CN109518008A - A method of extracting lithium from containing lithium minerals - Google Patents

A method of extracting lithium from containing lithium minerals Download PDF

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Publication number
CN109518008A
CN109518008A CN201910037326.4A CN201910037326A CN109518008A CN 109518008 A CN109518008 A CN 109518008A CN 201910037326 A CN201910037326 A CN 201910037326A CN 109518008 A CN109518008 A CN 109518008A
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China
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lithium
leaching
partial size
mill
minerals
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王国华
吴关
苏硕剑
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Ningde Sanyuan Technology Co Ltd
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Ningde Sanyuan Technology Co Ltd
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Priority to CN201910037326.4A priority Critical patent/CN109518008A/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10Obtaining alkali metals
    • C22B26/12Obtaining lithium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/12Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The present invention relates to ores to mention lithium technology field more particularly to a kind of method that lithium is extracted from containing lithium minerals.Method includes the following steps: mill leaching, the mixed material containing lithium minerals and calcareous material is leached in grinding, forms slurry;Wherein, the calcareous material and the partial size ratio containing lithium minerals are 0.1:1~10:1, the partial size of the calcareous material is less than or equal to 15 microns, the partial size containing lithium minerals be less than or equal to 15 microns, 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 containing in lithium minerals.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

A method of extracting lithium from containing lithium minerals
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 containing lithium minerals.
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 mineral 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 mineral, which mention lithium, more broad application prospect.
Mainly include spodumene, amblygonite, lepidolite, zinnwaldite, petalite etc. containing lithium minerals, 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.
In conclusion existing mention that although lithium technique route is more, and generally existing energy consumption is high, technique is multiple containing lithium minerals 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 containing lithium minerals, it is existing from containing lithium minerals to solve 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 middle method for extracting lithium.
The present invention provides a kind of method that lithium is extracted from containing lithium minerals, comprising the following steps:
Mill leaching: the mixed material containing lithium minerals and calcareous material is leached in grinding, forms slurry;Wherein, described to contain Calcium substance and the partial size ratio containing lithium minerals are 0.1:1~10:1, and it is micro- that the partial size of the calcareous material is less than or equal to 15 Rice, the partial size containing lithium minerals be less than or equal to 15 microns, 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 calcium oxide substance as main component One of or a variety of mixtures;
Pressure leaching: the slurry after opposite grinding leaching carries out autoclaving reaction, leaches the lithium ion containing in lithium minerals.
It is understood that it includes the grain that the calcareous material and the partial size ratio containing lithium minerals, which are 0.1:1~10:1, Diameter is than any point value in range, such as the calcareous material and the partial size ratio containing lithium minerals are 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 be less than or It include any point value in the particle size range equal to 15 microns, such as the partial size of the calcareous material is 1 micron, 2 microns, 3.5 Micron, 4 microns, 5 microns, 8 microns, 10 microns, 12 microns or 15 microns, the partial size containing lithium minerals are less than or equal to 15 Micron includes any point value in the particle size range, such as the partial size containing lithium minerals is 1 micron, 2 microns, 3.5 microns, 4 Micron, 5 microns, 8 microns, 10 microns, 12 microns or 15 microns.
Optionally, the lithium minerals that contains is beta spodumene, and the calcareous material is selected from calcium hydroxide, calcium oxide, with hydroxide Calcium substance as main component or with the mixture of one or more of calcium oxide substance as main component.
Preferably, in mill leaching step, the calcareous material is with the partial size ratio containing lithium minerals after mill leaching 0.5:1~2:1, the partial size of the calcareous material are 2~15 microns, and the partial size containing lithium minerals is 2~15 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.
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 (such as spodumene) containing lithium minerals is handled, can be achieved with the extraction to lithium, therefore this method can guarantee to mention the remaining tailings after lithium In only containing the elements such as calcium, aluminium, silicon, without containing sodium ion, sulfate radical, chloride ion etc., so that remaining tailings greatly improved Utility value avoids the problem of tailings is dangerous waste, such as can be used for the production (such as quick hardening cement building materials) of high-quality building materials, Thus fixed-end forces are solved the problems, such as, realize that the resource utilization of solid waste utilizes.Therefore, see that this method is more green on the whole It is environmentally friendly, environmentally friendly.
Secondly, this method by way of leaching (mainly grinding) in grinding to spodumene at calcareous material Reason, calcareous material and partial size ratio 0.1:1~10:1 containing lithium minerals, the partial size of calcareous material are less than or equal to after soaking mill 15 microns, the partial size containing lithium minerals is less than or equal to 15 microns, so that the lithium brightness that cannot sufficiently react with calcareous material originally The structure and properties of stone change a lot, and spodumene is destructurized, reacts required energy reduces, then again after opposite grinding leaching Mixed material carries out autoclaving, so that spodumene is sufficiently reacted with calcareous material, lithium ion is released, to realize higher Lithium leaching rate, well solved the problem that lithium leaching rate is very low when reacting only with calcareous material 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 containing lithium minerals.
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 containing lithium minerals, 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 containing lithium minerals, 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 containing lithium minerals, 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 containing lithium minerals, 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 containing lithium minerals, 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 containing lithium minerals, 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 containing lithium minerals, 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 Degree is bigger, therefore the partial size of the calcareous materials such as preferably calcium hydroxide is 2~15 microns in the present invention, and the partial size containing lithium minerals 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 containing lithium minerals, 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 Calcareous material processed and the partial size containing lithium minerals obtain 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 minerals, 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 containing lithium minerals, on the one hand, passes through process Exploitation --- under the premise of the calcareous materials such as calcium hydroxide are used only mentioning lithium from spodumene, using mill leaching and pressure leaching cooperation The process used, energy needed for making spodumene is destructurized, reduces it to react, then made in spodumene by autoclaving reaction Lithium ion is sufficiently discharged, and then leaches more lithium ion from spodumene.Moreover, the present invention is also to the technique for mentioning lithium Condition 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 containing lithium minerals to disclosed by the embodiments of the present invention above is described in detail, herein Apply that a specific example illustrates the principle and implementation of the invention, the explanation of above example is only intended to help Understand 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 the specific implementation manner and application range, in conclusion the content of the present specification should not be construed as to this The limitation of invention.

Claims (16)

1. a kind of method for extracting lithium from containing lithium minerals, which comprises the following steps:
Mill leaching: the mixed material containing lithium minerals and calcareous material is leached in grinding, forms slurry;Wherein, the calcic object Matter and the partial size ratio containing lithium minerals are 0.1:1~10:1, and the partial size of the calcareous material is less than or equal to 15 microns, institute The partial size containing lithium minerals is stated less than or equal to 15 microns, the calcareous material be calcium carbonate, calcium hydroxide, calcium oxide, with carbon Sour calcium substance as main component, with calcium hydroxide substance as main component or in calcium oxide substance as main component One or more mixtures;
Pressure leaching: the slurry after opposite grinding leaching carries out autoclaving reaction, leaches the lithium ion containing in lithium minerals.
2. the calcareous material selects the method according to claim 1, wherein the lithium minerals that contains is beta spodumene From calcium hydroxide, calcium oxide, with calcium hydroxide substance as main component or with one in calcium oxide substance as main component Kind or several mixtures.
3. the method according to claim 1, wherein grinding the calcareous material after leaching in mill leaching step It is 0.5:1~2:1 with the partial size ratio containing lithium minerals, the partial size of the calcareous material is 2~15 microns, described to contain lithium minerals Partial size be 2~15 microns.
4. 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 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. method according to any one of claims 1 to 3, which is characterized in that in mill leaching step, the mine containing lithium The mass ratio of object and the calcareous material is 1:0.5~1:3.
7. according to the method described in claim 6, it is characterized in that, the mass ratio containing lithium minerals and the calcareous material is 1:0.85~1:1.2.
8. method according to any one of claims 1 to 3, which is characterized in that the mill soaks step are as follows: Xiang Suoshu mixture Water is added in material and forms the slurry, and the mixed material solid content in the slurry is 10~50%, leaches, grinds in grinding Grinding media uses the zirconia ball of 0.1~4mm.
9. method according to any one of claims 1 to 3, which is characterized in that the pressure soaks step are as follows: the institute to after mill leaching It states and water progress autoclaving reaction is added in slurry, the liquid of water and the mixed material consolidates mass ratio greater than 3:1, the temperature of autoclaving reaction More than or equal to 120 DEG C, pressure is greater than or equal to 0.2MPa, and the reaction time is more than or equal to 30min.
10. according to the method described in claim 9, it is characterized in that, being soaked in step in the pressure, water and the mixed material It is 4:1~12:1 that liquid, which consolidates mass ratio, and the temperature of autoclaving reaction is 135~200 DEG C, and pressure is 0.3~0.6MPa, and the reaction time is 40~160min.
11. according to the method described in claim 10, it is characterized in that, the leaching rate of lithium is more than or equal to 75%.
12. according to the method for claim 11, which is characterized in that the leaching rate of lithium is more than or equal to 90%.
13. according to the method for claim 12, which is characterized in that the leaching rate of lithium is more than or equal to 97%.
14. 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.
15. according to the method for claim 14, which is characterized in that the method also includes: to described containing lithium ion Filtrate cleaned, sinker, obtains lithium salts product.
16. according to the method for claim 14, 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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