐山鑫丰锂业有限公司 | Process for producing lithium hydroxide from mica ore |
| CN116605892B (en) * | 2023-07-11 | 2024-02-09 | 唐山鑫丰锂业有限公司 | Process for producing lithium hydroxide from mica ore |
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