CN108341419A - The method that battery-level lithium carbonate is directly produced from salt lake brine with high magnesium-lithium ratio - Google Patents
The method that battery-level lithium carbonate is directly produced from salt lake brine with high magnesium-lithium ratio Download PDFInfo
- Publication number
- CN108341419A CN108341419A CN201710059675.7A CN201710059675A CN108341419A CN 108341419 A CN108341419 A CN 108341419A CN 201710059675 A CN201710059675 A CN 201710059675A CN 108341419 A CN108341419 A CN 108341419A
- Authority
- CN
- China
- Prior art keywords
- lithium
- brine
- liquid
- ion
- boric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/1045—Oxyacids
- C01B35/1054—Orthoboric acid
- C01B35/1063—Preparation from boron ores or borates using acids or salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The method that the invention discloses a kind of directly to produce out battery-level lithium carbonate from salt lake brine with high magnesium-lithium ratio, comprises the following steps that：(1) further stabilization forms the boron lithium brine of low potassium and sodium to brine in stabilization pond after salt pan being carried potassium；(2) boron lithium brine forms boric acid product and lithium brine after proposing boron processing；(3) lithium brine passes through, and there is the electrodialytic membranes of monovalent ion selection function to obtain primary purification liquid；(4) acid adding neutralizes to obtain secondary refining liquid after the demagging of primary purification liquid causticization；(5) secondary refining liquid obtains refined liquid three times after ion-exchanger removing calcium and magnesium；(6) refined liquid forms concentration lithium solution by forcing vaporiser three times；(7) concentration lithium solution forms even-grained lithium carbonate sediment with prepared calcium carbonate sodium solution by high efficiency reactor；(8) lithium carbonate sediment forms battery-level lithium carbonate product by being cleaned and dried packaging.The present invention has good operability, and the rate of recovery of lithium ion greatly improved.
Description
Technical field
The invention belongs to chemical industry of inorganic salt fields, in particular it relates to which one kind is straight from salt lake brine with high magnesium-lithium ratio
Connect the method for producing out battery-level lithium carbonate.
Background technology
Lithium is strategic resource indispensable in most important energy metal and modern industry, in battery chemistries, glass
Ceramics, aerial metal, nuclear industry, lubricant grease and refrigerant etc. play a significant role.Especially lithium battery in recent years
Explosion causes the lithium consumption in the whole world to be in Rapid Expansion state.The lithium production capacity 80% in the whole world comes from salt lake, and is easy to
The low Mg/Li ratio salt lake of exploitation has all fully been exploited, and the lithium of rapid growth is in urgent need needs and is carried from high Mg/Li ratio salt lake
Battery-level lithium carbonate is taken, to meet battery industry demand.
Global salt lake brine with high magnesium-lithium ratio has the characteristic of high sulfate radical and boron simultaneously mostly, while there is high sodium potassium to contain
Amount.This kind of salt lake bittern is shone by salt pan beach to be concentrated, can be there are three the apparent stage：Salt crystallization, carnallite crystalliser pan, soft potassium
Magnesium alum crystallizes, and carnallite crystalliser pan is respectively used to the production of potassium chloride and potash magnesium sulphate fertilizer with picromerite crystallization.In picromerite
After crystallization, Lithium from Salt Lake Brine has obtained higher enrichment with boron.
Salt lake brine with high magnesium-lithium ratio be enriched with by salt pan after boron lithium brine, according to endowment of resources difference, lithium concentration
Between 0.3g/L~6g/L, kalium ion and natrium ion total concentration 7g/L or more, for sulfate concentration generally in 25g/L or more, magnesium ion is dense
Degree is generally higher than 110g/L and is saturated close to magnesium chloride.
Further solarization concentrates the flood tide entrainment loss that can bischofite largely be precipitated and cause lithium to such brine.Simultaneously
In concentration process, high sulfate radical can cause sedimentation loss of the lithium sulfate in salt pan.It in summary it can be seen, high Mg/Li ratio salt lake
The lithium concentration of brine determines that the Mg/Li ratio of brine after the concentration of salt pan, salt pan concentrated brine have reached after magnesium saturation
A large amount of losses of lithium ion can be led to by being further concentrated by evaporation.
In existing salt lake puies forward lithium technique, because of many disadvantages of process for separating Mg and Li, to reduce the production for carrying lithium workshop
Cost all uses further natural evaporation concentration to improve the method for lithium concentration in brine, cause salt pan process lithium from
Sub- yield is as low as 30% or less.That is the deficiency of workshop process for separating Mg and Li leads to a large amount of wastes of saline lake lithium resource.
So in the lithium resource exploitation in global high Mg/Li ratio salt lake, it is badly in need of wanting to cope with the magnesium lithium under the conditions of complicated brine
Isolation technics extracts lithium carbonate technique in the slave high Mg/Li ratio brine of high efficiency, low cost.
In high Mg/Li ratio salt lake puies forward lithium technique, there is the process of following practical application at present：
(1) absorption method
Lithium ion is washed to adsorb lithium ion, then with fresh water or pickle using to the selective adsorbent of lithium ion
De-, Mg/Li ratio is less than 4 in usually comprehensive eluent:1, preliminary separating magnesium and lithium effect can be reached.
But absorption method largely consumes the fresh water of Yanhu District preciousness, and lithium concentration is relatively low in eluent, usually less than 0.7g/
The multistage concentration of L, backend process cause complicated for operation and high operation cost.Adsorbent is there are at high price simultaneously, in high magnesium
The problems such as being easily contaminated in brine and adsorbance is caused quickly to reduce, adsorbent itself is also easy to breakage can not grow with corroding
Time recycles.
(2) calcination method
The brine of enriching lithium is obtained into the dry powder of complicated component after evaporating, drying, dry powder is after high-temperature calcination, in dry powder
Basic magnesium chloride is converted to magnesia and hydrogen chloride gas.Solids after calcining is leached with fresh water, obtains lithium chloride solution.Cause
It is not soluble in water for magnesia, so calcination method has good separating magnesium and lithium effect.
But calcination method largely consumes natural gas, and the hydrogen chloride gas that calcination process is generated has equipment strong corrosivity
And environment is polluted, the entrainment of lithium is serious in waste residue.Tail gas treatment process causes the cost of calcination method technique to occupy height with huge energy consumption
Under not.
(3) Nanofiltering membrane
By the abundant fresh water dilution of the brine of enriching lithium, magnesium ion is diluted to 10g/L or so, magnesium lithium is carried out using NF membrane
Isolated NF membrane production water and NF membrane concentrated water.But NF membrane process for separating Mg and Li is required for the lithium brine (magnesium for being saturated magnesium
Ion concentration 115g/L or more) it carries out carrying out nanofiltration processing again after more than ten times of fresh water dilute, a large amount of fresh water will be caused to consume and made
It is extremely low that lithium concentration in water is produced at NF membrane.NF membrane process for separating Mg and Li will produce a large amount of NF membrane concentrated waters, in NF membrane concentrated water
Lithium concentration is slightly below NF membrane production water, causes lithium ion yield relatively low, the lithium ion yield of NF membrane process for separating Mg and Li
Less than 50%.The lithium concentration of NF membrane production water is even lower than the eluate concentration of absorbing process, and overall operation cost will
Higher than absorbing process.
The required battery-level lithium carbonate of anode material of lithium battery industry differs greatly, and every profession and trade association and area are made respectively
Industry or local LITHIUM BATTERY standard are determined.Different battery material manufactures require the difference with manufacturing process, cause the whole world
Battery-level lithium carbonate never has common standards.Battery-level lithium carbonate used by present cell positive material industry is
Industrial level lithium carbonate is formed after secondary operation purifies.After the practical control standard of each battery material factory of synthesis, it is proposed that use
Standard is controlled in the LITHIUM BATTERY of the method for the present invention.
Generally required battery-level lithium carbonate standard is as follows for anode material of lithium battery：
Invention content
The present invention provides in salt lake brine with high magnesium-lithium ratio, produce to meet the existing lithium electricity in the whole world without secondary purification
The lithium carbonate production technology of pond material common demands.
According to an aspect of the present invention, the present invention relates to one kind directly producing LITHIUM BATTERY from salt lake brine with high magnesium-lithium ratio
The method of lithium carbonate, comprises the following steps that：
(1) it is total using solar energy natural evaporation reduction sodium potassium ion therein in stabilization pond that salt pan is carried to the brine after potassium
Concentration, and potash fertilizer raw material is generated in regulating reservoir, concentration boron lithium brine (its control to form component stabilization is concentrated through natural evaporation
Focus on：1. preventing the sedimentation that sulfate concentration is excessively high and causes lithium sulfate in regulating reservoir from losing, a large amount of water chlorine are 2. prevented
Magnesite deposits the entrainment loss for causing boron-rich lithium brine)；
(2) boron lithium brine is subjected to coarse filtration, then by boron lithium brine and technical hydrochloric acid certainty ratio in high efficiency reactor
Mixing carries out acidification reaction, and thick boric acid solid and liquid after acidification are formed after cold filtration, make after acidification liquid and unloaded extractant into
Enter efficient centrifugal extractor, liquid forms lithium brine after extracting boron removal after acidification, and loaded extractant passes through efficient centrifugal with fresh water
Stripping process forms boric acid solution, carries out heating for dissolving and crystallisation by cooling to boric acid solution and thick boric acid, obtains smart boric acid；
(3) lithium brine is made to pass through the electric dialyzator with monovalent ion selection function, divalent ion is by ion in lithium brine
Selective membrane intercepts, and the monovalent ion in lithium brine penetrates ion-selective membrane, realizes separating magnesium and lithium and obtains primary purification liquid, described
Primary purification liquid is the concentrate of lithium ion, and wherein Mg/Li ratio is less than 2:1；The tail washings of the low lithium of high magnesium returns to salt pan；
(4) reaction of LiOH mixed solutions is added in primary purification liquid and generates magnesium hydrate precipitate object, demagging is obtained after filtering
Lithium liquid, adds HCl to neutralize, and the pH of demagging lithium liquid is adjusted to pH 6.5-7, forms secondary refining liquid, wherein magnesium ion concentration is less than
50ppm；
(5) the secondary refining liquid is passed through into calcium ions and magnesium ions selectivity cation resin exchange device deliming magnesium ion, obtained
Refined liquid three times, wherein calcium ions and magnesium ions concentration are less than 20ppm；
(6) refined liquid forms evaporation concentrated solution by forcing vaporiser three times by described in, and lithium concentration is high in concentrate
In 30g/L；
(7) industrial sodium carbonate is carried out matching liquid, double-filtration then is carried out to sodium carbonate liquor, it is molten to obtain prepared calcium carbonate sodium
Liquid is fully reacted by concentrated brine and prepared calcium carbonate sodium solution certainty ratio by high efficiency reactor in high efficiency reactor, is formed
Even-grained lithium carbonate sediment；
(8) lithium carbonate sediment is filtered, formed lithium carbonate solid blank, the semi-finished product using cleaning,
Battery-level lithium carbonate product is formed after dry, packaging.
Further, in step (1), further concentration forms the boron lithium halogen of low potassium and sodium to brine in stabilization pond after carrying potassium
Water, wherein kalium ion and natrium ion total amount are less than 5g/L, and sulfate concentration is less than 30g/L.
Further, in step (2), boron lithium brine completes acidification instead with hydrochloric acid certainty ratio by one step of high efficiency reactor
It answers, generates boric acid, obtain thick boric acid through filtering, the pH value of mixed liquor is 1-4.
Further, in step (2), liquid and unloaded extractant are by centrifugal extractor after acidification, after acidification in liquid
Boric acid forms lithium brine after being extracted, boric acid content is less than 0.6g/L in lithium brine, and loaded extractant is stripped with fresh water through centrifugation
Boric acid solution is formed after taking device, loaded extractant is reused after centrifugation reextractor boron removal forms unloaded extractant.
Further, it in step (2), is acidified instead with by boron lithium brine to being formed by boric acid solution by back extraction
Thick boric acid should be formed by be dissolved by heating, saturation boric acid solution is formed, the temperature for being saturated boric acid solution is 30-80 DEG C, warp
Cooling and crystallizing process obtains smart boric acid.
Further, in step (3), lithium brine is passed through to the electric dialyzator for being equipped with monovalent ion selective membrane, in electricity
Under field force effect, the monovalent ion in rich lithium brine penetrates ion-selective membrane, and divalent ion is blocked by ion-selective membrane in lithium brine
It cuts, this process is completed at the same time separating magnesium and lithium and realizes that lithium concentrates, and forms the primary purification liquid of the low magnesium of high lithium.Described has generation
The monovalent ion selective membrane of table include ASTOM companies K-192 and ACS-8T film and other companies production have it is similar
The monovalent ion selective membrane of performance.
Further, it in step (7), carries out matching liquid using calcined soda for industry, after double-filtration, forms prepared calcium carbonate sodium
Solution.
Further, in step (7), soda ash solution is rapidly completed with lithium chloride solution by high efficiency reactor and is mixed
Reaction and crystallization process, peritectoid phenomenon when effectivelying prevent crystallization of lithium carbonate to react are formed simultaneously even-grained lithium carbonate
Sedimentation.
The process of the present invention, has steps of (referring to Fig. 3)：
(1) brine forms boron lithium brine in stabilization pond by the control to evaporation capacity after carrying potassium
Lithium technique is put forward existing, using one of the following two kinds measure：(i) it is directed to the salt lake bittern containing lithium, in salt pan
It is used after directly being filtered after the picromerite crystallization of process.This can cause entry into potassium sodium content in the raw material lithium brine for carry lithium workshop
Higher, when directly contributing Workshop Production, the high potassium/sodium of Process liquor is run, and increases considerably operating cost and energy consumption, and cause
Contamination of products.Alternatively, (ii) by complicated solarization concentration process, with bischofite it is a large amount of settle, sacrifice a large amount of lithium from
Sub- entrainment loss is settled with lithium ion to be lost further to concentrate.
Since the present invention has the low cost of good separating magnesium and lithium effect and separating magnesium and lithium process, at high Mg/Li ratio brine
Reason has good result and cost-effectivenes.Existing potash fertilizer raw material salt field process can be directly utilized, in picromerite crystallization stage
Tail portion, brine importing regulating reservoir carries out stablizing concentration after carrying potassium, is largely settled before lithium sulfate sedimentation and in bischofite
In the past, sulfate concentration was controlled according to environment temperature.The operating difficulties in salt pan is greatly reduced, and greatly improves salt pan mistake
The lithium ion yield of journey.According to operating experience, in regulating reservoir, under conditions of not needing assistant medicament, control kalium ion and natrium ion is total
Amount is less than 5g/L, and sulfate concentration is less than 30g/L, to ensure the salt pan lithium ion yield under the conditions of potassium lithium coproduction.
Stabilization pond is used as boron lithium brine reserve pool simultaneously, and salt pan goes out halogen and adjusts its evaporation according to ambient condition in stabilization pond
Enrichment stage keeps the boron lithium brine deposit for stablizing component.
(2) boron lithium brine boron removal forms lithium brine and smart boric acid
A concentration of 2~8g/L of boron in boron lithium brine.Brine is warming up to 30~40 DEG C using commercial vapor in temperature adjustment slot,
The technical hydrochloric acid for being 20%~25% with content is sufficiently mixed and reacts in high efficiency reactor, and reaction solution is cooled down through thick boric acid and tied
Brilliant device forms thick boric acid crystal, thick boric acid solid and liquid after acidification is obtained by filtration by plate filter, boron lithium brine is passing through
Peracid reaction and after filtering, boron concentration is reduced to about 3g/L.
Liquid after acidification and boric acid extractant are passed through into centrifugal extractor.In centrifugal extractor, liquid extracts with unloaded after acidification
It takes agent to be sufficiently mixed, after boric acid is extracted in liquid after acidification, is respectively formed the loaded extractant of light phase and the lithium brine of heavy phase.Weight
Phase lithium brine forms finished product lithium brine later by deoiling treatment, and boron content is less than 0.4g/L in lithium brine, and pH value is about the left sides 1-4
It is right.
Loaded extractant is sufficiently mixed extraction with fresh water in back extraction machine, and it is unloaded with light phase to be respectively formed heavy phase boric acid solution
Extractant recycles after extractant dehydration.Boron content is 7g/L in boric acid solution, and boric acid solution is cold by thermosol with thick boric acid
Smart boric acid product is produced in crystallization.
Acidification is with boron extraction technology flow referring to Fig. 1.
(3) lithium brine selects electric dialyzator to form primary purification liquid by ion
Carry the lithium brine after boron, after fresh water dilutes, magnesium ion concentration between 50~100g/L, boron content 0.1~
Between 0.4g/L, lithium concentration is between 0.3~6g/L.This brine is very suitable for electrodialysis process.Ion-selective membrane is to boron
There is a good interception effect, boron content is relatively low in lithium brine, does not interfere with filtering and electrodialytic process.Electrodialysis process is different from
Electrolysis process will not generate chlorine and hydrogen in the process.
Lithium brine is after filtering, into the dilution chamber of monovalent ion selective membrane electrodialysis plant.Pure water enters electric osmose
The enriched chamber of desorption device.Under electric field force effect, monovalent cation (Li+) pass through anode membrane to reach enriched chamber from dilution chamber, and two
Valence cation (Mg2+) intercepted in dilution chamber by ion-selective membrane.Univalent anion (Cl-) cavity block is passed through to reach enriched chamber, and two
Valence anion (SO4 2-) intercepted in dilution chamber by ion-selective membrane.Anode membrane blocking anion passes through, same cavity block blocking cation
Pass through.After cycle, concentrate forms primary purification liquid, and wherein lithium concentration is higher than 10g/L, and magnesium ion concentration is less than
10g/L.Lithium concentration is less than 0.3g/L in dilution, and magnesium ion concentration is higher than 50g/L.Salt pan is drained into outside dilution to be converted
Halogen operates, and the lithium ion in exterior liquid forms boron lithium brine in salt pan concentration process and is recycled recycling.
Ion selects electrodialysis separating magnesium and lithium principle referring to Fig. 2.
(4) primary purification liquid is neutralized after causticizing reaction demagging with HCl, forms secondary refining liquid
In primary purification liquid after ion selects electrodialysis process, lithium concentration is higher than 10g/L, magnesium ion concentration
Less than 10g/L.By primary purification liquid and LiOH mixed solutions hybrid reaction in heating reaction kettle, controlled at 60 DEG C, shape
At magnesium hydrate precipitate object, and the pH in reaction end in control mixed liquor is more than 13.Mixed liquor after reaction is passed through into plate
Formula filter forms product and demagging lithium liquid among magnesium hydroxide.In the demagging lithium liquid, magnesium ion concentration is less than 50ppm.It removes
The pH value of magnesium lithium liquid is about 13, and HCl is added and carries out acid-base neutralization, and the pH of demagging lithium liquid is adjusted to pH6.5-7, forms secondary fine
Liquid processed.
(5) secondary refining liquid forms refined liquid three times by ion exchange
Secondary refining liquid directly carries out ionic adsorption by chelating resin to calcium ions and magnesium ions.Secondary refining liquid is by mixed bed
Afterwards, calcium ions and magnesium ions are less than 20ppm, form refined liquid three times.
(6) refined liquid forms evaporation concentrated solution by forced evaporation three times
Refined liquid is directly entered forcing vaporiser three times, and after evaporation and concentration, lithium concentration reaches 30g/L or more,
Fresh water reuse is formed while forming evaporation concentrated solution.
(7) prepared calcium carbonate sodium solution is reacted with sinker
Evaporation concentrated solution and prepared calcium carbonate sodium solution, enter high efficiency reactor, in high efficiency reactor with stoichiometric ratio
It is sufficiently mixed and reacts to form crystallization of lithium carbonate, a step forms evengranular lithium carbonate sediment, by plate filter mistake
Lithium carbonate sediment is obtained after filter.
(8) lithium carbonate precipitation article is washed and starched by water distribution, is filtered in filter centrifugal and is formed lithium carbonate solid blank,
It is eluted by centrifuge, then after drying, packaging, forms battery-level lithium carbonate product.
Advantageous effect
(1) present invention has good operability；
(2) separating magnesium and lithium technology of the invention is a kind of technique of high efficiency extraction lithium carbonate in the brine from high Mg/Li ratio；
(3) be not necessarily to it is secondarily purified, directly obtain standard compliant battery-level lithium carbonate product；
(4) while refined boric acid product is obtained；
(5) lithium carbonate of this technique productions is of low cost.
Description of the drawings
In order to more clearly describe technical scheme of the present invention, briefly introduce below in conjunction with attached drawing.It is clear that this
A little attached drawings are only some specific implementation modes that the application produces battery-level lithium carbonate, but are not intended to be defined it.
Fig. 1 is existing acidification and boron extraction technology flow chart；
Fig. 2 is that ion selects electrodialysis separating magnesium and lithium schematic diagram；And
Fig. 3 is the process flow chart of the present invention.
Specific implementation mode
For a further understanding of the present invention, the preferred embodiment of the present invention is described below in conjunction with embodiment.These
Description is merely illustrative the features and advantages of the present invention, the protection domain being not intended to limit the present invention.
Embodiment 1
By taking the salt lake intercrystalline bittern in the salt lakes Bolivia state Wu Youli (Uyuni) as an example：
(1) boron lithium brine is formed
The salt lake intercrystalline bittern for extracting the salt lakes Bolivia state Wu Youli carries out salt pan evaporation and concentration, in evaporation process,
Tail washings (predominantly magnesium chloride solution) carries out salt pan benefit magnesium operation after carrying lithium using workshop.Formation carries brine after potassium, imports and stablizes
Pond is evaporated stabilization, forms the boron lithium brine that component is stablized.Emphasis monitors magnesium ion and sulfate concentration.For investment reduction,
Stabilization pond is used as halogen storage pool simultaneously, according to the conditions such as the production schedule and ambient air temperature sunshine, by adjusting the hands such as evaporation capacity, moisturizing
Duan Jinhang carries the deposit of brine stabilization component after potassium.
Brine composition table after intercrystalline bittern is stablized with evaporation：
Uyuni salt lake (Uyuni) intercrystalline bittern component：
| Composition | Li+ | K+ | Na+ | Mg2+ | Ca2+ | B3+ | SO4 2- | Cl- | Proportion |
| g/L | 0.96 | 21.42 | 108.36 | 18.90 | 0.50 | 0.64 | 20.16 | 233.10 | 1.26 |
Brine component after Uyuni salt lake (Uyuni) evaporation is stablized：
| Composition | Li+ | K+ | Na+ | Mg2+ | Ca2+ | B3+ | SO4 2- | Cl- | Proportion |
| g/L | 6.63 | 0.53 | 1.21 | 112.22 | 0.33 | 8.64 | 23.17 | 346.12 | 1.37 |
(2) boron lithium boron from brines
Boron lithium brine is filtered, entrained solid object is removed, is then heated to 35-70 DEG C, then with 25%~30%
Technical hydrochloric acid high efficiency reactor is entered with certainty ratio, be sufficiently mixed and react in the reactor, to boracic object in boron lithium brine
It is acidified, is converted to boric acid, form boric acid crystal in the solution.
Acidification reaction liquid is cooled to 15 DEG C, is then filtered.Wherein, 60% boric acid is collected by filtration, 40% boric acid
It is dissolved in after being acidified in liquid.Liquid after forming thick boric acid much filtrate after filtering and being acidified.
In the liquid after cooling and filtered acidification, boron concentration is about 3g/L, pH value 1.
After liquid is by centrifugal extractor after acidification, it is 5g/L or more to obtain boron concentration less than 0.4g/L, lithium concentration
Lithium brine.The loaded extractant that Centrifugical extraction process generates enters centrifugation back extraction machine with fresh water and mixes and be stripped,
The heavy phase of generation is boric acid solution, and boron content is higher than 7g/L in boric acid solution；The light phase of generation is unloaded extractant, zero load extraction
Agent returns to centrifugal extractor and realizes recycling.
Boric acid solution and thick boric acid are dissolved by heating, boric acid saturated solution is formed, after filtering, is obtained by crystallisation by cooling
To the smart boric acid product of 99% or more purity.
(3) electrodialysis ion selection separation
Lithium brine is diluted with fresh water, subsequently into the dilution side of the electrodialysis plant equipped with ion-selective membrane, fresh water into
Enter the concentration side of electrodialysis plant.Ion-selective membrane is preferably K-192 and the ACS-8T film of ASTOM companies.Lithium brine is diluting
In side, monovalent ion reaches concentration side under electric field force effect across ion-selective membrane, and primary purification liquid is formed in concentration side.
In the primary purification liquid, lithium concentration 12g/L, magnesium ion concentration 1.7g/L.In dilution, lithium concentration is
0.2g/L, magnesium ion concentration 60g/L.
(4) after the demagging of primary purification liquid causticization in acid adding and formed secondary refining liquid
By primary purification liquid and LiOH mixed solutions hybrid reaction in heating reaction kettle, controlled at 60 DEG C, formed
Magnesium hydrate precipitate object, and the pH in reaction end in control mixed liquor is more than 13.Mixed liquor after reaction is passed through board-like
Filter forms product and demagging lithium liquid among magnesium hydroxide.In the demagging lithium liquid, magnesium ion concentration is less than 50ppm.Demagging
The pH value of lithium liquid is about 13, and HCl is added and carries out acid-base neutralization, and the pH of demagging lithium liquid is adjusted to pH 6.8, forms secondary refining
Liquid.
(5) ion exchange adsorption
Secondary refining liquid is subjected to ion exchange adsorption by chelating resin mixed bed.It is preferred that absorption resin is that Chinese blue dawn is public
Take charge of LSC-500 chelating resins.After absorption in liquid, magnesium ion concentration 8ppm, calcium ion concentration 2ppm.
(6) prepared calcium carbonate sodium solution
Solution preparation is carried out using native industry sodium carbonate, ceramic membrane mistake is used after carrying out bag type filtering to sodium carbonate liquor
Filter, then obtains prepared calcium carbonate sodium solution.Wherein magnesium ion concentration is 7ppm, calcium ion concentration 4ppm.
(7) battery-level lithium carbonate generates
It liquid forced evaporation will concentrate after absorption, 70 DEG C of concentrated brine be passed through with prepared calcium carbonate sodium solution certainty ratio efficient
Reactor is sufficiently mixed reaction in high efficiency reactor, forms even-grained lithium carbonate sediment.By filter centrifugal mistake
Filter forms lithium carbonate finished product after forcing washing, drying.Reach LITHIUM BATTERY standard after testing.
Embodiment 2
By taking Argentinian Lincoln salt lake (Rincon) intercrystalline bittern as an example：
(1) intercrystalline bittern for acquiring Argentinian Lincoln salt lake is controlled through evaporation and concentration before bischofite is largely precipitated,
Obtain boron lithium brine component.It is 6.42g/L, boron content 4.65g/L that this brine, which can also further be concentrated into lithium concentration,.
But concentration process can cause the lithium loss that a large amount of bischofites are precipitated, while a large amount of lithium sulfate sedimentations, overall lithium ion loss super
Cross 30%.
Lincoln salt lake (Rincon) intercrystalline bittern component：
| Composition | Li+ | K+ | Na+ | Mg2+ | Ca2+ | B3+ | SO4 2- | Cl- | Proportion |
| g/L | 0.40 | 7.51 | 115.95 | 3.42 | 0.49 | 0.33 | 12.52 | 188.43 | 1.204 |
Brine component after Lincoln salt lake (Rincon) further concentrates：
| Composition | Li+ | K+ | Na+ | Mg2+ | Ca2+ | B3+ | SO4 2- | Cl- | Proportion |
| g/L | 5.02 | 0.52 | 1.12 | 115.76 | 0.24 | 3.31 | 30.56 | 338.27 | 1.32 |
(2) 20% hydrochloric acid of above-mentioned boron lithium brine is adjusted into pH value to 1, forms acidifying solution, leads to together with unloaded extractant
Centrifugal extractor is crossed, obtained heavy phase is the lithium brine that boron concentration is higher than 4.5g/L or more less than 0.4g/L, lithium concentration.It is negative
It carries extractant and fresh water and enters and centrifuge back extraction machine and mix back extraction, heavy phase is boric acid solution, boron content in boric acid solution
For 7g/L.
Light phase is unloaded extractant, and unloaded extractant returns to centrifugal extractor and realizes recycling.Because back extraction is formed
Boric acid solution impurity it is seldom, boric acid solution is evaporated by forcing vaporiser to be formed 99.5% high-purity boracic acid and is precipitated, and is recycled
Fresh water.
(3) electrodialysis ion selection separation
Above-mentioned lithium brine is diluted with fresh water, it is light subsequently into the dilution side of the electrodialysis plant equipped with ion-selective membrane
Water enters the concentration side of electrodialysis plant.Ion-selective membrane is preferably K-192 and the ACS-8T ion-selective membrane of ASTOM companies.
For lithium brine in diluting side, monovalent ion reaches concentration side under electric field force effect across ion-selective membrane, is formed in concentration side
Primary purification liquid.In the primary purification liquid, lithium concentration 10g/L, magnesium ion concentration 2g/L.In dilution, lithium
Ion concentration is 0.2g/L, magnesium ion concentration 60g/L.
(4) after the demagging of primary purification liquid causticization in acid adding and formed secondary refining liquid
By primary purification liquid and LiOH mixed solutions hybrid reaction in heating reaction kettle, controlled at 60 DEG C, formed
Magnesium hydrate precipitate object, and the pH in reaction end in control mixed liquor is more than 13.Mixed liquor after reaction is passed through board-like
Filter forms product and demagging lithium liquid among magnesium hydroxide.In the demagging lithium liquid, magnesium ion concentration is less than 50ppm.Demagging
The pH value of lithium liquid is about 13, and HCl is added and carries out acid-base neutralization, and the pH of demagging lithium liquid is adjusted to pH 6.6, forms secondary refining
Liquid.
(5) ion exchange adsorption
By secondary refining liquid by chelating resin mixed bed, ion exchange adsorption is carried out.It is preferred that absorption resin is Lan Xiao companies
LSC-500 chelating resins.After obtained absorption in liquid, magnesium ion concentration 8ppm, calcium ion concentration 2ppm.
(6) prepared calcium carbonate sodium solution
It acquires industrial sodium carbonate and matches liquid, double-filtration then is carried out to sodium carbonate liquor, obtains prepared calcium carbonate sodium solution,
Middle magnesium ion concentration is 7ppm, calcium ion concentration 4ppm.
(7) battery-level lithium carbonate generates
It liquid forced evaporation will concentrate after absorption, 70 DEG C of concentrated brine be passed through with prepared calcium carbonate sodium solution certainty ratio efficient
Reactor is sufficiently mixed reaction in high efficiency reactor, forms even-grained lithium carbonate sediment.By filter centrifugal mistake
Filter forms lithium carbonate finished product after forcing washing, drying.Reach LITHIUM BATTERY standard after testing.
The explanation of above example is only intended to help to understand core of the invention thought.It should be pointed out that for this field
Those of ordinary skill for, without departing from the principle of the present invention, can also to the present invention carry out it is several improvement and repair
Decorations, but these improvement and modification are also fallen into the range of the claims in the present invention are claimed.
Claims (8)
1. a kind of method for directly producing battery-level lithium carbonate from salt lake brine with high magnesium-lithium ratio, comprises the following steps that：
(1) it is always dense using solar energy natural evaporation reduction sodium potassium ion therein in stabilization pond that salt pan is carried to the brine after potassium
Degree, and potash fertilizer raw material is generated in regulating reservoir, the concentration boron lithium brine to form component stabilization is concentrated through natural evaporation；
(2) boron lithium brine is subjected to coarse filtration, then boron lithium brine is mixed with technical hydrochloric acid in high efficiency reactor to progress acid
Change reaction, form thick boric acid solid and liquid after acidification after cold filtration, liquid enters efficient centrifugal with unloaded extractant after making acidification
Extractor, liquid forms lithium brine after extracting boron removal after acidification, and loaded extractant passes through efficient centrifugal stripping process shape with fresh water
At boric acid solution, heating for dissolving and crystallisation by cooling are carried out to boric acid solution and thick boric acid, obtain smart boric acid；
(3) lithium brine is made to pass through the electric dialyzator with monovalent ion selection function, divalent ion is selected by ion in lithium brine
Film intercepts, and the monovalent ion in lithium brine penetrates ion-selective membrane, realizes separating magnesium and lithium and obtains primary purification liquid, described primary
Refined liquid is the concentrate of lithium ion, and wherein Mg/Li ratio is less than 2:1；The tail washings of the low lithium of high magnesium returns to salt pan；
(4) it reacts primary purification liquid to form magnesium hydrate precipitate object with LiOH mixed solutions, demagging lithium liquid is obtained after filtering, is added
HCl is neutralized, and the pH of demagging lithium liquid is adjusted to pH 6.5-7, forms secondary refining liquid, and wherein magnesium ion concentration is less than 50ppm；
(5) the secondary refining liquid is passed through into calcium ions and magnesium ions selectivity cation resin exchange device deliming magnesium ion, obtained three times
Refined liquid, wherein calcium ions and magnesium ions are less than 20ppm；
(6) refined liquid forms evaporation concentrated solution by forcing vaporiser three times by described in, and lithium concentration is higher than in concentrate
30g/L；
(7) industrial sodium carbonate is carried out matching liquid, double-filtration then is carried out to sodium carbonate liquor, obtains prepared calcium carbonate sodium solution,
It by concentrate and prepared calcium carbonate sodium solution by high efficiency reactor, fully reacts, is formed even-grained in high efficiency reactor
Lithium carbonate sediment；
(8) lithium carbonate sediment is filtered, formed lithium carbonate solid blank, the semi-finished product using cleaning, drying,
Battery-level lithium carbonate product is formed after packaging.
2. the method as described in claim 1, it is characterised in that：In step (1), brine is further in stabilization pond after carrying potassium
Concentration forms the boron lithium brine of low potassium and sodium, and wherein kalium ion and natrium ion total amount is less than 5g/L, and sulfate concentration is less than 30g/L.
3. the method as described in claim 1, it is characterised in that：In step (2), boron lithium brine passes through highly effective reaction with hydrochloric acid
One step of device completes acidification reaction, generates boric acid, obtains thick boric acid through filtering, the pH value of mixed liquor is 1-4.
4. the method as described in claim 1, it is characterised in that：In step (2), after acidification liquid and unloaded extractant by from
Heart extractor, the boric acid after acidification in liquid form lithium brine after being extracted, boric acid content is less than 0.6g/L, load extraction in lithium brine
Agent is taken to form boric acid solution after centrifuging reextractor with fresh water, loaded extractant forms zero load by centrifugation reextractor boron removal
It is reused after extractant.
5. the method as described in claim 1, it is characterised in that：It is molten to being formed by boric acid by back extraction in step (2)
Liquid with thick boric acid be formed by by boron lithium brine acidification reaction dissolved by heating, form saturation boric acid solution, be saturated boric acid
The temperature of solution is 30-80 DEG C, and smart boric acid is obtained through cooling and crystallizing process.
6. the method as described in claim 1, it is characterised in that：In step (3), by lithium brine by being equipped with monovalent ion
The electric dialyzator of selective membrane, under electric field force effect, monovalent ion in rich lithium brine penetrates ion-selective membrane, two in lithium brine
Valence ion is intercepted by ion-selective membrane, this process is completed at the same time separating magnesium and lithium and realizes that lithium concentrates, and forms the one of the low magnesium of high lithium
Secondary refined liquid.
7. the method as described in claim 1, it is characterised in that：In step (7), concentrate and prepared calcium carbonate sodium solution are led to
It crosses high efficiency reactor and completes hybrid reaction and crystallization process.
8. the method as described in claim 1, it is characterised in that：In step (4), LiOH mixed solutions are LiOH's and NaOH
Mixed solution.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710059675.7A CN108341419A (en) | 2017-01-24 | 2017-01-24 | The method that battery-level lithium carbonate is directly produced from salt lake brine with high magnesium-lithium ratio |
| ARP170101440A AR108606A1 (en) | 2017-01-24 | 2017-05-26 | METHOD TO PREPARE LITHIUM CARBONATE GRADE BATTERY DIRECTLY FROM SALMUERA SALAR WITH HIGH PROPORTION OF MAGNESIUM-LITHIUM |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710059675.7A CN108341419A (en) | 2017-01-24 | 2017-01-24 | The method that battery-level lithium carbonate is directly produced from salt lake brine with high magnesium-lithium ratio |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108341419A true CN108341419A (en) | 2018-07-31 |
Family
ID=62963151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710059675.7A Pending CN108341419A (en) | 2017-01-24 | 2017-01-24 | The method that battery-level lithium carbonate is directly produced from salt lake brine with high magnesium-lithium ratio |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN108341419A (en) |
| AR (1) | AR108606A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109607578A (en) * | 2019-01-03 | 2019-04-12 | 青海中信国安锂业发展有限公司 | A method of extracting battery-level lithium carbonate from magnesium sulfate salt lake bittern |
| CN112461627A (en) * | 2020-11-30 | 2021-03-09 | 青海省柴达木综合地质矿产勘查院 | Method for determining mineral separation route of low-potassium high-sodium liquid potassium ore |
| CN115386740A (en) * | 2022-08-30 | 2022-11-25 | 中南大学 | Method and device for extracting lithium from brine or seawater based on electrodialysis principle |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976367A (en) * | 2012-12-20 | 2013-03-20 | 青海锂业有限公司 | Method for preparing battery-level lithium carbonate by using salt lake brine |
| CN104961143A (en) * | 2015-07-03 | 2015-10-07 | 青海恒信融锂业科技有限公司 | Method for extracting lithium from salt lake brine |
| CN105152191A (en) * | 2015-10-28 | 2015-12-16 | 中国科学院青海盐湖研究所 | Method for preparing lithium carbonate through salt lake brine with high ratio of magnesium to lithium |
| CN105540619A (en) * | 2015-08-17 | 2016-05-04 | 马培华 | Method for directly preparing battery grade lithium carbonate from salt lake brine with high magnesium-to-lithium ratio |
-
2017
- 2017-01-24 CN CN201710059675.7A patent/CN108341419A/en active Pending
- 2017-05-26 AR ARP170101440A patent/AR108606A1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976367A (en) * | 2012-12-20 | 2013-03-20 | 青海锂业有限公司 | Method for preparing battery-level lithium carbonate by using salt lake brine |
| CN104961143A (en) * | 2015-07-03 | 2015-10-07 | 青海恒信融锂业科技有限公司 | Method for extracting lithium from salt lake brine |
| CN105540619A (en) * | 2015-08-17 | 2016-05-04 | 马培华 | Method for directly preparing battery grade lithium carbonate from salt lake brine with high magnesium-to-lithium ratio |
| CN105152191A (en) * | 2015-10-28 | 2015-12-16 | 中国科学院青海盐湖研究所 | Method for preparing lithium carbonate through salt lake brine with high ratio of magnesium to lithium |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109607578A (en) * | 2019-01-03 | 2019-04-12 | 青海中信国安锂业发展有限公司 | A method of extracting battery-level lithium carbonate from magnesium sulfate salt lake bittern |
| CN112461627A (en) * | 2020-11-30 | 2021-03-09 | 青海省柴达木综合地质矿产勘查院 | Method for determining mineral separation route of low-potassium high-sodium liquid potassium ore |
| CN115386740A (en) * | 2022-08-30 | 2022-11-25 | 中南大学 | Method and device for extracting lithium from brine or seawater based on electrodialysis principle |
Also Published As
| Publication number | Publication date |
|---|---|
| AR108606A1 (en) | 2018-09-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105540619B (en) | Method for directly preparing battery grade lithium carbonate from salt lake brine with high magnesium-to-lithium ratio | |
| CN108341420A (en) | The method that lithium hydroxide and lithium carbonate are directly produced from salt lake brine with high magnesium-lithium ratio | |
| US20200189925A1 (en) | Process for recovery of lithium from a geothermal brine | |
| JP5406955B2 (en) | Method for producing lithium carbonate | |
| CN106315625B (en) | The method of the high-purity monohydrate lithium hydroxide of laminating production, pure Lithium Carbonate and battery-level lithium carbonate | |
| CN103708508B (en) | A kind of method of producing battery-level lithium carbonate from lithium concentrate | |
| KR20200090741A (en) | Method and system for manufacturing battery grade and high purity grade lithium hydroxide and lithium carbonate from high-purity lithium source | |
| CN105152191B (en) | A kind of method utilizing salt lake brine with high magnesium-lithium ratio to prepare lithium carbonate | |
| US4723962A (en) | Process for recovering lithium from salt brines | |
| CN106186002B (en) | A kind of preparation method of battery-level lithium carbonate | |
| CA2762601A1 (en) | Lithium carbonate production from brine | |
| CN106365181A (en) | Method of preparing battery-grade lithium carbonate from lithium-rich solution being high in content of impurities | |
| CN111960445B (en) | Method for preparing battery-grade lithium carbonate by using lithium sulfate coarse ore and recycling by-products | |
| CN107055575B (en) | A kind of production technology of LITHIUM BATTERY lithium hydroxide | |
| CN110330041A (en) | A kind of higher value application method of low grade lithium carbonate | |
| CA3077834A1 (en) | Method and system for preparing battery grade and high purity grade lithium hydroxide and lithium carbonate from high-impurity lithium sources | |
| CN103570043A (en) | Method for producing high-purity potassium chloride solution for preparation of potassium carbonate and co-producing low sodium salt | |
| CN110002476A (en) | A kind of preparation method of lithium hydroxide | |
| WO2021143809A1 (en) | Method for extracting lithium from lithium-containing low-magnesium brine | |
| CN106745102B (en) | A kind of preparation process of lithium carbonate | |
| CN108341419A (en) | The method that battery-level lithium carbonate is directly produced from salt lake brine with high magnesium-lithium ratio | |
| CN108341421A (en) | The method that lithium carbonate is directly produced from salt lake brine with high magnesium-lithium ratio | |
| CN108358221A (en) | A kind of technique for producing lithium chloride with magnesium sulfate salt lake bittern | |
| CN109987618A (en) | The preparation method of battery-level lithium carbonate | |
| CN108367934A (en) | The method that control forms the compound of sulfate in high environment temperature prepares potassium sulfate from mine containing potassium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |