CN108341420A - The method that lithium hydroxide and lithium carbonate are directly produced from salt lake brine with high magnesium-lithium ratio - Google Patents
The method that lithium hydroxide and lithium carbonate are directly produced from salt lake brine with high magnesium-lithium ratio Download PDFInfo
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- CN108341420A CN108341420A CN201710059740.6A CN201710059740A CN108341420A CN 108341420 A CN108341420 A CN 108341420A CN 201710059740 A CN201710059740 A CN 201710059740A CN 108341420 A CN108341420 A CN 108341420A
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/02—Oxides; Hydroxides
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Abstract
The method that the invention discloses a kind of directly to produce out lithium hydroxide and 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)~(5) lithium brine obtains refined liquid three times after refining three times；(6) refined liquid forms lithium hydroxide solution by bipolar membrane electrodialysis device three times；(7) lithium hydroxide solution is obtained into a hydronium(ion) lithia solid and evaporation mother liquor by crystallizing evaporator；(8) LITHIUM BATTERY lithium hydroxide and washing lotion are formed by recrystallization the hydronium(ion) lithia solid by washing；(9) evaporation mother liquor is formed into lithium carbonate with washing lotion by gas-liquid reactor and carbon dioxide gas precursor reactant.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 lithium hydroxide and 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 10% 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 3 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 0.5g/
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) electroosmose process
Lithium brine will be contained, electric dialyzator is selected by multipole ion, using ion-selective membrane to the good of divalent zwitterion
Interception effect, under electric field force effect, magnesium sulfate is intercepted, and lithium chloride forms rich lithium solution across ion-selective membrane.
Electroosmose process is pollution-free, cost is controllable, and to be existing high magnesium carry than salt lake, and lithium technique is unique to realize continuous scale life
The method of production.But the water consumption of multistage electrodialysis device is higher with power consumption, be formed by rich lithium brine magnesium ion concentration compared with
Height reaches 10g/L or more, needs to use hydrochloric acid leveling pH value, a large amount of sodium ion to import again after using a large amount of soda bath demaggings
Cause the high operation cost of subsequent evaporation concentration and sinker technique.
In addition to the high magnesium of three of the above practice puies forward lithium technique than salt lake, also application No. is 03108088.X,
Process disclosed in 201310571755.2 equal Chinese patent applications, these patent applications all use NF membrane into
Row separating magnesium and lithium.But these patent applications are all overlapped the lithium brine (magnesium ion concentration 115g/L or more) for having used magnesium to be saturated and carry out
Nanofiltration processing is carried out again after more than ten times of fresh water dilutions, these processes all can cause a large amount of fresh water to consume and cause lithium brine
Volume increases by more than ten times.Under conditions of NF membrane separating magnesium and lithium does not have preferable concentrated effect, it is dense that NF membrane produces lithium ion in water
Degree will be less than 0.5g/L, the even lower than eluate concentration of absorbing process, and overall operation cost will be above absorbing process.
It mentions in Chinese patent application 201310571755.2 and being kept away using calcium chloride to reduce sulfuric acid concentration in boron lithium brine
Exempt from lithium sulfate sedimentation loss, but this method can not solve flood tide bischofite salt Tanaka sedimentation and caused by entrainment loss,
The several times concentration of magnesium saturated bittern must cause to lose liquid lithium brine completely due to bischofite is precipitated and carries secretly in concentration basin.Together
When also introduce calcium contamination, it is extremely disadvantageous to later processing operation, at the same also cause salt pan operation complexity and calcium chloride buying,
Transport with match liquid, addition, the huge increasing of cost for the techniques such as mixing.
The Chinese required battery-level lithium carbonate of anode material of lithium battery industry differs greatly, and every profession and trade association and ground are distinguished
Industry or local LITHIUM BATTERY standard have not been formulated.Different battery material manufactures require the difference with manufacturing process, in causing
The battery-level lithium carbonate of state never has common standards.LITHIUM BATTERY carbonic acid used by present Chinese cell positive material industry
Lithium is that industrial level lithium carbonate is formed after secondary operation purifies.After the practical control standard of each battery material factory of synthesis, carry
The LITHIUM BATTERY control standard for the method for the present invention is gone out.
Generally required battery-level lithium carbonate standard is as follows for Chinese 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 of China 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 hydroxide from salt lake brine with high magnesium-lithium ratio
The method of lithium and 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) by primary purification liquid directly by nanofiltration membrane, wherein 90% or more magnesium ion is intercepted with sulfate radical,
Obtain secondary refining liquid and concentrated water, the concentrated water returns in lithium brine the dilution completed to lithium brine, while the lithium in concentrated water from
Son dilutes lithium brine by step (3) and is recycled, and in the secondary refining liquid, magnesium ion concentration is less than 1g/L；
(5) the secondary refining liquid is passed through into calcium ions and magnesium ions selectivity resin cation and dianion selective resin
Ion-exchanger removing calcium and magnesium and sulfate radical obtain refined liquid three times, and wherein calcium ions and magnesium ions and sulfate concentration are less than 20ppm；
(6) desalting chamber that the refined liquid three times is sent into bipolar membrane electrodialysis device refines three times under electric field force effect
Li in liquid+Alkali room, the OH generated with the water electrolysis by Bipolar Membrane are reached across anode membrane-Pairing forms lithium hydroxide solution,
X in refined liquid three times-Sour room, the H generated with the water electrolysis by Bipolar Membrane are reached across cavity block+Pairing forms HX solution；
The bipolar membrane electrodialysis device is five Room forms, and five Room is anode chamber, alkali room, sour room, desalting chamber and cathode
Room, wherein being pressed by extraordinary cation-exchange membrane, alkali room, Bipolar Membrane, sour room, anion-exchange membrane, desalting chamber, cation-exchange membrane
Sequentially multigroup superposition forms the film group of three Room forms, and anode plate is arranged in anode chamber, cathode plate is arranged in cathode chamber, in anode chamber
The film group is clamped between cathode chamber, to form bipolar membrane electrodialysis device；
During the continuous operation of the bipolar membrane electrodialysis device, there are four types of solution in bipolar membrane electrodialysis device respectively
Circular flow, four kinds of solution are respectively：Feed liquid, acid solution, lye and pole liquid, the feed liquid are the refined liquid three times,
Stabilization circulating of the feed liquid in the desalting chamber of the bipolar membrane electrodialysis device is realized by feed liquid equalizing and buffering slot
Row, while realizing that the continuous supplementation of reduction of feed volume is discharged with dilution balance；
Stabilization circular flow of the acid solution in the sour room of the bipolar membrane electrodialysis device is realized by acid solution equalizing and buffering slot,
The continuous supplementation for realizing acid solution amount simultaneously and the balance of concentrated acid liquid are discharged；
Stabilization circular flow of the lye in the alkali room of the bipolar membrane electrodialysis device is realized by lye equalizing and buffering slot,
The continuous supplementation and high alkali liquid balance for realizing lye amount simultaneously are discharged；
Directly using the high alkali liquid in the lye dashpot in lye equalizing and buffering slot as pole liquid, realize pole liquid described
It is molten to obtain lithium hydroxide from the lye dashpot overflow in addition for stabilization circular flow in the pole room of bipolar membrane electrodialysis device
Liquid；
(7) lithium hydroxide solution for obtaining the overflow carries out forced evaporation concentration by crystallizing evaporator, from described
The salt discharge angle of crystallizing evaporator is continuously discharged a hydronium(ion) lithia solid and evaporates the mixture of mother liquor, by the mixture mistake
Filter, respectively obtains a hydronium(ion) lithia solid and evaporation mother liquor, and the evaporation mother liquor is lithium hydroxide solution；
(8) LITHIUM BATTERY lithium hydroxide and washing lotion are formed by recrystallization the hydronium(ion) lithia solid by washing,
The washing lotion is lithium hydroxide solution；
(9) the evaporation mother liquor and the washing lotion are mixed into merga pass gas-liquid reactor, in the reactor with dioxy
Change carbon gas reaction and form lithium carbonate sediment, the lithium carbonate sediment is filtered, wash, is dried, LITHIUM BATTERY is obtained
Lithium carbonate.
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 lithium concentration is less than 150g with sulfate concentration product2/L2。
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, in step (4), selection has calcium ions and magnesium ions the NF membrane of iris action, and representative receives
Filter membrane includes the NF membrane with similar performance of DK films and the production of other companies, and primary purification liquid is made to enter nanofiltration device,
Mg/Li ratio is further decreased, secondary refining liquid is obtained, wherein for entering the primary purification liquid in NF membrane process unit, nanofiltration
Film concentrated water side magnesium ion concentration is less than 35g/L.
Further, in step (5), the bipolar membrane electrodialysis device is cationic friendship between anode chamber and cathode chamber
The film group for the three Room forms that film, alkali room, Bipolar Membrane, sour room, anion-exchange membrane, desalting chamber and cation-exchange membrane combine is changed,
In anode-side to being anode chamber, N × (alkali room+sour room+desalting chamber), cathode chamber between cathode side, wherein N is according to setting
Gas product flow readjustment is counted between 30-300,
Corrosion resistant extraordinary cation-exchange membrane is installed wherein between anode chamber and alkali room, is produced when to avoid anode reaction
Raw oxygen atom oxidation corrosion cation-exchange membrane and cause film damaged.
Further, it is provided with anode plate in the anode chamber of the bipolar membrane electrodialysis device, cathode is provided in cathode chamber
Plate,
The anode plate be titanium apply yttrium oxide material, the cathode plate be titanium or stainless steel,
The anode plate passes through cable connection to direct current by the anode of cable connection to DC power supply, the cathode plate
The cathode in source.
Further, the equalizing and buffering slot is double flute Parallel Design, and the double flute is compensating groove and dashpot, described flat
It is connected to by the trepanning of slot partition board bottom between weighing apparatus slot and the dashpot,
The top of the compensating groove is replenisher import, and the outlet at bottom pipe of the compensating groove connects circulating pump,
The top of the dashpot is circulation fluid import, and overflow is arranged at the top level of the dashpot and exports.
Further, the feed liquid is sent into feed liquid compensating groove, wherein top of the feed liquid by the feed liquid compensating groove
Import is continuously added to, and feed liquid is discharged by the bottom outlet of the feed liquid compensating groove, the feed liquid enters described double through feed pump supercharging
The desalting chamber of pole membrane electrodialysis device,
The feed liquid loses partial electrolyte in the desalting chamber of the bipolar membrane electrodialysis device, to obtain dilution,
The dilution is added by the jacking mouth of feed liquid dashpot, is entered feed liquid compensating groove by slot bottom trepanning, is formed feed liquid circulation,
With the addition of the feed liquid, the liquid level of feed liquid equalizing and buffering slot rises overally, and is returned by bipolar membrane electrodialysis device
The dilution overflows to acid solution compensating groove from the top spout hole of feed liquid dashpot.
Further, from the feed liquid dashpot overflow and come dilution continuously added by the jacking mouth of acid solution compensating groove
Enter,
Pickle in the acid solution compensating groove is entered by the bottom outlet of acid solution compensating groove through acid pump supercharging described bipolar
The sour room of membrane electrodialysis device,
In the sour room of the bipolar membrane electrodialysis device formed concentrated acid liquid, the concentrated acid liquid by acid solution dashpot jacking mouth
It is added, acid solution compensating groove is entered by slot bottom trepanning, forms acid cycle,
With the addition of dilution, the liquid level of acid solution equalizing and buffering slot rises overally, and the concentrated acid liquid is from acid solution dashpot
Liquid level spout hole overflow, then recycling use.
Further, it is continuously added to deionized water from the jacking mouth of lye compensating groove,
Sig water is discharged from the bottom outlet of the lye compensating groove, is pressurized through lye pump and enters the bipolar membrane electrodialysis
The alkali room of device,
High alkali liquid is formed in the alkali room of the bipolar membrane electrodialysis device, is added by the jacking mouth of lye dashpot, and
Lye compensating groove is entered by the bottom trepanning of lye dashpot, forms lye cycle,
With the addition of deionized water, the liquid level of lye equalizing and buffering slot rises overally, and the high alkali liquid is buffered from lye
The liquid level spout hole overflow of slot, subsequently into evaporization process.
Further, lithium hydroxide solution enters bipolar membrane electrodialysis by the bottom outlet of lye dashpot through the supercharging of pole liquid pump
The electrode chamber of device, pole liquid are returned by the jacking mouth of lye compensating groove, form pole liquid cycle.
Further, in step (7), the lithium hydroxide solution is evaporated concentration by crystallizing evaporator, from
The salt discharge angle of the crystallizing evaporator is discharged a hydronium(ion) lithia solid and evaporates the mixture of mother liquor,
By the mixture centrifugal filtration, a hydronium(ion) lithia solid and evaporation mother liquor are respectively obtained,
The one hydronium(ion) lithia solid is recrystallized by washing, one hydronium(ion) lithia of LITHIUM BATTERY is formed and washes
Liquid.
Further, by the evaporation mother liquor that centrifugal filtration is generated and the washing lotion that washing recrystallization process is generated, with two
Carbon oxide gas carries out carburizing reagent in gas-liquid reactor, reaction temperature control at 25 DEG C, the control of reaction end pH value 12,
Lithium carbonate sediment is formed,
The lithium carbonate sediment is washed, filtered and dried, battery-level lithium carbonate is formed.
Further, the base of the extraordinary cation-exchange membrane is manufactured by corrosion resistant material.
Further, the corrosion resistant material is polytetrafluoroethylene (PTFE).
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
Entrainment loss loses further to concentrate with sedimentation.
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 lithium concentration is less than 150g with sulfate concentration product2/L2, to ensure the salt pan lithium under the conditions of potassium lithium coproduction
Ion yield.
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 2g/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, and mother liquid of boric acid is used back to recycling before acidification, while being diluted to boron lithium brine.
Acidification is with boron extraction technology flow referring to Fig. 1.
(3) lithium brine selects electric dialyzator to form primary purification liquid by ion
The lithium brine after boron is carried, under the dilution that rear end nanofiltration technique returns to concentrated water, magnesium ion concentration is in 50~100g/L
Between, between 0.1~0.4g/L of boron content, lithium concentration is between 0.3~6g/L.This brine is very suitable for electrodialysis work
Skill.Ion-selective membrane has a good interception effect to boron, and boron content is relatively low in lithium brine, does not interfere with filtering and electrodialysis
Journey.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 forms secondary refining liquid by nanofiltration device demagging
In primary purification liquid after ion selects electrodialysis process, lithium concentration is higher than 10g/L, magnesium ion concentration
Less than 10g/L.Because the magnesium ion concentration of primary purification liquid be less than 15g/L, it is possible to directly by nanofiltration membrane without
A large amount of water consumptions are needed to dilute.Primary purification liquid passes through nanofiltration device pressure filtration, and NF membrane has good magnesium ion and sulfate radical
Interception effect, interception rate is 90% or more.Nanofiltration device produces water side magnesium ion and is less than 1g/L.
In nanofiltration device concentrated water side, there is the lithium concentration being about equal in primary purification liquid, magnesium ion concentration is because of quilt
It effectively intercepts and doubles.In nanofiltration process, primary purification liquid is pressurized to 1.8MPa by high-pressure pump and enters nano filter membrance device, allows one
Magnesium ion in secondary refined liquid is concentrated to three times.For primary purification liquid when passing through nanofiltration device, producing water ratio is about 66.6%, produces water
As secondary refining liquid.Concentrated water rate is about 33.3%, and nanofiltration device concentrated water is all returned to technique (3) leading portion, with lithium brine into
Row dilution configuration.
(5) secondary refining liquid forms refined liquid three times by ion exchange
In secondary refining liquid, lithium concentration about 11g/L, magnesium ion concentration is less than 1g/L, and sulfate concentration is less than
0.03g/L.This solution directly carries out ionic adsorption by chelating resin to calcium ions and magnesium ions.Secondary refining liquid after mixed bed,
Calcium ions and magnesium ions are less than 20ppm, form refined liquid three times.
(6) refined liquid obtains a hydronium(ion) lithia solid and evaporation mother liquor by bipolar membrane electrodialysis device three times
The refined liquid three times is sent into the desalting chamber of bipolar membrane electrodialysis device, under electric field force effect, refined liquid three times
In Li+Alkali room, the OH generated with the water electrolysis by Bipolar Membrane are reached across anode membrane-It matches and forms lithium hydroxide solution, three
X in secondary refined liquid-Sour room, the H generated with the water electrolysis by Bipolar Membrane are reached across cavity block+Pairing forms HX solution；
The bipolar membrane electrodialysis device is five Room forms, and five Room is anode chamber, alkali room, sour room, desalting chamber and cathode
Room, wherein being pressed by extraordinary cation-exchange membrane, alkali room, Bipolar Membrane, sour room, anion-exchange membrane, desalting chamber, cation-exchange membrane
Sequentially multigroup superposition forms the film group of three Room forms, and anode plate is arranged in anode chamber, cathode plate is arranged in cathode chamber, in anode chamber
The film group is clamped between cathode chamber, to form bipolar membrane electrodialysis device；
During the continuous operation of the bipolar membrane electrodialysis device, there are four types of solution in bipolar membrane electrodialysis device respectively
Circular flow, four kinds of solution are respectively：Feed liquid, acid solution, lye and pole liquid, the feed liquid are the refined liquid three times,
Stabilization circulating of the feed liquid in the desalting chamber of the bipolar membrane electrodialysis device is realized by feed liquid equalizing and buffering slot
Row, while realizing that the continuous supplementation of reduction of feed volume is discharged with dilution balance；
Stabilization circular flow of the acid solution in the sour room of the bipolar membrane electrodialysis device is realized by acid solution equalizing and buffering slot,
The continuous supplementation for realizing acid solution amount simultaneously and the balance of concentrated acid liquid are discharged；
Stabilization circular flow of the lye in the alkali room of the bipolar membrane electrodialysis device is realized by lye equalizing and buffering slot,
The continuous supplementation and high alkali liquid balance for realizing lye amount simultaneously are discharged；
Directly using the high alkali liquid in the lye dashpot in lye equalizing and buffering slot as pole liquid, realize pole liquid described
It is molten to obtain lithium hydroxide from the lye dashpot overflow in addition for stabilization circular flow in the pole room of bipolar membrane electrodialysis device
Liquid.
(7) lithium hydroxide solution is obtained into a hydronium(ion) lithia solid and evaporation mother liquor by crystallizing evaporator
The lithium hydroxide solution that the overflow is obtained carries out forced evaporation concentration by crystallizing evaporator, from the evaporation
The salt discharge angle of crystallizer is continuously discharged a hydronium(ion) lithia solid and evaporates the mixture of mother liquor, and the mixture is filtered,
A hydronium(ion) lithia solid and evaporation mother liquor are respectively obtained, the evaporation mother liquor is lithium hydroxide solution.
(8) LITHIUM BATTERY lithium hydroxide and washing lotion are formed by recrystallization the hydronium(ion) lithia solid by washing,
The washing lotion is lithium hydroxide solution.
(9) the evaporation mother liquor and the washing lotion are mixed into merga pass gas-liquid reactor, in the reactor with dioxy
Change carbon gas reaction and form lithium carbonate sediment, the lithium carbonate sediment is filtered, wash, is dried, LITHIUM BATTERY is obtained
Lithium carbonate.
Advantageous effect
(1) present invention has good operability；
(2) separating magnesium and lithium technology of the invention is one kind high efficiency extraction lithium hydroxide and carbonic acid from high Mg/Li ratio brine
The technique of lithium；
(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 LITHIUM BATTERY lithium hydroxide and lithium carbonate, but be not intended to its into
Row limits.
Fig. 1 is existing acidification and boron extraction technology flow chart；
Fig. 2 is that ion selects electrodialysis separating magnesium and lithium schematic diagram；
Fig. 3 is the process flow chart of the present invention；
Fig. 4 is the schematic diagram of the bipolar membrane electrodialysis device of the present invention；And
Fig. 5 is the work sheet of the bipolar membrane electrodialysis device of the present invention.
Wherein, reference numeral：
1：Anode chamber
2：Cathode chamber
3：Sour room
4：Desalting chamber
5：Alkali room
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 0.3g/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 9g/L in boric acid solution；The light phase of generation is unloaded extractant, unloaded extractant
It returns to centrifugal extractor and realizes recycling.Boric acid solution and thick boric acid are dissolved by heating, boric acid saturated solution, mistake are formed
After filter, the smart boric acid product of 99% or more purity is obtained by crystallisation by cooling.
(3) electrodialysis ion selection separation
Lithium brine concentrated water caused by back segment nanofiltration process is diluted, subsequently into the electrodialysis equipped with ion-selective membrane
The dilution side of equipment, fresh water enter the concentration side of electrodialysis plant.Ion-selective membrane be preferably ASTOM companies K-192 with
ACS-8T films.Lithium brine is in diluting side, and monovalent ion reaches concentration side under electric field force effect across ion-selective membrane, dense
Contracting side forms primary purification liquid.In the primary purification liquid, lithium concentration 12g/L, magnesium ion concentration 8g/L.Dilution
In liquid, lithium concentration 0.2g/L, magnesium ion concentration 60g/L.
(4) primary purification liquid forms secondary refining liquid after nanofiltration membrane
Primary purification liquid is pressurized to 2MPa by high-pressure pump, subsequently into nano filter membrance device.NF membrane preferably uses GE
The DK series membranes of company.The concentrated water rate of discharge for controlling nanofiltration equipment forms two parts of production water and portion is dense by three times concentration operation
Water.Concentrated water and the lithium concentration in production water are close, all in 12g/L or so.Magnesium ion concentration 24g/L in concentrated water, is discharged to lithium outside
It is diluted in concentraing pond.It is 0.3g/L, sulfate ion 0.06g/L to produce magnesium ion concentration in water.It is secondary fine to produce water
Liquid processed.
(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, liquid is after gained absorption
Lithium chloride solution.
(6) bipolar membrane electrodialysis technique
So that the lithium chloride solution of 2mol/l is passed through bipolar membrane electrodialysis device, forms the hydrochloric acid solution and 2mol/l of 2mol/l
Lithium hydroxide solution.Wherein hydrochloric acid solution returns in the hydrochloric acid solution of front (2) step, and lithium hydroxide solution enters MVR steamings
Send out crystallization processes.
(7) MVR (mechanical vapor recompression evaporator) evaporative crystallization technique
The lithium hydroxide solution of 2mol/l is set to pass through MVR evaporators, condensing crystallizing is formed in the vaporization chamber of MVR evaporators
One hydronium(ion) lithia.The solidliquid mixture of one hydronium(ion) lithia is discharged by the salt discharge angle of vaporization chamber bottom, by from
The heart filters to form a hydronium(ion) lithia filtrate and lithium hydroxide mother liquor.Lithium hydroxide mother liquor is used for backend process, production electricity
Pond level lithium carbonate.
The washing of (8) one hydronium(ion) lithias recrystallizes
One hydronium(ion) lithia filtrate is added in heating reaction kettle, and quantitative deionized water is added, is dissolved by heating
And agitator treating, it is then cooled down and is recrystallized by crystallizer, then filtered, formed and refine a hydronium(ion) lithia and lithium hydroxide
Washing lotion.A refined hydronium(ion) lithia is formed into LITHIUM BATTERY lithium hydroxide by drying, packaging.After lithium hydroxide washing lotion is used for
End technique produces battery-level lithium carbonate.
(9) lithium hydroxide solution is carbonized to form lithium carbonate
Lithium hydroxide mother liquor formed in MVR evaporative crystallization techniques is mixed to form lithium hydroxide with lithium hydroxide washing lotion
Lithium hydroxide solution and carbon dioxide gas are formed crystallization of lithium carbonate object by solution by gas-liquid reactor, by centrifugal filtration,
Form lithium carbonate filtrate and tail washings.Lithium carbonate filtrate is washed, dried, is packed, battery-level lithium carbonate is formed.Tail washings
Into comprehensive utilization process.
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 concentrated water caused by back segment nanofiltration process is diluted, subsequently into the electricity equipped with ion-selective membrane
The dilution side of electrodialysis equipment, fresh water enter the concentration side of electrodialysis plant.Ion-selective membrane is preferably the K-192 of ASTOM companies
With ACS-8T ion-selective membranes.In diluting side, monovalent ion reaches under electric field force effect across ion-selective membrane lithium brine
Concentration side forms primary purification liquid in concentration side.In the primary purification liquid, lithium concentration 11g/L, magnesium ion concentration
For 7g/L.In dilution, lithium concentration 0.2g/L, magnesium ion concentration 60g/L.
(4) primary purification liquid forms secondary refining liquid after nanofiltration membrane
Primary purification liquid is pressurized to 2.5MPa by high-pressure pump, subsequently into nano filter membrance device, NF membrane preferably uses
The DK series membranes of GE companies.The concentrated water rate of discharge for controlling nanofiltration equipment, by 3 times of concentration operations.Concentrated water with production water in lithium from
Sub- concentration is close, all in 11g/L or so.
Magnesium ion concentration is 21g/L in concentrated water, is discharged to outside in lithium concentraing pond and forms dilution.Magnesium ion concentration is in production water
0.3g/L, sulfate ion 0.06g/L.It is secondary refining liquid to produce water.
(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) bipolar membrane electrodialysis technique
So that the lithium chloride solution of 2mol/l is passed through bipolar membrane electrodialysis device, forms the hydrochloric acid solution and 2mol/l of 2mol/l
Lithium hydroxide solution.Wherein hydrochloric acid solution returns in the hydrochloric acid solution of front (2) step, and lithium hydroxide solution enters MVR steamings
Send out crystallization processes.
(7) MVR (mechanical vapor recompression evaporator) evaporative crystallization technique
The lithium hydroxide solution of 2mol/l is set to pass through MVR evaporators, condensing crystallizing is formed in the vaporization chamber of MVR evaporators
One hydronium(ion) lithia.The solidliquid mixture of one hydronium(ion) lithia is discharged by the salt discharge angle of vaporization chamber bottom, by from
The heart filters to form a hydronium(ion) lithia filtrate and lithium hydroxide mother liquor.Lithium hydroxide mother liquor is used for backend process, production electricity
Pond level lithium carbonate.
The washing of (8) one hydronium(ion) lithias recrystallizes
One hydronium(ion) lithia filtrate is added in heating reaction kettle, and quantitative deionized water is added, is dissolved by heating
And agitator treating, it is then cooled down and is recrystallized by crystallizer, then filtered, formed and refine a hydronium(ion) lithia and lithium hydroxide
Washing lotion.A refined hydronium(ion) lithia is formed into LITHIUM BATTERY lithium hydroxide by drying, packaging.After lithium hydroxide washing lotion is used for
End technique produces battery-level lithium carbonate.
(9) lithium hydroxide solution is carbonized to form lithium carbonate
Lithium hydroxide mother liquor formed in MVR evaporative crystallization techniques is mixed to form lithium hydroxide with lithium hydroxide washing lotion
Lithium hydroxide solution and carbon dioxide gas are formed crystallization of lithium carbonate object by solution by gas-liquid reactor, by centrifugal filtration,
Form lithium carbonate filtrate and tail washings.Lithium carbonate filtrate is washed, dried, is packed, battery-level lithium carbonate is formed.Tail washings
Into comprehensive utilization process.
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 (18)
1. a kind of method for directly producing lithium hydroxide and lithium carbonate from salt lake brine with high magnesium-lithium ratio, including following technique step
Suddenly：
(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) primary purification liquid is directly obtained by nanofiltration membrane wherein 90% or more magnesium ion is intercepted with sulfate radical
Secondary refining liquid and concentrated water, the concentrated water returns in lithium brine the dilution completed to lithium brine, while the lithium ion in concentrated water is logical
It crosses step (3) dilution lithium brine to be recycled, in the secondary refining liquid, magnesium ion concentration is less than 1g/L；
(5) the secondary refining liquid is passed through into calcium ions and magnesium ions selectivity resin cation and dianion selective resin ion
Exchanger removing calcium and magnesium and sulfate radical, obtain refined liquid three times, and wherein calcium ions and magnesium ions and sulfate concentration are less than 20ppm, and described three
Secondary refined liquid is feed liquid, is indicated with LiX, and wherein X indicates the anion of refined liquid three times；
(6) refined liquid three times is sent into the desalting chamber of bipolar membrane electrodialysis device, under electric field force effect, three times in refined liquid
Li+Alkali room, the OH generated with the water electrolysis by Bipolar Membrane are reached across anode membrane-Pairing forms lithium hydroxide solution, three times
X in refined liquid-Sour room, the H generated with the water electrolysis by Bipolar Membrane are reached across cavity block+Pairing forms HX solution；
The bipolar membrane electrodialysis device be five Room forms, five Room be anode chamber, alkali room, sour room, desalting chamber and cathode chamber,
In by extraordinary cation-exchange membrane, alkali room, Bipolar Membrane, sour room, anion-exchange membrane, desalting chamber, cation-exchange membrane in order
Multigroup superposition forms the film group of three Room forms, and anode plate is arranged in anode chamber, cathode plate is arranged in cathode chamber, in anode chamber and the moon
The film group is clamped between pole room, to form bipolar membrane electrodialysis device；
During the continuous operation of the bipolar membrane electrodialysis device, recycled in bipolar membrane electrodialysis device there are four types of solution respectively
Operation, four kinds of solution are respectively：Feed liquid, acid solution, lye and pole liquid,
Stabilization circular flow of the feed liquid in the desalting chamber of the bipolar membrane electrodialysis device is realized by feed liquid equalizing and buffering slot, together
The continuous supplementation of Shi Shixian reduction of feed volume is discharged with dilution balance；
Stabilization circular flow of the acid solution in the sour room of the bipolar membrane electrodialysis device is realized by acid solution equalizing and buffering slot, simultaneously
The continuous supplementation for realizing acid solution amount and the balance of concentrated acid liquid are discharged；
Stabilization circular flow of the lye in the alkali room of the bipolar membrane electrodialysis device is realized by lye equalizing and buffering slot, simultaneously
The continuous supplementation and high alkali liquid balance for realizing lye amount are discharged；
Directly using the high alkali liquid in the lye dashpot in lye equalizing and buffering slot as pole liquid, realize pole liquid described bipolar
Stabilization circular flow in the pole room of membrane electrodialysis device obtains lithium hydroxide solution from the lye dashpot overflow in addition；
(7) lithium hydroxide solution for obtaining the overflow carries out forced evaporation concentration by crystallizing evaporator, from the evaporation
The salt discharge angle of crystallizer is continuously discharged a hydronium(ion) lithia solid and evaporates the mixture of mother liquor, and the mixture is filtered,
A hydronium(ion) lithia solid and evaporation mother liquor are respectively obtained, the evaporation mother liquor is lithium hydroxide solution；
(8) LITHIUM BATTERY lithium hydroxide and washing lotion are formed by recrystallization the hydronium(ion) lithia solid by washing, it is described
Washing lotion is lithium hydroxide solution；
(9) the evaporation mother liquor and the washing lotion are mixed into merga pass gas-liquid reactor, in the reactor with carbon dioxide
Gas reaction forms lithium carbonate sediment, and the lithium carbonate sediment is filtered, wash, is dried, LITHIUM BATTERY carbonic acid is obtained
Lithium.
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, lithium concentration and sulfate concentration product
Less than 150g2/L2。
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 (4), selection has iris action to calcium ions and magnesium ions
NF membrane makes primary purification liquid enter nanofiltration device, further decreases Mg/Li ratio, obtains secondary refining liquid, wherein for entering
Primary purification liquid in NF membrane process unit, NF membrane concentrated water side magnesium ion concentration are less than 35g/L.
8. according to the method described in claim 1, the wherein described bipolar membrane electrodialysis device is sun between anode chamber and cathode chamber
The three Room forms that amberplex, alkali room, Bipolar Membrane, sour room, anion-exchange membrane, desalting chamber and cation-exchange membrane combine
Film group,
In anode-side to being anode chamber, N × (alkali room+sour room+desalting chamber), cathode chamber between cathode side, wherein N is according to design production
Amount adjusts between 30-300,
Corrosion resistant extraordinary cation-exchange membrane is installed wherein between anode chamber and alkali room, is generated when to avoid anode reaction
Oxygen atom oxidation corrosion cation-exchange membrane and cause film damaged.
9. cloudy according to the method described in claim 1, be provided with anode plate in the anode chamber of the wherein described bipolar membrane electrodialysis device
Cathode plate is provided in pole room,
The anode plate be titanium apply yttrium oxide material, the cathode plate be titanium or stainless steel,
The anode plate arrives DC power supply by the anode of cable connection to DC power supply, the cathode plate by cable connection
Cathode.
10. according to the method described in claim 1, the wherein described equalizing and buffering slot is double flute Parallel Design, the double flute is flat
Weigh slot and dashpot, is connected to by the trepanning of slot partition board bottom between the compensating groove and the dashpot,
The top of the compensating groove is replenisher import, and the outlet at bottom pipe of the compensating groove connects circulating pump,
The top of the dashpot is circulation fluid import, and overflow is arranged at the top level of the dashpot and exports.
11. according to the method described in claim 10, wherein by the feed liquid be sent into feed liquid compensating groove in, wherein the feed liquid by
The jacking mouth of the feed liquid compensating groove is continuously added to, and feed liquid is discharged by the bottom outlet of the feed liquid compensating groove, the feed liquid is through material
Liquid pump supercharging enters the desalting chamber of the bipolar membrane electrodialysis device,
The feed liquid loses partial electrolyte in the desalting chamber of the bipolar membrane electrodialysis device, described to obtain dilution
Dilution is added by the jacking mouth of feed liquid dashpot, is entered feed liquid compensating groove by slot bottom trepanning, is formed feed liquid circulation,
With the addition of the feed liquid, the liquid level of feed liquid equalizing and buffering slot rises overally, returned by bipolar membrane electrodialysis device described in
Dilution overflows to acid solution compensating groove from the top spout hole of feed liquid dashpot.
12. according to the method for claim 11, wherein from the feed liquid dashpot overflow and come dilution by acid solution
The jacking mouth of compensating groove is continuously added to,
Pickle in the acid solution compensating groove, which is pressurized by the bottom outlet of acid solution compensating groove through acid pump, enters Bipolar Membrane electricity
The sour room of dialyzer,
Concentrated acid liquid is formed in the sour room of the bipolar membrane electrodialysis device, the concentrated acid liquid is added by the jacking mouth of acid solution dashpot
Enter, acid solution compensating groove entered by slot bottom trepanning, forms acid cycle,
With the addition of dilution, the liquid level of acid solution equalizing and buffering slot rises overally, liquid of the concentrated acid liquid from acid solution dashpot
Position spout hole overflow, then recycling use.
13. according to the method for claim 11, wherein being continuously added to deionized water from the jacking mouth of lye compensating groove,
Sig water is discharged from the bottom outlet of the lye compensating groove, is pressurized through lye pump and enters the bipolar membrane electrodialysis device
Alkali room,
High alkali liquid is formed in the alkali room of the bipolar membrane electrodialysis device, is added by the jacking mouth of lye dashpot, and by alkali
The bottom trepanning of liquid dashpot enters lye compensating groove, forms lye cycle,
With the addition of deionized water, the liquid level of lye equalizing and buffering slot rises overally, and the high alkali liquid is from lye dashpot
Liquid level spout hole overflow, subsequently into evaporization process.
14. the method according to claim 11, wherein lithium hydroxide solution are by the bottom outlet of lye dashpot through pole liquid pump
Supercharging is into the electrode chamber of bipolar membrane electrodialysis device, and pole liquid is by the jacking mouth return of lye compensating groove, formation pole liquid cycle.
15. according to the method described in claim 1, wherein in step (7), the lithium hydroxide solution is passed through into evaporative crystallization
Device is evaporated concentration, and a hydronium(ion) lithia solid is discharged from the salt discharge angle of the crystallizing evaporator and evaporates the mixing of mother liquor
Object,
By the mixture centrifugal filtration, a hydronium(ion) lithia solid and evaporation mother liquor are respectively obtained,
The one hydronium(ion) lithia solid is recrystallized by washing, forms one hydronium(ion) lithia of LITHIUM BATTERY and washing lotion.
16. according to the method for claim 15, wherein evaporation mother liquor that centrifugal filtration is generated and washing were recrystallized
The washing lotion that journey is generated carries out carburizing reagent with carbon dioxide gas in gas-liquid reactor, and reaction temperature is controlled at 25 DEG C, instead
It answers endpoint pH control 12, forms lithium carbonate sediment,
The lithium carbonate sediment is washed, filtered and dried, battery-level lithium carbonate is formed.
17. according to the method described in claim 1, the base of the wherein described extraordinary cation-exchange membrane is corrosion resistant material institute
Manufacture.
18. according to the method for claim 17, wherein the corrosion resistant material is polytetrafluoroethylene (PTFE).
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| ARP170101438A AR108604A1 (en) | 2017-01-24 | 2017-05-26 | METHOD FOR PREPARING LITHIUM HYDROXIDE AND LITHIUM CARBONATE DIRECTLY FROM SALMUERA SALAR WITH HIGH PROPORTION OF MAGNESIUM-LITHIUM |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
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