CN108330298A - A method of extracting rubidium, caesium, lithium, potassium from more metal mica ores - Google Patents

A method of extracting rubidium, caesium, lithium, potassium from more metal mica ores Download PDF

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CN108330298A
CN108330298A CN201810151171.2A CN201810151171A CN108330298A CN 108330298 A CN108330298 A CN 108330298A CN 201810151171 A CN201810151171 A CN 201810151171A CN 108330298 A CN108330298 A CN 108330298A
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salt
minutes
roasting
leachate
lithium
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CN108330298B (en
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钟宏
雷祖伟
王帅
曹占芳
刘体煌
周梓楠
高鹏
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Yichun Lithium Mineral Industry Research Institute LLC
Central South University
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Yichun Lithium Mineral Industry Research Institute LLC
Central South University
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10Obtaining alkali metals
    • C22B26/12Obtaining lithium
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00Sulfates or sulfites of sodium, potassium or alkali metals in general
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/02Roasting processes
    • C22B1/06Sulfating roasting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/02Roasting processes
    • C22B1/08Chloridising roasting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10Obtaining alkali metals
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The method that the invention discloses a kind of to extract rubidium, caesium, lithium, potassium from more metal mica ores, including:It S1, more metal mica ores and is roasted after mixing as two or more salt in the sodium salt, sylvite or calcium salt of roasting additive, crushes, obtain calcining;S2, addition water is leached in the calcining, obtains leachate;S3, leachate process cleans, concentrates, processing of saltouing obtains Na2SO4、K2SO4Salt-mixture and scavenging solution;S4, Na is added in the scavenging solution2CO3, using being filtered, washed, be dried to obtain Li2CO3And contain Rb+With Cs+Solution.This method is environmentally friendly and realizes the comprehensive utilization of more metal mica ore resources.

Description

A method of extracting rubidium, caesium, lithium, potassium from more metal mica ores
Technical field
The present invention relates to mineral manufacture fields, extracted from more metal mica ores more particularly to one kind extraction rubidium, caesium, The method of lithium, potassium.
Background technology
Rubidium, caesium are typical rare and dispersed elements, have unique property.Caesium, rubidium rarely independent mineral deposit, usually all With more metal mica ore associations, it is difficult to detach.Lithium is important metallic element, in the energy, chemical industry, electronics, medicine and other fields It is widely used.Potassium sulfate is a kind of excellent potash fertilizer, and especially suitable for avoiding chlorine crops, China needs import sulfuric acid every year About 500,000 tons of potassium.Therefore, there is important meaning to the research of separation and extraction technology of rubidium in more metal mica ores, caesium, lithium, potassium Justice.Currently, the method for extracting the elements such as lithium from more metal mica ores mainly has lime-roasting method, autoclaving method, sulfuric acid process etc..
Lime burning method presses certain mass ratio by lime stone and mixing containing lithium minerals, and in certain pulp density Under conditions of after wet ball-milling to fine particulate, concentration is thickened, additive is added, is sintered certain time at high temperature, adds water It leaches, filtering, obtains lithium leachate, then impurity and purification obtain lithium hydroxide solution, last condensing crystallizing or carbonization obtain lithium product. The disadvantage is that lithium content is low in leachate, material circulation is very big, and energy consumption is big, and the rate of recovery is relatively low;It is also defective in process aspect:It removes Aluminium effect is bad;Evaporation efficiency is low;Evaporation energy consumption is big;Recrystallization method processing coarse-grain working hour is long and easily blocks pipeline.
Autoclaving method be by more metal mica ores in rotary kiln high temperature defluorinate roast, then plus sodium chloride, sodium carbonate or Sodium hydroxide autoclaving certain time, the purified concentration of leachate at a certain temperature, then handled with soda ash such as sodium carbonate, it obtains Lithium carbonate.The existing method for carrying lithium from more metal mica ores and preparing lithium carbonate, mainly comprises the following steps:High-temperature roasting defluorinate, It is levigate, autoclaving:More metal mica ores, calcium oxide, the sodium salt of milled are thrown into and carry out autoclaving in autoclave, is stirred continuously In the state of make more metal mica ore decompositions, alkali metal therein progress ion exchange become into salt dissolution, using removal of impurities, Concentrated frozen analyses sodium, last to be passed through CO toward analysis mother liquid of sodium2Precipitate lithium carbonate.The disadvantage is that the lithium rate of recovery is relatively low, autoclaving leaches will be It is carried out under high temperature and pressure, operation is more demanding, and wants CO when production2Gas reclamation system increases production cost.
Sulfuric acid process is to react more metal mica mineral powders and sulfuric acid at relatively low temperature, generate rubidium sulfate, caesium, Lithium, potassium, calcium, magnesium salts, purified deliming, magnesium, after separating potassium, rubidium, cesium salt lithium sulfate solution and sodium carbonate reaction generate lithium carbonate Precipitation.The method of existing sulfuric acid baking fado metal Mica Mine standby lithium carbonate made of stones, technical process are:Roast defluorinate; Cooling is levigate;It sizes mixing;Low-temperature bake;Leach separation;Removal of impurities;Concentration;Freezing;Carbonization sinker obtains lithium carbonate product.It is existing Using the mica treatment process of more metal Mica Mine standby lithium carbonate made of stones, mainly comprise the following steps:By more one dilute sulphur of metal mica ore Acid reacts under high-temperature pressure in input but reaction kettle by a certain percentage, using drying, roasts, leaches, crystallisation by cooling removes Miscellaneous, lithium carbonate product is finally made in concentration, sinker.The disadvantage is that sulfuric acid dosage is big, and will produce acid mist when roasting, cause air dirty Dye, and easily make equipment seriously corroded.In addition to this, sulfuric acid process handles more metal mica ores and is destroying original mineral phase structure Meanwhile lithium, potassium, caesium can be released, it subsequently needs to consume the excessive sulfuric acid of a large amount of alkali neutralization.
Invention content
It makes a low multiple use and to the disagreeableness technical problem of environment, the present invention to solve above-mentioned more metal mica ores It is proposed a kind of method for extracting rubidium, caesium, lithium, potassium from more metal mica ores.
The technical problem of the present invention is resolved by technical solution below:
A method of extracting rubidium, caesium, lithium, potassium from more metal mica ores, including:
S1, more metal mica ores and mixed as two or more salt in the sodium salt, sylvite or calcium salt of roasting additive Roasting after closing uniformly, crushes, obtains calcining;
S2, addition water is leached in the calcining, obtains leachate;
S3, leachate process cleans, concentrates, processing of saltouing obtains Na2SO4、K2SO4Salt-mixture and scavenging solution;
S4, Na is added in the scavenging solution2CO3, using being filtered, washed, be dried to obtain Li2CO3And contain Rb+With Cs+Solution.
Preferably, in step sl, the sodium salt in the roasting additive includes NaCl and/or Na2SO4, the potassium Salt includes KCl, and the calcium salt includes CaCl2And/or CaSO4
Preferably, in step sl, the roasting additive includes NaCl and CaSO4Salt-mixture or CaCl2With Na2SO4 Salt-mixture.
Preferably, in step sl, more metal mica ores and the NaCl and CaSO4The mass ratio packet of salt-mixture Include 1:0.3~1:1.2, the preferred mass ratio includes 1:0.5~1:1.2;And/or the temperature of the roasting includes 780 DEG C ~1000 DEG C, the temperature of the preferred roasting includes 830~930 DEG C;And/or the time of the roasting includes 15~90 points The time of clock, the preferred roasting is 30~90 minutes.
Preferably, in step sl, more metal mica ores include containing Li2O is 1%~5%, Rb2O be 0.1%~ 1%, Cs2O is 0.1%~1%, K2More metal mica ores that O is 2%~5%.
Preferably, in step s 2, it is 1 that the liquid of the water and the calcining, which consolidates mass ratio,:1~4:1, the preferred water It is 2 to consolidate mass ratio with the liquid of the calcining:1;And/or the temperature of the leaching includes 30~80 DEG C;And/or the leaching when Between include 2~30 minutes, the time of the preferred leaching includes 15~30 minutes.
Further, in step s3, described clean includes:It adds mass fraction and adjusts institute for 5%~30% NaOH The pH value of leachate is stated to 10~12, reaction is filtered after 5~90 minutes, obtains removal Mg2+And Mn2+Leachate;And/or It is described saltout including:Ethyl alcohol is added into the leachate after concentration, is filtered later, and the Na is obtained2SO4、K2SO4Salt-mixture, institute It is 1 that the leachate after concentration, which is stated, with the ethyl alcohol mass ratio:0.05~1:0.2.
Further, in step s3, further include to the removal Mg2+And Mn2+Leachate in Ca2+With Na2CO3 Mass ratio be 1:1~1:1.5 addition Na2CO3, controlled at 30~80 DEG C, 5~60 minutes are reacted to remove Ca2+
Further, further include the Na by gained in step s32SO4、K2SO4The processing of salt-mixture recrystallization, including:It presses The Na2SO4、K2SO4Na in salt-mixture2SO4It is 1 with the ratio between the amount of KCl substances:1~1:3 addition KCl are configured to saturated solution, Add methanol to saltout, obtains salting-out precipitate;The salting-out precipitate is pressed into the Na2SO4、K2SO4K in salt-mixture2SO4With Na2SO4Total object The ratio between the amount of matter and the amount of KCl substances are 1:1~1:3 addition KCl, are configured to saturated solution under the conditions of 50~90 DEG C, stand Recrystallization, obtains K2SO4Crystal.
Preferably, in step s 4, the Na2CO3Mass concentration be 10%~25%, wherein in the scavenging solution Li+With the Na2CO3The ratio between the amount of substance be 1:0.5~1:1, reaction temperature is 60~95 DEG C, and the reaction time is 5~30 points Clock.
Containing the Rb using prepared by any of the above-described method the invention also provides a kind of+With Cs+Solution exist Generate the application of rubidium salt and/or cesium salt.It is extractant that t-BAMAP, which can be used, with one in sulfonated kerosene, dimethylbenzene, diethylbenzene Kind or several prepare rubidium cesium salt with hydrochloric acid, sulfuric acid, carbon dioxide etc. for back washing agent for diluent.T-BAMAP in the present invention For 4- tertiary butyls -2- (α-methylbenzyl) phenol.
The beneficial effect of the present invention compared with the prior art includes:The present invention using more metal mica ores extraction rubidium, caesium, The method of lithium, potassium, sodium salt, sylvite, the two or more salt in calcium salt and the valuable metal one in more metal mica ores of addition Roasting is played, ion-exchange reactions has occurred, roasting process is generated without sour gas such as hydrogen chloride, sulfur dioxide;Adopt water as leaching Go out agent, do not add acid or alkali, reduces equipment corrosion, it is environmentally friendly;In leachate by cleaning, concentrating, processing of saltouing Obtain Na2SO4、K2SO4After salt-mixture, continue that Na is added into scavenging solution2CO3, using being filtered, washed, be dried to obtain Li2CO3And contain Rb+With Cs+Solution, prepare Li2CO3Na is prepared while product2SO4、K2SO4Salt-mixture, acquisition is most Whole leachate height contains Rb+With Cs+, which can be used for extracting rubidium salt and cesium salt, realize the comprehensive of more metal mica ore resources It closes and utilizes.
Other advantageous effects include:
1, rubidium, caesium, the leaching rate of lithium are high:In roasting process, with the metallic element in ore ion occurs for roasting additive Exchange interaction destroys the lattice structure of ore, relieves package of the gangue to rubidium, caesium, lithium.Sodium salt is used to be roasted with calcium salt to combine Additive is burnt, is conducive to destroy a variety of lattice structures in ore, to realize the high efficiency extraction of rubidium, caesium, lithium.Certain preferred Scheme in, rubidium, caesium, lithium leaching rate can be more than 90%, while by potassium feldspar in mica ore potassium leach.
2, purification process waste residue amount is reduced:Since leaching process uses water logging, foreign ion is less in leachate, cleans The quantity of slag generated in journey is considerably less, and dangerous substances are free of in waste residue, and entire process material circulation is low, is greatly decreased Equipment, the input in place and manpower, save production cost.
3, the K of high-purity is obtained2SO4Crystal:By Na2SO4、K2SO4Salt-mixture carries out recrystallization processing, by adding twice Add a certain amount of KCl, obtains the K that purity is 95%2SO4Crystal.
Description of the drawings
Fig. 1 is the technological process for extracting rubidium, caesium, lithium, potassium in the specific embodiment of the invention from more metal mica ores Figure.
Specific implementation mode
The present invention is described further with reference to specific embodiment, the present invention can be by the either type of invention content Implement, providing for these embodiments is in no way intended to limit the present invention.
It should be noted that more metal mica ores in present embodiment refer to containing there are many clouds of valuable metal Female ore, more metal mica ores generally include to contain Li2O is 1%~5%, Rb2O is 0.1%~1%, Cs2O be 0.1%~ 1%, K2More metal mica ores that O is 2%~5%.
It is as shown in table 1 using the main component of more metal mica ores and content (%) in embodiment.
Table 1
Component Li2O Rb2O Cs2O SiO2 Al2O3 K2O Na2O Other
Content 1.36 0.42 0.46 66.18 16.95 3.72 2.61 8.3
Embodiment 1
By more metal mica ores and different roasting additive (NaCl, CaCl2、Na2SO4、CaSO4, NaCl and CaSO4It is mixed Close salt or CaCl2With Na2SO4Salt-mixture) it is 1 in mass ratio:1 is uniformly mixed, wherein roasting additive NaCl, CaSO4Mixing NaCl and CaSO in salt4Mass ratio be 1:1, roasting additive NaCl, CaSO4CaCl in salt-mixture2With Na2SO4Mass ratio It is 1:1.It is placed in 880 DEG C of roaster and reacts 45 minutes, take out after complete reaction, be down to room temperature, crush, by liquid stereoplasm amount Than 3:1 addition water is leached, and extraction temperature is 70 DEG C, and extraction time is 20 minutes, and mechanical agitation frequency is 250r/ minutes, Filtering, obtains the leachate containing rubidium, caesium, lithium, sylvite, lithium, rubidium, the leaching rate of caesium are as shown in table 2.As can be seen from Table 2, with NaCl with CaSO4Or CaCl2With Na2SO4For roasting additive, rubidium, caesium, lithium leaching rate be apparently higher than the wherein a certain roasting of single use Burn additive.The gas of generation in roasting process is detected when showing using NaCl as roasting additive, has chlorine in gas Change hydrogen;And use other roasting additives, then there is not hydrogen chloride gas effusion.When with roasting additive be NaCl and CaSO4When, The reason of not having hydrogen chloride gas effusion may be that sodium chloride dosage is relatively fewer, the alkali metal in the hydrogen chloride and ore of generation It is reacted.
The different roasting additives of table 2 influence result to leaching rate
Embodiment 2
By more metal mica ores and roasting additive NaCl, CaSO4Salt-mixture presses different quality ratio (1:0.3~1: 1.2) it is uniformly mixed, NaCl and CaSO in roasting additive4Mass ratio is 1:1, it is placed in 880 DEG C of roaster and reacts 45 points Clock takes out after complete reaction, is down to room temperature, crushes, consolidates mass ratio 3 by liquid:1 addition water is leached, extraction temperature 70 DEG C, extraction time is 20 minutes, and mechanical agitation frequency is 250r/ minutes, and filtering obtains the leachate containing rubidium, caesium, lithium, sylvite, Lithium, rubidium, the leaching rate of caesium are as shown in table 3.By table 3 as it can be seen that when more metal mica ores and roasting additive mass ratio are 1:0.5 When, lithium, rubidium, caesium leaching rate more than 80%, when mass ratio be 1:When 0.7, lithium, caesium leaching rate are more than 90%, and rubidium leaches Rate is close to 90%.
The table mica of metal more than 3 ore compares leaching rate with roasting additive different quality influences result
Embodiment 3
By more metal mica ores and roasting additive NaCl, CaSO4Salt-mixture is 1 in mass ratio:0.7 is uniformly mixed, NaCl and CaSO in roasting additive4Mass ratio is 1:1, it is placed in the roaster of different temperatures and reacts 45 minutes, wait having reacted It is taken out after complete, is down to room temperature, crushed, consolidate mass ratio 3 by liquid:1 addition water is leached, and extraction temperature is 70 DEG C, extraction time It it is 20 minutes, mechanical agitation frequency is 250r/ minute, filter, obtain the leachate containing rubidium, caesium, lithium, sylvite, lithium, rubidium, caesium Leaching rate is as shown in table 4.By table 4 as it can be seen that calcination temperature between 830~930 DEG C lithium, rubidium, caesium leaching rate be all higher than 80%, Operable temperature range is big, and when calcination temperature is 880 DEG C, lithium, rubidium, caesium leaching rate are all higher than 90%.
Influence result of the different calcination temperatures of table 4 to leaching rate
Embodiment 4
By more metal mica ores and roasting additive NaCl, CaSO4Salt-mixture is 1 in mass ratio:0.7 is uniformly mixed, NaCl and CaSO in roasting additive4Mass ratio is 1:2, it is placed in 880 DEG C of roaster and reacts different time, wait for that the reaction was complete After take out, be down to room temperature, crush, consolidate mass ratio 3 by liquid:1 addition water is leached, and extraction temperature is 70 DEG C, and extraction time is 20 minutes, mechanical agitation frequency was 250r/ minutes, and filtering obtains the leachate containing rubidium, caesium, lithium, sylvite, the leaching of lithium, rubidium, caesium Extracting rate is as shown in table 5.By table 5 as it can be seen that after being more than 30 minutes between upon firing, lithium, rubidium, caesium leaching rate are all higher than 90%.
Influence result of the different roasting times of table 5 to leaching rate
Embodiment 5
By more metal mica ores and roasting additive NaCl, CaSO4Salt-mixture is 1 in mass ratio:0.7 is uniformly mixed, NaCl and CaSO in roasting additive4Mass ratio is 1:2, it is placed in 880 DEG C of roaster and reacts 45 minutes, after complete reaction It takes out, is down to room temperature, crush, consolidate mass ratio 3 by liquid:1 addition water is leached, and extraction temperature is 70 DEG C, when taking different leachings Between, mechanical agitation frequency is 250r/ minute, filters, obtains the leachate containing rubidium, caesium, lithium, sylvite, lithium, rubidium, caesium leaching rate As shown in table 6.By table 6 as it can be seen that when extraction time be more than 15 minutes after, lithium, rubidium, caesium leaching rate be all higher than 90%.
Influence result of the different extraction times of table 6 to leaching rate
Embodiment 6
By more metal mica ores and roasting additive NaCl, CaSO4Salt-mixture is 1 in mass ratio:0.7 is uniformly mixed, NaCl and CaSO in roasting additive4Mass ratio is 1:2, it is placed in 880 DEG C of roaster and reacts 45 minutes, after complete reaction It takes out, is down to room temperature, crush, consolidate mass ratio addition water by different liquid and leached, extraction temperature is 70 DEG C, extraction time 15 Minute, mechanical agitation frequency is 250r/ minutes, and filtering obtains the leachate containing rubidium, caesium, lithium, sylvite, the leaching of lithium, rubidium, caesium Rate is as shown in table 7.By table 7 as it can be seen that when liquid-solid ratio is equal to 2:When 1, lithium, caesium leaching rate be more than 90%, the leaching rate of rubidium is close In 90%, latter three leaching rate be all higher than 90%.
Influence result of the different liquid-solid ratioes of table 7 to leaching rate
Embodiment 7
By more metal mica ores, NaCl, CaSO4It is 1.00 in mass ratio:0.23:0.46 is uniformly mixed, and is placed in 880 DEG C Roaster in react 45 minutes, take out after complete reaction, be down to room temperature, crush, consolidate mass ratio 3 by liquid:1 addition water carries out It leaches, extraction temperature is 70 DEG C, and extraction time is 20 minutes, and mechanical agitation frequency is:250r/ minutes, filtering, obtain containing rubidium, The leachate of caesium, lithium, sylvite, lithium, rubidium, caesium leaching rate be respectively 93.77%, 91.12%, 92.81%.
Above-mentioned leachate is taken, the NaOH that mass fraction is 5% is added dropwise dropwise under conditions of mechanical agitation (250r/ minutes) Solution to pH value is 11, is reacted 60 minutes, filtering.Again into filtrate by the amount of substance ratio Ca2+:Na2CO3=1:1.1 addition Na2CO3Solid, reaction temperature are 60 DEG C, and the reaction time is 15 minutes, filtering.It takes previous step filtrate to be concentrated into just to sink It forms sediment, the concentrate in mass ratio under conditions of mechanical agitation (250r/ minutes):Ethyl alcohol=1:0.1 is added dropwise ethyl alcohol to concentration dropwise It in liquid, filters after complete reaction, it is Na to obtain solid2SO4、K2SO4Salt-mixture, filtrate are lithium, rubidium, caesium containing higher concentration Solution.
The Na that will be obtained2SO4、K2SO4Salt-mixture presses wherein Na2SO4The ratio between the amount of substance and the amount of KCl substances are 1:1.6 Addition KCl is configured to saturated solution, under stirring conditions, methanol is added dropwise dropwise by the volume fraction 50% of saturated solution, instead It answers 60 minutes, filters, drying.Again by the salting-out precipitate of drying at 90 DEG C, by K2SO4, Na2SO4The amount of total material and KCl substances The ratio between amount be 1:1.2 addition KCl are configured to saturated solution, stand, recrystallize, obtaining purity is in the environment of 5 DEG C 85.12% K2SO4Product.
Above-mentioned filtrate is taken, ethyl alcohol is distilled to recover and is used for previous action, then in the condition of mechanical agitation (250r/ minutes) Under by substance amount ratio Li+:Na2CO3=1:0.55 is added dropwise the Na that mass fraction is 20% dropwise2CO3Solution, reaction temperature 90 DEG C, the reaction time is 10 minutes, is filtered after complete reaction, and the Li that purity is 96.64% is obtained2CO3Product and containing more highly concentrated The Rb of degree+、Cs+Solution can be used as the material liquid of extraction rubidium salt, cesium salt.
Embodiment 8
By more metal mica ores, CaCl2、Na2SO4It is 1 in mass ratio:0.55:0.45 is uniformly mixed, and is placed in 900 DEG C It is reacted 60 minutes in roaster, takes out after complete reaction, be down to room temperature, crushed, consolidate mass ratio 2 by liquid:1 addition water is soaked Go out, extraction temperature is 60 DEG C, and extraction time is 15 minutes, and mechanical agitation frequency is:200r/ minutes, filtering, obtain containing rubidium, caesium, The leachate of lithium, sylvite, lithium, rubidium, caesium leaching rate be respectively 92.71%, 93.77%, 94.70%.
Above-mentioned leachate is taken, it is 10% that mass fraction is added dropwise dropwise under conditions of mechanical agitation (200r/ minutes) NaOH solution to pH value is 12, is reacted 90 minutes, filtering.Again into filtrate by the amount of substance ratio Ca2+:Na2CO3=1:1.2 adding Add Na2CO3Solid, reaction temperature are 60 DEG C, and the reaction time is 15 minutes, filtering.It takes previous step filtrate to be concentrated into just to sink It forms sediment, the concentrate in mass ratio under conditions of mechanical agitation (200r/ minutes):Ethyl alcohol=1:0.08 is added dropwise ethyl alcohol to concentration dropwise It in liquid, filters after complete reaction, it is Na to obtain solid2SO4、K2SO4Salt-mixture, filtrate are lithium, rubidium, caesium containing higher concentration Solution.
The Na that will be obtained2SO4、K2SO4Salt-mixture presses wherein Na2SO4The ratio between the amount of substance and the amount of KCl substances are 1:2.4 Addition KCl is configured to saturated solution, under stirring conditions, methanol is added dropwise dropwise by the volume fraction 60% of saturated solution, instead It answers 60 minutes, filters, drying.Again by the salting-out precipitate of drying at 90 DEG C, by K2SO4, Na2SO4The amount of total material and KCl substances The ratio between amount be 1:2 addition KCl are configured to saturated solution, stand, recrystallize in the environment of 5 DEG C, and it is 88.59% to obtain purity K2SO4Crude product is recrystallized to give the K that purity is more than 95% by crude product again2SO4Product.
Above-mentioned filtrate is taken, by the amount ratio Li of substance under conditions of mechanical agitation (200r/ minutes)+:Na2CO3=1:0.6 It is slowly added to Na2CO3Solid, reaction temperature are 85 DEG C, and the reaction time is 15 minutes, is filtered after complete reaction, obtaining purity is 93.21% Li2CO3Product and Rb containing higher concentration+、Cs+Solution can be used as the material liquid of extraction rubidium salt, cesium salt.
Embodiment 9
By more metal mica ores, CaCl2、Na2SO4, KCl in mass ratio be 1:0.55:0.45:0.15 is uniformly mixed, and sets It is reacted 45 minutes in 880 DEG C of roaster, takes out after complete reaction, be down to room temperature, crushed, consolidate mass ratio 2 by liquid:1 adds Water is added to be leached, extraction temperature is 70 DEG C, and extraction time is 15 minutes, and mechanical agitation frequency is 220r/ minutes, and filtering obtains To the leachate containing rubidium, caesium, lithium, sylvite, lithium, rubidium, caesium leaching rate be respectively 94.92%, 90.11%, 94.75%, potassium Leaching rate is 33.12%.
Above-mentioned leachate is taken, it is 20% that mass fraction is added dropwise dropwise under conditions of mechanical agitation (220r/ minutes) NaOH solution to pH value is 12, is reacted 60 minutes, filtering.Again into filtrate by the amount of substance ratio Ca2+:Na2CO3=1:1.1 adding Add Na2CO3Solid, reaction temperature are 60 DEG C, and the reaction time is 15 minutes, filtering.It takes previous step filtrate to be concentrated into just to sink It forms sediment, the concentrate in mass ratio under conditions of mechanical agitation (220r/ minutes):Ethyl alcohol=1:0.15 is added dropwise ethyl alcohol to concentration dropwise It in liquid, filters after complete reaction, it is Na to obtain solid2SO4、K2SO4Salt-mixture, filtrate are lithium, rubidium, caesium containing higher concentration Solution.
The Na that will be obtained2SO4、K2SO4Salt-mixture presses wherein Na2SO4The ratio between the amount of substance and the amount of KCl substances are 1:2.4 Addition KCl is configured to saturated solution, under stirring conditions, methanol is added dropwise dropwise by the volume fraction 50% of saturated solution, instead It answers 90 minutes, filters, drying.Again by the salting-out precipitate of drying at 80 DEG C, by K2SO4, Na2SO4The amount of total material and KCl substances The ratio between amount be 1:2 addition KCl are configured to saturated solution, stand, recrystallize, obtaining purity is in the environment of 10 DEG C 83.12% K2SO4Crude product is recrystallized to give the K that purity is more than 95% by crude product again2SO4Product.
Above-mentioned filtrate is taken, ethyl alcohol is distilled to recover and is used for previous action, then in the condition of mechanical agitation (220r/ minutes) Under by substance amount ratio Li+:Na2CO3=1:0.65 is added dropwise the Na that mass fraction is 25% dropwise2CO3Solution, reaction temperature are 90 DEG C, the reaction time is 15 minutes, is filtered after complete reaction, obtains the Li that purity is 95.61%2CO3Product and containing higher The Rb of concentration+、Cs+Solution can be used as the material liquid of extraction rubidium salt, cesium salt.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously Cannot the limitation to the scope of the claims of the present invention therefore be interpreted as.It should be pointed out that for those of ordinary skill in the art For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention Protect range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.

Claims (10)

1. a kind of method for extracting rubidium, caesium, lithium, potassium from more metal mica ores, which is characterized in that including:
S1, more metal mica ores and equal as two or more salt mixing in the sodium salt, sylvite or calcium salt of roasting additive Roasting after even, crushes, obtains calcining;
S2, addition water is leached in the calcining, obtains leachate;
S3, leachate process cleans, concentrates, processing of saltouing obtains Na2SO4、K2SO4Salt-mixture and scavenging solution;
S4, Na is added in the scavenging solution2CO3, using being filtered, washed, be dried to obtain Li2CO3And contain Rb+With Cs+'s Solution.
2. according to the method described in claim 1, it is characterized in that:In step sl, the sodium in the roasting additive Salt includes NaCl and/or Na2SO4, the sylvite includes KCl, and the calcium salt includes CaCl2And/or CaSO4
3. according to the method described in claim 1, it is characterized in that:In step sl, the roasting additive include NaCl with CaSO4Salt-mixture or CaCl2With Na2SO4Salt-mixture.
4. according to the method described in claim 3, it is characterized in that:In step sl, more metal mica ores and described NaCl and CaSO4The mass ratio of salt-mixture includes 1:0.3~1:1.2, the preferred mass ratio includes 1:0.5~1:1.2; And/or the temperature of the roasting includes 780 DEG C~1000 DEG C, the temperature of the preferred roasting includes 830~930 DEG C;And/or The time of the roasting includes 15~90 minutes, and the time of the preferred roasting is 30~90 minutes.
5. according to the method described in claim 1, it is characterized in that:In step sl, more metal mica ores include containing Li2O is 1%~5%, Rb2O is 0.1%~1%, Cs2O is 0.1%~1%, K2More metal Mica Mine that O is 2%~5% Stone.
6. according to the method described in claim 1, it is characterized in that:In step s 2, the liquid stereoplasm of the water and the calcining Amount is than being 1:1~4:1, it is 2 that preferably the liquid of the water and the calcining, which consolidates mass ratio,:1;And/or the temperature packet of the leaching Include 30~80 DEG C;And/or the time of the leaching includes 2~30 minutes, the time of the preferred leaching includes 15~30 points Clock.
7. according to the method described in claim 1, it is characterized in that:In step s3, described clean includes:Add mass fraction The pH value of the leachate is adjusted to 10~12 for 5%~30% NaOH, and reaction is filtered after 5~90 minutes, is removed Mg2+And Mn2+Leachate;And/or it is described saltout including:Ethyl alcohol is added into the leachate after concentration, is filtered later, is obtained The Na2SO4、K2SO4Salt-mixture, leachate and the ethyl alcohol mass ratio after the concentration are 1:0.05~1:0.2;And/or In step s3, further include to the removal Mg2+And Mn2+Leachate in Ca2+With Na2CO3Mass ratio be 1:1~1: 1.5 addition Na2CO3, controlled at 30~80 DEG C, 5~60 minutes are reacted to remove Ca2+
8. according to the method described in claim 1, it is characterized in that:Further include the Na in step s3 by gained2SO4、K2SO4It is mixed The processing of salt recrystallization is closed, including:By the Na2SO4、K2SO4Na in salt-mixture2SO4It is 1 with the ratio between the amount of KCl substances:1~1:3 Addition KCl is configured to saturated solution, adds methanol to saltout, obtains salting-out precipitate;The salting-out precipitate is pressed into the Na2SO4、K2SO4Mixing K in salt2SO4With Na2SO4The ratio between the amount of amount and KCl substances of total material be 1:1~1:3 addition KCl, in 50~90 DEG C of conditions Under be configured to saturated solution, stand recrystallization, obtain K2SO4Crystal.
9. according to the method described in claim 3, it is characterized in that:In step s 4, the Na2CO3Mass concentration be 10% ~25%, wherein the Li in the scavenging solution+With the Na2CO3The ratio between the amount of substance be 1:0.5~1:1, reaction temperature is 60~95 DEG C, the reaction time is 5~30 minutes.
10. a kind of containing Rb using described in any method preparations of claim 1-9+With Cs+Solution generate rubidium salt And/or the application of cesium salt.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109504857A (en) * 2018-11-30 2019-03-22 武汉工程大学 The method that magnesium ion exchange process extracts soluble potassium ion from biotite
CN110042225A (en) * 2019-04-26 2019-07-23 核工业北京化工冶金研究院 A kind of roasting of lepidolite ore sodium sulphate and leaching method
CN110835687A (en) * 2018-08-15 2020-02-25 中国科学院过程工程研究所 Method for extracting rubidium and cesium from steel smoke dust and/or volatile dust
CN111560513A (en) * 2020-06-30 2020-08-21 江西东鹏新材料有限责任公司 Method for extracting cesium from pollucite based on chloridizing roasting method
CN113955777A (en) * 2020-07-21 2022-01-21 承德石油高等专科学校 Method for extracting rubidium salt from soil by wet method
GB2608460A (en) * 2021-07-02 2023-01-04 British Lithium Ltd Process for the recovery and reuse of sulphate reagents from brines derived from lithium micas
GB2608461A (en) * 2021-07-02 2023-01-04 British Lithium Ltd Process for extraction of lithium from lithium-micas by calcination without pH adjustment

Citations (6)

* Cited by examiner, † Cited by third party
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
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
CN104876194A (en) * 2015-06-02 2015-09-02 南京鹳山化工科技有限公司 Method for recycling sulfuric acid and sulfate by sulfate-containing dilute sulfuric acid
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
WO2017200408A1 (en) * 2016-05-18 2017-11-23 Instituto Superior Técnico Process of lithium extraction from ores and concentrates by mechanical activation and reaction with sulphuric acid

Patent Citations (6)

* Cited by examiner, † Cited by third party
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
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
CN104876194A (en) * 2015-06-02 2015-09-02 南京鹳山化工科技有限公司 Method for recycling sulfuric acid and sulfate by sulfate-containing dilute sulfuric acid
WO2017200408A1 (en) * 2016-05-18 2017-11-23 Instituto Superior Técnico Process of lithium extraction from ores and concentrates by mechanical activation and reaction with sulphuric acid
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
储慰农: "氯化焙烧法从宜春锂云母提取Li_2CO_3", 《稀有金属》 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110835687A (en) * 2018-08-15 2020-02-25 中国科学院过程工程研究所 Method for extracting rubidium and cesium from steel smoke dust and/or volatile dust
CN110835687B (en) * 2018-08-15 2021-10-19 中国科学院过程工程研究所 Method for extracting rubidium and cesium from steel smoke dust and/or volatile dust
CN109504857A (en) * 2018-11-30 2019-03-22 武汉工程大学 The method that magnesium ion exchange process extracts soluble potassium ion from biotite
CN110042225A (en) * 2019-04-26 2019-07-23 核工业北京化工冶金研究院 A kind of roasting of lepidolite ore sodium sulphate and leaching method
CN111560513A (en) * 2020-06-30 2020-08-21 江西东鹏新材料有限责任公司 Method for extracting cesium from pollucite based on chloridizing roasting method
CN113955777A (en) * 2020-07-21 2022-01-21 承德石油高等专科学校 Method for extracting rubidium salt from soil by wet method
GB2608460A (en) * 2021-07-02 2023-01-04 British Lithium Ltd Process for the recovery and reuse of sulphate reagents from brines derived from lithium micas
GB2608461A (en) * 2021-07-02 2023-01-04 British Lithium Ltd Process for extraction of lithium from lithium-micas by calcination without pH adjustment

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