CN103924258B - The method utilizing salt lake bittern electrolytic preparation lithium hydroxide - Google Patents
The method utilizing salt lake bittern electrolytic preparation lithium hydroxide Download PDFInfo
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Abstract
The invention discloses a kind of method utilizing salt lake bittern electrolytic preparation lithium hydroxide, said method comprising the steps of: 1) the original salt lake bittern of lithium will be contained concentrated by salt pan solar evaporation, obtain high Mg/Li ratio bittern；2) high Mg/Li ratio bittern is obtained refined bittern through removal of impurities；3) it is electrolysed as catholyte as anolyte, lithium hydroxide solution using refined bittern, obtains lithium hydroxide monohydrate solution by cationic membrane at cathode chamber；4) lithium hydroxide monohydrate solution is dried through evaporation and concentration, crystallisation by cooling, washing, obtains lithium hydroxide monohydrate.Product purity height of the present invention, low cost, the yield height of lithium, technique are simple and easy to control.
Description
Technical field
The invention belongs to electrolytic preparation lithium hydroxide field, in particular it relates to one utilizes salt lake bittern electricity
Solution prepares the method for lithium hydroxide.
Background technology
Lithium is one of important strategic resource, has important strategic importance in national defense industry and country's development in Hi-Tech.
China is the country that a salt lake distributed pole is wide, and saline lake lithium resource is abundanter, only in the Yanhu District in Qinghai, and just storage
Deposit the lithium chloride of up to ten million ton, accelerate lithium resource exploitation, improve lithium level of industry, be China's present stage lithium industry
A brand new content in developing rapidly and urgently studying.
Lithium hydroxide, as one of preliminary working lithium product important in lithium and compound thereof, can be further used as producing vinegar
The products such as acid lithium, lithium fluoride, lithium bromide, lithium chloride, lithium nitrate and lithium benzoate.It is currently used primarily in lithium Ji Run
The aspects such as consistent lubricant, the electrolyte of alkaline storage battery and lithium bromide refrigerator absorbing liquid.The lithium base produced with lithium hydroxide
Lubricating grease, with potassium, sodium, calcium base class lubricating grease compared with, there is antioxygen, pressure, greasy property good, particularly
Operating temperature width, stable performance during heating for multiple times-cooling-heat cycles, service life is long, and water-resistance is strong, at-60 DEG C～
At 300 DEG C, lubricating grease viscosity changes hardly, even in the presence of a small amount of water, remains in that the most stable profit
Sliding characteristic, is widely used in military equipment, aircraft, automobile, rolling mill and the lubrication of various mechanical driving part,
And radio detection device, precision instrument etc., under the adverse weather condition such as be particularly applied to extremely to tremble with fear, extremely hot；
In battery industry, make an addition to lithium hydroxide, in the electrolyte of alkaline storage battery, Ni-MH battery, electricity to be extended
Pond life-span, increase charge capacity.
In addition, organic synthesis and the heat carrier of pharmacy, reagent and nuclear reactor and the guarantor of metal surface it are additionally operable to
Protect agent；The aspects such as material used in breathing gas cleaning system in space vehicle, submarine and rebreather.Cause
This, research and development purity is high, technique LiOH production method simple, eco-friendly has important practical significance and
Vast potential for future development.
United States Patent (USP) US3597340 provides one diaphragm process and produces lithium hydroxide, is by through being concentrated by evaporation
Natural bittern after purification (main containing LiCl and NaCl, the percentage composition of lithium chloride 8%～30%, its quality
Percentage composition is greater than the weight/mass percentage composition of sodium chloride) inject in diaphragm cell, add direct current at suitable electricity
Being electrolysed in the range of current voltage, electrolysis can only make partial oxidation lithium convert, and NaCl therein is on electrolysis not impact.
Then according to LiOH H2The O solubility in the LiCl and NaCl solution of different content at a certain temperature
Different and crystallization, through separation of solid and liquid, washing, the available purer lithium hydroxide product of recrystallization.
United States Patent (USP) US4036713 first concentrated brine makes lithium content reach 2%～7%, beyond precipitate and separate lithium
Alkali and alkaline earth metal ions；The most stoichiometrically add lithium hydroxide and Lithium carbonate solution adjustment brine ph is
10.5～11.5 precipitations remove magnesium, calcium, iron plasma, are neutralized with hydrochloric acid and obtain refined bittern；Using refined bittern as
Anolyte, water or lithium hydroxide solution are that catholyte is electrolysed, and have cation selective in electrolytic cell
Property permeable membrane, isolation catholyte and anolyte, the lithium ion in anolyte is logical under the function of current
Cross film and move in catholyte and be combined with hydroxide ion and generate lithium hydroxide, concentrated, recrystallization
The available impurity content lithium hydroxide monohydrate less than 0.5%.
United States Patent (USP) US20110044882 is selected suitable method to remove or reduces the boron in bittern, magnesium, calcium, sulphur
Acid group and sodium, potassium plasma are (as removed the boron in bittern with acidifying or organic extractant or ion exchange resin；
Add lime or white lime and remove magnesium by reaction；Use oxalic acid precipitation calcium；With barium salt precipitated sulfur acid group, evaporate dense
Contracting removes sodium salt and sylvite), the most stoichiometrically add lithium hydroxide and Lithium carbonate solution adjustment brine ph is
10.5～11.5, precipitation removes magnesium, calcium plasma, then is exchanged the content reducing calcium, magnesium ion further by ion,
Make calcium, magnesium ion total content less than 150ppb.Continuing concentrated brine makes the mass fraction of lithium reach 2%～7%,
Sodium, potassium precipitate in a chloride-form and are removed, and obtain refined bittern.
In electrolytic process, anolyte is refined bittern, and catholyte is water or LiOH solution；Use English
Man of great strength's chlor-alkali FM1500 one pole film, cation can pass through film, and anion is blocked from passing through.After powering up,
Chloride ion transport in anolyte loses electric charge to anode and produces chlorine, lithium ion enter cathode chamber and with the moon
The hydroxide ion that extremely indoor water is ionized into is combined into product lithium hydroxide, finally, the chlorine in anolyte
Changing lithium and be transformed into lithium hydroxide in catholyte, electrolysis can be with ongoing operation until the concentration of lithium hydroxide reaches
14% or close to saturated concentration.The available highly purified monohydrate lithium hydroxide of concentrated, crystallization.
Japan Patent JP54043174 provides a kind of method being electrolysed lithium sulfate production lithium hydroxide, is by lithium sulfate
Solution is electrolysed as catholyte as anolyte, water in membrane electrolysis cells device, wherein anolyte and the moon
With fluorine-containing cation exchange membrane between the electrolyte of pole, decomposition voltage is 3～6V, and current density is 1～100A/dm2,
Mass concentration can be obtained at negative electrode and be about the lithium hydroxide solution of 5%～10%, sulfuric acid can be obtained at anode molten simultaneously
Liquid.
Xu Ying et al. with providing a kind of method that three Room membrane electrolysis are prepared lithium hydroxide by lithium sulfate, the method
Experimental study is at the early-stage, and current efficiency is the highest by only 66.74%, and more influence factors and industrialization produce and need to be continued
Continuous research.
Lithium hydroxide is one of preliminary working lithium product important in lithium and compound thereof, the side of domestic production lithium hydroxide
Method has: the lime burning method used for raw material with lepidolite；The sodium carbonate pressurization leaching used for raw material with spodumene
Follow the example of.Although the two production method mature technical route, technological process is simple, but material circulation is big, energy consumption
Greatly, cost is high, environmental pollution ratio is more serious, and product quality is difficult to reach top grade standard.With lithium carbonate as raw material
Causticizing process is the main method the most abroad producing lithium hydroxide, by calcium hydroxide and lithium carbonate
Between water causticizing reaction and prepare.In this causticizing process product, calcium impurities content is high, it is difficult to remove thoroughly, serious shadow
Ringing product purity, additionally, this method purifying process is loaded down with trivial details, equipment investment is high, and production cost is higher.Use calcination method
The lithium hydroxide produced, although the impurity such as boron, magnesium can be removed in calcination process, improve the pure of lithium hydroxide
Degree, but content of magnesium makes this technological process complicated, and equipment corrosion is serious, and evaporated water is big, and energy consumption is high.
The research of Electrowinning lithium hydroxide technology is started to walk relatively early by foreign scholar, but tempo is slow.Through three
The time of more than ten years, the external main method producing lithium hydroxide still uses lithium carbonate causticizing process, world lithium salts grand duke
Department does not the most apply the method in the industrialized production of production LiOH.United States Patent (USP) US20110044882
It is the refinement of United States Patent (USP) US4036713, although cause electrolysis bittern and produce the attention of lithium hydroxide, and many
Individual national applications patent, each operating condition scope reduces further, but just for content of magnesium than relatively low bittern,
And the subtractive process of bittern is more complicated, current efficiency is low, uses ionic membrane costly, cost ratio
Higher.The method that electrolysis lithium sulfate produces lithium hydroxide, current efficiency is low, and energy consumption is high, and electric current is imitated by foreign ion
Rate, voltage, the impact of energy consumption need to continue to optimize.
Summary of the invention
It is an object of the invention to, it is provided that a kind of method utilizing salt lake bittern electrolytic preparation lithium hydroxide, the method
The product purity of preparation is high, low cost, and yield is high, and technique is simple.
For reaching above-mentioned purpose, present invention employs following technical scheme:
A kind of method utilizing salt lake bittern electrolytic preparation lithium hydroxide, said method comprising the steps of:
1) the original salt lake bittern of lithium will be contained concentrated by salt pan solar evaporation, obtain high Mg/Li ratio bittern；
2) high Mg/Li ratio bittern is obtained refined bittern through removal of impurities；
3) it is electrolysed as catholyte as anolyte, lithium hydroxide solution using refined bittern, passes through cationic membrane
Lithium hydroxide monohydrate solution is obtained at cathode chamber；
4) lithium hydroxide monohydrate solution is dried through evaporation and concentration, crystallisation by cooling, washing, obtains lithium hydroxide one
Hydrate, the mother liquor obtained after crystallisation by cooling is circulated electrolysis or for high Mg/Li ratio bittern as electrolysis cathode liquid
Removal of impurities regulates the pH of solution.
Preferably, described step 2) dedoping step be: first adjust its acid-base value with hydrochloric acid so that it is pH value protect
Holding 1.5～2.5, the boron ion in bittern separates out as boric acid, is proportionally added into lime or ripe after separation of solid and liquid
Lime, is sufficiently stirred for, is filtered to remove magnesium ion and sulfate radical, obtains the electrolysis material liquid of low boron, low-sulfur；
Then at temperature 50～70 DEG C, use two-step method demagging, first adjust the pH of electrolysis material liquid with lithium hydroxide
Being 8.5～9.5, the magnesium hydroxide of generation is combined the boron ion in positively charged adsorbent solution with the magnesium ion of excess, Gu
Liquid is separated off magnesium ion；Then by step 4) mother liquor that obtains after crystallisation by cooling and/or Lithium carbonate solution adjust molten
The pH of liquid is 11.5～12.5, removes magnesium ion, calcium ion and the iron ion of residual in solution, is neutralized with hydrochloric acid this
Solution, neutralizer is concentrated into lithium ion mass fraction and is higher than 3.6%, now, sodium chloride and potassium chloride Precipitation,
Remove precipitation and obtain the lithium chloride mass fraction refined bittern more than 22%.
Preferably, described step 3) ionization process be: selecting domestic cationic membrane and electrolytic cell, anolyte is essence
Brewed brine water, its lithium chloride mass fraction is more than 22%, and catholyte is lithium hydroxide solution, and its lithium hydroxide quality is divided
Number is less than 3%, and current density is 1.0～2.4kA/m2, electrolysis temperature >=55 DEG C, average working voltage is 3.0～3.4V,
The hydrogen of electrolysis generation and chlorine are as byproduct.
The hydrogen that the chlorine that described electrolysis produces and electrolysis produce reacts generation hydrochloric acid, or the chlorine that electrolysis produces passes through
Liquefaction obtains liquid chlorine.
Preferably, described step 4) process be: it is the most heated that electrolysis reaches the catholyte of nearly saturated concentration
Being concentrated by evaporation and separate out lithium hydroxide solid, solidliquid mixture is cooled to 30～50 DEG C of crystallizations, vacuum filters or centrifugal
Separate, obtain lithium hydroxide monohydrate, scrubbed, be dried to obtain lithium hydroxide monohydrate at 60～90 DEG C and contain
The amount lithium hydroxide monohydrate product more than 99.8%.
The high Mg/Li ratio bittern that salt pan solar evaporation is concentrated to give by the present invention passes through a series of dedoping step, obtains
Refined bittern (mainly containing LiCl, mass fraction is more than 22%), impurity ion content is (Mg+Ca)≤1ppm,
NaCl%≤5% (wt%).
The present invention is using refined bittern as anolyte, and certain density lithium hydroxide solution is electrolysed as catholyte,
By the selective penetrated property of cationic membrane, obtaining lithium hydroxide monohydrate solution at cathode chamber, catholyte is through evaporation
Concentration, crystallisation by cooling, washing are dried, available lithium hydroxide monohydrate product, and product purity is more than 99.8%,
Lithium yield is close to 100%.
The present invention with lithium hydroxide adjust solution pH 8.5～9.5, the magnesium hydroxide of generation with excess magnesium ion
In conjunction with the boron ion in positively charged adsorbent solution, separation of solid and liquid can remove most magnesium.
The present invention can also utilize effects of boron resin and magnesium, the ion exchange resin of calcium removes the boron ion in solution,
Magnesium ion and calcium ion.
The present invention adds direct current and is electrolysed, and electrolytic anode liquid is ionized into Li in a cell+And Cl-, wherein Li+?
Under charge effect, moving to cathode chamber by having selective cationic membrane, the Cl-stayed is in anode electrolysis effect
Lower generation chlorine.Water power in cathode chamber is from becoming H+And OH-, wherein OH-Be there is selective cationic membrane
Gear is at cathode chamber and the Li come from anode chamber+It is combined into product lithium hydroxide, H+Generate under catholyte effect
H2.Current efficiency is higher than 75%, and average working voltage is 3.0～3.4V, and hydrogen and chlorine that electrolysis produces can conducts
Byproduct is used.The a small amount of sodium chloride contained in anolyte lithium chloride does not produce impact to electrolysis and product,
According to electrolysis index and the physical property of product controlled hydrogen manufacturing sodium oxide molybdena and the separation of lithium hydroxide, NaOH in electrolytic process
Mother liquor after solution and part catholyte condensing crystallizing separate removes to adjust the pH of solution, hydroxide during refined bittern
The concentrated available lithium hydroxide monohydrate product of lithium solution.
Present invention process is simple, it is easy to control, and operating reliability is high, and the lithium hydroxide product purity obtained is high, can
It is directly used in the lithium source of lithium base grease, battery industry and other lithium product, need not again purify.
The present invention is to utilize salt lake bittern electrolytic preparation lithium hydroxide monohydrate, and current efficiency is higher than 75%, averagely
Operating voltage is 3.0～3.4V, and product purity is more than 99.8%.
This invention removes public hazards and environmental pollution that diaphragm process uses asbestos, mercury process to use mercury to cause.
The present invention is directed the salt lake bittern of high Mg/Li ratio, the impurity-removing method during brine refining is fairly simple,
Have employed domestic cationic membrane (such as Eastern Mountain DF988) during electrolysis, the rate of recovery of lithium is high, and cost ratio is relatively low, without secondary
Pollute.
The present invention compared with prior art has the advantage that
1) product purity is high: do not introduce other ion in the electrolytic chlorination lithium solution of the present invention, miscellaneous in the product obtained
Matter content is low.
2) low cost: electrolytic cell and ionic membrane are all domestic, and price is relatively low.
3) yield of lithium is high: anolyte cyclic electrolysis, the yield of lithium is close to 100%；Catholyte through be concentrated by evaporation,
Mother liquor after separation of solid and liquid can be circulated electrolysis as catholyte again.
4) technique is simple and easy to control: the salt lake bittern removal of impurities to Selective Separation high Mg/Li ratio is simple, electrolytic refining bittern,
Its technique is simple, it is easy to controlling, operating reliability is higher, applied widely.
5) sodium chloride impact on product purity in anolyte can be controlled during electrolysis.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the inventive method.
Detailed description of the invention
With Qinghai magnesium sulfate magnesium chloride saturated bittern Han lithium as raw material, by instantiation, the present invention is electrolysed
The method preparing lithium hydroxide is described further.
Concentrated by salt pan solar evaporation as it is shown in figure 1, the original salt lake bittern of lithium will be contained, obtain high Mg/Li ratio bittern.
Consisting of (g/L): Li5.11, Mg124.02, Ca0.82, Na1.93, K0.91, Cl334.79, SO4 2-35.60,H3BO3
51.4, the high Mg/Li ratio bittern obtained through removal of impurities, be electrolysed, evaporate, crystallize and obtain lithium hydroxide monohydrate.
Embodiment one
(1) preparation of refined bittern
First the bittern of the saturated magnesium chloride being concentrated to give by salt pan solar evaporation adjust its acid-base value with hydrochloric acid so that it is
PH value is maintained at 1.5, and in bittern, boron separates out with boric acid, is proportionally added into lime or white lime after separation of solid and liquid,
It is sufficiently stirred for, is filtered to remove magnesium and sulfate radical, obtain the electrolysis material liquid of low boron, low-sulfur.Then in temperature 50～
At 70 DEG C use two-step method demagging, first with lithium hydroxide adjust solution pH 8.5, the magnesium hydroxide of generation with
The magnesium ion of excess combines the boron ion in positively charged adsorbent solution, and separation of solid and liquid removes most magnesium, then
The pH adjusting solution with the mother liquor lithium hydroxide solution after Crystallization Separation and Lithium carbonate solution is 11.5, removes remaining
Magnesium and calcium, iron plasma, make magnesium in bittern, calcium, iron, boron plasma be down to minimum, be neutralized with hydrochloric acid this bittern,
If being necessary, the ion exchange resin recycling effects of boron resin and magnesium, calcium continues to remove boron ion, magnesium ion or calcium
Ion.
Continuing to concentrate bittern to the lithium ion mass fraction after purifying is 3.6% (being calculated as 22% with lithium chloride), chlorination
Concentrated brine insoluble in chloride containing lithium >=22% of sodium and potassium chloride and Precipitation, make sodium, the total concentration of potassium ion is protected
Hold below 5%, obtain refined bittern (main component is lithium chloride).
In salt lake brine with high magnesium-lithium ratio, Mg/Li ratio is at more than 40:1.
(2) electrolytic refining bittern
Selecting domestic cationic membrane Eastern Mountain DF988 and electrolytic cell, anolyte is refined bittern, and catholyte is that quality is divided
Number is 3% lithium hydroxide solution, and current density is 1.2kA/m2, electrolysis temperature is 55 DEG C, cathode and anode recycle stream
Amount is 0.2L/min, and now, current efficiency is 75.56%, and energy consumption is 4.475kWh/kg-1LiOH, average operation
Voltage is 3.02V, and hydrogen and chlorine that electrolysis produces can be used as byproduct.
Electrolysis before adjust anolyte acid-base value so that it is in pH between 2～3, can preferably suppress oxygen evolution reaction and
Chlorine dissolves the side reaction produced.
(3) catholyte condensing crystallizing
It is solid that electrolysis reaches can to separate out lithium hydroxide close to the most heated evaporation and concentration of catholyte of saturated concentration
Body, is cooled to 30 DEG C by solidliquid mixture, and vacuum filters or centrifugation, available lithium hydroxide monohydrate,
Scrubbed, be dried to obtain, at 60～90 DEG C, the lithium hydroxide monohydrate product that purity is higher.
After testing, in lithium hydroxide monohydrate product, lithium hydroxide monohydrate content is more than 99.8%, lithium yield
>=99.8%.
Embodiment two
(1) preparation of refined bittern
First the bittern of the saturated magnesium chloride being concentrated to give by salt pan solar evaporation adjust its acid-base value with hydrochloric acid so that it is
PH value is maintained at 2.5, and in bittern, boron separates out with boric acid, is proportionally added into lime or white lime after separation of solid and liquid,
It is sufficiently stirred for, is filtered to remove magnesium and sulfate radical, obtain the electrolysis material liquid of low boron, low-sulfur.Then in temperature 50～
At 70 DEG C use two-step method demagging, first with lithium hydroxide adjust solution pH 9.5, the magnesium hydroxide of generation with
The magnesium ion of excess combines the boron ion in positively charged adsorbent solution, and separation of solid and liquid removes most magnesium, then
The pH adjusting solution with the mother liquor lithium hydroxide solution after Crystallization Separation or Lithium carbonate solution is 12.5, removes remaining
Magnesium and calcium, iron plasma, make magnesium in bittern, calcium, iron, boron plasma be down to minimum, be neutralized with hydrochloric acid this bittern,
If being necessary, the ion exchange resin recycling effects of boron resin and magnesium, calcium continues to remove boron ion, magnesium ion or calcium
Ion.
Continuing to concentrate bittern to the lithium ion mass fraction after purifying is 3.7% (being calculated as 23% with lithium chloride), chlorination
Concentrated brine insoluble in chloride containing lithium >=22% of sodium and potassium chloride and Precipitation, make sodium, the total concentration of potassium ion is protected
Hold below 5%, obtain refined bittern (main component is lithium chloride).
In salt lake brine with high magnesium-lithium ratio, Mg/Li ratio is at more than 40:1.
(2) electrolytic refining bittern
Select domestic cationic membrane and electrolytic cell, anolyte be lithium chloride mass fraction be the refined bittern of 23%, cloudy
Pole liquid be mass fraction be 3% lithium hydroxide solution, current density is 2.0kA/m2, electrolysis temperature is 56 DEG C, cloudy,
Anode circulation flow is 0.33L/min, and now, current efficiency is 75.65%, and energy consumption is 5.032kWh/kg-1LiOH,
Average working voltage is 3.4V, and hydrogen and chlorine that electrolysis produces can be used as byproduct.
Electrolysis before adjust anolyte acid-base value so that it is in pH between 2～3, can preferably suppress oxygen evolution reaction and
Chlorine dissolves the side reaction produced.
(3) catholyte condensing crystallizing
It is solid that electrolysis reaches can to separate out lithium hydroxide close to the most heated evaporation and concentration of catholyte of saturated concentration
Body, is cooled to 50 DEG C by solidliquid mixture, and vacuum filters or centrifugation, available lithium hydroxide monohydrate,
Scrubbed, be dried to obtain, at 60～90 DEG C, the lithium hydroxide monohydrate product that purity is higher.
After testing, in lithium hydroxide monohydrate product, lithium hydroxide monohydrate content is more than 99.8%, lithium yield
>=99.9%.
Embodiment three
(1) preparation of refined bittern
First the bittern of the saturated magnesium chloride being concentrated to give by salt pan solar evaporation adjust its acid-base value with hydrochloric acid so that it is
PH value is maintained at 2, and in bittern, boron separates out with boric acid, is proportionally added into lime or white lime, fills after separation of solid and liquid
Divide stirring, be filtered to remove magnesium and sulfate radical, obtain the electrolysis material liquid of low boron, low-sulfur.Then temperature 50～70 DEG C
Lower employing two-step method demagging, first with the pH of lithium hydroxide adjustment solution 9, the magnesium hydroxide of generation and excess
Magnesium ion combines the boron ion in positively charged adsorbent solution, and separation of solid and liquid removes most magnesium, then with crystallization
It is 12 that mother liquor lithium hydroxide solution after separation and Lithium carbonate solution adjust the pH of solution, remove remaining magnesium and calcium,
Iron plasma, makes magnesium in bittern, calcium, iron, boron plasma be down to minimum, is neutralized with hydrochloric acid this bittern, must if having
The ion exchange resin of effects of boron resin to be recycled and magnesium, calcium continues to remove boron ion, magnesium ion or calcium ion.
Continuing to concentrate bittern to the lithium ion mass fraction after purifying is 3.6% (being calculated as 22% with lithium chloride), chlorination
Concentrated brine insoluble in chloride containing lithium >=22% of sodium and potassium chloride and Precipitation, make sodium, the total concentration of potassium ion is protected
Hold below 5%, obtain refined bittern (main component is lithium chloride).
In salt lake brine with high magnesium-lithium ratio, Mg/Li ratio is at more than 40:1.
(2) electrolytic refining bittern
Select domestic cationic membrane and electrolytic cell, anolyte be lithium chloride mass fraction be the refined bittern of 22%, cloudy
Pole liquid is mass fraction 2% lithium hydroxide solution, and current density is 2.4kA/m2, electrolysis temperature is 59 DEG C, cloudy,
Anode circulation flow is 0.2L/min, and now, current efficiency is 76.37%, and energy consumption is 4.443kWh/kg-1LiOH,
Average working voltage is 3.04V, and hydrogen and chlorine that electrolysis produces can be used as byproduct.
Electrolysis before adjust anolyte acid-base value so that it is in pH between 2～3, can preferably suppress oxygen evolution reaction and
Chlorine dissolves the side reaction produced.
(3) catholyte condensing crystallizing
It is solid that electrolysis reaches can to separate out lithium hydroxide close to the most heated evaporation and concentration of catholyte of saturated concentration
Body, is cooled to 40 DEG C by solidliquid mixture, and vacuum filters or centrifugation, available lithium hydroxide monohydrate,
Scrubbed, be dried to obtain, at 60～90 DEG C, the lithium hydroxide monohydrate product that purity is higher.
After testing, in lithium hydroxide monohydrate product, lithium hydroxide monohydrate content is more than 99.8%, lithium yield
>=99.9%.
Embodiment four
(1) preparation of refined bittern
First the bittern of the saturated magnesium chloride being concentrated to give by salt pan solar evaporation adjust its acid-base value with hydrochloric acid so that it is
PH value is maintained at 2, and in bittern, boron separates out with boric acid, is proportionally added into lime or white lime, fills after separation of solid and liquid
Divide stirring, be filtered to remove magnesium and sulfate radical, obtain the electrolysis material liquid of low boron, low-sulfur.Then temperature 50～70 DEG C
Lower employing two-step method demagging, first with the pH of lithium hydroxide adjustment solution 9, the magnesium hydroxide of generation and excess
Magnesium ion combines the boron ion in positively charged adsorbent solution, and separation of solid and liquid removes most magnesium, then with crystallization
It is 12 that mother liquor lithium hydroxide solution after separation and Lithium carbonate solution adjust the pH of solution, remove remaining magnesium and calcium,
Iron plasma, makes magnesium in bittern, calcium, iron, boron plasma be down to minimum, is neutralized with hydrochloric acid this bittern, must if having
The ion exchange resin of effects of boron resin to be recycled and magnesium, calcium continues to remove boron ion, magnesium ion or calcium ion.
Continuing to concentrate bittern to the lithium ion mass fraction after purifying is 4.6% (being calculated as 28% with lithium chloride), chlorination
Concentrated brine insoluble in chloride containing lithium >=22% of sodium and potassium chloride and Precipitation, make sodium, the total concentration of potassium ion is protected
Hold below 5%, obtain refined bittern (main component is lithium chloride).
In salt lake brine with high magnesium-lithium ratio, Mg/Li ratio is at more than 40:1.
(2) electrolytic refining bittern
Select domestic cationic membrane and electrolytic cell, anolyte be lithium chloride mass fraction be the refined bittern of 28%, cloudy
Pole liquid is mass fraction 3% lithium hydroxide solution, and current density is 1.6kA/m2, electrolysis temperature is 65 DEG C, cloudy,
Anode circulation flow is 0.2L/min, and now, current efficiency is 75.11%, and energy consumption is 4.934kWh/kg-1LiOH,
Average working voltage is 3.31V, and hydrogen and chlorine that electrolysis produces can be used as byproduct.
Electrolysis before adjust anolyte acid-base value so that it is in pH between 2～3, can preferably suppress oxygen evolution reaction and
Chlorine dissolves the side reaction produced
(3) catholyte condensing crystallizing
It is solid that electrolysis reaches can to separate out lithium hydroxide close to the most heated evaporation and concentration of catholyte of saturated concentration
Body, is cooled to 40 DEG C by solidliquid mixture, and vacuum filters or centrifugation, available lithium hydroxide monohydrate,
Scrubbed, be dried to obtain, at 60～90 DEG C, the lithium hydroxide monohydrate product that purity is higher.
After testing, in lithium hydroxide monohydrate product, lithium hydroxide monohydrate content is more than 99.8%, lithium yield
>=99.9%.
Claims (4)
1. the method utilizing salt lake bittern electrolytic preparation lithium hydroxide, said method comprising the steps of:
1) the original salt lake bittern of lithium will be contained concentrated by salt pan solar evaporation, obtain high Mg/Li ratio bittern；
2) high Mg/Li ratio bittern is obtained refined bittern through removal of impurities；
3) it is electrolysed as catholyte as anolyte, lithium hydroxide solution using refined bittern, passes through cationic membrane
Lithium hydroxide monohydrate solution is obtained at cathode chamber；
4) lithium hydroxide monohydrate solution is dried through evaporation and concentration, crystallisation by cooling, washing, obtains lithium hydroxide one
Hydrate, the mother liquor obtained after crystallisation by cooling is circulated electrolysis or for high Mg/Li ratio bittern as electrolysis cathode liquid
Removal of impurities regulates the pH of solution；
Described step 2) dedoping step be: first adjust its acid-base value with hydrochloric acid so that it is pH value be maintained at 1.5～
2.5, the boron ion in bittern separates out as boric acid, is proportionally added into lime or white lime, fills after separation of solid and liquid
Divide stirring, be filtered to remove magnesium ion and sulfate radical, obtain the electrolysis material liquid of low boron, low-sulfur；
Then at temperature 50～70 DEG C, use two-step method demagging, first adjust the pH of electrolysis material liquid with lithium hydroxide
Being 8.5～9.5, the magnesium hydroxide of generation is combined the boron ion in positively charged adsorbent solution with the magnesium ion of excess, Gu
Liquid is separated off magnesium ion；Then by step 4) mother liquor that obtains after crystallisation by cooling and/or Lithium carbonate solution adjust molten
The pH of liquid is 11.5～12.5, removes magnesium ion, calcium ion and the iron ion of residual in solution, is neutralized with hydrochloric acid this
Solution, neutralizer is concentrated into lithium ion mass fraction and is higher than 3.6%, now, sodium chloride and potassium chloride Precipitation,
Remove precipitation and obtain the lithium chloride mass fraction refined bittern more than 22%.
The method utilizing salt lake bittern electrolytic preparation lithium hydroxide the most according to claim 1, it is characterised in that
Described step 3) ionization process be: selecting domestic cationic membrane and electrolytic cell, anolyte is refined bittern, its chlorine
Changing lithium mass fraction and be more than 22%, catholyte is lithium hydroxide solution, and its lithium hydroxide mass fraction is less than 3%, electricity
Current density is 1.0～2.4kA/m2, electrolysis temperature >=55 DEG C, average working voltage is 3.0～3.4V, and electrolysis produces
Hydrogen and chlorine are as byproduct.
The method utilizing salt lake bittern electrolytic preparation lithium hydroxide the most according to claim 2, it is characterised in that
The hydrogen that the chlorine that described electrolysis produces and electrolysis produce reacts generation hydrochloric acid, or the chlorine that electrolysis produces is through liquefaction
Obtain liquid chlorine.
The method utilizing salt lake bittern electrolytic preparation lithium hydroxide the most according to claim 1, it is characterised in that
Described step 4) process be: electrolysis reaches the most heated evaporation and concentration of the catholyte of nearly saturated concentration and separates out
Lithium hydroxide solid, is cooled to 30～50 DEG C of crystallizations by solidliquid mixture, and vacuum filters or centrifugation, obtains hydrogen
Lithia monohydrate, scrubbed, at 60～90 DEG C of content being dried to obtain lithium hydroxide monohydrate more than 99.8%
Lithium hydroxide monohydrate product.
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| CN105177288B (en) * | 2015-10-28 | 2018-04-03 | 中国科学院青海盐湖研究所 | A kind of method that lithium hydroxide is prepared using salt lake brine with high magnesium-lithium ratio |
| CN106011917B (en) * | 2016-07-06 | 2017-06-27 | 启迪清源（北京）科技有限公司 | The production method of high-purity hydrogen lithia |
| CN108660476B (en) * | 2017-08-10 | 2019-04-02 | 青海盐湖工业股份有限公司 | A kind of new process of salt lake bittern production high-purity hydrogen lithia |
| CN108217670A (en) * | 2018-03-13 | 2018-06-29 | 西南科技大学 | A kind of method for being electrolysed salt lake bittern extraction boric acid |
| WO2020033988A1 (en) * | 2018-08-17 | 2020-02-20 | Lithtech Industries Pty Ltd | An improved electrochemical cell arrangement and method for separating impurities |
| CN112673119A (en) * | 2018-08-17 | 2021-04-16 | 利特科技工业有限公司 | Improved lithium processing method |
| CN109267086B (en) * | 2018-10-30 | 2021-01-05 | 吉首大学 | Device and method for separating magnesium/lithium and enriching lithium in salt lake brine |
| CN110029354B (en) * | 2019-05-08 | 2020-10-13 | 蓝星(北京)化工机械有限公司 | Method for preparing battery-grade lithium hydroxide by direct electrolysis of lithium chloride |
| RU2713360C2 (en) * | 2019-09-25 | 2020-02-04 | Общество с ограниченной ответственностью "Экостар-Наутех" | Method of producing lithium hydroxide monohydrate from brines |
| CN112830527B (en) * | 2021-04-22 | 2021-07-13 | 金驰能源材料有限公司 | Precursor of hollow cathode material and preparation method thereof |
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| US3597340A (en) * | 1968-11-05 | 1971-08-03 | Lithium Corp | Recovery of lithium as lioh.h20 from aqueous chloride brines containing lithium chloride and sodium chloride |
| US4036713A (en) * | 1976-03-04 | 1977-07-19 | Foote Mineral Company | Process for the production of high purity lithium hydroxide |
| JP5269186B2 (en) * | 2008-04-22 | 2013-08-21 | ロックウッド・リチウム・インコーポレイテッド | Method for producing high purity lithium hydroxide and hydrochloric acid |
| CN101712481A (en) * | 2009-12-08 | 2010-05-26 | 耿世达 | Method for preparing high-purity lithium carbonate and other available byproducts from salt lake brine |
| CN102602966B (en) * | 2012-04-06 | 2014-01-08 | 华东理工大学 | Method for separating magnesium and lithium in salt lake brine and preparing lithium carbonate |
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