CN110526263A - A kind of method that aluminium base richness lithium slag prepares lithium carbonate - Google Patents
A kind of method that aluminium base richness lithium slag prepares lithium carbonate Download PDFInfo
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- CN110526263A CN110526263A CN201910883497.9A CN201910883497A CN110526263A CN 110526263 A CN110526263 A CN 110526263A CN 201910883497 A CN201910883497 A CN 201910883497A CN 110526263 A CN110526263 A CN 110526263A
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- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
- C01F7/141—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent
- C01F7/142—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent with carbon dioxide
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Abstract
A kind of method that aluminium base richness lithium slag prepares lithium carbonate of the present invention, step are as follows: (1) aluminium base richness lithium slag and water are mixed with aluminium base richness lithium dreg slurry；(2) carbonization of aluminium base richness lithium dreg slurry, which is leached, obtains carbonization leachate and the leached mud that is carbonized；(3) be carbonized lithium content < 6.00g/L in leachate, to then leachate return step (1) be carbonized, it repeats carbonization and is leached to lithium content to be 6.00~9.00g/L, the carbonization leachate that lithium content is 6.00~9.00g/L is pyrolyzed to obtain Crude lithium Carbonate and pyrolysis mother liquor；(4) washing lotion and aluminium hydroxide are obtained with 80~95 DEG C of water washing carbonization leached mud；(5) mother liquor and washing lotion return step (1) are pyrolyzed；(6) Crude lithium Carbonate carbonization is refining to obtain to the lithium carbonate product of purity > 99.5%.The method of the present invention technical process is simple, preparation product purity is high, and easily grafts with existing alumina producing process, easy to promote and utilize.
Description
Technical field
The invention belongs to lithium salts preparation fields, and in particular to a kind of method that aluminium base richness lithium slag prepares lithium carbonate.
Background technique
Recently as the fast development of New Energy Sources In China technology, lithium ion battery production scale rapid development leads to carbon
The sour lithium market longer term is in a situation that supply falls short of demand, and the high-quality lithium ore resources of China are deficient, salt lake high-magnesium brine magnesium lithium
Separation is difficult, and external lithium industry giant's production capacity increase is limited to cause the market supply insufficient.
The Central China area universal lithium content of bauxite is higher, and by taking Henan Province mining area as an example, average oxide containing lithium is about
0.085%, lithium disperses preservation (Ji Qinghai, Ji fruit etc., Xinan County Yu Shan alumina in the mineral such as bauxite, kaolinite, illite
The research of mine geologic feature and accompanying element, " mineral products protection and utilization " the 3rd phase in 2014, P10-14), lithium is in Bayer Process digestion
About 80% enters solution in the process, and 20% drains with red mud, eventually enters into finished product aluminium oxide into the lithium in sodium aluminate solution.
Li in the aluminium oxide factory products of Central China area2O is generally higher, usual import aluminium oxide Li2O only 0.006%, if pressed
0.1% estimation, aluminium oxide yield is by 12,000,000 tons/year of estimations, the Li taken away every year via metallurgical-grade aluminum oxide2O is up to 12000
Ton, these lithium resources are not utilized rationally, and What is more, and the electrolysis plant that rich lithium aluminium is used for a long time as raw material is electrolysed
Lithium enrichment is more than reasonable interval in matter, causes electrolytic cell degrading.
The lithium of aluminium oxide process is removed and utilized, alumina product quality not only can be improved, eliminate lithium in product
Too high levels, and can be with the lithium resource in economic recovery bauxite to the adverse effect of Aluminum Electrolysis Production, and people have been thus
A series of correlative studys recycled lithium from alumina producing process, prepare lithium carbonate are carried out.Patent is " from aluminium oxide factory aluminium
The method of lithium carbonate is extracted in acid sodium solution " (CN107500318B) disclose a kind of sodium aluminate solution containing lithium and prepare lithium carbonate
Method, this method adds aluminium hydroxide absorption lithium first in sodium aluminate solution containing lithium and obtains primary high lithium aluminium hydroxide, by institute
State primary high lithium aluminium hydroxide with evaporation mother liquor weight it is molten after obtain high lithium sperm, aluminium hydroxide crystalline substance is added in the high lithium sperm
Secondary high lithium aluminium hydroxide can be obtained in kind, handles secondary high lithium aluminium hydroxide using the method for leaching by hydrothermal process, can obtain soaking containing lithium
Liquid out is added in the inorganic acids such as hydrochloric acid in leachate containing lithium and lithium salt solution can be obtained after being separated by filtration the aluminium glue of generation, by institute
It states lithium salt solution and is concentrated by evaporation to lithium content to be greater than after 30g/L and add sodium carbonate liquor sinker, be filtered, washed and drying and processing
The lithium carbonate product that purity is greater than 90% can be obtained afterwards, the process flow of this method is complicated, and evaporating concentration process evaporation volume is larger,
Energy consumption is higher.Patent " method and system of lithium in parsing aluminium oxide factory richness lithium adsorbent " (CN109761249A) is directed to aluminic acid
Sodium solution extracts the rich lithium adsorbent that lithium generates using absorption method, further carries out lithium using the principle of high temperature and pressure leaching by hydrothermal process
Parsing, hydro-thermal reaction unit using full pipeline material slurry with slurry heat transfer technology, hydro-thermal parsing reaction temperature be 160~
220 DEG C, the reaction time is 0.5~2h, and slurry L/S is 5~30 by repeatedly adverse current parsing technique, is greater than desorbed solution lithium content
0.5g/L, lithium resolution factor >=90% in adsorbent, this method process flow is more complicated, and the anti-of lithium is parsed from adsorbent
In requisition for carrying out under elevated temperature and pressure conditions, thus equipment investment is costly.Patent " purification concentration aluminium oxide factory solution containing lithium
Analyse liquid method and system " (CN109650416A) disclose it is a kind of purification concentration aluminium oxide factory desorbed solution containing lithium method and
System, this method are purified and are concentrated desorbed solution containing lithium, the lithium rate of recovery >=90%, concentrate using acid-base neutralization, UF membrane
Middle Li+Content >=8g/L, this method are easy to cause the impurity contents liter such as iron, aluminium in solution with sour neutralisation treatment desorbed solution containing lithium
Height, therefore will lead to solution purification processing technological flow complexity, membrane separation plant investment cost is high.Patent is " from aluminium oxide factory
The method and system of enriching lithium in sodium aluminate solution " (CN109650413A) proposes one kind and adds in factory's sodium aluminate solution
The method of aluminium hydroxide adsorbent enriching lithium, the obtained lithium content 4.0~6.0% in aluminium base richness lithium slag, this method are from work
Lithium is recycled in industry sodium aluminate solution, lithium carbonate product is prepared and provides technical support, but is not directed to utilize aluminium base richness lithium slag system
The related process technologies of standby high-purity lithium carbonate.
Mainly there are sulfuric acid process, sulfate process, limestone sintering process, chlorination with the method that solid raw material containing lithium prepares lithium carbonate
Roasting method and soda ash autoclaving method etc..Sulfuric acid process is will to contain after lithium raw material is mixed with the sulfuric acid of concentration 93~98% to roast, and makes raw material
In lithium be changed into readily soluble lithium sulfate, the advantages of this method is that the recovery rate of lithium is high, but impurity content is high in solution, and
It is easy to produce acid waste water；Sulfate process be will contain lithium ore and sodium sulphate and potassium sulfate by centainly than baking mixed, acidleach at
Reason, makes the lithium in raw material be changed into lithium sulfate, and the advantages of this method is the recovery rate height of lithium, but is equally impurity content in solution
Height, solution purification difficulty is big, and product is easy the pollution by K element；Lime sinter process is traditional lithium salts production method,
Its advantage is that process is simple, equipment corrosion is small, the disadvantage is that lithium content is low in solution, mass flow is big, and the rate of recovery of lithium is lower；Chlorine
Changing roasting method is to add the chlorides such as potassium, sodium, calcium in raw material containing lithium and roast that the lithium in raw material is made to be changed into lithium chloride,
Advantage is that process is simple, and without consuming valuable raw material, the rate of recovery of lithium is higher, but chloride dosage is larger, the corrosivity of furnace gas
By force, equipment seriously corroded；Soda ash autoclaving method has process short, and mass flow is small, and equipment corrosion is slight, does not generate acid waste water
Advantage, but need to be reacted under high temperature, condition of high voltage, operating technology is more demanding, currently without the elder generation of production application
Example.
Furthermore lithium carbonate can also be produced with sulfuric acid or salt Ore Leaching aluminium base richness lithium slag, but aluminium during with Ore Leaching
The impurity elements such as Ca, Al, Fe in base richness lithium slag enter solution simultaneously, and the difficulty of solution purification increases, is unfavorable for producing high-purity
The lithium carbonate product of degree.
Summary of the invention
Aiming at the shortcomings in the prior art, the invention proposes it is a kind of using aluminium base richness lithium slag production lithium carbonate method,
This method leaches recycling lithium using the method that carbonization is leached from aluminium base richness lithium slag, prepares lithium carbonate, the lithium carbonate product of preparation
Purity is high, technical process be simple, without waste water and solid waste discharge.
The invention adopts the following technical scheme:
A kind of method that aluminium base richness lithium slag prepares lithium carbonate, which is characterized in that the described method comprises the following steps:
(1) by aluminium base richness lithium slag and water mixing fine grinding, aluminium base richness lithium dreg slurry is prepared；
(2) the aluminium base richness lithium dreg slurry of step (1) obtains carbonization leachate and the leached mud that is carbonized after carrying out carbonization leaching；
(3) if lithium content < 6.00g/L in the carbonization leachate that step (2) obtains, carbonization in step (2) is leached
Liquid return step (1) is used to prepare aluminium base richness lithium dreg slurry, repeats step (2) until the lithium content in carbonization leachate is
6.00g/L~9.00g/L contains lithium if lithium content is 6.00g/L~9.00g/L in the carbonization leachate that step (2) obtains
Amount is that the carbonization leachate of 6.00g/L~9.00g/L is pyrolyzed, and obtains Crude lithium Carbonate after carbonization leachate pyrolysis and pyrolysis is female
Liquid；
(4) by carbonization 80 DEG C~95 DEG C of the water washing of leached mud in step (2), washing lotion and aluminium hydroxide are obtained；
(5) the washing lotion return step (1) in the pyrolysis mother liquor and step (4) in step (3) is used to prepare aluminium base richness lithium
Dreg slurry；
(6) Crude lithium Carbonate obtained in step (3) is subjected to carbonization purification, the lithium carbonate for obtaining purity > 99.5% produces
Product.
The method for preparing lithium carbonate according to above-mentioned aluminium base richness lithium slag, which is characterized in that aluminium base richness lithium slurry in step (1)
Solid content in liquid is 500g/L~800g/L, lithium content < 5.00g/L in+45 μm of granularity of granule content≤10%, solution.
The method for preparing lithium carbonate according to above-mentioned aluminium base richness lithium slag, which is characterized in that aluminium base richness lithium slurry in step (2)
Liquid carry out carbonization leaching condition are as follows: temperature be 10 DEG C~60 DEG C, CO2Intake be aluminium base richness lithium slag in lithium reaction generate carbon
The CO that sour hydrogen lithium theoretically consumes21.5~4.0 times of calculated value, pressure be 0.02MPa~2.00MPa, the time be 20min~
300min。
The method for preparing lithium carbonate according to above-mentioned aluminium base richness lithium slag, which is characterized in that lithium content obtained in step (3)
For 6.00g/L~9.00g/L carbonization leachate 70 DEG C~98 DEG C, 15min~120min under conditions of pass through pyrolytic reaction
The slurries containing Crude lithium Carbonate are obtained afterwards, obtain purity >=98.5% Crude lithium Carbonate after the slurries filtering containing Crude lithium Carbonate and pyrolysis is female
Liquid.
The method for preparing lithium carbonate according to above-mentioned aluminium base richness lithium slag, which is characterized in that thick carbonic acid obtained in step (3)
Lithium is by adding water slurrying, carbonization to leach, obtaining the lithium carbonate product of purity > 99.5% after pyrolysis, filtering and drying and processing.
The method for preparing lithium carbonate according to above-mentioned aluminium base richness lithium slag, which is characterized in that the aluminium hydroxide that step (4) obtains
The adsorbent that can serve as lithium generates aluminium base richness lithium slag for adsorbing lithium from the sodium aluminate solution containing lithium again；Step (4) obtains
Aluminium hydroxide can be used for being added in the flash vessel of Bayer Process digestion, under conditions of 140 DEG C~160 DEG C dissolution recycling oxygen
Change aluminium.
The method for preparing lithium carbonate according to above-mentioned aluminium base richness lithium slag, which is characterized in that aluminium base richness lithium slag comes in step (1)
Lithium content in the process of factory's sodium aluminate solution adsorbing and extracting lithium, aluminium base richness lithium slag is 0.20%~0.90%.
Advantageous effects of the invention: (1) carbonization extract technology CO proposed by the present invention2It is soaked instead of strong acid such as hydrochloric acid
Aluminium base richness lithium slag out can leach the lithium in recycling aluminium base richness lithium slag, the impurity elements such as aluminium, iron in rich lithium slag with high selectivity
It is insoluble, there is no need to the solution purification of complexity such as UF membrane and ion exchange, can use Li content for 0.20%~
0.90% aluminium base richness lithium slag produces the lithium carbonate product of purity > 99.5%.(2) carbonization extract technology proposed by the present invention
Compared with high temperature hydro-thermal method, reaction temperature is low, and process CIMS is simple, and used in the carbonization leaching and lithium carbonate carbonization purification of lithium
Equipment is essentially identical, and equipment investment expense is few.(3) the present invention is based on the characteristic of aluminium base richness lithium slag, using being passed through CO2Method into
The leaching of row lithium and purification, reaction condition is mild, the treatment process of no high temperature and strong acid, and equipment corrosion is slight.(4) this hair
The method for preparing lithium carbonate of bright proposition is convenient for grafting with existing alumina producing process, is conducive to promote and apply.
Detailed description of the invention
Fig. 1 is process flow diagram of the invention.
Specific embodiment
Referring to Fig. 1, a kind of method that aluminium base richness lithium slag prepares lithium carbonate, comprising the following steps: (1) by aluminium base richness lithium slag with
Water mixing fine grinding obtains mixture, or aluminium base richness lithium slag is mixed with water for the first time, lithium content obtained in subsequent and step (2)
The carbonization leachate mixing fine grinding of < 6.00g/L obtains mixture, will be prepared after mixture fine grinding solid content be 500g/L~
800g/L ,+45 μm of granularity of granule content≤10%, in solution lithium content < 5.00g/L aluminium base richness lithium dreg slurry.Aluminium base is rich
Lithium slag derives from the process of factory's sodium aluminate solution adsorbing and extracting lithium, and the mass percentage of the lithium in aluminium base richness lithium slag is
0.20%~0.90%.(2) aluminium base richness lithium dreg slurry prepared by step (1) is passed through containing CO2Gas carry out carbonization leach
To carbonization leaching slurry, the condition for the leaching that is carbonized is: temperature be 10 DEG C~60 DEG C, CO2Intake be aluminium base richness lithium slag in lithium
Reaction generates the CO that lithium bicarbonate theoretically consumes21.5~4.0 times of calculated value, pressure be 0.02MPa~2.00MPa, time
For 20min~300min.What is be passed through contains CO2Gas in CO2Volumn concentration be 15~40%, be passed through containing CO2Gas
Body is the flue gas of gas or alumina producing chamotte kiln that lime burning standby lime industrial processes made of stones generate；Carbonization is soaked
Out carbonization leachate is obtained after slurries filtering and the leached mud that is carbonized.(3) if lithium content in the carbonization leachate that step (2) obtains
Carbonization leachate return step (1) in step (2) is then used to prepare aluminium base richness lithium dreg slurry, repeats to walk by < 6.00g/L
Suddenly (2) 1~3 times, until the lithium content in carbonization leachate is 6.00g/L~9.00g/L, if lithium content in carbonization leachate
More than 9.00g/L, the leaching rate that will lead to lithium is reduced；By lithium content be 6.00g/L~9.00g/L carbonization leachate at 70 DEG C
It is pyrolyzed 15min~120min under conditions of~98 DEG C and obtains the slurries containing Crude lithium Carbonate, after the slurries filtering containing Crude lithium Carbonate
To purity >=98.5% Crude lithium Carbonate and pyrolysis mother liquor.If lithium content is 6.00g/L in the carbonization leachate that step (2) obtains
~9.00g/L, then by lithium content be 6.00g/L~9.00g/L carbonization leachate 70 DEG C~98 DEG C, 15min~120min
Under conditions of be directly pyrolyzed to obtain the slurries containing Crude lithium Carbonate, equally, obtain purity after the filtering of slurries containing Crude lithium Carbonate
>=98.5% Crude lithium Carbonate and pyrolysis mother liquor.(4) it by carbonization 80 DEG C~95 DEG C of the water washing of leached mud in step (2), obtains
To washing lotion and aluminium hydroxide；Aluminium hydroxide can serve as the adsorbent of lithium, for adsorbing lithium again from the sodium aluminate solution containing lithium
Aluminium base richness lithium slag is generated, aluminium hydroxide can be used for being added in the flash vessel of Bayer Process digestion, in 140 DEG C~160 DEG C of item
Dissolution recycling aluminium oxide under part.(5) by the washing lotion return step (1) in the pyrolysis mother liquor and step (4) in step (3) as leaching
Liquid out is used to prepare aluminium base richness lithium dreg slurry；(6) by purity obtained in step (3) >=98.5% Crude lithium Carbonate by adding water
Slurrying, carbonization leach, obtain the lithium carbonate product of purity > 99.5% after pyrolysis, filtering and drying and processing.
Explanation is further explained to the present invention combined with specific embodiments below.
Embodiment 1
The aluminium that solid content is 500g/L is made after the aluminium base richness lithium slag that Li mass percentage is 0.90% is added water fine grinding
Base richness lithium dreg slurry ,+45 μm of granularity of granule content is 0.50% in slurries, is passed through under conditions of 10 DEG C containing CO2Gas
Body, which be carbonized for the first time leaching, obtains the leaching slurry that is carbonized for the first time, and be carbonized CO when leaching for the first time2Intake be aluminium base
Lithium reaction generates the CO that lithium bicarbonate theoretically consumes in rich lithium slag24.0 times of calculated value, what carbonization leaching for the first time was passed through contains
There is CO2Gas in CO2Content is 15%, and the pressure that carbonization is leached for the first time is 2.00MPa, reaction time 20min, by the
Carbonization leached mud for the first time and for the first time carbonization leachate are obtained after primary carbonization leaching slurry filtering, for the first time carbonization leachate
Middle lithium content is 4.53g/L；Washing lotion will be obtained after first time carbonization 80 DEG C of water washing of leached mud and+45 μm of granule contents are
First time carbonization leachate and for the first time the washing lotion return of carbonization leached mud are used to grind again solid by 0.50% aluminium hydroxide
Content is the aluminium base richness lithium dreg slurry of 500g/L, and Li content is 2.75/L in solution；First time carbonization leach under conditions of into
Second of carbonization of row obtains second of carbonization leaching slurry after leaching, and will obtain second after second of carbonization leaching slurry filtering
Leached mud and the Li content of being carbonized are second of carbonization leachate of 7.26g/L, and will be carbonized for second 80 DEG C of washing of leached mud
Washing lotion and+45 μm of granule contents are obtained after washing as 0.50% aluminium hydroxide；After the leachate that will be carbonized for second is warming up to 70 DEG C
Pyrolysis 120min, the Crude lithium Carbonate that purity is 98.5% and the pyrolysis mother liquor that Li content is 1.72g/L are obtained after being filtered, it will
The washing lotion of pyrolysis mother liquor and second of carbonization leached mud grinds process back to aluminium base richness lithium slag, for modulating aluminium base richness lithium slag
Slurries.The slurries that liquid-solid ratio is 25:1 are made in Crude lithium Carbonate plus water, under conditions of 20 DEG C, every cubic metre of slurries are with 120m3/
The draft speed of h is passed through CO2The gas carbonization purification 60min that volumn concentration is 40%, obtains carbonization refined liquid after filtering,
Carbonization refined liquid is pyrolyzed after 60min under conditions of 80 DEG C and obtains purification pyrolysis slurries, purification pyrolysis slurries are filtered,
The lithium carbonate product that purity is 99.8% is obtained after washing and drying.
Embodiment 2
It is carbonized and leaches after adding water to mix aluminium base richness lithium slag, obtain the carbonization leachate that Li content is 2.10g/L, then to Li
The carbonization leachate that Li content is 2.10g/L is added in the aluminium base richness lithium slag that mass percentage is 0.20%, is made after fine grinding
Solid content is the aluminium base richness lithium dreg slurry of 800g/L, and+45 μm of granularity of granule content is 10% in slurries, under conditions of 60 DEG C
It is passed through containing CO2Gas carry out for the first time carbonization leach obtain for the first time be carbonized leaching slurry, for the first time carbonization leach when CO2
Intake be that lithium reaction generates the CO that theoretically consumes of lithium bicarbonate in aluminium base richness lithium slag21.5 times of calculated value, first time carbon
What change leaching was passed through contains CO2Gas in CO2Content is 40%, when the pressure that carbonization is leached for the first time is 0.02MPa, reacts
Between be 300min, will for the first time carbonization leaching slurry filtering after obtain for the first time be carbonized leached mud and for the first time carbonization leachate,
Lithium content is 4.20g/L in carbonization leachate for the first time；First time is carbonized after 95 DEG C of water washing of leached mud and obtains washing lotion
The aluminium hydroxide for being 10% with+45 μm of granule contents returns the washing lotion of first time carbonization leachate and first time carbonization leached mud
It is back to the aluminium base richness lithium dreg slurry for grinding that solid content is 800g/L again, Li content is 2.94g/L in solution.In first time carbon
Change and carries out obtaining second of carbonization leaching slurry after second of carbonization is leached under conditions of leaching, it will second of carbonization leaching slurry
Second of carbonization leached mud and Li content are obtained after filtering as second of carbonization leachate of 5.04g/L；It will second of carbonization leaching
It slags tap with the aluminium hydroxide for obtaining washing lotion after 95 DEG C of water washing and+45 μm of granule contents are 10%, second of carbonization is leached
The washing lotion of liquid and second of carbonization leached mud grinds process back to aluminium base richness lithium slag, is 800g/L's for modulating solid content
Aluminium base richness lithium dreg slurry, Li content is 3.52g/L in solution.Third time carbonization leaching is carried out under conditions of first time, carbonization was leached
Third time is obtained after out to be carbonized leaching slurry, will obtain that Li content is 5.63g/L after third time carbonization leaching slurry filtering
Three times carbonization leachate and third time carbonization leached mud, will third time carbonization 95 DEG C of water washing of leached mud after obtain washing lotion with
The aluminium hydroxide that+45 μm of granule contents are 10% returns to the washing lotion of third time carbonization leachate and third time carbonization leached mud
To aluminium base richness lithium sizing process, for modulating the aluminium base richness lithium dreg slurry that solid content is 800g/L, Li content is in solution
3.94g/L.Aluminium base richness lithium dreg slurry is carried out to obtain the 4th after the 4th carbonization is leached under conditions of first time, carbonization was leached
Secondary carbonization leaching slurry, the 4th time is carbonized the 4th carbonization leaching for obtaining that Li content is 6.04g/L after leaching slurry filtering
Liquid and the 4th carbonization leached mud will obtain the particle of washing lotion He+45 μm after the 4th carbonization 95 DEG C of water washing of leached mud
The aluminium hydroxide that content is 10%.After 4th carbonization leachate is warming up to 75 DEG C be pyrolyzed 60min, be filtered after obtain it is pure
The pyrolysis mother liquor that the Crude lithium Carbonate and Li content that degree is 99.0% are 1.70g/L, will pyrolysis mother liquor and the 4th carbonization leached mud
Washing lotion grind process back to aluminium base richness lithium slag, for modulating aluminium base richness lithium dreg slurry.Liquid is made in Crude lithium Carbonate plus water
Gu under conditions of 20 DEG C, every cubic metre of slurries are with 150m than the slurries for being 20:13The draft speed of/h is passed through CO2Volume basis
The gas carbonization purification 90min that content is 40%, obtains carbonization refined liquid, by carbonization refined liquid under conditions of 80 DEG C after filtering
Purification pyrolysis slurries are obtained after pyrolysis 60min, obtaining purity after purification pyrolysis slurries are filtered, wash and are dried is
99.6% lithium carbonate product.
Embodiment 3
The aluminium that solid content is 600g/L is made after the aluminium base richness lithium slag that Li mass percentage is 0.51% is added water fine grinding
Base richness lithium dreg slurry, granularity is free of+45 μm of particle in slurries, and+30 μm of solid content is 10%, in 10 DEG C of condition
Under be passed through containing CO2Gas carry out for the first time carbonization leach obtain for the first time be carbonized leaching slurry, for the first time carbonization leach when
CO2Intake be that lithium reaction generates the CO that theoretically consumes of lithium bicarbonate in aluminium base richness lithium slag22.5 times of calculated value, for the first time
What carbonization leaching was passed through contains CO2Gas in CO2Content is 15%, and the pressure that carbonization is leached for the first time is 0.60MPa, reacts
Time is 60min.Carbonization leached mud for the first time and lithium content will be obtained as 3.42g/L's after carbonization leaching slurry filtering for the first time
Carbonization leachate for the first time；First time is carbonized after 95 DEG C of water washing of leached mud and obtains the particle of washing lotion and+30 μm of granularity
First time carbonization leachate and for the first time the washing lotion return of carbonization leached mud are used to grind again by the aluminium hydroxide that content is 10%
Solid content processed is the aluminium base richness lithium dreg slurry of 600g/L, and Li content is 2.39g/L in solution；In the condition that first time carbonization is leached
Lower second carbonization of progress obtains second of carbonization leaching slurry after leaching, and the will be obtained after second of carbonization leaching slurry filtering
Second of carbonization leachate that secondary carbonization leached mud and lithium content are 5.80g/L, by second of carbonization leached mud with 95 DEG C
The aluminium hydroxide that+30 μm of granule contents of washing lotion and granularity are 10% is obtained after water washing；It will second of carbonization leachate and second
The washing lotion of secondary carbonization leached mud is returned for grinding the aluminium base richness lithium dreg slurry that solid content is 600g/L, Li content in solution again
For 4.06g/L.The carbonization of progress third time obtains third time carbonization leaching slurry under conditions of first time, carbonization was leached after leaching,
The third time carbonization leachate and third time carbonization leaching that Li content is 7.46g/L will be obtained after third time carbonization leaching slurry filtering
It slags tap, third time is carbonized and obtains the hydrogen that+30 μm of granule contents of washing lotion and granularity are 10% after 95 DEG C of water washing of leached mud
Aluminium oxide, by third time carbonization leachate be warming up to 98 DEG C after be pyrolyzed 15min, be filtered after obtain purity be 98.6% it is thick
The washing lotion for being pyrolyzed mother liquor and third time carbonization leached mud is returned to aluminium by the pyrolysis mother liquor that lithium carbonate and Li content are 1.32g/L
Base richness lithium slag grinds process, for modulating aluminium base richness lithium dreg slurry.The slurry that liquid-solid ratio is 20:1 is made in Crude lithium Carbonate plus water
Liquid, under conditions of 30 DEG C, every cubic metre of slurries are with 100m3The draft speed of/h is passed through CO2The gas that volumn concentration is 40%
Body carbonization purification 180min, obtains carbonization refined liquid, obtains after carbonization refined liquid is pyrolyzed 60min under conditions of 80 DEG C after filtering
Slurries are pyrolyzed to purification, the lithium carbonate that purity is 99.8% is obtained after purification pyrolysis slurries are filtered, wash and are dried and produces
Product.
Embodiment 4
It is carbonized and leaches after adding water to mix aluminium base richness lithium slag, obtain the carbonization leachate that Li content is 1.60g/L, then to Li
The carbonization leachate that Li content is 1.60g/L is added in the aluminium base richness lithium slag that mass percentage is 0.90%, is made after fine grinding
Solid content is the aluminium base richness lithium dreg slurry of 700g/L, and+45 μm of particle is free of in slurries, and+20 μm of solid content is
5%, it is passed through under conditions of 20 DEG C containing CO2Gas carry out for the first time carbonization leach obtain for the first time be carbonized leaching slurry,
CO when carbonization is leached for the first time2Intake be that lithium reaction generates the CO that theoretically consumes of lithium bicarbonate in aluminium base richness lithium slag2It calculates
1.7 times of value, what carbonization leaching for the first time was passed through contains CO2Gas in CO2Content is 30%, the pressure that carbonization is leached for the first time
Power is 1.00MPa, reaction time 90min, will obtain after carbonization leaching slurry filtering for the first time being carbonized for the first time leached mud and
The first time that Li content is 8.86g/L is carbonized leachate, and the leaching rate of lithium is 80% in aluminium base richness lithium slag.By first time carbonization leaching
It slags tap with the aluminium hydroxide for obtaining washing lotion after 95 DEG C of water washing and+20 μm of granule contents are 5%.By first time carbonization leachate
To obtain Crude lithium Carbonate that purity is 98.5% and Li content be 1.60g/L after being pyrolyzed 120min after being warming up to 80 DEG C, being filtered
Pyrolysis mother liquor, mother liquor will be pyrolyzed and the washing lotion of carbonization leached mud grinds process back to aluminium base richness lithium slag for the first time, be used for
Modulate aluminium base richness lithium dreg slurry.The slurries that liquid-solid ratio is 30:1, under conditions of 30 DEG C, every cube are made in Crude lithium Carbonate plus water
Rice & peanut milk liquid is with 200m3The draft speed of/h is passed through CO2The gas carbonization purification 90min that volumn concentration is 30%, after filtering
To carbonization refined liquid, carbonization refined liquid is pyrolyzed after 60min under conditions of 80 DEG C and obtains purification pyrolysis slurries, purification is pyrolyzed
Slurries obtain the lithium carbonate product that purity is 99.8% after being filtered, wash and drying.
Embodiment 5
It is carbonized and leaches after adding water to mix aluminium base richness lithium slag, obtain the carbonization leachate that Li content is 1.62g/L, then to Li
The carbonization leachate that Li content is 1.62g/L is added in the aluminium base richness lithium slag that mass percentage is 0.30%, is made after fine grinding
Solid content is the aluminium base richness lithium dreg slurry of 800g/L, and+45 μm of granularity of granule content is 10% in slurries, under conditions of 15 DEG C
It is passed through containing CO2Gas carry out for the first time carbonization leach obtain for the first time be carbonized leaching slurry, for the first time carbonization leach when CO2
Intake be that lithium reaction generates the CO that theoretically consumes of lithium bicarbonate in aluminium base richness lithium slag21.5 times of calculated value, first time carbon
What change leaching was passed through contains CO2Gas in CO2Content is 25%, when the pressure that carbonization is leached for the first time is 1.60MPa, reacts
Between be 150min.Carbonization leached mud for the first time and Li content will be obtained as 4.77g/L's after carbonization leaching slurry filtering for the first time
Carbonization leachate for the first time；Washing lotion will be obtained after first time carbonization 95 DEG C of water washing of leached mud and+45 μm of granule contents are
10% aluminium hydroxide, the leachate that will be carbonized for the first time returns to be used to grind again with the washing lotion of carbonization leached mud for the first time to be contained admittedly
Amount is the aluminium base richness lithium dreg slurry of 800g/L, and Li content is 3.34g/L in solution；It is carried out under conditions of first time, carbonization was leached
Second of carbonization obtains second of carbonization leaching slurry after leaching, and will obtain second of carbon after second of carbonization leaching slurry filtering
Change second of carbonization leachate that leached mud and Li content are 6.48g/L, will be carbonized for second 95 DEG C of water washing of leached mud
Obtain washing lotion and+45 μm of granule contents afterwards as 10% aluminium hydroxide；It will be carbonized for second after leachate is warming up to 75 DEG C and be pyrolyzed
90min, the Crude lithium Carbonate that purity is 98.8% and the pyrolysis mother liquor that Li content is 1.62g/L are obtained after being filtered, will be pyrolyzed
The washing lotion of mother liquor and second of carbonization leached mud grinds process back to aluminium base richness lithium slag, for modulating aluminium base richness lithium slurry
Liquid.The slurries that liquid-solid ratio is 20:1 are made in Crude lithium Carbonate plus water, under conditions of 30 DEG C, every cubic metre of slurries are with 180m3/h
Draft speed be passed through CO2The gas carbonization purification 90min that volumn concentration is 25%, obtains carbonization refined liquid after filtering,
Carbonization refined liquid is pyrolyzed after 60min under conditions of 80 DEG C and obtains purification pyrolysis slurries, purification pyrolysis slurries are filtered,
The lithium carbonate product that purity is 99.6% is obtained after washing and drying.
Embodiment 6
It is carbonized and leaches after adding water to mix aluminium base richness lithium slag, obtain the carbonization leachate that Li content is 1.60g/L, then to Li
The carbonization leachate that Li content is 1.60g/L is added in the aluminium base richness lithium slag that mass percentage is 0.30%, is made after fine grinding
Solid content is the aluminium base richness lithium dreg slurry of 800g/L, and+45 μm of granularity of solid content is 10% in slurries, in 25 DEG C of item
It is passed through under part containing CO2Gas carry out for the first time carbonization leach obtain for the first time be carbonized leaching slurry, for the first time carbonization leach
When CO2Intake be that lithium reaction generates the CO that theoretically consumes of lithium bicarbonate in aluminium base richness lithium slag22.5 times of calculated value, first
What secondary carbonization leaching was passed through contains CO2Gas in CO2Content is 36%, and the pressure that carbonization is leached for the first time is 1.8MPa, reacts
Time is 45min.Carbonization leached mud for the first time and Li content will be obtained as 4.59g/L's after carbonization leaching slurry filtering for the first time
Carbonization leachate for the first time；Washing lotion will be obtained after first time carbonization 80 DEG C of water washing of leached mud and+45 μm of granule contents are
10% aluminium hydroxide, the leachate that will be carbonized for the first time returns to be used to grind again with the washing lotion of carbonization leached mud for the first time to be contained admittedly
Amount is the aluminium base richness lithium dreg slurry of 800g/L, and Li content is 2.98g/L in solution；It is carried out under conditions of first time, carbonization was leached
Second of carbonization obtains second of carbonization leaching slurry after leaching, and will obtain second of carbon after second of carbonization leaching slurry filtering
Change second of carbonization leachate that leached mud and Li content are 5.96g/L, will be carbonized for second 80 DEG C of water washing of leached mud
Washing lotion and+45 μm of granule contents are obtained afterwards for 10% aluminium hydroxide, by second be carbonized leachate and the leaching that is carbonized for second
The washing lotion of slag grinds process back to aluminium base richness lithium slag, molten for modulating the aluminium base richness lithium dreg slurry that solid content is 800g/L
Li content is 3.76g/L in liquid；Third time carbonization is carried out under conditions of first time, carbonization was leached to leach, obtain Li after filtering and contain
Amount is the third time carbonization leachate and third time carbonization leached mud of 6.84g/L, and will be carbonized water of the leached mud with 80 DEG C for the third time
Washing lotion and+45 μm of granule contents are obtained after washing as 10% aluminium hydroxide.After third time carbonization leachate is warming up to 75 DEG C
Pyrolysis 90min, the Crude lithium Carbonate that purity is 98.9% and the pyrolysis mother liquor that Li content is 1.62g/L are obtained after being filtered, it will
The washing lotion of pyrolysis mother liquor and third time carbonization leached mud grinds process back to aluminium base richness lithium slag, for modulating aluminium base richness lithium slag
Slurries.The slurries that liquid-solid ratio is 30:1 are made in Crude lithium Carbonate plus water, under conditions of 30 DEG C, every cubic metre of slurries are with 100m3/
The draft speed of h is passed through CO2The gas carbonization purification 160min that volumn concentration is 36%, obtains carbonization purification after filtering
Carbonization refined liquid is pyrolyzed after 60min under conditions of 80 DEG C and obtains purification pyrolysis slurries by liquid, and purification pyrolysis slurries were carried out
The lithium carbonate product that purity is 99.7% is obtained after filter, washing and drying.
Claims (7)
1. a kind of method that aluminium base richness lithium slag prepares lithium carbonate, which is characterized in that the described method comprises the following steps:
(1) by aluminium base richness lithium slag and water mixing fine grinding, aluminium base richness lithium dreg slurry is prepared；
(2) the aluminium base richness lithium dreg slurry of step (1) obtains carbonization leachate and the leached mud that is carbonized after carrying out carbonization leaching；
(3) if lithium content < 6.00g/L in the carbonization leachate that step (2) obtains, carbonization leachate in step (2) is returned
It goes back to step (1) and is used to prepare aluminium base richness lithium dreg slurry, repeat step (2) until the lithium content in carbonization leachate is
6.00g/L~9.00g/L contains lithium if lithium content is 6.00g/L~9.00g/L in the carbonization leachate that step (2) obtains
Amount is that the carbonization leachate of 6.00g/L~9.00g/L is pyrolyzed, and obtains Crude lithium Carbonate after carbonization leachate pyrolysis and pyrolysis is female
Liquid；
(4) by carbonization 80 DEG C~95 DEG C of the water washing of leached mud in step (2), washing lotion and aluminium hydroxide are obtained；
(5) the washing lotion return step (1) in the pyrolysis mother liquor and step (4) in step (3) is used to prepare aluminium base richness lithium slurry
Liquid；
(6) Crude lithium Carbonate obtained in step (3) is subjected to carbonization purification, obtains the lithium carbonate product of purity > 99.5%.
2. the method that aluminium base richness lithium slag according to claim 1 prepares lithium carbonate, which is characterized in that aluminium base in step (1)
Solid content in rich lithium dreg slurry is 500g/L~800g/L, lithium content < in+45 μm of granularity of granule content≤10%, solution
5.00g/L。
3. the method that aluminium base richness lithium slag according to claim 1 prepares lithium carbonate, which is characterized in that aluminium base in step (2)
Rich lithium dreg slurry carry out carbonization leaching condition are as follows: temperature be 10 DEG C~60 DEG C, CO2Intake be aluminium base richness lithium slag in lithium it is anti-
The CO that lithium bicarbonate theoretically consumes should be generated21.5~4.0 times of calculated value, pressure be 0.02MPa~2.00MPa, the time is
20min~300min.
4. the method that aluminium base richness lithium slag according to claim 1 prepares lithium carbonate, which is characterized in that step obtains in (3)
Lithium content be 6.00g/L~9.00g/L carbonization leachate 70 DEG C~98 DEG C, 15min~120min under conditions of pass through
The slurries containing Crude lithium Carbonate are obtained after pyrolytic reaction, obtain purity >=98.5% Crude lithium Carbonate after the slurries filtering containing Crude lithium Carbonate
With pyrolysis mother liquor.
5. the method that aluminium base richness lithium slag according to claim 4 prepares lithium carbonate, which is characterized in that step obtains in (3)
Crude lithium Carbonate through adding water slurrying, carbonization leach, pyrolysis, filtering and drying and processing after obtain the lithium carbonate of purity > 99.5%
Product.
6. the method that aluminium base richness lithium slag according to claim 1 prepares lithium carbonate, which is characterized in that step (4) obtains
Aluminium hydroxide can serve as the adsorbent of lithium, generate aluminium base richness lithium slag again for adsorbing lithium from the sodium aluminate solution containing lithium；Step
Suddenly the aluminium hydroxide that (4) obtain can be used for being added in the flash vessel of Bayer Process digestion, under conditions of 140 DEG C~160 DEG C
Dissolution recycling aluminium oxide.
7. the method that aluminium base richness lithium slag according to claim 1 prepares lithium carbonate, which is characterized in that aluminium base in step (1)
Rich lithium slag derives from the process of factory's sodium aluminate solution adsorbing and extracting lithium, and the lithium content in aluminium base richness lithium slag is 0.20%~
0.90%.
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| CN112678851A (en) * | 2020-12-28 | 2021-04-20 | 河南科技大学 | Preparation method of low-cost battery-grade lithium carbonate |
| CN112941339A (en) * | 2021-01-29 | 2021-06-11 | 安徽工业大学 | Method for preparing metal lithium by taking aluminum-lithium symbiotic resource alkali leaching solution as raw material |
| CN115124052A (en) * | 2022-06-17 | 2022-09-30 | 中国铝业股份有限公司 | Preparation method of battery-grade lithium carbonate |
| CN116119689A (en) * | 2022-11-02 | 2023-05-16 | 四川顺应锂材料科技有限公司 | Method for self-adsorption separation recycling of aluminum nitrate salt solution containing trace lithium |
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