CN106365181A - Method of preparing battery-grade lithium carbonate from lithium-rich solution being high in content of impurities - Google Patents
Method of preparing battery-grade lithium carbonate from lithium-rich solution being high in content of impurities Download PDFInfo
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- CN106365181A CN106365181A CN201610729924.4A CN201610729924A CN106365181A CN 106365181 A CN106365181 A CN 106365181A CN 201610729924 A CN201610729924 A CN 201610729924A CN 106365181 A CN106365181 A CN 106365181A
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Abstract
The invention discloses a method of preparing battery-grade lithium carbonate from a lithium-rich solution being high in content of impurities. The method includes the steps of: a) pumping the lithium-rich solution into a reaction kettle and increasing the temperature to 60-80 DEG C, adding a first impurity remover and performing a temperature-maintained stirring reaction, regulating the pH to 11-12, and continuously performing the temperature-maintained stirring reaction and filtering the reaction product to obtain a refined lithium-rich solution; b) adding deionized water to the reaction kettle, and adding sodium carbonate with stirring clarification to obtain a sodium carbonate solution, adding a second impurity remover and sodium hydroxide to carry out a stirring reaction, and filtering the solution to prepare a refined sodium carbonate solution; c) performing a reaction to the refined lithium-rich solution and the refined sodium carbonate solution to obtain lithium carbonate slurry; d) performing solid-liquid separation to the lithium carbonate slurry to obtain lithium carbonate wet solid and a lithium precipitation mother liquid; e) leaching the lithium carbonate wet solid by deionized water, placing the solid into a washing trough, adding deionized water to perform re-slurrying washing, and performing solid-liquid separation to obtain a lithium carbonate wet material; and f) drying the lithium carbonate wet material to prepare the battery-grade lithium carbonate.
Description
Technical field
The present invention relates to the technical field of lithium carbonate preparation, more particularly, it is related to a kind of utilization containing higher impurity richness lithium
The method that solution prepares battery-level lithium carbonate.
Background technology
With the fast development of global new-energy automobile industry, drive the critical materialses battery-level lithium carbonate of electrokinetic cell
The market demand.
At present, battery-level lithium carbonate produces that Ore carries lithium and salt lake carries two kinds of routes of lithium, and Ore puies forward lithium technology through number
Year development is more ripe, and the raw material handled by this technique mostly is spodumene concentrate, and raw material chemical composition is stable, except silicon, aluminum etc.
Outside major impurity, other impurity contents are relatively low, and lithium carbonate technical process is easily controllable, stable and reliable product quality, and China is at present
Most of battery-level lithium carbonate is both from this process route.And salt lake has, and lithium resource reserves are big, carry the excellent of lithium low cost
Gesture, in global lithium carbonate, 80% carries lithium from salt lake, but because salt lake complicated component, impurity content are high and most of salt lake is equal
It is in High aititude extremely frigid zones, sunshine, temperature conditionss are unstable, lead to salt lake to put forward lithium process wayward, thus its lithium carbonate
The Yield and quality fluctuation of product is larger.
Up to the present, salt lake bittern carry the lithium carbonate product that lithium technology is directly produced be only capable of reaching technical grade (magnesium, sodium,
Chlorinity is not up to standard), producing battery-level lithium carbonate also needs further deep processing purification, takes the modes such as carbonization, acidifying, hydrogenation
It is processed further just obtaining battery-level lithium carbonate, lead to the cost of salt lake battery-level lithium carbonate and quality-advantage inconspicuous.
The method having been disclosed in existing technology much preparing battery lithium carbonate using salt lake bittern, these methods
Dominating process route includes salt remove impurity-carbonate deposition and goes out industrial level lithium carbonate, then with carbon dioxide, lithium carbonate is changed into carbon
Sour hydrogen lithium, filtration, resin remove impurity, obtain prepared calcium carbonate hydrogen lithium solution, heating lithia water splits the carbon dioxide off, and sinks
Form sediment lithium carbonate, obtains battery-level lithium carbonate product after solid-liquid separation, washing, drying.But, the technological process of this technology
Long, middle wastewater treatment capacity is big, pressure, reaction temperature, ph value, concentration control etc. is required strict, reaction fouling is severe, no
Beneficial to large-scale production.Although mentioning a lot of modes in patent cn103958412a can extract carbonic acid from salt containing lithium
Lithium, but do not exist standby high from the dense lithium making from brine containing significant quantity such as boron, magnesium, calcium, sodium, potassium, chloride and sulfate etc.
The Simplified flowsheet of purity (LITHIUM BATTERY) lithium carbonate.
Content of the invention
Cannot be directly produced battery-level lithium carbonate and need further purification processing to lead to solve existing salt lake and putting forward lithium technique
Cause the problem that production cost is high, operating procedure is complicated, it is an object of the invention to provide a kind of directly utilize containing higher impurity richness lithium
The method that solution prepares battery-level lithium carbonate.
The invention discloses a kind of method using preparing battery-level lithium carbonate containing higher impurity richness lithium solution, methods described
Comprise the following steps:
A, rich lithium solution refine: higher impurity richness lithium solution will be contained and pump in reactor and be warming up to 60～80 DEG C, Xiang Fu
Add the first cleaner in lithium solution and insulated and stirred reacts 0.5～1h, maintain 60～80 DEG C of temperature and add sodium hydroxide
Or its aqueous solution adjustment ph value, to 11～12, continues insulated and stirred and reacts 0.5～2h, it is filtrated to get refined richness lithium solution；
B, sodium carbonate liquor refine: to deionized water put into sodium carbonate solid stirring, dissolving preparation obtain concentration be 200～
The sodium carbonate liquor of 300g/l, adds the second cleaner and sodium hydroxide stirring reaction 15～30min, is filtrated to get refined
Sodium carbonate liquor；
C, sinker: described refined richness lithium solution is reacted with prepared calcium carbonate sodium solution and obtains lithium carbonate slurry, wherein, control
Reaction temperature is 70～95 DEG C and the response time is 1～3h, sinker mother solution in described lithium carbonate slurry when controlling reaction end
Carbon acid ion concentration is 13～18g/l；
D, solid-liquid separation: described lithium carbonate slurry is incubated after 0.5～1h and carries out solid-liquid separation, obtain lithium carbonate containing wet
Solid and sinker mother solution；
E, washing: described lithium carbonate is contained input sink, consolidating according to 1:3～5 after wet solid drip washing by deionized water
Liquor ratio adds 60～90 DEG C of deionized water to carry out plasm scouring again, obtains lithium carbonate wet feed after solid-liquid separation, and wash water can after collecting
Prepare for sodium carbonate liquor；
F, drying: described lithium carbonate wet feed is dried under conditions of 250～450 DEG C, obtains battery-level lithium carbonate.
Prepare an embodiment of the method for battery-level lithium carbonate, institute according to the present invention using the rich lithium solution containing higher impurity
Method of stating also includes the step carrying out except magnetic by described battery-level lithium carbonate, pulverizing and be packaged to be battery-level lithium carbonate product,
Wherein, grinding particle size, conventional grinding particle size d can be controlled according to customer demand50: 3～8 μm, d90: 9～15 μm.
Prepare an embodiment of the method for battery-level lithium carbonate, institute according to the present invention using the rich lithium solution containing higher impurity
Stating containing higher impurity richness lithium solution to be chloride type or sulfate type salt lake brine is most of through tedding evaporation and concentration precipitation
Sodium, potassium, magnesium and except the rich lithium salts lake bittern water obtaining after boron, the carbonic acid lithium concentrate hydrochloric acid alternatively being produced by carbonate type salt lake or
Rich lithium solution that the molten rear impurity removal and purification of sulphuric acid obtains or be refining to obtain after molten using high impurity crude product lithium carbonate hydrochloric acid or sulphuric acid
Rich lithium solution, contains li in the described richness lithium solution containing higher impurity+: 7～50g/l, na+≤100g/l、so4 -2≤200g/l、cl-
≤300g/l、k+≤20g/l、mg2+≤5g/l、ca2+≤ 10g/l and b :≤5g/l.
Prepare an embodiment of the method for battery-level lithium carbonate, institute according to the present invention using the rich lithium solution containing higher impurity
Stating the first cleaner is one or more of sodium carbonate, lithium carbonate, Disodium oxalate., potassium oxalate, lithium oxalate and oxalic acid, preferably carbon
The mass ratio of sour sodium and oxalic acid is the mixture of 1:1.
Prepare an embodiment of the method for battery-level lithium carbonate, institute according to the present invention using the rich lithium solution containing higher impurity
Stating the second cleaner is one or more of Disodium oxalate., potassium oxalate, lithium oxalate and oxalic acid.
Prepare an embodiment of the method for battery-level lithium carbonate according to the present invention using the rich lithium solution containing higher impurity,
In step a, the addition of described first cleaner is 3～5 times of calcareous amount in described richness lithium solution, and it is molten that gained refines richness lithium
Calcium ＜ 20ppm in liquid and magnesium≤1ppm；In stepb, in described sodium carbonate liquor purification step the second cleaner addition
Measure 0.5～1% for sodium carbonate addition, the addition of described sodium hydroxide is the 2～5% of sodium carbonate addition, gained essence
Calcium ＜ 20ppm in sodium carbonate liquor processed and magnesium≤1ppm.
Prepare an embodiment of the method for battery-level lithium carbonate according to the present invention using the rich lithium solution containing higher impurity,
In step a, described filtration includes coarse filtration and the fine straining carrying out successively, wherein；In step f, by lithium carbonate wet feed in swinging
It is dried in drying oven, infra-red furnace, continuous tunnel furnace, meshbeltfurnace or chain type resistance furnace.
Prepare an embodiment of the method for battery-level lithium carbonate according to the present invention using the rich lithium solution containing higher impurity, in step
In rapid c, when the lithium content in refined richness lithium solution is less than 35g/l, compound additive is added in sodium carbonate refined soln and stirs
Uniformly, carry out sinker with described refined richness lithium solution to react up to reaction end；When refined richness lithium solution in lithium content be 35～
During 50g/l, compound additive is added to stir toward in pure water or sinker mother solution, described refined richness lithium solution is molten with prepared calcium carbonate sodium
The common addition of liquid carries out reaction up to reaction end；Wherein, the addition of described compound additive is the 1～3% of sodium carbonate quality.
Prepare an embodiment of the method for battery-level lithium carbonate, institute according to the present invention using the rich lithium solution containing higher impurity
State compound additive by EDDA, lithium carbonate, gluconic acid, citric acid, sodium lauryl sulphate, polyvinyl alcohol and to gather
One or more of acrylamide forms, and wherein, the molecular weight of described polyvinyl alcohol is preferably 16000～20000, polypropylene
Amide is preferably anionic or nonionic and molecular weight is 5000000～12000000.
Prepare an embodiment of the method for battery-level lithium carbonate, institute according to the present invention using the rich lithium solution containing higher impurity
State the requirement that battery-level lithium carbonate meets battery-level lithium carbonate industry standard yst582-2013, wherein, li2co3>=99.5%, na
≤ 0.025%, k≤0.001%, mg≤0.008%, ca≤0.005%, fe≤0.001%, zn≤0.0003%, cu≤
0.0003%th, pb≤0.0003%, si≤0.003%, al≤0.001%, mn≤0.0003, ni≤0.001%, so4 2-≤
0.08%th, cl-≤ 0.003%.
Compared with prior art, the utilization of the present invention contains the method work that higher impurity richness lithium solution prepares battery-level lithium carbonate
Skill is simple, is not required to introduce extra lithium carbonate purification procedures and is directly synthesized battery-level lithium carbonate, has low production cost, product matter
Measure stable feature, there is good economic and social benefit.
Brief description
Fig. 1 shows according to an exemplary embodiment of the present invention utilization containing higher impurity richness lithium solution preparation LITHIUM BATTERY carbonic acid
The flow chart of the method for lithium.
Specific embodiment
All features disclosed in this specification, or disclosed all methods or during step, except mutually exclusive
Feature and/or step beyond, all can combine by any way.
Any feature disclosed in this specification, unless specifically stated otherwise, all can be equivalent or there is replacing of similar purpose by other
Replaced for feature.I.e., unless specifically stated otherwise, each feature is a series of equivalent or one of similar characteristics example.
Below the present invention is described in detail using the method preparing battery-level lithium carbonate containing higher impurity richness lithium solution.
Fig. 1 shows according to an exemplary embodiment of the present invention utilization containing higher impurity richness lithium solution preparation LITHIUM BATTERY carbonic acid
The flow chart of the method for lithium.As shown in figure 1, according to the exemplary embodiment of the present invention, described molten using the rich lithium containing higher impurity
The method that liquid prepares battery-level lithium carbonate includes following multiple step.
Step a: rich lithium solution refines
Higher impurity richness lithium solution will be contained pump in reactor and be warming up to 60～80 DEG C, add first in rich lithium solution
Cleaner insulated and stirred reaction 0.5～1h, maintain 60～80 DEG C of temperature simultaneously to add sodium hydroxide or its aqueous solution adjustment ph
It is worth to 11～12, continues insulated and stirred and react 0.5～2h, be filtrated to get refined richness lithium solution.Wherein, aforesaid reaction vessel is preferably
Enamel reaction still.
According to the present invention, the richness lithium solution containing higher impurity used by the present invention is preferably the salt of chloride type or sulfate type
Lake bittern water.Salt lake is a kind of salinization water body, typically refers to lake water salinity w (nacleq) > 3.5% (more than the average salinity of sea water)
Lake, also include surface salt dry up, by the playa (subsurface brine lake) forming containing mineralization and intercrystalline bittern.Salt lake halogen
Contain substantial amounts of saline mineralss in water, can be used for extracting multiple important source material.The type of lake containing lithium salts is divided into carbonate-type, chlorine at present
Compound type and sulfate type, wherein carbonate-type, lithium with lithium carbonate solid form exist exploitation directly obtain be lithium carbonate essence
Ore deposit, such as Tibet, China Salt Lake Zabuye；And in world wide most salt lake be chloride or sulfate type salt lake, lithium with
Presented in lithium chloride or lithium sulfate in salt, this two kinds of salt lake bittern is through tedding evaporation, concentration, extraction etc.
The rich lithium salts lake bittern water obtaining after the potassium of operation separating most, sodium, magnesium, boron can directly adopt the technique preparation of the invention described above
Battery-level lithium carbonate.
I.e. of the present invention can be chloride type or sulfate type salt lake brine process containing higher impurity richness lithium solution
Ted the rich lithium salts lake bittern water that evaporation and concentration separates out most of sodium, potassium, magnesium and obtains after removing boron.More specifically, described containing higher
Li is contained in impurity richness lithium solution+: 7～50g/l, na+≤100g/l、so4 -2≤200g/l、cl-≤300g/l、k+≤20g/l、
mg2+≤5g/l、ca2+≤ 10g/l and b :≤5g/l.
In this step, the addition of the first cleaner, primarily to making calcium ion form calcium precipitation, and adds hydrogen-oxygen
Change sodium or its aqueous solution adjusts ph value to 11～12 primarily to making magnesium ion form magnesium hydrate precipitate；Wherein, remove impurity
Order is first deliming, rear demagging, and mainly the oxalate precipitation of calcium begins to produce in ph 4～5, and calcium precipitation is in demagging
During as nucleus, growing up of magnesium hydrate precipitate granule can be accelerated, be conducive to filtration separation, and be removed by filtration
Calcium, magnesium obtain refined richness lithium solution.Wherein, carry out this step under 60～80 DEG C of temperature conditionss and be to provide for magnesium hydroxide
The required condition of growth so that magnesium hydroxide particle is grown up further, it is to avoid form colloid and lead to filterability poor.
Before carrying out this step, rich lithium solution can be sampled analyzing to understand its chemical composition, and then realize
Accurately feed.
According to the present invention, the first cleaner of above-mentioned richness lithium solution refining step can be sodium carbonate, lithium carbonate, oxalic acid
The mass ratio of one or more of sodium, potassium oxalate, lithium oxalate and oxalic acid, preferably sodium carbonate and oxalic acid is the mixture of 1:1.
Specifically, the addition that rich lithium solution refines calcium remover is 3～5 times of calcareous amount in solution, and gained refines richness lithium solution
In calcium ＜ 20ppm and magnesium≤1ppm.
And, filtering in this step coarse filtration and fine straining that inclusion is carried out successively.
It is true that the richness lithium solution containing higher impurity used in the present invention can also be the carbon being produced by carbonate type salt lake
Rich lithium solution that sour lithium concentrate hydrochloric acid or the molten rear impurity removal and purification of sulphuric acid obtain or adopt high impurity crude product lithium carbonate hydrochloric acid or sulphuric acid
The rich lithium solution being refining to obtain after molten, and it is not limited to the refined richness lithium solution being obtained in above-mentioned steps.Using the acid of crude product lithium carbonate
Molten prepared lithium-containing solution quality index is substantially in the above-mentioned indication range containing higher impurity richness lithium solution.
Step b: sodium carbonate liquor refines
Add in reactor deionized water and add sodium carbonate to stir molten clear preparation to obtain concentration be 200～300g/l's
Sodium carbonate liquor, adds the second cleaner and sodium hydroxide stirring reaction 15～30min, is filtrated to get prepared calcium carbonate sodium molten
Liquid.Wherein, reactor can be the conventional reactors such as rustless steel lye dissolving tank.
The present invention adopts sodium carbonate liquor as one of primary raw material of the present invention.But, because technical grade sodium carbonate is
Large basic chemical industry product, wherein contains some water-insolubles and part sodium bicarbonate, the impurity content such as calcium, magnesium is higher simultaneously.For
Avoid the wherein harmful effect to product for the impurity, the present invention also refined to sodium carbonate.Specifically, sodium carbonate liquor
Being added to of two cleaners makes calcium ion form calcium precipitation, and the addition of sodium hydroxide is partly in order to neutralization carbonic acid
Hydrogen sodium forms sodium carbonate, is on the other hand to react the insoluble magnesium hydroxide of generation with magnesium ion, and then can pass through
Filter mechanical admixture, calcium salt and magnesium hydroxide and obtain pure sodium carbonate liquor.Thus, refined purpose is carried out to sodium carbonate
It is the quality improving carbonic acid sodium utilization and product.
Similarly, above-mentioned second cleaner is one or more of Disodium oxalate., potassium oxalate, lithium oxalate and oxalic acid, preferably
For Disodium oxalate..Specifically, the addition that sodium carbonate liquor refines calcium remover is the 0.5～1% of sodium carbonate addition, sodium hydroxide
Addition be the 2～5% of sodium carbonate addition, and the calcium ＜ 20ppm in gained prepared calcium carbonate sodium solution and magnesium≤1ppm.
Step c: sinker
The prepared calcium carbonate sodium solution that the refined richness lithium solution that step a is obtained is obtained with step b reacts and obtains lithium carbonate slurry
Material, wherein, controlling reaction temperature is 70～95 DEG C and the response time is 1～3h, heavy in lithium carbonate slurry when controlling reaction end
The carbon acid ion concentration of lithium mother solution is 13～18g/l.
In this step, when the lithium content in refined richness lithium solution is less than 35g/l, compound additive is added sodium carbonate
Stir in refined soln, carry out sinker with described refined richness lithium solution and react up to reaction end；When refined richness lithium solution
In lithium content be 35～50g/l when, toward pure water or sinker mother solution in addition compound additive stir, by described refined richness
Common addition carries out reaction up to reaction end to lithium solution with prepared calcium carbonate sodium solution.Wherein, the addition of compound additive is
The 1～3% of sodium carbonate quality.
Specifically, the present invention be by aforesaid operations step to response parameter control so that control sinker reaction supersaturation
Degree, maintain stable reaction environment, avoid explosive nucleation, lead to produce excessive fine particle, simultaneously compound additive
Introduce and lithium carbonate growth course is regulated and controled, the intergranular impurity thus bringing is carried secretly and particle surface impurity absorption is few, leads to afterwards again
Cross centrifugation, washing etc. and process and obtain the higher lithium carbonate product of purity.
According to the exemplary embodiment of the present invention, above-mentioned compound additive is by EDDA, lithium carbonate, glucose
One or more of acid, citric acid, sodium lauryl sulphate, polyvinyl alcohol and polyacrylamide form, wherein, described poly- second
The molecular weight of enol is preferably 16000～20000, and polyacrylamide is preferably anionic or nonionic and molecular weight is
5000000～12000000.
Step d: solid-liquid separation
By step e be obtained lithium carbonate slurry be incubated 0.5～1h after carry out solid-liquid separation, obtain lithium carbonate contain wet solid and
Sinker mother solution.
Wherein, solid-liquid separation can adopt the conventional separation means such as centrifugation.And the process being incubated is conducive to lithium carbonate
Reaction is more thorough.
The lithium carbonate obtaining can get battery-level lithium carbonate containing wet solid through multiple post-processing steps；The sinker obtaining
Mother solution can serve as above-mentioned sinker step bottom liquid it is also possible to after concentrating solid-liquid separation obtain side product chlorinated sodium, but the present invention
Not limited to this.
Step e: washing
The lithium carbonate that step d is obtained is contained input sink, consolidating according to 1:3～5 after wet solid drip washing by deionized water
Liquor ratio adds 60～90 DEG C of deionized water to carry out plasm scouring again, obtains lithium carbonate wet feed.
In this step, drip washing and washing are mainly the sinker mother solution removing the absorption of lithium carbonate particle surface and solubility
na+、so4 -2、cl-、k+、b、co3 -2Deng.
Step f: dry
The lithium carbonate wet feed that step e is obtained is dried under conditions of 250～450 DEG C, obtains battery-level lithium carbonate.Dry
Time may be controlled to 1～2h, but the invention is not restricted to this.
In this step, can be by lithium carbonate wet feed in swinging drying oven, infra-red furnace, continuous tunnel furnace, meshbeltfurnace or chain type
It is dried in resistance furnace, be dried preferably by swinging drying oven or infra-red furnace.
Additionally, the battery-level lithium carbonate that the method for the present invention can also include step f is obtained is carried out except magnetic, pulverizing and bag
Fill the step obtaining battery-level lithium carbonate product, wherein, grinding particle size, conventional control grinding particle size d can be controlled according to demand50: 3
～8 μm, d90: 9～15 μm..
The LITHIUM BATTERY carbon that the method for battery-level lithium carbonate is obtained is prepared using containing higher impurity richness lithium solution using the present invention
Sour lithium can reach the requirement of battery-level lithium carbonate industry standard yst582-2013.Specifically, li therein2co3≥
99.5%th, na≤0.025%, k≤0.001%, mg≤0.008%, ca≤0.005%, fe≤0.001%, zn≤
0.0003%th, cu≤0.0003%, pb≤0.0003%, si≤0.003%, al≤0.001%, mn≤0.0003, ni≤
0.001%th, so4 2-≤ 0.08%, cl-≤ 0.003%.
It should be understood that the above-mentioned embodiment of present invention detailed description and following examples are merely to illustrate the present invention rather than limit
The scope of the present invention processed, those skilled in the art made according to the above of the present invention some nonessential improve and adjust
Whole belong to protection scope of the present invention.In following embodiments, specific parameter etc. is also only one of OK range example,
I.e. those skilled in the art can be done in suitable scope by the explanation of this paper and select, and do not really want to be defined in Examples below
In concrete numerical value and concrete steps.
In order that the purpose of the present invention, technical scheme and effect are more specific clear, below by the preferred reality to the present invention
Apply example to be described in detail.
Embodiment 1:
The richness lithium solution containing higher impurity that the present embodiment uses is chloride type richness lithium salts lake bittern water, its main component and containing
Amount is as shown in table 1.
Table 1 salt lake bittern main constituent and content (unit: g/l)
| li+ | na+ | k+ | ca2+ | mg2+ | so4 2- | b | cl- |
| 8.80 | 98.00 | 0.87 | 0.06 | 1.20 | 1.00 | 1.00 | 222 |
Pump into 2.0m in enamel reaction still3Above-mentioned richness lithium salts lake bittern water is simultaneously warming up to 60 DEG C, toward in rich lithium salts lake bittern water
The mass ratio of addition sodium carbonate and oxalic acid is the first cleaner 0.6kg of 1:1, and insulated and stirred reacts 0.5h；Maintain 60 DEG C of temperature
Spend and add the sodium hydrate aqueous solution that concentration is 80g/l, slowly ph value is adjusted and mix up follow-up continuous insulation reaction to 11, ph value
1.5h, the solution of remove impurity is squeezed into sheet frame and carries out coarse filtration, gained filtrate fine straining again with pump, obtains refined richness lithium solution.Wherein, should
Lithium content in refined richness lithium solution is 8.6g/l, calcium 15ppm, magnesium 1ppm.
0.4m is added in rustless steel lye dissolving tank3Deionized water simultaneously puts into the sodium carbonate of 140kg, and stirring is molten to be added clearly afterwards
Second cleaner of 1kg and the sodium hydroxide of 4.2kg, squeeze into filter with pump after reaction 20min and are filtered, obtain refining carbon
Acid sodium solution.The concentration of sodium carbonate of wherein prepared calcium carbonate sodium solution is 300g/l, calcium 10ppm, magnesium 1ppm.
Above-mentioned prepared calcium carbonate sodium solution pump is squeezed in sinker reactor and is warming up to 70 DEG C, add lithium carbonate, Fructus Vitis viniferae
Saccharic acid configuration forms compound additive 3kg, after stirring, adds above-mentioned refined richness lithium solution to carry out sinker reaction, sinker reacts
Time 1.5h, the carbon acid ion concentration recording sinker mother solution in lithium carbonate slurry is 14.3g/l, and insulation continues reaction 0.5h.
Completely reacted slurry is centrifuged, gained lithium carbonate is contained wet solid and puts into sink and according to 1:4's
Solid-to-liquid ratio adds 70 DEG C of deionized water to carry out plasm scouring again, obtain lithium carbonate wet feed after centrifugation, and lithium carbonate wet feed is sent into
Infrared dryer is simultaneously dried 1 hour under 300 DEG C of temperature conditionss, then obtains battery-level lithium carbonate after except magnetic, pulverizing, packaging
Product, the composition of products obtained therefrom is referring to table 6.
Embodiment 2:
The richness lithium solution containing higher impurity that the present embodiment uses is chloride type richness lithium salts lake bittern water, its main component and containing
Amount is as shown in table 2.
Table 2 salt lake bittern main constituent and content (unit: g/l)
| li+ | na+ | k+ | ca2+ | mg2+ | so4 2- | b | cl- |
| 13.7 | 110 | 6.4 | 0.6 | 0.5 | 20 | 2.0 | 260 |
Pump into 2.0m in enamel reaction still3Above-mentioned richness lithium salts lake bittern water is simultaneously warming up to 70 DEG C, toward in rich lithium salts lake bittern water
Sodium carbonate and oxalic acid mass ratio is added to be the first cleaner 6kg of 1:1, insulated and stirred reacts 1h；Maintain 70 DEG C of temperature and add
Enter the sodium hydrate aqueous solution that concentration is 80g/l, slowly ph value adjusted and mix up follow-up continuous insulation reaction 0.5h to 11, ph value,
The solution of remove impurity is squeezed into sheet frame with pump and carry out coarse filtration, gained filtrate fine straining again, obtain refined richness lithium salts lake bittern water.Wherein, should
Lithium content in refined richness lithium salts lake bittern water is 13.6g/l, calcium 12ppm, magnesium 1ppm.
0.65m is added in rustless steel lye dissolving tank3Deionized water simultaneously puts into the sodium carbonate of 226kg, and stirring is molten to be added clearly afterwards
Second cleaner of 1.8kg and the sodium hydroxide of 9kg, squeeze into filter with pump after reaction 20min and are filtered, obtain refining carbon
Acid sodium solution.The concentration of sodium carbonate of wherein prepared calcium carbonate sodium solution is 282g/l, calcium 8ppm, magnesium 1ppm.
Above-mentioned prepared calcium carbonate sodium solution pump is squeezed in sinker reactor and is warming up to 80 DEG C, add lithium carbonate and second two
The compound additive 7kg that amine oxalic acid is configured to, after stirring, adds above-mentioned refined richness lithium salts lake bittern water to carry out sinker anti-
Should, sinker response time 1.5h, the carbon acid ion concentration recording sinker mother solution in lithium carbonate slurry is 16.3g/l, and insulation continues
Continuous reaction 0.5h.
Completely reacted slurry is centrifuged, gained lithium carbonate is contained wet solid and puts into sink and according to 1:3's
Solid-to-liquid ratio adds 75 DEG C of deionized water to carry out plasm scouring again, obtain lithium carbonate wet feed after centrifugation, and lithium carbonate wet feed is sent into
Infrared dryer is simultaneously dried 1.5 hours under 280 DEG C of temperature conditionss, then obtains LITHIUM BATTERY carbonic acid after except magnetic, pulverizing, packaging
Lithium product, the composition of products obtained therefrom is referring to table 6.
Embodiment 3:
The richness lithium solution containing higher impurity that the present embodiment uses is sulfate type richness lithium salts lake bittern water, its main component and containing
Amount is as shown in table 3.
Table 3 salt lake bittern main constituent and content (unit: g/l)
| li+ | na+ | k+ | ca2+ | mg2+ | so4 2- | b | cl- |
| 24.00 | 50.00 | 3.90 | 0.50 | 3.30 | 160 | 2.70 | 30 |
Pump into 2.0m in enamel reaction still3Above-mentioned richness lithium salts lake bittern water is simultaneously warming up to 70 DEG C, toward in rich lithium salts lake bittern water
Sodium carbonate and oxalic acid mass ratio is added to be the first cleaner 1kg of 1:1, insulated and stirred reacts 1h；Maintain 70 DEG C of temperature and add
Enter the sodium hydrate aqueous solution that concentration is 80g/l, slowly ph value is adjusted and mix up follow-up continuous insulation reaction 2h to 11, ph value, will
The solution of remove impurity pump is squeezed into sheet frame and is carried out coarse filtration, gained filtrate fine straining again, obtains refined richness lithium salts lake bittern water.Wherein, this essence
Lithium content in the rich lithium salts lake bittern water of system is 23g/l, calcium 15ppm, magnesium 1ppm.
1.2m is added in rustless steel lye dissolving tank3Deionized water simultaneously puts into the sodium carbonate of 383kg, and stirring is molten to be added clearly afterwards
Second cleaner of 1.8kg and the sodium hydroxide of 15kg, squeeze into filter with pump after reaction 20min and are filtered, refined
Sodium carbonate liquor.Wherein prepared calcium carbonate sodium solution concentration of sodium carbonate is 260g/l, calcium 10ppm, magnesium 1ppm.
Above-mentioned prepared calcium carbonate sodium solution pump is squeezed in sinker reactor and is warming up to 85 DEG C, add lithium carbonate, second two
The compound additive 15kg that the acid of amine oxalic acid is formulated with dodecylbenzene sodium sulfonate, stirs, and adds above-mentioned refined richness
Lithium salts lake bittern water carries out sinker reaction, sinker response time 2h, and the carbanion recording sinker mother solution in lithium carbonate slurry is dense
Spend for 15.7g/l, insulation continuation reaction 1h.
Completely reacted slurry is centrifuged, gained lithium carbonate is contained wet solid and puts into sink and according to 1:3.5
Solid-to-liquid ratio add 80 DEG C of deionized water to carry out again plasm scouring, obtain lithium carbonate wet feed after centrifugation, lithium carbonate wet feed send
Enter infrared dryer and dry 1.5 hours under 320 DEG C of temperature conditionss, then obtain LITHIUM BATTERY carbon after except magnetic, pulverizing, packaging
Sour lithium product, the composition of products obtained therefrom is referring to table 6.
Embodiment 4:
The richness lithium solution containing higher impurity that the present embodiment uses is chloride type richness lithium salts lake bittern water, its main component and containing
Amount is as shown in table 4.
Table 4 salt lake bittern main constituent and content (unit: g/l)
| li+ | na+ | k+ | ca2+ | mg2+ | so4 2- | b | cl- |
| 37.2 | 24 | 15.6 | 0.6 | 0.5 | 8.6 | 0.9 | 236 |
Pump into 1.0m in enamel reaction still3Above-mentioned richness lithium salts lake bittern water is simultaneously warming up to 70 DEG C, toward in rich lithium salts lake bittern water
Sodium carbonate and oxalic acid mass ratio is added to be the first cleaner 2.4kg of 1:1, insulated and stirred reacts 1h；Maintain 70 DEG C of temperature simultaneously
Ph value is slowly adjusted and mixes up follow-up continuous insulation reaction 2h to 11, ph value by the sodium hydrate aqueous solution adding concentration to be 80g/l,
The solution of remove impurity is squeezed into sheet frame with pump and carry out coarse filtration, gained filtrate fine straining again, obtain refined richness lithium salts lake bittern water.Wherein, should
Lithium content in refined richness lithium salts lake bittern water is 37g/l, calcium 10ppm, magnesium 1ppm.
1.0m is added in rustless steel lye dissolving tank3Deionized water simultaneously puts into the sodium carbonate of 308kg, and stirring is molten to be added clearly afterwards
Second cleaner of 1.7kg and the sodium hydroxide of 9.5kg, squeeze into filter with pump after reaction 20min and are filtered, refined
Sodium carbonate liquor.Wherein prepared calcium carbonate sodium solution concentration of sodium carbonate is 260g/l, calcium 10ppm, magnesium 1ppm.
By sinker mother solution 0.8m3Squeezed in sinker reactor with pump and be warming up to and after 90 DEG C, add lithium carbonate, ethylenediamine two
Acetic acid, dodecylbenzene sodium sulfonate and citric acid are formulated compound additive 6.5kg, and dispersed with stirring is uniformly rear to be pumped into simultaneously
Above-mentioned refined richness lithium salts lake bittern water and prepared calcium carbonate sodium solution are reacted, and control response time 2h, record in lithium carbonate slurry
The carbon acid ion concentration of sinker mother solution is 17.7g/l, and insulation continues reaction 1h.
Completely reacted slurry is centrifuged, gained lithium carbonate is contained wet solid and puts into sink and according to 1:4's
Solid-to-liquid ratio adds 80 DEG C of deionized water to carry out plasm scouring again, obtain lithium carbonate wet feed after centrifugation, and lithium carbonate wet feed is sent into
Infrared dryer is simultaneously dried 1.0 hours under 400 DEG C of temperature conditionss, then obtains LITHIUM BATTERY carbonic acid after except magnetic, pulverizing, packaging
Lithium product, the composition of products obtained therefrom is referring to table 6.
Embodiment 5:
The richness lithium solution containing higher impurity that the present embodiment uses is rich lithium obtained by chloride type richness lithium salts lake bittern water concentrates
Solution, its main component and content are as shown in table 5.
Table 5 salt lake bittern main constituent and content (unit: g/l)
| li+ | na+ | k+ | ca2+ | mg2+ | so4 2- | b | cl- |
| 49.00 | 24.00 | 5.00 | 0.80 | 5.30 | 3.80 | 5.00 | 290 |
Pump into 1.0m in enamel reaction still3Above-mentioned richness lithium solution is simultaneously warming up to 80 DEG C, adds carbonic acid toward in rich lithium solution
Sodium and oxalic acid mass ratio are the first cleaner 3.2kg of 1:1, and insulated and stirred reacts 1h；Maintain 80 DEG C of temperature and add concentration
Ph value is slowly adjusted and mixes up follow-up continuous insulation reaction 2h to 11, ph value, by remove impurity by the sodium hydrate aqueous solution for 80g/l
Solution pump is squeezed into sheet frame and is carried out coarse filtration, gained filtrate fine straining again, obtains refined richness lithium solution.Wherein, this refined richness lithium solution
In lithium content be 48g/l, calcium 16ppm, magnesium 1ppm.
1.5m is added in rustless steel lye dissolving tank3Deionized water simultaneously puts into the sodium carbonate of 400kg, and stirring is molten to be added clearly afterwards
Second cleaner of 4kg and the sodium hydroxide of 15kg, squeeze into microfilter with pump after reaction 20min and are filtered, obtain essence
Sodium carbonate liquor processed.Wherein prepared calcium carbonate sodium solution concentration of sodium carbonate is 260g/l, calcium 10ppm, magnesium 1ppm.
By sinker mother solution 1.0m3Squeezed in sinker reactor with pump and be warming up to and after 95 DEG C, add lithium carbonate, ethylenediamine two
The compound additive 12kg that sodium acetate and gluconic acid are formulated, pump into toward in sinker reactor after dispersed with stirring simultaneously
State refined richness lithium solution and prepared calcium carbonate sodium solution is reacted, control response time 3h, record sinker in lithium carbonate slurry female
The carbon acid ion concentration of liquid is 16.7g/l, and insulation continues reaction 1h.
Completely reacted slurry is centrifuged, gained lithium carbonate is contained wet solid and puts into sink and according to 1:5's
Solid-to-liquid ratio adds 80 DEG C of deionized water to carry out plasm scouring again, obtain lithium carbonate wet feed after centrifugation, and lithium carbonate wet feed is sent into
Infrared dryer is simultaneously dried 1.0 hours under 450 DEG C of temperature conditionss, then obtains LITHIUM BATTERY carbonic acid after except magnetic, pulverizing, packaging
Lithium product, the composition of products obtained therefrom is referring to table 6.
The compositional data of the battery-level lithium carbonate product that above-described embodiment 1～5 is obtained is as shown in table 6.
The compositional data (unit: %) of the battery-level lithium carbonate product that table 6 embodiment 1～5 is obtained
As shown in Table 6, using the present invention using the method preparation preparing battery-level lithium carbonate containing higher impurity richness lithium solution
The lithium carbonate product obtaining can reach battery-level lithium carbonate standard.
In sum, the method that the present invention provides is directly using containing higher impurity richness lithium solution, particularly richness lithium salts lake halogen
It is hydrated into battery-level lithium carbonate, process is simple, be not required to introduce extra lithium carbonate purification procedures and be directly synthesized battery-level lithium carbonate,
Have the advantages that low production cost and product quality are stable.
The invention is not limited in aforesaid specific embodiment.The present invention expands to and any discloses in this manual
New feature or any new combination, and the arbitrary new method of disclosure or the step of process or any new combination.
Claims (9)
1. a kind of prepare the method for battery-level lithium carbonate it is characterised in that methods described using the rich lithium solution containing higher impurity
Comprise the following steps:
A, rich lithium solution refine: the rich lithium solution containing higher impurity pumped in reactor and is warming up to 60～80 DEG C, addition the
One cleaner insulated and stirred reaction 0.5～1h, maintain 60～80 DEG C of temperature simultaneously to add sodium hydroxide or the adjustment of its aqueous solution
Ph value, to 11～12, continues insulated and stirred and reacts 0.5～2h, is filtrated to get refined richness lithium solution；
B, sodium carbonate liquor refine: add deionized water in reactor and add sodium carbonate to stir molten clear preparation to obtain concentration and be
The sodium carbonate liquor of 200～300g/l, adds the second cleaner and sodium hydroxide stirring reaction 15～30min, filters
To prepared calcium carbonate sodium solution；
C, sinker: described refined richness lithium solution is reacted with prepared calcium carbonate sodium solution and obtains lithium carbonate slurry, wherein, control reaction
Temperature is 70～95 DEG C and the response time is 1～3h, the carbonic acid of sinker mother solution in described lithium carbonate slurry when controlling reaction end
Ion concentration is 13～18g/l；
D, solid-liquid separation: by described lithium carbonate slurry be incubated 0.5～1h after carry out solid-liquid separation, obtain lithium carbonate contain wet solid and
Sinker mother solution；
E, washing: described lithium carbonate is contained input sink after wet solid drip washing by deionized water, according to the solid-to-liquid ratio of 1:3～5
The deionized water adding 60～90 DEG C carries out plasm scouring again, obtains lithium carbonate wet feed after solid-liquid separation；
F, drying: described lithium carbonate wet feed is dried under conditions of 250～450 DEG C, obtains battery-level lithium carbonate.
2. the method preparing battery-level lithium carbonate using the rich lithium solution containing higher impurity according to claim 1, its feature
It is, methods described also includes carrying out except magnetic, pulverize and be packaged to be battery-level lithium carbonate product described battery-level lithium carbonate
Step, wherein, can according to customer demand control grinding particle size, conventional grinding particle size d50: 3～8 μm, d90: 9～15 μm.
3. the method preparing battery-level lithium carbonate using the rich lithium solution containing higher impurity according to claim 1 or claim 2, it is special
Levy and be, the described rich lithium solution containing higher impurity can be for chloride type or sulfate type salt lake brine through tedding evaporation and concentration
The rich lithium salts lake bittern water separating out most of sodium, potassium, magnesium and obtaining after removing boron, the lithium carbonate alternatively being produced by carbonate type salt lake
Rich lithium solution that concentrate hydrochloric acid or the molten rear impurity removal and purification of sulphuric acid obtain or using high impurity crude product lithium carbonate hydrochloric acid or sulphuric acid molten after
The rich lithium solution being refining to obtain, contains li in the described rich lithium solution containing higher impurity+: 7～50g/l, na+≤100g/l、so4 -2
≤200g/l、cl-≤300g/l、k+≤20g/l、mg2+≤5g/l、ca2+≤ 10g/l and b :≤5g/l.
4. the method that the rich lithium solution containing higher impurity according to claim 1 or claim 2 prepares battery-level lithium carbonate, its feature exists
In described first cleaner is one or more of sodium carbonate, lithium carbonate, Disodium oxalate., potassium oxalate, lithium oxalate and oxalic acid, excellent
The mass ratio electing sodium carbonate and oxalic acid as is the mixture of 1:1；Described second cleaner be Disodium oxalate., potassium oxalate, lithium oxalate and
One or more of oxalic acid.
5. the method preparing battery-level lithium carbonate using the rich lithium solution containing higher impurity according to claim 4, its feature
It is, in step a, the addition of described first cleaner is 3～5 times of calcareous amount in described salt lake bittern, gained refines
Calcium ＜ 20ppm in rich lithium solution and magnesium≤1ppm；In stepb, the second cleaner in described sodium carbonate liquor purification step
Addition be the 0.5～1% of sodium carbonate addition, the addition of described sodium hydroxide is the 2～5% of sodium carbonate addition,
Calcium ＜ 20ppm in gained prepared calcium carbonate sodium solution and magnesium≤1ppm.
6. the method preparing battery-level lithium carbonate using the rich lithium solution containing higher impurity according to claim 1 or claim 2, it is special
Levy and be, in step a, described filtration includes coarse filtration and the fine straining carrying out successively；In step f, lithium carbonate wet feed is being returned
It is dried in rotatable drying oven, infra-red furnace, continuous tunnel furnace, meshbeltfurnace or chain type resistance furnace.
7. according to claim 1 or claim 2 prepare the method for battery-level lithium carbonate using salt lake bittern it is characterised in that in step
In rapid c, when the lithium content in refined richness lithium solution is less than 35g/l, compound additive is added in sodium carbonate refined soln simultaneously
Stir, carry out sinker with described refined richness lithium solution and react up to reaction end；Lithium content in refined richness lithium solution
During for 35～50g/l, toward in pure water or sinker mother solution add compound additive stir, then will described refined richness lithium solution and
The common addition of prepared calcium carbonate sodium solution carries out reaction up to reaction end；Wherein, the addition of described compound additive is carbonic acid
The 1～3% of sodium quality.
8. prepare the method for battery-level lithium carbonate it is characterised in that described be combined using salt lake bittern according to claim 7
Additive is by EDDA, lithium carbonate, gluconic acid, citric acid, sodium lauryl sulphate, polyvinyl alcohol and polyacrylamide
One or more of amine forms, and wherein, the molecular weight of described polyvinyl alcohol is preferably 16000～20000, and polyacrylamide is excellent
Elect anionic or nonionic as and molecular weight is 5000000～12000000.
9. the method preparing battery-level lithium carbonate using the rich lithium solution containing higher impurity according to claim 1 or claim 2, it is special
Levy and be, described battery-level lithium carbonate meets the requirement of battery-level lithium carbonate industry standard yst582-2013, wherein, li2co3≥
99.5%th, na≤0.025%, k≤0.001%, mg≤0.008%, ca≤0.005%, fe≤0.001%, zn≤
0.0003%th, cu≤0.0003%, pb≤0.0003%, si≤0.003%, al≤0.001%, mn≤0.0003, ni≤
0.001%th, so4 2-≤ 0.08%, cl-≤ 0.003%.
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