CN107034355B - A kind of method that rubidium and caesium are extracted from lepidolite ore - Google Patents
A kind of method that rubidium and caesium are extracted from lepidolite ore Download PDFInfo
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- CN107034355B CN107034355B CN201710313309.XA CN201710313309A CN107034355B CN 107034355 B CN107034355 B CN 107034355B CN 201710313309 A CN201710313309 A CN 201710313309A CN 107034355 B CN107034355 B CN 107034355B
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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
- C22B1/06—Sulfating roasting
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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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- 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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- 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
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
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Abstract
The invention belongs to metallurgical technology field, disclose a kind of method that rubidium and caesium are extracted from lepidolite ore, α type lepidolites are converted into β type lepidolites with micro-wave oven, and crush the mix concentrated sulfuric acid and carry out microwave sulfating roasting, immersion obtain containing lithium, potassium, rubidium, caesium alkali metal soln mother liquor, then using caesium cationic ion-exchange resin exchange column circulation absorption cesium ion, afford cesium salt, rubidium cationic ion-exchange resin exchange column circulation absorption rubidium ion is used again, affords rubidium salt.Lepidolite ore is handled using the method for the present invention, energy consumption is low, will not produce sulfur trioxide, and rubidium and caesium recovery rate are high, and helps to simplify and follow-up put forward lithium technique.
Description
Technical field
The invention belongs to metallurgical technology field, is related to a kind of method that rubidium and caesium are extracted from lepidolite ore.
Background technology
Lepidolite is a kind of important mineral resources, and it contains abundant Rare Metals Materials, lithium, sodium, potassium, rubidium, caesium, aluminium
Deng.With the growing tension of world energy sources, utilization new energy is the common issue in the world, and lithium electricity new energy is as new energy
One of important industry of development, increasingly paid attention to by various countries；Lithium and the salt such as its esters lithium carbonate, lithium sulfate are lithium electricity new energy
The basic raw produce of industry, and the basic material lithium metal containing lithium electricity New Energy Industry in lepidolite, therefore to lithium cloud
Female development and application turn into current heat subject.During development and application lithium and its salt, due to containing in lepidolite raw material
Other metallic elements are enriched, and only extract lithium metal and its salt, do not make development and application to remaining metal, such significant wastage treasured
Expensive mineral resources, and certain pollution is will also result in environment, therefore lithium and its mistake of salt in lepidolite raw material is extracted
Cheng Zhong, the extraction to potassium, rubidium, caesium are also necessary；Such as when extracting lithium carbonate, while extract remaining metallic potassium, rubidium, cesium salt
The production cost of lithium carbonate can be greatly reduced.
CN201210307423.9 disclose it is a kind of from lepidolite raw material extract lithium after separating potassium rubidium cesium alum method, with
Lepidolite is raw material, including is impregnated after lepidolite is crushed with dilution heat of sulfuric acid, forms solid-liquid mixed liquor, solid-liquid mixed liquor is added
After heat is warming up to more than 70 DEG C, filtered, separated, slagging-off, carry after lithium obtaining filtrate, then repeatedly crystallisation by cooling and heating and filtering
Operation, progressively extract arcanite, cesium alum, rubidium alum.This method, not only crystallisation by cooling and heating and filtering number of repetition are more, and energy consumption is big,
And if crystallisation by cooling and heating and filtering number of repetition are inadequate, then arcanite, cesium alum, the purity of rubidium alum are difficult to composite demand.
CN201610379079.2 discloses a kind of method of the chloridising roasting processing preferential separating potassium rubidium caesium of lepidolite, and it is
Obtained lepidolite powder and ore phase reconstruction auxiliary agent batch mixing are prepared into raw material ball after lepidolite ore is activated by mechanical mill,
Raw material ball adds heavy alum into leachate after water logging and helped by the chloride or hydroxide of ore phase reconstruction reaction generation potassium rubidium caesium
Agent is reacted, and then progressively decrease temperature crystalline separates out potassium rubidium cesium alum salt, and the larger rubidium caesium of solubility is then converted into rubidium cesium salt causticization
Salt, rubidium salt, sylvite, cesium salt are obtained by extract and separate step by step respectively.Rubidium caesium is prepared to the potassium rubidium caesium solution extraction after concentration to mix
Salt is closed, uses t-BAMAP as extractant, with the one or more in sulfonated kerosene, dimethylbenzene, diethylbenzene for diluent, with salt
Acid, sulfuric acid, carbon dioxide etc. are back washing agent, and using Pyatyi cocurrent extraction, rubidium cesium salt is prepared.The rubidium cesium salt of extraction will not
Rubidium and caesium separation, and still contain higher potassium in rubidium cesium salt.
The content of the invention
It is an object of the invention to provide a kind of method that rubidium and caesium are extracted from lepidolite ore, at microwave sintering method
Lepidolite, the discharge of no sulfur trioxide are managed, and rubidium and caesium are first extracted before lithium is carried so that rubidium and caesium do not influence follow-up to put forward lithium work
Skill so that it is more simple to put forward lithium technique, and it is higher to put forward lithium purity.
To achieve these goals, present invention employs following technical proposals.One kind extracts rubidium and caesium from lepidolite ore
Method, α type lepidolites are converted into β type lepidolites with microwave device, and crush the mix concentrated sulfuric acid carry out microwave sulphation roasting
Burn, immersion obtain containing lithium, potassium, rubidium, caesium alkali metal soln mother liquor, then using caesium cationic ion-exchange resin exchange column circulate inhale
Attached cesium ion, affords cesium salt, then with rubidium cationic ion-exchange resin exchange column circulation absorption rubidium ion, affords rubidium salt.
Particularly, extraction step is as follows：
Step 1：α type lepidolites are positioned over progress microwave calcination, 780-900 DEG C of microwave calcination 20- in microwave device
30min, α type lepidolites are converted into β type lepidolites；Then will be more than β type lepidolite crushing grindings to 300 mesh thin, mix is dense
Progress sulfating roasting 5-15min in micro-wave oven is put into after sulfuric acid, the addition of the concentrated sulfuric acid is lepidolite miberal powder 150- per ton
250kg；
Step 2: the β type lepidolite miberal powders Jing Guo sulfating roasting are soaked in water, and ultrasound is stirred in immersion process
Mix, then adjust pH value to 5-7, stand after SS sedimentation, filtering supernatant obtain containing lithium, potassium, rubidium, caesium alkali
Metallic solution mother liquor；
Step 3: by the alkali metal soln mother liquor in step 2 by caesium cationic ion-exchange resin exchange column, absorption caesium from
Son, make alkali metal soln Recycling Mother Solution by caesium cationic ion-exchange resin exchange column using circulating pump, until original alkali metal solution
Caesium 99% in mother liquor is adsorbed by caesium cationic ion-exchange resin exchange column；Solution after circulation is without caesium alkali metal soln；
Step 4: eluting the caesium cationic ion-exchange resin exchange column in step 3 using diluted acid, primary metal ion is obtained
For the eluent of cesium ion, although the activity of cesium ion higher than rubidium, potassium, lithium, in eluent still can absorbed portion rubidium and
Potassium, eluent pass through caesium cationic ion-exchange resin exchange column exchange adsorption again, eluent are detected, until cesium ion accounts in eluent
The 99% of cations, then crystallization obtain cesium salt；In the step after caesium cationic ion-exchange resin exchange column exchange adsorption
Liquid after absorption, containing rubidium, potassium and part caesium, liquid is back to step 3 and caesium is crossed together with alkali metal soln mother liquor after the absorption
Cationic ion-exchange resin exchange column；
Step 5: by step 3 without caesium alkali metal soln by rubidium cationic ion-exchange resin exchange column, absorption rubidium from
Son, no caesium alkali metal soln is set to cycle through rubidium cationic ion-exchange resin exchange column using circulating pump, until molten without caesium alkali metal
Rubidium 99% in liquid is adsorbed by rubidium cationic ion-exchange resin exchange column, and the solution after circulation is without rubidium alkali metal soln, no rubidium alkali
Metallic solution is used for sinker；
Step 6: eluting the rubidium cationic ion-exchange resin exchange column in step 5 using diluted acid, primary metal ion is obtained
For the eluent of rubidium ion, although the activity of rubidium ion higher than potassium, lithium, in eluent still can absorbed portion potassium, elution
Liquid passes through rubidium cationic ion-exchange resin exchange column exchange adsorption again, eluent is detected, until rubidium ion accounts for eluent in eluent
The 99% of cations, then crystallization obtain rubidium salt；In the step after rubidium cationic ion-exchange resin exchange column exchange adsorption
Liquid after absorption, containing potassium and part rubidium, after the absorption liquid be back to step 5 with without crossing rubidium cation together with caesium alkali metal soln
Exchanger resin exchange column.
Preferably, the caesium cationic ion-exchange resin exchange column exchanges tree using strongly acidic styrene system macroporous cation
Fat, using styrene, divinylbenzene as primary raw material, by suspension copolymerization, it is skeleton to obtain beadlike polymer, then with solid stone
Wax is perforating agent, using the concentrated sulfuric acid as sulfonating agent, using dichloroethane as swelling agent, carries out sulfonating reaction, is prepared into sulfonic group
Large hole cation exchanger resin, this strongly acidic styrene system large hole cation exchanger resin has Selective adsorption, can be with
Preferential adsorption caesium cation.
Preferably, the rubidium cationic ion-exchange resin exchange column uses poly- metaantimmonic acid/polyacrylonitrile combination ion exchange resin,
Experiment finds that poly- metaantimmonic acid/polyacrylonitrile combination ion exchange resin has good Selective adsorption to rubidium cation, can be used for
Separate rubidium and potassium.
Preferably, in step 4, eluted using 7mol/L sulfuric acid solution.
Preferably, in step 6, eluted using 2mol/L sulfuric acid solution.
Preferably, in step 4, first using the caesium cationic ion-exchange resin in 1mol/L sulfuric acid solution elution step three
Exchange column, metal ion of the activity less than caesium is eluted out, step 3 of this elution fractions delivering to continued the friendship of caesium cation
Change resin-column；Then carry out second with 6mol/L sulfuric acid solution to elute, afford primary metal ion for the second time
For the eluent of cesium ion, the eluent of second of elution passes through caesium cationic ion-exchange resin exchange column exchange adsorption again, then
Eluted again with 6mol/L sulfuric acid solution, eluent is detected, until cesium ion accounts for the 99% of cations in eluent.
Preferably, in step 6, first using the rubidium cation exchange tree in 0.05mol/L sulfuric acid solution elution step five
Ester exchange post, foreign ion is first eluted, eluent return to step five, is then eluted for the second time with 2-3mol/L sulfuric acid solution,
The eluent that primary metal ion is rubidium ion is obtained, eluent passes through rubidium cationic ion-exchange resin exchange column exchange adsorption again,
Eluted again with 2-3mol/L sulfuric acid solution, eluent is detected, until rubidium ion accounts for eluent cation content in eluent
99%.
Advantages of the present invention：1. traditional lepidolite ore processing method is to make lepidolite by height using 1200 DEG C of high-temperature roastings
Temperature expansion causes mineral crystal structure to rupture, and makes the activity change of lepidolite and is used to burn with air oxygen, it is necessary to be heated at high temperature, adds
Hot time length, high energy consumption, cuts and produces a large amount of dust and carbon dioxide.It is micro- and the present invention carries out microwave heating using microwave device
Ripple is radiated in lepidolite, is largely penetrated into inside lepidolite and is absorbed and be changed into heat energy, and the crystal formation of lepidolite occurs
Change, microwave heating, there is heating rapidly, uniformly, heat utilization efficiency is high, does not produce dust and carbon dioxide, more energy-conserving and environment-protective,
And the microwave sulfating roasting heat time is short, will not produce sulfur trioxide.2. the characteristics of lithium, potassium, rubidium, caesium activity are different, and
And the characteristics of using cationic ion-exchange resin Preferential adsorption substitute activity high cation, exchanged by caesium cationic ion-exchange resin
Post and rubidium cationic ion-exchange resin exchange column distribution absorption caesium and rubidium, then elute crystallization and obtain cesium salt and rubidium salt, DNA purity is high,
And caesium and rubidium are first extracted, it is easy to simplify follow-up sinker technique, and do not need Repeat-heating in traditional handicraft and cold
The process of jelly, it is only necessary to circulated in cationic ion-exchange resin, greatly reduce energy consumption, cationic ion-exchange resin can be carried out
Absorption, elution cycles utilize, and reduce cost.
Embodiment
The present invention is further clarified with reference to embodiment.
The preparation method of poly- metaantimmonic acid/polyacrylonitrile combination ion exchange resin is：The poly- metaantimmonic acid particles of 10g are added to 150mL
Three neck round bottom flask in, add 40mL dimethyl sulfoxide (DMSO) and 0.3g Tween-80s, stir 1h at 60 DEG C, obtain mixed liquor；Will
Mixed liquor stirs 5h at 50 DEG C with 4g polyacrylonitrile and is well mixed, and obtains homogeneous white emulsion；By emulsion peristaltic pump to flow
Speed brings shower nozzle into for 10mL/m, instills in the deionized water that rotating speed is 250r/min, spheroidal particle is made, then uses deionized water
18h is dried at washing 3 times, 50 DEG C, obtains spherical poly- metaantimmonic acid/polyacrylonitrile combination ion exchange resin.Poly- metaantimmonic acid/polyacrylonitrile
Combination ion exchange resin has good Selective adsorption to rubidium cation, available for separation rubidium and potassium.In following embodiments
The microwave device uses different types of micro-wave oven as needed.
Embodiment 1
Step 1：α type lepidolites are positioned in microwave device, the microwave device is to carry out microwave in micro-wave oven to burn
Burn, 780 DEG C of microwave calcination 20min (power of micro-wave oven is 2KW here, and microwave frequency is 2 ± 50MHz, 0-900 DEG C of temperature),
α type lepidolites are converted into β type lepidolites；Then β type lepidolite crushing grindings to 300 mesh are put with thin after the mix concentrated sulfuric acid
Enter progress sulfating roasting 8min in micro-wave oven, (power of micro-wave oven is 2KW here, and microwave frequency is 2 ± 50MHz, temperature 0-
200 DEG C), the addition of the concentrated sulfuric acid is lepidolite miberal powder 250kg per ton；By detection, α type lepidolites are converted into β type lepidolites
Conversion ratio up to 100%.
Step 2: the β type lepidolite miberal powders Jing Guo sulfating roasting are soaked in water, and ultrasound is stirred in immersion process
Mix, then adjust pH value to 5-7, stand after SS sedimentation, filtering supernatant obtain containing lithium, potassium, rubidium, caesium alkali
Metallic solution mother liquor；Leaching of the leaching rate of lithium up to the leaching rate of 100%, potassium up to the leaching rate of 92%, rubidium up to 91%, caesium after testing
Extracting rate is up to 89%.
Step 3: by the alkali metal soln mother liquor in step 2 by caesium cationic ion-exchange resin exchange column, absorption caesium from
Son, make alkali metal soln Recycling Mother Solution by caesium cationic ion-exchange resin exchange column using circulating pump, until original alkali metal solution
Caesium 99% in mother liquor is adsorbed by caesium cationic ion-exchange resin exchange column；Solution after circulation is without caesium alkali metal soln；
Step 4: first using the caesium cationic ion-exchange resin exchange column in 1mol/L sulfuric acid solution elution step three, will
Activity is eluted out (mainly rubidium ion and part potassium, sodium, calcium impurities) less than the metal ion of caesium, and this elution fractions is delivered to
Step 3 continued caesium cationic ion-exchange resin exchange column；Then carry out second with 6mol/L sulfuric acid solution to elute, second
It is secondary to afford the eluent that primary metal ion is cesium ion, although the activity of cesium ion is higher than rubidium, potassium, lithium, elution
In liquid still can absorbed portion rubidium and potassium, the eluent of second elution exchanges by caesium cationic ion-exchange resin exchange column again to be inhaled
It is attached, then eluted again with 6mol/L sulfuric acid solution, eluent is detected, until cesium ion accounts for cations in eluent
99%, then crystallization obtain cesium salt；Liquid after absorption in the step after caesium cationic ion-exchange resin exchange column exchange adsorption,
Containing rubidium, potassium and part caesium, liquid is back to step 3 and caesium cation exchange tree is crossed together with alkali metal soln mother liquor after the absorption
Ester exchange post；
Caesium cationic ion-exchange resin exchange column uses strongly acidic styrene system large hole cation exchanger resin, with styrene,
Divinylbenzene is primary raw material, and by suspension copolymerization, it is skeleton to obtain beadlike polymer, then using solid paraffin as perforating agent,
Using the concentrated sulfuric acid as sulfonating agent, using dichloroethane as swelling agent, sulfonating reaction is carried out, is prepared into sulfonic macroporous cation
Exchanger resin, this strongly acidic styrene system large hole cation exchanger resin have Selective adsorption, can be used for adsorbing caesium sun
Ion.The preparation method of strongly acidic styrene system large hole cation exchanger resin is referring to CN105294907A.
Step 5: by step 3 without caesium alkali metal soln by rubidium cationic ion-exchange resin exchange column, absorption rubidium from
Son, no caesium alkali metal soln is set to cycle through rubidium cationic ion-exchange resin exchange column using circulating pump, until molten without caesium alkali metal
Rubidium 99% in liquid is adsorbed by rubidium cationic ion-exchange resin exchange column, and the solution after circulation is without rubidium alkali metal soln, no rubidium alkali
Metallic solution is used for sinker；Rubidium cationic ion-exchange resin exchange column uses poly- metaantimmonic acid/polyacrylonitrile combination ion exchange resin, gathers
Metaantimmonic acid/polyacrylonitrile combination ion exchange resin is just adding poly- metaantimmonic acid particle in polyacrylonitrile preparation process and obtained, poly- antimony
The specific preparation method of acid/polyacrylonitrile combination ion exchange resin can be found in CN106140108A, and poly- metaantimmonic acid/polyacrylonitrile is multiple
Closing ion exchange resin has good Selective adsorption to rubidium cation, available for separation rubidium and potassium.
Step 6: first using 0.05mol/L sulfuric acid solution elution step five in rubidium cationic ion-exchange resin exchange column,
The foreign ions such as potassium are first eluted, eluent return to step five, then with 3mol/L second of elution of sulfuric acid solution, are obtained main
Metal ion is the eluent of rubidium ion, still can absorbed portion in eluent although the activity of rubidium ion is higher than potassium, lithium
Potassium, eluent passes through rubidium cationic ion-exchange resin exchange column exchange adsorption again, then is eluted with 3mol/L sulfuric acid solution, and detection is washed
De- liquid, until rubidium ion accounts for the 99% of eluent cation content in eluent, then crystallization obtains rubidium salt；Rubidium sun in the step
Liquid after absorption after ion exchange resin exchange column exchange adsorption, containing potassium and part rubidium, liquid is back to step 5 after the absorption
With without together with caesium alkali metal soln cross rubidium cationic ion-exchange resin exchange column.
By detection, the extraction rate reached of ion exchange post separation caesium to 95%, the extraction rate reached of ion exchange post separation rubidium
To 97%, the extraction rate reached of caesium is extracted from lepidolite ore to 85%, the extraction rate reached of rubidium is extracted from lepidolite ore to 88%.
, can be by the Pureness control of cesium salt and rubidium salt more than 99% by controlling sorption cycle time and absorb-elute number.
Embodiment 2
Step 1：α type lepidolites are positioned over progress microwave calcination in micro-wave oven, 800 DEG C of microwave calcination 30min are (here
The power of micro-wave oven is 2KW, and microwave frequency is 2 ± 50MHz, 0-900 DEG C of temperature), α type lepidolites are converted into β type lepidolites；
Then by β type lepidolite crushing grindings, 300 mesh sieves point, progress sulfating roasting 5min in micro-wave oven is put into after the mix concentrated sulfuric acid,
(power of micro-wave oven is 2KW here, and microwave frequency is 2 ± 50MHz, 0-200 DEG C of temperature), the addition of the concentrated sulfuric acid is lithium per ton
Mica miberal powder 150kg；By detection, α type lepidolites are converted into the conversion ratios of β type lepidolites up to 100%.
Step 2: the β type lepidolite miberal powders Jing Guo sulfating roasting are soaked in water, and ultrasound is stirred in immersion process
Mix, then adjust pH value to 6, stand after SS sedimentation, it is golden that filtering supernatant obtains the alkali containing lithium, potassium, rubidium, caesium
Belong to solution mother liquor；Leaching of the leaching rate of lithium up to the leaching rate of 99%, potassium up to the leaching rate of 88%, rubidium up to 89%, caesium after testing
Rate is up to 87%.
Step 3: by the alkali metal soln mother liquor in step 2 by caesium cationic ion-exchange resin exchange column, absorption caesium from
Son, make alkali metal soln Recycling Mother Solution by caesium cationic ion-exchange resin exchange column using circulating pump, until original alkali metal solution
Caesium 99% in mother liquor is adsorbed by caesium cationic ion-exchange resin exchange column；Solution after circulation is without caesium alkali metal soln；
Step 4: using the caesium cationic ion-exchange resin exchange column in 6mol/L sulfuric acid solution elution step three, obtain
Primary metal ion is the eluent of cesium ion, although the activity of cesium ion is higher than rubidium, potassium, lithium, still can in eluent
Absorbed portion rubidium and potassium, eluent pass through caesium cationic ion-exchange resin exchange column exchange adsorption again, then use 6mol/L sulphur again
Acid solution is eluted, and detects eluent, and until cesium ion accounts for the 99% of cations in eluent, then crystallization obtains caesium
Salt；Liquid after absorption in the step after caesium cationic ion-exchange resin exchange column exchange adsorption, containing rubidium, potassium and part caesium,
Liquid is back to step 3 and caesium cationic ion-exchange resin exchange column is crossed together with alkali metal soln mother liquor after the absorption；
Step 5: by step 3 without caesium alkali metal soln by rubidium cationic ion-exchange resin exchange column, absorption rubidium from
Son, no caesium alkali metal soln is set to cycle through rubidium cationic ion-exchange resin exchange column using circulating pump, until molten without caesium alkali metal
Rubidium 99% in liquid is adsorbed by rubidium cationic ion-exchange resin exchange column, and the solution after circulation is without rubidium alkali metal soln, no rubidium alkali
Metallic solution is used for sinker；
Step 6: using the rubidium cationic ion-exchange resin exchange column in 3mol/L sulfuric acid solution elution step five, obtain
Primary metal ion is the eluent of rubidium ion, although the activity of rubidium ion is higher than potassium, lithium, still can be adsorbed in eluent
Part potassium, eluent passes through rubidium cationic ion-exchange resin exchange column exchange adsorption again, then is eluted with 3mol/L sulfuric acid solution, inspection
Eluent is surveyed, until rubidium ion accounts for the 99% of eluent cation content in eluent, then crystallization obtains rubidium salt；In the step
Liquid after absorption after rubidium cationic ion-exchange resin exchange column exchange adsorption, containing potassium and part rubidium, liquid is back to step after the absorption
Rapid five with without together with caesium alkali metal soln cross rubidium cationic ion-exchange resin exchange column.
By detection, the extraction rate reached of ion exchange post separation caesium to 90%, the extraction rate reached of ion exchange post separation rubidium
To 92%, the extraction rate reached of caesium is extracted from lepidolite ore to 78%, the extraction rate reached of rubidium is extracted from lepidolite ore to 82%.
, can be by the Pureness control of cesium salt and rubidium salt more than 99% by controlling sorption cycle time and absorb-elute number.
Embodiment 3
Step 1：α type lepidolites are positioned over progress microwave calcination, 750 DEG C of microwave calcination 25min, by α types in micro-wave oven
Lepidolite is converted into β type lepidolites；Then β type lepidolite crushing grindings to 300 mesh are put into microwave with thin after the mix concentrated sulfuric acid
Sulfating roasting 15min is carried out in stove, (power of micro-wave oven is 2KW here, and microwave frequency is 2 ± 50MHz, temperature 0-200
DEG C), the addition of the concentrated sulfuric acid is lepidolite miberal powder 200kg per ton；By detection, α type lepidolites are converted into turning for β type lepidolites
Rate is up to 100%.
Step 2: the β type lepidolite miberal powders Jing Guo sulfating roasting are soaked in water, and ultrasound is stirred in immersion process
Mix, then adjust pH value to 5, stand after SS sedimentation, it is golden that filtering supernatant obtains the alkali containing lithium, potassium, rubidium, caesium
Belong to solution mother liquor；Leaching of the leaching rate of lithium up to the leaching rate of 100%, potassium up to the leaching rate of 96%, rubidium up to 95%, caesium after testing
Rate is up to 95%.
Step 3: by the alkali metal soln mother liquor in step 2 by caesium cationic ion-exchange resin exchange column, absorption caesium from
Son, make alkali metal soln Recycling Mother Solution by caesium cationic ion-exchange resin exchange column using circulating pump, until original alkali metal solution
Caesium 99% in mother liquor is adsorbed by caesium cationic ion-exchange resin exchange column；Solution after circulation is without caesium alkali metal soln；
Step 4: first using 0.5mol/L sulfuric acid solution elution step three in caesium cationic ion-exchange resin exchange column,
Activity is eluted out (mainly rubidium ion and part potassium, sodium, calcium impurities) less than the metal ion of caesium, this elution fractions is sent
Continued caesium cationic ion-exchange resin exchange column to step 3；Then second is carried out with 7mol/L sulfuric acid solution to elute, the
It is secondary to afford the eluent that primary metal ion is cesium ion, although the activity of cesium ion is washed higher than rubidium, potassium, lithium
In de- liquid still can absorbed portion rubidium and potassium, the eluent of second of elution exchanges by caesium cationic ion-exchange resin exchange column again
Absorption, is then eluted with 7mol/L sulfuric acid solution again, detects eluent, until cesium ion accounts for cation and contained in eluent
The 99% of amount, then crystallization obtain cesium salt；Liquid after absorption in the step after caesium cationic ion-exchange resin exchange column exchange adsorption
Body, containing rubidium, potassium and part caesium, liquid is back to step 3 and the friendship of caesium cation is crossed together with alkali metal soln mother liquor after the absorption
Change resin-column；
Step 5: by step 3 without caesium alkali metal soln by rubidium cationic ion-exchange resin exchange column, absorption rubidium from
Son, no caesium alkali metal soln is set to cycle through rubidium cationic ion-exchange resin exchange column using circulating pump, until molten without caesium alkali metal
Rubidium 99% in liquid is adsorbed by rubidium cationic ion-exchange resin exchange column, and the solution after circulation is without rubidium alkali metal soln, no rubidium alkali
Metallic solution is used for sinker；
Step 6: first using 0.05mol/L sulfuric acid solution elution step five in rubidium cationic ion-exchange resin exchange column,
The foreign ions such as potassium are first eluted, eluent return to step five, then with 2mol/L second of elution of sulfuric acid solution, are obtained main
Metal ion is the eluent of rubidium ion, still can absorbed portion in eluent although the activity of rubidium ion is higher than potassium, lithium
Potassium, eluent passes through rubidium cationic ion-exchange resin exchange column exchange adsorption again, then is eluted with 2mol/L sulfuric acid solution, and detection is washed
De- liquid, until rubidium ion accounts for the 99% of eluent cation content in eluent, then crystallization obtains rubidium salt；Rubidium sun in the step
Liquid after absorption after ion exchange resin exchange column exchange adsorption, containing potassium and part rubidium, liquid is back to step 5 after the absorption
With without together with caesium alkali metal soln cross rubidium cationic ion-exchange resin exchange column.
By detection, the extraction rate reached of ion exchange post separation caesium to 98%, the extraction rate reached of ion exchange post separation rubidium
To 97%, the extraction rate reached of caesium is extracted from lepidolite ore to 93%, the extraction rate reached of rubidium is extracted from lepidolite ore to 92%.
, can be by the Pureness control of cesium salt and rubidium salt more than 99% by controlling sorption cycle time and absorb-elute number.
Claims (7)
1. a kind of method that rubidium and caesium are extracted from lepidolite ore, it is characterized in that：α type lepidolites are converted into β with microwave device
Type lepidolite, and crush the mix concentrated sulfuric acid carry out microwave sulfating roasting, immersion obtain containing lithium, potassium, rubidium, caesium alkali metal soln
Mother liquor, then using caesium cationic ion-exchange resin exchange column circulation absorption cesium ion, cesium salt is afforded, then handed over rubidium cation
Resin-column circulation absorption rubidium ion is changed, affords rubidium salt；
Step is as follows：
Step 1：α type lepidolites are positioned in microwave device and carry out microwave calcination, 780-900 DEG C of microwave calcination 20-30min,
α type lepidolites are converted into β type lepidolites；Then by more than β type lepidolite crushing grindings to 300 mesh, put after the mix concentrated sulfuric acid
Enter progress sulfating roasting 5-15min in microwave device, the addition of the concentrated sulfuric acid is lepidolite miberal powder 150-250kg per ton；
Step 2: the β type lepidolite miberal powders Jing Guo sulfating roasting are soaked in water, and it is stirred by ultrasonic in immersion process, so
PH value is adjusted afterwards to 5-7, is stood after SS sedimentation, filtering supernatant obtain containing lithium, potassium, rubidium, caesium alkali metal
Solution mother liquor；
Step 3: the alkali metal soln mother liquor in step 2 is adsorbed cesium ion, made by caesium cationic ion-exchange resin exchange column
Make alkali metal soln Recycling Mother Solution by caesium cationic ion-exchange resin exchange column with circulating pump, until in original alkali metal solution mother liquor
Caesium 99% by caesium cationic ion-exchange resin exchange column adsorb；Solution after circulation is without caesium alkali metal soln；
Step 4: eluting the caesium cationic ion-exchange resin exchange column in step 3 using diluted acid, it is caesium to obtain primary metal ion
The eluent of ion, eluent pass through caesium cationic ion-exchange resin exchange column exchange adsorption again, eluent are detected, until eluent
Middle cesium ion accounts for the 99% of cations, and then crystallization obtains cesium salt；Caesium cationic ion-exchange resin exchange column exchanges in the step
Liquid after absorption after absorption, containing rubidium, potassium and part caesium, liquid is back to step 3 and alkali metal soln mother liquor after the absorption
Caesium cationic ion-exchange resin exchange column is crossed together；
Step 5: by step 3 without caesium alkali metal soln by rubidium cationic ion-exchange resin exchange column, adsorb rubidium ion, make
No caesium alkali metal soln is set to cycle through rubidium cationic ion-exchange resin exchange column with circulating pump, in without caesium alkali metal soln
Rubidium 99% is adsorbed by rubidium cationic ion-exchange resin exchange column, and the solution after circulation is without rubidium alkali metal soln, no rubidium alkali metal soln
For sinker；
Step 6: eluting the rubidium cationic ion-exchange resin exchange column in step 5 using diluted acid, it is rubidium to obtain primary metal ion
The eluent of ion, eluent pass through rubidium cationic ion-exchange resin exchange column exchange adsorption again, eluent are detected, until eluent
Middle rubidium ion accounts for the 99% of eluent cation content, and then crystallization obtains rubidium salt；Rubidium cationic ion-exchange resin exchanges in the step
Liquid after absorption after post exchange adsorption, containing potassium and part rubidium, liquid is back to step 5 and without caesium alkali metal soln after the absorption
Rubidium cationic ion-exchange resin exchange column is crossed together.
2. the method according to claim 1 that rubidium and caesium are extracted from lepidolite ore, it is characterized in that：The caesium cation is handed over
Change resin-column and use strongly acidic styrene system large hole cation exchanger resin, using styrene, divinylbenzene to be main former
Material, by suspension copolymerization, it is skeleton to obtain beadlike polymer, then using solid paraffin as perforating agent, using the concentrated sulfuric acid as sulfonating agent, with
Dichloroethane is swelling agent, carries out sulfonating reaction, is prepared into sulfonic large hole cation exchanger resin.
3. the method according to claim 1 that rubidium and caesium are extracted from lepidolite ore, it is characterized in that：The rubidium cation is handed over
Change resin-column and use poly- metaantimmonic acid/polyacrylonitrile combination ion exchange resin.
4. the method according to claim 1 that rubidium and caesium are extracted from lepidolite ore, it is characterized in that：In step 4, use
7mol/L sulfuric acid solution is eluted.
5. the method according to claim 1 that rubidium and caesium are extracted from lepidolite ore, it is characterized in that：In step 6, use
2mol/L sulfuric acid solution is eluted.
6. the method according to claim 1 that rubidium and caesium are extracted from lepidolite ore, it is characterized in that：In step 4, first make
With the caesium cationic ion-exchange resin exchange column in 1mol/L sulfuric acid solution elution step three, activity is less than to the metal ion of caesium
It is eluted out, step 3 of this elution fractions delivering to continued caesium cationic ion-exchange resin exchange column；Then 6mol/L sulphur is used
Acid solution carries out second and eluted, and affords the eluent that primary metal ion is cesium ion for the second time, second of elution
Eluent passes through caesium cationic ion-exchange resin exchange column exchange adsorption again, is then eluted again with 6mol/L sulfuric acid solution,
Eluent is detected, until cesium ion accounts for the 99% of cations in eluent.
7. the method according to claim 1 that rubidium and caesium are extracted from lepidolite ore, it is characterized in that：In step 6, first make
With the rubidium cationic ion-exchange resin exchange column in 0.05mol/L sulfuric acid solution elution step five, foreign ion is first eluted, is eluted
Liquid return to step five, then with 2-3mol/L second of elution of sulfuric acid solution, obtain primary metal ion washing for rubidium ion
De- liquid, eluent passes through rubidium cationic ion-exchange resin exchange column exchange adsorption again, then is eluted with 2-3mol/L sulfuric acid solution, inspection
Eluent is surveyed, until rubidium ion accounts for the 99% of eluent cation content in eluent.
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| CN110358934B (en) * | 2019-08-26 | 2020-05-12 | 中国科学院地球化学研究所 | Method for extracting lithium from carbonate clay type lithium ore by ion exchange method |
| CN110550644B (en) * | 2019-10-08 | 2021-10-12 | 河北铸合集团兴隆县矿业有限公司 | Method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salts from lepidolite |
| CN111996392B (en) * | 2020-07-22 | 2022-07-15 | 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 |
| CN113337734B (en) * | 2021-04-25 | 2022-09-09 | 武汉科技大学 | Method for ultrasonic reinforced extraction of rubidium from rubidium-containing ore |
| CN114105171B (en) * | 2021-11-04 | 2023-10-31 | 四川顺应锂材料科技有限公司 | Method for comprehensively utilizing lepidolite resources and lithium hydroxide prepared by method |
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