CN109517981A - The method of lithium is extracted from spodumene - Google Patents
The method of lithium is extracted from spodumene Download PDFInfo
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- CN109517981A CN109517981A CN201910036648.7A CN201910036648A CN109517981A CN 109517981 A CN109517981 A CN 109517981A CN 201910036648 A CN201910036648 A CN 201910036648A CN 109517981 A CN109517981 A CN 109517981A
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- leaching
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- spodumene
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present invention relates to ores to mention lithium technology field more particularly to a kind of method that lithium is extracted from spodumene.Method includes the following steps: mill leaching, the mixed material of spodumene and calcareous material is leached in grinding, forms slurry；Wherein, the calcareous material be calcium carbonate, calcium hydroxide, calcium oxide, with calcium carbonate substance as main component, with calcium hydroxide substance as main component or with one of calcium oxide substance as main component or a variety of mixtures；Pressure leaching, the slurry after opposite grinding leaching carry out autoclaving reaction, leach the lithium ion in the spodumene.The method applied in the present invention has the multiple advantages such as environmentally friendly, higher lithium leaching rate, low energy consumption, technique simplification is easy to operate.
Description
Technical field
The present invention relates to ores to mention lithium technology field more particularly to a kind of method that lithium is extracted from spodumene.
Background technique
Lithium is the very extensive metal material of purposes, is also very important strategic resource.Either metallurgy, medicine,
The traditional industries such as chemical industry field, or in fields such as aviation, new energy, military projects, all there is important application.In various lithium materials
In product, lithium battery is one of current most widely used and most promising product, from smart phone, laptop etc.
Electronic equipment all be unable to do without the support of lithium battery to new-energy automobile industry.
China is the more rich big country of lithium resource, and lithium resource (in terms of lithium metal) is measured up to 6,670,000 tons, mainly with ore and halogen
The formal distribution of water, wherein brine lithium resource accounts for about the 80% of total amount.Companion although accounting is more, in China's salt lake bittern
Bioelement is more, especially magnesium elements, hence it is evident that and it is higher than the content of magnesium in external brine, so that extracting the difficulty of lithium more from brine
Greatly, cost is higher, and therefore, in China, progress ore, which mentions lithium, more broad application prospect.
Mainly include spodumene, amblygonite, lepidolite, zinnwaldite, petalite etc. containing lithium ore, wherein again with from
It is relatively conventional that lithium is extracted in spodumene.It is existing from spodumene extract lithium process include: sulfuric acid process, limestone-based process,
Sulfate process and Method of Soda etc..Wherein, sulfuric acid process is although applied widely, but energy consumption is also higher, needs to consume a large amount of valence
Lattice relatively high sulfuric acid and sodium carbonate, and the value of byproduct is lower, leads to the high process cost；Limestone-based process need by
The mineral such as lepidolite and lime stone are matched according to the mass ratio of about 1:3, are changed into the lithium in mineral by high-temperature calcination
Solvable state, the calcium-containing material amount of process requirement investment is larger, calcination condition requirement is very high, and it is very high to also belong to energy consumption of reaction
Technique, higher cost；Method of Soda can generate value lower filter residue containing sodium while extracting lithium, keep the recycling of filter residue available
Property it is poor, also produce that a large amount of to recycle value low, reluctant solid while extracting lithium so as to cause entire technique
It is useless, so that the technique is unfriendly to environment.
For example, Chinese patent CN104071811A discloses a kind of technique of spodumene sulfuric acid autoclaving method extraction lithium salts, it will
Concentrated sulfuric acid autoclaving is added in spodumene after high-temperature roasting, obtains soluble lithium sulfate.The process requirement is repeatedly roasted, also
It needs using a large amount of concentrated sulfuric acids, therefore process conditions are harsher, the high requirements on the equipment, cost of material is also costly.
For another example, Chinese patent CN103183366A discloses a kind of method that soda ash pressing immersion method extracts lithium salts from spodumene,
Spodumene after roasting is subjected to pressure leaching with soda ash, by the displacement of sodium and lithium, lithium carbonate pressure is leached.The technique is being extracted
Need the sequence of operations such as further progress filters pressing, acidification after pressure leaching that could convert lithium carbonate to soluble lithium when lithium
Salt, complex process, and amount containing sodium is higher in finally formed filter residue, causes filter residue value lower, handles more difficult.But for
For the spodumene of industrialized production proposes lithium technology, the filter residue of tons of such as cannot be recycled sufficiently, high value utilizes, then can only
Become the solid waste of substantial amounts, pollutes environment.
Although in conclusion existing spodumene mentions, lithium technique route is more, and generally existing energy consumption is high, technique is multiple
Miscellaneous, unfriendly to environment, a large amount of filter residues are difficult to the problems such as high value utilizes, it would be highly desirable to solve.
Summary of the invention
The method that the purpose of the present invention is to provide a kind of to extract lithium from spodumene, is mentioned with solving existing from spodumene
There is a series of problems, such as energy consumption is high, at high cost, waste residue value is low, unfriendly to environment in the method for taking lithium.
The present invention provides a kind of method that lithium is extracted from spodumene, comprising the following steps:
Mill leaching: the mixed material of spodumene and calcareous material is leached in grinding, forms slurry；Wherein, the calcic
Substance be calcium carbonate, calcium hydroxide, calcium oxide, with calcium carbonate substance as main component, as main component with calcium hydroxide
Substance or with one of calcium oxide substance as main component or a variety of mixtures；
Pressure leaching: the slurry after opposite grinding leaching carries out autoclaving reaction, leaches the lithium ion in the spodumene.
Optionally, the spodumene is beta spodumene, and the calcareous material is selected from calcium hydroxide, calcium oxide, with calcium hydroxide
Substance as main component or with the mixture of one or more of calcium oxide substance as main component.
Further, in mill leaching step, the partial size of the mixed material is less than or equal to 15 microns after mill leaching.
It is understood that it includes appointing in the particle size range that the partial size of the mixed material, which is less than or equal to 15 microns,
One point value, such as the partial size of the mixed material is 15 microns, 13 microns, 10 microns, 9 microns, 8 microns, 7 microns, 6 microns, 5
Micron, 4 microns or 3 microns.
Preferably, in mill leaching step, the partial size of the mixed material is less than or equal to 7 microns after mill leaching.
It is highly preferred that the partial size of the mixed material is 5 microns after mill leaching in mill leaching step.
As an implementation, in mill leaching step, the grain of the calcareous material and the spodumene after mill leaching
Diameter ratio is 0.1:1~10:1, and the partial size of the calcareous material is less than or equal to 15 microns, the partial size of the spodumene be less than or
Person is equal to 15 microns.
It is understood that it includes the partial size that the partial size ratio of the calcareous material and the spodumene, which is 0.1:1~10:1,
Than any point value in range, for example, the partial size ratio of the calcareous material and the spodumene is 0.1:1,0.2:1,0.5:1,
0.8:1,1:1,1.5:1,2:1,2.5:1,3:1,4:1,5:1,8:1 or 10:1.The partial size of the calcareous material is less than or waits
Include any point value in the particle size range in 15 microns, for example, the partial size of the calcareous material is 1 micron, 2 microns, it is 3.5 micro-
The partial size of rice, 4 microns, 5 microns, 8 microns, 10 microns, 12 microns or 15 microns, the spodumene is less than or equal to 15 microns
Partial size including any point value in the particle size range, such as the spodumene is 1 micron, 2 microns, 3.5 microns, 4 microns, 5
Micron, 8 microns, 10 microns, 12 microns or 15 microns.
Preferably, in mill leaching step, the partial size ratio of the calcareous material and the spodumene is 0.5:1~2:1,
The partial size of the calcareous material is 2~15 microns, and the partial size of the spodumene is 2~15 microns.
Further, in mill leaching step, the mass ratio of the spodumene and the calcareous material is 1:0.5~1:
3。
It is understood that it includes the numerical value model that the mass ratio of the spodumene and the calcareous material, which is 1:0.5~1:3,
Enclose interior any point value, such as the mass ratio of the beta spodumene and the calcareous material is 1:0.5,1:0.6,1:0.7,1:
0.8,1:0.9,1:1,1:1.2,1:1.5,1:2,1:2.5 or 1:3.
Preferably, the mass ratio of the spodumene and the calcareous material is 1:0.85~1:1.2.
Further, the mill soaks step are as follows: water is added in Xiang Suoshu mixed material and forms the slurry, and the slurry
In mixed material solid content be 10~50%, while grinding while leaches, abrasive media using 0.1~4mm zirconia ball.
Wherein, mill leaching step, which needs for mixed material to be placed in liquid environment, grinds, therefore mixed material solid content
Refer to, for the slurry formed after water is added into mixed material, mixed material accounts for the ratio of whole slurry gross mass,
Such as mixed material solid content shows in the slurry of entire mill leaching, the mass percent of mixed material is when being 33.33%
33.33%.
It is understood that the solid content of the mixed material is 10~50% solid including this in mill leaching step
Any point value in content range, for example, the mixed material solid content be 10%, 20%, 25%, 30%, 35%, 40%,
45% or 50%.
Preferably, in mill leaching step, the solid content of the mixed material is 25~40%.
Further, the pressure soaks step are as follows: water is added into the slurry after mill leaching and carries out autoclaving reaction, water and institute
The liquid for stating mixed material consolidates mass ratio greater than 3:1, and the temperature of autoclaving reaction is greater than or equal to 120 DEG C, and pressure is greater than or equal to
0.2MPa, reaction time are more than or equal to 30min.
Wherein, pressure leaching step is further to be added after water to carry out autoclaving into the slurry that mixed material and water are formed, water with
The liquid of the mixed material consolidates mass ratio and refers to mill leaching step and press the liquid of the summation and mixed material of soaking step addition water solid
Water 1000g is added in mass ratio, such as mill leaching step and pressure leaching step altogether, and the addition quality of the mixed material is 250g, then water
Consolidating mass ratio with the liquid of the mixed material is 4:1.
It is understood that the liquid of water and the mixed material consolidates mass ratio greater than 3:1 and includes in pressure leaching step
The liquid consolidates quality than any point value in range, such as the liquid of water and the mixed material consolidate mass ratio as 3.5:1,4:1,4.5:
1,5:1,5.5:1,6:1,8:1,10:1,12:1 or 15:1；It includes the temperature model that the temperature of autoclaving reaction, which is greater than or equal to 120 DEG C,
Enclose interior any point value, for example, the temperature of autoclaving reaction is 120 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 150 DEG C, 155 DEG C,
160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C or 200 DEG C；It includes any in the pressure limit that autoclaving pressure, which is greater than or equal to 0.2MPa,
Point value, such as autoclaving pressure are 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa or 0.6MPa；Reaction time is 30~480min packet
Include any point value in the time range, for example, the reaction time be 30min, 40min, 50min, 55min, 60min, 70min,
80min, 90min, 100min, 120min, 150min, 240min, 300min, 360min, 400min or 480min.
Preferably, in pressure leaching step, it is 4:1~12:1, autoclaving that the liquid of water and the mixed material, which consolidates mass ratio,
The temperature of reaction is 135~200 DEG C, and pressure is 0.3~0.6MPa, and the reaction time is 40~160min.
Further, in the method, the leaching rate of lithium is more than or equal to 75%.
It is understood that it includes any point value in the numberical range, example that the leaching rate of lithium, which is more than or equal to 75%,
As lithium leaching rate be 75%, 80%, 85%, 88%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%,
98% or 99%.
Preferably, in the method, the leaching rate of lithium is greater than or equal to 90%.
It is highly preferred that in the method, the leaching rate of lithium is more than or equal to 97%.
Further, it the method also includes being filtered after the pressure soaks step, respectively obtains containing lithium ion
Filtrate and filter residue.
Further, the method also includes: cleaned to the filtrate containing lithium ion, sinker, obtain lithium salts
Product.
Further, the method also includes: wash the filter residue and obtain tailings, the tailings include afwillite and
Alumina silicate, the tailings are used as the production of construction material.
Compared with prior art, the beneficial effects of the present invention are:
The method applied in the present invention have environmentally friendly, lithium leaching rate is high, low energy consumption, technique simplify it is easy to operate etc. more
Weight advantage.
Firstly, this method can only pass through calcareous material in the case where being added without the substances such as sodium hydroxide or sodium sulphate
Handle spodumene, can be achieved with the extraction to lithium, thus this method can guarantee to mention in the remaining tailings after lithium only containing calcium,
The elements such as aluminium, silicon, so that the utility value of remaining tailings greatly improved, are kept away without containing sodium ion, sulfate radical, chloride ion etc.
The problem of tailings is dangerous waste is exempted from, such as can be used for the production (such as quick hardening cement building materials) of high-quality building materials, has thus solved
Fixed-end forces problem realizes that the resource utilization of solid waste utilizes.Therefore, see on the whole this method it is more environmentally protective, to ring
Border is friendly.
Secondly, this method by way of leaching (mainly grinding) in grinding to spodumene at calcareous material
Reason, so that the structure and properties for the spodumene that cannot sufficiently react with calcareous material originally change a lot, spodumene structure
Energy needed for being destroyed, reacting reduces, and then the mixed material again after opposite grinding leaching carries out autoclaving, enables spodumene and calcic object
Matter is sufficiently reacted, and lithium ion is released, to realize higher lithium leaching rate, has been well solved only with calcareous material
Lithium leaching rate very low problem when being reacted with spodumene.
Finally, this method does not need using a variety of reaction masses, does not need using the higher sour agent of a large amount of prices, do not need
The harsher reaction condition such as high-temperature roasting or calcining does not need complicated cumbersome technical process, therefore the energy consumption of entire method
It is lower, cost is lower, operability is stronger, is more suitable for industrial application.
Detailed description of the invention
Fig. 1 is the process flow chart for the method that the embodiment of the present invention one extracts lithium from spodumene.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
It should be noted that the term " includes " of the embodiment of the present invention and " having " and their any deformation, it is intended that
Be to cover it is non-exclusive include, for example, containing the process, method, system, product or equipment of a series of steps or units not
Those of be necessarily limited to be clearly listed step or unit, but may include be not clearly listed or for these processes, side
The intrinsic other step or units of method, product or equipment.
Embodiment one
The method that the present embodiment provides a kind of to extract lithium from spodumene, as shown in Figure 1, comprising the following steps:
Mill leaching: it to water is added in the mixed material of beta spodumene and calcium hydroxide, leaches to form slurry in grinding, single
The mill leaching time is 10min, repeats mill leaching three times, and abrasive media uses the zirconia ball of 0.1~4mm, mixed material after soaking mill
Partial size (D90) be 5.3 microns.Wherein, the mass ratio of beta spodumene and calcium hydroxide is 1:1.2, and the mixed material in slurry is solid
Content is 30%.
Pressure leaching: into the slurry after mill leaching, water is added in supplement, and under the conditions of 140~160 DEG C, 0.4~0.5MPa, autoclaving is anti-
60min is answered, the lithium ion in spodumene is leached.Wherein, mill leaching step and pressure soak the summation of water that step is added with mix
It is 4:1 that the liquid of material, which consolidates mass ratio,.
Filtering: the product after pressure leaching is filtered, the filtrate containing lithium ion and filter residue is respectively obtained, is computed
Out, the leaching rate of lithium is 90.55%.It cleans to the filtrate containing lithium ion, soluble carbonate salt is added after removal of impurities and carries out
Precipitation reaction obtains lithium carbonate product.
Washing filter residue obtains tailings, and the ingredient of the tailings mainly includes afwillite and alumina silicate, iron close with slag
Content is lower, partial size is very thin and not containing sulfate.Mentioned component feature based on tailings, the tailings that this method obtains have higher
Resource utilization utility value, may be used as inorganic filling material, can also be used as cement main material, concrete superfine powder
The construction materials such as shape material.This is entirely different with the waste residue containing sulfate or sodium element, and the waste residue containing sulfate is still fallen within
Solid waste needs to handle it, cannot be directly used to the higher building materials of added value；Waste residue containing sodium element is then due to sodium
In the presence of being only used for low value-added common material, it is difficult to which recycling is used for high value building materials.
Embodiment two
The method that the present embodiment provides a kind of to extract lithium from spodumene, comprising the following steps:
Mill leaching: it to water is added in the mixed material of beta spodumene and calcium hydroxide, leaches to form slurry in grinding, single
The mill leaching time is 10min, repeats mill leaching three times, and the partial size (D90) of mixed material is 6.5 microns after soaking mill.Wherein, β lithium brightness
The mass ratio of stone and calcium hydroxide is 1:1.2, and the mixed material solid content in slurry is 33.33%.
Pressure leaching: into the slurry after mill leaching, water, under the conditions of 140~150 DEG C, 0.25~0.3MPa, autoclaving is added in supplement
60min is reacted, the lithium ion in spodumene is leached.Wherein, mill soaks the summation for the water that step and pressure leaching step are added and mixes
It is 6:1 that the liquid for closing material, which consolidates mass ratio,.
Filtering: the product after pressure leaching is filtered, the filtrate containing lithium ion and filter residue is respectively obtained, is computed
Out, the leaching rate of lithium is 91.90%.It cleans to the filtrate containing lithium ion, soluble carbonate salt is added after removal of impurities and carries out
Precipitation reaction obtains lithium carbonate product.
Washing filter residue obtains tailings, and the ingredient of the tailings mainly includes afwillite and alumina silicate, iron close with slag
Content is lower, partial size is very thin and not containing sulfate.
Embodiment three
The method that the present embodiment provides a kind of to extract lithium from spodumene, comprising the following steps:
Mill leaching: it to water is added in the mixed material of beta spodumene and quick lime, leaches to form slurry in grinding, single mill
The leaching time is 10min, repeats mill leaching three times, and the partial size (D90) of mixed material is 4.5 microns after soaking mill.Wherein, in quick lime
The mass fraction of calcium oxide is 91.5%, and the mass ratio of beta spodumene and quick lime is 1:1, the mixed material solid content in slurry
It is 27%.
Pressure leaching: into the slurry after mill leaching, water is added in supplement, and under the conditions of 145~155 DEG C, 0.3~0.4MPa, autoclaving is anti-
60min is answered, the lithium ion in spodumene is leached.Wherein, mill leaching step and pressure soak the summation of water that step is added with mix
It is 5:1 that the liquid of material, which consolidates mass ratio,.
Filtering: the product after pressure leaching is filtered, the filtrate containing lithium ion and filter residue is respectively obtained, is computed
Out, the leaching rate of lithium is 92.60%.It cleans to the filtrate containing lithium ion, soluble carbonate salt is added after removal of impurities and carries out
Precipitation reaction obtains lithium carbonate product.
Washing filter residue obtains tailings, and the ingredient of the tailings mainly includes afwillite and alumina silicate, iron close with slag
Content is lower, partial size is very thin and not containing sulfate.
Example IV
The method that the present embodiment provides a kind of to extract lithium from spodumene, comprising the following steps:
Mill leaching: it to water is added in the mixed material of beta spodumene and calcium hydroxide, leaches to form slurry in grinding, single
The mill leaching time is 10min, repeats mill leaching three times, and the partial size (D90) of mixed material is 5.3 microns after soaking mill.Wherein, β lithium brightness
The mass ratio of stone and calcium hydroxide is 1:0.9, and the mixed material solid content in slurry is 30%.
Pressure leaching: into the slurry after mill leaching, water, under the conditions of 135~145 DEG C, 0.3~0.35MPa, autoclaving is added in supplement
120min is reacted, the lithium ion in spodumene is leached.Wherein, mill soaks the summation for the water that step and pressure leaching step are added and mixes
It is 5:1 that the liquid for closing material, which consolidates mass ratio,.
Filtering: the product after pressure leaching is filtered, the filtrate containing lithium ion and filter residue is respectively obtained, is computed
Out, the leaching rate of lithium is 97.1%.It cleans to the filtrate containing lithium ion, soluble carbonate salt is added after removal of impurities and is sunk
It forms sediment and reacts, obtain lithium carbonate product.
Washing filter residue obtains tailings, and the ingredient of the tailings mainly includes afwillite and alumina silicate, iron close with slag
Content is lower, partial size is very thin and not containing sulfate.
Embodiment five
The method that the present embodiment provides a kind of to extract lithium from spodumene, comprising the following steps:
Mill leaching: it to water is added in the mixed material of beta spodumene and calcium hydroxide, leaches to form slurry in grinding, single
The mill leaching time is 10min, repeats mill leaching three times, and the partial size (D90) of mixed material is 5.3 microns after soaking mill.Wherein, β lithium brightness
The mass ratio of stone and calcium hydroxide is 1:0.9, and the mixed material solid content in slurry is 30%.
Pressure leaching: into the slurry after mill leaching, water, under the conditions of 135~145 DEG C, 0.35~0.4MPa, autoclaving is added in supplement
120min is reacted, the lithium ion in spodumene is leached.Wherein, mill soaks the summation for the water that step and pressure leaching step are added and mixes
It is 4.5:1 that the liquid for closing material, which consolidates mass ratio,.
Filtering: the product after pressure leaching is filtered, the filtrate containing lithium ion and filter residue is respectively obtained, is computed
Out, the leaching rate of lithium is 97.2%.It cleans to the filtrate containing lithium ion, soluble carbonate salt is added after removal of impurities and is sunk
It forms sediment and reacts, obtain lithium carbonate product.
Washing filter residue obtains tailings, and the ingredient of the tailings mainly includes afwillite and alumina silicate, iron close with slag
Content is lower, partial size is very thin and not containing sulfate.
Embodiment six
The method that the present embodiment provides a kind of to extract lithium from spodumene, comprising the following steps:
Mill leaching: it to water is added in the mixed material of beta spodumene and calcium hydroxide, leaches to form slurry in grinding, mill leaching
Time is 10min, and mill leaching one time, the partial size (D90) of mixed material is 14.4 microns after soaking mill.Wherein, beta spodumene and hydrogen-oxygen
The mass ratio for changing calcium is 1:1.2, and the mixed material solid content in slurry is 33.33%.
Pressure leaching: into the slurry after mill leaching, water is added in supplement, and under the conditions of 140~150 DEG C, 0.2~0.3MPa, autoclaving is anti-
60min is answered, the lithium ion in spodumene is leached.Wherein, mill leaching step and pressure soak the summation of water that step is added with mix
It is 4:1 that the liquid of material, which consolidates mass ratio,.
Filtering: the product after pressure leaching is filtered, the filtrate containing lithium ion and filter residue is respectively obtained, is computed
Out, the leaching rate of lithium is 80.1%.It cleans to the filtrate containing lithium ion, soluble carbonate salt is added after removal of impurities and is sunk
It forms sediment and reacts, obtain lithium carbonate product.
Washing filter residue obtains tailings, and the ingredient of the tailings mainly includes afwillite and alumina silicate, iron close with slag
Content is lower, partial size is very thin and not containing sulfate.
Embodiment seven
The method that the present embodiment provides a kind of to extract lithium from spodumene, comprising the following steps:
Mill leaching: it to water is added in the mixed material of beta spodumene and calcium hydroxide, leaches to form slurry in grinding, mill leaching
Time is 10min, repeats mill leaching three times, and the partial size (D90) of mixed material is 5.3 microns after soaking mill.Wherein, beta spodumene with
The mass ratio of calcium hydroxide is 1:0.7, and the mixed material solid content in slurry is 30%.
Pressure leaching: into the slurry after mill leaching, water, under the conditions of 140~160 DEG C, 0.35~0.4MPa, autoclaving is added in supplement
120min is reacted, the lithium ion in spodumene is leached.Wherein, mill soaks the summation for the water that step and pressure leaching step are added and mixes
It is 4:1 that the liquid for closing material, which consolidates mass ratio,.
Filtering: the product after pressure leaching is filtered, the filtrate containing lithium ion and filter residue is respectively obtained, is computed
Out, the leaching rate of lithium is 85.3%.It cleans to the filtrate containing lithium ion, soluble carbonate salt is added after removal of impurities and is sunk
It forms sediment and reacts, obtain lithium carbonate product.
Washing filter residue obtains tailings, and the ingredient of the tailings mainly includes afwillite and alumina silicate, iron close with slag
Content is lower, partial size is very thin and not containing sulfate.
Embodiment eight
The difference of the present embodiment eight and embodiment one is only that mill leaching step, in the present embodiment, mill leaching step are as follows: to β
Water is added in the mixed material of spodumene and calcium hydroxide, leaches to form slurry in grinding, the single mill leaching time is 10min,
Mill leaching three times is repeated, the partial size (D90) of mixed material is 3.9 microns after soaking mill.Wherein, the matter of beta spodumene and calcium hydroxide
For amount than being 1:1.2, the mixed material solid content in slurry is 10%.The leaching rate of finally obtained lithium is 97.3%.
Embodiment nine
The difference of the present embodiment nine and embodiment one is only that pressure leaching step.In the present embodiment, pressure leaching step are as follows: to mill
Water is added in supplement in slurry after leaching, and under the conditions of 155~190 DEG C, 0.45~0.6MPa, autoclaving reacts 60min, makes spodumene
In lithium ion leach.Wherein, the summation of water and the liquid of mixed material that mill leaching step and pressure leaching step are added consolidate mass ratio
For 4:1.The leaching rate of finally obtained lithium is 87.76%.
Embodiment ten
The difference of the present embodiment ten and embodiment one is only that the autoclaving reaction time of pressure leaching step.In the present embodiment,
Autoclaving reacts 160min, leaches the lithium ion in spodumene.The leaching rate of finally obtained lithium is 90.97%.
Embodiment 11
The difference of the present embodiment 11 and embodiment one is only that liquid consolidates mass ratio.In the present embodiment, mill leaching step with
It is 12:1 that the summation of water and the liquid of mixed material that pressure leaching step is added, which consolidate mass ratio,.The leaching rate of finally obtained lithium is
90.98%.
Embodiment 12
The difference of the present embodiment 12 and embodiment one is only that the type and mass ratio of reaction mass.In the present embodiment
In, mill leaching step is water to be added into the mixed material of beta spodumene and calcium carbonate, and the mass ratio of beta spodumene and calcium carbonate is
1:1.5.The leaching rate of finally obtained lithium is 82.57%.
Embodiment 13
The difference of the present embodiment 13 and embodiment one is only that the type and mass ratio of reaction mass.In the present embodiment
In, mill leaching step is that water is added into the mixed material of beta spodumene, calcium carbonate and calcium hydroxide, and beta spodumene, calcium carbonate, hydrogen
The mass ratio of calcium oxide is 1:0.75:0.75.The leaching rate of finally obtained lithium is 85.74%.
Embodiment 14
The difference of the present embodiment 14 and embodiment one is only that the type and mass ratio of reaction mass.In the present embodiment
In, mill leaching step is that water is added into the mixed material of beta spodumene, calcium carbonate and calcium oxide, and beta spodumene, calcium carbonate, oxidation
The mass ratio of calcium is 1:0.75:0.75.The leaching rate of finally obtained lithium is 84.01%.
Process conditions exploratory testing
One, influence of the partial size of mixed material to lithium leaching rate
Comparative example one: the difference of this comparative example one and embodiment one is only that the mill leaching parameter of mill leaching step, mill leaching time
For 4min, mill leaching one time, the solid content of mixed material is 40%, and the partial size (D90) of mixed material is 27.32 microns after mill leaching.
The leaching rate for the lithium that the method for using this comparative example one obtains is 58.04%.
Comparative example two: the difference of this comparative example two and embodiment one is only that the mill leaching parameter of mill leaching step, mill leaching time
For 4min, mill leaching one time, the solid content of mixed material is 33.33%, and the partial size (D90) of mixed material is 16.8 micro- after mill leaching
Rice.The leaching rate for the lithium that the method for using this comparative example two obtains is 56.99%.
By comparing embodiment one to 11 and comparative example one to two it is found that in the method for the present invention, the grain of mixed material
Diameter has great influence to the leaching rate of lithium, when the partial size for the mixed material that mill leaching obtains is less than or equal to 15 microns, lithium
Leaching rate it is ideal, can reach 75% or more, especially mixed material partial size be equal to or less than 5 microns when, the leaching of lithium
Extracting rate can reach 90%, even up to 97%.When the partial size of mixed material is greater than 15 microns, although still being able to from spodumene
Lithium is extracted, but effect is not so good as ideal when partial size is less than or equal to 15 microns.In addition, although the partial size of mixed material is smaller, lithium
Leaching rate it is higher, it is contemplated that the operations such as the partial size of mixed material is smaller, filtering for subsequent step require it is higher, difficult
Spend bigger, therefore the partial size of the calcareous materials such as preferably calcium hydroxide is 2~15 microns in the present invention, the partial size of spodumene is 2~
15 microns.
Two, the partial size of mixed material compares the influence of lithium leaching rate
Influence of the present invention also to the partial size and its ratio of material each in mixed material to lithium leaching rate, which has been done, further grinds
Study carefully, specifically implements embodiment 15 to 19 respectively.
Embodiment 15
The method that the present embodiment provides a kind of to extract lithium from spodumene, comprising the following steps:
Mill leaching: it to water is added in the mixed material of beta spodumene and calcium hydroxide, leaches to form slurry in grinding, mill leaching
Partial size (D90) to calcium hydroxide and beta spodumene is 4.5 microns, and the partial size ratio of calcium hydroxide and beta spodumene is 1:1.Its
In, the mass ratio of beta spodumene and calcium hydroxide is 1:1.2, and the mixed material solid content in slurry is 27%.
Pressure leaching: into the slurry after mill leaching, water is added in supplement, and under the conditions of 140~160 DEG C, 0.4~0.5MPa, autoclaving is anti-
60min is answered, the lithium ion in spodumene is leached.Wherein, mill leaching step and pressure soak the summation of water that step is added with mix
It is 4:1 that the liquid of material, which consolidates mass ratio,.
Filtering: the product after pressure leaching is filtered, the filtrate containing lithium ion and filter residue is respectively obtained, is computed
Out, the leaching rate of lithium is 92.35%.It cleans to the filtrate containing lithium ion, soluble carbonate salt is added after removal of impurities and carries out
Precipitation reaction obtains lithium carbonate product.
Embodiment 16
The difference of the present embodiment and embodiment 15 is only that mill leaching step, in the present embodiment, calcium hydroxide after mill leaching
Partial size (D90) be 4 microns, the partial size (D90) of beta spodumene is 8 microns, the partial size ratio of calcium hydroxide and beta spodumene is 0.5:
1.The leaching rate of final lithium is 90.78%.
Embodiment 17
The difference of the present embodiment and embodiment 15 is only that mill leaching step, in the present embodiment, calcium hydroxide after mill leaching
Partial size (D90) be 10 microns, the partial size (D90) of beta spodumene is 5 microns, the partial size ratio of calcium hydroxide and beta spodumene is 2:1.
The leaching rate of final lithium is 86.85%.
Embodiment 18
The difference of the present embodiment and embodiment 15 is only that mill leaching step, in the present embodiment, calcium hydroxide after mill leaching
Partial size (D90) be 15 microns, the partial size (D90) of beta spodumene is 1.5 microns, the partial size ratio of calcium hydroxide and beta spodumene is
10:1.The leaching rate of final lithium is 77.32%.
Embodiment 19
The difference of the present embodiment and embodiment 15 is only that mill leaching step, in the present embodiment, calcium hydroxide after mill leaching
Partial size (D90) be 1.5 microns, the partial size (D90) of beta spodumene is 15 microns, the partial size ratio of calcium hydroxide and beta spodumene is
0.1:1.The leaching rate of final lithium is 75.04%.
By studying different-grain diameter range and the partial size ratio of calcium hydroxide and beta spodumene, in conjunction with above-described embodiment it is found that working as
When the partial size of calcium hydroxide and beta spodumene ratio is 0.1:1~10:1, ideal lithium leaching rate, especially hydrogen can be reached
When the partial size of calcium oxide and beta spodumene ratio is 0.5:1~2:1, the leaching rate of lithium can be more than 86%, even up to 90% or more.
In the present invention, the main grinding by mill leaching step makes the destructurized of beta spodumene, and then makes beta spodumene
In lithium be released, can spread the surface of beta spodumene, which can mention for lithium with reacting for calcareous materials such as calcium hydroxides
For reacting environment, for reacting lithium with calcareous material.In the process, the particle size range of calcium hydroxide and beta spodumene
And its ratio has great influence for the extent of reaction, lithium leaching rate.When the partial size of calcium hydroxide and beta spodumene than it is excessive when,
Although the partial size of beta spodumene is smaller, more lithium can be made to be diffused into beta spodumene surface, due to calcium hydroxide partial size compared with
Greatly, the reacting environment that will lead to calcium hydroxide and lithium is limited, and then cannot fully cement out lithium.On the contrary, working as hydrogen-oxygen
Change the partial size of calcium and beta spodumene than it is too small when, although the partial size of calcium hydroxide it is smaller, can well reacting environment and lithium into
Row reaction will lead to that the lithium in beta spodumene is more difficult to be adequately diffused into beta spodumene surface but since the partial size of beta spodumene is larger
(such as may have little time to be diffused into beta spodumene surface and participate in react positioned at the lithium of center position), and then cause in beta spodumene
Lithium cannot be sufficiently displaced from, be extracted, influence the leaching rate of lithium.Therefore, the present invention is controlled by largely exploring with after test
The partial size of calcareous material and spodumene processed obtains ideal lithium recovery rate than the range in 0.1:1~10:1.
Three, soaking technology condition is pressed
There is great influence since pressure leaching reaction and reaction mass compare lithium leaching rate, the present invention is to pressure soaking technology
Condition and parameter and reacting material ratio are explored, to obtain ideal process conditions.Specifically: in addition to embodiment one
To 11, the research of lithium extraction is also carried out by the method for comparative example three to five respectively.
Comparative example three: this comparative example three and the difference of embodiment one are only that, during pressure leaching, mill leaching step and pressure leaching step
Suddenly it is 3:1 that the summation for the water being added and the liquid of mixed material, which consolidate mass ratio, and the leaching rate of final lithium is 57.45%.
Comparative example four: this comparative example four and the difference of embodiment one be only that, the quality of material of spodumene and calcium hydroxide
Than being 55% for the leaching rate of 1:0.4, final lithium.
By embodiment one to 11 being compared with comparative example three it is found that the dosage of water is less during pressure leaching
When, it is leached although also having a certain amount of lithium, its leaching rate is relatively relatively low, especially the liquid stereoplasm amount of water and mixed material
When than down to 3:1, the leaching rate of lithium is already less than 60%.Moreover, when the water consumption during pressure leaching is less, can also go out
Existing slurry agglomeration, is unfavorable for the progress of actual production.The present invention after a large number of experiments is tested determine, when pressure leaching during water with
When the liquid of mixed material consolidates mass ratio greater than 3:1, ideal lithium leaching rate, especially water and mixed material can be obtained
Liquid consolidate mass ratio be 4:1~6:1 when, not only can guarantee higher lithium leaching rate but can reduce slurry agglomerate risk.
By the way that embodiment one to seven is compared with comparative example four it is found that the dosage of calcium hydroxide is got in reaction mass
Few, the leaching rate of lithium is lower, and when the mass ratio of spodumene and calcium hydroxide is 1:0.6, the leaching rate of lithium is already less than 60%.
The present invention determines after a large number of experiments is tested, and when the mass ratio of spodumene and calcareous material is 1:0.7~1:3, can obtain
Lithium leaching rate that must be ideal both can guarantee when especially the mass ratio of spodumene and calcareous material is 1:0.85~1:1.2
The problem of higher lithium leaching rate can guarantee that the dosage of calcareous material is reasonable again, be not in material waste.In side of the invention
In method, the dosage of calcareous material is less, and the upper limit of used calcareous material is 3 times of lithium ore quality, and when using preferred
When calcareous material dosage, without 3 times of the quality containing lithium ore, that is, good lithium leaching rate can reach, further demonstrate that this
Method can under the premise of guaranteeing lithium leaching rate, production cost is effectively reduced.This is in the prior art either from spodumene
Or it is all difficult to when extracting lithium from lepidolite, it, must be using than lithium cloud when extracting lithium especially from lepidolite
The calcareous material that mostly several times of female dosage.It, can also be with calcareous material containing more other this is because in addition to lithium in lepidolite
The ingredient of reaction, these consume more calcareous material at branch, therefore not only need when extraction lithium using more from lepidolite
Calcareous material, but also more other compositions can be obtained, be unfavorable for proposing lithium purity, while it is more multiple also to generate a large amount of ingredients
Miscellaneous waste residue is unfavorable for recycling, and then unfriendly to environment.
In addition, in the present invention, water and the liquid of mixed material consolidate mass ratio be greater than greater than the temperature that 3:1, autoclaving are reacted or
When being greater than or equal to 0.2MPa, reaction time more than or equal to 30min equal to 120 DEG C, pressure, comparatively ideal lithium can be obtained and leach
Rate.But it is right by comparing embodiment one to 11 it is found that after above-mentioned liquid consolidates mass ratio and process conditions reach certain parameter
In the raising of lithium leaching rate, there is no further aids.Therefore comprehensively consider lithium leaching rate and process costs, the present invention is preferred
Water and the liquid of mixed material consolidate the temperature that mass ratio is 4:1~12:1, autoclaving is reacted be 135~200 DEG C, pressure be 0.3~
0.6MPa, reaction time are that 40~160min, especially water consolidate that mass ratio is 4:1~6:1, autoclaving is reacted with the liquid of mixed material
Temperature be 135~160 DEG C, pressure is 0.3~0.5MPa, the reaction time is 40~120min best.
The above embodiment of the present invention provides a kind of method that lithium is extracted from spodumene, on the one hand, passes through process
Exploitation --- under the premise of mentioning lithium from spodumene using only calcareous materials such as calcium hydroxides, being cooperated using mill leaching and pressure leaching is made
Process, energy needed for making spodumene is destructurized, reduces it to react, then lithium in spodumene is made by autoclaving reaction
Ion is sufficiently discharged, and then leaches more lithium ion from spodumene.Moreover, the present invention is also to the technique item for mentioning lithium
Part and parameter have conducted extensive research, by the optimization of process conditions and parameter further increase the leaching rate of lithium to 75% with
On in addition the leaching rate of lithium reach 90% or more, leach more lithiums from spodumene, to improve the recovery rate and benefit of lithium
With rate.
On the other hand, the present invention while extracting lithium, return by the resource for more paying attention to tailings caused by entire technical process
Receive utilizability.The present invention i.e. control ingredient for generating tailings from the type of reaction mass, by only with calcium hydroxide or
The calcareous materials such as calcium oxide mention lithium, simpler come the tailings ingredient that guarantees final, without containing the dangerous wastes such as sulfate, chloride ion at
Point, also without containing low ingredients of added values such as sodium salts, tailings ingredient ensure that tailings has based on afwillite, alumina silicate
There is higher use value.In actual industrial production, there are many tailings caused by extraction metal from mineral, substantial amounts
Tailings as can abundant recycling and reusing, not only can solve the processing problem of solid waste itself, avoids solid waste direct emission to environment
Caused by pollution, reduce business processes solid waste cost, and can using tailings replace part building material, reduction building material
Cost.
The method for extracting lithium from spodumene to disclosed by the embodiments of the present invention above is described in detail, and answers herein
With a specific example illustrates the principle and implementation of the invention, the explanation of above example is only intended to help to manage
Solve method and its core concept of the invention；At the same time, for those skilled in the art, according to the thought of the present invention,
There will be changes in specific embodiment and application range, in conclusion the content of the present specification should not be construed as to this hair
Bright limitation.
Claims (18)
1. a kind of method for extracting lithium from spodumene, which comprises the following steps:
Mill leaching: the mixed material of spodumene and calcareous material is leached in grinding, forms slurry；Wherein, the calcareous material
For calcium carbonate, calcium hydroxide, calcium oxide, with calcium carbonate substance as main component, with calcium hydroxide substance as main component
Or with one of calcium oxide substance as main component or a variety of mixtures；
Pressure leaching: the slurry after opposite grinding leaching carries out autoclaving reaction, leaches the lithium ion in the spodumene.
2. the calcareous material is selected from the method according to claim 1, wherein the spodumene is beta spodumene
Calcium hydroxide, calcium oxide, with calcium hydroxide substance as main component or with one of calcium oxide substance as main component
Or several mixture.
3. the method according to claim 1, wherein grinding the mixed material after leaching in mill leaching step
Partial size be less than or equal to 15 microns.
4. according to the method described in claim 3, it is characterized in that, grinding the mixed material after leaching in mill leaching step
Partial size be less than or equal to 7 microns.
5. according to the method described in claim 4, it is characterized in that, grinding the mixed material after leaching in mill leaching step
Partial size be 5 microns.
6. the method according to claim 1, wherein grinding the calcareous material after leaching in mill leaching step
Partial size ratio with the spodumene is 0.1:1~10:1, and the partial size of the calcareous material is less than or equal to 15 microns, the lithium
The partial size of pyroxene is less than or equal to 15 microns.
7. according to the method described in claim 6, it is characterized in that, the mill leaching step in, the calcareous material with it is described
The partial size ratio of spodumene is 0.5:1~2:1, and the partial size of the calcareous material is 2~15 microns, and the partial size of the spodumene is 2
~15 microns.
8. method according to any one of claims 1 to 3, which is characterized in that in mill leaching step, the spodumene
Mass ratio with the calcareous material is 1:0.5~1:3.
9. according to the method described in claim 8, it is characterized in that, the mass ratio of the spodumene and the calcareous material is 1:
0.85~1:1.2.
10. method according to any one of claims 1 to 3, which is characterized in that the mill soaks step are as follows: to the mixing
Water is added in material and forms the slurry, and the mixed material solid content in the slurry is 10~50%, is leached in grinding,
Abrasive media uses the zirconia ball of 0.1~4mm.
11. method according to any one of claims 1 to 3, which is characterized in that the pressure soaks step are as follows: to after mill leaching
The liquid of addition water progress autoclaving reaction in the slurry, water and the mixed material consolidates mass ratio greater than 3:1, the temperature of autoclaving reaction
Degree is greater than or equal to 120 DEG C, and pressure is greater than or equal to 0.2MPa, and the reaction time is more than or equal to 30min.
12. according to the method for claim 11, which is characterized in that in pressure leaching step, water and the mixed material
Liquid consolidate mass ratio be 4:1~12:1, autoclaving reaction temperature be 135~200 DEG C, pressure be 0.3~0.6MPa, the reaction time
For 40~160min.
13. according to the method for claim 12, which is characterized in that the leaching rate of lithium is more than or equal to 75%.
14. according to the method for claim 13, which is characterized in that the leaching rate of lithium is more than or equal to 90%.
15. according to the method for claim 14, which is characterized in that the leaching rate of lithium is more than or equal to 97%.
16. the method according to claim 1, wherein the method also includes in the laggard of pressure leaching step
Row filtering, respectively obtains the filtrate containing lithium ion and filter residue.
17. according to the method for claim 16, which is characterized in that the method also includes: to described containing lithium ion
Filtrate cleaned, sinker, obtains lithium salts product.
18. according to the method for claim 16, which is characterized in that the method also includes: it washs the filter residue and obtains tail
Slag, the tailings include afwillite and alumina silicate, and the tailings is used as the production of construction material.
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